JPH07335030A - Conductive laminated body - Google Patents

Abstract

PURPOSE:To provide a conductive laminated body excellent in durability in conductivity and light transmittance, and a conductive transparent substrate using the same. CONSTITUTION:A conductive lamination comprises a non-oxide ceramics layer mounted at a predetermined surface of a substrate directly or via an undercoat layer, and a top coat layer composed of transparent conductive oxide laminated on the non-oxide ceramics layer. A conductive transparent substrate comprises a transparent substrate, a non-oxide ceramics layer mounted at a given surface of the transparent substrate directly or via an undercoat layer, and a top coat layer composed of transparent conductive oxide superposed on the non-oxide ceramics layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive laminated body suitable as a transparent conductive material and the like, and a conductive transparent substrate using this conductive laminated body.

[0002]

2. Description of the Related Art A liquid crystal display device can be made lighter and thinner, and has a lower driving voltage, so that it has been actively introduced to OA equipment such as personal computers and word processors. The liquid crystal display device having the above-mentioned advantages is inevitably in the direction of increasing the area, increasing the number of pixels, and increasing the definition, and a high quality liquid crystal display element without display defects is required. ing. The liquid crystal display element has a sandwich structure in which a liquid crystal is sandwiched by two transparent electrodes arranged so as to face each other, and the transparent electrode is one of the important elements for obtaining a high quality liquid crystal display element. . This transparent electrode is produced, for example, by etching a transparent conductive film formed on a transparent substrate with a predetermined etching solution and patterning it into a desired shape.

At present, an ITO (indium tin oxide) film is mainly used as a transparent electrode material. However, the ITO film has drawbacks such that the light transmittance is reduced by reduction with hydrogen plasma or the like, In is easily diffused, moisture resistance and weather resistance are poor, and the resistivity is 3 × 10 ^−4.
Since it is about Ω · cm, it is difficult to meet the needs of future large-area display devices.

As a transparent conductive material having a lower electric resistance than that of the ITO film, a laminate composed of a metal oxide and a metal has been well known. Typical examples are TiO _x and Ag.
(See US Pat. No. 3,962,488), a laminate containing Bi ₂ O ₃ and Au (see Brit).
ish Journal of Applied Physics, Vol.9, PP359-361 (195
8)), a laminated body composed of ITO and Ag (Japanese Patent Application Laid-Open No. Hei 4-
340522). In addition, Japanese Examined Japanese Patent Sho 63-
Japanese Patent No. 13823 (JP-A-58-36448) discloses a laminate comprising a metal oxide such as titanium oxide, zirconium oxide and aluminum oxide and an Ag-Cu alloy, a silicon oxide-titanium oxide composite oxide and Ag. A laminate comprising a -Cu alloy is disclosed.

[0005]

Although the initial conductivity of the above-mentioned laminated body is improved as compared with the ITO film, the electrodes formed from these laminated bodies have metal layer components or alloys with long-term use. As a result of migration of the layer components, the conductivity and light transmittance of the entire electrode decrease over time. It is said that the cause of migration is that the metal layer or alloy layer is oxidized for some reason during long-term use. An object of the present invention is to provide a conductive laminate having excellent durability in terms of conductivity and light transmission, and a conductive transparent substrate using the conductive laminate.

[0006]

The electroconductive laminate of the present invention which achieves the above object comprises a non-oxide ceramic layer provided directly on a predetermined surface of a substrate or via an undercoat layer, and And a topcoat layer made of a transparent conductive oxide provided on the oxide ceramics layer.

Further, the conductive transparent substrate of the present invention which achieves the above object, is a transparent substrate, and a non-oxide ceramic layer provided directly or through an undercoat layer on a predetermined surface of the transparent substrate, And a top coat layer made of a transparent conductive oxide provided on the non-oxide ceramic layer.

