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CN101042946A - Silver alloy material, circuit board, electronic device and method of producing circuit board - Google Patents

Silver alloy material, circuit board, electronic device and method of producing circuit board Download PDF

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Publication number
CN101042946A
CN101042946A CN 200710092059 CN200710092059A CN101042946A CN 101042946 A CN101042946 A CN 101042946A CN 200710092059 CN200710092059 CN 200710092059 CN 200710092059 A CN200710092059 A CN 200710092059A CN 101042946 A CN101042946 A CN 101042946A
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CN
China
Prior art keywords
wiring
silver
indium
electrode
silver alloy
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CN 200710092059
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Chinese (zh)
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CN101042946B (en
Inventor
斋藤裕一
藤井晓义
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Sharp Corp
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Sharp Corp
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Priority claimed from JP2004185264A external-priority patent/JP4498835B2/en
Priority claimed from JP2004185228A external-priority patent/JP4421394B2/en
Application filed by Sharp Corp filed Critical Sharp Corp
Publication of CN101042946A publication Critical patent/CN101042946A/en
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Publication of CN101042946B publication Critical patent/CN101042946B/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Thin Film Transistor (AREA)

Abstract

A circuit substrate of the present invention uses as component materials for gate lines and gate electrodes, silver alloy material containing silver as a main component, and at least one element selected from the group consisting of tin, zinc, lead, bismuth, indium, and gallium. It is especially preferable that the silver alloy material mainly consisting of silver and containing indium is used for the gate lines and the gate electrodes. With this, it is possible to provide silver alloy material whose resistance value, adhesion, plasma resistance, and reflection characteristics can be appropriately adjusted by the adjustment of the content of indium. Further, it is also possible to apply the alloy in accordance with the characteristic required for each part of the circuit substrate.

Description

The manufacture method of silver alloy, circuit substrate, electronic installation and circuit substrate
Female case applying date of the application is on July 22nd, 2004, and application number is: 200410054483.X
Technical field
The present invention relates to silver alloy, be particularly related to silver alloy on the circuit substrate that uses the insulating properties substrate, that constitute wiring and/or electrode, with this material or mobile silver alloy material in addition, the circuit substrate of formed wiring and/or electrode and the manufacture method of circuit substrate, and the display unit and the electronic installations such as liquid crystal indicator, image-input device that use circuit substrate.
Background technology
As the liquid crystal indicator of one of electronic installation, have the FT array base palte that has most TFT (thin-film transistor), wiring as substrate.
In the past, tft array substrate was to use the series of processes shown in the non-patent literature 1 (" flat-panel monitor ", 1999, Nikkei microelectronics is write, Nikkei BP Co., Ltd., the 129th page) to be made, and wherein needed to carry out the photoetching about five times.
In the TFT manufacture of substrates that uses existing like this photoetching technique, because processing unit (plant)s such as film formation device that use is used in each film formation process and dry-etching device or the like many vacuum plants, so the TF substrate for needing to make nearly step maximization in recent years needs huge cost of equipment.
In order to solve this problem, the someone proposes to use ink-jetting style to form wiring etc.For this technology, for example as patent documentation 1 (the open communique of Japan Patent: the spy opens flat 11-203429 communique (on July 30th, 1999 is open)) is disclosed, by on the substrate that forms wiring, formation forms the affine zone and the non-affine zone of material to wiring, with drip in the affine zone drop of wiring material of ink-jet method, form wiring in this way.
And according to disclosing in patent documentation 2 (the open communique of Japan Patent: the spy opens 2000-353594 communique (on December 19th, 2000 is open)), forming in the technology of wiring with ink-jetting style equally, ooze out from wiring formation zone in order to control wiring material, the both sides that form the zone in wiring form storage lattice cofferdam (bank), the top in this storage lattice cofferdam made non-lyophily, wiring is formed the zone make lyophily.
Form the material of wiring usefulness with this ink-jetting style, shown in non-patent literature 2 (" Nikkei electron " on June 17th, 2002 (Nikkei BP Co., Ltd.) the 67th~78 page), use nano particle with silver and gold to be dispersed in the material that contains mobile metal (printing ink) in the solvent.These materials wait processing through burning till after predetermined location is dripped on the substrate, manifest contained metal, form to connect up etc.Thus, as the metal that can process mobile metal-containing material, except that gold and silver, can also enumerate palladium and platinum etc.Yet, consider raw-material price, it is real that silver is wherein only arranged.
Under this reason, as the constituent material that connects up on the tft array substrate, and the wiring material when making other circuit substrates, can consider the silver that can use with ink-jetting style.
Though and used aluminium mostly as wiring material on tft array substrate and so on circuit substrate and optical reflection film material in the past, but people know, silver has the advantage that resistivity is low, the reflectivity of visible region is high, so have the character more better than aluminium.
Given this, though silver as the wiring material on the circuit substrate extremely people gaze at, but be restricted in the qualitative scope of application.Silver for example uses vapour deposition method, sputtering method etc. under the situation of film forming on the glass substrate, even also can produce germination and surface hazeization in burning till about 250 ℃, obviously lacks thermal endurance.On this external glass substrate adhesive force also a little less than.
Especially when making tft array substrate, use the dry-etching method mostly for dielectric film etc. being carried out etching etc.Silver is significantly low for the patience (plasma-resistance) of this environment.Therefore, as the constituent material that connects up on the tft array substrate, be a kind of directly material of use that is unsuitable for silver.
In addition, existing silver-colored poor heat resistance also can make reflectivity descend significantly even for example burn till through 200 ℃.Therefore, existing silver needing under the stable on heating situation in manufacture process can not be used for.For example in reflection-type liquid-crystal display device, be difficult to use with material as the optical reflection film that is provided with on the tft array substrate.
And in above-mentioned non-patent literature 2, disclose a kind of use silver or gold particle have been dispersed in mobile wiring material in the solvent, as the material that forms wiring usefulness with above-mentioned ink-jetting style.These materials wait processing through burning till after predetermined location on the substrate is dripped, show contained metal and form and connect up.Therefore, as can enumerating palladium and platinum etc. beyond desilver or the gold to the metal of mobile wiring material processing.
Yet in case consider raw-material price, it is real wherein having only silver.About using this silver to form the problem of wiring, in patent documentation 3 (the open communique of Japan Patent: the spy opens 2003-80694 communique (on March 19th, 2003 is open)) a kind of Wiring method that does not use storage lattice cofferdam is disclosed.
Consider that with this reason the silver that has only use can use is as the material that constitutes wiring on this spr substrate of TFT in ink-jetting style.
But under the situation that forms the pellicular cascade substrate, for example be subjected under the situation of the tft array substrate that ejector half uses at liquid crystal, there is the resistance should be low for the desired performance of wiring, the surface should be level and smooth, have patience to process gas such as etching with in the plasma that uses this gas, with the tack of base material, and the electrically contacting property between the foreign material is that contact resistance should be low, and can not cause unwanted diffusion and should have corrosion resistance etc.
Yet, use a kind of material to be difficult to summarize all these performances, when sputter, evaporation and CVD film forming, simple substance or its alloy that will have the performance of fit for purpose carry out stacked film forming, have carried out pattern formation through photo-mask process, etching work procedure.
And in the method for the ink-jetting style formation wiring of using wiring formation operation to be simplified, as the ag material that can be used material by ink-jet, in the past the disperse particles colloidal materials form of microparticulate in dispersant obtained use, though enjoy as the wiring material on the circuit substrate with it and to gaze at, but limited the scope of application in nature.
For example, will make silver under the situation of film forming on the glass substrate with vapour deposition method, sputtering method etc., owing to about 250 ℃, burn till, make germination become remarkable, therefore level and smooth surface is become and slightly make, produce surface haze etc., thereby have Yin Wendu and make the significantly not enough problem of thermal endurance.
And, in order to use silver with form of film, must have adhesive force on glass, particularly during the silver coating material owing to can not expect the effect of squeezing on substrate, thus with the poor adhesive force of glass substrate, have the problem of processing characteristics and stability.In addition, if will use sintering method to improve adhesive force, then produce the problem of surface smoothing deterioration owing to above-mentioned silver-colored growth characteristics.
In addition, even under the situation that constitutes wiring on the tft array substrate, also have problems.Use etching dry-etching methods such as dielectric film when for example, making tft array substrate mostly.In case be exposed under the atmosphere of this dry etching gases, will produce the deterioration of film and peel off because of oxidation etc.Directly use silver as the problem that exists on the wiring material for this reason.
Therefore; use silver to do under the situation of wiring material; be necessary for the adhesive force of raising on the insulating properties substrate and handle for solving above-mentioned variety of issue; perhaps for preventing the surface smoothing deterioration that causes because of heating and prevent the film deterioration that etching causes, stop to peel off and in the silver wiring, form the film of diaphragm.That is to say that produce the problem that makes the film multiple stratification on the insulating properties substrate, its result will increase the number of circuit substrate manufacturing process, but also causes the problem that cost rises.
Summary of the invention
The object of the invention is to provide a kind of thermal endurance that can obtain to have, strong adhesion on glass substrate, and plasma-resistance height, and the silver alloy of the good material of light reflectivity, provide a kind of simultaneously and can prevent the multiple stratification of film, manufacturing process's number increases and cost rises circuit substrate and the manufacture method and the electronic installation of circuit substrate.
For achieving the above object, the inventor etc. find through the further investigation back, when being main component with silver, the alloy particle that adds indium therein is as material, forming on the insulating properties substrate under the situation of wiring or electrode, compare as material forms wiring or electrode on the insulating properties substrate situation with the particulate with silver-colored simple substance, wiring and the electrode adhesive force on the insulating properties substrate improves, and thermal endurance, the plasma-resistance of wiring and electrode also are improved simultaneously.And find not only above-mentioned silver, also can obtain same effect even in silver, added the alloy of tin, zinc, lead, bismuth, gallium.
But also find even then under 200 ℃ or 300 ℃, burn till, also can obtain the silver alloy film of the visible reflectance that maintenance is high as if film forming behind an amount of indium of adding in silver.Such silver alloy film is compared with the situation of the optical reflection film that used aluminium in the past, because reflectivity height generally, so in case when using, can obtain bright more display effect on the light reflective electrode of for example reflection-type liquid-crystal display device etc.
That is to say, silver alloy of the present invention, it is the constituent material of a kind of wiring that on the insulating properties substrate, forms and/or electrode, it is characterized in that, wherein with silver as main component, the content that contains with respect to silver is the indium of 0.5~28 weight %, also contains more than one elements of selecting from tin, zinc, lead, bismuth and gallium.
Use the material of above-mentioned formation, it is low to form resistance, strong wiring and/or the electrodes of technology patience such as thermal endurance or the adhesive force on glass substrate, plasma-resistance.
And present inventor etc. finds through the further investigation back, by necessary characteristic being adjusted at each position of wiring with same wiring, the number that can reduce electrode base board manufacturing process with reduce cost.
That is to say that power substrate of the present invention is characterized in that, on having substrate, formed in the circuit substrate of wiring that the characteristic at least two positions is different respectively.
Wherein, same wiring is meant continuous in shape wiring, and the circuit on substrate forms circuit substrate by converging a plurality of such wirings, and refers to a unit of these a plurality of wirings.
For the characteristic that makes certain position of same wiring is different with the characteristic at other positions, for example can use the different respectively mode of ratio of components of each part material to realize.But also can realize by the different respectively mode of constituent material that makes each position.
Other purposes of the present invention, feature and advantage will be more readily apparent from by explanation shown below.And advantage of the present invention, will be clearer by the following explanation of reference accompanying drawing.
Description of drawings
Fig. 1 is the plan view of the circuit substrate that relates to of one embodiment of the present invention.
Fig. 2 is along the cross section view of the A-A line direction of arrow among Fig. 1.
Fig. 3 (a) is near the plan view the expression circuit substrate upper terminal shown in Figure 1.
Fig. 3 (b) is along the cross section view of the B-B line direction of arrow among Fig. 3 (a).
Fig. 4 is the plan view of the tft array substrate of an expression circuit substrate example shown in Figure 1.
Fig. 5 is a structural representation of making circuit board use manufacturing installation of the present invention.
Fig. 6 is the process chart of expression circuit substrate of the present invention manufacturing process.
The plan view of pixel portion when Fig. 7 (a) is the termination of expression grid wiring pretreatment procedure.
The plan view of pixel portion when Fig. 7 (b) is the termination of expression grid wiring formation operation.
Fig. 7 (c) is along the cross section view of the C-C line direction of arrow in the presentation graphs 7 (b).
The plan view of portion of terminal when Fig. 8 (a) is the termination of expression grid wiring pretreatment procedure.
The plan view of portion of terminal when Fig. 8 (b) is the termination of expression grid wiring formation operation.
Fig. 8 (c) is along the cross section view of the D-D line direction of arrow among Fig. 8 (b).
Fig. 9 (a)~Fig. 9 (d) is the view that territory, close and distant liquid zone forms operation in the grid wiring pretreatment procedure.
The plan view of pixel portion when Figure 10 (a) is expression gate insulating film and the termination of semiconductor film film formation process.
Figure 10 (b) is the cross section view of Figure 10 (a) along the E-E line direction of arrow.
The plan view of terminal part when Figure 11 (a) is expression gate insulating film and the termination of semiconductor film film formation process.
Figure 11 (b) is the cross section view of Figure 11 (a) along the F-F line direction of arrow.
The plan view of pixel portion when Figure 12 (a) is expression gate insulating film and the termination of semiconductor film manufacturing procedure.
Figure 12 (b) is the cross section view of Figure 12 (a) along the G-G line direction of arrow.
The plan view of terminal part when Figure 13 (a) is expression gate insulating film and the termination of semiconductor film manufacturing procedure.
Figure 13 (b) is the cross section view of Figure 13 (a) along the H-H line direction of arrow.
The plan view of pixel portion when Figure 14 (a) is expression source wiring and the termination of leak routing pretreatment procedure.
The plan view of pixel portion when Figure 14 (b) is expression source wiring and the termination of leak routing formation operation.
Figure 14 (c) is the cross section view of Figure 14 (b) along the I-I direction of arrow.
Pixel portion when Figure 15 is the termination of expression channel part manufacturing procedure is with the suitable cross section view of I-I line position of Figure 14 (b).
The plan view of pixel portion when Figure 16 (a) is expression diaphragm and the termination of interlayer insulating film film formation process.
Figure 16 (b) is the cross section view of Figure 16 (a) along the J-J line direction of arrow.
The plan view of terminal part when Figure 17 (a) is expression diaphragm and the termination of interlayer insulating film film formation process.
Figure 17 (b) be Figure 17 (a) along the K-K line direction of arrow cross section view.
The view of pixel portion and portion of terminal when Figure 18 (a) is the termination of expression diaphragm manufacturing procedure, the cross section view of the direction of arrow on the J-J line position of Figure 16 (a).
The view of pixel portion and portion of terminal when Figure 18 (b) is the termination of expression diaphragm manufacturing procedure, the cross section view of the direction of arrow suitable with the K-K line position of Figure 17 (a).
Figure 19 (a) is the plan view of circuit substrate portion of terminal in expression another embodiment of the present invention.
Figure 19 (b) is the cross section view of Figure 19 (a) along the L-L line direction of arrow.
Figure 20 is the curve chart of visible reflectance of the silverskin of the comparative example 1 shown in the table 1.
Figure 21 is the curve chart of visible reflectance of the aluminium film of the comparative example 3 shown in the table 1.
Figure 22 is the curve chart of visible reflectance of the silver alloy film (indium 0.05 weight %) of the embodiment 7 shown in the table 1.
Figure 23 is the curve chart of visible reflectance of the silver alloy film (indium 0.2 weight %) of the embodiment 8 shown in the table 1.
Figure 24 is the curve chart of visible reflectance of the silver alloy film (indium 0.5 weight %) of the embodiment 3 shown in the table 1.
Figure 25 is the curve chart of visible reflectance of the silver alloy film (indium 1.6 weight %) of the embodiment 4 shown in the table 1.
The plan view of pixel portion when Figure 26 (a) is the termination of expression grid wiring formation operation.
Figure 26 (b) is the cross section view along the M-M line direction of arrow of Figure 26 (a).
The plan view of portion of terminal when Figure 27 (a) is the termination of expression grid wiring formation operation.
Figure 27 (b) is the cross section view of Figure 27 (a) along the N-N line direction of arrow.
Figure 28 is the plan view of the circuit substrate that relates to of expression the present invention other execution modes.
Figure 29 is the cross section view of Figure 28 circuit substrate along the O-O line direction of arrow.
Figure 30 (a) is near the plan view of terminal of expression circuit substrate shown in Figure 28.
Figure 30 (b) is the cross section view of Figure 30 (a) along straight line P-P.
Figure 31 (a) is near the plan view of other examples the expression circuit substrate terminal shown in Figure 1.
Figure 31 (b) is the cross section view of Figure 31 (a) along the Q-Q line direction of arrow.
Figure 32 (a)~32 (e) is the schematic diagram that expression circuit substrate wiring portion of the present invention and portion of terminal form operation.
Figure 33 (a) is expression has formed the state of wiring portion with material M figure.
Figure 33 (b) is expression forms the state of portion of terminal with material N figure.
Figure 34 (a)~Figure 34 (c) is the figure of the state of the boundary member that contacts with N of expression material M.
Figure 35 is the schematic diagram of grid wiring in the expression circuit substrate of the present invention.
Figure 36 (a) is the figure of the existing wiring pattern of expression.
Figure 36 (b) is the figure of expression wiring pattern of the present invention.
Figure 37 (a) and (b) are the figure that form other examples of wiring in the expression circuit substrate of the present invention.
Figure 38 (a) and (b) are the schematic diagrames that form the other example of wiring in the expression circuit substrate of the present invention.
Figure 39 (a) and (b) are the figure that form the another example of wiring in the expression circuit substrate of the present invention.
Figure 40 (a)~Figure 40 (c) is the figure that forms other examples of wiring in the expression circuit substrate of the present invention.
The plan view of pixel portion when Figure 41 (a) is the termination of expression grid wiring formation operation.
Figure 41 (b) is along the cross section view of the R-R line direction of arrow among Figure 41 (a).
The plan view of portion of terminal when Figure 42 (a) is the termination of expression grid wiring formation operation.
Figure 42 (b) is along the cross section view of the S-S line direction of arrow among Figure 42 (a).
Embodiment
(execution mode 1)
Embodiments of the present invention specify as follows.
In the embodiments of the present invention, silver alloy of the present invention is described at first, the tft array substrate and the liquid crystal indicator of this silver alloy used in explanation then.
Silver alloy of the present invention is the wiring that forms on insulating properties substrates such as glass substrate and/or the constituent material of electrode, it is characterized in that, with silver as main body, contain from tin, zinc, lead, bismuth, indium and gallium select at least a more than element.
According to the silver alloy that uses above-mentioned formation, can form that resistance is low, thermal endurance and to strong wiring and/or electrodes of operational characteristic such as the adhesive force of glass substrate and plasma-resistances.
Following with reference to embodiment 1~9 and comparative example 1 and 2, prove above-mentioned advantage to silver alloy of the present invention.
Silver alloy of the present invention is made in the following order, and on the insulating properties substrate film forming post-evaluation technology patience.
The preparation of silver alloy of the present invention and the film forming of this silver alloy on the insulating properties substrate are to use electron beam evaporation plating machine (ULVAC Corp makes, high vacuum vapor deposition device EBX-10D) to utilize vapour deposition method to carry out.
At first the block or granular raw material with the silver of purity more than 99.9%, tin, zinc, lead, bismuth, indium, gallium mixes as evaporation source according to predetermined ratio.
Then, mixed raw material is put into the crucible of molybdenum system, be higher than 1.33329 * 10 -3Pa (1 * 10 -5Holder) fuses under the vacuum, made alloy.
At last, after confirming fusion fully, film forming on alkali-free glass.Also have, the glass substrate temperature during with film forming is set in 100 ℃.And all be made for about 0.2 micron at the thickness of the alloy film of film forming on the glass substrate.
In the present embodiment,, be not limited to this though the preparation of alloy and film forming have been used this method.Also can use solid solution or sintered body, other sputtering methods, contain the coating process or the additive method of the mobile fluent material of metal with debita spissitudo with target.
The silver alloy film of making like this, (Parking Erma SAM670) has confirmed composition to utilize Auger formula electronics light-dividing device.Though the composition skewness on film thickness direction, but difference to some extent between all ratio of componentss of made silver alloy film and the mixing ratio of raw material.Yet this difference does not influence purpose of the present invention, means and effect etc.The silver alloy film of making is the representative embodiment of the present invention eventually.
