JPH06234522A - Electrically conductive material and its production - Google Patents

Abstract

PURPOSE:To obtain an electrically conductive material made of an oxide containing In and Zn in a specific ratio and excellent in moisture resistance or the like by forming a precipitate from a solution containing an In compound and a Zn compound in a prescribed ratio, separating, firing and reduction treating the precipitate. CONSTITUTION:The solution containing the indium compound (e.g. indium nitrate) and the zinc compound (e.g. zinc nitrate) in a prescribed ratio is prepared. Next, the precipitate is formed by adding a precipitate forming agent (e.g. aqueous ammonia) into the solution. Then, the formed precipitate is subjected to solid-liquid separation and, if necessary, is fired and reduction-treated. As a result, the electrically conductive material mainly containing In and Zn and made of the amorphous oxide in 0.1-0.9 atomic ratio of In/(In+Zn) is obtained. The electrically conductive material containing In, Zn and a third element having positive >=3 valence can be produced by preparing a solution in which a compound of element having positive >=3 valence (e.g. stannic chloride) is dissolved in addition to the indium compound and the zinc compound and treating as the same way.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic agent such as resin or an electrostatic control agent, a surface conductivity imparting agent, a conductive coating material, a sputtering target or a conductive material used for a transparent electrode of a display device. And a manufacturing method thereof.

[0002]

2. Description of the Related Art As transparent, white or light conductive materials, tin oxide added with antimony (ATO),
It is known that tin is added to indium oxide (ITO), aluminum is added to zinc oxide, and the like. These are added to a synthetic resin or the like in the powder state for antistatic or electrostatic control, and are used for adjusting the electric resistance value of the resin. It is also added to conductive paints and the like used to impart surface conductivity (for example, as a primer for electrostatic coating).

Further, a powder is formed into a predetermined shape and sintered to produce a sintered body, and a target material is obtained. A transparent electrode for a display device is formed on a glass or resin substrate by a sputtering method, a vapor deposition method, an ion plating method or the like using the target made of this sintered body.

[0004]

[Problems to be Solved by the Invention] However, IT
O and ATO have a relatively low moisture resistance in the powder state, and have the drawback that the electric resistance value increases due to moisture.
Also, since ITO and ATO powder turn black in the reduced state,
When it is added to a resin, it has a drawback that it is difficult to freely color a resin product. Further, a target made of a sintered body of ITO or ATO is also easily blackened by reduction, so that a change in its characteristics with time becomes a problem.

An object of the present invention is to provide a conductive material which is superior in moisture resistance to ITO and ATO, is less likely to be blackened, and has the same conductivity as ITO and ATO, and a method for producing the same.

[0006]

A conductive material of the present invention which achieves the above object is composed mainly of In and Zn and has an atomic ratio In / In / (In + Zn) of 0.1 to 0.9. Is a conductive material (hereinafter, this conductive material is referred to as a conductive material I). Further, the substantially amorphous oxide contains at least one kind of a third element having a valence of positive trivalence or more, a third element
A conductive material characterized in that the atomic ratio of the elements (total third element / (In + Zn + total third element)) is contained in a range of 20 atomic% or less also achieves the above object (hereinafter, this conductivity Material is called conductive material II).

On the other hand, the method for producing a conductive material according to the present invention, which achieves the above-mentioned object, uses an indium compound and a zinc compound and is formed from one or more solutions containing at least one of these by a precipitation forming agent. A method for producing a conductive material (hereinafter, this method is referred to as Method I), which comprises subjecting the precipitate to solid-liquid separation, and if necessary, firing and reduction treatment to obtain a substantially amorphous oxide. . Further, using at least one compound of an indium compound, a zinc compound and an element having a valence of positive trivalence or more, a precipitate formed by a precipitation forming agent is prepared from one or more solutions containing at least one of these compounds, Solid-liquid separation, firing if necessary,
A method for producing a conductive material, which is characterized in that a reduction treatment is performed to obtain a substantially amorphous oxide, also achieves the above object (hereinafter, this method is referred to as Method II).

The present invention will be described in detail below.

First, the conductive material I of the present invention is mainly composed of In and Zn as described above, and has an In atomic ratio of In / In.
(In + Zn) is a substantially amorphous oxide having a content of 0.1 to 0.9, and is made of a conductive material.

