Indium gallium aluminum oxide powder, target material, and preparation method of the powder and the target material

Abstract

The application belongs to the technical field of target material preparation, and discloses an indium gallium aluminum oxide powder, a target material and a preparation method of the powder and the target material. The indium gallium aluminum oxide powder is obtained by granulating mixed slurry containing indium oxide, gallium oxide and aluminum oxide through gas-water combined atomization. In the gas-water combined atomization, the gas pressure of gas atomization is 0.7-1 MPa, and the included angle between the gas injection direction and the vertical downward direction is 45-55°. The liquid used in water atomization is a mixed liquid of water and a dispersing agent, the pressure of the mixed liquid is 100-150 MPa, and the included angle between the injection direction of the mixed liquid and the vertical downward direction is 45-55°. In the gas-water combined atomization process, the liquid of water atomization is changed into the mixed liquid of water and the dispersing agent, so that the re-agglomeration of gallium oxide is effectively avoided, the average particle size of the indium gallium aluminum oxide powder is effectively reduced, and the indium gallium aluminum oxide powder with low oxygen content, small average particle size and good sphericity is produced.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of target materials, in particular to an indium gallium aluminum oxide powder, a target material and a preparation method of the powder and the target material. BACKGROUND

[0002] A transparent conductive oxide (TCO) film has photoelectric properties such as a wide band gap, high light transmittance in a visible spectrum and low resistivity, and is widely used in the fields of solar cells, display devices and other optical elements.

[0003] With the development of heterojunction solar cells, improving the uniformity of a TCO film and the contact characteristics with a metal electrode is one of the most important key points; gallium oxide and aluminum oxide are a new type of semiconductor oxide, have high optical transmittance (80-90%) in the visible light range (380-780 nm), and are a thin film with high mobility and high carrier concentration, and are widely used in electronic devices such as solar cell windows and photosensitive detectors.

[0004] Indium oxide doped gallium oxide and aluminum oxide can realize the adjustability of the light transmission band of an indium-based conductive film, so that more sunlight can be absorbed by a solar cell semiconductor structure, thereby maximizing the light utilization efficiency of the solar cell, and therefore indium oxide doped gallium aluminum oxide target material is also one of the current research hotspots.

[0005] Currently, there are few technologies for studying indium oxide doped gallium aluminum oxide target material, so generally, other oxide metal target materials are referred to for research and experimental production, such as D1: Chinese patent application 202310678889.8 discloses an indium oxide doped titanium tantalum cerium target material and a preparation method thereof. The preparation method is as follows: indium oxide, titanium oxide, tantalum oxide and cerium oxide powders are weighed according to a molar ratio of 90.5-92.5:1.5-2.5:3-5:1.5-2.5, then added to pure water with a dispersing agent and stirred to disperse uniformly to obtain slurry one; then indium oxide powder, a dispersing agent and water are added and wet ground to obtain slurry two; a binder is added and mixed, and then wet ground to obtain slurry three; through spray granulation, mixing and screening, a mixed powder is obtained; finally, after being subjected to die pressing and cold isostatic pressing, the mixed powder is subjected to debinding and sintering to obtain the indium oxide doped titanium tantalum cerium target material. The application can significantly improve the performance of the target material by limiting the component ratio of the oxide powders and cooperating with a specific preparation process.

[0006] According to the technical solution of the above-mentioned patent, indium gallium aluminum oxide target materials can be produced through raw material spray granulation, followed by molding, cold isostatic pressing and other processes. However, experimental production found that the particle size uniformity and sphericity of the indium gallium aluminum oxide powder obtained by the above-mentioned oxide powder preparation process are difficult to balance. Either the sphericity of the oxide particles is good but the particle size distribution of the powder is uneven, or the particle size distribution of the powder is even but the sphericity of the oxide particles is poor. Both of these will lead to a decrease in the performance of the prepared indium gallium aluminum oxide target material.

[0007] Therefore, it is necessary to find a better method for preparing indium gallium aluminum oxide powder so as to improve the performance of the prepared indium gallium aluminum oxide target.

[0008] D2: Chinese patent application 201710137910.8 discloses a method for preparing an indium gallium zinc oxide composite powder. The method comprises first smelting an indium gallium zinc alloy, dissolving the alloy in nitric acid to form a polymer of indium nitrate, gallium nitrate, and zinc nitrate. Ammonia is then added to form a precipitate, which is then calcined. Because the present invention uses an indium gallium zinc alloy as the raw material and reacts the indium gallium zinc alloy with nitric acid to simultaneously generate indium nitrate, gallium nitrate, and zinc nitrate, it avoids the severe deviations in particle size and specific surface area that occur in the prior art process of separately preparing indium oxide, gallium oxide, and zinc oxide due to the difficulty in achieving homogeneous control conditions. This ensures that the prepared indium gallium zinc oxide composite powder has a uniform particle size and controllable specific surface area, resulting in excellent sintering performance.