The present invention will be described in detail below. First, the conductive laminate of the present invention will be described. As described above, the conductive laminate has the non-oxide ceramic layer provided directly on the predetermined surface of the substrate or through the undercoat layer. . The non-oxide ceramics layer may be made of non-oxide ceramics having conductivity or this non-oxide ceramics containing one or more kinds of metal particles having conductivity. Specific examples of conductive non-oxide ceramics include TiB ₂ and Z.
Boride ceramics such as rB ₂ , TiC, WC, MoC
And the like, nitride ceramics such as TiN and ZrN, and sulfide ceramics such as Ti ₂ S, Ti ₃ S, and TiS ₂ . Specific examples of the conductive metal particles include particles of one kind (single body) or plural kinds (alloys and the like) selected from the group consisting of Au, Ag, Cu, Pt and Al.

The thickness of the non-oxide ceramic layer is 10 to 1
It is preferable to select it appropriately within the range of 000 Å. When the film thickness is less than 10 Å, it is difficult to obtain a conductive laminate having sufficient conductivity. On the other hand, when the film thickness exceeds 1000 angstroms, the light transmittance of the resulting electroconductive laminate is significantly lowered. The preferable thickness of the non-oxide ceramic layer is 10-5.
In the range of 00 Angstroms, especially 10 to 10
It is preferably within the range of 0 angstrom. When the above-mentioned metal particles are contained in the non-oxide ceramic layer, the content thereof is preferably 10 wt% or less. Although it becomes possible to improve the conductivity of the non-oxide ceramic layer by containing the above-mentioned metal particles, when the content of the metal particles exceeds 10 wt%, the light transmittance of the obtained conductive laminate is remarkably high. descend. The preferable content of the metal particles is 8 wt% or less, and particularly preferably 5 wt% or less.

In the electroconductive laminate of the present invention, the top coat layer is provided on the above-mentioned non-oxide ceramic layer. This topcoat layer functions as a protective layer for the non-oxide ceramic layer and as a conductive layer,
The top coat layer is made of a transparent conductive oxide. Specific examples include In ₂ O ₃ , ZnO, SnO ₂ and Ga ₂
A layer having a resistivity of 1 × 10 ² Ω · cm or less made of one or more kinds selected from the group consisting of O ₃ can be mentioned. Those having a resistivity of more than 1 × 10 ² Ω · cm are not preferable because they may lower the conductivity of the laminate.

The thickness of the top coat layer is preferably in the range of 10 to 1000 angstroms. When the film thickness is less than 10 Å, the effect of the non-oxide ceramic layer as a protective layer is substantially lost. On the other hand, if the film thickness exceeds 1000 angstroms, it takes a long time to form the film, resulting in reduced economic efficiency. The preferable film thickness of the top coat layer is in the range of 10 to 500 angstroms, and the particularly preferable film thickness is in the range of 10 to 300 angstroms.

The electrically conductive laminate of the present invention has the above-mentioned non-oxide ceramic layer and the above-mentioned top coat layer, and the non-oxide ceramic layer is directly or undercoated on a predetermined surface of the substrate. It is provided through. The undercoat layer is provided as necessary for the purpose of improving the smoothness of the substrate, improving the adhesion between the substrate and the non-oxide ceramics layer, blocking gas, and the like. ₂ , TiO ₂ , In ₂ O
A layer of a transparent metal oxide composed of one or more kinds selected from the group consisting of ₃ , SnO ₂ , ZnO and Ga ₂ O ₃ and transparent such as epoxy resin, urethane resin, acrylic resin, epoxy acrylate, urethane acrylate Examples thereof include a resin layer or a laminate of the transparent resin layer and the transparent metal oxide layer. The material of the undercoat layer is the material of the substrate, the material of the non-oxide ceramic layer,
It is appropriately selected depending on the intended use of the conductive laminate.

