JPH0218233B2 - - Google Patents

Description

[Detailed description of the invention]

B. Industrial Application Field The present invention relates to a conductive laminate, and more specifically, to a conductive laminate suitable for use in a display device such as a liquid crystal display device. B. Prior Art Transparent conductive films or transparent conductive laminates are used, for example, as electrodes for liquid crystal displays, electrodes for electroluminescent displays, electrodes for photoconductive photoreceptors, cathode ray tubes, and window portions of various measuring instruments. It is widely used in electrical and electronic fields such as electrostatic shielding layers, antistatic layers, and heating elements. Among these, transparent conductive films having selective light transmittance are used as window materials for collectors for utilizing solar energy or as window materials for buildings due to their infrared light reflecting ability. In addition, with the development of information processing, various solid-state displays using electroluminescence, liquid crystal, plasma, and ferroelectric materials have been developed as display devices to replace cathode ray tubes, and these displays have transparent electrodes. is always used. Furthermore, new electro-optical elements and recording materials that interact with or mutually convert electrical and optical signals are being considered useful for future information processing technology, but these also have transparency and conductivity. A membrane is required. On the other hand, such a transparent conductive layer can also be used as a window glass for preventing condensation in automobiles, airplanes, etc., as an antistatic film for polymers, glass, etc., and as a transparent heat insulating window for preventing the dissipation of solar energy. In particular, in recent years, there has been an increasing demand for high pixel displays in liquid crystal displays, electroluminescent displays, plasma displays, electrochromic displays, fluorescent displays, etc. It has been proposed to form a pixel portion using an electrode and at the same time form a signal application line using a low resistance electrode made of a metal layer in order to improve the display speed of the pixel and the image quality. By the way, in display devices such as liquid crystal displays, patterning of the transparent conductive layer of the conductive laminate is generally done by photo-etching, and in order to remove the photoresist remaining on the conductive laminate, it is immersed in an alkaline solution. There is a step of washing the surface of the conductive laminate with acid after patterning. In these steps, cracks or localized peeling may occur in the transparent conductive layer, which will cause serious defects in the conductive laminate as described below. Although the cause of the above phenomenon is not clearly understood, it is thought that internal stress generated within the transparent conductive layer due to the difference in coefficient of thermal expansion between the substrate and the transparent conductive layer acts. That is, when depositing a transparent conductive layer on a substrate by vapor deposition, the substrate is heated to, for example, 300°C in order to increase the degree of oxidation of the vapor-deposited layer and improve transparency and conductivity.
Heat to the following temperature. Furthermore, the coefficient of thermal expansion of the substrate is 5.5 x 10 ^-5 cm/cm/°C for the widely used polyether sulfone (PES), and 1.5 x 10 ^-5 cm/cm/°C for polyethylene terephthalate (PET).
℃, whereas indium oxide (In ₂ Ox,
x≦3) and that of indium-tin oxide (ITO) is on the order of 10 ^-6 cm/cm/°C, and there is a large difference in thermal expansion coefficient between the substrate and the transparent conductive layer. Therefore, internal stress is generated in the transparent conductive layer at room temperature due to contraction of the substrate, and it is thought that this internal stress causes corrosion to progress in the acid or alkaline solution, causing cracks and localized peeling. . On the other hand, a two-layer transparent conductive film has been proposed in which an indium oxide film is formed on a transparent substrate and then a tin oxide film is formed (Japanese Patent Laid-Open No. 52-22789).
However, when this transparent conductive film is used, for example, as a transparent electrode plate for a liquid crystal display device element, the temperature is set to 500°C or higher to firmly seal the panel using a glass sealing material.
The purpose is to maintain good transparency and conductivity after this heat treatment. In this transparent conductive film, if there are pinholes or cracks in the tin oxide layer, the resistance to the aforementioned acids and alkalis will decrease; side etching will be large due to the difference in solubility between the indium oxide layer and the tin oxide layer. , patterning is difficult; when an indium oxide layer is provided on the substrate side, both acid resistance and alkali resistance are unsatisfactory, and as a result, the transparent conductive film is likely to crack or peel. C. Purpose of the Invention The present invention aims to solve the above-mentioned problems of conventional conductive laminates and to provide a conductive laminate that exhibits sufficient resistance to acids and alkalis. . D. Structure of the Invention That is, in the present invention, there is only one laminated structure in which an intermediate layer and a transparent conductive film are formed on the same side of the substrate in this order on a substrate, and the intermediate layer is inorganic and substantially inorganic. The present invention relates to a conductive laminate characterized in that the transparent conductive layer is essentially amorphous and the transparent conductive layer is crystalline. The above-mentioned "substrate" is a substrate whose coefficient of thermal expansion is clearly different from that of the transparent conductive layer, and its material is a polymeric organic material such as polyethylene terephthalate (PET), polyethylene naphthalate, polyhexane, etc. methylene diamide, poly-
