CN100511687C - Display device and sputtering target for producing the same - Google Patents
Display device and sputtering target for producing the same Download PDFInfo
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- CN100511687C CN100511687C CNB200610009047XA CN200610009047A CN100511687C CN 100511687 C CN100511687 C CN 100511687C CN B200610009047X A CNB200610009047X A CN B200610009047XA CN 200610009047 A CN200610009047 A CN 200610009047A CN 100511687 C CN100511687 C CN 100511687C
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Abstract
一种显示器，其中Al合金膜和导电氧化物膜在没有插入高熔点金属的情况下直接连接，并且部分或全部Al合金组分沉积或富集在所述Al合金膜和所述导电氧化物膜之间的接触界面上。所述Al合金膜包括作为合金组分的0.1～6at%的选自Ni，Ag，Zn，Cu和Ge中的至少一种元素，以及还包括1)0.1～2at%的选自Mg，Cr，Mn，Ru，Rh，Pd，Ir，Pt，La，Ce，Pr，Gd，Tb，Sm，Eu，Ho，Er，Tm，Yb，Lu和Dy中的至少一种元素，或2)0.1～1at%的选自Ti，V，Zr，Nb，Mo，Hf，Ta和W中的至少一种元素。
A display in which an Al alloy film and a conductive oxide film are directly connected without intervening a high-melting point metal, and part or all of Al alloy components are deposited or enriched on the Al alloy film and the conductive oxide film on the interface between them. The Al alloy film includes 0.1-6 at% of at least one element selected from Ni, Ag, Zn, Cu and Ge as an alloy component, and further includes 1) 0.1-2 at% of an element selected from Mg, Cr, At least one element of Mn, Ru, Rh, Pd, Ir, Pt, La, Ce, Pr, Gd, Tb, Sm, Eu, Ho, Er, Tm, Yb, Lu and Dy, or 2) 0.1 to 1 at % of at least one element selected from Ti, V, Zr, Nb, Mo, Hf, Ta and W.
Description
Technical field
The present invention relates to the display of the similar film of a kind of shape and the sputtering target that is used to prepare this display, more particularly, relate to a kind of new display that comprises oxide conductive film and Al alloy film, this display is used for the flat-panel monitor of semiconductor device, active and passive matrix type such as LCD, reflectance coating, optical element etc., and relates to a kind of sputtering target that is used to prepare this display.
Background technology
Thin-film transistor (TFTs) for example is used as switch element in the LCD of active matrix type, and described LCD has the tft array substrate that comprises pixel electrode and interconnection line part as scan line and holding wire, comprises the liquid crystal layer between common electrode and the subtend substrate of settling in the face of tft array substrate with preset distance, insertion tft array substrate and the subtend substrate.The LCD of passive matrix type comprises interconnection line part as scan line and holding wire, comprise common electrode and the subtend substrate settled in the face of this interconnect substrates with preset distance and the liquid crystal layer between insertion interconnect substrates and the subtend substrate.Pixel electrode can be by oxide conductive film such as the tin oxide (SnO) of about 10 quality % is sneaked into indium oxide (In
2O
3) middle tin indium oxide (ITO) film preparation that obtains.
When pure Al or Al alloy such as Al-Nd be used for the pixel electrode of this conductive oxide film (below, be also referred to as " pixel electrode ") during the holding wire of the interconnection line part that is electrically connected, multilayer film by refractory metal such as Mo, Cr, Ti and W preparation inserts between holding wire and the pixel electrode, so that holding wire can directly not contact pixel electrode as barrier metal.Yet attempting omitting this refractory metal, make pixel electrode directly be connected with holding wire recent years.
For example, (JP, 11-337976 A), use by the zinc oxide of about 10 quality % being sneaked into the pixel electrode of the IZO film that obtains in the indium oxide, can realize that pixel electrode contacts with the direct of holding wire according to patent documentation 1.
Patent documentation 2 (JP, 11-283934, A) a kind of surface treatment method by means of the plasma treatment that drains, ion injection etc. has been described, and patent documentation 3 (JP, 11-284195 A) has described the method that impure second multilayer film that stacks mutually as N, O, Si, C etc. forms gate pole, source electrode and the drain electrode of ground floor.When using these methods, clearly,, also can make with the contact resistance maintenance of pixel electrode low-level even when above-mentioned this refractory metal is omitted.
The reason that these conventional arts insert barrier metal is because the quality that the direct contact between the interconnection line of the Al of formation holding wire and pixel electrode or Al alloy has increased contact resistance and reduced display image.This is because Al is easy to oxidized, and its surface in atmosphere with regard to oxidized cause, and because when the oxygen oxidation that produces or add in the Al tunicle deposition process, the pixel electrode that belongs to metal oxide produces the cause of high resistance Al oxide skin(coating) in its surface.Increase contact resistance between holding wire and the pixel electrode forming insulating barrier on the contact interface between holding wire and the pixel electrode, and reduced the quality of display image.
Meanwhile, prevent the oxidation of Al alloy surface and make Al alloy film and pixel electrode keep the function that well contacts though barrier metal has, but is indispensable owing to form the step of barrier metal for the traditional structure that the formation barrier metal inserts this contact surface, therefore except that the film deposition sputter that need be used to form gate pole, source electrode and drain electrode, also need to guarantee to be used to form the film settling chamber of barrier metal.Yet, because the batch process of liquid crystal panel has realized low cost, therefore, because the formation production cost that barrier metal caused increases and the decline of productivity ratio all will become very obvious.
Under this background, recently a kind of electrode material that is used to omit barrier metal of demand, preparation technology etc.Under this requirement of response, patent documentation 2 proposes to increase a kind of surface treatment step.Simultaneously, make gate pole, source electrode or drain electrode carry out the continuous film deposition in same film settling chamber, patent documentation 3 unavoidably just needs more processing step.In addition, owing to have different thermal coefficient of expansions between impure film and the film free from foreign meter, therefore, film can spread from the phenomenon that the wall surface of chamber comes off in use continuously, thereby keep in repair just needs frequent arrestment.In addition, because patent documentation 1 need become indium zinc oxide (IZO) film with current prevailing tin indium oxide (ITO) film, so material cost is expensive.
Note after this situation, the inventor has developed at patent documentation 4 (JP, 2004-214606, A) technology of describing in, with result as further investigation and a kind of like this technology of trial foundation, promptly, use this technology, can simplify processing step, under the situation that does not increase processing step, omit above-mentioned barrier metal simultaneously, and use this technology, and can obtain excellent electrical property and thermal endurance, it must realize that under low-resistivity low contact resistance and realization have the standardization of material in display of reflecting electrode, TAB connection electrode etc.
This technology addresses the above problem in trial, its use contains 0.1～0.6at% and is selected from the material of the Al alloy of at least a element among Au, Ag, Zn, Cu, Ni, Sr, Sm, Ge and the Bi as the Al alloy film, and these alloy compositions of a part are appeared on the above-mentioned contact interface as deposit or enriched layer, and this technology confirms, in these elements, the Al alloy that contains scheduled volume Ni shows excellent performance.
Incidentally, for better productive rate and improve productivity, the processing temperature of producing display recently trends towards step-down, and in order further to improve productive rate and to improve productivity ratio, is attempting using the resin with low heat resisting temperature as base material.Therefore, although be not very strong, but very strong for the demand of interconnection material with low-resistivity for the needs of heat resisting temperature.
For example, amorphous silicon TFTs is that a kind of source electrode and drain material of display device need have low resistivity and heat resistance, and this requirement specification is for example 8 μ Ω cm or lower resistivity and about 350 ℃ heat resisting temperature.This heat resisting temperature determines that by the maximum temperature that is applied in the production process in source electrode and the drain electrode this maximum temperature is the temperature that forms dielectric film, and described dielectric film is formed on the electrode as diaphragm.
Because advanced film deposition technique,, thereby will become possibility in source electrode and drain electrode, forming diaphragm especially under about 250 ℃ even therefore also can obtain required dielectric film at low temperatures.So just increased the demand that heat resisting temperature is about the enough low interconnection material of 250 ℃ and resistivity.