When an undercoat layer is interposed between the substrate and the non-oxide ceramic layer, the thickness of the undercoat layer is preferably in the range of 0.1 to 10 μm. If the film thickness is less than 0.1 μm, it is difficult to improve the smoothness of the substrate, the adhesion between the substrate and the non-oxide ceramic layer, or the gas barrier property. On the other hand, the film thickness is 1
When it exceeds 0 μm, the light transmittance of the electroconductive laminate is remarkably reduced, and it cannot be used as an electroconductive transparent laminate.
A preferable film thickness of the undercoat layer is in the range of 0.1 to 4 μm, and a particularly preferable film thickness is in the range of 0.1 to 2 μm.

The total film thickness of the conductive laminate of the present invention in which the non-oxide ceramic layer and the top coat layer are essential constitutional requirements and the undercoat layer is an optional constitutional requirement is the layer constitution and the conductive laminate. It can be changed as appropriate according to the intended use. When the electroconductive laminate of the present invention is constituted only by the above-mentioned essential constituents, if the film thickness of each layer is within the respective ranges described above, the electroconductivity is set to any value for the film thickness of each layer. Light transmittance that can be used as a transparent material (transmittance of visible light is approximately 70 to 80%, or wavelength 550 nm
It is possible to obtain a conductive laminated body having a light transmittance of 73 to 80%. Further, in the case of being constituted by the above essential constitutional requirements and optional constitutional requirements, by appropriately selecting the film thickness of each layer within the respective ranges described above,
It is possible to easily obtain a light-transmitting conductive laminate that can be used as a conductive transparent material.

The conductive laminate of the present invention is formed on the predetermined surface of the substrate as described above, and the substrate at this time may be a transparent substrate or a non-transparent substrate. Good. When a transparent substrate is used as the substrate and the above-mentioned conductive laminate is formed on a predetermined surface of this transparent substrate,
The conductive transparent substrate of the present invention is obtained. As the transparent substrate at this time, a plate-like material or a film-like material made of transparent glass, quartz, transparent plastic, transparent ceramics or the like can be used.

Here, as specific examples of the transparent glass, soda-lime glass, lead silicate glass, borosilicate glass,
Examples thereof include silicate glass, high silicate glass, non-alkali glass, phosphate glass, alkali silicate glass, quartz glass, aluminoborosilicate glass, barium borosilicate glass, sodium borosilicate glass and the like. Further, specific examples of the transparent plastic include polycarbonate, polyarylate, polyester, polystyrene, polyether sulfone resin, amorphous polyolefin, acrylic resin, polyimide, polyphosphazene, polyether ether ketone, polyamide, polyacetal resin and the like. . Specific examples of the transparent ceramics include sapphire, PLZT, CaF ₂ , MgF ₂ , Zn.
S etc. are mentioned. The material and thickness of the transparent substrate
It is appropriately selected depending on the intended use of the conductive transparent substrate and the transparency required for the conductive transparent substrate.

The conductive laminated body of the present invention is, for example, a sputtering method (eg, RF magnetron sputtering method, DC magnetron sputtering method, etc.), a reactive sputtering method, an ion plating method, a reactive ion plating method on a predetermined surface of a substrate. After forming a non-oxide ceramic layer by a physical vapor deposition method such as a coating method or a cluster ion beam method or a chemical vapor deposition method such as a thermal CVD method or a plasma CVD method, a sputtering method (for example, RF It can be obtained by forming the top coat layer by a physical vapor deposition method such as a magnetron sputtering method, a DC magnetron sputtering method), a reactive sputtering method, an ion plating method, or a reactive ion plating method. The non-oxide ceramic layer containing the conductive metal particles is, for example, a sputtering target mixed with desired metal particles (the composition excluding the metal particles is a non-oxide ceramic layer containing no metal particles). (For example, the RF magnetron sputtering method, D
C magnetron sputtering method). At this time, the atmosphere during sputtering is preferably an inert gas atmosphere.

When an undercoat layer is interposed between the substrate and the non-oxide ceramics layer, the undercoat layer is formed by a sputtering method (eg, RF magnetron sputtering method, DC magnetron sputtering method, etc.), reactive sputtering method, Physical vapor deposition methods such as ion plating method and reactive ion plating method,
It can be formed by a coating method such as a spin coating method. The method for forming the undercoat layer is appropriately selected according to the intended composition of the undercoat layer and the like. When a transparent substrate is used as the substrate, by forming each layer as described above, the conductive laminate of the present invention can be obtained and at the same time the conductive transparent substrate of the present invention.