γ-butyroamide, polymethaxylene diamine terephthalamide, aromatic polyester or aromatic polyester carbonate whose main components are bisphenol A and its halides and acid dichloride, copolymers of metaphenylene diamine and isophthalic acid and terephthalic acid. Polyamide, polycarbonate, polypropylene, polyimide, etc.
Polyamide, imidopolybenzimidazole, polyethersulfone (PES), polyetheretherketone, polysulfone, polyetherimide, triacetylcellulose can be used. In addition, it may have a deflection filter function,
If stretching is required during production, both uniaxial and biaxial stretching can be used. A plurality of polymer resins may be laminated or mixed on the surface of the substrate opposite to the surface on which the intermediate layer or transparent conductive layer is formed, or between the substrate and the intermediate layer. For example, it is possible to laminate a vinylidene chloride resin saran coat as a barrier layer to prevent water permeation, and it is also possible to laminate layers with other functions, such as anti-reflection, anti-scratch effects, and gas barrier resins. . For example, when a polyvinylidene chloride material made of Saran Latex (registered trademark) L520 and L511 manufactured by Asahi Kasei Corporation is coated with a wire bar on a polymer film substrate, the effect of preventing water permeation becomes extremely large. The coating conditions include, for example, the substrate is a PET or PES film with a thickness of 100 μm, the Saran latex stock solution (solid content 48%) is diluted 1.0 to 3 times with water, the wire bar wet film thickness is 3 to 60 μm, and the conveyance speed is 100~200m/min, dry hot air of 90~140℃,
The dry thickness of the coating layer may be 1 to 30 μm. The thickness of the base is preferably about 100 μm. Materials for the transparent conductive layer include Au, Pd, Cr, and Ni.
Metal thin films such as SnO ₂ , In ₂ O ₃ , ZnO, TiO ₂ ,
CdO, CdO-SnO ₂ and the above-mentioned ITO are suitable.
Moreover, its thickness is 200~10000Å, especially 200~
1000 Å is preferred. However, in the case of ITO, the tin content is preferably less than 10 atomic %, and in addition to the above components, those containing Cd, Zn, Al, etc. can also be used. The intermediate layer provided between the substrate and the transparent conductive layer is made of amorphous material, and is made of oxidized metal or semimetal such as ITO, tin oxide, silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), etc. Particularly suitable are those containing a substance as a component. The thickness is preferably 70 Å or more, particularly 70 to 300 Å. The deposition can be by reactive vapor deposition or reactive sputtering. FIG. 1 shows a cross-section of a conductive laminate according to the invention, in which an intermediate layer 3 and a transparent conductive layer 4 are successively deposited on a substrate 2. FIG. Between the intermediate layer 3 and the transparent conductive layer 4, there is, for example, an Al ₂ O ₃ layer or a layer made of another inorganic substance for improving light transmittance by optical interference effect.
Alternatively, other intermediate layers such as layers made of polymeric substances (these layers may be crystalline) may be provided. E Example In the following, indium oxide or
An example using ITO will be explained. First, the progress that led to the completion of the present invention will be explained. In all of the tests below, the substrate has a thickness
100μm PES or uniaxial or biaxial stretching
PET is used, and the intermediate layer and transparent conductive layer are formed by reactive vapor deposition (evaporation source In, In-Sn, In ₂ O ₃ , ITO) or reactive sputtering method (target In, In-Sn,
In ₂ O ₃ , ITO). Preliminary Test 1 Regarding a conventional conductive laminate without an intermediate layer, the relationship between the tin content of the transparent conductive layer and the sheet resistance was determined. However, the film formation temperature (substrate temperature during vapor deposition)
The temperature is 10 to 200°C, and the film thickness is 600 Å. The test results are shown in Figure 2. Sheet resistance R is 100Ω/□ for tin content up to 7 atomic%
When this value exceeds 7 atomic%, the sheet resistance gradually increases, and at 10 atomic% it reaches 170Ω/
Reach □. When the tin content exceeds 10 at %, the sheet resistance rapidly increases, making it difficult to control the sheet resistance at a constant level and making it impossible to maintain a low resistance value. Therefore, the tin content of the transparent conductive layer should be 10 atomic % or less, and preferably 7 atomic % or less. Preliminary Test 2 (i) The acid resistance of a conventional conductive laminate without an intermediate layer was investigated from the relationship between the substrate temperature during film formation (film formation temperature) and the change in sheet resistance before and after immersion in acid. The film forming temperature ranges from 10 to 200°C.
However, the transparent conductive layer is made of indium oxide or ITO with a tin content of up to 10 at%, film thickness 500 Å, and acid 0.05N.
Hydrochloric acid, liquid temperature is 20℃, immersion time is 30 minutes. The sheet resistance before acid immersion is R ₀ and the sheet resistance after acid immersion is R, and R/R ₀ ≦2 (R/R ₀ is preferably as close to 1 as possible, and preferably 2.0 or less). The film-forming temperature varied depending on the tin content of the transparent conductive layer, and was as shown in Table 1 below.

