JP4803726B2 - Electronic circuit and manufacturing method thereof - Google Patents

Description

  The present invention relates to an electronic circuit and a method for manufacturing the same.

  Conventionally, a substrate having a thin film made of metal, an insulator or the like, or a substrate having a circuit pattern formed by further patterning this thin film has been used as a computer, communication, information appliance, various display devices, etc. (this thin film) Hereinafter, it is also referred to as a substrate having a circuit pattern or the like including a substrate having a circuit pattern and a substrate having a circuit pattern.)

  Thus, a substrate having a circuit pattern or the like usually has a plurality of layers made of a plurality of substances or a layer obtained by patterning the same on the substrate. In manufacturing a substrate having such a circuit pattern, some heat treatment such as annealing may be performed. At that time, a chemical reaction occurs between these layers, and some layers are deteriorated (mainly In some cases, the resistivity of the electrode pattern increases due to increase in specific resistance or corrosion.

This point will be specifically described below with reference to a front substrate of a plasma display panel (hereinafter also referred to as PDP) which is a representative example of a substrate having the circuit pattern and the like.
FIG. 5 shows a cross-sectional view of a typical PDP. As shown here, the PDP has a transparent front substrate 61 and a rear substrate 62 facing each other. The front substrate 61 has a display electrode 65, a bus electrode 66, and a dielectric layer 68 made of a transparent conductive film formed by patterning on the surface.
Here, the dielectric layer 68 secures insulation between the display electrode 65 and the address electrode 67 on the rear substrate 62 to stably generate plasma, and prevents the electrode from being eroded by plasma. Therefore, it is an indispensable element in PDP (see Patent Document 1, Non-Patent Document 1, and Non-Patent Document 2).

When manufacturing such a PDP front substrate, after forming the display electrode 65 and the bus electrode 66 on the upper surface of the front substrate 61 by patterning, a dielectric material is attached to the upper surface and heated to melt or When the dielectric layer 68 is formed by sintering, the resistance value increases when the display electrode 65 or the bus electrode 66 is eroded by the heating or the dielectric raw material having a high temperature. was there.
JP-A-7-65727 Tatsuo Uchida and Hiiraki Uchiike, “Flat Dictionary of Flat Panel Displays”, Industrial Research Committee, December 25, 2001, p. 583-585 Takeshi Okumura, “Flat Panel Display 2004 Practice”, Nikkei Business Publications, p. 176-183

When manufacturing a substrate having a circuit pattern or the like as described above, if a heat treatment such as an annealing process is performed, the resistance value of the electrode pattern formed on the substrate may increase.
For example, in the case of a PDP front substrate, the resistance value of the display electrode and the bus electrode may increase due to the influence of heating when a dielectric layer is formed or when an annealing process is performed.
That is, an object of the present invention is to provide a substrate having a circuit pattern or the like in which such a resistance value hardly increases.

In addition, as described above, a substrate having a circuit pattern or the like that has been used in the past may have some layers in a plurality of layers on the substrate deteriorate due to the influence of other layers. .
For example, in the case of a PDP front substrate, the display electrodes and bus electrodes existing in contact therewith may be deteriorated due to the influence of the dielectric layer.
That is, another object of the present invention is to provide a substrate having a circuit pattern or the like that hardly causes deterioration as described above.

It is another object of the present invention to provide an electronic circuit using a substrate having such a circuit pattern.
It is another object of the present invention to provide a plasma display front substrate using a substrate having such a circuit pattern and the like and a PDP using the same.
Furthermore, it is providing the manufacturing method of these.

That is, the present invention includes the following (1) to (13).
(1) A transparent substrate with a thin film for an electronic circuit having a transparent conductive film layer on the upper surface of the transparent substrate and an Si compound thin film layer on the upper surface.
(2) The transparent substrate with a thin film according to (1), further comprising a dielectric layer on the upper surface of the Si compound thin film layer.
(3) In the above (1) or (2), a patterned electrode layer is further provided between the transparent substrate and the transparent conductive film layer or between the transparent conductive film layer and the Si compound thin film layer. The transparent substrate with a thin film as described.
(4) The transparent substrate with a thin film according to any one of (1) to (3), wherein the Si compound thin film layer is a thin film layer containing SiO ₂ as a main component.
(5) The transparent substrate with a thin film according to any one of (1) to (4), wherein the transparent conductive film layer is a SnO ₂ thin film layer, an ITO thin film layer, or a ZnO thin film layer.

(6) A pattern for an electronic circuit, wherein at least the transparent conductive film layer is subjected to a patterning process by a laser patterning method or a lift-off method in the transparent substrate with a thin film according to any one of (1) to (5) above. With transparent substrate.
(7) The patterned transparent substrate according to (6) above, which is subjected to heat treatment at 400 ° C. or higher before and / or after the patterning treatment.
(8) The pattern according to (6) or (7), wherein the transparent conductive film layer is a SnO ₂ thin film layer, and is subjected to a heat treatment at 250 ° C. or higher before and / or after the patterning treatment. With transparent substrate.