In the electroconductive laminate of the present invention and the electroconductive transparent substrate of the present invention obtained as described above, even when the electroconductive laminate is molded into an electrode having a desired shape and used for a long period of time, the conductivity of the electrode is reduced. Property and light transmittance decrease little with time. The conductive laminate and the conductive transparent substrate of the present invention having such characteristics are suitable as a transparent electrode material for liquid crystal display devices and the like and an electrode material for solar cells, and also a transparent electrostatic shield and a heat ray reflector. It can also be used as a material for films, transparent surface heating elements, automotive glass antennas, and the like.

[0020]

EXAMPLES Examples of the present invention will be described below. Example 1 First, a boride ceramics layer was formed on one main surface of a transparent glass substrate (# 7059 manufactured by Corning Incorporated) by an RF magnetron sputtering method using TiB ₂ as a sputtering target. At this time, the degree of vacuum during sputtering is 1 × 10 ⁻³ Torr and the atmosphere gas is Ar.
The gas was 100%, the output was 100 W, the substrate temperature was 20 ° C., and the sputtering time was 1 minute. Next, In ₂ O was deposited on the boride ceramics layer by RF magnetron sputtering using a sintered body (In: Zn = 2: 1 (molar ratio)) made of In ₂ O ₃ and ZnO as a sputtering target. _A top coat layer made of _3- ZnO was formed. At this time, the degree of vacuum during sputtering is 1 ×
10 ^-3 Torr, atmosphere gas is a mixed gas of Ar gas and O ₂ gas (O ₂ gas concentration is 0.28%), output is 100 W,
The substrate temperature was 20 ° C. and the sputtering time was 5 minutes.
As described above, the desired laminate was obtained by successively laminating the boride ceramics layer and the top coat layer on one main surface of the transparent glass substrate, and at the same time the intended transparent substrate was obtained.

Regarding the laminate thus obtained,
When the composition analysis of the boride ceramics layer and the top coat layer constituting this was conducted by ICP analysis (inductively coupled plasma emission spectroscopy), the composition of the boride ceramics layer was TiB ₂ , and the proportion of In element in the top coat layer ( Proportion of In element in the total amount of In element and Zn element =
In / (In + Zn). The same applies to the following examples. ) Was 0.7. The resistivity of this top coat layer was 5.8 × 10 ⁻⁴ Ω · cm. Then, when the film thickness of each layer constituting the laminated body was measured by AES (Auger electron spectroscopy) depth profile,
The B ₂ layer had a thickness of 50 Å, and the top coat layer had a thickness of 400 Å.

A patterning width of 1.2 mm was applied to this laminate.
The electrode was etched to have an etching width of 100 μm, and the light transmittance (the transmittance of light having a wavelength of 550 nm with respect to that including a transparent substrate. The same applies to the following Examples and Comparative Examples) and the electrical resistance value of this electrode. It was measured. Further, the above-mentioned electrode was connected to an AC power supply of 30 V via a lead wire, and the light transmittance after continuous energization for 1000 hours (the light transmittance of 550 nm with respect to that including the transparent substrate. The same applies to Examples and Comparative Examples) and the electric resistance value was measured. The results are shown in Table 1.

Examples 2 to 7 A transparent glass substrate (# 7059 manufactured by Corning Incorporated) was formed by the RF magnetron sputtering method under the same conditions as in Example 1.
After forming a TiB ₂ layer on one main surface, RF magnetron sputtering in which the composition of the sputtering target was changed for each example was performed to form a top coat layer having the composition shown in Table 1 on the TiB ₂ layer. Formed. The conditions for forming the top coat layer were the same as in Example 1 except for the composition of the sputtering target and the sputtering time. With respect to each laminated body thus obtained, the film thickness, composition and resistivity of the top coat layer were examined by the same method as in Example 1. Further, each laminate was etched under the same conditions as in Example 1 to form electrodes, and the light transmittance and electric resistance of these electrodes were measured. In addition, each electrode
Connect to the AC power source of V separately via the lead wires, and
The light transmittance and the electric resistance value were measured after the current was continuously applied for 000 hours. The results are shown in Table 1.

