JP4994068B2 - Oxide conductive material and manufacturing method thereof - Google Patents

Description

  The present invention relates to an oxide conductive material and a manufacturing method thereof.

  BACKGROUND ART Conductive oxide powders mainly composed of indium-tin oxide (ITO) are actively used for transparent conductive films. In order to make the conductive oxide powder into a transparent conductive film, for example, a conductive oxide powder having a primary particle size of about 0.1 μm or less is dispersed in a solution composed of a solvent and a binder resin, and this is made into glass or plastic. There is a method of applying to a substrate such as coating, printing, dipping, spin coating or spraying and drying.

  The transparent conductive film produced in this way is effective for preventing charging of glass, plastics and the like and preventing adhesion of dust, and is used for preventing charging of window glass of displays and measuring instruments and preventing adhesion of dust.

  Furthermore, it can be used for applications such as IC package circuit formation, clean room interior materials, antistatic and dust adhesion prevention of various glass and films, coated transparent electrodes or infrared shielding materials, and future demand growth is expected. ing.

With the expansion of such fields of use, there is an increasing demand for conductive fine particles having excellent conductivity and transparency.
However, indium is a metal obtained as a by-product during the refining of zinc, and the amount of resources is limited. In recent years, ITO has been used extensively as a transparent electrode for liquid crystals, so there are concerns about supply restrictions and the price is rapidly rising. Is rising. In addition, the difficulty of obtaining indium has increased.

  Patent Document 1 discloses a compound having a specific metal atomic ratio of indium oxide, tin oxide and zinc oxide, a hexagonal layered compound composed of indium oxide and zinc oxide, and a compound having a spinel structure composed of tin oxide and zinc oxide. A sintered body is disclosed. In addition, in the metal atomic ratio of each component, it is described that indium is in a range of In / (In + Sn + Zn) = 0.50 to 0.75. However, there is no description regarding the corundum structure.

Patent Document 2 describes a manufacturing method for forming an ITO film containing a corundum crystal phase, but only a material having a high indium content is disclosed. Patent Document 3 discloses an ITO powder having a particle diameter of 0.05 μm or less obtained by heat treatment at 350 to 1000 ° C. in an inert gas hermetically pressurized atmosphere. In this document as well, a material with a high indium content is disclosed. Only is disclosed. Patent Document 4 discloses a method for producing indium oxide fine particles similar to the production method of the present invention. However, there is no disclosure of an oxide conductive material composed of oxides of In, Sn, and Zn having a specific composition.
JP 2000-72537 A JP 2004-75427 A JP-A-7-21831 JP 2004-75472 A

An object of the present invention is to provide an oxide conductive material having good conductivity even when the indium content is small.
Another object of the present invention is to provide an oxide conductive material having a small particle size and usable in a conductive paste or a conductive coating solution.
Another object of the present invention is to provide a method for producing the oxide conductive material.

The present invention has been made in view of the above problems, and includes an oxide of In, Sn, and Zn having a corundum structure, and the proportion of In, Sn, and Zn in all atoms excluding oxygen is 20 mol% ≦ In ≦ 70 mol. %, 5 mol% ≦ Sn ≦ 60 mol%, 5 mol% ≦ Zn ≦ 60 mol% was found to exhibit good conductivity, and the present invention was completed.
According to the present invention, the following conductive oxide materials and methods for producing the same are provided.
1. The ratio of In, Sn, and Zn in the total atoms excluding oxygen, including oxides of In, Sn, and Zn having a corundum structure, is 20 mol% ≦ In ≦ 70 mol%, 5 mol% ≦ Sn ≦ 60 mol%, 5 mol% ≦ An oxide conductive material in which Zn ≦ 60 mol%.
2. The oxide conductive material according to 1, wherein the electric conductivity under a pressure of 100 kg / cm ² is 0.001 S / cm or more.
3. 3. The oxide conductive material according to 1 or 2, wherein the average particle size is 0.2 μm or less.
4). The oxidation according to any one of 1 to 3, comprising an oxide containing one or more metal elements selected from Mg, Ca, Ti, Zr, Al, Ga, Si, Ge and / or an oxide of a rare earth element Conductive material.
5. A content of In, Sn, and Zn is prepared from a metal salt solution containing In, Sn, and Zn by a precipitation method, and the content is heat-treated in an inert gas having an oxygen concentration of 0.1% by volume or less. The manufacturing method of the oxide electroconductive material in any one of 1-4 which obtains the oxide containing Sn and Zn.
The sputtering target obtained using the oxide electroconductive material manufactured by the manufacturing method in any one of 6.1-4 or 5.