Here, "substantially amorphous" means that when the amount of a substance exhibiting crystallinity is quantified by X-ray diffraction measurement and the remaining amount is an amorphous substance, It refers to a substance containing a fixed amount of an amorphous substance.

More specifically, the substantially amorphous oxide contains 50% by weight or more of the amorphous oxide, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.

In the conductive material I of the present invention, In and Z
The atomic ratio of n (In / (In + Zn)) is 0.1 to 0.9.
Is preferred. The reason is that if it is less than 0.1, the conductivity of the conductive material is low, and if it exceeds 0.9, the moisture resistance and heat resistance of the conductive material are lowered. Atomic ratio (In
/ (In + Zn)) is more preferably 0.5 to 0.9,
0.6 to 0.75 is particularly preferable.

The above atomic ratio of In and Zn can be obtained by adjusting the mixing ratio of the indium compound and the zinc compound during precipitation formation.

The conductive material I of the present invention is ITO or ATO.
It has more excellent moisture resistance than that, is less likely to be blackened by reduction, and has the same conductivity as ITO and ATO, and has the various applications described above (antistatic agent, surface conductivity imparting agent, conductive coating, sputtering target). , Transparent electrodes of display devices, etc.).

The conductive material I can be manufactured by various methods such as a vapor phase method (CVD method) and a solid phase method (physical mixing method), and the liquid phase method is carried out according to the method I of the present invention described later. It is preferable to manufacture by (coprecipitation method).

Next, the conductive material II of the present invention will be described.

This conductive material II is, in addition to In and Zn,
At least one element having a valence of positive trivalence or more,
Atomic ratio of third element (all third element / (In + Zn + all third
Element)) is a substantially amorphous oxide containing 20 atomic% or less. Here, as the element having a valence of positive trivalence or more, Al, Ga (positive trivalence), S
Examples of the element include i, Ge, Sn (positive tetravalent) and Sb (positive pentavalent), and Sn having a large effect of improving conductivity is preferable.

In the conductive material II of the present invention, an element having a valence of positive trivalence or more, such as Sn, Al, G
If the elements a, Sb, Si and Ge are added in an amount of more than 20 atomic%, the conductivity may decrease.

The conductive material II of the present invention is made of ITO or ATO.
Moisture resistance is superior to that of ITO, A
Since it has the same conductivity as TO, it is used for the various applications described above (antistatic agents, surface conductivity imparting agents, conductive coatings, targets for sputtering, transparent electrodes for display devices, etc.).

The conductive material II can also be produced by various methods such as a vapor phase method (CVD method) and a solid phase method (physical mixing method). However, according to the method II of the present invention described later, the solution method ( Coprecipitation method) is preferred.

Next, the method I and the method II of the present invention will be described.

First, in the method I of the present invention, as described above, the indium compound and the zinc compound are used, and the precipitate formed by the precipitation forming agent is subjected to solid-liquid separation from one or more solutions containing at least one of them. Then, if necessary, firing and reduction treatments are performed to obtain a conductive material made of a substantially amorphous oxide.

The indium compound and the zinc compound used as raw materials in Method I may be oxides or compounds that become oxides after firing (oxide precursors). As an indium oxide precursor and a zinc oxide precursor, indium,
Zinc sulfide, sulfate, nitrate, halide (chloride, bromide, etc.), carbonate, organic acid salt (acetate, propionate, naphthenate, etc.), alkoxide (methoxide, ethoxide, etc.), organic metal Examples thereof include complexes (acetylacetonate, etc.).

Of these, nitrates, organic acid salts, alkoxides, and organic metal complexes are preferably used in order to completely decompose heat at low temperature and prevent impurities from remaining.

In Method I, a precipitate is first formed, but the precipitation can be specifically formed by the following method.

First, a solution in which an indium compound and a zinc compound are dissolved, or a solution in which at least an indium compound is dissolved and a solution in which at least a zinc compound is dissolved, and a solution in which a precipitation-forming agent is dissolved are prepared and prepared separately. A precipitate can be formed by adding and mixing the above-mentioned solutions at the same time or sequentially while stirring (if necessary, a solvent may be added).