Meanwhile, form by sputter though be generally used for the Al alloy film of the interconnection material of display in the past, under the situation that the Al alloy film forms by this method, the alloy compositions that exceeds the adding of Al solubility limit has to exist with dissolved state.The resistivity of Al alloy of alloying element that contains dissolved state is usually than the resistivity height of fine aluminium.But when the Al alloy film that contains the alloying element that exceeds solubility limit was heated, on crystal boundary, and when the Al alloy film further heated, carried out and Al begins recrystallization by grain growth as the interphase precipitating for alloy compositions.Although and different, the precipitating of alloy compositions and grain growth have reduced the resistivity of Al alloy film to the temperature when occurring precipitating with grain growth by this way according to alloying element.
When heating causes grain growth when progress, the compression in the film increases, and when causing grain growth further to make progress along with further heating, can break through the limit, and will appear on the film surface as hillock (hillock) for crystal grain for the purpose of the stress relaxation.Alloying is effective make crystal grain keep interrupting, suppressing hillock and improve heat-resisting by the interphase of precipitating on crystal boundary in nature.For low resistivity and the thermal endurance that realizes the Al alloy film, traditional method utilizes this phenomenon to advance the precipitating and the grain growth of alloy compositions.But it is interphase that the processing temperature of step-down can't help the abundant precipitating of common alloy compositions, the problem that will cause grain growth not have progress and resistivity to be not easy to reduce like this.
For example, though the heat resisting temperature of disclosed Al-2at% Nd is up to 350 ℃ or higher in the patent documentation 4, but after 250 ℃ of following heat treated 30 minutes, its resistivity has only 11.5 μ Ω cm, though the heat resisting temperature of Al-2at%Ni-0.6%Nd is up to 350 ℃ or higher, but after 250 ℃ of following heat treated 30 minutes, its resistivity drops to has only 8.7 μ Ω cm, therefore still has the space of further improving.
Summary of the invention
As mentioned above, though the influence of the processing temperature that source electrode and drain electrode are reduced most, but because these electrodes always carry the electric current that reads and write pixel, the resistivity that therefore suppresses in these electrode parts is very effective on the power consumption that reduces display.In addition, the low resistivity in the electrode part has reduced the time constant of being determined by the product of resistance and electric capacity, even so just make when display floater prepares with large scale, also can keep superior display quality.
The present invention is according to obtaining under the above-mentioned situation, therefore it is intended to set up so a kind of technology: suppose above-mentionedly to be fine with respect to conventional art omission barrier metal, and use this technology that the Al alloy film is directly also contacted securely with pixel electrode, even and when hot processing temperature is hanged down in the use of Al alloy film, also can realize lower resistivity between the pixel electrode.More particularly, even when under 250 ℃ of low temperature, carrying out hot working in 30 minutes, the resistivity that also can realize the Al alloy film under the situation that does not form defective such as hillock is 7 μ Ω cm or lower, a kind of display that is suitable for reducing processing temperature also can be provided, and a kind of sputtering target that is used to form the Al alloy film that is of value to the so a kind of display of preparation is provided.
In the structure of the display of the present invention that has solved the problems referred to above, Al alloy film and conductive oxide film are connected to each other directly under the situation of not inserting any refractory metal, and in this display, partly or entirely alloy compositions precipitating or be enriched on this contact interface, and described Al alloy film is by so a kind of Al alloy preparation: it comprises the Ni that is selected from as 0.1～6at% of alloy compositions, Ag, Zn, at least a element among Cu and the Ge and contain 1) 0.1～2at% be selected from by Mg Cr, Mn, Ru, Rh, Pd, Ir, Pt, La, Ce, Pr, Gd, Tb, Sm, Eu, Ho, Er, Tm, Yb, at least a element in the group that Lu and Dy form (below, be called " group X " sometimes); Or 2) being selected from of 0.1～lat% by Ti, V, Zr, Nb, Mo, Hf, at least a element in the group that Ta and W form (below, be also referred to as " group Z ").
After the deposition, Al alloy film of the present invention preferably after 30 minutes, obtains 7 μ Ω cm or lower resistivity 250 ℃ of following hot working on transparency carrier.
Other structure according to the present invention relates to a kind of sputtering target that is used to prepare the Al alloy film, and described Al alloy film is the feature member of aforementioned display device, and by so a kind of Al alloy preparation: comprise and be selected from Ni, Ag as 0.1～6at% of alloy compositions, Zn, at least a element among Cu and the Ge and comprise that also 0.1～2at%'s is selected from by Mg Cr, Mn, Ru, Rh, Pd, Ir, Pt, La, Ce, Pr, Gd, Tb, Sm, Eu, Ho, Er, Tm, Yb, at least a element in the group that Lu and Dy form or 0.1～1at% are selected from by Ti, V, Zr, Nb, Mo, Hf, at least a element in the group that Ta and W form.
According to the present invention, the Al alloy film can directly contact under the situation that does not form barrier metal layer with pixel electrode, even and when using low hot processing temperature as 250 ℃ or when lower, also can guarantee enough low resistivity.Hot processing temperature in context is represented for example to become the highest processing temperature in the process of producing tft array; and in the film deposition process that forms various films by CVD this example that is used for the temperature of heated substrates, in the curing process of diaphragm the temperature of heat-treatment furnace, etc.
When being applied to the source/drain interconnection line in the process of the display panels that Al alloy film according to the present invention production and processing temperature therein becomes recently lower, can under low hot processing temperature, realize low resistivity, and not damage and the direct-connected advantage of pixel electrode.
Description of drawings
Fig. 1 is the schematic explanatory view of amplification cross section of the schematic structure of base plate of liquid crystal panel and LCD, in the described LCD, has used display array substrate of the present invention;
Fig. 2 is the signal key-drawing of cross section of the schematic structure of thin-film transistor, and described thin-film transistor is used for the display array substrate according to first embodiment of the invention;
Figure 3 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 2;
Figure 4 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 2;
Figure 5 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 2;
Figure 6 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 2;
Figure 7 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 2;
Figure 8 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 2;
Figure 9 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 2;
Figure 10 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 2;
Figure 11 shows the temperature-stress curve of Al alloy film;
Figure 12 is the cross section schematic explanatory view of the demonstrative structure of the thin-film transistor that uses in the display array substrate of other embodiment according to the present invention;
Figure 13 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 12;
Figure 14 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 12;
Figure 15 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 12;
Figure 16 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 12;
Figure 17 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 12;
Figure 18 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 12;
Figure 19 shows that order expression is used to produce the key-drawing of the step example of display array substrate shown in Figure 12; With
Figure 20 shows that the Kelvin pattern that is used to measure the contact resistance between Al alloy film and the transparent conductive oxide film.
Embodiment
According to the present invention, for contacting of pixel electrode and Al alloy film, this Al alloy film be comprise as it alloy compositions 0.1～6at% be selected from Ni, Ag, Zn, at least a element among Cu and the Ge and also comprise 0.1～2at% be selected from group among the X at least a element or 0.1～1at% be selected from least a element among the group Z.
As the Ni that contains 0.1～6at% etc. and comprise that also 0.1～2at%'s is selected from least a element among the group X or the Al alloy film that is selected from least a element among the group Z of 0.1～1at%, under low hot processing temperature, enriched layers such as precipitating thing or Ni are formed on the contact interface with pixel electrode, thereby have reduced contact resistance.
In addition, as following detailed description, the recrystallization of Al has been quickened in precipitating effect (improving group X that thermal endurance adds and the metallic compound of the element among the Z as belonging to be mainly used in), has reduced the resistance of Al alloy film self, and has greatly reduced the resistance of the integral body that comprises contact surface.
Meanwhile, comprise the Ni etc. of 0.1～6at% when the Al alloy film and comprise the Mg that is selected from of 0.1～2at%, La, Mn, Gd, Ta, when at least a element among Dy and the Tb (these elements all are selected among group X and the Z) or the V of 0.1～1at%, this Al alloy film can significantly improve the character of alkaline-resisting developing solution effectively.
In the process of producing display, the interconnection line pattern forms in the step that is known as photolithography.That is, photosensitive resin (photoresist) uses the exposure of UV light source, and develops with the alkali developing solution, and this resin has just formed the interconnection line pattern.Subsequently, use this resin as mask, etching Al alloy film has obtained interconnection line thus.In this development phase, the surface of Al alloy film is exposed in the alkali developing solution.Normally used developing solution comprises the TMAH (Tetramethylammonium hydroxide) of 2.38 weight %, and when the Al alloy film that contains 0.1～6at% Ni was exposed to this developing solution, the speed that is etched with 80～120nm/min was carried out.