According to the present invention, it is possible to provide a conductive oxide material having good conductivity even when the indium content is small.
According to the present invention, it is possible to provide a conductive oxide material having a small particle size and usable for a conductive paste or a conductive coating solution.
According to this invention, the manufacturing method of the said electroconductive oxide material can be provided.

  The oxide conductive material of the present invention includes an oxide of In, Sn, and Zn having a corundum structure, and the proportion of In, Sn, and Zn in all atoms excluding oxygen is 20 mol% ≦ In ≦ 70 mol%, 5 mol% ≦ Sn ≦ 60 mol%, 5 mol% ≦ Zn ≦ 60 mol%.

A crystalline phase having a corundum structure is known as a high-temperature phase of In ₂ O ₃ (Inorganic Chemistry, (1969), 8, 1985-1993). In the oxide conductive material of the present invention, the corundum-structured In, Sn, and Zn oxides are those in which Sn and Zn are randomly substituted at the In ₂ O ₃ In site of the corundum structure.

The proportions of In, Sn and Zn in all atoms excluding oxygen are preferably 30 mol% ≦ In ≦ 60 mol%, 15 mol% ≦ Sn ≦ 60 mol%, 5 mol% ≦ Zn ≦ 50 mol%. Within this range, the conductivity can be further improved.
If In is less than 20 mol%, the conductivity may be very low. Further, when In exceeds 70 mol%, expensive In is increased and the cost is increased, and it is difficult to cope with the difficulty of obtaining In.
When Sn or Zn is less than 5 mol%, the conductivity may be very low. Moreover, when Sn or Zn exceeds 60 mol%, there exists a possibility that electroconductivity may become low.

The oxide conductive material of the present invention is preferably 1 or 2 selected from Mg, Ca, Ti, Zr, Al, Ga, Si, and Ge other than the oxides of In, Sn, and Zn having the corundum structure. An oxide containing the above metal element and / or an oxide of a rare earth element is included. By containing these oxides, high conductivity can be maintained even if the expensive In content is reduced. Moreover, electroconductivity improves by containing these oxides.
Among the above oxides, it is more preferable to include an oxide containing one or more metal elements selected from Mg, Al, Ga, and Si from the viewpoint of improving conductivity.
In the oxide conductive material of the present invention, the ratio of one or more metal elements selected from Mg, Al, Ga, Si to the total atoms excluding oxygen in the oxide is usually 0.1 mol%. ˜20 mol%. When the above oxide is included in this range, the effect is large. Preferably it is 0.2 mol%-10 mol%.

The oxide conductive material of the present invention has good conductivity. Specifically, the electric conductivity under a pressure of 100 kg / cm ² is preferably 0.001 S / cm or more, and more preferably 0.01 S / cm or more.
When the electrical conductivity is 0.001 S / cm or more, a molded product or a film effective for preventing charging and preventing adhesion of dust can be obtained. Further, by reducing the blending amount of the oxide conductive material, both antistatic and light weight can be achieved.
Although it is not necessary to define the upper limit of electrical conductivity, considering that the oxide conductive material of the present invention is mainly used in the form of fine particles and sintered bodies, the upper limit of electrical conductivity is 10 A value of about ⁴ S / cm is conceivable.
Since the oxide conductive material of the present invention is usually obtained as fine particles, it is measured under a pressure of 100 kg / cm ^{2 in} order to obtain a highly reliable measured value of electric conductivity.

The average particle size of the oxide conductive material of the present invention may be adjusted according to the application. For example, when used as a white conductive filler for rubber or plastic or a raw material of a sintered body, 0.1 μm to several μm.
The oxide conductive material of the present invention preferably has an average particle size of 0.2 μm or less, more preferably 0.1 μm or less. When the average particle size is 0.2 μm or less, it can be used for applications requiring transparent conductivity. A typical lower limit of the particle size can be 1 nm.

The oxide conductive material of the present invention is prepared by preparing a content of In, Sn, and Zn from a metal salt solution of In, Sn, and Zn by a precipitation method. It can be obtained by heat treatment under an active gas.
A uniform oxide conductive material can be obtained by using the precipitation method.

  In the method for producing an oxide conductive material according to the present invention, the metal salt solution is preferably selected from Mg, Ca, Ti, Zr, Al, Ga, Si and Ge in addition to In, Sn and Zn. The metal element of the above metal element and / or rare earth element is included.

