JP2000256061A - Transparent conductive material, transparent conductive glass and transparent conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive material which can be manufactured at low cost, has excellent conductivity and transparency, and has excellent etching processability of a transparent conductive film when formed, and a film formed therefrom. To provide a sputtering target, a transparent conductive glass and a transparent conductive film having the transparent conductive film. Kind Code: A1 Abstract: Tin / indium oxide / zinc oxide has a metal atomic ratio of Sn / (Sn + In + Zn) = 0.250 to 0.475 In / (Sn + In + Zn) = 0.025 to 0.550 Zn / (Sn + In + Zn) = 0.025 to 0.575, and indium oxide and zinc oxide are composed of In ₂
O ₃ (ZnO) _m [wherein m represents an integer of 2 to 20]
A transparent conductive material comprising a composition containing tin oxide and zinc oxide in the form of a spinel structure compound represented by Zn ₂ SnO ₄ , which is contained in the form of a hexagonal layered compound represented by
A transparent conductive glass and a transparent conductive film having a sputtering target made of the material, and a transparent conductive film formed using the target.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transparent conductive material having high utility as a material of a transparent conductive film for a display device, a sputtering target for the transparent conductive film, a transparent conductive glass having the transparent conductive film, and a transparent conductive film. .

[0002]

2. Description of the Related Art In recent years, display devices have been remarkably developed, and liquid crystal display devices, electroluminescence display devices, field emission displays, and the like have been developed for office equipment such as personal computers and word processors, and control systems in factories. Each of these display devices has a sandwich structure in which a display element is sandwiched between transparent conductive films.

As a transparent conductive film used in these display devices, an indium tin oxide film is mainly used. This is because the indium tin oxide film has excellent transparency and conductivity, can be etched by a strong acid, and has excellent adhesion to the substrate. And
This indium tin oxide film is generally formed by a sputtering method, an ion plating method, or an evaporation method. As described above, indium tin oxide has excellent performance as a material for a transparent conductive film, but has a disadvantage that it is expensive because the main material is indium.

Therefore, for example, Japanese Patent Application Laid-Open Nos. 3-50148 and 8-171824 propose a transparent conductive film mainly composed of zinc oxide or tin oxide. However, in the transparent conductive film using zinc oxide as a main material, there is a problem that not only the conductivity is not sufficient, but also sufficient performance is not obtained with respect to wet heat resistance. Further, a transparent conductive film containing tin oxide as a main material has good heat resistance, but is not suitable as a transparent electrode for a high-definition display because sufficient performance in etching processability cannot be obtained. There is a disadvantage.

[0005] Indium tin oxide has excellent performance with respect to the above properties. However, since indium tin oxide itself is a crystalline metal oxide, sputtering is performed using an indium tin oxide target. When forming a film by a method or the like, crystallization of indium tin oxide proceeds,
When the crystal grows, crystal grains are generated on the surface of the transparent conductive film, and there is a problem that the surface accuracy of the film is reduced.

Further, since the indium tin oxide has crystallinity, it is etched from a portion at an interface between crystal grains of the transparent conductive film during etching. Then, there is a problem that the crystal particles are left behind in the etched portion of the transparent conductive film, which causes display failure due to conduction when the display device is used.

[0007]

Under such circumstances, the present invention is inexpensive, has excellent conductivity and transparency,
The purpose of the present invention is to provide a transparent conductive film formed at the time of film formation, a transparent conductive material having excellent surface accuracy and etching processability, a sputtering target used for film formation, a transparent conductive glass having the transparent conductive film, and a transparent conductive film. Is what you do.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventor has found that tin oxide, indium oxide and zinc oxide are contained in specific ratios, and that indium oxide and zinc oxide are contained. The above problem can be solved by using a hexagonal layered compound composed of: and a transparent conductive material composed of a composition contained in the form of a compound having a spinel structure represented by Zn ₂ SnO ₄ composed of tin oxide and zinc oxide. The present invention was completed based on these findings.