On the contrary, if in the Al alloy film, add the Mg that is derived from group X and Z, La, Mn, V, Gd, Ta, Dy and Tb, then etching speed is suppressed to 10～40nm/min.Notice that in using usually, the etching speed of pure Al is 20nm/min, on experience, double approximately this speed will can not cause the problem of film attenuation.
In addition, developing time changes according to resin, conditions of exposure etc., and since Al alloy film surface is exposed to that time in the developing solution is about tens seconds or at most in one minute and the film thickness of interconnection line be about 100～400nm usually, if therefore the etching of etching speed induce deceleration be reduced to approximately half or lower, prevented not only that then the Al alloy film is eliminated at lithography step, and avoided film to become extremely thin.So just realized the accurate processing of interconnection line pattern.
Lithography step will repeat usually.This just means peeling off of photoresist and when unusual pattern etc. occurs and carry out lithography step again again, and suppresses the film attenuation and can guarantee the advantage that can repeat more than once.
Therefore, can significantly reduce procedure of processing number and production cost, can make the display quality of display such as LCD keep high level simultaneously.
Although the embodiment of display of the present invention will be described hereinbelow in detail with reference to the accompanying drawings, the present invention is limited to the embodiment that is explained, satisfies the front to a certain extent and mentions the suitable improvement of describing intention with the back but can adopt.These improvement all fall in the technical scope of the present invention.
In addition, though also can be applied in the display of passive matrix type according to Al alloy film of the present invention, but such embodiment is not described, the display of described passive matrix type do not comprise the LCD of thin-film transistor, reflection type etc. reflecting electrode, amorphous silicon TFT gate pole and under the situation that does not form barrier metal layer between TAB connection electrode and the TAB electrode, be used for the signal I/O to outside TAB connection electrode.
Fig. 1 is mounted in the schematic explanatory view of the amplification cross section of the liquid crystal panel structure on the LCD device that the present invention is applied to.
The subtend substrate 2 that liquid crystal panel shown in Figure 1 comprises tft array substrate 1, settle towards tft array substrate 1 and be placed in tft array substrate 1 and subtend substrate 2 between and play the liquid crystal layer 3 of light regulating course effect.Tft array substrate 1 is by being placed in the thin-film transistor (TFTs) 4 on insulation transparent substrate (glass substrate) 1a, and pixel electrode 5 forms with the interconnection line part 6 that comprises scan line, holding wire etc.
Subtend substrate 2 comprises the whole lip-deep common electrode 7 that is formed on tft array substrate 1 side, the colour filter of on the opposite location of pixel electrode 5, settling 8, and the optical screen film of settling on the position opposite with interconnection line part 69 with thin-film transistor (TFTs) 4 on the tft array substrate 1.
Polarizing plate 10 and 10 is placed on the outer surface of the insulated substrate that forms tft array substrate 1 and subtend substrate 2, and subtend substrate 2 is placed in along predetermined direction and arranges on the alignment films 11 of liquid crystal molecule of liquid crystal layer 3.
In having the liquid crystal panel of this structure, between subtend substrate 2 and the pixel electrode 5 development electric field controls the direction of orientation of liquid crystal molecule in liquid crystal layer 3, and regulated by the light that is placed in liquid crystal layer 3 transmission between tft array substrate 1 and the subtend substrate 2, control the amount of the light of subtend substrate 2 transmission thus, and demonstrated image.
In addition, because TAB is with 12 outsides of having guided to tft array, so tft array is driven by drive circuit 13 and control circuit 14.
In Fig. 1; 15 the expression be spacer, 16 the expression be encapsulant; 17 the expression be diaphragm, 18 the expression be diffusing panel (diffusion plate), 19 the expression be prismatic thin slice; 20 the expression be optical plate; 21 the expression be reflecting plate, 22 the expression be backlight, 23 the expression be fixed frame; 24 the expression be printed circuit board (PCB), these all will be described below.
Fig. 2 is according to first embodiment of using array base palte of the present invention, the schematic explanatory view of the amplification cross section of the structure of film crystal tube portion.As shown in Figure 2, scan line 25 forms by the Al alloy film on transparency carrier 1a, and a part of scan line 25 plays a part the gate pole of opening and closing 26 of control TFT.Holding wire is formed by the Al alloy film, make this holding wire and the scan line 25 that passes gate pole dielectric film 27 intersect, and a part of holding wire plays a part the source electrode 28 of thin-film transistor.The so-called bottom of this type gate pole type.
In the pixel region on gate pole dielectric film 27, have by for example mixing SnO and In
2O
3The pixel electrode 5 of the ITO film that obtains.Drain electrode 29 by the film formed thin-film transistor of Al alloy is electrically connected as contacting with the direct of pixel electrode 5.
When gate voltage was fed on the gate electrode 26 by the scan line on the tft array substrate 1 25, thin-film transistor was opened, and was supplied to the driving voltage of holding wire to arrive pixel electrode 5 from source electrode 28 through drain electrode 29 in advance.When the driving voltage of predetermined extent is supplied to pixel electrode 5, form electrical potential difference by the subtend substrate 2 that relates to Fig. 1 description, the liquid crystal molecule that is included in the liquid crystal layer 3 is arranged, and light obtains to regulate.
Now Short Description is used to prepare the method for tft array substrate shown in Figure 21.When thin-film transistor forms as switch element, use amorphous hydrogenated silicon will be described as an example as the amorphous silicon TFT of semiconductor layer.
An embodiment who is used to describe the step for preparing tft array substrate 1 will be mentioned in Fig. 3～10.
At first, by sputter etc., the Al alloy film is at the film thickness of the about 200nm of the last formation of glass substrate (transparency carrier) 1a, and then, the Al alloy film is formed pattern, forms gate pole 26 and scan line 25 (Fig. 3) thus.In this stage, it is desirable to be etched with about 30～40 and spend the edge of the Al alloy film of convergents, so that the covering of the gate pole dielectric film 27 that describes below is good.Then, as shown in Figure 4, by plasma CVD etc., gate pole dielectric film 27 is silica (SiOx) the film formation of for example about 300nm by film thickness, and for example forms amorphous hydrogenated silicon fiml (a-Si:H) that film thickness is about 500nm and the silicon nitride film (SiNx) that film thickness is about 300nm.
Then, use gate pole 26 as mask, silicon nitride shown in Figure 5 (SiNx) film forms pattern by back of the body face exposure, thereby forms the path protection film.On this diaphragm, further form by phosphorus doping and film thickness be about the n of 50nm
+Amorphous hydrogenated silicon fiml (n
+A-Si:H) afterwards, amorphous hydrogenated silicon fiml (a-Si:H) and n
+Amorphous hydrogenated silicon fiml (n
+A-Si:H) form pattern as shown in Figure 6.
Then, form the Al alloy film that film thickness for example is about 300nm thereon,, form and the source electrode 28 of holding wire combination and the drain electrode 29 that will contact with pixel electrode 5 through formation pattern as shown in Figure 7.Then, use source electrode 28 and drain electrode 29, remove the n on path protection film (SiNx) as mask
+Amorphous hydrogenated silicon fiml (n
+A-Si:H).
As shown in Figure 8, use for example plasma CVD instrument etc., silicon nitride film 30 is deposited as the film thickness that for example is about 300nm, obtains diaphragm thus.Film deposition is preferably for example being carried out under about 250 ℃.After forming photoresist layer 31 on this silicon nitride film 30, silicon nitride film 30 is passed through patternings such as for example dry ecthing, and forms contact hole 32 in silicon nitride film 30.In addition, though do not illustrate among the figure, simultaneously, contact hole is formed in face plate edge and partly locates TAB coupling part on the gate pole.
In addition, after for example using the oxygen plasma ashing as shown in Figure 9, photoresist layer 31 uses the solvent of peeling off that contains amine for example etc. to peel off, at last, in for example about 8 hours retention time, form the ITO film that thickness for example is about 40nm as shown in Figure 10, obtain pixel electrode 5 by forming pattern.Simultaneously, the ITO film forms and carry out pattern in order to combine with TAB in the TAB coupling part of partly locating gate pole in face plate edge, has finished tft array substrate 1 thus.