[Table] In the table, at.% represents atomic percent (the same applies below). From the same table, in order to make R/R ₀ 2.0 or less,
It can be seen that the higher the tin content of the transparent conductive layer, the higher the film forming temperature needs to be. Furthermore, under the conditions shown in Table 1, R/R ₀ is
Although the value was 2.0 or less, cracks had occurred in the transparent conductive layer after immersion in the acid, and the acid resistance was not satisfactory. Moreover, the transparent conductive layer formed at the required film-forming temperature shown in Table 1 or higher was found to be crystalline by an X-ray diffraction test. Therefore,
In order to achieve at least R/R≦2.0 in terms of acid resistance, it is effective to make the transparent conductive layer crystalline. (ii) When the tin content of the transparent conductive layer was set to 3 at % and the relationship between film formation temperature and alkali resistance was investigated,
The results shown in Table 2 below were obtained. In addition, the alkali resistance is 5% by weight KOH aqueous solution (20℃)
_R0 before immersion and R after immersion when immersed for 10 minutes in
The sheet resistance change R/R ₀ and the surface state change were investigated. In the same table, ○, △, and × indicate the following conditions (the same applies to subsequent tests). 〇: R/R ₀ ≦2.0, neither cracking nor peeling was observed △: R/R ₀ ≦2.0, no cracking or peeling was observed ×: R/R ₀ >2.0, both cracking and peeling occurred