That is, the gist of the present invention is as follows. (1) Tin oxide, indium oxide and zinc oxide have a metal atomic ratio of Sn / (Sn + In + Zn) = 0.250 to 0.475 In / (Sn + In + Zn) = 0.025 to 0.550 Zn / (Sn + In + Zn) = 0.025 to 0.575, and In ₂ O ₃ (ZnO) _m [where
m is an integer of 2 to 20], and a transparent conductive material comprising a composition containing a hexagonal layered compound represented by the following formula: and a compound having a spinel structure represented by Zn ₂ SnO ₄ . (2) The metal atom ratio of tin oxide to indium oxide and zinc oxide is: Sn / (Sn + In + Zn) = 0.250 to 0.500 In / (Sn + In + Zn) = 0.0025 to 0.500 Zn / (Sn + In + Zn) = 0 0.25 to 0.500, wherein the transparent conductive material according to the above (1). (3) The metal atomic ratio of tin oxide to indium oxide and zinc oxide is as follows: Sn / (Sn + In + Zn) = 0.275-0.450 In / (Sn + In + Zn) = 0.50-0.450 Zn / (Sn + In + Zn) = 0 The transparent conductive material according to (1), wherein the transparent conductive material has a thickness of 0.050 to 0.450. (4) The metal atom ratio of tin oxide to indium oxide and zinc oxide is: Sn / (Sn + In + Zn) = 0.300 to 0.450 In / (Sn + In + Zn) = 0.500 to 0.400 Zn / (Sn + In + Zn) = 0 The transparent conductive material according to the above (1), wherein the transparent conductive material has a thickness of 0.050 to 0.400. (5) Sn / (Sn + In + Zn) = 0.250-0.475 In / (Sn + In + Zn) = 0.025-0.550 Zn / (Sn + In + Zn) = 0.025 to 0.575. The method for producing a transparent conductive material according to (1), wherein the raw material powder is contained at a temperature of 1400 ° C or higher at a temperature of 1400 ° C or higher. (6) A sputtering target comprising the transparent conductive material according to any one of (1) to (4). (7) The sputtering target according to (6), wherein the relative density of the transparent conductive material is 6.0 or more and the specific resistance is less than 5 mΩ · cm. (8) Tin oxide, indium oxide, and zinc oxide are provided on the surface of the glass substrate at a metal atomic ratio of Sn / (Sn + In + Zn) = 0.250-0.475 In / (Sn + In + Zn) = 0.025-0. 550 Zn / (Sn + In + Zn) = 0.025 to 0.575. A transparent conductive glass having an amorphous transparent conductive film made of a composition. (9) A transparent conductive glass having an amorphous transparent conductive film formed on the surface of a glass substrate using the sputtering target according to (6) or (7). (10) The transparent conductive glass according to (8) or (9), wherein the light transmittance is 80% or more and the specific resistance is less than 1 mΩ · cm. (11) Tin / indium oxide / zinc oxide on the surface of the transparent resin film, Sn / (Sn + In + Zn) = 0.250-0.475 In / (Sn + In + Zn) = 0.025-0 .550 Zn / (Sn + In + Zn) = 0.025 to 0.575 A transparent conductive film having an amorphous transparent conductive film made of a composition. (12) A transparent conductive film having an amorphous transparent conductive film formed on the surface of the transparent resin film using the sputtering target according to (6) or (7). (13) The transparent conductive film according to (11) or (12), wherein the light transmittance is 80% or more and the specific resistance is less than 1 mΩ · cm.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the transparent conductive material of the present invention, tin oxide, indium oxide and zinc oxide have a metal atomic ratio of Sn / (Sn + In + Zn) = 0.250 to 0.475 In / (Sn + In + Zn). = 0.025-0.550 Zn / (Sn + In + Zn) = 0.025-0.575, and In ₂ O ₃ (ZnO) _m [where,
m is an integer of 2 to 20], which is a transparent conductive material comprising a composition containing a hexagonal layered compound represented by the following formula: and a compound having a spinel structure represented by Zn ₂ SnO ₄ .