Example 8 First, as a sputtering target, In ₂ O ₃ and Z were used.
By a RF magnetron sputtering method using a sintered body (In: Zn = 2: 1 (molar ratio)) made of nO, and made of In ₂ O ₃ —ZnO on one main surface of a polycarbonate film (thickness 100 μm). An undercoat layer was formed. At this time, the degree of vacuum during sputtering is 1 × 10 ⁻³ Torr, the atmosphere gas is a mixed gas of Ar gas and O ₂ gas (O ₂ gas concentration is 0.28%), and the output is 100.
W, the substrate temperature was 20 ° C., and the sputtering time was 5 minutes. Next, a carbide ceramic layer was formed on the undercoat layer by an RF magnetron sputtering method using WC as a sputtering target.
At this time, the degree of vacuum during sputtering is 1 × 10 ⁻³ Tor.
r, atmosphere gas is 100% Ar gas, output is 100W,
The substrate temperature was 20 ° C. and the sputtering time was 1 minute.
Finally, RF magnetron sputtering was performed under the same conditions as the above undercoat layer deposition conditions to form a topcoat layer made of In ₂ O ₃ —ZnO on the carbide ceramic layer. As described above, the undercoat layer, the carbide ceramics layer, and the topcoat layer were sequentially laminated on one main surface of the polycarbonate film to obtain the intended laminate, and at the same time, the intended transparent substrate was obtained.

With respect to the laminated body thus obtained,
When the composition analysis of the undercoat layer, the carbide ceramics layer and the topcoat layer constituting this was carried out by ICP analysis, the composition of the carbide ceramics layer was WC, the ratio of the In element in the undercoat layer and the topcoat layer was In / (In + Zn ) Were both 0.7. The resistivity of the top coat layer is 5.8 × 10 ⁻⁴ Ω · cm.
Met. Then, the film thickness of each layer constituting the laminated body is set to AE
The thicknesses of the undercoat layer and the topcoat layer were both 400 Å and the thickness of the WC layer was 50 Å as measured by the S depth profile. This laminate was etched under the same conditions as in Example 1 to form an electrode, and the light transmittance and electric resistance value of this electrode were measured. Further, this electrode was connected to an AC power source of 30 V via a lead wire, and the light transmittance and the electric resistance value after continuous energization for 1000 hours were measured. The results are shown in Table 1.

Example 9 A polycarbonate film having an epoxy acrylate layer with a film thickness of 20000 angstroms on one side (polycarbonate layer thickness is 100 μm) was used as a transparent substrate, and the film forming conditions for each layer were the same as in Example 8 ₂
O ₃ —ZnO layer, WC layer and top coat layer (In ₂
The O ₃ -ZnO layer) were sequentially stacked on the epoxy acrylate layer. This gives the desired laminate,
At the same time, the desired transparent substrate was obtained. In this laminated body, an undercoat layer is formed by the epoxy acrylate layer and the In ₂ O ₃ —ZnO layer formed on the epoxy acrylate layer.

Regarding the laminated body thus obtained,
When the composition analysis of the In ₂ O ₃ —ZnO layer constituting the undercoat layer and the In ₂ O ₃ —ZnO layer as the topcoat layer was performed by ICP analysis, the ratio of the In element in these layers was In / (In + Zn). Are both 0.7
Met. Moreover, the resistivity of the top coat layer is 5.8 × 1.
It was 0 ⁻⁴ Ω · cm. Then, the film thickness of each layer constituting the laminated body was measured by SEM (scanning electron microscope) cross-sectional observation of the laminated body and AES depth profile. As a result, the thickness of the undercoat layer was 20400 angstroms (of which In ₂ O ₃ The film thickness of the —ZnO layer was 400 Å), the film thickness of the WC layer was 50 Å, and the film thickness of the top coat layer was 400 Å. This laminate was etched under the same conditions as in Example 1 to form an electrode, and the light transmittance and electric resistance value of this electrode were measured. Further, the above electrode was connected to a 30 V AC power source via a lead wire, and the light transmittance and the electric resistance value were measured after continuously energizing for 1000 hours. The results are shown in Table 1.