(9) An electronic circuit using the transparent substrate with a thin film according to any one of (1) to (5) or the transparent substrate with a pattern according to any one of (6) to (8).
(10) A plasma display front substrate using the transparent substrate with a thin film according to any one of (1) to (5) or the transparent substrate with a pattern according to any one of (6) to (8) .
(11) A plasma display panel using the plasma display front substrate according to (10).

(12) The method for producing a patterned transparent substrate for an electronic circuit according to any one of (6) to (8), comprising a step of performing a patterning process by a laser patterning method or a lift-off method.
(13) A plasma display front substrate manufactured by the manufacturing method according to (12) above.

  Further, according to the present invention, when a heat treatment (a treatment for forming a dielectric layer or an annealing treatment in the case of a PDP front substrate) is performed, the transparent conductive film layer on the substrate or the patterning is performed. Thus, it is possible to provide a transparent substrate with a thin film and a transparent substrate with a pattern, in which the resistance value of the electrode (display electrode or bus electrode made of a transparent conductive film layer in the case of a PDP front substrate) does not easily increase. By suppressing the resistance increase in this way, an electronic circuit using the resistance is improved in performance. In addition, since the resistance does not increase, a thin film can be formed, which contributes to cost reduction.

Further, according to the present invention, a substrate having a circuit pattern or the like (in the present invention, a transparent substrate with a thin film and a transparent substrate with a pattern), which is a part of a plurality of layers on the substrate (PDP front surface) A transparent substrate with a thin film and a transparent with a pattern, in which the display electrode and bus electrode in the case of a substrate are prevented from deteriorating due to the effect of forming other layers (dielectric layer in the case of a PDP front substrate) A substrate can be provided.
Furthermore, in the present invention, it is preferable to apply laser patterning or lift-off patterning, but in this case, there are fewer steps and less environmental impact compared to conventional photolithography / etching processes, for example. preferable.

This invention is a transparent substrate with a thin film for electronic circuits which has a transparent conductive film layer on the upper surface of a transparent substrate, and has a Si compound thin film layer on the upper surface.
Hereinafter, such a transparent substrate with a thin film is also referred to as a “transparent substrate with a thin film of the present invention”.

Moreover, this invention is a transparent substrate with a pattern for electronic circuits in which the transparent conductive film layer is patterned by the laser patterning method or the lift-off method in the transparent substrate with a thin film of this invention.
Hereinafter, such a patterned transparent substrate is also referred to as a “patterned transparent substrate of the present invention”.

The transparent substrate with a thin film of the present invention will be described.
The transparent substrate with a thin film of the present invention has a transparent conductive film layer on the surface of the transparent substrate, and further has a Si compound thin film layer on the upper surface thereof. Such a transparent substrate with a thin film of the present invention can be used as an electronic circuit (for example, PDP) or a material or component thereof (for example, a plasma display front substrate).

Since the transparent substrate with a thin film of the present invention has a Si compound thin film layer, when a heat treatment (in the case of a PDP front substrate, a treatment for forming a dielectric layer or an annealing treatment is applicable), An increase in the resistance value of the transparent conductive film layer can be suppressed. Even if the transparent substrate with a thin film of the present invention has a dielectric layer, a transparent conductive film layer (display electrode in the case of a PDP front substrate) existing between the Si compound thin film layer and the transparent substrate. And an electrode layer described later (corresponding to a bus electrode in the case of a PDP front substrate) can be prevented from deteriorating due to the influence of the formation of the dielectric layer. That is, this Si compound thin film layer increases the specific resistance of the transparent conductive film layer during the heat treatment, or, for example, reacts with the glass frit during firing of the low melting point glass frit used as the dielectric layer. And it functions as a barrier film that prevents the specific resistance of the electrode layer from increasing.
Without this Si compound thin film layer, the transparency of the transparent conductive film layer is usually improved by crystallinity due to heating, but the density of oxygen vacancies generating carriers is significantly reduced by oxidation, and resistance is increased. The value rises.
Therefore, the performance of electronic circuits and the like manufactured using the transparent substrate with a thin film of the present invention is improved. Furthermore, since the resistance does not increase, the transparent conductive film layer or the electrode layer can be thinned, which contributes to cost reduction.

<Si compound thin film layer>
The Si compound thin film layer of the transparent substrate with a thin film of the present invention is a thin film layer whose main component is a Si compound.
Here, “Si compound” means a compound containing Si element, and examples thereof include oxides and nitrides containing Si element.
Among these, SiO ₂ and / or SiN are preferable, and SiO ₂ is more preferable. This is because an extremely dense thin film layer that is transparent and suitable as a barrier film can be easily formed.

