JPH0849070A - Ito sintered compact and its production - Google Patents

Abstract

PURPOSE:To produce an ITO sintered compact excellent in thermal shock resistance, usable also as powder because it is easily crushed by hand, ensuring satisfactory work efficiency, excellent in utilization efficiency and capable of forming an ITO film having satisfactory specific resistance. CONSTITUTION:When powder consisting essentially of indium, tin and oxygen and so blended as to regulate the tin content of the resultant sintered compact to <20wt.% is compacted and sintered, grain size-regulating powder obtd. by heat-treating indium oxide powder and tin oxide powder is added to powdery starting material based on indium oxide powder and they are granulated, compacted and sintered.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an ITO used as a vapor deposition material when forming a transparent conductive film by sputtering.
The present invention relates to a sintered body and a method for manufacturing the same.

[0002]

2. Description of the Related Art A transparent conductive film obtained from an ITO sintered body by vapor deposition, sputtering, ion plating or the like has been attracting attention as a promising film because of its low specific resistance value. For example, by forming a film from an ITO sintered body under appropriate conditions by electron beam heating (hereinafter referred to as EB vapor deposition), high transparency and a good sheet resistance value of the film are obtained.

Such an ITO sintered body is manufactured as follows. That is, blended in the desired composition,
After forming a powder consisting essentially of indium, tin, and oxygen, the powder is heated to 150 in air or in an oxygen atmosphere.
A method such as sintering at a temperature of about 0 to 1600 ° C. is used.

[0004]

With the rapid development of the liquid crystal industry centering on color liquid crystal displays in recent years, the demand for ITO thin films used for display electrodes is expanding. In response, ITO thin films are required to have low cost in addition to high film characteristics. Further, as a method for enhancing the effect of using the sintered body, the film forming apparatus has been improved by scanning the electron beam with which the sintered body is irradiated. It has not been improved because of high cost.

On the other hand, there is also a demand for an ITO sintered body which is a raw material for an ITO thin film, which has excellent utilization efficiency.

In the ITO sintered body disclosed in the above-mentioned prior art, although a film having a low specific resistance value can be obtained by EB vapor deposition by heating the substrate, the ITO sintered body is irradiated with a focused electron beam. , To heat and evaporate a small part of the IT
A temperature difference occurs between the surface and the inside of the O sintered body, and the ITO sintered body is cracked (cracked by thermal shock) due to the difference in thermal expansion. In particular, it is known that when the ITO sintered body is cracked, the discharge state becomes unstable or unusable.

In order to solve the problem of reuse, there has been proposed a method in which an ITO sintered body that has been used up by EB vapor deposition is powdered by hand pulverization and subjected to EB vapor deposition again. However, in the case of the conventionally known sintered body, the IT after being used up
Since the O sintered body itself is hard, it cannot be pulverized by crushing,
The utilization efficiency of the ITO sintered body has not improved.

Therefore, according to the present invention, I having a good specific resistance value is used.
Not only can a TO film be formed, but it also has excellent thermal shock resistance,
And since it can be easily crushed by hand, it can be used as a powder in the end, and it has good workability and excellent utilization efficiency.
The object is to provide an O sintered body.

[0009]

In order to solve the above problems, the method for producing an ITO sintered body of the present invention is an ITO sintered body in which a powder mainly composed of indium, tin and oxygen is molded and sintered. In the manufacturing method, the indium oxide powder and the tin oxide powder are mixed and heat-treated to obtain a particle size adjusting powder, and the particle size adjusting powder is added to a raw material powder mainly containing indium oxide powder to obtain a granulated powder. It is characterized in that the granulated powder is molded and sintered.

From one aspect, the tin composition is 1 to 50% by weight.
Indium oxide powder and tin oxide powder are mixed and heat treated to produce a particle size adjusting powder, and the particle size adjusting powder is added to a raw material powder mainly containing indium oxide powder and mixed to form a granulated powder. , Molding and sintering the granulated powder.