[0009] Although the technical solution of the above patent application is not applicable to indium gallium aluminum oxide, its technology is worthy of reference. However, the above technical solution is not highly selective, and its selectivity for some metal ions is not high. For example, metal ions with different oxidation states may be precipitated at the same time, making it difficult to obtain high-purity products. Its applicability is relatively limited. Its precipitation generally requires relatively harsh physical and chemical conditions, such as pH value, temperature, and the ratio of nitric acid and salt, etc., making it difficult to finely control the process parameters. Therefore, this technical solution is not suitable for the preparation of indium gallium aluminum oxide powder and indium gallium aluminum oxide targets.

[0010] D3: An article entitled "Preparation of Fine Spherical Metal Powder by Water-Gas Combined Atomization Method" was published in the 3rd issue of Volume 10 of Materials Research and Applications in September 2016. It disclosed a water-gas combined atomization method, combining the advantages of water atomization and gas atomization, and developed a water-gas atomization powder making method. During the atomization process, it was found that the molten metal liquid flow was successively broken by the air flow and the high-pressure water flow, and the broken metal droplets shrank into spheres under the action of surface tension; the research results showed that the yield of 316L metal powder D50 (8-13μm) produced by this atomization method reached 78.3%, and the tap density exceeded 4.7g / cm3; the morphology of the powder was nearly spherical, and the structure was the coexistence of austenite and ferrite.

[0011] And D4: Chinese patent 202220283288.8 discloses a water gas combined atomization powder making device. Its technical scheme includes: cylinder, support frame, atomizing pipe, electric push rod, rotating shaft and connecting ring, the atomizing pipe is inserted and connected on the inner wall of the cylinder, the electric push rod is installed on the inner wall of the cylinder away from the atomizing pipe, the first motor is arranged on the outer wall of the lower end of the electric push rod, the support frame is installed on the outer wall of the lower end of the first motor, the bearing is embedded on the outer wall of the support frame, the rotating shaft is rotatably installed in the bearing, the fixed frame is installed on the outer wall of the upper end of the rotating shaft, and the connecting ring is installed on the outer wall of the fixed frame. By setting the atomizing pipe, the rotating shaft and the connecting ring, the effect of facilitating the cleaning of the inner wall of the atomizing pipe is achieved, the movement direction of the fine droplets in the atomizing pipe is avoided, and the atomizing pipe is avoided from being blocked, so that the smoothness of the movement of the fine droplets in the atomizing pipe is ensured.

[0012] Based on the technical inspiration of D3 and D4, water gas combined atomization method can be used to balance the sphericity and average particle size of indium gallium aluminum oxide, but experiments show that the performance of indium gallium aluminum oxide target is not greatly improved by using the process disclosed in D2. After several rounds of performance testing, it is found that there are two reasons:

[0013] (1) The oxygen content of the oxide has a great influence on the performance of the target. Too high oxygen content will cause uneven distribution of oxygen in the target, thereby affecting the performance of the target. Too low oxygen content will make the target lose its own characteristics as an oxide target, becoming an unqualified product.

[0014] (2) Because gallium oxide is a powder that is easy to agglomerate, small particles of gallium oxide will slowly agglomerate to form large particles of gallium oxide during the water gas combined atomization process, resulting in a significant increase in the average particle size of the indium gallium aluminum oxide powder and a decrease in the performance of the target.

[0015] Therefore, it is necessary to develop a method for preparing indium gallium aluminum oxide powder that can improve the performance of indium gallium aluminum oxide target to improve the comprehensive performance of indium gallium aluminum oxide target. SUMMARY

[0016] One of the purposes of the present application is to provide a kind of indium gallium aluminum oxide powder, which can solve the technical problems that the particle size uniformity and sphericity of the indium gallium aluminum oxide powder produced by the prior art are difficult to balance, and the average particle size of the indium gallium aluminum oxide powder increases due to the easy agglomeration of gallium oxide powder. The oxygen content of the powder is low and the average particle size is small, the powder has good sphericity, and the comprehensive performance of the target can be effectively improved when the powder is used to prepare indium gallium aluminum oxide target.

[0017] Another purpose of the present application is to provide a preparation method of indium gallium aluminum oxide powder, which can effectively solve the problem of easy agglomeration of gallium oxide in the gas-water combined atomization process, and prepare indium gallium aluminum oxide powder with low oxygen content, small average particle size and good particle sphericity.

[0018] Meanwhile, the present application also provides an indium gallium aluminum oxide target material, which has the advantages of high density, uniform organization, no segregation, high bending strength and other good performance.

[0019] The present application further provides a preparation method of indium gallium aluminum oxide target material, which can prepare indium gallium aluminum oxide target material with good sputtering effect.

[0020] To achieve the above-mentioned purposes, the present application provides an indium gallium aluminum oxide powder obtained by gas-water combined atomization granulation of a mixed slurry containing indium oxide, gallium oxide and aluminum oxide; wherein the gas pressure of the gas atomization of the gas-water combined atomization granulation is 0.7-1MPa, and the included angle between the gas injection direction and the vertical downward direction is 45-55°; the liquid used for water atomization is a mixed liquid of water and a dispersing agent, the pressure of the mixed liquid is 100-150MPa, and the included angle between the injection direction of the mixed liquid and the vertical downward direction is 45-55°.