Further, the solution in which the precipitation forming agent is dissolved may be added to the solution in which the indium compound and the zinc compound are dissolved, and vice versa.

For example, a solution in which an indium compound and a zinc compound are dissolved and a solution in which a precipitation forming agent is dissolved are prepared, and both solutions are simultaneously added and mixed while stirring in a container containing a solvent to form a precipitate. The case will be described in detail below.

First, a solution (hereinafter referred to as solution A) in which the above indium compound and zinc compound are dissolved in a suitable solvent is prepared. The solvent may be appropriately selected depending on the solubility of the indium compound or zinc compound used,
For example, water, alcohol, aprotic polar solvent (DM
SO, NMP, sulfolane, THF, etc. can be used, and alcohols having 1 to 5 carbon atoms (methanol, ethanol, isopropanol, methoxyethanol, ethylene glycol, etc.) are particularly preferable because of low solubility of the formed precipitate. The concentration of each metal in solution A was 0.
01 to 10 mol / liter is preferable. The reason is that if the amount is less than 0.01 mol / liter, the productivity is inferior, and 10
This is because if it exceeds mol / liter, a non-uniform precipitate is formed. Furthermore, in order to accelerate the dissolution of the raw materials, an acid (nitric acid, hydrochloric acid, etc.), acetylacetones, polyhydric alcohol (ethylene glycol, etc.), ethanolamines (monoethanolamine, diethanolamine, etc.) are appropriately added to the solution by various solvents. You may add about 0.01-10 times the metal amount.

In Method I, a solution in which a precipitation forming agent is dissolved (hereinafter referred to as solution B) is also prepared together with the above solution A. As the precipitation forming agent to be dissolved in the solution B, alkali (sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, etc.), organic acid (Formic acid, oxalic acid, citric acid, etc.) is used, but it is preferable to use an organic acid (particularly oxalic acid) in order to avoid mixing of impurities.

The precipitate is converted into a hydroxide, an inorganic acid salt or an organic acid salt by the precipitation forming agent.

As the solvent for dissolving the precipitate forming agent and the solvent put in the container for forming the precipitate, the above-mentioned solvents used for dissolving the raw materials can be used.

The solvents used for the various solutions should be the same in operation, but different solvents may be used.

In Method I, a precipitate is formed by any of the above means, and the temperature at the time of forming the precipitate may be above the melting point of the solvent and below its boiling point. Further, aging may be performed for 1 to 50 hours after formation.

According to method I, the precipitate obtained as described above is then solid-liquid separated and dried. Solid-liquid separation of the precipitate is carried out by a conventional method such as centrifugation or filtration. After the solid-liquid separation, it is desirable to thoroughly wash the filtered material with the solvent used in the solutions A and B or another solvent for the purpose of removing anions, alkali metal ions and the like from the precipitate. Drying after filtration is preferably carried out at 40 to 200 ° C. for 0.1 to 100 hours. At low temperatures, it takes too long to dry, and at high temperatures, particles tend to agglomerate.

According to the method I, the solid-liquid separation and the drying are followed by firing, pulverization and reduction treatment.

The firing is preferably carried out at 200 to 600 ° C. for 1 to 100 hours, depending on the indium compound and zinc compound used. The decomposition of the oxide precursor of indium or zinc into an oxide becomes insufficient at a low temperature for a short time, and the oxide may crystallize at a high temperature for a long time.

The crushing after firing is performed by a ball mill, a roll mill,
The particle size is 0.0 with a jet mill, pearl mill, etc.
It is preferable to carry out until it becomes 1 to 10 μm. The crushing time is usually 1 minute to 500 hours.

The reducing treatment is performed by using a reducing gas (hydrogen, CO
Etc.), vacuum, an atmosphere of an inert gas (nitrogen, argon), etc., preferably at a temperature of 100 to 800 ° C. for 1 minute to 100 hours. At low temperature and short time, reduction is insufficient,
Agglomeration of particles and scattering of components easily occur at high temperature for a long time. This reduction treatment is preferably performed after the firing step or the crushing step.