[0011] With regard to the composition of tin oxide, indium oxide and zinc oxide, which are constituents of this transparent conductive material, when the metal atomic ratio of the tin oxide component is less than 0.250, the wet heat resistance of the transparent conductive material decreases. As a result, the durability of the sputtering target may be reduced, and if the metal atom ratio of the tin oxide component exceeds 0.475, the etching processability is deteriorated, which is not preferable. Also,
As for the indium oxide component, the metal atomic ratio is set to 0.1.
When the value is less than 025, the conductivity of the obtained transparent conductive material is reduced, and when the value exceeds 0.550, the price of the transparent conductive material becomes unpreferably high. Further, for the zinc oxide component, the metal atomic ratio is set to 0.0
When the value is less than 25, the metal oxide in the obtained transparent conductive film may be crystallized to lower the etching processability of the film, and when the value exceeds 0.575,
It is not preferable because the wet heat resistance of the transparent conductive material is reduced. Therefore, the composition ratio of the components in the transparent conductive material of the present invention is appropriately set within the above numerical range to a composition ratio according to the performance required for the use of the transparent conductive glass or the transparent conductive film having the transparent conductive film. Just choose.

The composition ratio of these components is such that the metal atom ratio of tin oxide to indium oxide and zinc oxide is: Sn / (Sn + In + Zn) = 0.250 to 0.500 In / (Sn + In + Zn) = 0.025 to Those having a range of 0.500 Zn / (Sn + In + Zn) = 0.025 to 0.500 are preferable because they exhibit more excellent performance in the transparency and conductivity of the obtained transparent conductive film.

Further, the metal atomic ratio of tin oxide to indium oxide and zinc oxide is as follows: Sn / (Sn + In + Zn) = 0.275-0.450 In / (Sn + In + Zn) = 0.50-0.450 Zn / (Sn + In + Zn) = 0.050 to 0.450 is preferable for the same reason as above, and the metal atom ratio of tin oxide to indium oxide and zinc oxide is: Sn / (Sn + In + Zn) = 0.300 to 0.450 In / (Sn + In + Zn) = 0.500-0.400 Zn / (Sn + In + Zn) = 0.50-0.400 The transparent conductive film obtained is inexpensive, and the transparency and conductivity are obtained. It is particularly preferable because excellent performance can be exhibited.

Next, among these constituents of the transparent conductive material, indium oxide and zinc oxide are composed of In ₂ O ₃ (Zn
O) _m [where m is an integer of 2 to 20] in the form of a hexagonal layered compound represented by the following formula, and tin oxide and zinc oxide are compounds having a spinel structure represented by Zn ₂ SnO ₄ It must be contained in the form. The hexagonal layered compound of indium oxide and zinc oxide in the transparent conductive material of the present invention may be any compound in which the value of m in the above general formula is 2 to 20, and the value of m in the hexagonal layer is 3 to 8. Those which are crystalline layered compounds are preferred. Then, compared to the case where each of these indium oxide and zinc oxide is present as a simple mixture of metal oxides in the transparent conductive material, the inclusion of this hexagonal layered compound in the form of a sputtering made of this material When the target is formed, the density thereof is high and the conductivity is improved, so that the stability when the target is mounted on an RF magnetron sputtering device or a DC magnetron sputtering device to perform sputtering can be increased. Furthermore, since generation of nodules is suppressed during film formation by this sputtering method and generation of foreign substances is also suppressed, a high-quality transparent conductive film suitable for use in a liquid crystal display element or an electroluminescence display element can be obtained with a high yield. be able to.