  Examples of metal salts include nitrates, chloride salts, acetates, alkoxides, and the like. Examples of the alkoxide include methoxide and ethoxide.

  The metal salt is dissolved in water or an organic solvent such as alcohol or oxygen-containing compound. Examples of the alcohol include methanol, ethanol, isopropanol, methoxyethanol, ethoxyethanol and the like. Examples of the oxygen-containing compound include esters such as ethyl acetate, carboxylic acids such as acetic acid and propionic acid, and the like.

  The concentration of the metal salt solution is usually in the range of 0.001 mol / l to 10 mol / l. When the concentration is less than 0.001 mol / l, the productivity is poor, and when the concentration is higher than 10 mol / l, it is difficult to stir the precipitation solution.

  Examples of the precipitant used in the precipitation method include alkaline solutions such as ammonium hydroxide, sodium hydroxide, ammonium carbonate, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, organic acids such as oxalic acid, formic acid, ammonium oxalate, and organic acids. Examples thereof include acid salts and urea that decomposes when heated to generate ammonia. Among them, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, oxalic acid, ammonium oxalate, and urea are preferable because a uniform precipitate is easily formed.

The amount of precipitant used is usually 50% or more of the chemical equivalent required for each of the above metal salts to become a compound such as hydroxide or oxalate, and preferably the washing time due to residual alkali ions or the like. From the viewpoint of shortening, the chemical equivalent is 80% to 2000%.
When the amount of the precipitant used is less than 50% of the chemical equivalent, the composition of the precipitate may be different from the solution composition.

  The formation temperature of the precipitate is usually preferably from the freezing point of the solvent to the boiling point of the solvent. Since the formation rate of the precipitate is low at low temperatures, it is more preferable that the temperature be from the freezing point of the solvent + 5 ° C. to the boiling point of the solvent.

  After the formation of the precipitate, aging may be performed for several minutes to about 100 hours by raising the temperature from the same temperature as the formation of the precipitate to the boiling point of the solvent at normal pressure or 300 ° C. under pressure. By aging, the precipitate can be easily filtered, and more complete compounds such as hydroxide and oxalate can be obtained.

The obtained compound (precipitate) is separated from the solution by means of filtration, centrifugation, decantation, etc., and then washed with water or solvent to remove unnecessary ions and the like. Examples of the solvent used in the solvent washing include alcohols such as ethanol and isopropanol, and ethers such as THF.
The removal of unnecessary ions or the like can be taken as a measure that the electrical conductivity of the solvent used for cleaning is 0.5 mS or less.

  After washing, water and solvent are removed by drying at 50 to 400 ° C. for 30 minutes to 100 hours. After the drying, the obtained compound may be converted into an oxide by, for example, further heat treatment. This heat treatment may be the same step as the heat treatment described later, but may be a preliminary heat treatment for removing water and solvent more completely. In the case of preliminary heat treatment, it is usually performed at about 200 to 800 ° C. In this case, it is not necessary to perform heat treatment under an inert gas.

In the method for producing an oxide conductive material of the present invention, the compound obtained by the precipitation method is heat-treated to form an oxide. By performing the heat treatment, the crystallinity of the compound is improved and the conductivity is improved.
When the heat treatment is performed at a high temperature, since the grain growth is severe, it is preferably performed in a short time. On the other hand, when the heat treatment is performed at a low temperature, the grain growth is suppressed, but the reaction proceeds slowly. For this reason, when the heat treatment is performed at a low temperature, the conductivity is improved by performing the heat treatment for a longer time.

  The heat treatment conditions such as the heat treatment temperature and the heat treatment time may be determined in consideration of the particle size required for the oxide conductive material and the required degree of conductivity. For example, the heat treatment temperature is preferably 1300 ° C. or lower. When the heat treatment temperature exceeds 1300 ° C., the grain growth is particularly intense, and it may be difficult to produce fine particles.

The heat treatment time is usually a very short time of about several seconds at a high temperature, and about several hours or less is sufficient even at a low temperature. For example, when the heat treatment temperature is 1000 ° C. or higher, it is preferably 10 minutes or shorter. When heat processing temperature is 500-1000 degreeC, Preferably it is 30 minutes or less. When the heat treatment temperature is 500 ° C. or less, it is preferably about several hours or less. Grain growth is high at high temperatures, so heat treatment in a short time is preferable. Grain growth is suppressed at low temperatures, but the solid-phase reaction is slow, so a longer heat treatment was performed to improve conductivity. Is preferred.
The heat treatment temperature is usually 200 ° C. or higher as in the case of the preliminary heat treatment described above. Preferably, it is 300 ° C. or higher.

