Indium titanium tantalum cerium oxide target material, preparation method and application thereof

Abstract

This invention belongs to the field of solar energy target materials and discloses a method for preparing indium titanium tantalum cerium target material. The method involves first mixing metal oxides, additives, and deionized water to form a slurry, ball milling, and sieving to obtain powder one; then drying, crushing, and sieving the powder one to obtain powder two; subsequently, molding and cold isostatic pressing of powder two to obtain a target material precursor; finally, placing the target material precursor in a sintering furnace, sintering, and cooling to room temperature to obtain the indium titanium tantalum cerium target material. Furthermore, this invention also discloses an indium titanium tantalum cerium target material that, by doping the indium cerium tantalum titanium target material with tin elements of similar ionic radii and employing a two-step sintering process, achieves improved target material density and electron mobility.

Description

Technical Field

[0001] This invention relates to the field of solar energy targets, and more particularly to an indium titanium tantalum cerium target, its preparation method, and its application. Background Technology

[0002] Transparent conductive oxide (TCO) thin films are thin film materials with high transmittance and low resistivity in the visible light spectrum range of 380nm to 780nm. Due to their excellent conductivity like metals, high transmittance like glass, high reflectivity in the infrared region, and other excellent semiconductor properties, they are widely used in displays, solar cells, light-emitting diodes, touch screens, gas sensors, as well as microelectronics, vacuum electronic devices, and other fields. In the field of solar cells, when light is incident from the top cell onto the surface of the intermediate connecting layer TCO, light reflection and transmission occur: in tandem solar cells, the top cell needs to absorb ultraviolet-visible light (300-780nm) while the near-infrared light (780-1400nm) is absorbed and utilized by the bottom cell. Therefore, the intermediate TCO layer is required to have the following characteristics: (1) good optical transmittance: its transmittance in the visible light band of 380nm to 780nm is greater than 80%; (2) good conductivity: its resistivity is generally lower than 10. -3 Ω.cm; (3) Wide bandwidth.

[0003] There are many types of TCO thin films. The most common ones are films doped with neighboring cations or anions, such as zinc oxide-based ZnO, tin oxide-based SnO2, and indium oxide-based In2O3. Since tin replaces indium, this target material improves the mobility of impurity ions, thereby increasing the carrier mobility and reducing the resistivity of the target material. Tin doping has always been a research hotspot.

[0004] Among them, Chinese patent application 202310691428.4 discloses an indium cerium oxide target material and its preparation method based on high-temperature sintering. The preparation method is as follows: indium oxide, titanium oxide, tantalum oxide, cerium oxide, dispersant, binder and deionized water are mixed and ball-milled into a slurry; the ball-milled slurry is dried and calcined to obtain powder; the powder is subjected to hydraulic forming and cold isostatic pressing to obtain an indium cerium oxide tantalum titanium oxide precursor; and the indium cerium oxide tantalum titanium oxide precursor is then subjected to high-temperature sintering to obtain an indium cerium oxide tantalum titanium oxide target material.

[0005] This scheme utilizes indium oxide, titanium oxide, tantalum oxide, and cerium oxide for further high-temperature sintering to obtain indium cerium tantalum titanium oxide target material, thereby improving the relative density and mobility of the target material.

[0006] Chinese patent application 202410193760.2 discloses a high-density, high-mobility indium oxide doped target and its preparation method. The preparation method is as follows: indium oxide, tin oxide, rare earth oxide, binder, dispersant and stabilizer are mixed and ground, and spray granulation, molding and cold isostatic pressing are performed in sequence to obtain a green blank. Then the green blank is sintered at high temperature to obtain a high-density, high-mobility indium oxide doped target.

[0007] This method involves doping with tin oxide and holding the sintering process at a maximum temperature of 1500–1600°C to obtain an indium oxide-doped tin target, thereby improving the target's density and mobility.

[0008] It is easy to see from the two schemes above that the density and mobility of the target material can be improved by sintering with a combination of various metal oxides or by doping with tin oxide and holding at the highest temperature during sintering.