From another aspect, indium oxide and tin oxide are mixed so as to have a tin composition of 1 to 50% by weight and heat-treated, and the particle size adjusting powder is mixed with a raw material powder made of indium oxide or tin oxide and molded. After that, sintering is performed in the air, a vacuum, or an oxygen atmosphere. And this
I that can be crushed with a compressive strength of 30 to 80 kg / cm ² or less
A TO sintered body is obtained. The ITO sintered body of the present invention is
_{The 2} O ₃ —SnO ₂ system is substantially composed of indium, tin and oxygen, and the tin composition of the ITO sintered body is preferably 20% by weight or less.

[0012] From still another aspect, a powder consisting essentially of indium, tin, and oxygen, in which a tin component is mixed in a desired composition and particle size distribution, is molded, and the powder is molded in the air, a vacuum, or an oxygen atmosphere. And sintered to produce an ITO sintered body. This makes it possible to obtain an ITO sintered body that can be crushed with a compressive strength of 30 to 80 kg / cm ² or less and that does not crack when quenched in water from 600 ° C.

The ITO sintered body obtained according to the present invention is
The thermal shock resistance is high, cracking during film formation is effectively suppressed, and therefore a good quality ITO film can be stably obtained.
Further, since it is easy to pulverize by hand, the ITO sintered body that has been used up by EB evaporation can be finally formed into a film by EB evaporation again as a powder.

[0014]

As described above, I produced by a conventionally known method
The cracks that occur when EB vapor deposition is performed using a TO sintered body are the temperatures generated on the surface and inside of the ITO sintered body in order to apply a focused electron beam to the sintered body and heat-deposit only a small portion. This is due to the difference in thermal expansion caused by the difference. It is considered that the cause of the difference in thermal expansion and cracking is largely due to the degree of bonding between the particles during the progress of sintering, and is strongly due to the degree of adhesion between the particles.

The inventor of the present invention has noticed that not only can the cracks during film formation be effectively suppressed by controlling the degree of adhesion between the grains, but also the manual crushing work after film formation can be facilitated. Then, by controlling the degree of adhesion between the particles based on the above-mentioned manufacturing conditions, it has succeeded in solving cracks during film formation of the ITO sintered body and crushing conditions after film formation.

The degree of adhesion between the particles is determined by IT using a compression tester.
The value obtained by measuring the compressive strength of the O sintered body was 8
0 kg / cm ² or less, preferably 40 to 60 kg / cm
The range of ² is easy to pulverize even by hand, and has a great effect on thermal shock resistance.

When the compressive strength exceeds 80 kg / cm ² , the ITO sintered body is not only cracked due to the difference in thermal expansion caused by local heating at the time of EB irradiation for film formation, but also easy to crush by hand. Therefore, it is difficult to provide an ITO sintered body which is time-consuming for powdering work and has excellent utilization efficiency.

On the other hand, when the compressive strength is 30 kg / cm ² or less, the adhesion between the grains becomes too weak, and
The beam may penetrate the ITO sintered body immediately after the EB irradiation, or a problem may occur in the film characteristics.

The thermal shock resistance of the ITO sintered body is 60
After heating for 1 hour at 0 ° C., it is placed in water and examined for cracks.

The following is a description based on each of the other elements relating to the present invention.

(Raw Material Powder) As the raw material powder, indium oxide powder, indium oxide-tin oxide composite powder, mixed powder of indium oxide-tin oxide composite powder and tin oxide powder, and the like can be used. .

(Particle size adjusting powder) Particle size adjusting powder (A): Indium oxide powder is compounded with tin oxide in a desired composition (preferably tin oxide powder is compounded so that the tin composition is 1 to 50% by weight). ), And after mixing
The powder is heated to 1300 ° C. in an atmosphere, a vacuum or an oxygen atmosphere by a gas flow type atmospheric furnace or a vacuum heating furnace.
1 to above (preferably 1300 to 1600 ° C)
Heat treatment is carried out for 15 hours, and grains are grown to an average grain size of 5 to 30 μm to obtain grain size adjusting powder.