Alloy film about silver and indium are formed for knowing its composition more accurately, has carried out quantitative analysis by the ICP emission spectrometry method.This method is as follows.
At first use will the silver alloy film of film forming strips down on alkali-free glass substrate by the little spoon of metallic film as sample.Before peeling off, the thickness of silver alloy film is about 0.2 micron on the glass substrate, and the sample size that obtains is about 10 milligrams in each embodiment.Then with solution the mensuration liquid that as ICP emission spectrographic analysis use of this sample dissolution in 3N, 50 milliliters of nitric acid.The SPS-1700HVR that determinator uses SIINano Technology Co., Ltd. to make, plasma gas has used argon gas.
In the present embodiment, estimated adhesive force, thermal endurance, resistivity and plasma-resistance technology patience as silver alloy film.These projects are the most basic projects as the wiring on the circuit substrate etc.Projects are described in detail as follows.
Adhesive force is directly being studied after the film forming on the alkali-free glass substrate.
Just as the present invention, when imagination was used to target with circuit substrate, the adhesive force on glass substrate was a useful index.
Here adhesion test carries out after burning till processing through 1 hour under 200 ℃ in nitrogen atmosphere.After burning till, use and pasting adhesive tape, the method that stripping tape strips down face on the face that lancinates.See a part of face be stripped from be judged to be bad, and will can't see fully peel off be judged to be good.
Thermal endurance is estimated, and is that (Hitachi, S-4100) method of Guan Chaing is carried out with electron microscope to the film surface after burning till through 1 hour under 300 ℃ in nitrogen atmosphere.At face concavo-convex situation not taking place fully and be judged to be very, be judged to be well slightly less than the situation of the projection of thickness and will produce height on the part of face, is judged to be other situations bad.
Resistivity is estimated, and is just to carry out in 200 ℃ of substrates after burning till 1 hour under the nitrogen atmosphere.(Mitsubishi chemical Co., Ltd makes, and Loresta-GP) obtains the face resistance value according to four probe method, utilizes and obtains resistivity by the thickness of other mensuration to utilize analyzer.
Plasma-resistance is estimated, and is to use dry-etching device (RIE, active-ion-etch mode) to carry out.Specifically, send into substrate in the processing chamber after, Yi Bian feed various etching gases, Yi Bian discharge.
Appreciation condition uses and feeds chlorine (Cl 2), carbon tetrafluoride (CF 4) and oxygen (O 2) mist, and oxygen (O 2) wait three kinds of conditions.
Below respectively these three kinds of conditions are called Cl 2Condition, CF 4+ O 2Condition and O 2Condition.Be respectively discharge time 180 seconds, 60 seconds, 60 seconds.And this discharging condition is under the situation of recognizing five kinds of microprocesses described later, has a mind to the condition enactment of strictness.
Studied the face resistance value of film in order to judge plasma-resistance.The face resistance value is measured with resistivity is same.As determinating reference, with the face resistance value be in respect to before handling below 2.5 times and 2.5 times, surpass 2.5 times and be in 7 times with interior situation be judged to be respectively very, good and bad slightly.
These assessment items are the example of setting for the character that shows silver alloy of the present invention eventually.For the difference between clear and definite each condition, have a mind to stricter than the service condition that sets.Implement when of the present invention, the evaluation of these projects is not necessarily necessary, about the details of Observations Means, determinating reference and condition etc. a kind of example only.So the scope of application of the present invention is not limited on these assessment items and the every kind of condition.
Evaluation result example about silver alloy of the present invention will be shown among table 1 and the table 2.
In each table, the example of the metal film that comparative example 1 is made up of silver-colored simple substance, comparative example 2 is the examples that mixed the silver alloy film of 2 weight % aluminium in evaporation source.Embodiment 1 to embodiment 9 is with respect to the silver meter, having mixed the example of the silver alloy film of the indium of indium, 0.3 weight % of indium, the 0.1 weight % of indium, the 10 weight % of indium, the 5 weight % of indium, the 3 weight % of zinc, the 1 weight % of 10 weight % tin, 10 weight % and 20 weight % indiums respectively in evaporation source, is embodiments of the invention.Though wherein in various raw materials, all should contain impurity, owing to its amount does not exert an influence to the result, so omit the explanation of relative substance.
At first ICP emission spectrographic analysis value, adhesive force and stable on heating evaluation result are shown among the table 1.
Table 1
The evaporation source mixing ratio Adhesive force (200 ℃ 1 hour burn till back) Thermal endurance (300 ℃ 1.5 hours burn till back) The ICP spectrum analysis
Element beyond the silver Silver Element beyond the silver
Kind Combined amount (%) Ratio (weight %) with respect to silver
Comparative example 1 (nothing) 0 Surplus Bad Bad -
Embodiment 1 Tin 10 Surplus Very Good slightly -
Embodiment 2 Zinc 10 Surplus Very Good slightly -
Embodiment 3 Indium 1 Surplus Very Good slightly 0.5
Embodiment 4 Indium 3 Surplus Very Very 1.6
Embodiment 5 Indium 5 Surplus Very Very 3.4
Embodiment 6 Indium 10 Surplus Very Very 9.3
Comparative example 2 Aluminium 2 Surplus Very Good slightly -
Embodiment 7 Indium 0.1 Surplus Bad Good slightly 0.05
Embodiment 8 Indium 0.3 Surplus Bad Good slightly 0.2
Embodiment 9 Indium 20 Surplus Very Very -
In the result who utilizes the ICP spectrum analysis quantitative analysis that illustrates previously, embodiment 3 to the embodiment 8 indium content with respect to silver are respectively 0.5 weight %, 1.6 weight %, 3.4 weight %, 9.3 weight %, 0.05 weight % and 0.2 weight %.
As table 1 show, the film of the comparative example of forming by silver-colored simple substance 1, adhesive force and thermal endurance are all bad.Even relax more than it in 250 ℃ of 1 hour firing tests, also obviously produce surface haze etc., obviously lack thermal endurance.Here it is was difficult to one of reason of using as wiring with silver in the past.
On the other hand, shown in the embodiments of the invention 1 to embodiment 9, in silver, added the silver alloy film of tin, zinc, indium, can see that the adhesive force on glass substrate increases.About adding indium, shown in embodiment 3 grades, indium approximately is under the situation more than the 0.5 weight % with respect to the content of silver, can see that adhesive force significantly improves.
About thermal endurance, can see also that in embodiments of the invention 1 to embodiment 9 thermal endurance improves.Particularly in embodiment 7 and embodiment 8,, can see that also thermal endurance improves although indium calculates the seldom amount that is respectively 0.05 weight % and 0.2 weight % with respect to silver content by assay value.Therefore we can say that adding indium is very effective for stable on heating raising.
About the reason that adhesive force improves, it is believed that it is that the cohesion energy that adheres to energy and main body under the situation of interface disappearance is approaching, reaches peaked cause because the elements such as tin, zinc and indium of formation silver alloy of the present invention are diffused on the glass substrate with denier.The principle of this view institute foundation is: in silver alloy film of the present invention, compares with the state of substrate film forming under 100 ℃ of temperature, and under the state after burning till processing through 1 hour under 200 ℃, this fact of a narrow increase.That is to say, the present invention is based on the principle that obtains adhesive force because of the diffusion of the tin in the silver alloy film, zinc and indium etc.
In addition, scope of the present invention as shown in this embodiment, is not limited to use and burns till this method after the film forming and obtain adhesive force, comprises that also the substrate temperature when improving film forming obtains the situation of adhesive force.
On the other hand, the reason that thermal endurance improves it is believed that it is to contain under the situation of elements such as tin, zinc, indium in film, and the size of lattice constant or crystallite dimension changes, and can suppress moving of silver atoms in the film, makes it be difficult to produce the cause of germination.
Wherein, in the silver alloy of present embodiment, also be that the important point is suitably to set resulting film to form, the element of mixing is in the zone that is formed on the elementary solid solution that dissolves in the silver-colored crystallization.If be set in the zone that forms this elementary solid solution, even then film is burnt till, silver-colored crystallization is difficult to separate out intermediate solid solution and the intermetallic compound with other crystal structures, is difficult to produce the growth of new crystal grain on the surface of film.Therefore, also can not change even burn till surface characteristic, thermal endurance improves as a result.
Also depend on ambient temperature though make the compositing range of this one-level solid solution, but under the situation of tin, zinc, indium, their content is in respectively less than 11~14 weight %, less than 25~39 weight %, less than in the scope about 27~28 weight % for silver.
Thus, the explanation of evaluation result in the table 1, silver alloy of the present invention is compared with silver, and thermal endurance improves, and is particularly forming under the situation of alloy with indium, contains the raising that just can see adhesive force under the situation of the above indium of 0.5 weight %.
And silver alloy of the present invention, also can be with the periodic table of elements in indium gallium of the same clan, with tin lead of the same clan, the bismuth formation alloy close with plumbous character, show good adhesive force and thermal endurance equally.
Below the result of study of resistivity and plasma-resistance is shown among the table 2.
Table 2
Resistivity (μ Ω cm) Plasma-resistance
Cl 2Condition CF 4+O 2Condition O 2Condition
Comparative example 1 1.9 Bad Bad Bad
Embodiment 1 2.8 Bad Bad Good slightly
Embodiment 2 6.8 Very Bad Good slightly
Embodiment 3 2.7 Very Bad Bad
Embodiment 4 4.0 Very Bad Very
Embodiment 5 6.1 Very Very Very
Embodiment 6 12.3 Very Very Very
Comparative example 2 2.4 Bad Bad Bad
Embodiment 7 2.2 Bad Bad Bad
Embodiment 8 2.3 Bad Bad Bad
Embodiment 9 21.8 Very Very Very
The explanation of evaluation result from table 2, resistivity are the low-resistivity below the 7 μ Ω cm except that embodiment 6 and embodiment 9, with in the past aluminium alloy quite or be in below it.Explanation thus, silver alloy of the present invention are suitable for using as the materials such as wiring of low-resistivity.Wherein resistivity then can be used with circuit base material as large-scale display device if be lower than 10 μ Ω cm.
Particularly in embodiment 7,8 and 3, though indium is in below the 0.5 weight % than all with respect to the content of silver, its resistivity but reaches the utmost point low value of 2.2 μ Ω cm, 2.3 μ Ω cm and 2.7 μ Ω cm respectively.Under the situation of aluminium, though under subjective situation because its resistivity is 2.7 μ Ω cm, so in film, can not reach below the 2.7 μ Ω cm, these data be aluminium the low resistivity value that can not obtain.
Therefore in silver alloy of the present invention, especially indium is under the following situation of 0.5 weight % with the content ratio of silver, can form the low-resistance wiring that is difficult to obtain with existing aluminium wiring.Under the situation of the special low resistanceization that need connect up, for example use and wait in the liquid crystal indicator that uses at liquid crystal TV, can make circuit substrate with silver alloy of the present invention.
But,, generally speaking need stacked other metal films etc. so the anti-plasma performance is insufficient because the indium amount is low.About with the adhesive force of substrate, also because indium content is low and not enough, so often need to carry out base treatment etc.
For the anti-plasma performance, in embodiments of the invention 1 to embodiment 6 and embodiment 9, all increase.Particularly, under situation about containing more than the 0.5 weight %, just can see the raising of anti-plasma performance about indium.But strictly say the alloy material that also has some to become bad because of condition of plasma.
Though under the situation of the silver-colored simple substance of comparative example 1 and all bad under the situation of comparative example 2 by silver and aluminium component alloy, at the O of embodiment 1 2The condition end is good, the Cl of embodiment 2 2Good, O under the condition 2The condition end is good.Especially it is characterized in that containing under the situation of the embodiment 3 to embodiment 6 of indium and embodiment 9 as silver alloy.At Cl 2All become good under the condition, it is remarkable that the anti-plasma performance improves effect.In the higher embodiment 5 of indium amount, although all good under whole anti-plasma performance conditions, reach 6.1 μ Ω cm and resistivity is low, have anti-plasma performance and low resistance performance concurrently, be extremely useful.Looking in 6 and 9 in addition, though resistivity is higher in the table, the anti-plasma performance is compared but with embodiment 5 and has further been improved.
Like this; the raising of anti-plasma performance; it is believed that it is, and force down than silver-colored steam, play a part to delay these compounds face etched protective layer by the vapour pressure of compounds such as the chlorine of supplying with in the gas that in chamber, imports, fluorine, oxygen because of the tin in the silver alloy, zinc, indium etc.
On the other hand, as embodiment 7 and 8, under the situation that contains the ratio indium below the 0.5 weight % with respect to silver, it is bad that the anti-plasma performance also all becomes.
Like this, silver alloy of the present invention, particularly contain under the situation of indium with the ratio more than the 0.5 weight %, owing to be a kind of material that has low resistive and anti-plasma performance concurrently, especially the wiring on the tft array substrate needs the anti-plasma performance mostly, so silver alloy of the present invention will become a kind of useful especially material.But silver alloy of the present invention and tin, zinc, indium etc. constitute the ratio of elements, not necessarily satisfy the complete characteristic in the table, so need can according to circumstances to select the patience that satisfies.
And silver alloy of the present invention, particularly containing under the situation of indium with the ratio below the 0.5 weight %, resistivity is in below the 2.7 μ Ω cm, and resistance is very low.Therefore, be particularly suitable in the liquid crystal indicator of usefulness such as liquid crystal TV, using in the circuit substrate purposes.
In addition, silver alloy of the present invention, also can be with the periodic table of elements in indium gallium of the same clan, with the alloy of tin lead of the same clan, the bismuth close with plumbous character, will show good character equally.
In sum, silver alloy of the present invention is to have a kind of material adhesive force, thermal endurance, low resistance and anti-plasma performance, very useful simultaneously as technology patience.
In addition, these evaluation results are to be result for show that silver alloy character of the present invention obtains under the condition of setting eventually.For the difference of clear and definite each condition between material, have a mind to set harshly more than contemplated service condition.The scope of application of the present invention is not subjected to any restriction of result shown in table 1 and the table 2.
Silver alloy of the present invention is characterized in that, wherein can also contain the element of selecting from aluminium, copper, nickel, gold, platinum, palladium, cobalt, rhodium, iridium, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and neodymium.By adding these elements, thermal endurance, anti-plasma performance, adhesive force are further improved, obtain best alloy material.
Use under the situation of silver alloy of the present invention as the constituent material use of connecting up on the tft array substrate, required material is based on silver, wherein contains the silver alloy of zinc.Therefore, adding under the situation of zinc in silver, can obtain the effect that thermal endurance, adhesive force and anti-plasma performance improve, will be a kind of material that is suitable for making tft array substrate.
Also have, can also contain other elements of having a mind to interpolation beyond the silver alloy of the present invention, desilver and zinc.The present invention just is being based in silver and is adding zinc and can improve thermal endurance, adhesive force and anti-plasma performance this point effectively.Therefore, even under the situation that contains other elements beyond these, can obtain the silver alloy of effect also with within the scope of the present invention involved because of adding zinc.
And use under the situation of silver alloy of the present invention as wiring constituent material on the tft array substrate, most preferred material is based on silver, wherein contains the silver alloy of indium.So, in silver, added under the situation of indium, if indium is in below the 0.5 weight % with respect to the ratio of silver, then it is characterized in that obtaining the effect that the anti-plasma performance increases substantially, will become a kind of material that is suitable for the tft array substrate manufacturing process.
Use under the situation of silver alloy of the present invention as wiring constituent material on the tft array substrate,, particularly contain the material of the following indium of 0.5 weight % with respect to silver as the low resistance most preferred material.At this moment, resistivity is in below the 2.7 μ Ω cm, can form with the wiring of existing aluminium low-resistance wiring that can not obtain.Make when special needs under the situation of wiring low resistanceization, for example use and wait in the liquid crystal indicator that uses, can make circuit substrate with silver alloy of the present invention at liquid crystal TV.
Another good characteristic of silver alloy of the present invention is to have a high visible reflectance under the situation that suitably contains indium, even and still can keep through after the burning till of 200 ℃ or 300 ℃.Below will make an explanation with regard to this point.
Used equal silver or silver alloy film as test sample, and, used the aluminium film made from same operation as comparative example 3 with reference to usefulness with comparative example, embodiment shown in the table 1,2.With these whole film forming on alkali-free glass substrate, the glass substrate temperature is set in 100 ℃ during film forming, and thickness is made for 0.2 micron left and right thickness.For the mensuration of visible reflectance, (the tester Service of Hitachi system U-4100), is measured in the visible region of 380~780nm is all to use spectrophotometer.
The visible reflectance of silver alloy film of the present invention will be described among Figure 20 to Figure 25.In these figure, transverse axis is represented the light wavelength to the metal film sample irradiation, and the longitudinal axis represents that then visible reflectance is as this reflection of light rate.In each figure, what put down in writing is through after burning till under 200 ℃, again through 300 ℃ of reflectivity after burning till, and because of burning till the reflectance varies that causes after the film forming.Wherein these burn till treatment conditions, use clean stove (clean oven), condition such as burn till 1 hour under nitrogen atmosphere.
If will be elaborated to the result, then at first under the situation of as shown in figure 20 comparative example 1 (silver), thermal endurance is significantly bad as mentioned above.Although through reflectivity height after 100 ℃ of film forming, significantly reduce through the back reflection rate of burning till of 200 ℃ and 300 ℃.Therefore, can not tolerate the manufacture process that 200 ℃ of left and right sides firing process are followed, very difficult conduct is for example used in the purposes of the optical reflection film of reflection-type liquid-crystal display device.
And then in comparative example shown in Figure 21 3 (aluminium), light reflectivity is after film forming, and is almost constant through burning till of 200 ℃ and 300 ℃.Aluminium is the material that in the past is widely used as optical reflection film in the reflection-type liquid-crystal display device.
Figure 22 is a silver alloy example of the present invention, is the example that contains the silver alloy film of 0.5 weight % indium with respect to silver.In this case, significantly different with the result of silver among Figure 20, even reduce significantly through the reduction of burning till the back reflection rate of 200 ℃ and 300 ℃.And compare with the situation of aluminium film among Figure 21, burn till the back through 200 ℃ and almost all increase, even after burning till through 300 ℃, except that short wavelength's one side pole is narrow region, all reflectivity is all high in whole wavelength region may internal reflection rates.Hence one can see that, and the visible reflectance height of the silver alloy film of present embodiment is a kind of good optical reflection film.
Figure 23 also is the example of silver alloy of the present invention, is the silver alloy film that contains 0.2 weight % indium with respect to silver.In this case, the embodiment 7 of result and Figure 22 much at one.Even little, compare with aluminium alloy film and can find that all visible reflectances are all high, so also be good optical reflection film through 200 ℃ and 300 ℃ of reductions of burning till the back reflection rate.
Figure 24 is the situation that contains 0.5 weight % ratio indium with respect to silver.After burning till through 200 ℃, remove beyond short wavelength's one side pole other part, all can both see better than the reflectivity of aluminium film.But especially reduce after burning till through 300 ℃, compare with the aluminium film and do not preponderate in short wavelength's one lateral reflection rate.Just as shown in this embodiment, can add an amount of indium with respect to silver, in case too much increase indium, reflectivity can reduce on the contrary.
Figure 25 is the example that contains indium with respect to silver with 1.6 weight % ratios.In this case, because indium content increases, all reflectivity reduce.Therefore do not take advantage with respect to aluminium.
In sum, contain under the situation of indium with the ratio below the 0.5 weight % among the present invention, even burn till and become membrane stage to compare reflectivity slight variations only to be arranged, compare almost all high with aluminium in all regional internal reflection rates of visible light through 200 ℃.Therefore, be suitable for using as optical reflection film.
And among the present invention, contain under the situation of indium with the following ratio of 0.2 weight %, even through 300 ℃ burn till also can the inhibitory reflex rate reduction, compare almost all high in all regional internal reflection rates of visible light with aluminium.Therefore when being particularly suitable for needing the optical reflection film under the thermal endurance situation to use.
Silver alloy wherein of the present invention beyond desilver and the indium, can also contain other elements of having a mind to interpolation.Why the present invention adds indium and just is being based on and can improves anti-plasma performance this point most effectively in silver.Therefore, even contain under the situation of other elements beyond these,, be also contained in the scope of the invention because of adding the silver alloy that indium can obtain the formation of effect.
Scope of the present invention relates to the situation of the material that contains silver, zinc and indium as its execution mode, contains the situation of the material of silver, tin and indium, and contains the situation of the material of silver, zinc and tin.
Silver alloy of the present invention can be suitably as constituting the material that connects up on the tft array substrate.And this tft array substrate can be suitably as in the liquid crystal indicator as one of electronic installation.