[0009] The problem this solution aims to address is: how to propose a method to improve the target material process and thus enhance its performance. Summary of the Invention

[0010] The purpose of this invention is to provide a method for preparing indium titanium tantalum cerium target material. By doping the indium titanium tantalum titanium target material with metal elements of similar ionic radius and using a two-step sintering method during the sintering process, the density and mobility of the obtained indium titanium tantalum cerium target material are significantly improved.

[0011] To achieve the above objectives, this application discloses a method for preparing an indium titanium tantalum cerium target, comprising the following steps:

[0012] Step 1: Mix the metal oxide, additives, and deionized water, then ball mill and sieve to obtain powder one;

[0013] Step 2: Dry, crush, and sieve the powder obtained in Step 1 to obtain powder 2;

[0014] Step 3: The powder obtained in Step 2 is molded and cold isostatically pressed to obtain the target precursor;

[0015] Step 4: Place the target precursor obtained in Step 3 in a sintering furnace, sinter, and cool to obtain indium titanium tantalum cerium target material;

[0016] The metal oxides in step 1 are indium oxide, titanium oxide, tantalum oxide, and cerium oxide;

[0017] The sintering process in step 4 is as follows: under aerobic conditions, the temperature is increased to 400-900℃ at a rate of 0.05-0.5℃ / min and held for 3-6 hours; then the temperature is increased to 1350-1500℃ at a rate of 0.5-1℃ / min, and then decreased to 1200-1350℃ at a rate of 1-3℃ / min and held for 15-30 hours.

[0018] Preferably, step 1 further includes a dopant selected from one or more of tin oxide, cadmium oxide, and antimony trioxide.

[0019] Preferably, the mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and dopant is 97.5–99.5: 0.02–0.2: 0.05–0.5: 0.1–1: 0.01–0.1.

[0020] Preferably, the additives in step 1 are dispersants and binders. The dispersant is selected from one or more of polyvinylpyrrolidone, polycarboxylic acid compounds, and polyvinyl salts; the binder is selected from one or more of polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, polyacrylates, and polyethylene glycol.

[0021] Preferably, the mass of the dispersant is 1% to 3% of the total mass of the metal oxide and dopant; the mass of the binder is 1% to 3% of the total mass of the metal oxide and dopant; and the mass of the deionized water is 30% to 40% of the total mass of the metal oxide and dopant.

[0022] Preferably, in step 1, the D10 particle size of powder one is 0.05-0.1 μm, the D50 particle size is 0.1-0.5 μm, and the D90 particle size is 0.5-1 μm.

[0023] Preferably, in step 2, a 60-80 mesh sieve is used for sieving.

[0024] Preferably, the molding pressure in step 3 is 30-60 MPa; the cold isostatic pressing pressure is 350-450 MPa.

[0025] In addition, it also includes an indium titanium tantalum cerium target material, which is prepared by a method for preparing an indium titanium tantalum cerium target material.

[0026] The beneficial effects of this invention are:

[0027] This invention provides a method for preparing indium tin oxide (ITO) titanium tantalum tantalum cerium target material. By doping the ITO titanium tin oxide target material with metal elements of similar ionic radius, the crystal structure of indium oxide shrinks, acting as a sintering aid, thereby greatly increasing the density and conductivity of the ITO titanium tantalum tantalum tin-doped target material. In the sintering process, a two-step sintering method is used. At the highest temperature, the target material eliminates large pores at the critical density. Then, it is held at a temperature 50-200°C below the highest temperature. The remaining small-sized unstable pores are gradually eliminated during the T2 stage of holding, along with the densification of the target material, reducing the grain growth rate and slowly eliminating pores in the billet, thereby achieving a high density. Detailed Implementation

[0028] In the description of this invention, it should be noted that unless specific conditions are specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0029] Example 1

[0030] Step 1: Indium oxide, titanium oxide, tantalum oxide, cerium oxide, and tin oxide are mixed with polyvinyl chloride, polyvinyl alcohol, and deionized water in a mass ratio of 98.8:0.1:0.45:0.6:0.05, and then ball-milled and sieved to obtain powder with D10 = 0.075 μm, D50 = 0.3 μm, and D90 = 0.75 μm.