According to Method I, by carrying out the above-mentioned steps, a conductive material containing In and Zn as main components and consisting of a substantially amorphous oxide can be obtained. The conductive powder I has a higher moisture resistance than ITO and ATO, is less likely to be blackened, and has the same conductivity as ITO and ATO. The volume solid resistance (generally referred to as “powder resistance”) of this powder is, for example, 40 Ω · cm or less.

Next, the method II of the present invention will be described.

As described above, this method II is selected from indium compounds and zinc compounds having elements having a valence of positive trivalence or more (for example, tin compounds, aluminum compounds, gallium compounds, antimony compounds, silicon compounds and germanium compounds). Which differs from the above method I only in that at least one of
Others are the same as in the above method I.

The element having a valence of positive trivalence or more (for example, tin compound, aluminum compound, gallium compound, antimony compound, silicon compound and germanium compound) used in the method II is an oxide or one which becomes an oxide after firing (oxidation). Precursor). As these oxide precursors, each element (for example, Sn, Al,
Ga, Ab, Si and Ge) sulfide, sulfate, nitrate, halide (chloride, bromide, etc.), carbonate, organic acid salt (acetate, propionate, naphthenate, etc.), alkoxide (methoxide) , Ethoxide, etc.), and organometallic complexes (acetylacetonate, etc.).

Of these, nitrates, organic acid salts, alkoxides, and organometallic complexes are preferably used in order to completely decompose thermally at low temperature and prevent impurities from remaining.

The obtained conductive material II is superior in moisture resistance to ITO and ATO, hard to be blackened by reduction, and has the same conductivity as ITO and ATO.

The conductive powder of the present invention can be used as an antistatic resin composition by mixing with various resins.

Resins that can be used include polyethylene,
Polypropylene, polystyrene, vinyl chloride, vinyl acetate, polyvinyl alcohol, vinylidene chloride, AB
Thermoplastic resins such as S resin, polyester, methyl methacrylate, polyurethane, polyamide, polyacetal, polycarbonate, silicon resin, fluororesin; phenol resin, urea resin, melamine resin, xylene resin, furan resin, alkyd resin, epoxy resin, polyimide Thermosetting resins such as resins may be mentioned.

Further, it is preferable to add 1 to 600 parts by weight of the conductive powder to 100 parts by weight of the resin. If the added amount is small, the conductivity becomes insufficient, and if the added amount is large, the physical properties of the resin may be impaired. In order to improve the dispersibility of the conductive powder, the surface of the conductive powder may be treated with a surface treatment agent (silane coupling agent, titanium coupling agent, aluminate coupling agent, etc.).

Various other additives (plasticizer, stabilizer, lubricant, inorganic filler (calcium carbonate, mica, glass, talc, etc.), inorganic fiber (glass fiber, carbon fiber, etc.), whiskers (potassium titanate, oxidation) Zinc whiskers, etc.), surfactants, etc. may be added.

The method for mixing the conductive powder and the resin is 2
It is possible to use an ordinary means such as a method of kneading using a main roll, a three roll or an injection molding machine in a heated state or at room temperature, or a method of mixing a solution in which a resin is dissolved and a powder.

[0051]

EXAMPLES Examples of the present invention will be described below.
First, the method for measuring the physical properties of the substances obtained in the examples will be described.

[Measurement method] (1) Measurement of particle size and composition Particle size is SEM (scanning electron microscope), composition is XMA
(X-ray micro analyzer).

(2) Quantification of Amorphous Oxide Using a powder X-ray diffractometer, "Ceramics characterization technology", published by The Ceramic Society of Japan, 198
The content of the crystalline substance was quantified by the method described on pages 44 to 45 for 7 years. Next, the amount of the amorphous oxide was quantified assuming that the remaining amount was the amorphous oxide.

(3) Measurement of volume solid resistance For volume solid resistance (generally referred to as "powder resistance"), 1 g of a sample is put in a resin cylinder having an inner diameter of 10 mm,
The pressure was applied at 100 kg / cm ² , the resistance was measured with a tester, and the resistance was determined by the following formula.

Volume solid resistance (Ω · cm) = [(total resistance (Ω) × inner area of cylinder (cm ² )] / thickness of sample (cm)

Example 1 First, 118.28 g of indium nitrate and 49.
58 g was dissolved in 1 liter of ion-exchanged water to prepare an aqueous solution in which an indium salt and a zinc salt were dissolved. Also, 78.0 g of ammonia water (concentration 28%) is added to 750 c
It was dissolved in ion-exchanged water of c to prepare an alkaline aqueous solution.