Below referring to figs. 1 through Fig. 4 tft array substrate and the liquid crystal indicator that present embodiment relates to is described.
The liquid crystal indicator that present embodiment relates to has pixel shown in Figure 1.Wherein, be to be illustrated in plan view that the pixel signal constitutes in the tft array substrate 11 of liquid crystal indicator at Fig. 1.And among Fig. 2 in the presentation graphs 1 along the cross section view of the A-A line direction of arrow.
As depicted in figs. 1 and 2, in tft array substrate 11, on glass substrate (insulating properties substrate) 12, grid wiring 13 and source wiring 14 are arranged to rectangular, the TFT15 that uses as switch element is set near its cross section.And between adjacent grid wiring 13, be provided with auxiliary capacitor wiring 16.
As shown in Figure 2, on glass substrate 12, be formed with the gate electrode 17 and the auxiliary capacitor wiring 16 that form by grid wiring 13 branches, be formed with gate insulation layer 18 thereon.
On gate electrode 17, form amorphous si-layer 19, n+ type silicon layer 20, source electrode 21 and drain electrode wiring 22, form TFT15 by means of above-mentioned gate insulation layer 18.Wherein source electrode 21 can be formed by source wiring 14 branches.
Till drain electrode wiring 22 extends to contact hole 23 from TFT15, have the effect of the drain electrode that forms TFT15, TFT15 and pixel electrode 24 are realized the effect that is electrically connected and connect up at auxiliary capacitor forming the effect of electric capacity between 16 by contact hole 23.In addition, the interlayer insulating film 26 of usefulness such as the protective layer 25 of the covering of layer formation thereon TFT15, planarization and the pixel electrode 24 that liquid crystal applied voltages is used.
Below zone on the glass substrate 12 of this pixel can be set be called pixel and form zone 61, shown in Figure 4 as the back.
And the liquid crystal indicator that present embodiment relates to has the terminal 28 shown in Fig. 3 (a).Terminal 28 be for external circuit substrate, drive the connecting portion of realizing being electrically connected usefulness with driver IC etc. and tft array substrate 11.And, be to be illustrated in the plan view that the signal of portion of terminal in the tft array substrate 11 of liquid crystal indicator constitutes with figure.And Fig. 3 (b) expression is along the cross section view with the B-B line direction of arrow among the figure.
Shown in Fig. 3 (b), portion of terminal 28 is to constitute from glass substrate 12 sides configuration terminal wiring 30, gate insulation layer 18 and terminal electrode 29.The purpose of configuration terminal 29 is to make and drive with electrically contacting well of driver IC etc.Terminal wiring 30 and pixel form realizations such as grid wiring 13 in regional 61, source wiring 14 and are connected.
Below will be provided with zone on the glass substrate 12 of this portion of terminal 28 and be called portion of terminal and form zone 62, be shown among following Fig. 4.
Fig. 4 is the plan view of tft array substrate 11, as shown in the figure pixel is formed zone 61, portion of terminal forms the zone and 62 is configured on the glass substrate 12.Pixel forms zone 61 and portion of terminal forms zone 62, respectively as shown in Figure 1 to Figure 3, has a plurality of pixels and portion of terminal.
In the present embodiment, when making tft array substrate 11, can use for example as ink-jetting style, to spray or the pattern of the cambium layer material that drips forms device.This pattern forms device, as shown in Figure 5, have plummer 32, the Y direction drive division 35 that is provided with ink-spraying-head 33 simultaneously, makes the directions X drive division 34 that ink-spraying-head 33 moves along directions X and make it to move along the Y direction with bearing substrate 31 (with respect to above-mentioned glass substrate).Ink-spraying-head 33 is for the substrate on the plummer 32 31, and for example ejection contains the mobile drop of wiring material.
And in above-mentioned pattern formation device, be provided with ink supply system 36 from printing ink to ink-spraying-head 33 that supply with, carry out the control unit 37 of various controls to the ejection control of ink-spraying-head 33, to the drive controlling of directions X drive division 34 and Y direction drive division 35 etc.To X and Y direction drive division 34,35 output coating positional informations, the shower nozzle driver (not shown) of ink-spraying-head 33 is exported ejection information from control unit 37.Can make X and 34,35 interlocks of Y direction drive division like this, make ink-spraying-head 33 actions, the destination locations on substrate 31 is supplied with purpose amount drop.
Above-mentioned ink-spraying-head 33 can be to use the piezoelectricity mode of piezoelectric element, have the pulse mode of heater in shower nozzle, perhaps other modes.From the printing ink spray volume control of ink-spraying-head 33, can use control to apply the mode of voltage.And drop ejection means, in order to replace ink-spraying-head 33, also can use the mode of the drop that simply drips etc., all can use as long as can supply with the drop variety of way.Perhaps also can utilize the wiring that forms on substrate is in advance formed material demonstration lyophily zone and non-lyophily zone, according to the mode of deciding pattern application or dipping.
The following manufacture method of tft array substrate 11 in the liquid crystal indicator of explanation present embodiment.
In the present embodiment; the manufacture method of tft array substrate 11; as shown in Figure 6, by grid wiring pretreatment procedure 101, grid wiring form operation 102, gate insulating film and semiconductor film film formation process 103, gate insulating film and semiconductor film manufacturing procedure 104, source-drain electrode wiring pretreatment procedure 105, source-drain electrode wiring formation operation 106, channel part manufacturing procedure 107, diaphragm interlayer insulating film film formation process 108, diaphragm manufacturing procedure 109 and pixel electrode form operation 110 and form.
(grid wiring pretreatment procedure 101)
In this grid wiring pretreatment procedure 101, use above-mentioned pattern to form device, carry out to forming the pre-treatment of usefulness such as grid wiring 13, gate electrode 17 and auxiliary capacitor wiring 16.Followingly it is illustrated with reference to Fig. 7 (a) and Fig. 8 (a).Fig. 7 (a) and Fig. 8 (a) are the plan views that has the glass substrate 11 of tft array substrate 11.
In this grid wiring pretreatment procedure 101, spray (dripping) mobile wiring materials by forming zone 41, gate electrode 17 formation zones 42 and auxiliary capacitor wiring formation zone 43 with pattern formation device to these grid wirings shown in the figure, carrying out is the suitably required processing of the mobile wiring material of coating.
This processing is as follows substantially.
At first on substrate (glass substrate 12), give easily by the character of the moistening substrate of mobile wiring material or rubber-like character.Be to form zone 41, gate electrode 17 and form zone 42, auxiliary capacitor wiring and form the hydrophilic region (lyophily zone) that zone 43 and terminal wiring form regional 44 usefulness, and carry out the close and distant water treatment (close and distant liquid processing) of patterning as the non-hydrophobic region (lyophobic areas) that forms the zone for forming grid wiring.
Next is the guide plate that forms restriction liquid stream, promptly forms the processing that the guide plate of regional 41 grades is used along grid wiring.
The close and distant liquid that the photochemical catalyst that is to use titanium dioxide that the former is representative carries out is handled.And the latter is to use anticorrosive additive material to utilize photoetching process to carry out guide plate formation.In addition, imported CF in order to give above-mentioned guide plate or real estate with close and distant fluidity, often to be exposed to 4, O 2Deng plasma atmosphere in exposure handle.Wherein after forming wiring, the resist that uses is peeled off.
As described below, be to use titanium dioxide to carry out photocatalyst treatment here.That is to say, on the glass substrate 12 of tft array substrate 11, be coated on the material of the ZONYL FSN (trade name, E.I.Du Pont Company makes) that has mixed in the isopropyl alcohol as fluorine-containing nonionic surface active agent.And utilize spin-coating method coating on the mask of grid wiring pattern etc. under 150 ℃, to burn till as the titanium dioxide fine particles dispersion of photochemical catalyst and the mixture of ethanol.And then use aforementioned mask that glass substrate 12 is carried out ultraviolet exposure.Conditions of exposure is for using the 365nm ultraviolet ray, with 70mW/cm 2Intensity irradiation 2 minutes.
Wherein just utilizing titanium dioxide to form territory, close and distant liquid zone with reference to Fig. 9 (a)~Fig. 9 (d) is described as follows.
Fig. 9 (a) expression utilizes spin-coating method to be coated on to have mixed in the isopropyl alcohol situation behind first film 2 of the ZONYL FSN (trade name, E.I.Du Pont Company makes) that makes fluorine-containing nonionic surface active agent and use on glass substrate 1.
Fig. 9 (b) is that the mask 4 that is used on the transparent glass substrate 3 the grid wiring pattern that is provided with etc. carries out the UV exposure, but the mixture of above-mentioned titanium dioxide fine particles dispersion of coating and ethanol is as photocatalyst layer 5,150 ℃ of following heat treatments on the pattern plane of mask 4.
After above-mentioned condition exposure, shown in Fig. 9 (c) and Fig. 9 (d), only wettability improves on the part 6 of UV exposure, has formed the lyophily zone.
(grid wiring forms operation 102)
Following with reference to Fig. 7 (b) (c) and Fig. 8 (b) (c) illustrate that grid wiring forms operation 102.
Fig. 7 (b) (c) and Fig. 8 (b) be that the expression grid wiring forms the state diagram after operation 102 finishes (c).Fig. 7 (b) and Fig. 8 (b) are illustrated respectively in pixel on the glass substrate 12 and form the plan view that zone 61 and portion of terminal form zone 62.Fig. 7 (c) and Fig. 8 (c) represent the cross section view C-C line direction of arrow and the D-D line direction of arrow in Fig. 7 (b) and Fig. 8 (b) respectively.
In this grid wiring forms operation 102, form at grid wiring on the lyophily zone such as zone 41 and be coated with mobile wiring material.For it, use pattern to form device, for the wiring material of flowability, used the dispersion liquid that in organic solvent, has disperseed the AI alloy particulate that has been coated with organic membrane.This moment contained silver and indium in mobile wiring material, the ratio that is set in indium for silver is in about about 5 weight %.About 50 microns of the width of wiring, the spray volume of wiring material from ink-spraying-head 33 set 40pl.
In addition; the silver that this mobile wiring material is contained and the ratio of indium; should consider the dry-etching that carry out the back in gate insulating film and semiconductor film manufacturing procedure 104, channel part manufacturing procedure 107 and diaphragm manufacturing procedure 109, should select to such an extent that have an anti-plasma performance.But this ratio can be according to the suitably selections such as performance of manufacturing process and desired tft array substrate.
On the face of being handled by lyophily, the mobile wiring material of ejection from ink-spraying-head 33, is coated with so ejection suitably should be adjusted between about 100~500 microns at interval in this case owing to can form zone 41 expansions along grid wiring.Burnt till under 300 ℃ 1 hour the coating back, has formed grid wiring 13, gate electrode 17, auxiliary capacitance line 16 and the terminal wiring 30 be made up of silver and indium.
Wherein grid wiring 13 etc. owing to be to be made of silver and indium, so have enough thermal endurances for 300 ℃ condition, can not lost surface smoothing.Use existing silver,,, become bad so leakage with the upper strata can take place because surface smoothing significantly loses.
And grid wiring 13 etc. directly contacts with glass substrate 12, but owing to be made of silver and indium in the present embodiment, so have the adhesive force enough with glass substrate, can not peel off in subsequent handling.Use existing when silver,, peel off, become bad so in subsequent handling, can produce because adhesive force is little.
In addition, why firing temperature being set in 300 ℃, is because will be heated to about 300 ℃ cause in the gate insulating film of next stage and semiconductor film film formation process 103.Therefore firing temperature is not limited under this temperature.
(gate insulating film semiconductor film film formation process 103)
Following with reference to Figure 10 (a) and (b) and Figure 11 (a) and (b) explanation gate insulating film and semiconductor film film formation process 103.
Figure 10 (a) and (b) and Figure 11 (a) and (b) are views of expression gate insulating film and semiconductor film film formation process 103 done state lower glass substrate 12.Figure 10 (a) and Figure 11 (a) are respectively that pixel forms zone 61 on the glass substrate 12, terminal forms regional 62 plan view.Figure 10 (b) and Figure 11 (b) are respectively along the cross section view of the E-E line direction of arrow with along the cross section view of the F-F line direction of arrow among Figure 10 (a) and Figure 11 (a).
In this gate insulating film semiconductor film film formation process 103, form on the glass substrate 12 of operation 102 at the experience grid wiring, make the gate insulating film 45 that forms gate insulation layer 18 subsequently respectively, form the amorphous silicon film 46 of amorphous si-layer 19 and will form n+ type silicon fiml 47 continuous film formings of n+ type silicon layer 20.Wherein returning dielectric film 45 is the films that formed by silicon nitride.These films all use CVD method film forming, and its thickness is followed successively by 0.3 micron, 0.15 micron and 0.04 micron.Film-forming temperature is 300 ℃.
Described for grid wiring 13 as the operation of front, improve thermal endurance by adding silver indium in addition, can suppress new crystalline growth.Therefore,, compare, can obtain the good grid wiring 13 in surface with the situation that silver-colored simple substance forms even also can slightly not make at 300 ℃ of hot conditions lower surfaces.Therefore, by means of gate insulation layer 18, semiconductor layer 27 of Xing Chenging and the leakage phenomenon between the source electrode 21 will disappear thereon, and rate of finished products improves, and the characteristic of TFT is also stable simultaneously.
(gate insulating film semiconductor film manufacturing procedure 104)
Following with reference to Figure 12 (a) and (b) and Figure 13 (a) and (b) explanation gate insulating film and semiconductor film film formation process 104.
Figure 12 (a) and (b) and Figure 13 (a) and (b) are views that expression gate insulating film and semiconductor film manufacturing procedure 104 stop the back state.Figure 12 (a) and Figure 13 (a) are respectively that pixel forms zone 61 on the glass substrate 12, terminal forms regional 62 plan view.Figure 12 (b) and Figure 13 (b) are respectively along the cross section view of the G-G line direction of arrow with along the cross section view of the H-H line direction of arrow among Figure 12 (a) and Figure 13 (a).
In this gate insulating film semiconductor film manufacturing procedure 104, utilize photoetching process to process.
At first amorphous silicon film 46 and n+ type silicon fiml 47 are processed by first photoetching process.Be processed in pixel and form in the zone residual one-tenth island above gate electrode 17, and form in the zone 62 not by residual at terminal.Obtain amorphous si-layer 19 like this and will form the n+ type silicon processing of films 48 of n+ type silicon layer 20 thereafter.The dry-etching method is used in etching, to import sulphur hexafluoride (SF 6) mode of mist of gas, hydrogen chloride (HCl) gas carries out.So far owing to all surfaces of gate insulating film 45 covered substrates, 30 grades can not be exposed among the dry etching gases so terminal connects up.
Then utilize second photoetching process that gate insulating film 45 is processed.Form in the zone 62 at terminal, partially-etched gate insulating film 45 obtains gate insulation layer 18 and opening portion 49.The dry-etching method is used in etching, to import CF 4And O 2The mode of mist carry out.
In this dry-etching process to gate insulating film 45, form the opening portions 49 that zone 62 forms at terminal, though not shownly among the figure is being electrically connected in the part of usefulness with other parts, terminal connects up and 30 is exposed in the dry etching gases atmosphere.This is because the dry-etching method is the good method of a kind of control performance, can prevent etching in actual manufacturing.
Wherein connect up 30, so there is not the anti-plasma performance owing to form terminal with silver as prior art.Therefore, become bad in peristome 49 terminals wiring 30 by remarkable etching.In contrast to this, terminal wiring 30 is made of silver and indium in the present embodiment, and indium is set at about 5 weight % to the ratio of silver.Therefore have the anti-plasma performance, can tolerate this dry-etching and handle.
(source leak routing pretreatment procedure 105)
Followingly source leak routing pretreatment procedure 105 is described with reference to Figure 14 (a).Figure 14 (a) is illustrated on the glass substrate 12 that has experienced gate insulating film and semiconductor film manufacturing procedure 104 to form the connect up plan view of wiring guide plate 52 back states of 22 usefulness of source wiring 14, source electrode 21 and drain electrode.
Form in the operation 106 at this source leak routing, do not form wiring etc., make an explanation so only form zone 61 with regard to pixel at this owing to forming on the zone 62 at terminal.
In this operation, except that the formation zone (source is leaked and formed zone 53) of source wiring 14, source electrode 21 and drain electrode wiring 22, form wiring guide plate 52.Wiring guide plate 52 utilizes photoetching process to form.That is to say that painting erosion resistant agent material on through the glass substrate 112 of gate insulating film and semiconductor film manufacturing procedure 104 carries out utilizing photomask to expose after the prebake and developing, carries out the back then and bakes.The wiring guide plate 52 of Xing Chenging wherein should form to such an extent that to make the live width in the zone that forms source wiring 14 and source electrode 21 be 10 microns, and the regional live width that constitutes drain electrode wiring 22 is 10~40 microns.Interval between source electrode 21 and the drain electrode wiring 22, promptly the length of TFT channel part 51 reaches 4 microns.
In addition, also can handle by the top enforcement oxygen plasma lyophily to gate insulation layer 18, the surface energy that makes the wiring material that is coated with by pattern formation device will form basal surface soaks into well, uses simultaneously to be exposed to CF 4Method in the plasma gas is implemented lyophoby to wiring guide plate 52 and is handled.
But also can carry out the above-mentioned wiring guide plate 52 of method replacement formation that close and distant liquid is handled by the photochemical catalyst that forms usefulness at above-mentioned gate electrode, implement close and distant liquid according to wiring or electrode pattern and handle.
(the source leak routing forms operation 106)
Then source leak routing formation operation 106 is described as follows with reference to Figure 14 (b) with (c).Figure 14 (b) and (c) be that expression origin leak routing forms the views that operation 106 stops the back states.Figure 14 (b) is the plan view that pixel forms zone 61 on the glass substrate 12.Figure 14 (c) is along the cross section view of the I-I line direction of arrow among Figure 14 (b).
Form in the operation 106 at the origin leak routing, do not form wiring etc., describe so only form zone 61 with regard to pixel owing to forming on the zone 62 at terminal.
This provenance leak routing forms operation 106, is to utilize to go up the wiring guide plate 52 that is provided with in the operation, forms the operation of source wiring 14, source electrode 21 and drain electrode wiring 22.In apparatus for coating, used pattern shown in Figure 5 to form device.
At this moment, mobile wiring material has used the AI alloy dispersion of nano-particles liquid that has disperseed to be coated with organic membrane in organic solvent.This moment mobile wiring material in contained silver and indium, indium is set in about 5 weight % for the ratio of silver.
In addition, the silver that this mobile wiring material is contained and the ratio of indium are considered in the channel part manufacturing procedure 107 of back and diaphragm manufacturing procedure 109 and will be carried out dry-etching, should select to such an extent that have an anti-plasma performance.But this ratio can also suitably be selected according to the performance of the manufacturing process or the tft array substrate that requires.
Here the spray volume of mobile wiring material from ink-spraying-head 33 is set in 2pl.The thickness that forms is decided to be 0.3 micron.Because amorphous silicon film 46 grades are in about 300 ℃ of following film forming, so firing temperature is set in than under its low temperature promptly 200 ℃.Utilize organic solvent to remove wiring guide plate 52.
(channel part manufacturing procedure 107)
Followingly describe with regard to channel part manufacturing procedure 107 with reference to Figure 15.Figure 15 is the views that expression this channel part manufacturing procedure 107 stops the back states, be with Figure 14 (b) in the cross section view of the suitable direction of arrow of I-I line position.
In this channel part manufacturing procedure 107, carry out the processing of the channel part 51 of TFT.This processing uses the dry-etching method of chlorine to carry out, but does not carry out new photoetching this moment, but utilizes the pattern of source electrode 21 and drain electrode wiring 22 to process.
In the present embodiment, the pattern of ink-jet apparatus that use front operation is used and so on forms device.Thus, under the situation that forms source wiring 14, source electrode 21 and electric leakage wiring 22, residual thereon in advance resist is impossible on operation.Therefore, in this channel part manufacturing procedure 107, owing to carry out the processing of channel part 51 as mask with these source wiring 14 grades itself, so these source wiring 14 self etchings such as grade begin to be exposed on for a long time in the dry etching gases atmosphere to etch-stop.
That is to say, form under the situation of device at the pattern that uses ink-jet apparatus and so on especially, require source wiring 14 grades that dry etching gases is had high patience (anti-plasma performance).
Source wiring 14 grades that are made of existing silver-colored simple substance so wiring is almost all etched, can not obtain required conductivity owing to do not have the anti-plasma performance, thereby bad.In contrast to this, in the present embodiment, source wiring 14 grades are made of silver and indium, and indium is set in about 5 weight % with respect to the ratio of silver.Therefore have the anti-plasma performance, can tolerate this dry-etching and handle.