[0021] Preferably, the dispersing agent is one or more of polyvinylpyrrolidone, triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives and polyacrylamide, and the mass ratio of water to dispersing agent in the mixed liquid is 10:1.

[0022] The present application also provides a preparation method of indium gallium aluminum oxide powder, which comprises the following steps:

[0023] Step 1: mixing aluminum oxide powder, gallium oxide powder, pure water and a first dispersing agent for pre-dispersion, and then wet grinding to obtain slurry one;

[0024] Step 2: adding indium oxide powder, pure water and a second dispersing agent to the slurry one for pre-dispersion, and then wet grinding to obtain slurry two;

[0025] Step 3: adding a binder to the slurry two for pre-dispersion, and then wet grinding to obtain slurry three;

[0026] Step 4: sequentially subjecting the slurry three to gas-water combined atomization granulation, standing and drying, mixing and screening to obtain the indium gallium aluminum oxide powder;

[0027] The gas pressure of the gas atomization of the gas-water combined atomization and granulation is 0.7-1 MPa, and the included angle between the gas injection direction and the vertical downward direction is 45-55°; the liquid used for water atomization is a mixed liquid of water and a dispersing agent, the mixed liquid pressure is 100-150 MPa, the included angle between the mixed liquid injection direction and the vertical downward direction is 45-55°, and the mass ratio of the water to the dispersing agent is 10:1.

[0028] Preferably, the particle size of the alumina powder, gallium oxide powder and indium oxide powder is ≤10 μm, and the mass ratio of the alumina powder, gallium oxide powder and indium oxide powder is 0.1-1:1.2-2.8:96.2-98.7.

[0029] Further, in the step 1, the first dispersing agent accounts for 5-10% of the total mass of the added alumina powder, gallium oxide powder, pure water and first dispersing agent, the solid content in the slurry one is between 40-70%, the first dispersing agent is one or more of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, methyl amyl alcohol, polyacrylamide and fatty acid polyethylene glycol ester, the pre-dispersing time is 10-30 min, the wet milling speed is 600-1800 r / min, the wet milling time is 12-24 h, and the Malvern particle size D50 of the slurry one is <5 μm.

[0030] Further, in the step 2, the second dispersing agent accounts for 5-10% of the total mass of the added indium oxide powder, pure water and second dispersing agent; the second dispersing agent is one or more of polyvinylpyrrolidone, acrylic ester and ethylene bis-stearyl amide; the solid content in the slurry is between 40-70%; the pre-dispersing time is 10-30 min; the wet milling speed is 600-1800 r / min, the wet milling time is 12-24 h, and the Malvern particle size D50 of the slurry two is <3 μm.

[0031] Further, in the step 3, the binder accounts for 1-15% of the total mass of the added alumina, gallium oxide and indium oxide, the binder is one or more of a mixed agent of polyvinyl alcohol and polyethylene glycol, polyvinyl alcohol or polyvinyl butyral, the pre-dispersing time is 10-30 min; the wet milling speed is 600-1800 r / min, the wet milling time is 2-10 h, and the Malvern particle size D50 of the slurry three is <1 μm.

[0032] The application also provides an indium gallium aluminum oxide target prepared by the above method.

[0033] The application further provides a preparation method of an indium gallium aluminum oxide target, comprising the following steps:

[0034] Step a: the indium gallium aluminum oxide powder is sequentially subjected to die pressing and cold isostatic pressing to obtain a target blank;

[0035] Step b: the target blank is placed in a debinding furnace to perform pre-sintering and debinding to obtain a preform;

[0036] Step c: the preform is placed in a sintering furnace to perform sintering, and the indium gallium aluminum oxide target is obtained after being cooled to room temperature;

[0037] In step a, the pressure of die pressing is 20-100 Mpa, the forming time is 60-180 s, the pressure of cold isostatic pressing is 200-500 Mpa, and the forming time is 60-180 s; in step c, the sintering temperature is 1200-1550℃, the heating rate is 0.5-1℃ / min, the holding time is 8-20 h, and the cooling rate is 1℃ / min.

[0038] In step b, the specific operation of pre-sintering and debinding is as follows: the target blank is placed on an alumina burning plate uniformly sprinkled with 1-2 μm alumina particles, then placed in a debinding furnace, heated to 400-600℃ at a heating rate of 0.1-0.5℃ / min, and held for 10-15 h, and then cooled to room temperature at a cooling rate of 1℃ / min to obtain the preform.