Example 10 First, In ₂ O ₃ —ZnO was formed on one main surface of a polycarbonate film (thickness: 100 μm) by the RF magnetron sputtering method under the same conditions as the film forming conditions for the undercoat layer in Example 8. An undercoat layer was formed. Next, Ag was deposited on the undercoat layer by RF magnetron sputtering using WC containing 5 wt% of Ag as a sputtering target.
A containing WC layer was formed. At this time, the degree of vacuum during sputtering is 1 × 10 ⁻³ Torr, and the atmosphere gas is Ar gas 100.
%, The output was 100 W, the substrate temperature was 20 ° C., and the sputtering time was 1 minute. Finally, In ₂ O was deposited on the Ag-added WC layer by the RF magnetron sputtering method under the same conditions as those for forming the top coat layer in Example 8.
_A top coat layer made of _3- ZnO was formed. As described above, by sequentially laminating the undercoat layer, the Ag-added WC layer and the topcoat layer on one main surface of the polycarbonate film, the intended laminate was obtained, and at the same time, the intended transparent substrate was obtained. .

With respect to the laminated body thus obtained,
When the composition analysis of the undercoat layer and the topcoat layer constituting this was carried out by ICP analysis, the In element ratio In / (In + Zn) in these layers was both 0.7. The resistivity of the top coat layer is 5.
It was 8 × 10 ⁻⁴ Ω · cm. Then, when the Ag-added WC layer was observed using a TEM (transmission electron microscope), it was confirmed that Ag particles having a particle size of 90 to 100 angstrom were dispersed in the Ag-added WC layer. Further, when the film thickness of each layer constituting the laminate was measured by the AES depth profile, both the undercoat layer and the topcoat layer had a film thickness of 400 Å, and the Ag-added WC layer had a film thickness of 50 Å. This laminate was etched under the same conditions as in Example 1 to form an electrode, and the light transmittance and electric resistance value of this electrode were measured. Further, this electrode was connected to an AC power source of 30 V via a lead wire, and the light transmittance and the electric resistance value after continuous energization for 1000 hours were measured. The results are shown in Table 1.

Example 11 The same polycarbonate film as in Example 9 (having an epoxy acrylate layer on one side) was used as a transparent substrate, and a SiO ₂ layer was formed on the epoxy acrylate layer by the RF magnetron sputtering method. WC layer and topcoat layer on the SiO ₂ layer (in ₂
O ₃ —ZnO layers) were sequentially laminated by the RF magnetron sputtering method under the same conditions as in Example 8. As a result, the intended laminate was obtained, and at the same time, the intended transparent substrate was obtained. In this laminated body, an undercoat layer is formed by the epoxy acrylate layer and the SiO ₂ layer formed on this epoxy acrylate layer. When forming the SiO ₂ layer, SiO ₂ (sintered body density 80%) was used as a sputtering target.
And the vacuum degree during sputtering is 1 × 10 ⁻³ Torr,
The atmosphere gas is a mixed gas of Ar gas and O ₂ gas (O ₂ gas concentration is 0.28%), the output is 100 W, and the substrate temperature is 2
The temperature was 0 ° C. and the sputtering time was 5 minutes.