Particle size adjusting powder (B): Indium oxide powder alone is heated in a gas flow type atmospheric furnace or a vacuum heating furnace in the atmosphere, in a vacuum or in an oxygen atmosphere at a temperature of 1300 ° C. or higher (preferably 1300 to 1600 ° C.). 1 to 15
Heat treatment is performed for a period of time to grow the particles to an average particle size of 5 to 30 μm to obtain a particle size adjusting powder.

When the heat treatment temperature is lower than 1300 ° C., the escape of the impurity gas is insufficient, or Sn is contained in the heat treated powder.
Due to the presence of the O ₂ phase, it is difficult to obtain a good ITO film, that is, a clean ITO film. Further, when the heat treatment temperature exceeds 1600 ° C., the tin dispersibility deteriorates due to the coarsening of tin, and the discharge state during film formation is hindered.

(Granulated powder) The particle size-adjusted powder obtained as described above is mixed with the raw material powder, and then mixed and pulverized to obtain a granulated powder. However, the compounding amount of the particle size adjusting powder (A) alone or the total amount of the particle size adjusting powder (A) and the particle size adjusting powder (B) of only indium oxide powder is 40% with respect to the raw material powder.
The amount is not less than wt%, preferably 50 to 70 wt%. 50% to 70% by weight of the raw material powder is added to the raw material powder by the heat treatment so that the average particle size is grown to 5 to 30 μm to broaden the particle size distribution and facilitate molding, and at the time of sintering. Relaxes the adhesion between the generated particles,
It is possible to suppress cracking during film formation.

(Mixing / Pulverizing) As a method for performing mixing / pulverization, there is, for example, ball mill mixing. When performing ball mill mixing, the mixing time is preferably 12 hours or longer, more preferably 24 hours or longer. A binder such as paraffin wax or polyvinyl alcohol can be added in an amount of 1 to 4% by weight when mixing and pulverizing.

(Molding) The granulated powder is molded by cold pressing. At this time, there was almost no shrinkage due to sintering.
Since the dimensions of the TO sintered body are determined at the time of molding, IT
It must be formed by considering the specifications of the O sintered body. For example, a molding pressure of about 1 ton / cm ² is preferable in order to make the relative density of the ITO sintered body 4.3 g / cm ³ .

(Sintering-heating rate) Sintering is carried out in a gas flow type atmospheric furnace or a vacuum heating furnace in the air, in a vacuum or in an oxygen atmosphere, but the method in the air is the cheapest method. preferable. The temperature rising rate is set within a range where debinding can be easily performed, and for example, the heating time from room temperature to the debinding completion temperature of 400 ° C. is set to about 13 hours.

(Sintering-Sintering temperature) The sintering temperature is 500.degree.
~ 1100 ° C. If the temperature is lower than 500 ° C., the sintering does not proceed, resulting in a very brittle ITO sintered body, which lowers the workability. If it exceeds 1100 ° C., the sintering becomes too strong and the compressive strength becomes 60 kg / cm ² or more, so that not only the ITO sintered body is cracked during film formation but also hand grinding becomes difficult.

(Sintering-holding time) It is also important to control the holding time when the sintering temperature is reached. The holding time when reaching the sintering temperature is preferably about 1 to 5 hours. If the holding period is less than 1 hour, a problem occurs in soaking in the sintering furnace and stable production cannot be performed.

[0031]

EXAMPLES The present invention will be described below with reference to examples.

Example 1 Tin oxide powder having an average particle size of 3 μm was mixed in indium oxide powder having an average particle size of 1 μm or less so that the tin composition was 10% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
Mix for 8 hours, dry and grind. After that, heat treatment is performed in the air at 1500 ° C. for 15 hours to obtain an average particle size of 30
The particle size-adjusted powder (A) having a particle size of μm was used.