[0039] Beneficial effects

[0040] Compared with the prior art, the present application has at least the following advantages:

[0041] (1) The present application provides a preparation method of indium gallium aluminum oxide powder, which adopts gas-water combined atomization method under specific gas pressure, gas injection angle, water pressure and water injection angle, so as to balance the improvement of the sphericity and average particle size of the indium gallium aluminum oxide powder, and reduce the oxygen content of the indium gallium aluminum oxide powder, thereby improving the performance of the indium gallium aluminum oxide target;

[0042] (2) The present application finds that when the conventional gas-water combined atomization method is used to prepare the indium gallium aluminum oxide powder, the gallium oxide will re-agglomerate during the atomization process, thereby increasing the average particle size of the indium gallium aluminum oxide powder and leading to the performance decline of the indium gallium aluminum oxide target, the present application changes the water atomization liquid into a mixed liquid of water and dispersant during the gas-water combined atomization process, thereby effectively avoiding the re-agglomeration of the gallium oxide, effectively reducing the average particle size of the indium gallium aluminum oxide powder, and producing the indium gallium aluminum oxide powder with low oxygen content, small average particle size and good sphericity;

[0043] (3) the application adopts specific proportion of water and dispersant as the mixed liquid for water atomization in the gas-water combined atomization process, which can further effectively balance the sphericity and average degree of particle size of the indium gallium aluminum oxide powder, and make the particles of the indium gallium aluminum oxide powder keep a low oxygen content, so that the oxygen can be uniformly distributed in the particles, and further improve the performance of the indium gallium aluminum oxide target;

[0044] (4) the application adopts the indium gallium aluminum oxide powder with high oxygen content, small average particle size and good sphericity to prepare the indium gallium aluminum oxide target, and the prepared indium gallium aluminum oxide target has the advantages of high density, uniform organization, no segregation (the phenomenon that the oxides are unevenly distributed in the densification process), high bending strength and good performance. BRIEF DESCRIPTION OF DRAWINGS

[0045] The application will be further described below in combination with the drawings and examples;

[0046] Figure 1 is the sphericity diagram of Example 1 of the application;

[0047] Figure 2 is the morphology diagram of Comparative Example 9 of the application;

[0048] Figure 3 is the metallographic diagram of Application Example 1 of the application;

[0049] Figure 4 is the metallographic diagram of Application Comparative Example 9 of the application. DETAILED DESCRIPTION

[0050] The application will be further described below in combination with the examples, but does not constitute any limitation on the application, and any limited modification made within the scope of the claims of the application is still within the scope of the claims of the application.

[0051] In order to describe the technical content of the application in detail, the following further describes the application in combination with the embodiments.

[0052] It should be noted that standing drying, mixing and screening are conventional technical means for powder preparation in the art, and the specific process will not be described in detail.

[0053] Example 1

[0054] An indium gallium aluminum oxide powder is prepared by the following steps:

[0055] Step 1: take aluminum oxide powder, gallium oxide powder and indium oxide powder with a purity of 4N according to the mass ratio of 0.1:1.2:98.7 for standby;

[0056] Step 2: The alumina powder, gallium oxide powder and pure water are added into a slurry tank containing the first dispersant polyvinylpyrrolidone and mixed for pre-dispersion for 15 minutes, and then pumped into a sand mill for wet grinding to obtain slurry one, wherein the first dispersant accounts for 5% of the total mass of the added alumina, gallium oxide, pure water and first dispersant, the solid content in the slurry is 60%, the sand mill grinding speed is 1200 r / min, the wet grinding time is 8 hours, and the Malvern particle size D50 of the slurry one is 2.365 μm;

[0057] Step 3: The indium oxide powder, pure water and the second dispersant polyvinylpyrrolidone are added into the slurry one and mixed for pre-dispersion for 30 minutes, and then pumped into a sand mill for wet grinding to obtain slurry two, wherein the second dispersant accounts for 8% of the total mass of the added indium oxide, pure water and second dispersant, the solid content in the slurry is 65%, the sand mill grinding speed is 1200 r / min, the wet grinding time is 12 hours, and the Malvern particle size D50 of the slurry is 1.248 μm;

[0058] Step 4: The binder polyvinyl alcohol and polyethylene glycol are added into the slurry two and mixed for pre-dispersion for 30 minutes, and then pumped into a sand mill for wet grinding to obtain slurry three, wherein the binder accounts for 5% of the total mass of the added alumina, gallium oxide and indium oxide, the wet grinding speed is 1200 r / min, the wet grinding time is 5 hours, and the Malvern particle size D50 of the slurry is 0.569 μm;

[0059] Step 5: The slurry three is sequentially subjected to gas-water combined atomization granulation, standing and drying, mixing and screening to obtain the indium gallium aluminum oxide powder;

[0060] In the gas-water combined atomization granulation, the gas pressure of the gas atomization is 0.7 MPa, the gas is nitrogen, and the angle between the gas jet direction and the vertical downward direction is 45°; the liquid used in the water atomization is a mixed liquid of water and polyvinylpyrrolidone, the mixed liquid pressure is 100 MPa, the angle between the mixed liquid jet direction and the vertical downward direction is 45°, and the mass ratio of the water to polyvinylpyrrolidone is 10:1.

[0061] Example 2

[0062] Generally the same as Example 1, except that in the gas-water combined atomization granulation, the mass ratio of the water to polyvinylpyrrolidone is 8:1.

[0063] Example 3

[0064] Generally the same as Example 1, except that in the gas-water combined atomization granulation, the mass ratio of the water to polyvinylpyrrolidone is 12:1.