Therefore, the wiring material that is made of silver-colored and indium of the present invention owing to have high anti-plasma performance, makes the method that in the past is difficult to pattern formation device manufacturing tft array substrate become easy.
(diaphragm interlayer insulating film film formation process 108)
And then it is as follows with reference to Figure 16 (a) and (b) and Figure 17 (a) and (b) explanation diaphragm interlayer insulating film film formation process 108.Figure 16 (a) and (b) and Figure 17 (a) and (b) are views that this diaphragm of expression interlayer insulating film film formation process 108 stops the back state.Figure 16 (a) and Figure 17 (a) are respectively that the pixel on glass substrate 12 forms zone 61 and terminal forms regional 62 plan view.Figure 16 (b) and figure (b) are respectively along the cross section view of the J-J line direction of arrow with along the cross section view of the K-K line direction of arrow among Figure 16 (a) and Figure 17 (a).
In this diaphragm interlayer insulating film film formation process 108, at first utilize the CVD method on the glass substrate 12 that has experienced the front operation, to make silicon nitride film 55 film forming.The substrate temperature of this moment is set in 200 ℃.
On this silicon nitride film 55, be coated with photonasty allyl resin material then.Then with mask exposure and development, obtained after burning till having decide the interlayer insulating film 26 of pattern.At this moment, on the lap of drain electrode wiring 22 and auxiliary capacitor wiring 16, opening portion 56 is set.On the other hand, form not formation comprehensively of interlayer insulating barrier 26 in the zone 62 at terminal.
(diaphragm manufacturing procedure 109)
With reference to Figure 18 (a) and (b) diaphragm manufacturing procedure 109 is described as follows then.Figure 18 (a) and (b) are views that this diaphragm of expression manufacturing procedure 109 stops the back state.Figure 18 (a) and (b) are respectively the cross section views of the middle J-J line of Figure 16 (a) and Figure 17 (a) and the represented locational direction of arrow of K-K line.
In this diaphragm manufacturing procedure 109, the silicon nitride film 55 that forms in the diaphragm interlayer insulating film film formation process 108 is processed with the pattern of interlayer insulating film 26.Form in the zone 61 at pattern, etching is in the silicon nitride film 55 under the peristome 56, has obtained protective layer 25 and contact hole 23.On the other hand, form in the zone 62 at terminal, silicon nitride film 55 is so that be removed comprehensively.The dry-etching method is used in etching, to import CF 4And O 2The mode of mist is carried out.
In the dry-etching process of this silicon nitride film 55, contact hole 23, be in the opening portion 49 of terminal 28, the part in drain electrode wiring 22 or the terminal wiring 30 all is exposed under the dry etching gases atmosphere.This be because, though the dry-etching method is controlled good method, in actual manufacture process, can not prevent overetched cause.
The silver of prior art does not have the anti-plasma performance.Therefore the part in drain electrode wiring 22 or the terminal wiring 30 thereby is formed bad by significantly etching in this case.In contrast to this, in the present embodiment, drain electrode wiring 22 or terminal wiring 30 be owing to be to be made of silver and indium, and indium is set in about 5 weight % with respect to the ratio of silver.Thereby have the anti-plasma performance, can tolerate this dry-etching and handle.
(pixel electrode forms operation 110)
As last operation, ITO (indium tin oxide) the film film forming of utilizing sputtering method that the back is made of pixel electrode 24 and terminal electrode 29.The substrate temperature of this moment is set in 200 ℃.Make this ITO film form pattern with photoetching process then, obtained as Fig. 1, Fig. 2, Fig. 3 (a) and (b) and tft array substrate 11 shown in Figure 4.
So, material of the present invention is owing to have in the past the good adhesive force to glass substrate that silver-colored simple substance did not have, so can tolerate a series of manufacture processes, can not produce that grid wiring etc. is peeled off and the bad defective that causes.
And material of the present invention, owing to have the excellent heat resistance that silver-colored simple substance did not have in the past, even, can obtain the good grid wiring of surface smoothing 13, auxiliary capacitor wiring 16 and gate electrode 17 etc. so as present embodiment, exposure of substrates can slightly not made at 300 ℃ of hot conditions lower surfaces yet.Therefore, and can not produce leakage accident between the source wiring 14 that forms by means of gate insulation layer 18, semiconductor layer 27, source electrode 21 etc. thereon, productivity ratio improves, and the characteristic of TFT is also stable simultaneously.
So compare with any material, material of the present invention has high anti-plasma performance this point, makes this manufacturing process become possibility.
In the present embodiment; the etching of gate insulating film 18 in gate insulating film semiconductor film manufacturing procedure 104; in channel part manufacturing procedure 1 to the etching of n+ type silicon processing of films 48; amount in these three kinds of operations with etching in diaphragm manufacturing procedure 109, can use the dry-etching method silicon nitride film 55.At this moment, form under the situation of wiring and electrode etc. with silver-colored simple substance in the past and all can produce etching, etched when perhaps making the etching mask of other films, it is bad to become.Yet as present embodiment, contain the wiring material of the present invention of silver and indium and can not become bad owing to have good anti-plasma performance.
Therefore, when making tft array substrate, use the dry-etching method mostly, the thing followed is that the material of the wiring of requirement formation, electrode etc. has high dry-etching patience (anti-plasma performance).Of the present invention is the material that main body contains indium with silver, has high anti-plasma performance, special very good as material uses such as the wiring on the formation tft array substrate, electrodes.
And material of the present invention, as present embodiment, form device and describe to form under the situation of source wiring 14, source electrode 21 etc. for the pattern that uses ink jet mode and so on, effective especially.In this case because source wiring 14 grades are formed the etching mask of usefulness as n+ type silicon layer 20, so begin from etching to finish long-time in be exposed under the atmosphere of dry etching gases.Therefore, used technology such under the situation of silver-colored simple substance to be difficult to realize in the past.But material of the present invention but can form device by means of pattern and make tft array substrate.
So, silver alloy of the present invention is particularly suitable for using the manufacturing process of ink discharge device and so on apparatus for coating, is useful material contained in the mobile wiring material.Wherein just as described later, even, be useful material too not using pattern to form in the manufacture method of device.
In the present embodiment, amount to and used that photomask exposes, six pieces of mask process of developing procedure for six times.In order under more low-cost, to produce tft array substrate, also be extensive use of its minimizing five pieces of mask process once.In this case, not using the easier method of photograph halftone exposure etc., is that gate insulating film 45 and silicon nitride film 55 are carried out etching and processing continuously, to form the method for gate insulation layer 18 and protective layer 25.Yet the part that particularly can expose in drain electrode wiring 22 will be exposed under the dry etching gases atmosphere for a long time in this case, so need the harsh more service condition of tolerance.
In order to seek wherein former thereby to have investigated the situation of substrate in etching.At first, film is arranged comprehensively during the etching of silicon nitride film 55, do not have problem.But the thing followed is in the etching process of gate insulating film 45, the part that can expose in the contact hole 23 of drain electrode wiring for example, and self etching begins to finishing all to be directly exposed under the atmosphere of dry etching gases.Compole is long at that time, is a kind of process conditions of harshness.
Therefore, use under the situation of this five pieces of mask process, require extra high anti-plasma performance for drain electrode wiring 22, but the silver alloy with argentiferous and indium is the silver alloy of the present invention of representative, owing to have high anti-plasma performance, even so also can use in this case, the scope of application is wide.
In addition, present embodiment is six pieces of mask process, forming terminal wiring 30 with grid wiring 13 grades in same operation, but the present invention is not limited to this situation.Existing almost whole manufacture method; all are the silicon nitride film film forming on substrate is comprehensive that make gate insulation layer 18 or will form protective layer 25; utilize the dry-etching method that its part is removed; its part must be removed in this case so that realize being electrically connected, therefore need have overetched anti-plasma performance in its electrode that disposes down, wiring etc.The invention provides anti-plasma performance excellent material, for the manufacture process performance excellent results of these tft array substrates.
In the present embodiment, mobile wiring material has used and will be coated with alloy particle organic membrane, that contain silver-colored indium and be dispersed in dispersion liquid in the organic solvent.This moment, contained indium was set at about 5 weight % with respect to the ratio of silver in mobile wiring material.But indium can suitably be selected according to manufacture process with respect to the ratio of silver, makes it to have suitable anti-plasma performance, perhaps suitably selects according to the performance of requirement tft array substrate etc.
And the form of this mobile wiring material is not limited to contain the silver and the form of indium with the AI alloy particulate form.Also can make silver-colored particulate and indium particulate respectively, it independently is dispersed in the solvent.In addition, not necessarily be limited to particulate, silver or indium also can be that the form with metallic compound is comprised in the form in the solvent.
In the present embodiment,, be not limited to this situation, also can use the silver alloy that contains silver-colored and zinc though be to form wiring such as source wiring 14, grid wiring 13 and electrode etc. with containing the silver and the silver alloy of indium.Can also use it is characterized in that containing silver and, contain the silver alloy of more than one elements of from tin, zinc, lead, bismuth, indium and gallium, selecting at least, form grid wiring 13 etc.And can be it is characterized in that, except containing these elements, contain the silver alloy of from aluminium, copper, nickel, gold, platinum, palladium, cobalt, rhodium, iridium, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and neodymium, selecting element at least.
(execution mode 2)
About other execution modes of the present invention, be described as follows with reference to Fig. 6 and Figure 19 (a) and (b).
Above-mentioned execution mode 1 forms in operation 102 and the source leak routing formation operation 106 at grid wiring, has used the ink jet type pattern to form device.
The tft array substrate 71 that present embodiment relates to, though be to make according to manufacturing procedure picture shown in Figure 6 equally with the situation of execution mode 1, difference is to use two or more mobile wiring materials each several part in substrate to form on the different this point such as wiring of (coating respectively) composition.
In the following description, have in fact the inscape of said function with execution mode 1 and will give identical reference marks, omit its explanation here.
Figure 19 (a) and (b) are represented tft array substrate 71 in the present embodiment.Figure 19 (a) is that the portion of terminal of tft array substrate 71 forms zone 62 plan view, and Figure 19 (b) is along the cross section view of the L-L line direction of arrow among Figure 19 (a).The pixel of representing at Fig. 4 forms the pixel portion that zone 61 forms, and constitutes in the same manner with execution mode 1.Shown in Figure 19 (a) and (b), on the tft array substrate 71 of present embodiment, terminal wiring 72 and the terminal connecting portion 73 that connects up is connected, and they all have and conduct.
Terminal wiring 72 in order to be covered by gate insulation layer 18, can be selected to such an extent that have thermal endurance in technology patience and to the adhesive force of glass substrate.About the anti-plasma performance, so do not need owing to not being exposed in the dry etching gases atmosphere.On the other hand, particularly in order to make the circuit substrate that large-scale liquid crystal indicator is used, should reduce the resistance of terminal wiring 72 as far as possible in advance.Under this reason, terminal wiring 72 constituted indium and reach 3 weight % with respect to the content of silver.The resistivity of this part is approximately 6 μ Ω cm.And be in pixel and form grid wiring 13, gate electrode 17 and the auxiliary capacitors wiring 16 of zone in 61, also, reason equally has lower resistance because of constituting, and make indium reach 3 weight % with respect to the content of silver.
On the other hand, terminal wiring portion 73 in being electrically connected required etching work procedure, is exposed in the dry etching gases atmosphere because of crossing etching.Therefore, should pay attention to the anti-plasma performance, should be configured so that indium reaches 10 weight % with respect to the content of silver.This terminal wiring connecting portion 73 also can make resistivity bigger than other parts than the grid wiring on the tft array substrate 13 and source wiring 14, terminal 72 much shorters that connect up.
Certainly, same with execution mode 1, terminal wiring 72 is identical with terminal wiring connecting portion 73 the two formation, that is to say it is configured so that indium reaches 5 weight % with respect to the content of silver.Yet as present embodiment, by being coated with respectively, owing to can form wiring than all lower electronics, electrode etc., can realize the large scale circuit substrate more and the advantage of large-scale display device etc. more so have according to the required performance of each several part.
Below describe with regard to the manufacture method of present embodiment.
Described as described above, tft array substrate 71 in the present embodiment, though be to use with the almost same method of the situation of above-mentioned execution mode 1 to make, difference is to form in the operation 102 at grid wiring, and mobile wiring material separately is coated with on this point.Making pattern shown in Figure 5 form device by use has the device that can spray the function of two or more mobile wiring materials at least in advance, realizes this point.That is to say, by two ink-spraying-heads 33 are set at least, be formed in the two kinds of mobile wiring materials of to pack in the same ink-spraying-head 33, ink supply system 36, control unit 37 and ejection positional information etc. are also made the mode of corresponding disposal and can realize.
Use such pattern to form device, sprayed the indium two kind mobile wiring materials different equally with respect to silver content with execution mode 1.With in the zone, reach the mobile wiring material of 3 weight % with respect to the content of silver in the formation of terminal wiring 72 when having formed connect up ejection indium 72 time of terminal.On the other hand, form with in the zone at terminal wiring connecting portion 73, when having formed terminal wiring connecting portion 73, the ejection indium reaches the mobile wiring material of 10 weight % with respect to the content of silver.In addition, form grid wiring 13, gate electrode 17 and the auxiliary capacitor of zone in 61 and connect up in 16 the formation zone being in pixel, sprayed and the terminal 72 identical mobile wiring materials that connect up.After the ejection, with execution mode 1 equally after burning till 1 hour under 300 ℃, obtained predetermined terminal wiring 72, terminal wiring connecting portion 73.
In the present embodiment, the pattern of ink jet mode and so on forms device should separate coating in real estate, the wiring that forms in same operation etc. should have required different anti-plasma performances or conductivity at each several part, and carry out best of breed etc. between indium content, conductivity and the technology patience to material of the present invention, all be very important.The large-scale tft array substrate that can produce easy manufacturing like this, have the good electrical characteristic.
In addition, in the present embodiment,, be not limited to this though terminal wiring 72 has the border 74 different with the indium content shown in (b) as Figure 19 (a) with terminal wiring connecting portion 73.Indium content also can change at boundary vicinity.Its formation method both can have been used the method for mutual natural mixed flow wiring material, also can use the method for intentionally two kinds of materials being mixed mutually.In addition, the position on border 74 not necessarily is limited to illustrated position.As long as can obtain in fact as above-mentioned identical effect, also can in how many parts inequality connections.
Certainly, need as tft array substrate 71, and be in the part that is exposed in the dry etching gases atmosphere in manufacturing process wiring that indium content increases and electrode etc. are set, this point is important for present embodiment.
Like this, silver alloy of the present invention, even when indium reaches when separately being coated with under the lower situation of 1 weight % or 3 weight % and so on the content of silver is for example low, also can use suitable use corresponding with a plurality of manufacturing process constitute wiring such as grid wiring 13 and electrode, particularly the method for low-resistance material obtains.
And the form of mobile wiring material in the present embodiment, be not limited to contain the form of silver and indium with the particulate of AI alloy.Also can make silver-colored particulate and indium particulate respectively, it independently is dispersed in form in the solvent.In addition, not necessarily be limited to particulate, can also be silver or indium be contained in form in the solvent with the form of metallic compound.
In addition, in the present embodiment,, also can use the silver alloy of argentiferous and zinc though, be not limited to this situation with the wirings such as silver alloy formation grid wiring 13 that contain silver and indium.Can also use in addition to it is characterized in that containing silver, contain the silver alloy of more than one elements of from tin, zinc, lead, bismuth, indium and gallium, selecting simultaneously at least, form grid wiring 13 etc.And can be it is characterized in that, except containing these elements, contain the silver alloy of the element of from aluminium, copper, nickel, gold, platinum, palladium, cobalt, rhodium, iridium, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and neodymium, selecting at least.
But also can be according to the place, separately use silver and indium, silver and zinc etc. to make on the tft array substrate 71 formation different.
(execution mode 3)
Be described as follows about another embodiment of the invention.
In above-mentioned execution mode 2, in grid wiring formation operation 102, used with the pattern formation device of spray regime as representative, on tft array substrate 71, constitute the separately coating of different wiring material.
In the following description, have in fact the inscape of said function with above-mentioned execution mode 1 and execution mode 2 and will give identical reference marks, omit explanation here it.
In the present embodiment, form in the operation continuity process, form in the operation 106, form the separately coating of different wiring materials at the source leak routing at grid wiring.For example, indium is decided to be 3 weight % with respect to the content of silver under the situation of source electrode 21 and source wiring 14, and is decided to be 10 weight % under the situation of drain electrode wiring 22.
And can connect up at drain electrode and separate coating in 22, make the content of indium with respect to silver, reach 3 weight % and 10 weight % respectively, near contact hole 23, can also improve the anti-plasma performance.In addition, any part on the tft array substrate of present embodiment also can be separated coating.
The form of mobile wiring material in the present embodiment is not limited to contain silver and indium with the AI alloy particulate form with execution mode 2 equally.Also can make silver-colored particulate and indium particulate respectively, it independently is dispersed in the solvent.In addition, not necessarily be limited to particulate, silver or indium can also be contained in the solvent with the form of metallic compound.
Also have, the wiring material of Shi Yonging is same with execution mode 2 in the present embodiment, is not limited to the material be made up of silver and indium, also can use the silver alloy that contains silver-colored and zinc.Can also use in addition to it is characterized in that containing silver, contain the silver alloy of more than one elements of from tin, zinc, lead, bismuth, indium and gallium, selecting simultaneously at least, form source wiring 14 etc.And can be it is characterized in that, except that containing these elements, at least also contain the silver alloy of the element of from aluminium, copper, nickel, gold, platinum, palladium, cobalt, rhodium, iridium, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and neodymium, selecting.
But also can be according to the place, separately use silver and indium, silver and zinc etc. can make on the tft array substrate formation different.
In addition, execution mode 2 and 3 can make up enforcement.That is to say, also can form operation 102 and source leak routing and form operation 106 the two all separates coating grid wiring.
In above-mentioned embodiments of the present invention 1~3, used the pattern formation device that sprays mobile wiring material drop with spray regime.Yet silver alloy of the present invention does not use this pattern to form under the situation of device and can use equally effectively yet.In this case, in the operation of correspondence, will make tft array substrate by using existing sputtering method or vapour deposition method and the most general photolithographic method.But, wherein use sputtering target and evaporation source etc. and need not mobile wiring material, the wiring that obtains forming, electrode etc. by silver alloy of the present invention.Silver alloy of the present invention, even also can be effective as the technology patience with thermal endurance, adhesive force and these function admirables of anti-plasma performance in this case, and the low material of resistance is used.
In addition, silver alloy of the present invention, can also be effective as can two-layer above material is overlapping the multilayer wiring material in one deck use.For example, even burn till, can as silver-colored simple substance, not lose surface smoothing through the heat under 300 ℃ of temperature yet.And particularly ought contain indium, and its content for example accounts under the more relatively situation such as 5 weight % or 10 weight % with respect to silver, has sufficient anti-plasma performance, and the protection metal level that can be effective as its lower-layer wiring of protection uses.And can be used as with execution mode 1 in semiconductor layer 27 directly contact, to be electrically connected source electrode 21, drain electrode wiring 22 whole of usefulness, perhaps wherein a part is used, and can bring into play good thermal endurance and adhesive force equally, is used for effectively among the manufacture process of tft array substrate.
Perhaps silver alloy of the present invention can also be used as the light reflective electrode on the tft array substrate of reflection-type TFT liquid crystal indicator and so on.In this case, because silver alloy of the present invention has good thermal endurance, so can as silver-colored simple substance, not lose surface smoothing even for example under 300 ℃, burn till also.Therefore, can not produce design light scattering in addition, can keep enough light reflectivities etc., can give full play to characteristic as tft array substrate as the light reflective electrode.
And in the silver alloy of the present invention, under indium with respect to the content of silver was situation below the 0.5 weight %, resistivity was below the 2.7 μ Ω cm, can help forming the low resistance that can not obtain with existing aluminium wiring institute and connect up.But because indium content is low, the anti-plasma performance is insufficient, generally speaking needs stacked other metal films.About adhesive force, also because of indium content is low and insufficient, so often need to carry out base treatment etc. to substrate.
(execution mode 4)
Be described as follows about another embodiment of the present invention.
In addition, in the following description, have in fact the inscape of said function with above-mentioned execution mode 1 to execution mode 3 and represent, omit its explanation here with identical reference marks.
Grid wiring at above-mentioned execution mode 2 forms in the operation 102, uses with the pattern formation device of spray regime as representative, has carried out forming the separately coating of different wiring materials on tft array substrate 71.On the other hand, form in the operation, carried out separately coating forming different wiring materials at the source of above-mentioned execution mode 3 leak routing.