[Table] Note that cracks may occur in terms of acid resistance at film forming temperatures higher than the required film forming temperature (3 atomic % tin; 140°C or higher) shown in Table 1.
R/R ₀ ≦2.0. However, in terms of alkali resistance, the higher the temperature, the more severe the cracks on the surface caused by immersion in alkali, and the more severe the cracks on the surface, which may even cause peeling, and eventually R/R ₀ will exceed 2.0. The reason why cracks occur in the transparent conductive layer during immersion in acid or alkali when the film forming temperature increases is because the internal stress generated in the transparent conductive layer due to the difference in thermal expansion coefficient between the substrate and the transparent conductive layer becomes large. This is thought to be due to the induction of cracks during immersion in acid or alkali. As described above, a conductive laminate in which a transparent conductive layer is directly formed on a substrate has not been able to provide satisfactory acid resistance and alkali resistance. In addition, in Table 2, the transparent conductive layer formed at a film formation temperature of 140°C or higher has crystallinity in the X-ray diffraction test, whereas at a film formation temperature of 80°C or lower, it becomes amorphous as the film formation temperature decreases. Highly qualitative. From the above results, in order to lower R/R ₀ in terms of acid resistance, it is necessary to set the film formation temperature of the transparent conductive layer to a certain temperature or higher (crystalline) depending on the tin content. Increasing the film temperature increases the tendency for cracks to occur in acid resistance and alkali resistance. If the cracks that occur in the transparent conductive layer are minute, the increase in R/R ₀ will be small, but when the transparent conductive layer is patterned into fine patterns (especially when fine wiring is provided) Even minute cracks can cause disconnection, resulting in areas inoperable in liquid crystal displays and other display devices using this conductive laminate. In such cases, even minute cracks are serious defects for the conductive laminate. In view of the above circumstances, it would be extremely advantageous if cracking could be prevented even if the film formation temperature was raised. Preliminary Test 3 Regarding the conductive laminate 1 having the structure shown in Fig. 1, the material of the intermediate layer 3 was amorphous tin oxide, and the relationship between its thickness and the change in sheet resistance R/R ₀ before and after immersion in acid was determined. I asked for it. The film forming temperature is below 200℃, e.g. 100℃
It is ℃. The transparent conductive layer 4 is made of indium oxide or ITO containing 0 to 8 atomic percent of tin, and the film formation temperature is higher than the required film formation temperature shown in Table 1, particularly 100 to 200°C.
(100°C for 0 atomic% tin, 200°C for 6 atomic% tin), and the thickness is 400 Å. R ₀ is 400-600Ω/□, and the light transmittance before acid immersion is 82-75%. Film thickness measurement is 300
Thicknesses of Å or more were determined by Talystep, and thicknesses below that were determined by calculation from the evaporation rate and film formation time (the same applies to subsequent tests). The test results are shown in Figure 3. When the intermediate layer thickness is less than 80 Å, R/
R ₀ increases rapidly. This is the result of a large number of cracks (some of which cause peeling) in the transparent conductive layer due to acid immersion. When the thickness of the intermediate layer is 80 Å, R/R ₀ is 1.4, and as this thickness increases, R/R ₀ becomes smaller, and at 500 Å or more, R/R ₀ becomes 1. middle layer thickness
No cracks were observed in the transparent conductive layer at a thickness of 80 Å or more. When the material of the intermediate layer was ITO containing 10 atomic % of tin, almost the same results as above were obtained. Also, the intermediate layer is amorphous in X-ray diffraction tests, while the transparent conductive layer is crystalline. From the above results, it can be understood that the thickness of the intermediate layer is preferably 80 Å or more and is preferably amorphous, and furthermore, the transparent conductive layer is preferably crystalline. Next, examples of the present invention will be specifically described while comparing them with comparative examples. Acid resistance and alkali resistance tests similar to those described above were conducted on conductive laminates in which intermediate layers with varying tin contents were provided between the substrate and the transparent conductive layer. Using the vapor deposition apparatus shown in Figure 4, a water permeation prevention layer made of vinylidene chloride resin with a thickness of 1 to 30 μm, for example 20 μm, is previously deposited on one side.