[0065] Example 4

[0066] It is generally the same as Example 1, except that the gas pressure of the gas-water combined atomization granulation is 1 MPa, the gas is nitrogen, and the angle between the gas injection direction and the vertical downward direction is 55°.

[0067] Example 5

[0068] It is generally the same as Example 1, except that the liquid used for water atomization is a mixed liquid of water and sodium lauryl sulfate, the pressure of the mixed liquid is 150 MPa, the angle between the spray direction of the mixed liquid and the vertical downward direction is 55°, and the mass ratio of water to sodium lauryl sulfate is 10:1.

[0069] Example 6

[0070] An indium gallium aluminum oxide powder is prepared by the following steps:

[0071] Step 1: Weigh 4N purity aluminum oxide powder, gallium oxide powder, and indium oxide powder in a mass ratio of 0.5:2:97.5 for later use;

[0072] Step 2: Alumina powder and gallium oxide powder were added to a slurry barrel containing pure water and a first dispersant, sodium dodecylbenzenesulfonate, and mixed for pre-dispersion for 15 minutes. The mixture was then pumped into a sand mill for wet grinding to obtain slurry 1, wherein the first dispersant accounted for 5% of the total mass of the added aluminum oxide, gallium oxide, pure water, and the first dispersant, the solid content in the slurry was 60%, the sand mill grinding speed was 1200 r / min, the wet grinding time was 8 hours, and the Malvern particle size of slurry 1 was D50 = 2.304 μm;

[0073] Step 3: Add indium oxide powder, pure water, and the second dispersant ethylene bisstearamide to slurry one and mix them for pre-dispersion for 30 minutes. Then, pump them into a sand mill for wet grinding to obtain slurry two, wherein the second dispersant accounts for 8% of the total mass of the added indium oxide, pure water, and the second dispersant. The solid content in the slurry is 65%, the sand mill grinding speed is 1200 r / min, the wet grinding time is 12 hours, and the slurry Malvern particle size D50 = 1.119 μm;

[0074] Step 4: Adding a binder, polyvinyl butyral, to slurry 2 and pre-dispersing the mixture for 30 minutes, then pumping the mixture into a sand mill for wet grinding to obtain slurry 3, wherein the binder accounts for 5% of the total mass of the added aluminum oxide, gallium oxide, and indium oxide, the wet grinding speed is 1200 r / min, the wet grinding time is 5 hours, and the slurry Malvern particle size D50 = 0.601 μm;

[0075] Step 5: subjecting the slurry 3 to air-water combined atomization granulation, static drying, mixing and screening in sequence to obtain the indium gallium aluminum oxide powder;

[0076] The gas pressure of the gas atomization of the gas-water combined atomization is 0.7 MPa, the gas is nitrogen, and the included angle between the gas injection direction and the vertical downward direction is 45°; the liquid used for water atomization is a mixed liquid of water and methylpentanol, the pressure of the mixed liquid is 100 MPa, the included angle between the injection direction of the mixed liquid and the vertical downward direction is 45°, and the mass ratio of the water to the methylpentanol is 10:1.

[0077] Example 7

[0078] An indium gallium aluminum oxide powder is prepared by the following steps:

[0079] Step 1: aluminum oxide powder, gallium oxide powder and indium oxide powder with a purity of 4N are weighed according to a mass ratio of 1:2.8:96.2 for standby;

[0080] Step 2: the aluminum oxide powder and the gallium oxide powder are added into a slurry barrel containing pure water and a first dispersant polyacrylamide, mixed and pre-dispersed for 15 min, then pumped into a sand mill for wet grinding to obtain a slurry one, wherein the first dispersant accounts for 5% of the total mass of the added aluminum oxide, gallium oxide, pure water and the first dispersant, the solid content in the slurry is 60%, the sand mill grinding speed is 1200 r / min, the wet grinding time is 8 h, and the Malvern particle size D50 of the slurry one is 2.310 μm;

[0081] Step 3: the indium oxide powder, pure water and a second dispersant acrylate are added to the slurry one, mixed and pre-dispersed for 30 min, then pumped into a sand mill for wet grinding to obtain a slurry two, wherein the second dispersant accounts for 8% of the total mass of the added indium oxide, pure water and the second dispersant, the solid content in the slurry is 65%, the sand mill grinding speed is 1200 r / min, the wet grinding time is 12 h, and the Malvern particle size D50 of the slurry is 1.089 μm;

[0082] Step 4: a binder polyvinyl alcohol is added to the slurry two, mixed and pre-dispersed for 30 min, then pumped into a sand mill for wet grinding to obtain a slurry three, wherein the binder accounts for 5% of the total mass of the added aluminum oxide, gallium oxide and indium oxide, the wet grinding speed is 1200 r / min, the wet grinding time is 5 h, and the Malvern particle size D50 of the slurry is 0.546 μm;

[0083] Step 5: the slurry three is sequentially subjected to gas-water combined atomization, standing and drying, mixing and screening to obtain the indium gallium aluminum oxide powder;

[0084] In the gas-water combined atomization granulation, the gas pressure of the gas atomization is 0.7 MPa, the gas is nitrogen, the angle between the gas injection direction and the vertical downward direction is 45°; the liquid used for the water atomization is a mixed liquid of water and polyacrylamide, the pressure of the mixed liquid is 100 MPa, the angle between the injection direction of the mixed liquid and the vertical downward direction is 45°, and the mass ratio of the water to the polyacrylamide is 10:1.