The Si compound thin film layer contains such a Si compound as a main component.
Here, “main component” means 70% by mass or more based on the total mass of the substance forming the thin film layer. The remaining species are not particularly limited, and examples include Al, B, Sn, Zr, and the like.
Thus, although the said Si compound thin film layer contains the said Si compound 70 mass% or more, it is preferable that it is 80 mass% or more, It is more preferable that it is 90 mass% or more, It is 95 mass% or more Is most preferred. This is because when the amount of the Si compound component is large, chemical and thermal durability as a barrier film is further improved.

The Si compound thin film layer is a thin film layer containing such a Si compound as a main component.
Here, although the thickness of the thin film layer is not particularly limited, it is preferably 50 to 200 nm from the viewpoint of obtaining an oxidation barrier property. Furthermore, 100 to 200 nm is particularly preferable in that the deterioration due to the dielectric and the increase in resistance during heating can be more effectively suppressed.

<Transparent conductive film layer>
The transparent substrate with a thin film of the present invention has a transparent conductive film layer on the surface of the transparent substrate.
Here, the material of the transparent conductive film layer is not particularly limited, and for example, a material used as a transparent electrode of the plasma display front substrate can be used. For example, indium oxide, tin oxide, zinc oxide, indium oxide doped with tin oxide (ITO), and zinc oxide doped with aluminum oxide (AZO) are the main components (the definition of “main component” is the above Similar to the Si compound thin film layer, the content can be determined using, for example, a fluorescent X-ray analysis method or a plasma emission analysis method in which the transparent conductive film layer is dissolved in a solution.

Among these, those containing SnO ₂ as a main component are preferable (that is, the transparent conductive film layer is preferably a SnO ₂ thin film layer), and at least one selected from the group consisting of antimony, tantalum and niobium is an oxide. SnO ₂ doped with 0.1 to 10% by mass, preferably 2 to 5% by mass, is more preferable.
Further, ITO doped with tin oxide is preferable (that is, the transparent conductive film layer is preferably an ITO thin film layer), and ITO with a SnO ₂ doping amount of 3 to 15% by mass is particularly preferable.
In addition, it is preferable that zinc oxide is the main component (that is, the transparent conductive film layer is preferably a ZnO thin film layer) and at least one selected from the group consisting of aluminum oxide, gallium and indium is 0.1 to More preferred is ZnO doped at 15% by weight.

Of these, the SnO ₂ thin film layer is most preferable. This is because the resistance to the dielectric is higher as will be described later.

Conventionally, for example, ITO is preferably used for the transparent conductive film layer of the plasma display front substrate, and there are very few examples of applying SnO ₂ in the past. This is because it is difficult to apply a photolithography etching process that can be easily applied to ITO when SnO ₂ is used. In addition, the resistance value increases when the heating process is performed in the manufacturing process. On the other hand, in recent years, the price of indium has risen due to concerns about depletion of indium resources, and the practical application of a transparent conductive film layer made of SnO ₂ is strongly desired as an alternative material.
In the present invention, SnO ₂ can be preferably used as the transparent conductive film layer, which meets such a demand.

In addition, the said transparent conductive film layer may contain another component in the range with the effect of this invention. For example, an element that forms a pentavalent oxide such as Nb may be contained in the film in an amount of about 5% by mass or less in terms of M ₂ O ₅ (M is an element that forms a pentavalent oxide).

  Further, the thickness of the transparent conductive film layer is not particularly limited. If it is used for a PDP front substrate, it is preferably 200 to 500 nm. This is because the resistance value becomes lower.

  The transparent conductive film layer may be a single layer made of one kind of material or a layer having two or more layers made of different kinds of materials.

The transparent substrate with a thin film of the present invention has such a transparent conductive film layer on the transparent substrate, but when the transparent substrate with a thin film of the present invention is heat-treated, the transparent conductive film layer before the heat treatment is transparent. It is preferable to adjust the conditions for forming the conductive film layer to obtain properties in the vicinity of the oxidized state where the carrier concentration is maximized.
For example, in the case of a vapor deposition method, this oxidation state can be controlled by the introduced oxygen amount, the film formation speed, the substrate temperature, and the oxygen content in the film forming raw material, which are conditions at the time of forming the transparent conductive film layer. it can.
The carrier concentration can be obtained from the measured Hall effect value and the measured specific resistance value.
The specific resistance of the transparent conductive film layer obtained after the heat treatment also depends on the heat treatment conditions, so the properties of the transparent conductive film layer before the heat treatment should be optimized as appropriate near the oxidation conditions where the carrier concentration is maximum. Is preferred.