An intermediate layer and a transparent conductive layer were sequentially deposited on the surface of a 100 μm PES sheet substrate opposite to the water permeation prevention layer to obtain a transparent conductive laminate. The vapor deposition apparatus is partitioned into chambers 30, 31b, 31a, and 32, and a take-up roll 36 and a supply roll 33 for the sheet substrate 2 are arranged in the chambers 32 and 30 on both sides, and the substrate 2 is sequentially transferred between the two rolls. The following processing is performed while the data is being sent. First, the sheet substrate 2 is conveyed in a meandering manner by five conveyance rollers 26 in the chamber 30, and is preheated by a halogen heater lamp 27 arranged between the sheet substrates 2 to adsorb the sheet substrate 2. Moisture is removed and the material is subjected to electrical discharge treatment in the electrical discharge device 25 to be cleaned. The operating conditions within the chamber 30 are as follows. Heating temperature: 80 ~ 150℃, degree of decompression: 10 ^-4 ~
10 ^-5 Torr, Discharge treatment: Gas used is O ₂ gas, Ar gas or Ar
+ _O2 mixed gas, DC or AC discharge (0~1000W
(0W does not perform discharge treatment.)) Next, the sheet substrate 2 is transported into the chamber 31b,
The evaporation source 42b is maintained at a predetermined temperature in close contact with a constant temperature roller 29 (controllable between -10°C and 250°C).
The intermediate layer is formed by vapor deposition using the vapor generated from the wafer. The thickness of the intermediate layer is detected and controlled by a crystal vibrating film thickness monitor 28. The operating conditions within the chamber 31b are as follows. Evaporation source 42b: Sn, binary evaporation of Sn and In,
ITO containing SnO ₂ or Sn7 atomic % or more Heating method: Electron gun heating (SnO ₂ or ITO) Resistance heating (Sn or binary evaporation of Sn and In) Gas discharge device 37: High frequency discharge (details will be described later) Evaporation rate: 100 to 1000 Å/min Oxygen pressure: 5 x 10 ^-4 to 3.0 x 10 ^-3 Torr High frequency power: 200 to 800 W (13.56 MHz) Substrate holding temperature: 70 to 100°C Next, the sheet substrate 2 is placed in the chamber 31b. It is transported into a chamber 31a having a similar structure, and a transparent conductive layer is formed on the intermediate layer. The operating conditions within the chamber 31a are as follows. Evaporation source 42a: In or ITO with 10 atomic % or less of Sn Heating method: Electron gun heating or resistance heating Discharge device 37: Same as above Evaporation rate: 100 to 2000 Å/min Oxygen pressure: 3 × 10 ^-4 to 3.0 × 10 ^-3 Torr High frequency power: Same as above Substrate holding temperature: 90°C or higher when the evaporation source does not contain Sn, e.g. 130°C, when the evaporation source contains 5 at.% of Sn
180° C. or higher, for example 190° C. Other conditions are the same as in the chamber 31b. Finally, the sheet substrate 2 is transported into the chamber 32,
The sheet resistance monitor 24 measures the sheet resistance between the two conveyance rollers 26, and the sheet resistance is measured between the two conveyance rollers 26.
It is wound up. The details of the high frequency discharge device 37 arranged in the chambers 31b and 31a are as follows. As shown in FIG. 5, the discharge electrode consists of a plurality of rings 45a and 45b arranged to enclose the circumferential surface of the gas (oxygen) introduction tube 43. A water-cooled tube is wrapped around the entire discharge device 37 to cool it, but this water-cooled tube is not shown. One ring-shaped electrode 45a is connected to the lead wire 6
7 to the high frequency introduction terminal 48, and the other ring-shaped electrode 45b is connected to the metal adhesion prevention member 44 by a lead wire 58 and grounded via the metal mounting plate 39. The electrode 45a,