[0085] Comparative Example 1

[0086] The same as Example 1, except that the gas pressure of the gas atomization in the gas-water combined atomization granulation is 0.5 MPa.

[0087] Comparative Example 2

[0088] The same as Example 1, except that the gas pressure of the gas atomization in the gas-water combined atomization granulation is 1.2 MPa.

[0089] Comparative Example 3

[0090] The same as Example 1, except that the angle between the gas injection direction and the vertical downward direction in the gas-water combined atomization granulation is 30°.

[0091] Comparative Example 4

[0092] The same as Example 1, except that the angle between the gas injection direction and the vertical downward direction in the gas-water combined atomization granulation is 70°.

[0093] Comparative Example 5

[0094] The same as Example 1, except that the pressure of the mixed liquid for the water atomization in the gas-water combined atomization granulation is 80 MPa.

[0095] Comparative Example 6

[0096] The same as Example 1, except that the pressure of the mixed liquid for the water atomization in the gas-water combined atomization granulation is 180 MPa.

[0097] Comparative Example 7

[0098] The same as Example 1, except that the angle between the injection direction of the mixed liquid and the vertical downward direction in the gas-water combined atomization granulation is 30°.

[0099] Comparative Example 8

[0100] The same as Example 1, except that the angle between the injection direction of the mixed liquid and the vertical downward direction in the gas-water combined atomization granulation is 70°.

[0101] Comparative Example 9

[0102] The same as example 1, except that pure water is used for water atomization in the gas-water combined atomization.

[0103] Performance test

[0104] The morphology of the indium gallium aluminum oxide powder obtained in examples 1-7 and comparative examples 1-9 is measured and observed by a specific surface area pore size analyzer, a scanning electron microscope and an oxygen-nitrogen analyzer, to obtain the average particle size and oxygen content percentage of the indium gallium aluminum oxide powder, and the results are shown in Table 1.

[0105] Table 1: Performance test results of the indium gallium aluminum oxide powder obtained in examples 1-7 and comparative examples 1-9

[0106]

[0107]

[0108] According to the results in Table 1, it can be seen that:

[0109] According to the comparison of the data in example 1 and example 2, it can be seen that the ratio of water and dispersant also affects the performance of the indium gallium aluminum oxide powder. The reason is that excessive dispersant can weaken the repulsive force between the powder particles. In addition, the excess dispersant molecules can also form a network structure, which increases the viscosity of the water and dispersant mixture, and makes the fluidity, dispersibility and stability of the water and dispersant mixture worse, so that the internal component distribution of the spray granulation powder is uneven, which leads to an increase in the oxygen content of the powder and a poor broken powder particle effect, thereby affecting the performance of the powder particles.

[0110] According to the comparison of the data in example 1 and example 3, it can be seen that too little dispersant also affects the performance of the indium gallium aluminum oxide powder. The reason is that too little dispersant content cannot cover all the powder, the ion distribution on the surface of the powder particles is uneven, the steric hindrance mechanism is weak, the viscosity between the powder particles is large, and the powder is unstable and agglomerates. The oxygen content is increased during the agglomeration process, resulting in a large average powder particle size and affecting the subsequent process.

[0111] According to the comparison of the data in example 1 and comparative examples 1, 3 and 4, it can be seen that the gas pressure and the angle between the gas injection direction in the gas-water combined atomization of the application have a greater effect on the average particle size and oxygen content of the indium gallium aluminum oxide powder. When the gas pressure is less than 0.7 MPa or the angle between the gas injection direction is not within the range of the application, the average particle size of the powder is larger and the oxygen content is higher.

[0112] The data of Comparative Example 2 and Comparative Example 6 prove that, in the gas-water combined atomization, if the gas pressure of the gas atomization is too large or the liquid pressure of the water atomization is too large, the influence on the average particle size and oxygen content of the powder is not large, which proves that the excessively large gas pressure or liquid pressure does not have a very large impact on the performance of the indium gallium aluminum oxide powder, but the production cost will be increased, and thus it is not the preferred technical solution of the present application.

[0113] According to the data comparison of Example 1 and Comparative Examples 5, 7 and 8, it can be known that, in the gas-water combined atomization, the mixed liquid pressure and the angle between the mixed liquid injection direction have a large influence on the average particle size and oxygen content of the indium gallium aluminum oxide powder. When the mixed liquid pressure is less than 100 MPa or the angle between the mixed liquid injection direction is not within the range of the present application, the average particle size of the powder is large and the oxygen content is high.