50% by weight of the particle size adjusting powder (A) was added to and mixed with a raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, to obtain a granulated powder. Further, the granulated powder was molded into a predetermined shape and then sintered in the atmosphere. In the sintering process, the temperature is raised from room temperature to 400 ° C in 13 hours,
The temperature was raised to 600 ° C. in 3 hours. And 600
The temperature was kept at 3 ° C. for 3 hours to obtain an ITO sintered body having a size of 25 mmφ and a thickness of 15 mm. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.

The ITO sintered body thus obtained had a relative density of 4.4 g / cm ³ and a tin composition (average composition) by chemical analysis of 4.8% by weight. Further, the compressive strength of the sintered body was determined with a RU type universal material testing machine, and the thermal shock resistance was examined by heating the sintered body at 600 ° C. for 1 hour and then pouring it into water. Table 2 shows the results.

Example 2 Tin oxide powder having an average particle size of 3 μm was mixed in indium oxide powder having an average particle size of 1 μm or less so that the tin composition would be 10% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
Mix for 8 hours, dry and grind. After that, heat treatment is performed in the air at 1500 ° C. for 10 hours to obtain an average particle size of 24
The particle size-adjusted powder (A) having a particle size of μm was used. Furthermore, average particle size 1μ
m indium oxide powder and 3% by weight of vinyl acetate binder were added, mixed in a wet ball mill for 18 hours, dried and pulverized to have an average particle size of 10 μm or less, and dried at 1500 ° C. in the atmosphere at 3 ° C. for 3 hours. Heat treatment was performed for a time to obtain a particle size-adjusted powder (B) having an average particle size of 15 μm. Then, 50% by weight of the particle size adjusting powder (A) and 20% by weight of the particle size adjusting powder (B) are added to and mixed with the raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, and then the granulated powder. And Further, the granulated powder was molded into a predetermined shape and then sintered in the atmosphere. In the sintering step, the temperature was raised from room temperature to 400 ° C in 13 hours, and the temperature was raised to 600 ° C in 3 hours. And hold at 600 ℃ for 3 hours 25mm
An ITO sintered body having a size of φ and a thickness of 15 mm was obtained. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.

The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Example 3 Tin oxide powder having an average particle size of 3 μm was mixed in indium oxide powder having an average particle size of 1 μm or less so that the tin composition was 50% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and pulverizing, the mixture was dried at 1500 ° C. for 1 hour in an oxygen atmosphere containing O ₂ at a flow rate of 10 l / min.
Heat treatment was performed for 0 hours to obtain a particle size-adjusted powder (A) having an average particle size of 25 μm. In addition, after adding 3% by weight of a vinyl acetate binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, drying and pulverizing to make the average particle size 10 μm or less, and then in air. Heat treatment at 1300 ℃ for 15 hours at
The particle size-adjusted powder (B) was set to m. And the average particle size 1
10% by weight of the particle size adjusting powder (A) and 30% by weight of the particle size adjusting powder (B) in the raw material powder mainly composed of indium oxide powder having a particle size of μm or less
After adding by weight% and mixing, a granulated powder was obtained. further,
After molding using the granulated powder, sintering was performed in the atmosphere.
In the sintering step, the temperature was raised from room temperature to 400 ° C in 13 hours, and the temperature was raised to 600 ° C in 3 hours. And
It was kept at 500 ° C. for 5 hours to obtain an ITO sintered body having a size of 25 mmφ and a thickness of 15 mm. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.

The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Example 4 Indium oxide powder having an average particle size of 1 μm or less was mixed with tin oxide powder having an average particle size of 3 μm so that the tin composition was 20% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and pulverizing,
Heat treatment was performed at a temperature of 00, 1500, 1600 ° C. for 1 hour each to obtain a particle size adjusting powder (A) having an average particle size of 5, 8, 14 μm. Further, after adding 3% by weight of a vinyl acetate-based binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, drying and pulverizing to make the average particle size 10 μm or less, and then in air. Heat treatment at 1500 ℃ for 3 hours, average particle size 15μ
The particle size-adjusted powder (B) was set to m. And the average particle size 1
25% by weight of the particle size adjusting powder (A) and 20% of the particle size adjusting powder (B) in the raw material powder mainly composed of indium oxide powder having a particle size of μm or less
After adding by weight% and mixing, a granulated powder was obtained. further,
After molding using the granulated powder, sintering was performed in the atmosphere.
In the sintering step, the temperature was raised from room temperature to 400 ° C in 13 hours, and the temperature was raised to 600 ° C in 3 hours. And 6
The temperature was maintained at 00 ° C. for 3 hours to obtain an ITO sintered body having a size of 25 mmφ and a thickness of 15 mm. Heat treatment conditions for the particle size adjusted powder,
The compounding ratio and sintering conditions are shown in Table 1 (Examples 4-1 and 4).
-2, 4-3).