The ring 45b is made of copper, stainless steel, or platinum and has an inner diameter of 2 to 10 cmφ and a width of 0.5 to 10 cm, and generates a C-coupling type (capacitive coupling type) discharge in the introduction tube 43. By wrapping a water-cooled tube around the band ring and cooling it, high-power and high-frequency waves can be introduced for a long period of time. The reactive vapor deposition method using the gas discharge device 37 as described above has the following features (1) to (6) as compared to conventional methods. (1) Since the reaction gas is activated or ionized by applying a high frequency voltage to the discharge device, it is possible to increase the reactivity of the reaction gas and promote the reaction with the vapor deposition material, and at the same time, in the discharge section, the discharge electrode 45 can be provided at a position not in contact with the discharge region 57.
Therefore, the electrode 45 is not bombarded during discharge, and the electrode material does not mix into the gas and contaminate the deposited film. On the other hand, it is conceivable to apply a DC voltage to the discharge device to cause discharge, but in this case it is inappropriate because the electrodes need to be placed in contact with the discharge region. (2) By arranging the discharge electrode 45 around the outer periphery of the introduction tube 43, the gas in the introduction tube 43, which maintains a high gas pressure, can be efficiently ionized or activated without increasing the gas pressure in the vapor deposition space. . Therefore, it is also possible to increase the amount and rate of gas introduction. In addition, the gas pressure in the evaporation space can be lowered, eliminating the need for electric field acceleration of the evaporation material, and the evaporation material can be either a metal or an oxide.
The range of selection is widened, and the material of the substrate to be deposited can be selected from a wide range, and a high-quality deposited film can be formed. Moreover, the selection range of substrate temperature is expanded, and heating and cooling of the substrate can be easily performed. (3) The gas discharge area is limited to the inlet tube 43, and the electrode 4
Since the electrode 45 is isolated from the electrode 45, it is possible to prevent the electrode 45 from being bombarded by gas ions generated during discharge. In other words, it is possible to prevent the electrode material from being heated or evaporated by bombardment, thereby preventing contamination of the deposition space. (4) Since the adhesion prevention members 44 and 46 are provided so as to enclose the introduction tube 43 and the electrode 45, it is possible to prevent evaporated substances from adhering to the introduction tube 43, the electrode 45, and the high frequency introduction terminal 48, and also to prevent the attachment of evaporated substances to the introduction tube 43, the electrode 45, and the high frequency introduction terminal 48. Electrode 4
5. Leakage of high frequency waves through the introduction tube 43 can also be effectively prevented, allowing stable discharge. (5) Since the gas discharge device 37 can be installed in the bell gear with a simple structure via an installation stand, installation or removal work becomes easy. However, when forming a film on a large-area substrate, uniform film formation becomes possible by adjusting and optimizing the installation position and number of the substrates. For example, a discharge device can be set at an appropriate position, or a plurality of discharge devices can be set for uniform film formation. (6) Since the direction of the gas discharge port can be easily changed, it can be set so that the discharge is not disturbed even when the evaporation rate changes. In particular, if the gas discharge device is installed so that the gas discharge port is not directed between the evaporation source and the substrate, the discharge can be maintained stably and the quality of the deposited film can be made uniform. (7) By cooling the mount, the discharge electrode 45, and the adhesion prevention member 44 with water, heating during discharge can be prevented, high-power radio frequency waves can be introduced, and reactive vapor deposition can be promoted. In this way, as shown in FIG. 6, an intermediate layer 3 and a transparent conductive layer 4 are sequentially formed on one surface of the substrate 2.
A transparent conductive laminate having a water permeation prevention layer 5 formed on the other surface was obtained. The sheet resistance, light transmittance, and acid resistance and alkali resistance of the obtained transparent conductive laminate were evaluated in the same manner as in Tests 5 and 6 under the operating conditions in the chambers 31b and 31a described above. Ivy. Examples of the results are shown in Table 3 below. In the same table, Ts is the substrate holding temperature.