The tin oxide and zinc oxide in the transparent conductive material of the present invention can be used to increase the density of the sintered body by being present in the form of a compound having a spinel structure represented by Zn ₂ SnO _4. By further improving the conductivity, the stability at the time of performing sputtering can be further increased. Next, in the method for producing the transparent conductive material of the present invention, tin / indium oxide / zinc oxide is used as a raw material in a metal atomic ratio of Sn / (Sn + In + Zn) = 0.250 to 0.475 In / (Sn + In + Zn) = 0.025 to 0.550 Zn / (Sn + In + Zn) = 0.025 to 0.575 A method of sintering the raw material powder at a temperature of 1400 ° C. or more can be used.

The raw material metal oxide used here is mixed with a raw material powder by appropriately selecting a compounding composition according to the use of the transparent conductive film within the range of the above-mentioned metal atomic ratio, and mixing and milling the raw material powder. For example, the mixture is uniformly mixed and pulverized by a wet ball mill, bead mill, ultrasonic wave or the like. The mixing and pulverization of the raw material powder here is preferably as fine as possible, but it is generally desirable that the raw material powder be mixed and pulverized so as to have an average particle diameter of 1 μm or less.

Then, after granulating the obtained fine powder, it may be formed into a desired shape by press molding and sintered by firing. The firing conditions in this case are usually from 1,400 to
The firing may be performed at 1,600 ° C., preferably 1,430 to 1,550 ° C., for 4 to 72 hours, preferably 10 to 48 hours. In this case, the heating rate is 1 to 50 ° C.
/ Min. The sintering temperature here is 1400 ° C
The sintering temperature must be 1400 or more.
When the temperature is lower than 0 ° C., the formation of the above-mentioned hexagonal layered compound from indium oxide and zinc oxide and the formation of Z from tin oxide and zinc oxide
The formation of a compound having a spinel structure represented by n ₂ SnO ₄ is not sufficient, and the effect of improving the density and conductivity of the sintered body may not be obtained.

Then, in order to form a sputtering target from the sintered body obtained here, it is sufficient to cut into a shape suitable for mounting on a sputtering apparatus and mount a mounting jig. The sputtering target thus obtained is composed of each metal oxide component at a metal atomic ratio according to the composition of the raw materials, and indium oxide and zinc oxide of these components are represented by the above general formula. 5. Since the transparent conductive material is contained in the form of a hexagonal layered compound represented by the formula, and tin oxide and zinc oxide are contained in the form of a compound having a spinel structure represented by Zn ₂ SnO ₄ , the relative density is 6. It has high conductivity of 0 or more and high specific resistance of less than 5 mΩ · cm. Therefore, it is excellent in stability when forming a transparent conductive film using this sputtering target.

Next, as a transparent substrate used for forming a transparent conductive film using the sputtering target, a glass substrate conventionally used, a synthetic resin film having high transparency, Sheets are used. As the synthetic resin, a polycarbonate resin, a polymethyl methacrylate resin, a polyester resin, a polyether sulfone resin, a polyarylate resin, and the like are preferable.

When a transparent conductive film is formed on a transparent substrate by a sputtering method using the sputtering target, a magnetron sputtering apparatus is preferably used. As a condition for forming a film by sputtering using this apparatus, the plasma output varies depending on the surface area of the target and the film thickness of the transparent conductive film. Usually, this plasma output is applied per 1 cm ^{2 of} the target surface area. A transparent conductive film having a desired film thickness can be obtained by setting the range of 0.3 to 4 W and setting the film formation time to 5 to 120 minutes. Although the thickness of the transparent conductive film varies depending on the type of the display device, it is usually from 200 to
6,000 angstroms, preferably 300 to 2,
000 angstroms.