Next, the aqueous solution obtained above and the alkaline aqueous solution were simultaneously added dropwise at room temperature to a container having a volume of 5 liters containing 100 cc of ion-exchanged water with vigorous stirring to react the two solutions. At this time, the dropping rate was adjusted so that the pH of the reaction system was maintained at 9.0. And
After the dropping was completed, the mixture was further stirred for 1 hour. In this way, a precipitate was generated by reacting the aqueous solution with the alkaline aqueous solution, and a slurry was obtained. The metal (In and Zn) concentration in this reaction system was 0.32 mol / liter.

Next, the obtained slurry was thoroughly washed with water and the precipitate was collected by filtration. Then, the precipitate collected by filtration is 12
Dry overnight at 0 ° C.

Thereafter, the dried product obtained was calcined at 600 ° C. for 5 hours, and then the calcined product was put together with alumina balls having a diameter of 2 mm in a polyimide pot having a volume of 80 cc, ethanol was added, and the mixture was pulverized for 2 hours by a planetary ball mill. To obtain a powder.

The powder thus obtained was found to contain 60 wt% of an amorphous part from the result of X-ray diffraction measurement, and the atomic ratio of In to Zn was In / Zn from the result of XMA composition analysis.
It was confirmed that the conductive material I was (In + Zn) = 0.66, and its composition was substantially uniform. Also, S
As a result of EM (scanning electron microscope) observation, it was confirmed that the obtained powder had an average particle diameter of 0.15 μm and had a substantially uniform particle diameter.

The volume solid resistance of the obtained powder is 10
It was 0 Ωcm. And this volume solid resistance is 40
Moisture resistance test under conditions of 90 ° C and 90% RH (relative humidity) 10
Even after 00 hours, it was as low as 105 Ωcm, and it was confirmed that the obtained powder had excellent moisture resistance.

Example 2 First, 59.14 g of indium nitrate and 99.1 of zinc nitrate
6 g was dissolved in 1 liter of ion-exchanged water to prepare an aqueous solution in which an indium salt and a zinc salt were dissolved, and this aqueous solution and an alkaline aqueous solution prepared in the same manner as in Example 1 were treated in the same manner as in Example 1. And reacted to obtain a slurry. The metals (In and Zn) in this reaction system
The concentration was 0.3 mol / liter.

Next, the obtained slurry was thoroughly washed with water and the precipitate was collected by filtration. Then, the precipitate collected by filtration is 12
Dry overnight at 0 ° C.

Thereafter, the obtained dried product was fired at 500 ° C. for 5 hours, and then the fired product was pulverized in the same manner as in Example 1 to obtain a powder.

The powder thus obtained was found to contain 70 wt% of an amorphous portion from the result of X-ray diffraction measurement, and the atomic ratio of In to Zn was In / Zn from the result of XMA composition analysis.
It was confirmed that the conductive material I was (In + Zn) = 0.33, and its composition was substantially uniform. Also, S
As a result of EM observation, the obtained powder had an average particle size of 0.23.
It was confirmed that the particle size was substantially uniform at μm.

The volume solid resistance of the obtained powder is 55.
It was 0 Ωcm. And this volume solid resistance is 40
Even after 1000 hours of humidity resistance test under conditions of ° C and 90% RH, it was as low as 560 Ωcm, and it was confirmed that the obtained powder has excellent humidity resistance.

Example 3 Similar to Example 1, an aqueous solution prepared by dissolving metal salts of indium and zinc was prepared in the same manner as in Example 1, and then 7.7 g of stannic chloride was added, and the same solution as in Example 1. The alkaline aqueous solution prepared as described above was reacted in the same manner as in Example 1 to obtain a slurry.

Next, the obtained slurry was thoroughly washed with water and the precipitate was collected by filtration. Then, the precipitate collected by filtration is 12
After drying at 0 ° C, it was baked at 600 ° C for 5 hours. It was put in a polyimide pot having a volume of 80 cc together with a ball mill, ethanol was added, and the mixture was pulverized for 2 hours in a planetary ball mill.