In the present embodiment, form in the operation 102, use sputtering method to form wiring etc., these wirings etc. are stacked silver alloy of the present invention and titanium at grid wiring.
Figure 26 (a) and (b) and Figure 27 (a) and (b) are that the expression grid wiring forms the view that operation 102 stops the back state in the present embodiment.Figure 26 (a) and Figure 27 (a) are respectively that pixel forms zone 61 on the glass substrate 12, terminal forms regional 62 plan view.Figure 26 (b), Figure 27 (b) are respectively along the cross section view of the M-M line and the N-N line direction of arrow among Figure 26 (a) and Figure 27 (a).
Among these figure, grid wiring 80, gate electrode 81, auxiliary capacitor 82, terminal wiring 83 are made of two-layer by having the identical layer stack structure.Each layer 80a, 81a, 82a and 83a near glass substrate 12 1 sides are made of silver alloy of the present invention, and indium is 0.2 weight % with respect to the content of silver.Each layer 80b, the 81b, 82b and the 83b that are in its upper strata one side are made up of titanium.Each layer 80a, 81a, 82a and 83a, and the film thickness of each layer 80b, 81b, 82b and 83b is 0.2 micron.
In the present embodiment, each layer 80a, 81a, 82a and the 83a of close glass substrate 12 sides have thermal endurance owing to the alloy of being made up of silver and indium forms, also can be to adverse effect such as generation such as grid wiring 80 grades even burn till through 300 ℃ in the subsequent handling.But formed under the situation of these layers with silver-colored simple substance in the past, thermal endurance and significant concave-convex surface can occur for want of, thereby generation and upper strata sew bad.
If the indium content following silver alloy that is 0.5 weight %, as mentioned above, resistivity is low to be reached below the 2.7 μ Ω cm, thus can form with aluminium the low resistance that can not form connect up.In the present embodiment, resistivity is low to be reached about 2.3 μ Ω cm, very low.Therefore, need wiring to have under the situation of resistance when special, for example in liquid crystal indicators such as liquid crystal TV usefulness, silver alloy of the present invention is a kind of useful material.
In the present embodiment, describe with regard to the formation method of grid wiring 80 grades.Wherein in grid wiring forms operation 102, owing to uses, so do not carry out the operation suitable with grid wiring pretreatment procedure 101 with the pattern formation device of ink-jetting style as representative.
At first make the silver alloy film forming on glass substrate 12 that contains 0.2 weight % indium with respect to silver reach 0.2 micron thickness by sputtering method.Used the alloys target that make indium in silver solid solution as sputtering target this moment.
And then utilize sputtering method to make titanium continuous film forming in a vacuum.Utilize photoetching process that the film that obtains is like this processed, obtained grid wiring shown in Figure 26 (a) and (b) and Figure 27 (a) and (b) etc.The dry-etching method has been used in the etching of this moment.
Consider subsequent handling, terminal 83 grades that connect up need have the anti-plasma performance, but in the present embodiment, and the titanium by the upper strata has obtained this performance.
So, can also use as one deck of Miltilayer wiring structure, under indium with respect to silver is situation below the 0.5 weight %, can make in the past with the irrealizable low resistance wiring of aluminium institute as silver alloy of the present invention.
In addition, though use above-mentioned formation method directly on glass substrate 12, to make silver alloy film forming of the present invention, but under the situation that can not obtain to the enough adhesive force of substrate, the intermediate layer that is formed by metal etc. can also be set in the middle of the two, glass substrate carried out also can obtaining adhesive force under the surface-treated situation with plasma, medicine etc.
Among the present invention, each layer 80b, the 81b of upper strata one side, the material of 82b, 83b are not limited to titanium, also can be chromium, molybdenum, tantalum, tungsten or make its material that contains nitrogen, oxygen or ITO metal oxides such as (indium tin oxides).In order to form grid wiring 80 etc., both can fold mobile wiring material with same coating layer such as execution mode 1 grade, also can use the evaporation source of forming by silver and indium, by the vapour deposition method film forming, the processing back forms.
In the present embodiment, form in the operation 102 at grid wiring, though be to use the film of forming by silver alloy of the present invention and titanium to form wiring,, also can form the wiring that same formation is made of stacked film in the operation 106 at the source leak routing as other execution modes of the present invention.Even in this case, because the alloy of being made up of silver and indium has thermal endurance, so can not produce adverse effect even in subsequent handling, burn till also.
In this case, be 0.5 weight % when following when making indium with respect to silver content, can realize using the irrealizable low-resistance wiring of aluminium in the past.
Perhaps can also be with silver alloy of the present invention, as the light reflective electrode on the middle the sort of tft array substrates that use such as reflection-type TFT liquid crystal indicator.In this case, because silver alloy of the present invention has good thermal endurance, so unlike silver-colored simple substance, lose surface smoothing even burn till also at 300 ℃.Therefore, can not produce design light scattering in addition, can keep enough light reflectivities etc., can give full play to characteristic as tft array substrate as the light reflective electrode.
In this case, wish to use the silver alloy that contains the following indium of 0.5 weight % with respect to silver, more preferably use the silver alloy that contains the following indium of 0.2 weight % with respect to silver.
(execution mode 5)
Be described as follows about another embodiment of the present invention.
In the following description, have in fact the inscape of said function with above-mentioned execution mode 1 to execution mode 4 and represent, omit its explanation here with identical reference marks.
Shown in present embodiment 1, in the silver alloy of the present invention, be the film that the silver alloy below the 0.5 weight % is made with respect to silver content with indium, even through 200 ℃ burn till after visible reflectance also high.Be the film that the silver alloy below the 0.2 weight % is made with respect to silver content more preferably with indium, though through 300 ℃ burn till after visible reflectance also high.Therefore being suitable for the optical reflection film purposes uses.
In the present embodiment, be that silver alloy below the 0.2 weight % forms the light reflective electrode with indium with respect to silver content.This light reflective electrode is forming a plurality of on tft array substrate.It is described as follows.
The reflection-type TFT liquid crystal indicator that present embodiment relates to has pixel shown in Figure 28.Wherein, Figure 28 is plan view that the pixel signal constitutes on the tft array substrate 91 of expression reflection-type TFT liquid crystal indicator.And Figure 29 represents among Figure 28 the cross section view along the O-O line direction of arrow.In the present embodiment, about with a difference of the liquid crystal indicator of present embodiment 1 grade, be to have light reflective electrode 84 this point.This light reflective electrode is that the liquid crystal layer (not shown) that liquid crystal indicator possesses is applied the electrode that voltage is used, simultaneously by making light reflection or the scattering incided in the liquid crystal indicator obtain the effect that image shows.
And the liquid crystal indicator that relates to of present embodiment, have the portion of terminal 28 shown in Figure 30 (a).Terminal 28 is with external circuit substrate, drives the connecting portion of realizing being electrically connected usefulness with driver IC etc. and tft array substrate 91.Wherein Figure 30 (a) is illustrated in the plan view that the signal of a portion of terminal in the tft array substrate 91 of liquid crystal indicator constitutes.And among Figure 30 (b) expression Figure 30 (a) along the cross section view of the P-P line direction of arrow.
Shown in Figure 30 (b), with constituting of portion of terminal 28, from glass substrate 12 1 sides configuration terminal wiring 30, gate insulation layer 18 and terminal electrode 85.Terminal electrode 85 is different with embodiments of the present invention 1 etc., is to be that silver alloy below the 0.2 weight % is made with indium with respect to silver content.
And, in the reflection-type TFT liquid crystal indicator,, control outside reflection of light or scattering though on interlayer insulating film 26, be provided with concaveconvex shape sometimes, owing to can not exert an influence, omit here content of the present invention.
In order to make reflection-type TF liquid crystal indicator, after forming, the light reflective electrode need burn till substrate at about about 160~200 ℃.For example, this is in order to make liquid crystal orientation film (not shown) film forming etc.Therefore, light reflex electrode 84 thermal endurances need.
Existing silver is complete out of use material because of the very poor gonorrhoea of thermal endurance.Silver alloy of the present invention for example is that indium is under the situation of 0.2 weight % with respect to silver content, anti-burning till, but also can obtain on all, having higher visible reflectance with respect to the aluminium that often used in the past.Compare with the existing situation of aluminium of using, the demonstration that can become clear can obtain the effect that display performance improves.
The light reflective electrode 84 that present embodiment relates to and the manufacture method of terminal electrode 85 are described as follows.
In the present embodiment, shown in Figure 18 (a) and (b), the substrate after the diaphragm manufacturing procedure 109 that is through with is carried out film forming.Film build method is a sputtering method, and film-forming temperature is 100 ℃, with making the alloys target of indium solid solution in silver as sputtering target.The silver alloy film that to make with respect to silver-colored indium content like this be 0.2 weight % forms the film of 0.2 micron thickness.
The silver alloy film that utilizes photoetching process to obtain like this be processed into decide pattern, obtain Figure 28 to light reflective electrode 84 and terminal electrode 85 shown in Figure 30.The etching of this moment is to utilize the etching solution that contains acetate, phosphoric acid, nitric acid, uses wet process to carry out.
Therefore, in the silver alloy of the present invention, be the film that the silver alloy below the 0.5 weight % is made with respect to the content of silver with indium, though through 200 ℃ burn till after visible reflectance also high, since its reflectivity on all than aluminium excellence, so be very useful on industry.Be the film that the silver alloy below the 0.2 weight % is made with respect to silver content more preferably with indium, though through 300 ℃ burn till after visible reflectance also high, have and can tolerate more harsh advantage of creating conditions.
In addition, there is no particular restriction about the manufacture method of light reflective electrode 84 and terminal electrode 85, both can be same with execution mode 1 grade, carry out at the mobile wiring material wall thickness of coating, also can use the evaporation source of making by the silver that contains indium, utilize the vapour deposition method film forming and shape.
And in above-mentioned manufacturing process, though be directly to make silver alloy film of the present invention film forming on interlayer insulating film 26, but when adhering under the hypodynamic situation, the intermediate layer of formation such as metal both can be set between the two, also can carry out surface treatment and obtain adhesive force with plasma, medicine etc. by surface to interlayer insulating film.
In addition, silver alloy of the present invention also can use bus (bus) electrode on the glass substrate that constitutes PDP (plasma display panel) as data electrode.These electrodes are configured on the glass substrate of peeling off the substrate or the back side of front so that drive PDP, are made of silver, chromium/copper/chromium, aluminium/chromium in the past.Because copper or aluminium is a little less than the adhesive force on the glass substrate, thus have to use and glass substrate between insert the structure of chromium layer.On the other hand, existing silver has the thermal endurance problem, and Yin Gaowen burns till and makes grain growth, is the material that is difficult to use.
In contrast to this, silver alloy of the present invention because have good thermal endurance and with the adhesive force of glass substrate, so can replace material such as existing silver, successfully use as bus electrode, data electrode.
(execution mode 6)
Below describe with regard to another embodiment of the invention
In the present embodiment, just use the silver alloy that illustrates in the respective embodiments described above, the wiring material as wiring (comprising electrode) on a kind of tft array substrate of circuit substrate describes with regard to this tft array substrate and liquid crystal indicator.
Silver alloy used herein is to be formed in the wiring that forms on the insulating properties substrates such as glass substrate or the material of electrode, wherein based on silver, and contains more than one elements of selecting at least from tin, zinc, lead, bismuth, indium and gallium.
According to the silver alloy that use has above-mentioned formation, it is low then can to form a kind of resistance, high wiring or the electrodes of technology patience such as thermal endurance, the adhesive force on glass substrate and anti-plasma performance.
Followingly describe with regard to tft array substrate and the liquid crystal indicator that present embodiment relates to reference to Fig. 1, Fig. 2, Fig. 4 and Figure 31.
The liquid crystal indicator that present embodiment relates to has pixel shown in Figure 1.Wherein Fig. 1 is the plan view that roughly constitutes that is illustrated in a pixel in the tft array substrate 11 of liquid crystal indicator.And Fig. 2 is along the cross section view of the A-A line direction of arrow in the presentation graphs 1.
Illustrated in figures 1 and 2 as these, in tft array substrate 11, on glass substrate (insulating properties substrate) 12, grid wiring 13 and source wiring 14 are arranged to rectangular, near its cross section, be provided with the TFT15 that uses as switch element.And, between adjacent grid wiring 13, be provided with auxiliary capacitor wiring 16.
As shown in Figure 2, on glass substrate 12, form the gate electrode 17 and the auxiliary capacitor wiring 16 that form by grid wiring 13 branches, form gate insulation layer 18 thereon.
On gate electrode 17, form amorphous si-layer 19, n+ type silicon layer 20, source electrode 21 and drain electrode wiring 22 by means of above-mentioned gate insulation layer 18, form TFT15.Wherein, source electrode 21 is formed by source wiring 14 branches.
Till drain electrode wiring 22 extends to contact hole 23 from TFT15, have the effect of the drain electrode that forms TFT15, TFT15 and pixel electrode 24 realized the effect that is electrically connected, and by contact hole 23 and auxiliary capacitor connect up and form the effect of electric capacity between 16.In addition, the interlayer insulating film 26 of usefulness such as the protective layer 25 of the covering of layer formation thereon TFT15, planarization and the pixel electrode 24 that liquid crystal applied voltages is used.
Below zone on the glass substrate 12 of this pixel can be set be called pixel and form zone 61, shown in Fig. 4 of back.
The liquid crystal indicator that present embodiment relates to has the terminal 28 shown in Figure 31 (a).Terminal 28 is with external circuit substrate, drives the coupling part of realizing being electrically connected usefulness with driver IC etc. and tft array substrate 11.In addition, be to be illustrated in plan view that the portion of terminal signal constitutes in the tft array substrate 11 of liquid crystal indicator with figure.And represent along cross section view among Figure 31 (b) with the L-L line direction of arrow among the figure.
Shown in Figure 31 (b), portion of terminal 28 constitutes from glass substrate 12 sides configuration terminal wiring 30, gate insulation layer 18 and terminal electrode 29.The purpose of configuration terminal 29 is to make with external circuit substrate, drive with electrically contacting well of driver IC etc.Terminal wiring 30 and pixel form grid wiring 13 in regional 61, source wiring 14 etc. and are being connected.
And in the present embodiment, wiring 30 of above-mentioned terminal and terminal electrode 29 all form on glass substrate 12, form by the silver alloy as the silver alloy of same composition.But in terminal wiring 30 and terminal electrode 29, indium is with respect to the content difference of silver.Wherein indium is adjusted forr a short time with respect to the content of silver than indium in the terminal electrode 29 with respect to the content of silver in the terminal wiring 30.
Below will be provided with zone on the glass substrate 12 of this portion of terminal 28 and be called portion of terminal and form zone 62, be shown among following Fig. 4.
Fig. 4 is the plan view of tft array substrate 11, as shown in the figure pixel is formed zone 61, portion of terminal forms the zone and 62 is configured on the glass substrate 12.Pixel forms zone 61 and portion of terminal forms zone 62, has a plurality of respectively as Fig. 1, Fig. 2 and pixel and portion of terminal shown in Figure 31.
When making tft array substrate 11 in the present embodiment owing to used the pattern of explanation in the above-mentioned execution mode 1 to form device, so will omit detailed description to this device.
In addition, in the present embodiment, shown in Figure 31 (a), terminal wiring 30 and terminal electrode 29 all form on glass substrate 12, and for respectively by forming with respect to the different silver alloy of silver-colored indium content, ink-spraying-head 33 need have the mechanism of the mobile wiring material that ejection is made up of the different silver alloy of proportioning at least.
For example, shown in Figure 32 (a) and (b), it is contemplated that and possess the first shower nozzle 33a that uses with the mobile wiring material of low electrical resistant material along direction of advance (direction of arrow) the ejection wiring portion of ink-spraying-head 33 successively, with the second shower nozzle 33b that uses with the mobile wiring material of anti-plasma performance material of ejection portion of terminal, suitably switch these the first shower nozzle 33a and the second shower nozzle 33b, to spray mobile wiring material.
Be elaborated in the back the ink-spraying-head 33 with above-mentioned formation being formed portion of terminal.
Wherein, though will describe with regard to the manufacture method of tft array substrate 11 in the liquid crystal indicator of present embodiment, about omitting with the explanation of above-mentioned execution mode 1 identical content.
That is to say, same in the present embodiment with above-mentioned execution mode 1, will use manufacturing process shown in Figure 6 to make tft array substrate 11.
Therefore, the difference of main explanation and above-mentioned execution mode 1 below.
(grid wiring pretreatment procedure 101)
This grid wiring pretreatment procedure 101 omits the explanation identical with above-mentioned execution mode 1.
(grid wiring forms operation 102)
Followingly illustrate that with reference to Fig. 7 (b), (c) and Fig. 8 (b), (c) grid wiring forms operation 102.
Fig. 7 (b), (c) and Fig. 8 (b), (c) are that the expression grid wiring forms the state diagram after operation 102 finishes.Fig. 7 (b) and Fig. 8 (b) are illustrated respectively in pixel on the glass substrate 12 and form the plan view that zone 61 and portion of terminal form zone 62.Fig. 7 (c) and Fig. 8 (c) represent respectively along the cross section view of the direction of arrow of Fig. 7 (b) and middle C-C line of Fig. 8 (b) and D-D line.
Then on forming the hydrophilic region (lyophily zone) of regional 41 grades, grid wiring has been coated with mobile wiring material.Coating uses pattern to form device, and mobile wiring material used be coated with organic membrane, can in wirings such as yellow gold, silver palladium alloy, silver alloy, use, but used herein is shown in the above-mentioned execution mode 3~6, with the dispersion liquid of AI alloy microparticulate in organic solvent.This is because indium content can be extensively corresponding with flatness, anti-plasma performance and low resistance, as requested the cause that is used of low resistance, the situation that requires the anti-plasma performance and purposes.Contained silver and indium in the mobile wiring material of this moment suitably adjusted to respect to silver and contained the following indium of 10 weight %.Wiring width is about 50 microns, and the spray volume of wiring material from ink-spraying-head 33 is set in 40pl.
Alloy particle also can use in advance with because of and indium mix in right amount, to utilize the material of method alloyings such as electric arc dissolving and ion beam as stock, make particulate by the method for evaporation in rare gas, organic solvent atmosphere again, it is dispersed among the solvent.
And; the contained silver and the ratio of indium in this mobile printing ink; should consider the dry-etching that carry out in gate insulating film semiconductor film manufacturing procedure 104, channel part manufacturing procedure 107 and diaphragm manufacturing procedure 109 back, part makes that the indium content ratio with respect to silver approximately reaches 10 weight % in the silver alloy in being exposed to plasma.
On the other hand, when the gate insulating film semiconductor film film formation process 103 that is in as after this operation, owing to be heated to 300 ℃, do not cause the thick good fortune in surface so the crystal growth that therefore temperature causes for grid wiring, should not occur.In addition, be as short as tens of microseconds because grid wiring is applied the time of signal, need make that grid wiring resistance causes, by near the TFT of driver be in the response characteristics that causes away from the signal delay between the TFT of position and change as far as possible for a short time, have low resistance so require to connect up.Consider this point, be not directly exposed to part in the plasma being insulated layer and diaphragm covering, used indium to be approximately the silver alloy of 5 weight % with respect to the ratio of silver.But this ratio can suitably be selected according to the performance of manufacturing process and desired tft array substrate.
On the face of being handled by lyophily, the mobile wiring material of ejection is owing to forming zone 41 expansions along grid wiring, so should be coated with spraying under the situation about suitably adjusting at interval between about 100~500 microseconds from ink-spraying-head 33.Burnt till under 300 ℃ 1 hour the coating back, forms grid wiring 13, gate electrode 17, auxiliary capacitance line 16 and the terminal wiring 30 be made up of silver and indium.
Wherein, because grid wiring 13 grades are made of silver and indium,, can not lose surface smoothing so have enough thermal endurances for 300 ℃ condition.Use existing silver because surface smoothing is significantly lost,, become bad so can take place and the sewing of upper strata.
And, though grid wiring 13 grades directly contact with glass substrate 12, constitute by silver and indium in the present embodiment, so glass substrate is had enough adhesive force, can in subsequent handling, not peel off.Use existing when silver because adhesive force is little, peel off, become bad so in subsequent handling, can produce.
In addition, why firing temperature being set in 300 ℃, is because be heated to about 300 ℃ cause in the gate insulating film of next stage and semiconductor film film formation process 103.Therefore firing temperature is not limited to this temperature.