In the tft array substrate that is formed by said method, the drain electrode 29 and the pixel electrode 5 of Al alloy are in direct contact with one another, and gate pole 26 be used for the ITO film that TAB is connected and be in direct contact with one another.
In this stage, as the material that forms 29 the Al alloy film of for example draining, Al-Ni alloy or Al and be selected from Au, Ag, Zn, Cu, Sr, Sm, the alloy that at least a element forms among Ge and the Bi can use, and the condition that forms drain electrode 29 can suitably control, so still reduced to form drain 29 Al alloy film and the contact resistance between the pixel electrode 5 highly significant, this as patent documentation 4 set forth.
For containing for example alloy of Al-Ni, after under 250 ℃ of temperature, handling 30 minutes, under the situation of Al-2at%Ni, resistivity is 3.8 μ Ω cm, under the situation of Al-4at%Ni, resistivity is 5.8 μ Ω cm, and under the situation of Al-6at%Ni, resistivity is 6.5 μ Ω cm, means that like this alloy film that contains Al-Ni will obtain the desired value of low resistivity well.
Yet the heat resisting temperature of this Al-Ni alloy is low to moderate 150～200 ℃.When source electrode that is used for regular display or drain electrode, notice that the maximum heating temperature is about 250 ℃, therefore this Al-Ni alloy considers it is not enough from thermal endurance, thereby can not actually use.
As for by Al be selected from Ni, Ag, Zn, the Al alloy that at least a element among Cu and the Ge forms, further study from the kind of the 3rd component element and the viewpoint of addition, to be devoted to explain such alloy: about 250 ℃ guarantee down stable on heating heat-treat simultaneously after, it shows 7 μ Ω cm or lower resistivity.
The result, from countless elements, find, the element that belongs to previously described group of X and Z mixes with scheduled volume will form such Al multi-component alloys: guarantee down that at about 250 ℃ thermal endurance is (even under heating, can not produce hillock etc. yet) time heat-treat after, it shows 7 μ Ω cm or lower resistivity.
Belong to the element of organizing X and can be Mg, Cr, Mn, Ru, Rh, Pd, Ir, Pt, La, Ce, Pr, Gd, Tb, Sm, Eu, Ho, Er, Tm, Yb, Lu and Dy, wherein one or both elements can use.In order effectively to show the thermal endurance that adds the improvement that these alloying elements caused and the resistivity of reduction, the amount of addition element need be 0.1～2at%.Meanwhile, belong to the element of organizing Z and can be Ti, V, Zr, Nb, Mo, Hf, Ta and W, wherein one or both elements can use.In order effectively to show the thermal endurance that adds the improvement that these alloying elements caused and the resistivity of reduction, the amount of addition element need be 0.1～1at%.
Belong among group X and the Z any element of arbitrary group, if add with the amount that is lower than 0.1at%, the stable on heating degree that can not obtain to want among the present invention then, and the content that surpasses 2at% and belong to the element of organize Z when the content that belongs to the element of organizing X is during above 1at%, although the stable on heating improvement of membrane material will be above needed, the effect that reduces resistivity will be not enough.Consider the thermal endurance of membrane material and reduce resistivity, for belonging to the element of organizing X, preferably its addition is 0.3～1.8at%, and for belonging to the element of organizing Z, preferably its addition is 0.2～0.8at%.If add two or more elements, then the addition of each element can be determined with reference to total content.
Shown in the following table 1 that will describe, the element that belongs to group X and Z is selected based on the embodiment that relates to thermal endurance and resistivity reduction effect (being confirmed by test), and choice criteria can make an explanation with reference to the temperature-stress curve of Al alloy film shown in Figure 11.
That is, in Figure 11, symbol A represents pure Al, and symbol B represents wherein to add the Al alloy that belongs to the element of organizing X, and symbol C represents wherein to add the Al alloy that belongs to the element of organizing Z.
Wherein add the Al alloy film B that belongs to the element of organizing X and show bigger compression with the temperature increase.Though grain growth was constrained in the starting stage that temperature increases, grain growth begins at a lower temperature and stress relaxation can occur suddenly in the narrow temperature scope.It is believed that the fusion element that exists is deposited as interphase in the short-term in this stage in this alloy, and the grain growth of Al carries out, resistivity reduces with deposition.That is, resistivity fully reduces under low heating-up temperature.On the other hand, further heating and complete stress relaxation have promoted to have developed the crystal growth that compression caused owing in the film, and are easy to cause forming hillock etc.The heat resisting temperature of this alloy is thought near the stress relaxation temperature.
On the other hand, wherein add the Al alloy film that belongs to the element of organizing Z and show bigger compression with the temperature increase similarly, and the grain growth of Al is similarly beginning in the temperature range.But, belong to the element of organizing Z from the molten state diffusion and being interphase than the low velocity precipitating, this interphase precipitating gradually in wide temperature range, and also along with the generation of precipitating, stress relaxation engenders.Therefore, before stress relaxation obviously occurs, all need effectively heating and long time, the fusion element basically fully precipitating be interphase, the grain growth of Al is simultaneously carried out and the resistivity of the parent material of film becomes enough low, this means that thermal endurance has improved.In a word, compare with belonging to the element of organizing X, belong to the element of organizing Z and improving on the thermal endurance more effectively, because they are deposited as interphase more lentamente, therefore, even suppress for hour when the addition of these elements, thermal endurance also can substantially improve.
Although resistivity also depends on the addition of alloying element, when belonging to the element of organize Z than belonging to the element of organizing X and add fashionable, even, also reduced resistivity relevant with embodiment described below than hanging down under the heating-up temperature with littler amount.
(table 1)
In addition, though belong to organize Z element can not with belong to the same big addition of the element of organizing X and add, belong to the elemental characteristic of organizing Z and be when it is deposited as electrode film, they can not have space (hole).In other words, in the narrow temperature scope in being chosen in heating process at once precipitating be that the element of interphase is when looking like to belong to those elements of organizing X, grain growth is carried out more, becomes strong more in the process of the tensile stress cool to room temperature after heating that produces in the film, has so just caused the space.But, as the element that belongs to group Z in the time that increases along with temperature gradually precipitating be under the situation of alloy of interphase, then be interrupted when being heated to the temperature range identical with grain growth with the temperature range of organizing X owing to precipitating, therefore stress relaxation is not fully carried out, thereby the tensile stress that remains in the film reduces in the process of cool to room temperature subsequently.For this reason, for preventing to help the space of tensile stress, need to select to belong to the element of organizing Z.
The reason that is set at 0.1～6at% in the present invention as the content of the Ni on the basis (base) of the alloy that is added into etc. be because this content range be the thermal endurance of guaranteeing the Al alloy film, with the contact interface of pixel electrode on form the essential condition of the contact resistance of enriched layer such as Ni and reduction and pixel electrode.If the content of Ni etc. is lower than 0.1at%, then can not realize the stable on heating level that the present invention wants, with the contact interface of pixel electrode on the enriched layer of the Ni that forms etc. become insufficient, and the promising result that reduces contact resistance does not obtain yet.On the contrary, if the content of Ni etc. surpasses 6at%, then the resistivity of Al alloy film self increases, and the response speed of pixel is slack-off, and consumed power increases, and display quality degenerates to unpractical degree.Note these merits and demerits, the content that therefore it is desirable to Ni etc. is preferably 0.1at% or bigger, 0.2～6at% more preferably, also 5at% or lower more preferably.
According to the present invention, can effectively be reduced in contact resistance (directly contact resistance) on the contact interface with pixel electrode at enriched layers such as forming Ni on the surface of Al alloy film, and the thickness of this enriched layer is preferably 0.5nm or thicker, 1.0nm～10nm more preferably, also 5nm or thinner more preferably.The average N i concentration of this enriched layer is preferably the twice of mean concentration in the whole Al alloy film or more times, also more preferably 2.5 times or more times.
In containing the Al alloy film of Ni etc., exceed in the Al alloy film Ni etc. solubility limit Ni etc. since heat treatment etc. and precipitating on the crystal boundary of Al alloy, diffusion such as the Ni of a part of precipitating also is enriched on the surface of Al alloy film, and has formed enriched layer such as Ni.In addition, according to the present invention, the halide of Ni etc. is owing to have lower vapour pressure, therefore for example be not easy to volatilize and rest on the surface of Al alloy film in the process of contact hole in etching, thereby become the concentration of the Ni that is higher than Al alloy bulk material etc. in the concentration of the lip-deep Ni of Al alloy film etc.The concentration of Ni that therefore, can be by suitable control etching condition control table surface layer etc., the thickness of enriched layer, etc.Although according to the element that belongs to group X and Z, element can be towards the enrichment of photons part in this stage, technical scope of the present invention has also been contained the situation of this part enrichment.