The target made of the sintered body is as follows:
It can also be used when forming a film using an electron beam apparatus or an ion plating apparatus. When a film is formed using these apparatuses, a transparent conductive film can be formed under the same film forming conditions as in the case of the above sputtering apparatus. The transparent conductive glass of the present invention obtained in this manner has tin / indium oxide / zinc oxide on the surface of the glass substrate, wherein Sn / (Sn + In + Zn) = 0.250 to 0.475 In / An amorphous transparent conductive film made of a composition having a composition of (Sn + In + Zn) = 0.025 to 0.550 Zn / (Sn + In + Zn) = 0.025 to 0.575 is formed. The transparent conductive glass has a wavelength of 50
The light transmittance for light of 0 nm is 80% or more;
And the specific resistance is less than 1 mΩ · cm.

In the transparent conductive film obtained as described above, tin oxide, indium oxide and zinc oxide have a metal atomic ratio of Sn / (Sn + In + Zn) = 0.250 to 0.475 In on the transparent resin film surface. /(Sn+In+Zn)=0.025 to 0.550 Zn / (Sn + In + Zn) = 0.025 to 0.575 An amorphous transparent conductive film made of a composition having the following composition is formed. Has a light transmittance of 80% or more and a specific resistance of less than 1 mΩ · cm.

Therefore, the transparent conductive glass and the transparent conductive film of the present invention can be suitably used as transparent electrodes of various display devices such as liquid crystal display devices and organic electroluminescence display devices which require high transparency and conductivity. Can be.

[0024]

[Example 1]

(1) Production of transparent conductive material Powders of tin oxide, indium oxide and zinc oxide were used as raw materials, and the atomic ratio of these metals was Sn / (In + Zn + Sn) = 0.45 In / (In + Zn + Sn) = 0.10 Zn / (In + Zn + Sn) = 0.45 and the mixture was supplied to a wet ball mill.
The mixture was pulverized over time to obtain a raw material fine powder.

After granulating the raw material powder obtained here,
It was press-formed into dimensions of 4 inches in diameter and 5 mm in thickness, charged into a firing furnace, and fired at 1400 ° C. for 36 hours to obtain a sintered body made of a transparent conductive material. This sintered body has a density of 6.3 g / cm ³ and a bulk electric resistance measured by a four probe method of 4.9 mΩ · c.
m. Further, as a result of observing the state of the metal oxide in the transparent conductive material by X-ray diffraction for a sample collected from the sintered body, it was found that tin oxide crystals and In ₂ O ₃ (ZnO It was confirmed that a hexagonal layered compound composed of indium oxide and zinc oxide represented by ₃ existed. Further, this observation confirmed that tin oxide and zinc oxide were present as a compound having a spinel structure represented by Zn ₂ SnO ₄ . Table 1 shows the measurement results of the composition and physical properties of the transparent conductive material.

(2) Production of Transparent Conductive Glass The sintered body obtained in the above (1) is cut to a diameter of about 4 mm.
A sputtering target [A] having an inch and a thickness of about 5 mm was produced. Then, this target [A] is changed to D
A transparent conductive film was formed on a glass substrate at room temperature by mounting in a C magnetron sputtering apparatus. The sputtering conditions used here are such that an appropriate amount of oxygen gas is mixed with argon gas and the sputtering pressure is 3 × 10 ^-1 P
a, the ultimate pressure was 5 × 10 ⁻⁴ Pa, the substrate temperature was 25 ° C., the input power was 100 W, and the film formation time was 20 minutes. As a result, a transparent conductive glass having a transparent conductive film with a thickness of 1,200 angstroms was obtained.

(3) Evaluation of Transparent Conductive Glass Regarding the conductivity of the transparent conductive film on the transparent conductive glass obtained in the above (2), the specific resistance of the transparent conductive film was measured by a four-point probe method. .98 mΩ · cm, which was excellent in conductivity. Further, the metal oxide in the transparent conductive film was amorphous, and had excellent smoothness on the film surface. Further, regarding the transparency of this transparent conductive film,
The light transmittance of the light having a wavelength of 500 nm was 81% as measured by a spectrophotometer, and the transparency was excellent.