[0114] According to the data comparison of Example 1 and Comparative Example 9, it can be known that, in the present application, the use of the mixed liquid of water and dispersant as the liquid for water atomization can greatly reduce the average particle size and oxygen content of the prepared indium gallium aluminum oxide powder. The reason is that, in the absence of dispersant, indium, gallium and aluminum are prone to agglomeration during atomization, and in the process of agglomeration, oxygen is wrapped inside the particles, resulting in an increase in the average particle size and oxygen content of the indium gallium aluminum oxide powder. The spherical images of the indium gallium aluminum oxide powder particles of Example 1 and Comparative Example 9 are observed by a scanning electron microscope, and specific comparison can be seen in Figs. 1 and 2. Figure 1 and Figs. 3 and 4. Figure 2 When the average particle size of the indium gallium aluminum oxide powder is greatly increased, the sphericity of the indium gallium aluminum oxide powder particles will also be affected. The sphericity of Example 1 is high, while the sphericity of Comparative Example 9 is poor.

[0115] The sphericity of the remaining Comparative Examples 1, 3, 4, 5, 7 and 8 is also poor compared to Example 1 and Comparative Example 9, and thus no more figures are shown here.

[0116] Preparation and performance test of indium gallium aluminum oxide target material

[0117] The indium gallium aluminum oxide powder prepared in Examples 1-7 and Comparative Examples 1-9 is used to prepare an indium gallium aluminum oxide target material according to the following steps to obtain Application Examples 1-7 and Application Comparative Examples 1-9.

[0118] Step a: The indium gallium aluminum oxide powder is sequentially subjected to die pressing and cold isostatic pressing to obtain a target blank;

[0119] Step b: The target blank is placed into a debinding furnace for pre-burning and debinding to obtain a preform;

[0120] Step c: The preform is placed into a sintering furnace for sintering, and after being cooled to room temperature, an indium gallium aluminum oxide target material is obtained;

[0121] wherein the pressure of the step a is 100T, the forming time is 120s, the pressure of the step b is 2400Mpa, and the forming time is 120s;

[0122] In the step b, the specific operation of the pre-burning and debinding is as follows: the target blank is placed on the alumina burning plate uniformly scattered with 1-2μm alumina particles, and then is put into the debinding furnace, and then is heated to 400-600℃ at the heating rate of 0.1-0.5℃ / min, and then is kept for 10-15h, and then is cooled to room temperature at the cooling rate of 1℃ / min to obtain the preform.

[0123] In the step c, the sintering is performed at the heating rate of 0.5℃ / min to 1510℃, and then is kept for 20h, and then is cooled to room temperature at the cooling rate of 1℃ / min to obtain the indium gallium aluminum oxide target.

[0124] Application Comparative Example 10

[0125] The application example 1 is basically the same, except that in the step b, the specific operation of the pre-burning and debinding is as follows: the target blank is directly placed on the alumina burning plate, and then is put into the debinding furnace, and then is heated to 400-600℃ at the heating rate of 0.1-0.5℃ / min, and then is kept for 10-15h, and then is cooled to room temperature at the cooling rate of 1℃ / min to obtain the preform.

[0126] Performance test

[0127] The relative density of the target is measured by the Archimedes drainage method;

[0128] The conductivity of the target is measured by the four-probe test technology;

[0129] The average grain size of the target is measured by using the X-ray diffractometer;

[0130] The bending strength of the target is measured by the universal testing machine;

[0131] The overall grain size distribution of the target is observed by the metallographic analyzer to see whether the target has segregation or not;

[0132] The indium gallium aluminum oxide targets prepared in the application examples 1-7 and the application comparative examples 1-10 are tested according to the above test methods, and the results are shown in Table 2.

[0133] Table 2: Performance test results of the indium gallium aluminum oxide targets prepared in the application examples 1-7 and the application comparative examples 1-10

[0134]

[0135] According to the results in Table 2, it can be seen that:

[0136] The gas-water combined atomization technology adopted by the present application, the pressure and the spray angle of the gas atomization and the pressure and the spray angle of the water atomization are more critical to the performance of the indium gallium aluminum oxide target, and the reason is that the indium gallium aluminum oxide powder prepared by the gas-water combined atomization has the advantages of small average particle size and low oxygen content.

[0137] The indium gallium aluminum oxide target prepared by the present application has the advantages of high density, high conductivity, excellent average grain size and bending strength performance, and does not produce target segregation phenomenon.

[0138] According to the comparison of the results of the application examples and application comparative example 10, it can be known that the sintering of the target blank on the alumina sintering plate uniformly covered with 1-2 mu alumina particles in the pre-burning and debinding step can effectively prevent the cracking of the target, and the reason is that when the target is directly sintered on the alumina sintering plate, the additives and gases in the target cannot be effectively discharged, resulting in the cracking of the target, and the performance of the target is reduced to a certain extent.

[0139] According to the attached Figure 3 and the attached Figure 4 It can be known that the performance of the indium gallium aluminum oxide powder will also have a greater impact on the average grain size of the indium gallium aluminum oxide target, and the indium gallium aluminum oxide powder of the present application can effectively reduce the average grain size of the indium gallium aluminum oxide target and improve the performance of the indium gallium aluminum oxide target.

[0140] The embodiments presented herein are only selected from the combination of all possible embodiments. The appended claims should not be limited by the embodiments of the present application. Some numerical ranges used in the claims include sub-ranges within them, and variations in these ranges should also be covered by the appended claims.