When the display that contains by this way the tft array substrate that forms during as liquid crystal indicator for example, owing to be included in the element coexistence among group X and the Z, resistance between the interconnection line part that therefore not only can make pixel electrode and be used to connect minimizes, and can prevent that defective is as owing to improve the hillock that stable on heating effect caused.In addition, because near the precipitating thing of element Al host material (matrix material), Ni etc. and crystal boundary that is contained among group X and the Z formed interphase, therefore promoted recrystallization as the Al of host material, reduced the resistance of host material, thereby, can suppress to suppress as far as possible adverse effect to image quality.
The Experiment Preparation of liquid crystal indicator conduct above-mentioned embodiment according to the present invention, and confirmed that productivity ratio and display quality will be the same good, perhaps better than it with the display unit that is used in combination ITO film and barrier metal (Mo etc.) acquisition.Therefore, for this liquid crystal indicator, can obtain the performance identical, and need not settle barrier metal with traditional liquid crystal indicator.Therefore, omit barrier metal and simplified production technology, and help to reduce production costs.In addition, can obtain enough low resistivity down as 250 ℃, can further widen the kind range of choice, processing conditions of display material etc. in low heating-up temperature.
Figure 12 is the schematic explanatory view according to the amplification cross section of the thin-film transistor structure of other embodiment of using array base palte of the present invention, in the embodiment of this explanation, uses the thin-film transistor with top gate structure.
As shown in figure 13, the scan line of Al alloy film is formed on the transparency carrier 1a, and a part of scan line plays a part gate pole 26, the Kai Heguan of described gate pole 26 control TFT.The holding wire of Al alloy forms, and makes holding wire and the scan line that passes interlayer insulating film (SiOx) intersect, and a part of holding wire plays a part the source electrode 28 as thin-film transistor.
In the pixel region of interlayer insulating film (SiOx), exist by for example SnO and In
2O
3The pixel electrode 5 that mixes the ITO film that obtains, and the drain electrode 29 of the Al alloy of thin-film transistor plays a part the connection electrode part, described connection electrode part is electrically connected with pixel electrode 5.That is, the drain electrode 29 of the Al alloy of thin-film transistor directly contacts and is electrically connected with pixel electrode 5.
Therefore, the situation of embodiment shown in Fig. 2 is the same as described previously, when gate voltage is applied on the gate pole 26 by the scan line on the tft array substrate, thin-film transistor is opened, and the driving voltage that is applied in advance on the holding wire arrives pixel electrodes 5 from source electrode 28 through drain electrode 29, when the driving voltage of predetermine level is supplied to pixel capacitors 5, such as described in Figure 1, produce potential difference from counter electrode 10, so that the liquid crystal molecule that is included in the liquid crystal layer 3 is arranged, light obtains to regulate.
The method of producing tft array substrate shown in Figure 12 is described now.According to the present embodiment, the thin-film transistor that is formed in the array base palte has the top gate structure of use polysilicon (poly-Si) film as semiconductor layer.Figure 13～19th schematically shows the figure of preparation according to the step of the array base palte of second embodiment.
At first, use for example plasma CVD instrument etc., under for example about 300 ℃ substrate temperature, deposit film thickness and be about silicon nitride (SiNx) film of 50nm and silica (SiOx) film that film thickness is about 100nm, in addition, deposit amorphous hydrogenated silicon (a-Si:H) film that film thickness is about 50nm then, subsequently, heat-treat and laser annealing, so that this amorphous hydrogenated silicon (a-Si:H) film is transformed into polysilicon.Heat treatment can be to handle about 1 hour in about 470 ℃ of following atmospheric heat, after the dehydrogenation, uses for example quasi-molecule laser annealing instrument, will have for example about 230mJ/cm
2The laser irradiation of energy thus, obtains to have polysilicon (poly-Si) film (Figure 13) of for example about 0.3 μ m thickness on amorphous hydrogenated silicon (a-Si:H) film.
Subsequently, as shown in Figure 14, polysilicon (poly-Si) film is by formation patterns such as plasma etchings.As shown in figure 15, silica (SiOx) film is deposited as for example thickness of about 100nm, obtains gate pole dielectric film 27 thus.Film deposition at the Al alloy film that will become the gate pole 26 that combines with scan line on acquisition gate pole dielectric film 27, for example by sputter etc., when being about the film of 200nm thickness, this Al alloy film forms pattern by plasma etching etc., and the gate pole 26 that combines with scan line of acquisition.
As shown in figure 16, then, mask uses photoresist 31 to form, and for example uses ion to inject instrument etc. and mix 1 * 10 under about 50kev
15/ cm
2Phosphorus, the local n that forms in polysilicon (poly-Si) film thus
+Polysilicon (n
+Poly-Si) film subsequently, is peeled off photoresist 31, again in the heat treatment that for example causes spreading under about 500 ℃.
After this, as shown in figure 17, silica (SiOx) film for example uses under about 250 ℃ substrate temperature, and the plasma CVD instrument is deposited as for example thickness of about 500nm, form interlayer insulating film then, photoresist is formed pattern similarly, the interlayer insulation of dry ecthing gate pole dielectric film 27 (SiOx) film and silicon oxide film thus, form contact hole, and by sputter Al alloy film film is being deposited as for example for after the thickness of 450nm, the Al alloy film is formed pattern, forms the source electrode 28 and the drain electrode 29 that combine with holding wire.As a result, contact hole and n are passed through in source electrode 28 and drain electrode 29 separately
+Polysilicon (n
+Poly-Si) film contact.
As interlayer insulating film, as shown in figure 18, silicon nitride (SiNx) film for example uses the plasma CVD instrument to be for example thickness of about 500nm in for example about 250 ℃ substrate temperature deposit then.Form thereon after the photoresist layer 31, silicon nitride (SiNx) film is formed pattern, then for example by dry ecthing, forms contact hole 32 on this silicon nitride (SiNx) film.
Then, as shown in figure 19, photoresist uses amine-Ji stripping solution etc. to peel off with the similar fashion of top described mode after passing through for example oxygen plasma ashing, the ITO film deposits like that as previously described and forms pattern by wet etching, forms pixel electrode 5 thus.Drain electrode 29 in this process beginning with when pixel electrode 5 directly contacts, enriched layers such as Ni form, and contact resistance reduces on Al alloy film that forms drain electrode 29 and the interface between the pixel electrode 5, for Al alloy film self, Ni or the element deposition that belongs to group X and Z are interphase, this has promoted the recrystallization of Al, and the resistance of this film self significantly reduces.
For stable transistor character, under about 250 ℃, annealed about 1 hour subsequently, so just finished the multi-crystal TFT array substrate.
Use obtains and the previously described first embodiment similar effects according to the tft array substrate of above-mentioned second embodiment and the liquid crystal indicator that comprises this tft array substrate.In addition, as among first embodiment, second embodiment also allows to use the reflecting electrode of Al alloy according to the present invention as reflection type crystal display.
The material of above-described pixel electrode 5 is preferably tin indium oxide or indium zinc oxide, and it is desirable to, by being deposited as interphase with some or all alloy compositions of nonequilibrium state fusion or forming enriched layer, make the resistivity of Al alloy film be adjusted to 7 μ Ω cm or littler, or 5 μ Ω cm or littler more preferably.
Can be vapour deposition, sputter etc. although form the method for above-mentioned Al alloy film, preferred especially sputter.
Therefore, the sputtering target that is made by the Al alloy is contained in the present invention, and it comprises (as the material that is used to form the Al alloy film with above-mentioned composition) identical with above-mentioned composition basically composition, promptly, comprise the Ni that is selected from as 0.1～6at% of alloy compositions, Ag, Zn, at least a element among Cu and the Ge and 0.1～2at% are selected from Mg, Cr, Mn, Ru, Rh, Pd, Ir, Pt, La, Ce, Pr, Gd, Tb, Sm, Eu, Ho, Er, Tm, Yb, at least a element among Lu and the Dy or be selected from Ti, V, Zr, Nb, Mo, Hf, at least a element among Ta and the W.