Next, regarding the etching processability of this transparent conductive film, a part of the transparent conductive film on the transparent conductive glass was etched at 40 ° C. with a 5% by weight oxalic acid aqueous solution, and the etched portion was not etched. As a result of observing the cross section of the boundary part with the electron microscope with the electron microscope, no transparent conductive film remained in the etched part, and the edge of the transparent conductive film remaining in the non-etched part was smooth toward the etched part. It was confirmed that the cross-sectional shape was inclined, and it was found that it had excellent etching workability. Table 2 shows the evaluation results of the transparent conductive glass.

Example 2 (1) Production of Transparent Conductive Material Tin oxide, indium oxide and zinc oxide powders were used as raw materials, and the atomic ratio of these metals was Sn / (In + Zn + Sn) = 0.40 In / ( (In + Zn + Sn) = 0.20 Zn / (In + Zn + Sn) = 0.40, except that the mixture was used as in Example 1, (1). Table 1 shows the measurement results of the composition and physical properties of the obtained transparent conductive material.

(2) Production of transparent conductive glass A sputtering target [B] was prepared in the same manner as in (2) of Example 1, except that the sintered body obtained in (1) was used. A transparent conductive glass was manufactured using this target [B]. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Example 3 (1) Production of Transparent Conductive Material Tin oxide, indium oxide and zinc oxide powders were used as raw materials, and the atomic ratio of these metals was Sn / (In + Zn + Sn) = 0.40 In / ( Inventive Example 1 was the same as (1) except that a mixture of In + Zn + Sn) = 0.30 Zn / (In + Zn + Sn) = 0.30 was used. Table 1 shows the measurement results of the composition and physical properties of the obtained transparent conductive material.

(2) Production of transparent conductive glass A sputtering target [C] was prepared in the same manner as in (2) of Example 1, except that the sintered body obtained in (1) was used. A transparent conductive glass was manufactured using this target [C]. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Example 4 (1) Production of Transparent Conductive Film Using the sputtering target [C] obtained in (2) of Example 3, a polycarbonate resin film was mounted on a sputtering apparatus instead of a glass substrate. Then, a transparent conductive film was produced by sputtering. Table 2 shows the evaluation results of the obtained transparent conductive films.

Example 5 (1) Production of Transparent Conductive Material Tin oxide, indium oxide and zinc oxide powders were used as raw materials, and the atomic ratio of these metals was Sn / (In + Zn + Sn) = 0.40 In / ( Inventive Example 1 was the same as (1) except that a mixture of In + Zn + Sn) = 0.40 Zn / (In + Zn + Sn) = 0.20 was used. Table 1 shows the measurement results of the composition and physical properties of the obtained transparent conductive material.

(2) Production of transparent conductive glass A sputtering target [D] was prepared in the same manner as (2) of Example 1, except that the sintered body obtained in (1) was used. A transparent conductive glass was manufactured using this target [D]. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Example 6 (1) Production of Transparent Conductive Glass Using the sputtering target [D] obtained in (2) of Example 5, the temperature of the glass substrate mounted on the sputtering apparatus was heated to 215 ° C. A transparent conductive glass was manufactured by sputtering in the state as described above. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Example 7 Using the sputtering target [D] obtained in (2) of Example 5, the operations of sputtering and reverse sputtering were continuously repeated for 35 hours. After the end of these sputtering operations, the surface of the finally obtained transparent conductive glass was observed. As a result, no blackening of the film surface or generation of nodules was found.