Thereafter, the obtained fired product was pulverized in the same manner as in Example 1 to obtain a powder. From the result of X-ray diffraction measurement, it was found that the powder thus obtained contains 60 wt% of an amorphous part. Moreover, from the composition analysis, In and Zn
The atomic ratio [In / (In + Zn)] = 0.63,
It was found to contain 6 atomic% of Sn. The volume solid resistance of the powder was 90 Ωcm. And this volume solid resistance is measured by the humidity resistance test 1000 under the conditions of 40 ° C. and 90% RH.
Even after the lapse of time, it was as low as 100 Ωcm, and it was confirmed that the obtained powder had excellent moisture resistance.

Example 4 First, 682 g of indium nitrate hexahydrate and 248 g of zinc nitrate hexahydrate were dissolved in 5 liters of ethanol to prepare a solution in which an indium salt and a zinc salt were dissolved. Further, 462 g of oxalic acid dihydrate was dissolved in 5 liters of ethanol to prepare an oxalic acid aqueous solution.

At room temperature, 1 liter of ethanol was separately placed in a separate container and well stirred, and two kinds of solutions controlled to the same flow rate were simultaneously added dropwise thereto. After the dropping is completed, the temperature is set to 40.
The temperature was raised to ℃ and aged for 4 hours. Then, it was filtered, washed well with ethanol, and dried at 110 ° C. for 12 hours. Furthermore, it baked at 300 degreeC for 2 hours.

After crushing with a ball mill (20 hours), the powder was subjected to reduction treatment in vacuum at 200 ° C. for 2 hours to obtain a pale yellow powder.

The powder thus obtained was subjected to X-ray diffraction measurement in the same manner as in Example 1. As a result, 90
%, And it was confirmed to be substantially amorphous. From the composition analysis, the atomic ratio of In and Zn [In / (In +
Zn)] = 0.67. Further, the volume solid resistance of the powder was measured and found to be 5 Ωcm. The volume solid resistance was 6 Ωcm even after 1000 hours of the humidity resistance test under the conditions of 60 ° C. and 95% RH, and it was found that there was almost no change and the humidity resistance was excellent. Also, S
EM and XMA analysis showed that the powder had an average particle size of 0.20
It was found to have a uniform composition in μm.

Example 5 First, 623 g of indium chloride tetrahydrate and 82 g of zinc acetate dihydrate were dissolved in 1 liter of methoxyethanol to prepare a solution in which an indium salt and a zinc salt were dissolved. Further, 494 g of oxalic acid dihydrate was dissolved in 5 liters of methoxyethanol to prepare an oxalic acid aqueous solution.

Powders were prepared in the same manner as in Example 4 using these solutions. However, the firing temperature was 350 ° C. This powder was also pale yellow.

When the X-ray diffraction measurement of the powder was carried out in the same manner as in Example 1, it was confirmed that the amorphous portion was 80% and was substantially amorphous. Moreover, from the composition analysis, In and Z
The atomic ratio of n was [In / (In + Zn)] = 0.85. Furthermore, when the volume solid resistance of the powder was measured, it was 4Ω.
It was cm. And this volume solid resistance is 60 ° C,
Moisture resistance test under conditions of 95% RH 6 after 1000 hours
It was found to be excellent in moisture resistance, with almost no change.

Further, by SEM and XMA analysis, it was found that this powder had an average particle size of 0.15 μm and a uniform composition.

Example 6 First, a solution in which 682 g of indium nitrate hexahydrate, 248 g of zinc nitrate hexahydrate and 108 g of nasem tin were dissolved in 5 liters of isopropanol to dissolve indium salt, zinc salt and tin salt Was prepared. Also, 532 g of oxalic acid dihydrate was dissolved in 5 liters of ethanol to prepare an oxalic acid aqueous solution.

Powders were prepared in the same manner as in Example 4 using these solutions. This powder was also pale yellow.

When X-ray diffraction measurement of the powder was carried out, it was confirmed that the amorphous portion was 90% and was substantially amorphous. From the composition analysis, the atomic ratio of In and Zn [I
n / (In + Zn)] = 0.67, and the tin content was 9 atom%.