Use the tft array substrate that obtains like this, finished as shown in Figure 1 the liquid crystal indicator of display as described previously.
In a word, the tft array substrate surface applied polyimides of finishing like this, dry and friction forms alignment films thus.
On the other hand, for subtend substrate 2, for example chromium is patterned as the matrix on glass substrate, and at first forms optical screen film 9.Then, the colour filter 8 of red, green and blue resins is formed in the slit in the optical screen film 9.The nesa coating of ITO etc. is deposited as the common electrode 7 on optical screen film 9 and colour filter 8, has so just finished counter electrode.The coated for example polyimides of the superiors of counter electrode, dry and friction obtains alignment films 11 thus.
The surface of array base palte 1 and support alignment films 11 subtend substrate 2 the surface toward each other, and except being used to introduce the injection import of liquid crystal, these two kinds of substrates are bonded to each other by encapsulant 16, described encapsulant 16 can be a resin.In this stage, by between two substrates, inserting spacer 15 or, making the slit between these two kinds of substrates keep constant basically by other suitable manner.
The empty element that obtains is by this way placed in a vacuum, utilizes the injection import that is immersed in the liquid crystal, and pressure returns to atmospheric pressure gradually, thereby the liquid crystal material that contains liquid crystal injects this sky element, and liquid crystal layer forms and injects import and is closed.At last, polarizing plate 10 combines with two outer surfaces of element, has so just finished liquid crystal panel.
In addition, as shown in Figure 1, be used to drive LCD drive circuits and be electrically connected, and be placed in the lateral parts and the back of the body surface portion of liquid crystal panel with liquid crystal panel.Utilization comprises opening as the display surface of liquid crystal panel, play backlight 22, the optical plate 20 of surface source of light effect and the framework of fixed frame 23, fixed liquid crystal panel, and finished liquid crystal indicator.
Embodiment
Although the present invention now is described in more detail reference example, the present invention is limited to these embodiment, but can have the suitable improvement of satisfying the intention of mentioning and describing below in the front to a certain extent.These improvement all fall in the technical scope of the present invention.
For at the Al alloy film that different-alloy is formed that has shown in the table 1,3,5,7,9 and 11, measure resistance and Al alloy film and begin the direct contact resistance that directly contact with pixel electrode, and studied the heat-resisting character (hillock density) of Al alloy film when heating 30 minutes 250 ℃ times.
The test that obtains measurement result is described below.
1) structure of pixel electrode: the tin indium oxide (ITO) that obtains by the tin oxide that in indium oxide, adds 10 quality %.
2) formation condition of film: atmosphere=Ar, pressure=3mTorr, thickness=200nm
3) heating condition: 250 ℃ * 30 minutes
4) be included in the content of the various elements in the Al alloy: the content that is included in the various elements in the Al alloy of research in the present embodiment uses ICP (inductively coupled plasma) emission spectrographic determination.
5) method of mensuration Al alloy firm resistivity: the resistivity of Al alloy firm uses the Kelvin pattern to measure by 4-terminals measurement method (4-terminal measurement), and resistivity is that 7 μ Ω cm or lower Al alloy film are rated as well (zero), and resistivity surpasses be rated as poor (*) of 7 μ Ω cm.
6) method of the direct contact resistance of mensuration: preparation Kelvin pattern (the contact hole size is 10 μ m * 10 μ m) as shown in figure 20, use 4-terminals measurement method (electric current is applied on the ITO-Al alloy and uses the method for pressure drop between the different terminals measurement ITO-Al alloys) to carry out.In a word, at I shown in Figure 20
1And I
2Between apply electric current I, the monitoring V
1And V
2Between voltage V, therefore be calculated as [R=(V in view of the above at the direct contact resistance R of contact portion C
2-V
1)/I
2], contact resistance is 1k Ω or lower is be evaluated as good (zero) that contact resistance surpasses be rated as poor (*) of 1k Ω.
7) measure stable on heating method: 3) under the condition described, the Al alloy firm is formed on the glass substrate separately.Then, form width and be the line of 10 μ m-and-intermittent pattern, under 250 ℃, carried out vacuum heat 30 minutes, observe the surface of interconnection line with SEM, calculated diameter is the quantity of 0.1 μ m or bigger hillock.Hillock density is 1 * 10
-9Individual/m
2Or lower those are rated as well (zero), and hillock density surpasses 1 * 10
-9Individual/m
2Those be rated as poor (*).
8) measure the thickness of the enriched layer contain α and the method for the content of α in this enriched layer: at a part of sample shown in the table 1,3,5,7,9 and 11, film thickness after α enriched layer (the Ni-enriched layer in the table 1, the Ag-enriched layer in the table 2, the Zn-enriched layer in the table 3, the Cu-enriched layer in the table 4 and the Ge-enriched layer in the table 5) heat treatment is by using Hitachi, and " the FE-TEM HF-2000 " that Ltd. produces carries out the cross section tem observation and determine.In addition, the content of α in this enriched layer is determined by using EDX (Sigma of KEVEX preparation) that cross section TEM sample is carried out component analysis.
These the results are listed in table 1～10.
Table 1
Notice that in table 1, the thickness of Ni-enriched layer and the Ni content in the Ni-enriched layer is to measure after each satisfies the sample heat treatment of condition of the present invention.In this result, the film thickness of each Ni-enriched layer is in the scope of about 0.5～2nm, and the content of Ni in each Ni-enriched layer 2～9 times of the average content (in table 1 not shown) of Ni in each Al alloy firm normally.
In table 1, show some result of experiment, the amount that is selected from the element in the element that belongs to group X or Z in these experiments is changed.Confirm, when other element that belongs to group X or Z but list is used as element, can obtain similar experimental result in table 1.
Table 2
Table 3
Notice that in table 3, the thickness of Ag-enriched layer and the Ag content in the Ag-enriched layer is to measure after each satisfies the sample heat treatment of condition of the present invention.In this result, the film thickness of each Ag-enriched layer is in the scope of about 0.5～2nm, and the content of Ag in each Ag-enriched layer 2～9 times of the average content (in table 3 not shown) of Ag in each Al alloy firm normally.
In table 3, show some result of experiment, the amount that is selected from the element in the element that belongs to group X or Z in these experiments is changing.Confirm, when other element that belongs to group X or Z but list is used as element, can obtain similar experimental result in table 3.
Table 4
Table 5
Notice that in table 5, the thickness of Zn-enriched layer and the Zn content in the Zn-enriched layer is to measure after each satisfies the sample heat treatment of condition of the present invention.In this result, the film thickness of each Zn-enriched layer is in the scope of about 0.5～2nm, and the content of Zn in each Zn-enriched layer 2～9 times of the average content (in table 5 not shown) of Zn in each Al alloy firm normally.
In table 5, show some result of experiment, the amount that is selected from the element in the element that belongs to group X or Z in these experiments is changing.Confirm, when other element that belongs to group X or Z but list is used as element, can obtain similar experimental result in table 5.
Table 6
Table 7
Notice that in table 7, the thickness of Cu-enriched layer and the Cu content in the Cu-enriched layer is to measure after each satisfies the sample heat treatment of condition of the present invention.In this result, the film thickness of each Cu-enriched layer is in the scope of about 0.5～2nm, and the content of Cu in each Cu-enriched layer 2～9 times of the average content (in table 7 not shown) of Cu in each Al alloy firm normally.
In table 7, show some result of experiment, the amount that is selected from the element in the element that belongs to group X or Z in these experiments changes.Confirm, when other element that belongs to group X or Z but list is used as element, can obtain similar experimental result in table 7.
Table 8
Table 9
Notice that in table 9, the thickness of Ge-enriched layer and the Ge content in the Ge-enriched layer is to measure after each satisfies the sample heat treatment of condition of the present invention.In this result, the film thickness of each Ge-enriched layer is in the scope of about 0.5～2nm, and the content of Ge in each Ge-enriched layer 2～9 times of the average content (in table 9 not shown) of Ge in each Al alloy firm normally.
In table 9, show some result of experiment, in these experiments, be selected from the amount change of the element in the element that belongs to group X or Z.Confirm, when other element that belongs to group X or Z but list is used as element, can obtain similar experimental result in table 9.