[0031] Step 2: Dry the powder obtained in Step 1 at 100℃, crush it, and sieve it through an 80-mesh sieve to obtain powder 2;

[0032] Step 3: The powder obtained in Step 2 is molded at 45MPa and then cold isostatically pressed at 400MPa to obtain the target precursor.

[0033] Step 4: Place the target precursor obtained in Step 3 in a sintering furnace, and under aerobic conditions, heat it to 600℃ at 0.3℃ / min and hold it for 4.5h; then heat it to 1400℃ at 0.7℃ / min, and then cool it to 1300℃ at 2℃ / min and hold it for 23h. Cool it to room temperature to obtain indium titanium tantalum cerium target material.

[0034] Example 2

[0035] The process is basically the same as in Example 1, except that the mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and tin oxide in step 1 is 97.5:0.1:0.45:0.6:0.1.

[0036] Example 3

[0037] The process is basically the same as in Example 1, except that the mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and tin oxide in step 1 is 99.5:0.1:0.45:0.6:0.01.

[0038] Example 4

[0039] The process is basically the same as in Example 1, except that the mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and cadmium oxide in step 1 is 98.8:0.1:0.45:0.6:0.05.

[0040] Example 5

[0041] The process is basically the same as in Example 1, except that the mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and antimony trioxide in step 1 is 98.8:0.1:0.45:0.6:0.05.

[0042] Example 6

[0043] It is basically the same as Example 1, except that:

[0044] Step 4: Place the target precursor obtained in Step 3 in a sintering furnace, and under aerobic conditions, heat it to 400℃ at 0.05℃ / min and hold it for 3 hours; then heat it to 1350℃ at 0.5℃ / min, and then cool it to 1200℃ at 1℃ / min and hold it for 15 hours. Cool it to room temperature to obtain indium titanium tantalum cerium target material.

[0045] Example 7

[0046] It is basically the same as Example 1, except that:

[0047] Step 4: Place the target precursor obtained in Step 3 in a sintering furnace, and under oxygen-containing conditions, heat it to 900℃ at 0.5℃ / min and hold it for 6 hours; then heat it to 1500℃ at 1℃ / min, and then cool it to 1350℃ at 3℃ / min and hold it for 30 hours. After cooling to room temperature, indium titanium tantalum cerium target material is obtained.

[0048] Example 8

[0049] It is basically the same as Example 1, except that in step 1, the powder has D10 = 0.05um, D50 = 0.1um, and D90 = 0.5um.

[0050] Example 9

[0051] It is basically the same as Example 1, except that in step 1, the powder has D10 = 0.1 μm, D50 = 0.5 μm, and D90 = 1 μm.

[0052] Comparative Example 1

[0053] The process is basically the same as in Example 1, except that the mass ratio of indium oxide, titanium oxide, tantalum oxide and cerium oxide in step 1 is 97.5:0.1:0.45:0.6.

[0054] Comparative Example 2

[0055] It is basically the same as Example 1, except that:

[0056] Step 4: Place the target precursor obtained in Step 3 in a sintering furnace, and heat it to 600℃ at 0.3℃ / min under oxygen conditions, and hold it for 4.5h; then heat it to 1400℃ at 0.7℃ / min, hold it for 23h, and then cool it to room temperature to obtain indium titanium tantalum cerium target material.

[0057] Comparative Example 3

[0058] It is basically the same as Example 1, except that:

[0059] Step 4: Place the target precursor obtained in Step 3 in a sintering furnace, and heat it to 600℃ at 0.3℃ / min under oxygen conditions, and hold it for 4.5h; then heat it to 1300℃ at 0.7℃ / min, hold it for 23h, and then cool it to room temperature to obtain indium titanium tantalum cerium target material.

[0060] Comparative Example 4

[0061] It is basically the same as Example 1, except that:

[0062] Step 1: Indium oxide, titanium oxide, tantalum oxide, cerium oxide, and tin oxide are mixed with polyvinyl chloride, polyvinyl alcohol, and deionized water in a mass ratio of 98.8:0.1:0.45:0.6:0.05, and then ball-milled and sieved to obtain powder one.