The heat treatment is performed under an inert gas. As the inert gas, nitrogen, helium, argon or the like can be used, and nitrogen or argon is preferable in terms of availability.
The oxygen concentration of the inert gas is 0.1% by volume or less, preferably 0.05% by volume or less. If the concentration exceeds 0.1% by volume, the conductivity may decrease.

  The heat treatment under the inert gas is not particularly limited as long as the conditions that can be filled with the inert gas and can maintain the inside of the furnace in the inert gas atmosphere are not particularly limited. For example, the heat treatment can be performed using an electric furnace or the like.

  After the heat treatment, oxide particles can be obtained by crushing the heat treatment compound. Crushing can be performed by dry pulverization using a mechanical pulverization method such as a planetary ball mill or a jet mill, whereby fine oxide particles having a smaller particle diameter can be obtained.

The oxide conductive material of the present invention thus obtained is used for various applications such as an antistatic agent by utilizing its own function. Further, this material can be used as a raw material, pressure-molded by a known method, and sintered in air or an inert gas to obtain a sintered body.
The sintered body is formed, for example, by mixing the oxide conductive material of the present invention with a binder and molding it into a predetermined shape, and sintering in air or in an inert atmosphere at 900 ° C. to 1700 ° C. for 1 minute to 100 hours. It can be obtained by doing. Examples of the binder include polyvinyl alcohol, polybutyral, polyacrylic acid and the like.

  Since the sintered body using the oxide conductive material of the present invention is excellent in conductivity, it can be suitably used, for example, as a sputtering target used when forming a conductive film.

  Moreover, the oxide conductive material of the present invention is dispersed in a solution composed of a solvent, a dispersant, and a binder resin using a bead mill, a vibration mill, or the like, so that the dispersion solution becomes a conductive paste or a coating liquid. Can do. These conductive pastes and coating solutions can be applied to a substrate such as glass or plastic by means such as coating, printing, dipping, spin coating or spraying, and dried to form a transparent conductive film. This film is effective for preventing charging of glass, plastic, etc. and preventing adhesion of dust. In addition, it can be used for preventing charging of window glass of displays and measuring instruments and adhesion of dust.

  Furthermore, the oxide conductive material of the present invention can be used for applications such as IC package circuit formation, clean room interior materials, antistatic of various glasses and films, dust adhesion prevention, coated transparent electrodes or infrared shielding materials. In addition, it can be applied to touch panels.

Example 1
170 g of indium nitrate (trihydrate) (manufactured by Kanto Chemical Co., Inc.), stannic chloride (5 water) so that the molar ratio of In, Zn, and Sn is In: Zn: Sn = 60: 20: 20 56 g of Japanese product (manufactured by Kanto Chemical Co., Ltd.) and 47.5 g of zinc nitrate (hexahydrate) (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 2.5 L of ion-exchanged water (referred to as solution A). Further, 132.2 g of ammonium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 0.9 L of ion exchange water (referred to as B solution).

  While stirring the A solution, the B solution was added dropwise over 30 minutes while maintaining the temperature at 25 ° C. Thereafter, the temperature of the solution was heated to 80 ° C., and aging was performed for 30 minutes to obtain a precipitate. Next, the precipitate is washed with 2 L of ion exchange water at a time by decantation, and the electrical conductivity of the solution is measured by a conductivity meter Combo2 (manufactured by Hanna Instruments). Washing was repeated until 5 mS or less. Thereafter, the precipitate was dried at 300 ° C.

  The obtained compound was heated to 800 ° C. in about 10 minutes while flowing nitrogen (oxygen concentration: 10 ppm) at a flow rate of 0.5 L / min in an infrared image furnace (manufactured by Motoyama Co., Ltd.) After maintaining the temperature, it was rapidly cooled to room temperature.

The obtained oxide particles were light blue-gray and the average particle size was about 0.035 μm. The average particle diameter is a value calculated from the following formula by measuring the specific surface area by the BET specific surface area measurement method by nitrogen adsorption.
Average particle diameter (μm) = 6 / (density × specific surface area)
The density was calculated from the lattice constant calculated from the X-ray diffraction measurement result, and the calculated lattice volume and the weight of atoms present in the lattice.