【table】

[Table] Among these conductive laminates, the conductive laminates with excellent acid resistance and alkali resistance are No. 1, 3, 5, 8,
9, 12, 13, 15, 16, and 17, the tin content of the intermediate layer is 7 at% or more, and the results of X-ray diffraction tests with these intermediate layers formed are as follows: It was confirmed that the intermediate layer was amorphous. Other intermediate layers of the conductive laminate were crystalline or contained crystalline materials. Also, No. 1, 3, 5, 8, 9,
Transparent conductive layers Nos. 12, 13, 15, 16, and 17 were crystalline or partially contained crystalline materials. Note that if the intermediate layer having the same composition as Nos. 1, 5, 9, 13, and 15 is formed at a temperature higher than the film forming temperature listed in Table 3, the intermediate layer may contain crystalline material. In the conductive laminate on which a transparent conductive layer was formed, cracks and peeling were observed in the transparent conductive layer when immersed in acid or alkali. Also, the above No.
The same result was obtained when the tin content of the intermediate layer was lower than the above at film forming temperatures of 1, 5, 9, 13, and 15. From the above results, the higher the tin content in the intermediate layer, the more
Furthermore, it can be seen that the lower the film formation temperature of the intermediate layer, the more likely the intermediate layer becomes amorphous, and the more the acid resistance and alkali resistance of the conductive laminate are improved. This is considered to be due to the following reasons. (1) The lower the film formation temperature, the more likely the deposited layer will lose heat to the substrate during deposition and be rapidly cooled, becoming amorphous. (2) The higher the tin content of the ITO deposited layer, the more likely it is to become amorphous. (3) Therefore, the higher the tin content of the ITO vapor deposited layer, the higher the upper limit of the film formation temperature at which it can become amorphous. The intermediate layer is made of silicon oxide (SiO ₂ ) or aluminum oxide (Al ₂ O ₃ ), and the film formation temperature is 150°C or lower for the former and 170°C or lower for the latter, and the amorphous intermediate layer is formed by reactive vapor deposition or reactive sputtering. A conductive laminate in which a transparent conductive layer was formed on the conductive layer also exhibited excellent acid resistance and alkali resistance similar to the above examples. Examples of the intermediate layer formed of Al ₂ O ₃ (reactive vapor deposition) are shown in Table 4 below.

[Table] Next, an example of an experiment using a metal thin film as a transparent conductive layer is shown in Table 5 below.

[Table] FIG. 7 shows an example of a liquid crystal display formed by pattern-etching the transparent conductive layer and intermediate layer of the conductive laminate according to the present invention into a predetermined pattern. A transparent conductive laminate 1 is formed by sequentially laminating a patterned intermediate layer 3 and a transparent conductive layer 4 on a transparent substrate 2, with the transparent conductive layers 4 facing each other,
A liquid crystal display 9 is constructed in a sandwich-like configuration with a liquid crystal 6 sandwiched therebetween via an alignment film 7.
A water permeation prevention layer 5 and a deflection film 8 are provided on both sides of the transparent substrate 2.
are deposited sequentially. The conductive laminate according to the present invention is suitable for use not only in liquid crystal displays but also in various display devices such as electroluminescent displays, electrochromic displays, and fluorescent displays. F. Effects of the Invention As explained above, the conductive laminate according to the present invention has a structure in which a substantially amorphous intermediate layer is provided between the substrate and the crystalline transparent conductive layer. Therefore, the internal stress generated within the transparent conductive layer due to the difference in thermal expansion coefficient between the substrate and the transparent conductive layer is alleviated by the presence of the intermediate layer. As a result, it has a high resistance to acids and alkalis.For example, when used in liquid crystal displays, alkaline cleaning is required to remove resist during patterning post-processing, or acid is used to clean the surface of the transparent conductive layer. However, there is no cracking or peeling on the surface, and it can be used with full reliability.

[Brief explanation of drawings]

The drawings all show examples of the present invention, and FIG. 1 is a cross-sectional view of a conductive laminate, FIG. 2 is a graph showing the relationship between tin content and sheet resistance of a transparent conductive layer, and FIG. Figure 3 is a graph showing the relationship between the film thickness of the amorphous tin oxide intermediate layer and the change in sheet resistance due to acid immersion, Figure 4 is a schematic cross-sectional view of the evaporation equipment used for film formation, and Figure 5 is the evaporation equipment. FIG. 6 is a sectional view of another conductive laminate, and FIG. 7 is a sectional view of a liquid crystal display. In addition, in the symbols shown in the drawings, 1... conductive laminate, 2... base, 3... intermediate layer, 4...
Transparent conductive layer, 5...Water permeation prevention layer, 6...Liquid crystal, 7
... alignment film, 8 ... deflection film, 9 ... liquid crystal display, 29 ... constant temperature roller, 37 ... gas discharge device, 42a, 42b ... evaporation source.

Claims (1)

[Claims] 1.Only one laminated structure is provided on a substrate, in which an intermediate layer and a transparent conductive layer are formed in this order on the same side of the substrate, and the intermediate layer is inorganic and substantially amorphous, and A conductive laminate in which the transparent conductive layer is crystalline.