Table 10
According to the experimental result shown in table 1～10, can suppress the resistance of Al alloy film self, and will be suppressed at reduced levels with the contact resistance of pixel electrode, guaranteed again simultaneously in the enough thermal endurance of low heating-up temperature under as 250 ℃.Therefore, can use up to now and can not so just provide more material choice as the material of display material owing to its unsuitable thermal endurance.
In the present embodiment, as following description, approximately each Al alloy firm sample with the listed various alloy compositions in table 11～15 has all been studied the aqueous slkali of anti-use TMAH developing solution and whether has been had pitting corrosion.
Particularly, the foregoing description 1 3) under the condition described, on glass substrate, form the Al alloy film.Under 25 ℃, each the Al alloy film that obtains by above-mentioned steps all direct impregnation in common developing solution (solution that contains the TMAH of 2.38 quality %), mensuration is up to the consoluet time of film, the etch-rate of time per unit (a minute) is calculated by the amount of time that records like this and adhesive film, and alkaline-resisting SOLUTION PROPERTIES is according to following standard evaluation.Zero: etch-rate is for being lower than 40nm/min, Δ: etch-rate is 40nm/min or faster but be lower than 70nm/min, *: etch-rate is 70nm/min or faster.
The existence of pitting corrosion is (multiplication factor: 400X) by observing surface research, and by SEM (multiplication factor: 3000X) observe and determined under light microscope whether.As a result, those that do not have a foreign particles (pitting corrosion) are confirmed as " not existing ", and have a foreign particles (pitting corrosion) those be confirmed as " existence ".
For relatively, replace the Al alloy firm with the fine aluminium film, the existence of having studied etch-rate, alkaline-resisting developing solution and pitting corrosion is whether.
Table 11～15 show these results.
Annotate: " there is not " " presence " expression " existence " in " absence " expression among the table 11-15
Table 11
| Numbering | Form | Etch-rate in developing solution (nm/min) | The character of alkaline-resisting developing solution | Pitting corrosion |
| 1 | Al-6at％Ni | 80 | × | absence |
| 2 | Al-2at％Ni | 120 | × | absence |
| 3 | Al-0.5at％Ni | 105 | × | absence |
| 4 | Al-2at％Ni-0.6at％Nd | 61 | Δ | absence |
| 5 | Al-2at％Ni-0.2at％Nd | 90 | × | absence |
| 6 | Al-2at％Ni-0.6at％Mn | 40 | ○ | absence |
| 7 | Al-2at％Ni-0.5at％La | 29 | ○ | absence |
| 8 | Al-2at％Ni-0.3at％V | 24 | ○ | absence |
| 9 | Al-2at％Ni-1.8at％Mg | 10 | ○ | absence |
| 10 | Al-2at％Ni-0.08at％Mg | 110 | × | absence |
| 11 | Al-2at％Ni-0.8at％Gd | 7 | ○ | absence |
| 12 | Al-2at％Ni-1at％Dy | 38 | ○ | absence |
| 13 | Al-2at％Ni-1at％Tb | 40 | ○ | absence |
| 14 | Al-2at％Ni-0.5at％Pt | 120 | × | absence |
| 15 | Al-0.1at％Ni-0.6at％Mn | 26 | ○ | absence |
| 16 | Al-0.1at％Ni-0.5at％La | 18 | ○ | absence |
| 17 | Al-0.1at％Ni-0.3at％V | 16 | ○ | absence |
| 18 | Al-0.1at％Ni-1.8at％Mg | 7 | ○ | absence |
| 19 | Al-0.1at％Ni-0.8at％Gd | 5 | ○ | absence |
| 20 | Al-6at％Ni-0.6at％Mn | 32 | ○ | absence |
| 21 | Al-6at％Ni-0.5at％La | 24 | ○ | absence |
| 22 | Al-6at％Ni-0.3at％V | 20 | ○ | absence |
| 23 | Ai-6at％Ni-1.8at％Mg | 8 | ○ | absence |
| 24 | Al-6at％Ni-0.8at％Gd | 6 | ○ | absence |
| 25 | Al-2at％Ni-0.5at％Ta | 40 | ○ | absence |
| 26 | Al-2at％Ni-0.5at％Sm | 39 | ○ | absence |
| 27 | Al-2at％Ni-0.5at％Eu | 40 | ○ | absence |
| 28 | Al-2at％Ni-0.5at％Er | 40 | ○ | absence |
| 29 | Al | 20 | ○ | absence |
Table 12
| Numbering | Form | Etch-rate in developing solution (nm/min) | The character of alkaline-resisting developing solution | Pitting corrosion |
| 1 | Al-6at％Ag | 55 | × | presence |
| 2 | Al-2at％Ag | 42 | × | presence |
| 3 | Al-0.5at％Ag | 40 | × | presence |
| 4 | Al-2at％Ag-0.6at％Nd | 48 | Δ | absence |
| 5 | Al-2at％Ag-0.2at％Nd | 50 | × | presence |
| 6 | Al-2at％Ag-0.6at％Mn | 39 | ○ | absence |
| 7 | Al-2at％Ag-0.5at％La | 35 | ○ | absence |
| 8 | Al-2at％Ag-0.3at％V | 30 | ○ | absence |
| 9 | Al-2at％Ag-1.8at％Mg | 22 | ○ | absence |
| 10 | Al-2at％Ag-0.08at％Mg | 42 | × | presence |
| 11 | Al-2at％Ag-0.8at％Gd | 9 | ○ | absence |
| 12 | Al-2at％Ag-1at％Dy | 32 | ○ | absence |
| 13 | Al-2at％Ag-1at％Tb | 32 | ○ | absence |
| 14 | Al-2at％Ag-0.5at％Pt | 75 | × | presence |
| 15 | Al-0.1at％Ag-0.6at％Mn | 12 | ○ | absence |
| 16 | Al-0.1at％Ag-0.5at％La | 7 | ○ | absence |
| 17 | Al-0.1at％Ag-0.3at％V | 10 | ○ | absence |
| 18 | Al-0.1at％Ag-1.8at％Mg | 10 | ○ | absence |
| 19 | Al-0.1at％Ag-0.8at％Gd | 5 | ○ | absence |
| 20 | Al-6at％Ag-0.6at％Mn | 39 | ○ | absence |
| 21 | Al-6at％Ag-0.5at％La | 34 | ○ | absence |
| 22 | Al-6at％Ag-0.3at％V | 30 | ○ | absence |
| 23 | Al-6at％Ag-1.8at％Mg | 22 | ○ | absence |
| 24 | Al-6at％Ag-0.8at％Gd | 14 | ○ | absence |
| 25 | Al-2at％Ag-0.5at％Ta | 35 | ○ | absence |
| 26 | Al-2at％Ag-0.5at％Sm | 40 | ○ | absence |
| 27 | Al-2at％Ag-0.5at％Eu | 35 | ○ | absence |
| 28 | Al-2at％Ag-0.5at％Er | 37 | ○ | absence |
Table 13
| Numbering | Form | Etch-rate in developing solution (nm/min) | The character of alkaline-resisting developing solution | Pitting corrosion |
| 1 | Al-6at％Zn | 40 | × | presence |
| 2 | Al-2at％Zn | 30 | × | presence |
| 3 | Al-0.5at％Zn | 28 | × | presence |
| 4 | Al-2at％Zn-0.6at％Nd | 15 | Δ | absence |
| 5 | Al-2at％Zn-0.2at％Nd | 25 | × | presence |
| 6 | Al-2at％Zn-0.6at％Mn | 20 | ○ | absence |
| 7 | Al-2at％Zn-0.5at％La | 15 | ○ | absence |
| 8 | Al-2at％Zn-0.3at％V | 25 | ○ | absence |
| 9 | Al-2at％Zn-1.8at％Mg | 16 | ○ | absence |
| 10 | Al-2at％Zn-0.08at％Mg | 33 | × | presence |
| 11 | Al-2at％Zn-0.8at％Gd | 8 | ○ | absence |