The ITO sintered body thus obtained was evaluated in the same manner as in Example 1, and the results are shown in Table 2 (Examples 4-1 and 4-).
2, 4-3).

Example 5 Tin oxide powder having an average particle size of 3 μm was mixed in indium oxide powder having an average particle size of 1 μm or less so that the tin composition was 50% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and crushing, 15 in the air
Heat treatment was carried out at a temperature of 00 ° C. for 15 hours to obtain a particle size adjusting powder (A) having an average particle size of 30 μm. In addition, after adding 3% by weight of a vinyl acetate binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, and drying and pulverizing to obtain an average particle size of 1
The particle size was adjusted to 0 μm or less and heat-treated in the atmosphere at 1400 ° C. for 3 hours to obtain a particle size adjusting powder (B) having an average particle size of 7 μm. Then, 10% by weight of the particle size adjusting powder (A) and 40% by weight of the particle size adjusting powder (B) are added to and mixed with the raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, and then the granulated powder. And Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. Sintering process from room temperature to 40
The temperature was raised to 0 ° C. in 13 hours, and was raised to 600 ° C. in 3 hours. And it hold | maintained at 600 degreeC for 3 hours, and obtained the ITO sintered compact of 25 mm (phi) and the thickness of 15 mm. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.

The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Example 6 Indium oxide powder having an average particle size of 1 μm or less was mixed with tin oxide powder having an average particle size of 3 μm so that the tin composition was 20% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and crushing, 15 in the air
Heat treatment was carried out at 00 ° C. for 10 hours to obtain a particle size adjusting powder (A) having an average particle size of 24 μm. In addition, after adding 3% by weight of a vinyl acetate binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, drying and pulverizing to make the average particle size 10 μm or less, and then in air. Was heat-treated at 1500 ° C. for 3 hours to obtain a particle size adjusting powder (B) having an average particle size of 15 μm. Then, 50% by weight of the particle size adjusting powder (A) and 30% by weight of the particle size adjusting powder (B) are added to and mixed with the raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, and then the granulated powder. And Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. 13 steps from room temperature to 400 ℃
The temperature was raised over time, and the temperature was raised to 1100 ° C. over 11 hours. Then, hold at 1100 ° C for 1 hour and 25 mm
An ITO sintered body having a size of φ and a thickness of 15 mm was obtained. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.

The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Example 7 Indium oxide powder having an average particle size of 1 μm or less was mixed with tin oxide powder having an average particle size of 3 μm so that the tin composition was 20% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and crushing, 13 in the air
Heat treatment was carried out at 00 ° C. for 15 hours to obtain a particle size adjusting powder (A) having an average particle size of 12 μm. Further, after adding 3% by weight of a vinyl acetate-based binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, drying and pulverizing to make the average particle size 10 μm or less, and then in air. Was heat-treated at 1500 ° C. for 3 hours to obtain a particle size adjusting powder (B) having an average particle size of 15 μm. Then, 50% by weight of the particle size adjusting powder (A) and 20% by weight of the particle size adjusting powder (B) are added to and mixed with the raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, and then the granulated powder. And Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. 13 steps from room temperature to 400 ℃
The temperature was raised over time, and the temperature was raised to 600 ° C. over 3 hours. And it hold | maintained at 600 degreeC for 3 hours, and obtained the ITO sintered compact of 25 mm (phi) and the thickness of 15 mm. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.