The present inventor considers the reason why the transparent substrate with a thin film of the present invention has the above-described effects as follows.
The electrical resistance is determined by the product of the conduction electron concentration (carrier concentration) and the mobility (depending on crystallinity and scattering factors). In the transparent conductive film layer, the carrier concentration is determined by the number of oxygen defects and the number of donors formed by the additive element substituting for the cation site of the base. The number of oxygen defects is in the oxidized state of the film, and the additive element is more effectively the donor. It depends on the crystallinity of the film.
The general substrate temperature at the time of forming the transparent conductive film layer used in the application of the present invention is approximately 300 ° C. or less, and the carrier concentration due to oxygen defects can be relatively high, but a lower resistance film is required. In this case, the crystallinity of the film is insufficient, and higher mobility and more effective donor conversion of the additive element are necessary.
Although it is possible to improve the crystallinity of the film by a post-deposition heat treatment performed in a later step, the heat treatment step is an atmosphere containing a large amount of oxygen such as air firing or low-melting glass frit. Defects (carrier density) are significantly reduced.
Therefore, by covering the transparent conductive film layer with an oxidation barrier film, which is a Si compound thin film layer typified by the above-mentioned SiO ₂ thin film layer, the oxidation of this layer is suppressed, and while maintaining a high carrier density, It is considered that the crystallinity can be improved and as a result, the resistance of the transparent conductive film layer can be reduced.
Since SnO ₂ is difficult to crystallize, when using a SnO ₂ thin film layer as the transparent conductive film layer, it is preferable to perform crystallization by heat treatment in order to obtain a low specific resistance. At that time, the above-described oxidation barrier film It is preferable to prevent the decrease of oxygen defects (carrier density) by coating with.

<Transparent substrate>
The transparent substrate with a thin film of the present invention has the transparent conductive film layer and the Si compound thin film layer on the upper surface of the transparent substrate.
Here, the transparent substrate is not particularly limited as long as it is a transparent substrate such as glass, and is preferably a glass substrate, and further, a material that transmits laser light (such as YAG laser light) (transmittance is 80%). The above materials are more preferable.
Moreover, the thickness and size are not particularly limited. For example, a glass substrate of about 1 to 3 mm can be preferably used for a plasma display front substrate.

<Electrode layer>
The transparent substrate with a thin film of the present invention has the transparent conductive film layer on the surface of the transparent substrate, and further has the Si compound thin film layer on the upper surface, between the transparent substrate and the transparent conductive film layer, Alternatively, it is preferable that a patterned electrode layer is further provided between the transparent conductive film layer and the Si compound thin film layer.
It is preferable to have such an electrode layer because it can be used as a substrate for a plasma display front substrate, for example.

  The “patterned electrode layer” is an electrode layer formed in an arbitrary pattern by an arbitrary patterning method, and contains a metal as a main component. This patterning method is not particularly limited, and examples thereof include wet patterning, printing patterning, lift-off patterning, and laser patterning method. Among these, laser patterning method or lift-off method is preferable. This is because, for example, the number of steps is smaller and the influence on the environment is smaller than that of the photolithography / etching process.

  Furthermore, the metal forming this electrode layer is not particularly limited as long as it has conductivity, but Cu, Ag, Al and the like are preferably highly conductive (the definition of “main component” is the Si Same as compound thin film layer).

  Moreover, although the said electrode layer is formed by the method as mentioned later, Although the thickness is not specifically limited, It is preferable that it is 1-20 micrometers, and it is still more preferable that it is 1-5 micrometers.

  The electrode layer may be composed of a plurality of layers. For example, a three-layer structure of Cr layer / Cu layer / Cr layer is preferably exemplified as the bus electrode in the plasma display front substrate.

<Dielectric layer>
The transparent substrate with a thin film of the present invention preferably further has a dielectric layer on the upper surface of the Si compound thin film layer. In this case, it can be preferably used as a PDP front substrate.

Here, the kind of the dielectric layer forming material for forming the dielectric layer is not particularly limited as long as it is an electrical insulator. For example, a low-melting glass containing SiO ₂ as a main component and containing Al ₂ O ₃ , B ₂ O ₃ , MgO, or the like can be used.

  The dielectric layer is preferably a transparent dielectric layer. This is because the transparent substrate with a thin film of the present invention having such a dielectric layer can be used as a plasma display front substrate. Here, the transparent dielectric layer means a layer having a visible light transmittance of 70% or more.

  The thickness of this dielectric layer is not particularly limited, but is preferably 5 to 50 μm, and more preferably 10 to 40 μm.

Next, the manufacturing method of such a transparent substrate with a thin film of this invention is demonstrated.
The method for forming the transparent conductive film layer and the Si compound thin film layer on the upper surface of the transparent substrate is not particularly limited, and can be performed by, for example, a normal method, and a vapor deposition method can be preferably exemplified.

  Examples of the vapor deposition method include physical vapor deposition (PVD) such as vacuum deposition, ion plating, sputtering, and laser ablation. Moreover, thermal CVD, plasma CVD, etc. are mentioned as a chemical vapor deposition method (CVD). Among these, the sputtering method and the ion plating method are preferable in that the film thickness can be controlled with high accuracy.