[0063] Performance testing

[0064] Density testing: The density of the target material is measured using the Archimedes displacement method;

[0065] Mobility: Tested using the Hall effect method;

[0066] The performance test results are shown in Table 1 below:

[0067] Table 1

[0068] Group relative density % resistivity uΩ.cm <![CDATA[mobility cm 2 / V·s]]> Example 1 99.5 327.902 105 Example 2 99.3 373.47 104 Example 3 99.4 376.124 102 Example 4 97.7 676.709 92 Example 5 98.1 688.982 91 Example 6 99.2 382.022 99 Example 7 99.2 384.634 101 Example 8 98.6 581.056 95 Example 9 98.2 635.854 93 Comparative Example 1 97.6 854.264 74 Comparative Example 2 95.8 1065.475 79 Comparative Example 3 97.6 754.254 82 Comparative Example 4 96.5 952.465 89

[0069] Results Analysis

[0070] 1. As can be seen from Example 1 and Comparative Example 1, when tin oxide is used for doping, the relative density of the prepared indium titanium tantalum cerium target increases from 97.6% to 99.5%, and the mobility increases from 74 cm⁻¹. 2 / V·s increased to 105cm 2 The resistivity decreased from 854.264 uΩ·cm to 327.902 uΩ·cm per V·s, significantly improving the performance of the indium titanium oxide tantalum cerium target. Furthermore, as shown in Table 2:

[0071] Table 2

[0072] Group relative density % resistivity uΩ.cm <![CDATA[Mobility cm 2 / V·s]]> Example 1 99.5 327.902 105 Example 2 99.3 373.47 104 Example 3 99.4 376.124 102 Comparative Example 1 97.6 854.264 74

[0073] In Example 1, the mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and tin oxide was 98.8:0.1:0.45:0.6:0.05.

[0074] In Example 2, the mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and tin oxide was 97.5:0.1:0.45:0.6:0.1.

[0075] In Example 3, the mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and tin oxide was 99.5:0.1:0.45:0.6:0.01.

[0076] As can be seen from the above, when the mass ratio of indium oxide to tin oxide is 97.5–99.5:0.01–0.1, the performance of indium oxide titanium tantalum cerium target material is greatly improved.

[0077] 2. As can be seen from Examples 1 and 4-5, cadmium oxide and antimony trioxide were used to replace tin oxide in Examples 4 and 5, respectively. Table 3 shows that:

[0078] Table 3

[0079]

[0080]

[0081] When using metal oxides of adjacent elements such as tin, cadmium, and antimony to dope indium oxide, tin oxide doping has a better effect on improving the performance of indium oxide titanium tantalum cerium targets.

[0082] 3. As can be seen from Example 1 and Comparative Examples 2-3, in Example 1, the sintering process in step 4 is as follows: under oxygen-containing conditions, the temperature is increased to 600℃ at 0.3℃ / min and held for 4.5h; then the temperature is increased to 1400℃ at 0.7℃ / min, and then decreased to 1300℃ at 2℃ / min and held for 23h, and then cooled to room temperature;

[0083] In Comparative Example 2, the sintering process in step 4 is as follows: under oxygen-containing conditions, the temperature is increased to 600℃ at 0.3℃ / min and held for 4.5h; then the temperature is increased to 1400℃ at 0.7℃ / min and held for 23h, and then cooled to room temperature.

[0084] In Comparative Example 3, the sintering process in step 4 is as follows: under oxygen-containing conditions, the temperature is increased to 600℃ at 0.3℃ / min and held for 4.5h; then the temperature is increased to 1300℃ at 0.7℃ / min and held for 23h, and then cooled to room temperature.

[0085] The properties of the indium titanium tantalum cerium sputtering targets prepared by the above process are shown in Table 4:

[0086] Table 4

[0087] Group relative density % resistivity uΩ.cm <![CDATA[mobility cm 2 / V·s]]> Example 1 99.5 327.902 105 Comparative Example 2 95.8 1065.475 79 Comparative Example 3 97.6 754.254 82

[0088] It is evident that the performance of the indium titanium tantalum cerium target materials prepared in Comparative Examples 2 and 3 is significantly lower than that of the indium titanium tantalum cerium target material prepared in Example 1.