Below putting up with the problem of using ink-jetting style to form grid wiring describes.Figure 35 is the schematic diagram of expression grid wiring.What represent is that grid wiring is all, so be made up of grid wiring 13, auxiliary capacitor wiring 16 and terminal wiring 30.Grid wiring 13 links to each other at the terminal of edge of substrate with the driver IC (not shown).And auxiliary capacitor 16 1 ends that connect up converge in terminal 30 places that connect up.The numbering of each several part among Figure 35 with Fig. 7 (a)~figure (c) and Fig. 8 (a)~corresponding part of Fig. 8 (c), is used same reference numeral in addition.
As mentioned above, constitute with respect to the silver alloy that silver accounts for 5 weight % ratios by indium in the grid wiring part, and constitute with respect to the silver alloy that silver accounts for 10 weight % ratios by indium in terminal wiring and portion of terminal.These diverse wiring materials are respectively charged in the drop feedway of ink discharge device shown in Figure 5, and ink-spraying-head 33 is also only prepared the number with the kind quasi-equal of mobile wiring material.That has prepared wherein that indium accounts for respect to silver that 5 weight % ratios use accounts for two shower nozzles that 10 weight % ratios use (with reference to Figure 32 (a) and (b)) with indium with respect to silver.
That represent this situation is Figure 32 (a) and (b).Expression is used as the first nozzle specially used shower nozzle 33a of this material in Figure 32 (a), indium is accounted for the wiring material of 5 weight % ratios with respect to silver, and form situation about being coated with on the zone 41 at the grid wiring of Fig. 7 (a).Below, then represent to be used as the second nozzle specially used shower nozzle 33b of this material as Figure 32 (b), indium is accounted for the wiring material of 10 weight % ratios with respect to silver, form situation about being coated with on the zone 44 in the terminal wiring of Fig. 8 (a).
At this moment, two kinds of materials all are free-flowing materials, so mix mutually on glass substrate 12 the ejection back, behind follow-up firing process formation are electrically contacted.And in the zone of mixing mutually, though two kinds of liquid can partly form intermediateness, but the terminal wiring that all flows into Fig. 8 (a) for example forms under the situation of portion of terminal in zone 44, in the time can not forming the purpose proportioning also can terminal wiring form zone 44 near changing wiring material nearby, for example, hundreds of microns left and right sides parts in front of portion of terminal, it is sufficient changing various materials.Can certainly at first be coated with from portion of terminal.
In addition, the gate electrode 17 shown in Fig. 7 (b) also can form with the many silver alloys of indium content.Because particularly this gate electrode 17, in subsequent handling owing on this gate electrode 17, form semiconductor layer, especially wish to have the cause of good flatness, perhaps for suppressing crystal growth, use indium to account for 10 weight % and can obtain when accounting for 5 weight % the cause of more stable effect with respect to silver.And, for example can also in silver, mix refractory metals such as cobalt, titanium, niobium, molybdenum as the other materials that obtains same surface smoothing.
If will further specify the feature of such formation wiring, then the characteristic difference at the position, at least two places in same wiring.Here, make the wiring portion of grid wiring 30 different with electrode part branch characteristic.Specifically, as mentioned above,, make it the characteristic difference of each several part (position) by making as the ratio difference of indium in the AI alloy of wiring material with respect to silver.
In addition, in order to make the characteristic difference at position, also can make the wiring material difference.
Same wiring described here is continuous in shape wiring, and the circuit on the substrate is converged by so a plurality of wirings and forms, and forms circuit substrate, and these a plurality of wirings are called a unit.
In addition, as mentioned above, wiring is preferably formed by individual layer.In contrast to this, used multilayer because of following reason in the past.
In the past, do not change with respect to the heat that applies in order to make surface property, promptly tolerate the etching gas in the dry-etching course of processing ionic medium body, it is the anti-plasma performance, performances such as adhesive force, and satisfactory to both parties as these the two kinds of performances between the resistance of wiring, on existing stratiform, wiring material is carried out for overlapping time.That is to say, for example used and be major metal with low resistive metals such as aluminium, by add Trace Silicon therein, copper is given thermal endurance, on this wiring material or under form adhesive force materials such as titanium, molybdenum, form the material of anti-plasma performances such as tantalum, niobium more thereon.
Be to use two-layer or three-decker acquisition purpose performance so, in the past.Particularly the sort of wiring material used of tft array substrate need satisfy two or more performances described here mostly simultaneously.Therefore, form a kind of wiring membrane needs to carry out twice, three times repeatedly in film formation process, owing to also need device in these operations, causes the equipment investment expense to increase.Add man-hour even carry out pattern at the film to formation, process with same etching material for making the film that forms stratiform, its selection also can change.
In addition, concerning the tft array base, the thickness that forms for the reason of subsequent handling is restricted.This is because produce jump by overlapping film, makes the cause of the film fracture of the wiring that forms etc. thereon.In addition, in the restriction that this thickness is existed, form the material of stratiform, promptly above-mentioned tantalum, niobium etc. are the high material of resistivity mostly.
Therefore, for the low resistive metal part of mainly giving conductivity, require to have lower resistance.Therefore, exploring low-resistance material, or, all running into very big difficulty because of requiring other performances to carry out exploring substitution material under the situation of alloying.
And, though, for example for liquid crystal board,, on the increase wiring width, also have difficulties owing to when enlarging the pixel openings area, also require picture bright in addition along the method for the direction finding countermeasure that increases wiring width.
From these viewpoints, as the application, use the mode that forms the individual layer wiring to solve above-mentioned problem, on the cost and all be very important on the performance.This is not only liquid crystal material, and also is no less important in sputter or the evaporation.
Use fluent material, when particularly using ink-jetting style to form because can separately be coated with, so the meaning of single-layered is more great.In addition, use fluent material and make fluent material form stratiform with ink-jet method, the viewpoint of slave unit investment and this manufacturing cost of rhythm of production, this problem also is irreplaceable.
And, use other advantages of fluent material to be, particularly in being, silver-colored indium adjusts under the situation of indium proportioning according to present embodiment, can use the material of same system.So-called same system is meant; the solvent that use disperses microparticle material, or have and the material that prevents the protecting colloid similarity that disperse particles condenses is when metal is contained in situation in the solvent with metallic compound under; make between this solvent and mix mutually, can not separate out unwanted material.If will enumerate the example of particulate, then the impact when mixed is little in the homologous ray solvent, is mixed and the cohesion or the precipitation that produce are few by particulate.In a single day fluent material by the excessive solvent composition of polarity difference mixes, and just is easy to generate to separate or cohesion.And the ink-spraying-head of the such fluent material of relevant ejection, constitute shower nozzle material with respect to mobile wiring material, the inner sticker that uses of shower nozzle for example, its range of choice is wide, and shower nozzle is easy with respect to the adjustment of mobile wiring material.Certainly, should careful selection get and can not produce xenogenesis cohesion and precipitation, even the different solvents system also can mix.But this selection and adjustment are wanted the expensive time mostly, consider that it is very useful that this point is used the homologous ray material.
In addition, individual layer described here is formed by one deck wiring when being meant film forming, with the liquid coating once, forms and can satisfy the required functional membrane of performance that connects up.For example, as close and distant water (close and distant liquid) is handled, only when needs separately are coated with, with the layer multiple stratification that does not play the effect of positive raising adhesive force, in subsequent handling, make it film forming, perhaps separate, and formerly form the film that improves tack with giving of tack, use a rubbing method to form situations such as foregoing formation thereon, be not excluded at so-called individual layer.
(gate insulating film semiconductor film film formation process 103)
In the present embodiment,, omit explanation owing to identical with above-mentioned execution mode 1 about gate insulating film semiconductor film film formation process 103.
(gate insulating film semiconductor film manufacturing procedure 104)
Following with reference to Figure 12 (a) and (b) and Figure 13 (a) and (b) explanation gate insulating film semiconductor film film formation process 104.
Figure 12 (a) and (b) and Figure 13 (a) and (b) are views that expression gate insulating film semiconductor film manufacturing procedure 104 stops the back state.Figure 12 (a) and Figure 13 (a) are respectively that the pixel on the glass substrate 12 forms zone 61, portion of terminal forms regional 62 plan view.Figure 12 (b) and Figure 13 (b) are respectively along the cross section view of the G-G line direction of arrow with along the cross section view of the H-H line direction of arrow among Figure 12 (a) and Figure 13 (a).
In this gate insulating film semiconductor film manufacturing procedure 104, utilize photoetching process to process.
At first amorphous silicon film 46 and n+ type silicon fiml 47 are processed by first photoetching process.Form the zone in pixel and be processed into residual one-tenth island above gate electrode 17 in 61, process it not by residual in the zone 62 and form at terminal.Obtain amorphous si-layer 19 like this, will form the n+ type silicon processing of films 48 of n+ type silicon layer 20 thereafter.The dry-etching method is used in etching, to import sulphur hexafluoride (SF 6), the mist mode of hydrogen chloride (HCl) gas carries out.So far owing to all surfaces of gate insulating film 45 covered substrates, 30 grades can not be exposed among the dry etching gases so terminal connects up.
Then gate insulating film 45 is processed by second photoetching process.Form part etch-gate dielectric film 45 in the zone 62 at terminal, obtain gate insulation layer 18, opening portion 49.The dry-etching method is used in etching, to import CF 4And O 2The mist mode carry out.
In the dry-etching process of this gate insulating film 45, form the peristomes 49 that zone 62 forms at terminal, though not shownly among the figure is electrically connected in the part of usefulness with other parts, terminal connects up and 30 is exposed in the dry etching gases atmosphere.This is because the dry-etching method is the good method of a kind of control performance, prevents that in actual manufacturing etching is excessive.
Wherein, form terminal wiring 30 with silver, do not have the anti-plasma performance by prior art.Therefore, terminal wiring 30 is become bad by remarkable etching in opening portion 49.In contrast to this, terminal wiring 30 is made of silver and indium in the present embodiment, and indium is set in about 10 weight % with respect to the ratio of silver.Therefore have the anti-plasma performance, can tolerate this dry-etching and handle.
(source leak routing pretreatment procedure 105)
About this provenance leak routing pretreatment procedure 105, omit its explanation owing to identical with above-mentioned execution mode 1.
(the source leak routing forms operation 106)
Form operation 106 about this provenance leak routing, omit its explanation owing to identical with above-mentioned execution mode 1.
In addition, the wiring here also is an individual layer, with illustrate in the grid wiring operation identical, have advantage.
(channel part manufacturing procedure 107)
About this channel part manufacturing procedure 107, omit its explanation owing to identical with above-mentioned execution mode 1.
(diaphragm interlayer insulating film film formation process 108)
About this diaphragm interlayer insulating film film formation process 108, omit its explanation owing to identical with above-mentioned execution mode 1.
(diaphragm manufacturing procedure 109)
About this diaphragm manufacturing procedure 109, omit its explanation owing to identical with above-mentioned execution mode 1.
(pixel electrode forms operation 110)
As last operation, ITO (indium tin oxide) the film film forming that the back is made of with sputtering method pixel electrode 24 and terminal electrode 29.The substrate temperature of this moment is set in 200 ℃.Make this ITO film form pattern with photoetching process then, obtained as Fig. 1, Fig. 2, Figure 31 (a) and (b) and tft array substrate 11 shown in Figure 4.
Therefore, material of the present invention is owing to have in the past the good adhesive force to glass substrate that silver-colored simple substance did not have, thus can tolerate a series of manufacture processes, can not produce grid wiring etc. peel off and cause bad.
And material of the present invention, owing to have the excellent heat resistance that silver-colored simple substance did not have in the past, even also can slightly not make, can obtain the good grid wiring of surface smoothing 13, auxiliary capacitor wiring 16 and gate electrode 17 etc. so be exposed to 300 ℃ of such hot conditions infrabasal plate surfaces of present embodiment.Therefore, and can not produce leakage between the source wiring 14 that forms by means of gate insulation layer 18, semiconductor layer 27, source electrode 21 etc. thereon, productivity ratio improves, and the characteristic of TFT is also stable simultaneously.
So compare with any material, material of the present invention has high anti-plasma performance, makes this manufacturing process become possibility.
In the present embodiment; the etching of gate insulating film 18 in gate insulating film semiconductor film manufacturing procedure 104; in the channel part manufacturing procedure to the etching of n+ type silicon processing of films 48; etching to silicon nitride film 55 in diaphragm manufacturing procedure 109 amounts in these three kinds of operations, can use the dry-etching method.At this moment, form under the situation of wiring and electrode etc. with silver-colored simple substance, during the mistake etching, etched when perhaps making the etching mask of other films, it is bad to become in the past.Yet as present embodiment, contain the wiring material of the present invention of silver and indium and can not become bad owing to have good anti-plasma performance.
So, make when the tft array substrate, use the dry-etching method mostly, thing followed requirement is to have high dry-etching patience (anti-plasma performance) as the material that constitutes wiring, electrode etc.Of the present invention is the material that main body contains indium with silver, has high anti-plasma performance, especially uses very good as materials such as the wiring on the formation tft array substrate, electrodes.
And material of the present invention, using the pattern of ink jet mode and so on to form device as present embodiment, to describe, form the situation of source wiring 14, semiconductor layer 27, source electrode 21 etc. be effective especially.In this case because source wiring 14 grades are formed the etching mask of usefulness as n+ type silicon layer 20, so begin from etching to finish long-time in be exposed under the atmosphere of dry etching gases.Therefore, used technology such under the situation of silver-colored simple substance to be difficult to realize in the past.But material of the present invention but can form device by means of this pattern and make tft array substrate.
So, silver alloy of the present invention is particularly suitable for using the manufacturing process of ink discharge device and so on apparatus for coating, is useful material contained in the mobile wiring material.And just as described later, even, be useful material too not using pattern to form in the manufacture method of device.
In the present embodiment, be that six uses of total photomask exposes, six pieces of mask process of developing procedure.In order under more low-cost, to produce tft array substrate, also be extensive use of its minimizing five pieces of mask process once.In this case, be by gate insulating film 45 and silicon nitride film 55 being carried out etching and processing continuously, forming the method for gate insulation layer 18 and protective layer 25.Yet the exposed division that particularly can form drain electrode wiring 22 in this case will be exposed in the dry etching gases atmosphere for a long time, need the harsh more service condition of tolerance.
In order to seek wherein former thereby to have investigated the situation of substrate in etching.At first no problem owing to film is arranged comprehensively during the etching of silicon nitride film 55.But in thing followed gate insulating film 45 etching processes, for example can form the part of exposing of the contact hole 23 of drain electrode wiring, self etching begins all to be directly exposed in the atmosphere of dry etching gases to end.Compare with only etching excessively under six pieces of mask situations, compole is long at that time, is a kind of process conditions of harshness.
Therefore, under the situation of this five pieces of mask process, has high anti-plasma performance for drain electrode 22 special requirement that connect up, but the silver alloy with argentiferous and indium is the silver alloy of the present invention of representative, owing to possess high anti-plasma performance, even so also can use in this case, the scope of application is wide.
And present embodiment is six pieces of mask process, though terminal wiring 30 is the forms that form simultaneously with grid wiring etc., the present invention is not limited to this situation.Existing almost whole manufacture method; all are the silicon nitride film film forming on substrate is comprehensive that make gate insulation layer 18 or will form protective layer 25; utilize the dry-etching method that its part is removed; must be removed part in this method so that realization is electrically connected, therefore require to have overetched anti-plasma performance in its electrode that disposes down and wiring etc.The invention provides anti-plasma performance excellent material, performance excellent results for the manufacture process of these tft array substrates.
In the present embodiment, used in the mobile wiring material will be coated with alloy particle organic membrane, that contain silver-colored indium and be dispersed in dispersion liquid in the organic solvent.This moment, contained silver and indium in mobile wiring material was to use the ratio of indium and silver to be approximately that wiring material below the 10 weight % forms.But indium can suitably be selected make it to have suitable anti-plasma performance with respect to the ratio of silver according to manufacture process, perhaps suitably selects according to the performance of requirement tft array substrate etc.
And the form of this mobile wiring material is not limited to contain the silver and the form of indium with the AI alloy particulate form.Also can make silver-colored particulate and indium particulate respectively, it independently is dispersed in form in the solvent.In addition, not necessarily be limited to particulate, silver or indium can also be included in the form in the solvent with the form of metallic compound.
In the present embodiment, though be to form wiring such as source wiring 14, grid wiring 13 and electrode etc. with containing the silver and the silver alloy of indium, being not limited to this situation, also can be the silver alloy that contains silver-colored and zinc.Can also be to it is characterized in that at least also containing the silver alloy of more than one elements of from tin, zinc, lead, bismuth, indium and gallium, selecting simultaneously, form grid wiring 13 etc. by containing silver.But also can be to it is characterized in that not only with silver, also can be with aluminium, copper, as major metal, except that these elements, contain the silver alloy of the element of from aluminium, copper, nickel, gold, silver, platinum, palladium, cobalt, rhodium, iridium, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and neodymium, selecting at least.
Here it is as follows to form the specification specified that wiring forms in operation 102 and the source leak routing formation operation 106 for above-mentioned grid wiring.
At first illustrate that with reference to Figure 32 (a)~Figure 32 (e) grid wiring forms operation 102.
Shown in Figure 32 (a), utilize the first shower nozzle 33a of ink-spraying-head 33, in grid wiring pretreatment procedure 101, the wiring of the surface having been implemented the glass substrate 12 after close and distant water (close and distant liquid) is handled forms on the zone, ejection wiring portion is with the mobile wiring material of low electrical resistant material, to form terminal wiring 30.
Shown in Figure 32 (b), utilize the second shower nozzle 33b of ink-spraying-head 33 then, the terminal electrode on the glass substrate 12 after having formed terminal wiring 30 forms the zone, and the ejection terminal is with the mobile wiring material of anti-plasma performance, to form terminal electrode 39.
And then shown in Figure 32 (c), will be after the terminal wiring 30 that has formed on the glass substrate 12 and terminal electrode 29 burn till, formation will become the gate insulating film 45 of diaphragm so that terminal wiring 30 and terminal electrode 29 are covered.
Thereafter shown in Figure 32 (d), in order to carry out terminal processing, be provided with and will form the anticorrosive additive material 100 of mask, make the gate insulating film 45 of the part corresponding form openings with terminal electrode 29, form pattern through mask exposure etc.
Last as Figure 32 (e) shown in, after etching is carried out in the zone of gate insulating film 45 that will be corresponding with terminal electrode 29, peel off resist 100, formation portion of terminal 28.
Like this, ink-spraying-head 33 according to two shower nozzles of function setting, is handled under the situation of two kinds of mobile wiring materials, ink supply system 36, control unit 37, ejection positional information etc. also need corresponding therewith in advance.
The portion of terminal 28 of Xing Chenging will form the shape shown in Figure 31 (a) and (b) like this.And terminal wiring 30 is connected with terminal electrode 29, makes to have the property of conducting therebetween.
Terminal wiring 30 owing to covered by gate insulation layer 18, so can suitably select to such an extent that make it in the anti-plasma performance, has thermal endurance and to the adhesive force of glass substrate.About the anti-plasma performance, owing to be not exposed in the dry etching gases atmosphere, so be unnecessary.
For example, if be that example describes to make the circuit substrate that large-scale especially liquid crystal indicator uses, then since in the large-scale liquid crystal indicator length of arrangement wire prolong, so should reduce the resistance that connects up as far as possible.In this case, terminal can be connected up and 30 make indium and reach 3 weight % with respect to the content of silver.At this moment, the resistivity of this part is approximately 4 μ Ω cm.And be in pixel and form grid wiring 13, gate electrode 17, the auxiliary capacitors wiring 16 of zone in 61, also because of length of arrangement wire prolongs, with terminal wiring 30 same reasons under so that the lower resistance of acquisition can make indium reach 3 weight % with respect to the content of silver.
On the other hand, terminal electrode 29 in being electrically connected required etching work procedure, is exposed in the dry etching gases atmosphere because of crossing etching.Therefore, should pay attention to the anti-plasma performance, can be configured so that indium reaches 10 weight % with respect to the content of silver.This terminal electrode 29 also can make resistivity bigger than other parts than the grid wiring on the tft array substrate 13 or source wiring 14, terminal 30 much shorters that connect up.
Certainly, the two also can have identical formation terminal wiring 30 and terminal electrode 29, and indium reached 10 weight % with respect to the content of silver during promptly it constituted.Yet, as present embodiment, separate coating according to the required performance of each several part, owing to can form, can make the large scale circuit substrate more and the advantage of large-scale display device etc. more so have than all lower resistance wirings and electrode etc.