For example, in order to form a SnO ₂ thin film layer as a transparent conductive film layer on a transparent substrate by a sputtering method, a target of tin or tin oxide is installed on the cathode side, and in a reaction atmosphere gas of about 1 to 10 ⁻² Pa. There is a method in which glow discharge is caused between the electrodes, the reaction atmosphere gas is ionized, tin or the like is knocked out of the target, and a tin oxide is coated on a transparent substrate placed on the anode side. Here, when Ta or Sb is contained in the tin oxide thin film, these or these oxides may be mixed in the target. The reaction atmosphere gas may be an inert gas such as argon or a gas mixed with oxygen.
The SnO ₂ thin film layer formed on the transparent substrate by mainly adjusting the oxidation degree of the target, the oxygen concentration (oxygen partial pressure) in the reaction atmosphere gas for sputtering, the thin film formation rate (vapor deposition rate), and the substrate temperature. The degree of oxidation changes and the carrier concentration also changes.

  The Si compound thin film layer can also be formed in the same manner as this transparent conductive film layer.

Moreover, when the transparent substrate with a thin film of the present invention has a further patterned electrode layer between the transparent substrate and the transparent conductive film layer, after forming the patterned electrode layer on the upper surface of the transparent substrate The transparent conductive film layer and the Si compound thin film layer are formed on the upper surface of the electrode layer by the method as described above.
The same applies to the case where a further patterned electrode layer is formed between the transparent conductive film layer and the Si compound thin film layer.

The method for forming the patterned electrode layer is not particularly limited, and a laser patterning method, a lift-off method, a photolithography / etching process, or the like can be applied. Among these, the laser patterning method or the lift-off method is preferable. This is because, for example, the number of steps is smaller and the influence on the environment is smaller than in the photolithography / etching process.
Specifically, for example, in the case of lift-off method (lift-off patterning), after forming a negative resist pattern on the upper surface of the transparent substrate or the transparent conductive film layer in advance, for example, the transparent conductive film layer and the Si compound thin film A metal thin film is formed by applying a vapor deposition method applied in the formation of the layer, and then unnecessary portions are peeled off together with the resist. In this manner, a patterned electrode layer can be formed on the upper surface of the transparent substrate or the transparent conductive film layer.

In the method for producing a transparent substrate with a thin film according to the present invention, the transparent conductive film layer is formed on the upper surface of the transparent substrate, and if necessary, the patterned electrode layer is formed on the upper surface. An annealing treatment is preferably performed after the Si compound thin film layer is formed on the upper surface. By carrying out the annealing treatment, the carrier concentration of the transparent conductive film layer formed on the transparent substrate also changes. As a result, for example, the absorption rate of laser light at 1064 nm, which is the oscillation wavelength of YAG laser light, can be optimized, and patterning with high reproducibility and efficiency becomes possible. Further, by performing the annealing process in the state having the Si compound thin film layer, an increase in the resistance value of the transparent conductive film layer can be suppressed.
As a specific method of annealing treatment, the transparent substrate having the transparent conductive film layer is annealed in the atmosphere, oxygen, or nitrogen atmosphere while being heated to 400 ° C. or higher, preferably 400 to 650 ° C. A method can be mentioned.
Further, when the transparent conductive film layer is a thin film of SnO ₂ layer is preferably heated in the same manner at a temperature of 250 ° C. or higher.

Moreover, after manufacturing the transparent substrate with a thin film of this invention by such a method, the method of forming a dielectric material layer further on the upper surface of the said Si compound thin film layer is not specifically limited, For example, it can carry out by a normal method .
For example, after a powdery dielectric forming material is dispersed in a diluent (for example, butyl carbitol acetate), this is applied to the upper surface of the Si compound thin film layer existing on the surface of the transparent substrate with a thin film of the present invention. For example, heating is performed at a temperature of about 600 ° C. for about 30 minutes.
Even when heated at such a temperature, since the transparent substrate with a thin film of the present invention has the Si compound thin film layer, an increase in the resistance value of the transparent conductive film layer can be suppressed.
By such a method, the transparent substrate with a thin film of the present invention having the dielectric layer can be produced.

Next, the transparent substrate with a pattern and the manufacturing method thereof according to the present invention will be described.
The transparent substrate with a pattern of the present invention is a transparent substrate with a pattern for an electronic circuit in which at least the transparent conductive film layer is patterned by a laser patterning method or a lift-off method in the transparent substrate with a thin film of the present invention.
That is, in the transparent substrate with a pattern of the present invention, the transparent conductive film layer of the transparent substrate with a thin film of the present invention is patterned. Further, the Si compound thin film layer may be patterned.