Example 8 (1) Production of Transparent Conductive Material Tin oxide, indium oxide and zinc oxide powders were used as raw materials, and the atomic ratio of these metals was Sn / (In + Zn + Sn) = 0.30 In / ( Inventive Example 1 was the same as (1) except that a mixture of In + Zn + Sn) = 0.30 Zn / (In + Zn + Sn) = 0.40 was used. Table 1 shows the measurement results of the composition and physical properties of the obtained transparent conductive material. (2) Production of transparent conductive glass Except for using the sintered body obtained in (1) above, a sputtering target [E] was prepared in the same manner as in (2) of Example 1, and this target [ E] was used to produce a transparent conductive glass. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Comparative Example 1 (1) Production of Transparent Conductive Material Example 1 was repeated except that only tin oxide powder was used as a raw material.
A transparent conductive material was obtained in the same manner as (1). Table 1 shows the measurement results of the composition and physical properties of the obtained transparent conductive material.

(2) Production of Transparent Conductive Glass A sputtering target [F] was prepared in the same manner as in (2) of Example 1, except that the sintered body obtained in (1) was used. A transparent conductive glass was manufactured using this target [F]. (3) Evaluation of transparent conductive glass Regarding the conductivity of the transparent conductive film on the transparent conductive glass obtained in the above (2), the specific resistance value is slightly higher at 8.8 mΩ · cm, and the conductivity is slightly inferior. Met. Further, the metal oxide in the transparent conductive film was crystalline, and the surface smoothness of the film was slightly inferior. Further, regarding the transparency, the light transmittance was 78%, which was sufficiently high.

Next, the etching processability of the transparent conductive film was evaluated in the same manner as in Example 1. As a result, the edge of the transparent conductive film remaining in the non-etched portion was uneven at the boundary region with the etched portion. It was confirmed that the cross-sectional shape was large, and it was found that the etching workability was insufficient. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Comparative Example 2 (1) Production of Transparent Conductive Material A transparent conductive material was obtained in the same manner as in (1) of Example 1, except that only zinc oxide powder was used as a raw material. Table 1 shows the measurement results of the composition and physical properties of the obtained transparent conductive material. (2) Production of transparent conductive glass Except for using the sintered body obtained in (1) above, a sputtering target [G] was prepared in the same manner as in (2) of Example 1, and this target [ G] was used to produce a transparent conductive glass. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Comparative Example 3 (1) Production of Transparent Conductive Material Tin oxide and zinc oxide powders were used as raw materials, and the atomic ratio of these metals was Sn / (Sn + Zn) = 0.75 Zn / (Sn + Zn) = A transparent conductive material was obtained in the same manner as in (1) of Example 1, except that a mixture of 0.25 was used. Table 1 shows the measurement results of the composition and physical properties of the obtained transparent conductive material.

(2) Production of transparent conductive glass A sputtering target [H] was prepared in the same manner as in (2) of Example 1, except that the sintered body obtained in (1) was used. A transparent conductive glass was manufactured using this target [H]. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Comparative Example 4 (1) Production of Transparent Conductive Material Tin oxide and indium oxide powders were used as raw materials, and the atomic ratio of these metals was Sn / (Sn + In) = 0.10 In / (Sn + In) = A transparent conductive material was obtained in the same manner as in (1) of Example 1, except that a mixture of 0.90 was used. Table 1 shows the measurement results of the composition and physical properties of the obtained transparent conductive material.

(2) Production of transparent conductive glass A sputtering target [I] was prepared in the same manner as in (2) of Example 1, except that the sintered body obtained in the above (1) was used. A transparent conductive glass was manufactured using this target [I]. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Comparative Example 5 (1) Production of Transparent Conductive Glass Using the sputtering target [I] obtained in (2) of Comparative Example 4, the temperature of a glass substrate mounted on a sputtering device was heated to 215 ° C. A transparent conductive glass was manufactured by sputtering in the state as described above. Table 2 shows the evaluation results of the obtained transparent conductive glasses.