Wherein, above-mentioned printing ink ink discharge device 33 is by with the first shower nozzle 33a and the second shower nozzle 33b, and the ejection indium two kind mobile wiring materials different with respect to silver content are to form terminal wiring and terminal electrode.Specifically, connecting up on the zone of 30 usefulness for forming terminal, connecting up 30 the time when forming terminal, the ejection indium is the mobile wiring material of 3 weight % with respect to silver content.On the other hand, on for the zone that forms terminal electrode 29 usefulness, when forming terminal cloth electrode 29, the ejection indium is the mobile wiring material of 10 weight % with respect to silver content.
On the other hand, be on the zone that pixel forms zone 61 grid wiring 13, gate electrode 17, auxiliary capacitor wiring 16 ejection and the terminal 30 identical mobile wiring materials that connect up will forming.After the ejection, under 300 ℃, burnt till 1 hour, obtained predetermined terminal wiring 30 and terminal electrode 29.Therefore using indium by the wiring portion that forms zone 61 in pixel is the mobile wiring material of 3 weight % with respect to silver content, can obtain more low-resistance wiring.
In the present embodiment, the pattern of ink jet mode and so on forms device should separate coating in real estate, the wiring that forms in same operation etc. must have required different anti-plasma performance or conductivity at each several part, and to carry out best of breed between indium content, conductivity and the technology patience to material of the present invention all be very important.The large-scale tft array substrate that can produce easy manufacturing like this, have the good electrical characteristic.
In addition, in the present embodiment,, be not limited to this though terminal wiring 30 and terminal electrode 29 have the border of indium content different materials.Indium content also can change at boundary vicinity.Its formation method both can be the method for mutual natural mixed flow wiring material, also can be the method for intentionally two kinds of materials being mixed mutually.
Certainly, in tft array substrate 11 needed parts, being exposed on the part in the dry etching gases atmosphere in manufacturing process, wiring that indium content increases and electrode etc. are set, is important for present embodiment.
Therefore, silver alloy of the present invention, even when indium reaches when separately being coated with under the lower situation of 1 weight % and 3 weight % and so on the content of silver is for example low, also suitably use corresponding with a plurality of manufacturing process constitute wiring such as grid wiring 13 and electrode, particularly the method for low-resistance material obtains.
In addition, in the present embodiment, though form wiring such as grid wiring 13 etc. with containing the silver and the silver alloy of indium, being not limited to this situation, also can be the silver alloy that contains silver-colored and zinc.Can also use to it is characterized in that containing silver, contain the silver alloy of more than one elements of from tin, zinc, lead, bismuth, indium and gallium, selecting simultaneously at least, form grid wiring 13 etc.And can be to it is characterized in that not only with silver, also can be with aluminium, copper as major metal, except that these elements, contain the silver alloy of the element of from aluminium, copper, nickel, gold, silver, platinum, palladium, cobalt, rhodium, iridium, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and neodymium, selecting at least.
But also can according to circumstances separate use, with silver and indium, silver and zinc etc., make to constitute difference on the tft array substrate.
Below describe the source leak routing in detail and form operation 106.Wherein, constituting and making indium is 3 weight % under the situation of source electrode 21 and source wiring 14 with respect to the content of silver, is 10 weight % under the situation of drain electrode wiring 22.
And in drain electrode wiring 22, separately be coated with to such an extent that to make indium be 3 weight % and 10 weight % with respect to the content of silver, also can near contact hole 23, improve the anti-plasma performance.In addition, any place on this spr substrate of the TFT of present embodiment all can be coated with like this.
Also have, the wiring material of formation source leak routing is not limited to the material by silver and indium, also can be the alloy material that contains silver and zinc.In addition can also be with it is characterized in that containing silver, the silver alloy that contains more than one elements of selecting simultaneously at least from tin, zinc, lead, bismuth, indium and gallium forms source wiring 14 etc.And can be to it is characterized in that not only with silver, also can be with aluminium, copper as major metal, except that these elements, at least also contain the silver alloy of the element of from aluminium, copper, nickel, gold, silver, platinum, palladium, cobalt, rhodium, iridium, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and neodymium, selecting.
But also can according to circumstances separate use, utilize silver and indium, silver and zinc etc. to make on the tft array substrate formation different.
In addition, under the situation of making tft array substrate 11, as mentioned above, both can form in operation 102, source leak routing formation operation 106 these two operations and separate coating, also can only separate coating in an operation therein at grid wiring.
At this, when just according to purposes wiring materials such as wiring portion and portion of terminal separately being coated with, the part that each material connects describes.
For example shown in Figure 33 (a), do terminal wiring 30 in the wiring portion with material M coating after, shown in Figure 33 (b), at the part coating material N suitable with the terminal electrode 29 that forms terminal.The boundary member of material M and material N is in and contacts with each other at this moment, perhaps under the state that mixes mutually.
As Figure 34 (a)~34 (c) expression, the state of being suspected when utilizing generation border under ink-jet method coating back different materials M and the situation that N contacts.
The situation that Figure 34 (a) expression material M, N mix with liquid form mutually in the border, produce because of mixing mutually with material M and material N state all inequality, i.e. intermediateness (zone line).
This state, different because of the mixed proportion of material M and material N, or to a certain degree form intermediateness because of being mixed to, all relevant with the residual degree of the contained solvent in coating back.That is to say,, the mutual mixing that the flowability because of liquid produces then can not occur if volume is dried.But, it is believed that the intermediateness that produces because of the metal particle fusion when burning till, to compare scope minimum with the intermediateness that this zone mixes with liquid condition.What pay close attention to here is mutual mixing with liquid condition, and this moment, the border of material M and material N was indefinite.
Under the situation of the dry substantially back coating material N of solvent composition process among the material M that Figure 34 (b) expression formerly is coated with, the mutual as yet state that mixes of material M under the liquid state and material N.
This state is down owing to material M and material N mixing mutually as yet, so there is clearer and more definite border between the two.But when burning till, because of mutual fusion particles contained among material M and the material N forms intermediateness.
Figure 34 (c) expression is under the situation of Figure 34 (a) and Figure 34 (b) centre, and the solvent composition among the material N that is coated with later makes material M liquefy once more, and the zone of material M and material becomes indefinite state.The zone that mix this moment mutually is narrower in Figure 34 (a), so can dream up imaginary border from its intermediate distance.
In the present embodiment, importantly burn till between back material M and the material N and realize being electrically connected.The state of Figure 34 (a)~34 (c) is the state that is electrically connected respectively, and it is all no problem to be among the present invention under which kind of state.But just as described later, form under the situation of resistance the state of preferred Figure 34 (a), the state of preferred Figure 34 in the end of this resistance (b) and Figure 34 (c) in the intermediateness of actively utilizing material M and material N to dissolve each other to form.In addition, be only to emphasize here with regard to the border of material M and material N, but since in coating process the flatness on surface have nothing to do with this explanation, so all accompanying drawing is illustrated with flat condition.
Utilize the invention among the application,, can regulate the resistance of low-resistance formation and wiring by with low resistance wiring material and alloy and high resistance wiring material appropriate combination.Below be illustrated with regard to the example.
In the grid wiring schematic diagram of Figure 35, in order to utilize the terminal electrode that connects driver IC and the terminal wiring polishing length of arrangement wire of grid wiring, the short part of distance between terminal and grid wiring, promptly be connected part with the middle body of driver IC, wiring shape is made meander-like, with distance part between driver terminal and grid wiring, promptly be connected part and make linearity with the terminal of driver IC, be connected to each other.
Wherein, with the length D shown in Figure 36 (a), the meander-like pattern that to be envisioned for a length of arrangement wire be L.There are four times in the complications shown in Figure 36 (a), so total length is approximately 8L.Therefore, compare with the situation that straight line is connected with distance D, resistance approximately becomes 8L/D doubly.
For example, if the D=600 micron, L=micron 150,8L/D=2 then is so if change wiring width, thickness, then Bu Xian resistivity can reach two times.
In order to adjust the cloth line resistance, below can considering to use
(1) material with required resistance forms
(2) by cooperating the different material adjustment of resistivity
(3) these three kinds of methods of thickness of change wiring shape.
In the method (1), shown in Figure 33 (a) and (b), prepare low high material, the material N of material, material M and resistivity of resistivity of containing metal part, form wiring with material M, forming resistance part materials used N, can form resistance this moment.This method is used in D=600 micron among above-mentioned Figure 36 (a), under the situation of L=150 micron, resistivity when indium is in 5 weight % with respect to the ratio of silver is approximately 6.1 μ Ω cm (embodiment 5), the resistivity that the ratio of indium and silver is in 10 weight % is approximately 12.3 μ Ω cm (embodiment 6), so if alloy when material M is decided to be indium and is 5 weight % with respect to the ratio of silver, alloy when material N is decided to be indium and is 5 weight % with respect to the ratio of silver, and change thickness and live width, then shown in Figure 36 (b), do not use straight line can form resistance even do not use meander-like yet.
Utilize the material M and the material N of method (2) adjust the method for interlaminated resistance, shown in Figure 37 (a) and (b), in ink-spraying-head 33, after spraying material M off and on by the first shower nozzle 33a that goes ahead of the rest, spray material N in the crack betwixt by means of the second shower nozzle 33b, mix the wiring (intermediate) that can obtain having combined resistance with material N because of material M in this case.
At this moment, the mixing ratio that can adjust material M and material N according to the ejection interval that changes material M and material N, ejection ratio.
Below explanation forms other examples of above-mentioned intermediate.
In Figure 38 (a) and (b) and Figure 39 (a) and (b), the ejection ratio difference of material M, Figure 38 (a) and (b) represent with one the example of ratio ejection material M in three, and Figure 39 (a) and (b) are then represented with two the example of ratio ejection material M in three.Thickness is identical, the cloth live width is identical, spray volume one is identical, ejection is identical at interval, and as if the mode according to Figure 34 (b), the resistance value under Figure 38 (a) and (b) situation improves.Like this, can adjust resistance value with the ratio of material M and material N ejection number of times.Certainly also can do suitable adjustment at interval by change thickness, live width, spray volume and ejection.
In addition, be the mode of Figure 34 (a) as if state according to section inside, its resistance value not necessarily can become the median that is directly proportional with mixing ratio.Under the situation of metal alloy, when mixing different materials, often the resistance value than the two increases.And form at metal under the situation of mixing ratio of compound, resistance value tends to reduce.This is because help the cause that the situation of random likelihood ratio simple mixing of the conduction electrons of electrical conductivity increases when foreign material mixes mutually, and under the situation of compound, owing to depend on crystal structure, so probability can reduce.It is believed that under the situation of present embodiment that particulate fuses mutually when burning till after the mixing, cause due to the situation similar phenomena with metal alloy.If convert resistance value to mean value, then often need to study in advance resistance characteristic like this.
On the other hand, behind the droplet drying that is ejected under the overlapping situation, when promptly being in the border shown in Figure 34 (b), (c), because material M sits on the top of the other under the state that is connected with material N, so resistance value and the mean value of the two are approaching.Therefore, can adjust to the median of material M and material N in this case with the ratio of spray volume.Therefore under the state after the coating, also can adjust resistance value.
But in Figure 34 (a), because the boundary portion between material M and material N is clear and definite, so that become indeterminate with the length of arrangement wire of resistance form performance, it is uneven that resistance value becomes, and should make the part end that forms resistance clear and definite border occur according to being dried shown in Figure 34 (b).
Figure 38 (b) and Figure 39 (b), the cross section view of representing Figure 38 (a) and Figure 39 (a) respectively, for making resistive element length clear and definite, shown in Figure 34 (b), it after the end intensive drying makes the border clear and definite, is sprayed material M, N, shown in Figure 34 (a) off and on, by mixing, make the clear and definite example in border of material M, N at active component with liquid condition.
The following situation that changes wiring width and thickness with reference to Figure 40 (a)~Figure 40 (c) illustration method (3).
The narrow at interval situation of Figure 40 (a) expression ejection in this case if change ejection concentration of material and wiring width, then will make thickness increase.
In contrast to this, Figure 40 (b) is the example that ejection is enlarged at interval.By fine rule ellipse representation part is the position that the drop bullet falls.This figure represents that the material N in that the two place's bullets that utilize close and distant water (close and distant liquid) processing to make resistance form change zone, position hydrophilic (liquid) in advance fall will compare the thickness attenuate with the situation at the ejection interval of filling up Figure 40 (a) along the situation of hydrophilic (liquid) pattern expansion.Make under the situation of thickness attenuate at interval by such expansion ejection, can form higher resistance value.
By with said method (1)~(3) appropriate combination, can make the different material of resistance value like this.
This is effective under the situation that is formed IC on the glass substrate by amorphous silicon.In the technical process of processing silicon wafer, though carry out the operation that proper resistor forms with ion implantation, but for this routine mode of use, for example as the display panel of liquid crystal indicator, in the display panel with the large substrate making, the ion implantation unit scale increases, and considers that device itself and device price are all unrealistic.Therefore, in order to form the circuit substrate with required resistance like this on substrate, such method is very effective.
And, for resistance for material, as the present embodiment explanation, can either use with indium with respect to the ratio change of silver material, and as the higher material of resistance, also can use and in silver, mix cobalt for example, material that the nickel constant resistance is high, or the alloy of high-melting-point material such as tantalum, molybdenum, tungsten, niobium, can use silver-colored simple substance in addition and without silver alloy.
And shown in Figure 40 (c), when using close and distant water (liquid) facture to make wiring form the close and distant water in position (liquid) change, wiring width is narrowed down.In this case, if the identical then resistance of thickness increases.Therefore can do resistance control according to wiring width.
Wherein in Figure 38 (a), Figure 39 (a) of using and Figure 40 (a), for the purpose of illustrating easily, be resistive element part just have been illustrated under the situation of the droplet profile that falls behind of bullet clearly having marked, but present embodiment is not limited to the shape defined in these figure.Under the situation that regional bullet after close and distant water (liquid) is handled falls, can go up expansion at hydrophilic region (lyophily zone) for the droplet profile that bullet is fallen behind and go down, the shape that the bullet shown in clear and definite falls behind among the figure can be not residual yet.Particularly if the bullet backwardness remains the drop state, shown in Figure 38 (b) and Figure 39 (b), then material M and material N can mix the formation one mutually.
In addition, in the present embodiment, used the pattern formation device that sprays mobile drop in the ink jet mode.Yet, can equally suitably not use even silver alloy of the present invention does not use this pattern to form device yet.In this case, in the operation of correspondence, will utilize the most general method such as existing sputtering method or vapour deposition method and photoetching process etc. to make tft array substrate.But be mobile wiring material, and use sputtering target and evaporation with evaporation source etc., can access by silver alloy of the present invention and form the wiring that forms, electrode etc.Even silver alloy of the present invention in this case, also have thermal endurance, adhesive force, these good technology patience of anti-plasma performance, and can use as low electrical resistant material easily.
And silver alloy of the present invention also can be easily as the one deck in the overlapping Miltilayer wiring structure that forms of two-layer above material is used.For example; can as silver-colored simple substance, not lose surface smoothing even burn till through 300 ℃ yet; and particularly contain indium, its content and for example account under the more situation of 10 weight % equal sizes with respect to silver; still have sufficient anti-plasma performance, can effectively use as the coat of metal of protecting its lower-layer wiring.And can be used as make it with execution mode 1 in semiconductor layer 27 directly contact, be the source electrode 21 that obtains to be electrically connected usefulness, whole or its a part of can use of drain electrode wiring 22, good thermal endurance and the adhesive force of same performance can use in the manufacture process of tft array substrate easily.
Perhaps, silver alloy of the present invention uses as the light reflective electrode on the sort of tft array substrate that can also use in reflection-type TFT liquid crystal indicator etc.In this case, silver alloy of the present invention is owing to have a good thermal endurance, so even through for example burning till under 300 ℃, also lose the flatness on surface unlike silver-colored simple substance.Therefore, can not cause the light scattering that design is outer, can keep sufficient light reflectivity etc., the characteristic as tft array substrate is not fully exerted as the light reflective electrode.
In addition, the formation of silver alloy of the present invention, wiring and Wiring method can also use as the bus electrode on the glass substrate that constitutes PDP (plasma display panel), data electrode.These electrodes are to be configured on the front glass substrate of using for driving PDP or the electrode on the glass substrate of the back side, are made of silver, chromium/copper/chromium, aluminium/chromium in the past.As the adhesive force that improves on copper or aluminium base, solve the different countermeasure of the coefficient of expansion, have to use and glass substrate between insert the structure of chromium layer.On the other hand, existing silver has the thermal endurance problem, and high temperature burns till and causes grain growth, is the material that is difficult to use.
In contrast to this, silver alloy of the present invention because have good thermal endurance and with the adhesive force of glass substrate, so can replace existing silver to wait these materials, be effective as bus electrode, data electrode uses.
The formation of silver alloy of the present invention, wiring and Wiring method also can use in the display unit of using EL (electroluminescence).Compare with liquid crystal indicator, the EL display unit is utilized magnitude of current control luminosity gray scale often.In this case, become the electric current supplying wire of the light-emitting component supplying electric current of pixel, require to use low-resistance material for synform.This is because the cloth line resistance can consume electric power, makes the luminous efficiency variation, perhaps makes display unit generate heat, occur the cause of spot on display surface.
And the circuit substrate that drives EL element is to use the circuit of tft array substrate to form mostly, often will through with present embodiment in the same operation of operation represented make.Therefore, the content described in the present embodiment can be used on the display unit of using EL.Particularly form the wiring of electric current supplying wire, from the outside to the line that drives the driver supplying electric current, can use selectivity to form low-resistance wiring material, be that indium is the silver alloy of 3 weight % with respect to silver content, can use indium at holding wire and terminal electrode is the silver alloy of 10 weight % with respect to silver content.
The formation and the Wiring method of silver alloy of the present invention in addition, wiring also can be as the wiring materials of flexible base, board or glass epoxy resin substrate.Splicing ear in these substrates, indium are that sludge proof constitutes with respect to the content height of silver as emphasis, in the internal wiring part, can reduce the content of indium with respect to silver, and wiring is used as low resistance.
And in above-mentioned silver alloy, particularly be under the situation below the 0.5 weight % in the content ratio of indium with silver, resistivity reaches below the 2.7 μ Ω cm, can form with existing silver wiring the low resistance that can not obtain connect up, thereby be useful.But because indium content is low, the anti-plasma performance is insufficient, needs stacked other metal films etc. in general.About adhesive force to substrate, because of indium content low also insufficient, so often need to carry out situation such as base treatment.Therefore, even indium is a silver alloy below the 0.5 weight % with respect to silver content, use if then also can be used as this line that connects up on the circuit substrate through base treatment.
Below putting up with indium is that silver alloy below the 0.5 weight % describes as the manufacture method of wiring material situation infrabasal plate circuit with respect to silver content.
Form in the operation 102 at grid wiring shown in Figure 6, use, on tft array substrate 71, carry out the separately coating of the different wiring materials that constitute with the pattern formation device of ink-jetting style as representative.On the other hand, in above-mentioned execution mode 3, form in the operation 106, carried out separately coating constituting different wiring materials at the source leak routing.
Wherein in grid wiring formation operation 102, the use sputtering method has carried out wiring formation etc., and these wirings etc. are folded by silver alloy of the present invention and titanium layer and formed.
Figure 41 (a) and (b) and Figure 42 (a) and (b) represent that in the present embodiment grid wiring forms the state after operation 102 finishes.Figure 41 (a) and Figure 42 (a) represent that respectively pixel on the glass substrate 12 forms the plan view that zone 61 and portion of terminal form zone 62.Figure 41 (b) and Figure 42 (b) are respectively along the cross section view of straight line M-M arrow with along the cross section view of the N-N line direction of arrow among Figure 41 (a) and Figure 42 (a).
Among these figure, grid wiring 80, gate electrode 81, auxiliary capacitance line 82 and terminal wiring 83 have identical stepped construction, are made of two-layer.Each layer 80a, 81a, 82a and 83a near glass substrate 12 1 sides are made of silver alloy of the present invention, and indium is 0.2 weight % with respect to the content of silver.Each layer 80b, the 81b, 82b and the 83b that are in its upper strata one side are made up of titanium.Each layer 80a, 81a, 82a and 83a, and the film thickness of 80b, 81b, 82b and 83b is 0.2 micron.
So wherein near each layer 80a, 81a, 82a and the 83a of glass substrate 12 1 sides owing to be to have a thermal endurance by what the alloy that silver and indium constitute formed, also can be even in subsequent handling, burn till to adverse effect such as generation such as grid wiring 80 grades through 300 ℃.But forming under the situation of these layers with silver-colored simple substance in the past, thermal endurance and can produce significant concave-convex surface for want of, thereby the leakage on generation and upper strata is bad.