When applying the laser patterning method, a transparent conductive film layer is formed on the upper surface of the transparent substrate, an arbitrary pattern is formed by applying the laser patterning method, and then the Si compound thin film layer is further formed on the upper surface. However, after forming a transparent conductive film layer on the upper surface of the transparent substrate and forming the Si compound thin film layer on the upper surface, the two layers can be patterned simultaneously.
The same applies when the lift-off method is applied. After forming a negative resist pattern in advance on the upper surface of the transparent substrate, the transparent conductive film layer and the Si compound thin film layer are formed, and the vapor phase is formed on the upper surface. By forming a metal thin film by a vapor deposition method or the like and then peeling off unnecessary portions together with the resist, the two layers can be patterned simultaneously.
That is, since the Si compound thin film layer cannot be etched with an etching solution usually used in a photolithography / etching process, patterning simultaneously with the transparent conductive film layer by a laser patterning method or a lift-off method shortens the processing step and further reduces the cost. From the viewpoint of environmental load such as treatment of waste liquid.

Here, the laser patterning method is not particularly limited. For example, patterning can be performed by irradiating YAG laser light having a wavelength of 1064 nm. Specifically, for example, as shown in FIG. 3, a transparent conductive film layer 23 and a SiO ₂ thin film layer 24 are formed on the upper surface of an electrode layer (bus electrode 21) formed in an arbitrary pattern (FIG. 3A). (B)), and a method of irradiating an arbitrary laser beam 26 (for example, a YAG laser beam having an arbitrary energy and a wavelength of 1064 nm) through a mask having an arbitrary opening (FIG. 3 ( c)). Thereafter, a dielectric layer 25 may be further formed on the upper surface thereof (FIG. 3D).

Also, the lift-off method is not particularly limited. For example, as shown in FIG. 2, after a negative resist 22 pattern is formed in advance on the upper surface of the transparent substrate 10 having an electrode layer (bus electrode 21) formed in an arbitrary pattern (FIG. 2 (a)), The transparent conductive film layer 23 is formed, and the SiO ₂ thin film layer 24 is formed on the upper surface thereof by the above vapor deposition method or the like (FIG. 2B), and then an unnecessary portion is removed together with the resist 22 (FIG. 2). (C)). Thereafter, a dielectric layer 25 may be further formed on the upper surface thereof (FIG. 2D).

In addition, the transparent substrate with a pattern of this invention can also be manufactured by the wet type patterning method. In this case, the Si compound layer is formed after the transparent conductive film layer is formed by wet patterning, and there is no particular problem in terms of performance. However, for example, the lift-off method (lift-off patterning) shown in FIG. Further, the laser patterning method shown in FIG. 3 is preferable from the standpoint that no chemical solution such as a resist, a developing solution thereof, or a stripping solution is used.
In particular, lift-off patterning and laser patterning are optimal for tin oxide-based films (the SnO ₂ thin film layer) that are difficult to chemically wet etch practically.

Further, the patterned transparent substrate of the present invention is preferably subjected to a heat treatment at 400 ° C. or higher before and / or after the patterning treatment by the laser patterning method or the lift-off method.
A specific method for the heat treatment is the same as the method described in the thin film-coated substrate of the present invention.

  Here, the “step of heating at 400 ° C. or higher” includes, for example, the above-described annealing treatment and a step of forming a dielectric layer.

Further, a patterned transparent substrate of the present invention, the transparent conductive film layer may of SnO ₂ thin film layer, patterning process before and / or after, it is preferable that the heat treatment is performed above 250 ° C..
Here, the “heating process at 250 ° C. or higher” includes, for example, the annealing process described above.

The patterned transparent substrate of the present invention can be preferably produced by a method comprising a step of performing a patterning treatment by such a laser patterning method or a lift-off method.
In addition, as described above, this manufacturing method includes a heat treatment step of 400 ° C. or higher (step of performing a heat treatment of 400 ° C. or higher before and / or after the patterning treatment) and a heat treatment step of 250 ° C. or higher ( A step of performing a heat treatment at 250 ° C. or higher before and / or after the patterning treatment may be further provided. This heat treatment step at 250 ° C. or higher is a particularly preferred treatment step when the transparent conductive film layer is a SnO ₂ thin film layer.
By such a manufacturing method, the plasma display front substrate can be preferably manufactured.
Moreover, this invention is an electronic circuit (for example, PDP) which uses the transparent substrate with a thin film of this invention, or the transparent substrate with a pattern of this invention.
Moreover, this invention is a plasma display front substrate which uses the transparent substrate with a thin film of this invention, or the transparent substrate with a pattern of this invention, and PDP which uses this.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these.