| 12 | Al-2at％Zn-1at％Dy | 28 | ○ | absence |
| 13 | Al-2at％Zn-1at％Tb | 25 | ○ | absence |
| 14 | Al-2at％Zn-0.5at％Pt | 65 | × | presence |
| 15 | Al-0.1at％Zn-0.6at％Mn | 17 | ○ | absence |
| 16 | Al-0.1at％Zn-0.5at％La | 10 | ○ | absence |
| 17 | Al-0.1at％Zn-0.3at％V | 12 | ○ | absence |
| 18 | Al-0.1at％Zn-1.8at％Mg | 3 | ○ | absence |
| 19 | Al-0.1at％Zn-0.8at％Gd | 4 | ○ | absence |
| 20 | Al-6at％Zn-0.6at％Mn | 31 | ○ | absence |
| 21 | Al-6at％Zn-0.5at％La | 25 | ○ | absence |
| 22 | Al-6at％Zn-0.3at％V | 28 | ○ | absence |
| 23 | Al-6at％Zn-1.8at％Mg | 20 | ○ | absence |
| 24 | Al-6at％Zn-0.8at％Gd | 10 | ○ | absence |
| 25 | Al-2at％Zn-0.5at％Ta | 25 | ○ | absence |
| 26 | Al-2at％Zn-0.5at％Sm | 25 | ○ | absence |
| 27 | Al-2at％Zn-0.5at％Eu | 30 | ○ | absence |
| 28 | Al-2at％Zn-0.5at％Er | 28 | ○ | absence |
Table 14
| Numbering | Form | Etch-rate in developing solution (nm/min) | The character of alkaline-resisting developing solution | Pitting corrosion |
| 1 | Al-6at％Ge | 33 | × | presence |
| 2 | Al-2at％Ge | 25 | × | presence |
| 3 | Al-0.5at％Ge | 25 | × | presence |
| 4 | Al-2at％Ge-0.6at％Nd | 9 | Δ | absence |
| 5 | Al-2at％Ge-0.2at％Nd | 21 | × | presence |
| 6 | Al-2at％Ge-0.6at％Mn | 15 | ○ | absence |
| 7 | Al-2at％Ge-0.5at％La | 18 | ○ | absence |
| 8 | Al-2at％Ge-0.3at％V | 22 | ○ | absence |
| 9 | Al-2at％Ge-1.8at％Mg | 11 | ○ | absence |
| 10 | Al-2at％Ge-0.08at％Mg | 28 | × | presence |
| 11 | Al-2at％Ge-0.8at％Gd | 9 | ○ | absence |
| 12 | Al-2at％Ge-1at％Dy | 20 | ○ | absence |
| 13 | Al-2at％Ge-1at％Tb | 40 | ○ | absence |
| 14 | Al-2at％Ge-0.5at％Pt | 63 | × | presence |
| 15 | Al-0.1at％Ge-0.6at％Mn | 13 | ○ | absence |
| 16 | Al-0.1at％Ge-0.5at％La | 14 | ○ | absence |
| 17 | Al-0.1at％Ge-0.3at％V | 18 | ○ | absence |
| 18 | Al-0.1at％Ge-1.8at％Mg | 13 | ○ | absence |
| 19 | Al-0.1at％Ge-0.8at％Gd | 5 | ○ | absence |
| 20 | Al-6at％Ge-0.6at％Mn | 32 | ○ | absence |
| 21 | Al-6at％Ge-0.5at％La | 30 | ○ | absence |
| 22 | Al-6at％Ge-0.3at％V | 31 | ○ | absence |
| 23 | Al-6at％Ge-1.8at％Mg | 25 | ○ | absence |
| 24 | Al-6at％Ge-0.8at％Gd | 19 | ○ | absence |
| 25 | Al-2at％Ge-0.5at％Ta | 22 | ○ | absence |
| 26 | Al-2at％Ge-0.5at％Sm | 21 | ○ | absence |
| 27 | Al-2at％Ge-0.5at％Eu | 33 | ○ | absence |
| 28 | Al-2at％Ge-0.5at％Er | 32 | ○ | absence |
Table 15
| Numbering | Form | Etch-rate in developing solution (nm/min) | The character of alkaline-resisting developing solution | Pitting corrosion |
| 1 | Al-6at％Cu | 58 | × | presence |
| 2 | Al-2at％Cu | 48 | × | presence |
| 3 | Al-0.5at％Cu | 48 | × | presence |
| 4 | Al-2at％Cu-0.6at％Nd | 43 | Δ | absence |
| 5 | Al-2at％Cu-0.2at％Nd | 48 | × | presence |
| 6 | Al-2at％Cu-0.6at％Mn | 40 | ○ | absence |
| 7 | Al-2at％Cu-0.5at％La | 31 | ○ | absence |
| 8 | Al-2at％Cu-0.3at％V | 22 | ○ | absence |
| 9 | Al-2at％Cu-1.8at％Mg | 15 | ○ | absence |
| 10 | Al-2at％Cu-0.08at％Mg | 42 | × | presence |
| 11 | Al-2at％Cu-0.8at％Gd | 12 | ○ | absence |
| 12 | Al-2at％Cu-1at％Dy | 33 | ○ | absence |
| 13 | Al-2at％Cu-1at％Tb | 38 | ○ | absence |
| 14 | Al-2at％Cu-0.5at％Pt | 85 | × | presence |
| 15 | Al-0.1at％Cu-0.6at％Mn | 20 | ○ | absence |
| 16 | Al-0.1at％Cu-0.5at％La | 12 | ○ | absence |
| 17 | Al-0.1at％Cu-0.3at％V | 16 | ○ | absence |
| 18 | Al-0.1at％Cu-1.8at％Mg | 10 | ○ | absence |
| 19 | Al-0.1at％Cu-0.8at％Gd | 10 | ○ | absence |
| 20 | Al-6at％Cu-0.6at％Mn | 40 | ○ | absence |
| 21 | Al-6at％Cu-0.5at％La | 30 | ○ | absence |
| 22 | Al-6at％Cu-0.3at％V | 35 | ○ | absence |
| 23 | Al-6at％Cu-1.8at％Mg | 25 | ○ | absence |
| 24 | Al-6at％Cu-0.8at％Gd | 22 | ○ | absence |
| 25 | Al-2at％Cu-0.5at％Ta | 40 | ○ | absence |
| 26 | Al-2at％Cu-0.5at％Sm | 27 | ○ | absence |
| 27 | Al-2at％Cu-0.5at％Eu | 26 | ○ | absence |
| 28 | Al-2at％Cu-0.5at％Er | 38 | ○ | absence |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2008101005187A Division CN101281913A (en) | 2005-02-17 | 2006-02-17 | Display device and sputtering target for producing the same |
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| CN1822372A CN1822372A (en) | 2006-08-23 |
| CN100511687C true CN100511687C (en) | 2009-07-08 |
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| JP4160110B2 (en) * | 2006-10-26 | 2008-10-01 | 三井金属鉱業株式会社 | Element structure of display device and manufacturing method thereof |
| JP4611417B2 (en) | 2007-12-26 | 2011-01-12 | 株式会社神戸製鋼所 | Reflective electrode, display device, and display device manufacturing method |
| US20110008640A1 (en) * | 2008-03-31 | 2011-01-13 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel Ltd.) | Display device, process for producing the display device, and sputtering target |
| JP5139134B2 (en) * | 2008-03-31 | 2013-02-06 | 株式会社コベルコ科研 | Al-Ni-La-Cu-based Al-based alloy sputtering target and method for producing the same |
| JP5432550B2 (en) * | 2008-03-31 | 2014-03-05 | 株式会社コベルコ科研 | Al-based alloy sputtering target and manufacturing method thereof |
| US8741738B2 (en) * | 2011-06-08 | 2014-06-03 | Taiwan Semiconductor Manufacturing Company, Ltd. | Method of fabrication of a semiconductor apparatus comprising substrates including Al/Ge and Cu contact layers to form a metallic alloy |
| CN103187451B (en) * | 2012-01-03 | 2017-04-05 | 管炜 | Thin film transistor (TFT) |
| CN103400822A (en) * | 2013-08-01 | 2013-11-20 | 京东方科技集团股份有限公司 | Array substrate and display device |
| WO2015072485A1 (en) * | 2013-11-12 | 2015-05-21 | 株式会社神戸製鋼所 | Electrode and method for producing same |
| JP2018032601A (en) * | 2016-08-26 | 2018-03-01 | 株式会社神戸製鋼所 | Reflective electrode and Al alloy sputtering target |
| CN107881353A (en) * | 2016-09-29 | 2018-04-06 | 宁波江丰电子材料股份有限公司 | The forming method of aluminum bronze tungsten alloy |
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| CN1822372A (en) | 2006-08-23 |
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