Comparative Example 6 Using the sputtering target [I] obtained in Comparative Example 4 (2), the operations of sputtering and reverse sputtering were continuously repeated for 35 hours. After the end of these sputtering operations, the surface of the finally obtained transparent conductive glass was observed. As a result, blackening had progressed on the film surface, and nodules had been generated.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

The transparent conductive material of the present invention can be manufactured at a low cost because the content ratio of indium oxide is much lower than that of the conventional indium tin oxide, and has excellent conductivity and transparency. I have. Then, a transparent conductive film obtained by forming this on a glass substrate or a transparent resin film has an effect that a surface having good smoothness and excellent etching processability can be obtained.

Claims (13)

[Claims] 1. Tin oxide, indium oxide and zinc oxide have a metal atomic ratio of Sn / (Sn + In + Zn) = 0.250 to 0.475 In / (Sn + In + Zn) = 0.025 to 0.550 Zn / (Sn + In + Zn) = 0.025 to 0.575, and In ₂ O ₃ (ZnO) _m [where,
m is an integer of 2 to 20], and a transparent conductive material comprising a composition containing a hexagonal layered compound represented by the following formula: and a compound having a spinel structure represented by Zn ₂ SnO ₄ . 2. The metal atomic ratio of tin oxide to indium oxide and zinc oxide is as follows: Sn / (Sn + In + Zn) = 0.250 to 0.500 In / (Sn + In + Zn) = 0.025 to 0.500 Zn / (Sn + In + Zn) = 0.025 to 0.500. The transparent conductive material according to claim 1. 3. The metal atomic ratio of tin oxide to indium oxide and zinc oxide is as follows: Sn / (Sn + In + Zn) = 0.275-0.450 In / (Sn + In + Zn) = 0.50-0.450 Zn / (Sn + In + Zn) = 0.050 to 0.450. The transparent conductive material according to claim 1. 4. The metal atom ratio of tin oxide to indium oxide and zinc oxide is as follows: Sn / (Sn + In + Zn) = 0.300 to 0.450 In / (Sn + In + Zn) = 0.500 to 0.400 Zn / (Sn + In + Zn) = 0.050 to 0.400. The transparent conductive material according to claim 1. 5. The method according to claim 5, wherein tin oxide, indium oxide, and zinc oxide are expressed by the following metal atomic ratio: Sn / (Sn + In + Zn) = 0.250 to 0.475 In / (Sn + In + Zn) = 0.025 to 0.550 Zn / The method for producing a transparent conductive material according to claim 1, wherein the raw material powder containing (Sn + In + Zn) = 0.025 to 0.575 is sintered at a temperature of 1400 ° C. or higher. 6. A sputtering target comprising the transparent conductive material according to claim 1. 7. The sputtering target according to claim 6, wherein the relative density of the transparent conductive material is 6.0 or more and the specific resistance is less than 5 mΩ · cm. 8. Tin / indium oxide / zinc oxide on the surface of the glass substrate, wherein Sn / (Sn + In + Zn) = 0.250-0.475 In / (Sn + In + Zn) = 0.025- A transparent conductive glass having an amorphous transparent conductive film made of a composition in which 0.550 Zn / (Sn + In + Zn) = 0.025 to 0.575. 9. A transparent conductive glass having an amorphous transparent conductive film formed on the surface of a glass substrate using the sputtering target according to claim 6 or 7. 10. The transparent conductive glass according to claim 8, which has a light transmittance of 80% or more and a specific resistance of less than 1 mΩ · cm. 11. The transparent resin film has tin oxide, indium oxide, and zinc oxide on the surface thereof in a metal atomic ratio of Sn / (Sn + In + Zn) = 0.250 to 0.475 In / (Sn + In + Zn) = 0.025. The transparent conductive film which has an amorphous transparent conductive film which consists of a composition which is -0.550 Zn / (Sn + In + Zn) = 0.025-0.575. 12. A transparent conductive film having an amorphous transparent conductive film formed on the surface of the transparent resin film using the sputtering target according to claim 6 or 7. 13. The transparent conductive film according to claim 11, which has a light transmittance of 80% or more and a specific resistance of less than 1 mΩ · cm.