<Comparative Example 1>
A plurality of glass substrates (PD200, manufactured by Asahi Glass Co., Ltd.) having a 100 mm square and a thickness of 2.8 mm were prepared as transparent substrates. Then, an SnO ₂ thin film layer having a thickness of 200 nm was formed on each surface by an ion plating method.
Here, the SnO ₂ thin film layer was formed by changing the oxygen partial pressure during film formation in the ion plating method to 7 levels to obtain seven transparent (glass) substrates with SnO ₂ thin film layers. Incidentally, SnO ₂ was used sintered body as deposition material. The glass substrate was not heated during film formation.
The specific resistance of the seven types of transparent substrates with SnO ₂ thin film layers thus formed was measured. The measurement method is the van der Pauw 4-terminal method.
The results are shown in Table 1 and FIG. 1 (triangular plot in the figure). In this case, when the oxygen partial pressure (PO ₂ ) is around 2.5 × 10 ⁻³ Pa, the specific resistance is minimum and the carrier concentration is maximum.

Next, each of the transparent substrates with SnO ₂ thin film layers was heat-treated in the atmosphere at 550 ° C. for 30 minutes. Then, it was measured in the same manner the specific resistance of the thin film of SnO ₂ layer-carrying transparent substrate of each after the heat treatment. Further, similarly, heat treatment was performed at 600 ° C. for 30 minutes.
These results are shown in Table 1 and FIG. In FIG. 1, the triangular plot is the specific resistance before the heat treatment, the black circle plot is the specific resistance after the heat treatment at 550 ° C., and the double circle plot is the specific resistance after the heat treatment at 600 ° C.
From the comparison with the triangular plot in the figure, the resistance value of the tin oxide thin film layer increases when the oxygen partial pressure (PO ₂ ) is 2.5 × 10 ⁻³ Pa or higher in both cases of 550 ° C. and 600 ° C. heat treatment, and lower than that. It can be seen that the resistance value decreases at the oxygen partial pressure (PO ₂ ). However, in any case, the resistance value is not a sufficiently low value (can withstand practical use).

<Example 1>
Next, among the glass substrates having seven types of SnO ₂ thin film layers obtained by the same method as described above, the one having the highest carrier concentration (oxygen partial pressure (PO ₂ ) of 2.5 × 10 ⁻³ Pa) On the SnO ₂ thin film layer, a SiO ₂ thin film layer was further formed to obtain a SnO ₂ thin film layer and a transparent substrate with a SiO ₂ thin film layer. Here, the formation method of the SiO ₂ thin film layer was the same ion plating method as that of the SnO ₂ thin film layer, and the thickness of this layer was 100 nm.
And it heat-processed by the method similar to the above after that, and measured the specific resistance by the same method.
The results are shown in Table 1 and FIG. 1 (x plots in the figure).
Thus, even when compared with the lowest resistance before the heat treatment, the resistivity decreased to a sufficiently low specific resistance of 6.6 × 10 ⁻³ Ω · cm.

<Comparative example 2>
A transparent substrate with a SnO ₂ thin film layer was obtained by the same ion plating method as in Comparative Example 1, with the oxygen partial pressure being 2.6 × 10 ⁻³ (Pa).
And when this specific resistance was measured by the same method as Comparative Example 1, it was 2.0 × 10 ⁻² (Ω · cm).
Next, the temperature of 550 ° C. in the heat treatment of Comparative Example 1 was set to 250 ° C., and the others were treated in the same manner. And when this specific resistance was measured by the method similar to the comparative example 1, it was 5.32 * 10 < ^-3 > (ohm * cm).

<Example 2>
Further, in the heat treatment of Example 1, the temperature set to 550 ° C. was set to 250 ° C., and the other processes were performed in the same manner. And when this specific resistance was measured by the method similar to the comparative example 1, it was 3.31 * 10 < ^-3 > (ohm * cm).
Thus, even when the heat treatment temperature is 250 ° C., it has been found that the configuration in which the transparent conductive film layer and the SiO ₂ thin film layer are laminated is effective for reducing the specific resistance by the heat treatment. .

<Example 3>
The transparent substrate with the SnO ₂ thin film layer and the SiO ₂ thin film layer obtained in Example 1 is irradiated with laser light through a projection mask having a T-shaped pattern used for the transparent electrode of the PDP. An electrode pattern in which a number of T-shaped patterns used are arranged can be formed.
For example, Nd: YAG laser, SL401 laser (oscillation wavelength: 1064 nm) manufactured by Spectron is used as the light source, the pulse width of the irradiation laser is 84 ns, and the irradiation energy is 11 J / cm ² . The basic configuration of the laser is shown in FIG. The laser irradiated from the oscillator 1 is directly irradiated on the sample 7 through the beam shaper 2, the homogenizer 3, the projection mask 4, the mirror 5, and the projection lens 6. Here, except for a part of the projection mask 4, a T-shape that can be used to evaluate a processed shape and is used in a plasma display is used. As a result, a good T-shaped pattern shape is formed, and sufficient insulation between the electrode arrays can be obtained as an electrode for PDP.