Further, when X-ray diffraction measurement was performed, an oxide having a corundum structure was formed as shown in FIG. From the X-ray diffraction data, Rietveld analysis was performed and it was determined that Sn and Zn were randomly substituted at the In site.
The measurement conditions for X-ray diffraction measurement (XRD) were as follows.
Device: Rigaku Ultima-III
X-ray: Cu-Kα ray (wavelength 1.5406mm, monochromatized with graphite monochromator)
2θ-θ reflection method, continuous scan (1.0 ° / min)
Sampling interval: 0.02 °
Slit DS, SS: 2/3 °, RS: 0.6 mm

The electrical conductivity was measured by a two-terminal method while pressing the particles. Specifically, particles to be measured were placed in a cylindrical container (diameter 12 mm) made of acrylic resin, and sandwiched between copper cylindrical electrodes from above and below. While measuring the electrical resistance between the electrodes using an electrical resistance measuring device, pressure was applied to the sample with a hydraulic jack. The electrical resistance and the thickness of the sample when the pressure reached 100 kg / cm ² were measured, and the electrical conductivity was calculated from the following formula.
Electrical conductivity = (reciprocal of resistance × sample thickness) / sample area As a result, the electrical conductivity when a weight of 100 kg / cm ² is applied is 2.5 × 10 ⁻¹ S / cm, and good electrical conductivity It became clear that it has sex.

Example 2
The amount of indium nitrate is 170 g, the amount of stannic chloride is 126 g, the amount of zinc nitrate is 106.9 g, and the amount of ammonium carbonate so that the molar ratio of In, Zn, and Sn is In: Zn: Sn = 40: 30: 30 Was prepared in the same manner as in Example 1 except that 198.5 g was used.

The obtained oxide particles were light blue-gray and the average particle size was about 0.045 μm. When the X-ray diffraction measurement was performed, almost all oxides having a corundum structure were formed as shown in FIG. Further, Rietveld analysis was performed and it was determined that Sn and Zn were randomly substituted at the In site.
The electrical conductivity was measured by a two-terminal method while pressing the particles. The electrical conductivity when a load of 100 kg / cm ² was applied was 2.2 × 10 ⁻¹ S / cm, and it was revealed that the material had good conductivity.

Example 3
The amount of indium nitrate was 80.0 g, the amount of stannic chloride was 131.7 g, and the amount of zinc nitrate was 44.7 g so that the molar ratio of In, Zn, and Sn was In: Zn: Sn = 30: 20: 50. This was prepared in the same manner as in Example 1 except that the amount of ammonium carbonate was changed to 137 g.

The obtained oxide particles were light blue-gray and the average particle diameter was about 0.042 μm. As a result of X-ray diffraction measurement, almost all oxides having a corundum structure were formed as shown in FIG. Further, Rietveld analysis was performed and it was determined that Sn and Zn were randomly substituted at the In site.
The electrical conductivity was measured by a two-terminal method while pressing the particles. The electrical conductivity when a load of 100 kg / cm ² was applied was 3.9 × 10 ⁻¹ S / cm, and it was revealed that the material had good conductivity.

Example 4
The amount of indium nitrate was 160 g, the amount of stannic chloride was 135.5 g, and the amount of zinc nitrate so that the molar ratio of In, Zn, Sn, and Mg was In: Zn: Sn: Mg = 35: 30: 30: 5 Was prepared in the same manner as in Example 1, except that 115 g of magnesium nitrate, 16.5 g of magnesium nitrate hexahydrate, and 198.5 g of ammonium carbonate were used.
The obtained oxide particles were light blue-gray, and the average particle size was about 0.044 μm. When the X-ray diffraction measurement was performed, an oxide having a corundum structure was formed. Further, Rietveld analysis was performed and it was determined that Sn and Zn were randomly substituted at the In site.
The electrical conductivity was measured by a two-terminal method while pressing the particles. The electrical conductivity when a load of 100 kg / cm ² was applied was 3.1 × 10 ⁻¹ S / cm, and it was revealed that the material had good conductivity.