Further, the volume solid resistance of the powder was measured and found to be 4 Ωcm. And this volume solid resistance is
It was found that even after 1000 hours of humidity resistance test under conditions of 60 ° C. and 95% RH, it was 6 Ωcm, and there was almost no change, and the humidity resistance was excellent. Further, it was found by SEM and XMA analysis that this powder had a uniform composition with an average particle size of 0.17 μm.

Example 7 First, 613 g of indium nitrate hexahydrate and 298 g of zinc nitrate hexahydrate were dissolved in 5 liters of butanol to prepare a solution in which an indium salt and a zinc salt were dissolved. Further, 451 g of oxalic acid dihydrate was dissolved in 5 liters of butanol to prepare an oxalic acid aqueous solution.

Powders were prepared in the same manner as in Example 5 using these solutions. This powder was also pale yellow.

When X-ray diffraction measurement of the powder was carried out, it was confirmed that the amorphous portion was 80% and was substantially amorphous. From the composition analysis, the atomic ratio of In and Zn [I
n / (In + Zn)] = 0.60.

Further, the volume solid resistance of the powder was measured and found to be 20 Ωcm. And this volume solid resistance is measured by the humidity resistance test 1000 under the conditions of 60 ° C. and 95% RH.
It was 22 Ωcm even after the lapse of time, and it was found that there was almost no change and the moisture resistance was excellent.

Further, by SEM and XMA analysis, it was found that this powder had an average particle size of 0.19 μm and a uniform composition.

Example 8 First, 102 g of indium acetate hexahydrate and zinc acetate 42
g and 140 ml of monoethanolamine and 8
Dissolve in a mixture of 60 ml of ethanol,
A solution was prepared.

The solution was pyrolyzed by removing the solvent at 80 ° C. under reduced pressure and baking at 400 ° C. for 1 hour. next,
When the powder was reduced in a vacuum at 200 ° C. for 2 hours,
A pale yellow powder was obtained.

When X-ray diffraction measurement of the powder was carried out, it was confirmed that the amorphous portion was 80% and was substantially amorphous. From the composition analysis, the atomic ratio of In and Zn [I
n / (In + Zn)] = 0.70. Further, the volume solid resistance of the powder was measured and found to be 7 Ωcm.
And this volume solid resistance is 8 Ωcm even after 1000 hours of the humidity resistance test under the conditions of 60 ° C. and 95% RH,
It was found that there was almost no change and the moisture resistance was excellent.

Further, it was found by SEM and XMA analysis that this powder had an average particle size of 0.15 μm and a uniform composition.

[0091]

According to the present invention, there is provided a conductive material which is superior in moisture resistance to ITO and ATO, is less likely to be blackened, and has the same conductivity as ITO and ATO, and a method for producing the same.

Claims (7)

[Claims] 1. A conductive material comprising In and Zn as a main component and a substantially amorphous oxide having an atomic ratio In / In / (In + Zn) of 0.1 to 0.9. material. 2. The amorphous oxide is substantially In and Zn.
The conductive material according to claim 1, which is composed of only. 3. The substantially amorphous oxide is In and Zn.
In addition, at least one kind of the third element having a valence of positive trivalence or more is added to the atomic ratio of all the third elements (total third element / (In
The conductive material according to claim 1, wherein the content of + Zn + all third elements) is 20 atomic% or less. 4. A conductive material obtained by subjecting the substantially amorphous oxide according to claim 1 to a reduction treatment. 5. The conductive material according to claim 1, wherein the volume solid resistance of the substantially amorphous oxide is 40 Ω · cm or less. 6. An indium compound and a zinc compound are used to perform solid-liquid separation of a precipitate formed by a precipitation forming agent from one or more solutions containing at least one of these compounds,
The method for producing a conductive material according to claim 1 or 2, wherein a substantially amorphous oxide is obtained by firing and reduction treatment if necessary. 7. A precipitation-forming agent is formed from at least one compound of an indium compound, a zinc compound and an element having a valence of positive trivalence or more, and from at least one solution containing at least one of these compounds. The method for producing a conductive material according to claim 3, wherein the precipitate is subjected to solid-liquid separation, and if necessary, subjected to firing and reduction treatment to obtain a substantially amorphous oxide.