<Example 4>
After forming a Cr / Cu / Cr pattern electrode on the upper surface of the glass substrate, a transparent substrate with a SnO ₂ thin film layer and a SiO ₂ thin film layer was formed in the same manner as in Example 1, and the same as in Example 3 Laser patterning was performed by the method, and further, printing and baking were performed to form a dielectric layer.
Specifically, for the Cr / Cu / Cr pattern electrode, a laminated film composed of a Cr layer having a thickness of 100 nm, a Cu layer having a thickness of 3000 nm, and a Cr layer having a thickness of 100 nm was formed on the upper surface of the glass substrate by sputtering. Thereafter, a bus electrode pattern is formed by a lift-off method.
The dielectric layer has a softening point of 480 ° C. and a glass transition point of 420 ° C., in terms of oxide, 12 mol% of SiO ₂ , 40 mol% of B ₂ O ₃ , 41.5 mol% of PbO, 6 mol% of ZnO, SnO ₂ Is mixed with an organic vehicle made of α-terpineol or ethyl cellulose to prepare a glass paste, printed on the upper surface of the SiO ₂ thin film layer, dried, and then in an electric furnace. Baking is performed at 600 ° C. for 30 minutes to form a transparent dielectric layer having a thickness of about 30 μm.

  Through the above steps, the transparent electrode and the bus electrode are transparent with a Cr / Cu / Cr bus electrode pattern without causing corrosion or the like, and without deteriorating the conductivity and inter-electrode insulation of the transparent electrode and the bus electrode. An electrode substrate is obtained.

FIG. 1 is a diagram showing a change in resistance of an example of the present invention and a comparative example. FIG. 2 is a schematic diagram of lift-off patterning used in the present invention. FIG. 3 is a schematic diagram of laser patterning used in the present invention. FIG. 4 is a schematic view of a laser patterning apparatus used in the present invention. FIG. 5 is a schematic diagram showing a schematic configuration of a conventional PDP.

Explanation of symbols

1 Oscillator 2 Beam Shaper 3 Homogenizer 4 Projection Mask 5 Mirror 6 Projection Lens 7 Sample 10 Transparent Substrate 21 Bus Electrode 22 Resist 23 Transparent Conductive Film Layer 24 SiO ₂ Thin Film Layer 25 Dielectric Layer 26 Laser Light 61 Front Substrate 62 Rear Substrate 63 Partition 64 Black stripe 65 Display electrode 66 Bus electrode 67 Address electrode 68 Dielectric layer 69 MgO protective layer 70 Phosphor layer 71 Dielectric layer

Claims (12)

Has a thin film of SnO ₂ layer on the upper surface of the transparent substrate, have a Si compound thin layer on the upper surface thereof,
A transparent substrate with a thin film for electronic circuits, wherein a heat treatment at 250 ° C. or higher is performed after the formation of the Si compound thin film layer .   The transparent substrate with a thin film according to claim 1, further comprising a dielectric layer on an upper surface of the Si compound thin film layer. The transparent substrate with a thin film according to claim 1, further comprising a patterned electrode layer between the transparent substrate and the SnO ₂ thin film layer , or between the SnO ₂ thin film layer and the Si compound thin film layer. . The Si compound thin film layer is a thin film with a transparent substrate according to any one of claims 1 to 3 is a thin film layer mainly composed of SiO _2. The transparent substrate with a thin film according to any one of claims 1 to 4, wherein the SnO ₂ A thin film layer alone or the SnO ₂ A transparent substrate with a pattern for an electronic circuit, wherein the thin film layer and the Si compound thin film layer are subjected to a patterning process by a laser patterning method or a lift-off method. An electronic circuit comprising the transparent substrate with a thin film according to claim 1 or the transparent substrate with a pattern according to claim 5. The plasma display front substrate which uses the transparent substrate with a thin film in any one of Claims 1-4, or the transparent substrate with a pattern of Claim 5. A plasma display panel using the plasma display front substrate according to claim 7. SnO on top of transparent substrate ₂ A thin film layer is formed, an Si compound thin film layer is formed on the upper surface,
Then, the manufacturing method of the transparent substrate with the thin film for electronic circuits characterized by heat-processing above 250 degreeC. SnO on top of transparent substrate ₂ Forming a thin film layer,
SnO ₂ The thin film layer is patterned by a laser patterning method or a lift-off method,
Patterned SnO ₂ A Si compound thin film layer is formed on the upper surface of the thin film layer,
Then, the manufacturing method of the transparent substrate with a pattern for electronic circuits characterized by heat-processing above 250 degreeC. SnO on top of transparent substrate ₂ A thin film layer is formed, an Si compound thin film layer is formed on the upper surface,
SnO ₂ The thin film layer and the Si compound thin film layer are patterned by a laser patterning method or a lift-off method,
Then, the manufacturing method of the transparent substrate with a pattern for electronic circuits characterized by heat-processing above 250 degreeC. A plasma display front substrate manufactured by the manufacturing method according to claim 9 .

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