With respect to the laminated body thus obtained,
When the composition analysis of the In ₂ O ₃ —ZnO layer that is the top coat layer was performed by ICP analysis, the In element ratio In / (In + Zn) in the top coat layer was 0.7.
Met. The resistivity of this top coat layer is 5.8.
It was × 10 ^-4 Ω · cm. Then, the film thickness of each layer constituting the laminate was measured by SEM cross-section observation of the laminate and by AES depth profile. As a result, the thickness of the undercoat layer was 20400 angstroms (of which S
The thickness of the iO ₂ layer was 400 Å, the thickness of the WC layer was 50 Å, and the thickness of the top coat layer was 400 Å. This laminate was etched under the same conditions as in Example 1 to form an electrode, and the light transmittance and electric resistance value of this electrode were measured. In addition, the electrode is 3
It was connected to a 0 V AC power source via a lead wire, and the light transmittance and the electric resistance value were measured after continuously energizing for 1000 hours. The results are shown in Table 1.

Comparative Example 1 First, ITO (Sn;
A transparent glass substrate (# 705 manufactured by Corning Incorporated) by an RF magnetron sputtering method using 5 mol%).
9) An ITO layer was formed on one main surface. At this time, the degree of vacuum during sputtering is 1 × 10 ⁻³ Torr, the atmosphere gas is a mixed gas of Ar gas and O ₂ gas (O ₂ gas concentration is 0.28%), the output is 100 W, and the substrate temperature is 20 ° C. The sputtering time was 3 minutes. Next, an Ag layer was formed on the ITO layer by an RF magnetron sputtering method using Ag as a sputtering target. At this time, the degree of vacuum during sputtering is 1 × 10 ⁻³
Torr, atmosphere gas is 100% Ar gas, output is 50W,
The substrate temperature was 20 ° C. and the sputtering time was 1 minute.
Finally, RF magnetron sputtering was performed under the same conditions as the above ITO layer deposition conditions, and IT was formed on the Ag layer.
An O layer was formed. As described above, the target laminate was obtained by successively stacking the ITO layer, the Ag layer, and the ITO layer on one main surface of the transparent glass substrate, and at the same time, the target transparent substrate was obtained.

When the film thickness of each layer constituting the laminate thus obtained was measured by the AES depth profile, the two ITO layers had a film thickness of 400 Å and the Ag layer had a film thickness of 50 Å. It was Further, this laminated body was etched under the same conditions as in Example 1 to form an electrode, and the light transmittance and electric resistance value of this electrode were measured. Further, the electrode was connected to a 30V AC power source via a lead wire, and the light transmittance and the electric resistance value were measured after continuously energizing for 1000 hours. The results are shown in Table 1.

[0034]

[Table 1]

As can be seen from Table 1, the conductivity of each electrode obtained in Examples 1 to 11 was in the initial stage (1000).
In the stage before continuous energization for a period of time), it is lower than the conductivity of the electrode obtained in Comparative Example 1, but is stable with almost no change from before energization even after continuous energization for 1000 hours,
Moreover, after continuous energization, the conductivity is higher than that of the electrode obtained in Comparative Example 1. Further, the light transmittance of each electrode obtained in Examples 1 to 11 is substantially unchanged before and after continuous energization. From this, it can be seen that each of the laminates obtained in Examples 1 to 11 has excellent durability in terms of conductivity and light transmittance. On the other hand, the conductivity of the electrode obtained in Comparative Example 1 was higher than that of the Example in the initial stage, but was 100%.
After energizing continuously for 0 hours, it greatly decreases.

Reference Example 1 RF using TiB ₂ as a sputtering target
TiB was formed on one main surface of a transparent glass substrate (# 7059 manufactured by Corning Incorporated) by a magnetron sputtering method.
_Two layers were formed. At this time, the degree of vacuum during sputtering was 1 × 10 ⁻³ Torr, the atmosphere gas was 100% Ar gas, the output was 100 W, the substrate temperature was 20 ° C., and the sputtering time was 1 minute. When the film thickness of this TiB ₂ layer was measured by the AES depth profile, it was 50 Å. The TiB ₂ layer was etched under the same conditions as in Example 1 to form an electrode, and the light transmittance and electric resistance value of this electrode were measured. Further, this electrode was connected to an AC power source of 30 V via a lead wire, and the light transmittance and the electric resistance value after continuous energization for 1000 hours were measured. The results are shown in Table 2.