The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1) Tin oxide powder having an average particle diameter of 3 μm was mixed in indium oxide powder having an average particle diameter of 1 μm or less so that the tin composition was 5% by weight, and 3% by weight of a vinyl acetate binder was added. 18 in a wet ball mill after addition
It was mixed for time, dried and pulverized to obtain a granulated powder. Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. In the sintering step, the temperature was raised from room temperature to 400 ° C in 13 hours, and the temperature was raised to 600 ° C in 3 hours. Then, hold at 600, 800, 1000 ° C. for 3 hours to obtain 25
An ITO sintered body having a size of mmφ and a thickness of 15 mm was obtained.
The sintering conditions are shown in Table 1 (Comparative Examples 1-1, 1-2, 1-
3).

The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2 (Comparative Examples 1-1, 1-
2, 1-3).

Comparative Example 2 Indium oxide powder having an average particle size of 1 μm or less was mixed with tin oxide powder having an average particle size of 3 μm so that the tin composition was 10% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and crushing, 12 in the air
Heat treatment was performed at 00 ° C. for 3 hours to obtain a particle size-adjusted powder having an average particle size of 4 μm. 30% by weight of this particle size adjusting powder was added to and mixed with a raw material powder mainly containing indium oxide powder having an average particle size of 1 μm or less, and then a granulated powder was obtained. Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. In the sintering process, the temperature is raised from room temperature to 400 ° C in 13 hours, and 600
The temperature was raised to 3 ° C. in 3 hours. Then, it was held at 600 ° C. for 3 hours, and the size of I of 25 mmφ and thickness of 15 mm was used.
A TO sintered body was obtained. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.

The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[0051]

[Table 1] [Particle size control powder (A)] Heat treatment temperature Time Average particle size Blending ratio Atmosphere (° C) (hr) (μm) (%) Example 1 1500 15 30 50 50 air Example 2 1500 10 24 50 air Example 3 1500 10 25 10 O ₂ Example 4-1 1400 1 525 25 air Example 4-2 1500 1 8 25 air Example 4-3 1600 1 14 25 air Example 5 1500 1500 15 30 10 air Example 6 1500 10 24 50 air Example 7 1300 15 12 50 air Comparative example 1 --- --- Comparative example 1-2 --- --- Comparative example 1-3 --- --- Comparative example 2 1200 3 4 30 air [Particle size Conditioning powder (B)] Heat treatment temperature Time Average particle size Blending ratio Atmosphere (° C) (hr) (μm) (%) Example 1 ----- air Example 2 1500 3 15 20 air Example 3 1300 15 21 30 air Example 4-1 1500 3 15 20 air Example 4-2 1500 3 15 20 air Example 4-3 1500 3 15 20 air Example 5 1400 3 7 40 air Example 6 1500 3 15 30 30 air Example 7 1500 3 15 20 20 air Comparative example 1-1 − − − − − Comparative example 1-2 − − − − − Comparative example 1-3 − − − − − Comparative Example 2 − − − − −

[0052]

[Table 2] Relative density Tin average composition Compressive strength Thermal shock resistance (g / cm ³ ) (wt%) (kg / cm ² ) (Visual observation) Example 1 4.4 4.8 64 ○ Example 2 4. 2 5.0 45 ○ Example 3 3.8 4.9 57 ○ Example 4-1 4.6 5.1 5.1 76 ○ Example 4-2 4.5 4.8 63 ○ Example 4-3 4. 2 4.8 52 ○ Example 5 4.3 4.9 47 ○ Example 6 4.0 9.8 56 ○ Example 7 4.0 9.7 32 ○ Comparative example 1-1 4.8 9.8 81 x Comparative example 1-2 5.1 9.9 97 x Comparative example 1-3 5.4 9.8 112 x Comparative example 2 4.3 9.8 86 x

In Table 2, ◯ of thermal shock resistance indicates that no crack was observed, and x indicates that crack was observed.