[0089] 4. As can be seen from Examples 1, 8-9 and Comparative Example 4, in Example 1, the particle size of the powder in step 1 is D10 = 0.075 μm, D50 = 0.3 μm and D90 = 0.75 μm;

[0090] In Example 8, the particle size of powder one in step 1 is D10 = 0.05 μm, D50 = 0.1 μm, and D90 = 0.5 μm;

[0091] In Example 9, the particle size of powder one in step 1 is D10 = 0.1 μm, D50 = 0.5 μm, and D90 = 1 μm;

[0092] In Comparative Example 4, no screening was performed in step 1, and the powder contained particles with a diameter greater than 1 μm or less than 0.05 μm. The properties of the indium titanium oxide tantalum cerium target material prepared by the above process are shown in Table 5:

[0093] Table 5

[0094] Group relative density % resistivity uΩ.cm <![CDATA[mobility cm 2 / V·s]]> Example 1 99.5 327.902 105 Example 8 98.6 581.056 95 Example 9 98.2 635.854 93 Comparative Example 4 96.5 952.465 89

[0095] It is evident that when the particle size range of powder one is controlled within the range of 0.05–0.1 μm for D10, 0.1–0.5 μm for D50, and 0.5–1 μm for D90, the performance of the indium titanium tantalum cerium target material is improved.

[0096] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing an indium titanium tantalum cerium target, characterized in that, It includes the following steps: Step 1: Mix the metal oxide, additives, dopants, and deionized water, then ball mill and sieve to obtain powder one; Step 2: Dry, crush, and sieve the powder obtained in Step 1 to obtain powder 2; Step 3: The powder obtained in Step 2 is molded and cold isostatically pressed to obtain the target precursor; Step 4: Place the target precursor obtained in Step 3 into a sintering furnace for sintering and cooling to obtain indium titanium tantalum cerium target material; The metal oxides in step 1 are indium oxide, titanium oxide, tantalum oxide, and cerium oxide; The dopant in step 1 is selected from one of tin oxide, cadmium oxide, and antimony trioxide; The sintering process in step 4 is as follows: under aerobic conditions, the temperature is increased to 400-900℃ at a rate of 0.05-0.5℃ / min and held for 3-6 hours; then the temperature is increased to 1350-1500℃ at a rate of 0.5-1℃ / min, and then decreased to 1200-1350℃ at a rate of 1-3℃ / min and held for 15-30 hours.

2. The method for preparing the indium titanium tantalum cerium target material according to claim 1, characterized in that, The mass ratio of indium oxide, titanium oxide, tantalum oxide, cerium oxide, and dopant is 97.5–99.5: 0.02–0.2: 0.05–0.5: 0.1–1: 0.01–0.

1.

3. The method for preparing the indium titanium tantalum cerium target material according to claim 1, characterized in that, The additives in step 1 are dispersants and binders, and the dispersants are selected from one or more of polyvinylpyrrolidone, polycarboxylic acid compounds, and polyvinyl salts; The adhesive is selected from one or more of polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, polyacrylate, and polyethylene glycol.

4. The method for preparing the indium titanium tantalum cerium target material according to claim 3, characterized in that, The mass of the dispersant is 1% to 3% of the total mass of the metal oxide and dopant; the mass of the binder is 1% to 3% of the total mass of the metal oxide and dopant; and the mass of the deionized water is 30% to 40% of the total mass of the metal oxide and dopant.

5. The method for preparing the indium titanium tantalum cerium target material according to claim 1, characterized in that, In step 1, the particle size of powder one is 0.05-0.1 μm for D10, 0.1-0.5 μm for D50, and 0.5-1 μm for D90.

6. The method for preparing the indium titanium tantalum cerium target material according to claim 1, characterized in that, In step 2, a 60-80 mesh sieve is used for sieving.

7. The method for preparing the indium titanium tantalum cerium target material according to claim 1, characterized in that, In step 3, the molding pressure is 30-60 MPa; the cold isostatic pressing pressure is 350-450 MPa.

8. An indium titanium tantalum cerium target material, characterized in that, It is prepared by the method of any one of claims 1-7 for the preparation of indium titanium tantalum cerium target.

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