Reference Examples 2 to 4 R was changed by changing the composition of the sputtering target for each reference example.
F magnetron sputtering was performed to form non-oxide ceramic layers having the compositions shown in Table 2 on one main surface of a transparent glass substrate (# 7059 manufactured by Corning Incorporated). The conditions for forming the non-oxide ceramic layer were the same as in Reference Example 1 except for the composition of the sputtering target. The thickness of each non-oxide ceramic layer thus obtained was examined by the same method as in Reference Example 1.
Further, each non-oxide ceramic layer was etched under the same conditions as in Example 1 to form electrodes, and the light transmittance and electric resistance value of these electrodes were measured. Furthermore, each electrode was separately connected to an AC power source of 30 V via a lead wire, and the light transmittance and the electric resistance value were measured after continuously energizing for 1000 hours. The results are shown in Table 2.

[0038]

[Table 2]

As shown in Table 2, Reference Examples 1 to 4
The electroconductivity and the light transmittance of each of the electrodes obtained in 1 above are stable after being continuously energized for 1000 hours, with almost no change from before energization. From this, it is understood that the non-oxide ceramic layers of Reference Examples 1 to 4 are excellent in durability in terms of conductivity and light transmission.

[0040]

As described above, the electroconductive laminate of the present invention and the electroconductive transparent substrate using the electroconductive laminate have excellent durability in terms of electroconductivity and light transmission. Therefore, according to the present invention, it is possible to provide a low electrical resistance transparent conductive material or the like having high stability of conductivity and light transmittance.

Claims (10)

[Claims] 1. A non-oxide ceramic layer provided on a predetermined surface of a substrate directly or through an undercoat layer,
A conductive laminate, comprising a top coat layer made of a transparent conductive oxide provided on the non-oxide ceramic layer. 2. The electrically conductive laminate according to claim 1, wherein the non-oxide ceramic layer is made of boride ceramics, carbide ceramics, nitride ceramics or sulfide ceramics. 3. The non-oxide ceramic layer contains one or more types of metal particles having conductivity, and the metal particles are selected from the group consisting of Au, Ag, Cu, Pt and Al. The electroconductive laminate according to claim 1 or 2, comprising one or more species. 4. The transparent conductive oxide is In ₂ O ₃ , Zn
A transparent conductive oxide layer comprising one or more selected from the group consisting of O, SnO ₂ and Ga ₂ O ₃ , and having a resistivity of 1 × 10 ² Ω · cm or less. The electroconductive laminate according to any one of claims 1 to 3. 5. The conductive laminate according to claim 1, wherein the undercoat layer is made of a transparent metal oxide and / or a transparent resin. 6. A transparent substrate, a non-oxide ceramic layer provided on a predetermined surface of the transparent substrate directly or via an undercoat layer, and a transparent conductive oxide provided on the non-oxide ceramic layer. A conductive transparent substrate comprising a topcoat layer made of a material. 7. The conductive transparent substrate according to claim 6, wherein the non-oxide ceramic layer is made of boride ceramics, carbide ceramics, nitride ceramics or sulfide ceramics. 8. The non-oxide ceramic layer contains one or more kinds of metal particles having conductivity, and the metal particles are selected from the group consisting of Au, Ag, Cu, Pt and Al. The conductive transparent substrate according to claim 6 or 7, comprising one or more species. 9. The transparent conductive oxide is In ₂ O ₃ , Zn
A transparent conductive oxide layer comprising one or more selected from the group consisting of O, SnO ₂ and Ga ₂ O ₃ , and having a resistivity of 1 × 10 ² Ω · cm or less. The conductive transparent substrate according to any one of claims 6 to 8. 10. The conductive transparent substrate according to claim 6, wherein the undercoat layer is made of a transparent metal oxide and / or a transparent resin.