Example 5
120 g of indium chloride (tetrahydrate) (manufactured by Shinsei Chemical Industry Co., Ltd.) and stannic chloride (in order for the molar ratio of In, Zn, and Sn to be In: Zn: Sn = 40: 30: 30) 107.6 g of pentahydrate) (made by Wako Pure Chemical Industries, Ltd.) and 41.8 g of zinc chloride (made by Wako Pure Chemical Industries, Ltd.) were dissolved in 3.4 L of ion-exchanged water (A ′ Called solution). Further, 1843 g of urea (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 6.1 L of ion exchange water (referred to as B ′ solution).
The A ′ solution and the B ′ solution were mixed, the temperature of the solution was heated to 93 ° C., and aging was performed for 180 minutes to obtain a precipitate. Next, the precipitate is washed with 5 L of ion exchange water at a time by decantation, and the electrical conductivity of the solution is measured by a conductivity meter Combo2 (manufactured by Hanna Instruments). Washing was repeated until 5 mS or less. Thereafter, the precipitate was dried at 300 ° C.

Subsequent firing in nitrogen was prepared in the same manner as in Example 1 except that the firing temperature was 700 ° C.
The obtained oxide particles were light blue-gray and the average particle diameter was about 0.023 μm. When the X-ray diffraction measurement was performed, an oxide having a mostly corundum structure was formed as shown in FIG.

The electrical conductivity was measured by the two-terminal method while pressing the particles in the same manner as in Example 1. The electrical conductivity when a load of 100 kg / cm ² was applied was 2.2 × 10 ⁰ S / cm, and it was revealed that the film had good conductivity.

Comparative Example 1
The amount of indium nitrate is 40 g, the amount of stannic chloride is 79 g, the amount of zinc nitrate is 129.9 g, and the amount of ammonium carbonate so that the molar ratio of In, Zn, and Sn is In: Zn: Sn = 15: 55: 30 A precipitate was obtained in the same manner as in Example 1 except that 114.2 g was used, and dried.
While flowing 0.5 volume% oxygen / nitrogen atmosphere gas at a flow rate of 0.5 L / min, the temperature was raised to 800 ° C. in about 10 minutes, held at that temperature for 1 minute, and then rapidly cooled to room temperature.

The obtained oxide particles were colored yellow-green. The average particle size was about 0.055 μm. As a result of X-ray diffraction measurement, tin oxide and Zn ₂ SnO ₄ were formed instead of the corundum-structured oxide as shown in FIG.
As a result of measuring the electrical conductivity in the same manner as in Example 1, the electrical conductivity of the particles was as low as 2.3 × 10 ⁻⁴ S / cm.

The oxide conductive material of the present invention includes transparent conductive paint or coating liquid, plastic additives (white filler, antistatic, antistatic, electromagnetic shield, etc.), transparent conductive thin film material, infrared / ultraviolet shielding material, function It can be used for conductive paint materials (conductive paint, heat ray reflective paint) or functional coating liquid materials (conductive coating liquid, heat ray reflective coating liquid).
Moreover, the sintered compact which consists of an oxide electroconductive material of this invention can be used for the sputtering target etc. for forming a transparent conductive thin film.

1 is a diagram showing X-ray diffraction of oxide particles obtained in Example 1. FIG. 4 is a diagram showing X-ray diffraction of oxide particles obtained in Example 2. FIG. 4 is a diagram showing X-ray diffraction of oxide particles obtained in Example 3. FIG. FIG. 3 is a diagram showing X-ray diffraction of oxide particles obtained in Comparative Example 1. 6 is a diagram showing X-ray diffraction of oxide particles obtained in Example 5. FIG.

Claims (6)

Including oxides of In, Sn and Zn having a corundum structure;
Oxide conductivity in which the proportion of In, Sn and Zn in all atoms excluding oxygen is 30 mol% ≦ In ≦ 60 mol%, 15 mol% ≦ Sn ≦ 60 mol%, 5 mol% ≦ Zn ≦ 50 mol% material. ^2. The oxide conductive material according to claim 1, wherein the electric conductivity under a pressure of 100 kg / cm ² is 0.001 S / cm or more.   3. The oxide conductive material according to claim 1, wherein the oxide conductive material has an average particle diameter of 0.2 μm or less.   4. The oxide according to claim 1, comprising an oxide containing one or more metal elements selected from Mg, Ca, Ti, Zr, Al, Ga, Si and Ge and / or an oxide of a rare earth element. Oxide conductive material. A content of In, Sn and Zn is prepared by precipitation from a metal salt solution containing In, Sn and Zn,
The oxide containing In, Sn, and Zn is obtained by heat-treating the inclusion under an inert gas having an oxygen concentration of 0.1% by volume or less at a heat treatment temperature of 200 ° C or higher and 1300 ° C or lower . The manufacturing method of the oxide electroconductive material in any one.   The sputtering target obtained using the oxide electroconductive material manufactured by the manufacturing method of any one of Claims 1-4 or Claim 5.

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