If the indium content following silver alloy that is 0.5 weight, as mentioned above, resistivity is low to be reached below the 2.7 μ Ω cm, thus can form with aluminium the low resistance that can not form connect up.In the present embodiment, resistivity is low to be reached about 2.3 μ Ω cm, and numerical value is extremely low.Therefore special hope realizes that for example in liquid crystal indicators such as liquid crystal TV usefulness, silver alloy of the present invention is a kind of useful material under the situation of wiring low resistanceization.
To describe with regard to the formation method of grid wiring 80 grades among the present invention.Wherein in grid wiring forms operation 102, owing to uses, so do not carry out the operation suitable with grid wiring pretreatment procedure 101 with the pattern formation device of ink-jetting style as representative.
At first, utilize sputtering method to make the silver alloy film film forming on glass substrate 12 that contains 0.2 weight % indium with respect to silver.Used solid solution the silver alloy target of indium to be arranged as sputtering target this moment.Utilize sputtering method to make the titanium continuous film forming in a vacuum then.Utilize photoetching process that the film that obtains is like this processed, obtained grid wiring shown in Figure 41 (a) and (b) and Figure 42 (a) and (b) etc.The dry-etching method has been used in the etching of this moment.
Consider subsequent handling, terminal 83 grades that connect up need have the anti-plasma performance, but the titanium by upper layer side has obtained this performance among the present invention.
So, one deck that this silver alloy also can be used as in the Miltilayer wiring structure uses, and is under the situation below the 0.5 weight % with respect to silver content when making indium, can obtain connecting up with the irrealizable low resistance of existing aluminium institute.
In addition, in said method, though be on glass substrate 12, directly to make silver alloy film film forming of the present invention, but when with the inadequate situation of the adhesive force of substrate under, both can use the intermediate layer that is made of metal etc. is set in the middle of the two, and also can use the mode of glass substrate being handled with plasma, medicine etc. to obtain adhesive force.
Among the present invention, the material of each of upper layer side layer 80b, 81b, 82b and 83b is not limited to titanium, also can be chromium, molybdenum, tantalum, tungsten or makes its material that contains nitrogen, oxygen or ITO metal oxides such as (indium tin oxides).In order to form grid wiring 80 etc., as mentioned above, both can be coated with behind the mobile wiring material stackedly, also can use the evaporation source that constitutes by silver and indium by means of the vapour deposition method film forming, the formation of processing back.
In this explanation, form in the operation 102 at grid wiring, though be to use the film that constitutes by silver alloy of the present invention and titanium to form wiring,, also can form the wiring that same formation is made of stacked film in the operation 106 at the source leak routing as other execution modes of the present invention.Even in this case, because the alloy that is made of silver and indium has thermal endurance, so can not produce adverse effect even in subsequent handling, burn till also.
In this case, when indium is 0.5 weight % when following with respect to silver content, can make and use the irrealizable low-resistance wiring of aluminium in the past.
But for silver,, under the situation of burning till, can form than the aluminium film of high reflectance more by making it to contain indium.Under the situation of double as reflecting plate and reflecting electrode of particularly connecting up, can form wiring with the silver alloy that contains the following indium of 0.5 weight % with respect to silver.
In sum, silver alloy of the present invention is to be formed on the insulating properties substrate to form the material that wiring and/or electrode are used, and it is characterized in that with silver wherein containing more than one elements of selecting as main component from tin, zinc, lead, bismuth, indium and gallium.
According to the material that uses above-mentioned formation, it is low to form resistance, strong wiring and/or the electrodes of technology patience such as thermal endurance or the adhesive force on glass substrate, plasma-resistance.
And described element also can contain zinc at least.
In this case, if use with silver as main component, the silver alloy that makes it to contain at least zinc forms wiring, electrode etc., and then the low resistance performance can significantly not lost, can improve thermal endurance and adhesive force, and can also high anti-plasma performance under the condition that imports chlorine or oxygen.
Described in addition element can also contain indium at least.
In this case, if use with silver as main body, the silver alloy that makes it to contain at least indium forms wiring, electrode etc., and then the low resistance performance can significantly not lost, and can improve thermal endurance and adhesive force, and feature increase substantially the anti-plasma performance.
And, if in silver, add an amount of indium film forming, even the silver alloy film of the high visible reflectivity that then when burning till for 200 or 300 ℃, also can be maintained.This silver alloy film is compared with the situation of the optical reflection film of existing use aluminium, because reflectivity height generally, so for example in case be used for the light reflective electrode etc. of reflection-type liquid-crystal display device, can carry out bright more demonstration.
And the AI alloy material, if adjust the content of indium with respect to silver, then thermal endurance, adhesive force, anti-plasma performance and high visible reflectivity etc. can cover very wide scope.
Preferred 0.5~28 weight % of indium amount (indium/silver (weight %)).If indium content is low, then the anti-plasma performance reduces, but can realize low resistanceization.Yet,, can produce the problem that the anti-plasma performance reduces if indium content is lower than 0.5 weight %.And when indium content increased, resistance value rose, and the anti-plasma performance improves.Yet, if indium content, can produce the problem that can not form solid solution with silver greater than 28 weight %.Therefore, suitably regulate under the situation of indium with respect to silver content, even the different position of desirable characteristics wiring on circuit substrate or the portion of terminal etc. also can make characteristic change easily.
The compositing range of above-mentioned silver and above-mentioned element also can be set to such an extent that the resistivity of silver alloy is in below the 10 μ Ω cm.
In this case, in as the aluminium of prior art, aluminium alloy wiring technique, resistivity approximately is in 4~10 μ Ω cm scopes.Therefore, this silver alloy of the present invention, the electrology characteristic that can obtain being scheduled to can use under the condition that changes existing wiring hardly.
For above-mentioned silver alloy, can also contain at least a element of from aluminium, copper, nickel, gold, platinum, palladium, cobalt, rhodium, iridium, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and neodymium, selecting.
Above-mentioned each element, for silver alloy owing to can be used as the auxiliary material that further raising thermal endurance, adhesive force and anti-plasma performance use and use, so, thermal endurance, adhesive force and anti-plasma performance are further improved by making it to contain at least a element in these elements.
Circuit substrate of the present invention is characterized in that having wiring and/or the electrode that is made of the above-mentioned silver alloy that constitutes.
Foregoing circuit substrate owing to can make has the formation of low resistance wiring, thus can make with existing aluminium, aluminium alloy wiring technique equal, the large scale circuit substrate.
Electronic installation of the present invention is characterized in that having used the foregoing circuit substrate.
As electronic installation display unit and liquid crystal indicator are for example arranged.
Under the situation of display unit, owing to be extensive use of large-scale circuit substrate, so can use low-resistance electric base board of the present invention especially.
And in manufacturing, because of using the dry-etching method, so require wiring and/or electrode etc. to have thermal endurance, adhesive force and anti-plasma performance with material as the tft array substrate of the circuit substrate that constitutes liquid crystal indicator.Therefore, using the circuit substrate that is formed by silver alloy of the present invention, is very useful for liquid crystal indicator.
Sputtering target of the present invention is characterized in that wherein containing the silver alloy formation of more than one elements of selecting at least by based on silver from tin, zinc, lead, bismuth, indium and gallium.
According to this silver alloy as sputtering target, can obtain the high wiring of technology patience, can make circuit substrate of the present invention and display unit etc. with good productivity ratio.
Evaporation source of the present invention is characterized in that wherein containing the silver alloy formation of more than one elements of selecting at least by based on silver from tin, zinc, lead, bismuth, indium and gallium.
According to using this silver alloy as evaporation source, can obtain the high wiring of technology patience, can make circuit substrate of the present invention, display unit etc. with good productivity ratio.
Mobile metal-containing material of the present invention is characterized in that based on silver, wherein contains the silver alloy of more than one elements of selecting from tin, zinc, lead, bismuth, indium and gallium at least.
The material that contains metal of the flowability by using this formation can obtain the high wiring of technology patience, can form or make circuit substrate of the present invention, display unit etc. with good productivity ratio.
Silver alloy of the present invention forms the zone owing to can make the primary solid solution of making main body with silver, thus in this case with silver same as liquidation (printing inkization) easily, use the wiring of ink-spraying-head to form process materials to use.
Silver alloy of the present invention is characterized in that, is formed in the material that forms wiring and/or electrode or optical reflection film on the insulating properties substrate, based on silver, wherein contains indium at least.
Indium preferably is in below the 0.5 weight % with respect to the content of silver.
In this case, if indium content lacks than 0.5 weight %, though can be in the problem of anti-plasma performance reduction, but indium content is under the situation below the 0.5 weight % in silver alloy, even through 200 ℃ burn till after, almost all in the visible regions, all can obtain the visible reflectance higher than aluminium.
And under indium with respect to the content of silver is situation below the 0.5 weight %, can form with existing aluminium wiring the low resistance that can not obtain connect up.Under the situation of special hope wiring low resistanceization, for example use etc. under the situation about using on the liquid crystal indicator of usefulness at liquid crystal TV, can utilize silver alloy of the present invention to make circuit substrate.
And indium preferably is in below the 0.2 weight % with respect to the content of silver.
In this case, when indium content in the silver alloy is 0.2 weight % when following, even through 300 ℃ burn till after, almost all can obtain the visible reflectance higher in the visible regions than aluminium.
Therefore, can be used in the light reflective electrode (electrode structure of double as electrode and reflectance coating), can carry out than produced brighter demonstration when the aluminium in the past.
The manufacture method of circuit substrate of the present invention is characterized in that using above-mentioned sputtering target or above-mentioned evaporation source, forms wiring and/or electrode on the insulating properties substrate.
Use this manufacture method, can on circuit substrate, form strong wiring of technology patience and/or electrode, so can make circuit substrate with good productivity ratio.
Use the material that contains metal of above-mentioned flowability, also can on the insulating properties substrate, form wiring and/or electrode.
Use the manufacture method of this mobile metal-containing material,, can make circuit substrate with good productivity ratio owing to can on circuit substrate, form the strong wiring of technology patience.
Here as the example of circuit substrate, tft array substrate that liquid crystal indicator uses, PDP (plasma display panel) are arranged with electrode base board, printed circuit board (PCB), flexible printed circuit board etc.
Instantiation as the display unit of utilizing these circuit substrates to make and image-input device has, and display unit, fingerprint detector, X ray camera heads etc. such as liquid crystal indicator, PDP (plasma display panel), organic EL (electroluminescence) plate, inorganic EL plate are the two dimensional image input unit of representative etc.
Though the insulating properties substrate that enforcement the present invention uses is insulating properties substrates such as alkali glass substrate, alkali-free glass substrate, plastic base, but for example also comprise the metal substrate etc. that has been coated with insulating barrier in surface one side that forms wiring etc., and with the same in fact purposes of insulating properties substrate in the substrate that uses.
Circuit substrate of the present invention is characterized in that in the circuit substrate with the wiring that forms on substrate, and the characteristic at the position, at least two places in the same wiring is different respectively.
Here, same wiring is meant it is continuous wiring in shape, and the circuit on the substrate is converged by so a plurality of wirings and forms circuit substrate, and these a plurality of wirings are called a unit.
For the characteristic that makes a part in the same wiring is different with the characteristic at inflator position, for example can use the proportion of composing diverse ways of each part material to realize.And by the different method of material that constitutes each position also can be realized.
For example, the tft array substrate that uses in liquid crystal indicator is during as circuit substrate, and the wiring portion in the same wiring is different with the characteristic that portion of terminal needs.Though wiring portion needs low resistanceization, needn't too require the anti-plasma performance owing to form diaphragm.In contrast to this, though the terminal part also needs low resistanceization, in order to be connected with realization such as driver and without the diaphragm protection, so need technology patience (particularly plasma-resistance).
Therefore, perhaps utilize the proportion of composing that changes wiring material, by changing the constituent material of wiring, be the characteristic of attention so that the wiring of wiring portion is turned into low resistance perhaps, the wiring of terminal part then just can as the characteristic of paying attention to the anti-plasma performance.
And above-mentioned same wiring preferably forms with form of single sheet.
In this case, because when realizing the circuit substrate slimming, the jump of going up between other wirings that form that can also make and connect up reduces, so can prevent the fracture of other wirings of causing because of jump, the result can improve the rate of finished products of circuit substrate.
Above-mentioned in addition same wiring also can be formed by multilayer.
For example, when the connecting airtight property difference between wiring material and substrate, both can between substrate and wiring material, form the layer good, and also can make and be coated with wiring material thereon and same one deck of bilayerization with connecting airtight property of substrate.
And above-mentioned wiring preferably forms with the free-flowing material that contains conductive material.
In addition owing under the situation of stacked other films not, also form wiring easily, so can realize that the process number purpose reduces and the reduction of manufacturing cost.
The multiple fluent material that contains conductive material that the characteristic different parts uses also can contain solvent, the organic substance of same system respectively.
In this case, even the different wiring material of characteristic, if solvent is a homology, then molten easily mixing between the liquid is difficult to cohesion and is difficult to separate, so the formation that can connect up effectively operation.
And above-mentioned wiring can also be formed by the metal that with any metal in silver, aluminium, the copper is main material.
In this case, owing to use with the metal formation wiring of any metal in the lower silver of resistance value, aluminium, the copper, so can realize all low resistanceizations that connects up as main material.Wherein, can utilize as the wiring main material with silver, aluminium, copper composition in addition, regulate surperficial flatness, anti-plasma performance, tack.
As such composition, the preferred at least a above metal of from aluminium, indium, tin, bismuth, gallium, lead, copper, gold, silver, cobalt, nickel, palladium, platinum, rhodium, vanadium, titanium, zirconium, niobium, tantalum, tungsten, hafnium, osmium, iridium, selecting.
And, discoveries such as the inventor, wiring material is that main component has wherein been added the alloy of indium as material with silver, forming on the insulating properties substrate under the situation of wiring and electrode, with with silver-colored simple substance as material on the insulating properties substrate, form the wiring compare with the situation of electrode, wiring and electrode adhesive force on the insulating properties substrate will improve, and thermal endurance, the anti-plasma performance of wiring and electrode also can improve simultaneously.In addition, be not only above-mentioned indium, also can obtain same effect even in silver, added the alloy of tin, zinc, lead, bismuth, gallium.
Therefore this alloy material of preferred use in the above-mentioned material.
Especially preferably use as wiring material with AI alloy.
AI alloy material in this case, if adjust the content of indium with respect to silver, then can be on a large scale covering surfaces flatness, adhesive force and anti-plasma performance etc.
Preferred 0.5 weight % to the 28 weight % of indium content (indium/silver (weight %)).If indium content reduces, anti-plasma performance step-down then, but can realize low resistanceization.But indium content is if be lower than 0.5 weight %, the problem that the anti-plasma performance reduces then can occur.And, then can produce the problem that can not form solid solution with silver if indium content is increased to above 20 weight %.Like this, only suitably regulating under the situation of indium and the content of silver,, also can make the feature change easily even make the different positions of needed characteristic such as wiring portion in the wiring or portion of terminal.
And if with ink-jetting style coating wiring material, then owing to can separately using the different wiring material of indium content simply, so form the wiring that has because of the position different qualities easily.
In addition, to the circuit substrate of said structure, add the anti-plasma performance that adds man-hour in man-hour, portion of terminal at passage, and the low resistanceization in the wiring portion, if be suitable for the tft array substrate that there is desired surface smoothing in gate electrode portion, then can improve the rate of finished products of TF array base palte and reduce cost.
And, if use circuit substrate of the present invention as above-mentioned the sort of tft array substrate, as mentioned above owing to having the advantage that improves rate of finished products, so also can be applicable to well on the display unit such as other electronic installations, liquid crystal indicator and plasm display device.
At detailed description part of the present invention cited embodiment and embodiment, at most for illustrating that technology contents of the present invention uses, should not only limit to these instantiations narrow definition is done in invention, in inventive concept and aim scope, can make and variously being implemented after changing.

Claims (8)

1, a kind of silver alloy is to be formed in the wiring that forms on the insulating properties substrate and/or the material of electrode or reflectance coating, it is characterized in that, as main component, contains content with respect to silver at least and be the indium below the 0.5 weight % with silver.
2, silver alloy according to claim 1 is characterized in that indium is below the 0.2 weight % with respect to the content of silver.
3, a kind of circuit substrate, it is characterized in that, have a kind of wiring and/or electrode that constitutes by silver alloy, described silver alloy is to be formed in the wiring that forms on the insulating properties substrate and/or the material of electrode or reflectance coating, as main component, contain indium at least, indium is below the 0.5 weight % with respect to the content of silver with silver.
4, a kind of electronic installation, it is characterized in that, have the wiring that constitutes by a kind of silver alloy and/or the circuit substrate of electrode, described silver alloy is to be formed in the wiring that forms on the insulating properties substrate and/or the material of electrode or reflectance coating, as main component, contain indium at least, indium is below the 0.5 weight % with respect to the content of silver with silver.
5, a kind of display unit, it is characterized in that, use a kind of circuit substrate to use circuit substrate as showing, the feature of described circuit substrate is to have wiring and/or the electrode that is made of silver alloy, described silver alloy is to be formed in the wiring that forms on the insulating properties substrate and/or the material of electrode or reflectance coating, as main component, contain indium at least, indium is below the 0.5 weight % with respect to the content of silver with silver.
6, a kind of liquid crystal indicator, it is characterized in that, use a kind of circuit substrate as the liquid crystal display circuit substrate, the feature of described circuit substrate is to have a kind of wiring and/or electrode that is made of silver alloy, described silver alloy is to be formed in the wiring that forms on the insulating properties substrate and/or the material of electrode or reflectance coating, as main component, contain indium at least, indium is below the 0.5 weight % with respect to the content of silver with silver.
7, a kind of display unit, it is characterized in that, has a kind of optical reflection film that constitutes by silver alloy, and utilize this optical reflection film to show, described silver alloy is to be formed in the material that forms wiring and/or electrode or reflectance coating on the insulating properties substrate, wherein with silver as main component, contain indium at least, indium is below the 0.5 weight % with respect to the content of silver.
8. display unit according to claim 7 is characterized in that, indium is below the 0.2 weight % with respect to the content of silver.
CN 200710092059 2003-07-23 2004-07-22 Silver alloy material, circuit board, electronic device and method of producing circuit board Expired - Fee Related CN101042946B (en)

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JP2004185264A JP4498835B2 (en) 2003-07-23 2004-06-23 Circuit board, manufacturing method thereof, and electronic device
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CN102312120A (en) * 2011-09-01 2012-01-11 王一平 Electromigration-resistant silver-indium alloy bonding wire and preparation method thereof
CN104118222A (en) * 2013-04-26 2014-10-29 中国科学院理化技术研究所 Liquid metal needle type printing equipment and printing method
CN111455209A (en) * 2020-04-26 2020-07-28 曾庆峰 Formula of 925 silver and preparation method thereof
CN113175566A (en) * 2020-01-27 2021-07-27 劳士领汽车集团 Channel component for a motor vehicle with integrated electrical lines dimensioned as required
CN113281802A (en) * 2020-02-04 2021-08-20 西门子医疗有限公司 Detector for electromagnetic radiation and method for producing the same

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US7465424B2 (en) * 2001-03-16 2008-12-16 Ishifuku Metal Industry Co., Ltd. Sputtering target material
JP2004002929A (en) * 2001-08-03 2004-01-08 Furuya Kinzoku:Kk Silver alloy, sputtering target, reflector for reflection lcd, reflection wiring electrode, thin film, manufacturing method therefor, optical recording medium, electro magnetic wave shield, metal material for electronic part, wiring material, electronic part, electronic appliance, processing method of metal film, electron optical part, laminate, and glass of building material
JP2004131747A (en) * 2002-10-08 2004-04-30 Sumitomo Metal Mining Co Ltd Silver alloy for display device, and display device using electrode film or reflection film formed by using the silver alloy

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Publication number Priority date Publication date Assignee Title
CN102312120A (en) * 2011-09-01 2012-01-11 王一平 Electromigration-resistant silver-indium alloy bonding wire and preparation method thereof
CN104118222A (en) * 2013-04-26 2014-10-29 中国科学院理化技术研究所 Liquid metal needle type printing equipment and printing method
CN104118222B (en) * 2013-04-26 2016-03-02 中国科学院理化技术研究所 Liquid metal needle type printing equipment and printing method
CN113175566A (en) * 2020-01-27 2021-07-27 劳士领汽车集团 Channel component for a motor vehicle with integrated electrical lines dimensioned as required
CN113281802A (en) * 2020-02-04 2021-08-20 西门子医疗有限公司 Detector for electromagnetic radiation and method for producing the same
CN111455209A (en) * 2020-04-26 2020-07-28 曾庆峰 Formula of 925 silver and preparation method thereof

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