[0054]

EFFECTS OF THE INVENTION Since the ITO sintered body of the present invention is configured as described above, it has high thermal shock resistance, so that cracking of the sintered body during EB vapor deposition is effectively suppressed, and good quality I
A TO film can be obtained stably. In addition, since it is easy to pulverize by hand, the sintered body that has been used up by EB vapor deposition can be finally used as a powder again by EB vapor deposition, and an ITO sintered body that has excellent utilization efficiency and can be manufactured at low cost can be obtained. Can be provided.

Claims (12)

[Claims] 1. A method for producing an ITO sintered body, which comprises forming a powder of mainly indium, tin and oxygen and sintering the mixture, wherein the indium oxide powder and the tin oxide powder are mixed and heat-treated to obtain a particle size adjusting powder. A method for producing an ITO sintered body, comprising the step of adding the particle size adjusting powder to a raw material powder mainly composed of indium oxide powder to obtain a granulated powder, and molding and sintering the granulated powder. 2. An indium oxide powder and a tin oxide powder having a tin composition of 1 to 50% by weight in a method for producing an ITO sintered body, which comprises forming a powder of mainly indium, tin and oxygen and sintering the powder. Are mixed and heat-treated to generate a particle size adjusting powder, and the particle size adjusting powder is added to and mixed with a raw material powder mainly containing indium oxide powder to form a granulated powder, and the granulated powder is molded and sintered. Manufacturing method of ITO sintered body. 3. A method for producing an ITO sintered body, which comprises forming a powder of mainly indium, tin and oxygen and sintering the powder, wherein the indium oxide powder and the tin oxide powder have a tin composition of 1 to 50% by weight. Are mixed and heat-treated to generate a first particle size adjusting powder, and further only the indium oxide powder is heat-treated to generate a second particle size adjusting powder, and the first powder is mainly added to the raw material powder mainly containing indium oxide powder. 2. A method for producing an ITO sintered body, comprising adding the particle size-adjusted powder and the second particle size-adjusted powder to a mixture to form a granulated powder, and molding and sintering the granulated powder. 4. A method for producing an ITO sintered body, wherein the particle size-adjusted powder according to claim 1 has an average primary particle diameter of 5 to 30 μm. 5. A method for producing an ITO sintered body, wherein the total amount of the grain size adjusting powder added to the raw material powder according to claim 1 is 40% by weight or more based on the raw material powder. 6. The average primary particle diameter of the particle size adjusting powder according to claim 1, which is 5 to 30 μm,
Heat treatment at a temperature of 00 to 1600 ° C. for 1 to 15 hours I
Method of manufacturing TO sintered body. 7. The average primary particle diameter of the particle size-adjusted powder according to claim 1 is set to 5 to 30 μm.
A method for producing an ITO sintered body, wherein heat treatment is performed at a temperature of 00 to 1600 ° C. for 1 to 15 hours, and the total amount of grain size adjusting powder added to the raw material powder is 40% by weight or more based on the raw material powder. 8. A method for producing an ITO sintered body, which comprises molding the granulated powder according to any one of claims 1 to 3 and then sintering at a temperature of 500 to 1100 ° C. for 1 to 5 hours. 9. The method according to claim 1, wherein the raw material powder is indium oxide powder, indium oxide-tin oxide composite powder, or a mixed powder of indium oxide-tin oxide composite powder and tin oxide powder. A method for producing an ITO sintered body as described above. 10. A tin composition of 20% by weight or less and 30 to 8
Grinding with a compressive strength of 0 kg / cm ² is possible.
An ITO vapor deposition material comprising a sintered body produced by the production method described in 1. 11. A tin composition of 20% by weight or less at 600 ° C.
Claim 1 which does not cause a crack even if it is rapidly cooled in water.
To ITO made of a sintered body manufactured by the manufacturing method described in
Evaporation material. 12. A sintered body produced by the manufacturing method according to claim 1, which has a tin composition of 20% by weight or less and a sintered body density of 3.8 to 4.6 g / cm ^3. ITO vapor deposition material.