Claims

1. An indium gallium aluminum oxide powder, characterized in that: The indium gallium aluminum oxide powder is prepared by the following steps: Step 1: pre-dispersing aluminum oxide powder, gallium oxide powder, pure water, and a first dispersant, and then wet-grinding to obtain a slurry 1; Step 2: adding indium oxide powder, pure water and a second dispersant to the first slurry to mix and pre-disperse, and then wet-grinding to obtain the second slurry; Step 3: adding a binder to the slurry 2 and mixing to pre-disperse, and then wet grinding to obtain slurry 3; Step 4: subjecting the slurry 3 to air-water combined atomization granulation, static drying, mixing and screening in sequence to obtain the indium gallium aluminum oxide powder; Among them, the gas atomization pressure of the gas-water combined atomization granulation is 0.7-1MPa, and the angle between the gas injection direction and the vertical downward direction is 45-55°; the liquid used for water atomization is a mixed liquid of water and dispersant, the pressure of the mixed liquid is 100-150MPa, the angle between the injection direction of the mixed liquid and the vertical downward direction is 45-55°, and the mass ratio of water to dispersant is 10:1; The mass ratio of the aluminum oxide powder, the gallium oxide powder and the indium oxide powder is 0.1-1:1.2-2.8:96.2-98.

7.

2. The indium gallium aluminum oxide powder according to claim 1, characterized in that The dispersant is one or more of polyvinyl pyrrolidone, triethylhexyl phosphoric acid, sodium lauryl sulfate, methyl amyl alcohol, cellulose derivatives, and polyacrylamide.

3. The indium gallium aluminum oxide powder according to claim 1, characterized in that The particle sizes of the aluminum oxide powder, gallium oxide powder and indium oxide powder are all less than or equal to 10 μm.

4. The indium gallium aluminum oxide powder according to claim 1, characterized in that In step 1, the first dispersant accounts for 5-10% of the total mass of the added alumina powder, gallium oxide powder, pure water and the first dispersant, the solid content in the slurry one is between 40-70%, the first dispersant is one or more of polyvinyl pyrrolidone, sodium dodecylbenzene sulfonate, methyl pentanol, polyacrylamide, and fatty acid polyethylene glycol ester, the pre-dispersion time is 10-30 min, the wet grinding speed is 600-1800 r / min, the wet grinding time is 12-24 h, and the Malvern particle size D50 of the slurry one is less than 5 μm.

5. The indium gallium aluminum oxide powder according to claim 1, characterized in that In step 2, the second dispersant accounts for 5-10% of the total mass of the added indium oxide powder, pure water and the second dispersant; the second dispersant is one or more of polyvinyl pyrrolidone, acrylate, and ethylene bisstearamide; the solid content in the slurry is between 40-70%; the pre-dispersion time is 10-30 minutes; the wet grinding speed is 600-1800 r / min, the wet grinding time is 12-24 hours, and the Malvern particle size D50 of the slurry 2 is less than 3 μm.

6. The indium gallium aluminum oxide powder according to claim 1, characterized in that In step 3, the binder accounts for 1-15% of the total mass of the added aluminum oxide, gallium oxide and indium oxide, and the binder is a mixture of polyvinyl alcohol and polyethylene glycol, polyvinyl alcohol or polyvinyl butyral, and the pre-dispersion time is 10-30 minutes; the wet grinding speed is 600-1800 r / min, the wet grinding time is 2-10 hours, and the Malvern particle size D50 of slurry three is less than 1 μm.

7. An indium gallium aluminum oxide target, characterized in that: The indium gallium aluminum oxide powder according to any one of claims 1 to 6 is subjected to molding, cold isostatic pressing, pre-calcination and degreasing, and sintering in sequence to obtain the powder.

8. A method for preparing an indium gallium aluminum oxide target according to claim 7, characterized in that: The steps include: Step a: molding and cold isostatically pressing indium gallium aluminum oxide powder in sequence to obtain a target blank; Step b: placing the target material blank into a degreasing furnace for pre-sintering and degreasing to obtain a preform; Step c: placing the preform into a sintering furnace and sintering it until the temperature drops to room temperature to obtain the indium gallium aluminum oxide target; In step a, the molding pressure is 20-100 MPa, the molding time is 60-180 s, the cold isostatic pressing pressure is 200-500 MPa, and the molding time is 60-180 s; in step c, the sintering temperature is 1200-1550°C, the heating rate is 0.5-1°C / min, the holding time is 8-20 h, and the cooling rate is 1°C / min.

9. The method for preparing an indium gallium aluminum oxide target according to claim 8, characterized in that: In the step b, the specific operation of pre-calcination and degreasing is as follows: placing the target blank on an alumina sintering plate evenly sprinkled with 1-2 μm alumina particles, then placing it in a degreasing furnace, heating it to 400-600°C at a heating rate of 0.1-0.5°C / min, and then keeping it warm for 10-15 hours. After the insulation is completed, cooling it to room temperature at a cooling rate of 1°C / min to obtain a preform.

Images