Conductive oxide ceramic target material and preparation method thereof
By preparing ZnSb2O6-based TCO thin films and doping them with elements such as Ga2O3, In2O3, and Sc2O3, and combining ball milling, dry pressing and hot pressing sintering processes, the problem of high cost of ITO transparent conductive films was solved, and low-cost and high-performance TCO thin film preparation was achieved.
Patent Information
- Application Number
- CN202511846091.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-09
- Publication Date
- 2026-03-17
AI Technical Summary
Existing ITO transparent conductive film materials are expensive and scarce, resulting in high costs. Furthermore, alternative materials suffer from issues such as low stability and low migration rate.
By using ZnSb2O6-based TCO thin films and doping with elements such as Ga2O3, In2O3, and Sc2O3, combined with ball milling, dry pressing and hot pressing sintering processes, a low-cost ceramic target material was prepared for sputtering TCO thin films.
Low-cost TCO thin film preparation was achieved, exhibiting high electron mobility and near-infrared transmittance, making it suitable for optoelectronic products.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of materials technology, specifically relating to a low-cost conductive oxide ceramic target and its preparation method. Background Technology
[0002] Indium tin oxide (ITO) transparent conductive films possess excellent photoelectric properties, but their main drawback lies in the use of expensive indium metal. While potential alternatives include ZnO-based and SnO2-based transparent conductive films, these suffer from issues such as low stability and low mobility. Continued research into novel transparent conductive films is crucial for reducing the cost of optoelectronic products such as solar cells and liquid crystal displays. Summary of the Invention
[0003] To address the issues of high raw material prices and resource scarcity in existing ITO transparent conductive films, this invention provides a ZnSb2O6-based TCO film with low-cost advantages, exhibiting high electron mobility and near-infrared transmittance.
[0004] The technical solution of the present invention is as follows:
[0005] (1) Powder preparation: ZnO, Ga2O3, Sb2O3 components with a molar ratio of 0.92:0.08:2, ZnO, Ga2O3, In2O3, Sb2O3 components with a molar ratio of 0.92:0.04:0.04:2, ZnO, Ga2O3, In2O3, Sb2O3 components with a molar ratio of 1:0.04:0.04:1.92, or ZnO, Ga2O3, In2O3, Sc2O3, Sb2O3 components with a molar ratio of 1:0.04:0.02:0.02:1.92 are mixed in a ball mill jar, anhydrous ethanol is added as a dispersant, and zirconia balls are added to the ball mill jar according to a weight ratio of 3:1 between zirconia balls and powder; the ball mill jar is then installed on a planetary ball mill for ball milling. After ball milling, the slurry is transferred to an evaporating dish and dried in a forced-air drying oven. The dried material is then sieved to obtain target powder. The obtained powder is then pre-calcined in a muffle furnace, and the pre-calcined powder is ball-milled a second time under the same conditions as the first ball milling. The same subsequent steps are then performed to obtain target powder.
[0006] (2) Powder granulation: Take the above target powder, place it in an agate mortar, add a PVA and PEG mixed solution, grind and mix thoroughly, then put it in a forced-air drying oven to dry, and then sieve to obtain granulated powder with good flowability.
[0007] (3) Dry pressing: Pour the granulated powder into a cylindrical mold with a set inner diameter, and use a dry pressing machine to press it for 3 minutes at a pressure of 200MPa to prepare a block blank.
[0008] (4) Hot pressing sintering: The graphite mold containing the green blank is placed in a hot press furnace, sealed, and evacuated to 1×10-3 Pa; the temperature is first raised to 600℃ at a heating rate of 3℃ / min and held for 3 hours for low-temperature degreasing; then the temperature is raised to 1000~1150℃ at a heating rate of 5℃ / min, nitrogen is introduced, and the temperature is held for 4 hours for high-temperature sintering. After cooling in the furnace, Zn is obtained. 0.92 Ga 0.08 Sb₂O₆, Zn 0.92 Ga 0.04 In 0.04 Sb₂O₆, ZnGa 0.04 Sc 0.040.04 Sb 1.92 O6 or ZnGa 0.04 In 0.02 Sc 0.02 Sb 1.92 O6 ceramic target material.
[0009] Technical features and beneficial effects of the present invention:
[0010] Zn and Sb are abundant in the Earth's crust, resulting in low costs. By modifying their bandgap, carrier concentration, and mobility through doping, combined with high-density targets prepared by hot pressing, they are ideally suited for sputtering TCO thin films. Detailed Implementation
[0011] The technical solution of the present invention and its beneficial effects compared with the prior art can be fully understood through the embodiments given below.
[0012] Example 1:
[0013] Powder preparation: 4.0045g ZnO, 0.4010g Ga2O3, and 15.5946g Sb2O3 (molar ratio 0.92:0.08:2) were weighed and mixed in a 500mL ball mill jar. 80mL anhydrous ethanol was added as a dispersant. 60g of zirconia balls were added to the ball mill jar at a weight ratio of 3:1 (zirconia balls to powder). The ball mill jar was mounted on a planetary ball mill and milled at 360rpm for 6 hours. After milling, the slurry was transferred to an evaporating dish and dried in an 80℃ forced-air drying oven for 24 hours. The dried material was sieved through a 150-mesh sieve to obtain the target powder. The obtained powder was then placed in a muffle furnace and pre-calcined at 800℃ for 3 hours. The pre-calcined powder was then subjected to a second ball milling, consistent with the first milling process, and the same steps were repeated to obtain the target powder.
[0014] Powder granulation: Take the above target powder, place it in an agate mortar, add 5% wt.% PVA and 5% wt.% PEG mixed solution, grind and mix thoroughly for 30 minutes, then put it in a forced-air drying oven to dry, and then pass it through a 150-mesh sieve to obtain granulated powder with good flowability.
[0015] Dry pressing: Pour the granulated powder into a cylindrical mold with an inner diameter of 50 mm, and press it for 3 minutes at a pressure of 200 MPa using a dry pressing machine to prepare a block blank. The relative density of the block blank is measured to be 58%.
[0016] Hot pressing sintering: The graphite mold containing the green blank is placed in a hot press furnace, sealed, and evacuated to 1×10-3 Pa. First, the temperature is raised to 600℃ at a heating rate of 3℃ / min and held for 3 hours for low-temperature degreasing; then, the temperature is raised to 1150℃ at a heating rate of 5℃ / min, nitrogen gas is introduced, and the temperature is held for 4 hours for high-temperature sintering. After cooling in the furnace, the ceramic target material is obtained.
[0017] Performance testing: The obtained product Zn 0.92 Ga 0.08 The Sb₂O₆ ceramic target was tested using a four-probe method. The sample surface must be flat and clean; otherwise, poor probe contact and voltage jumps will occur. The probes must be kept perpendicular to the sample surface with uniform spacing, avoiding probe tilting or spacing deviations. The measured resistivity was 5.1025 × 10⁻⁶. -1 Ω·m.
[0018] Example 2:
[0019] Powder preparation: 3.9857g ZnO, 0.1996g Ga2O3, 0.2956g In2O3, and 15.5189g Sb2O3 were weighed in a molar ratio of 0.92:0.04:0.04:2 and mixed in a 500mL ball mill jar. 80mL of anhydrous ethanol was added as a dispersant. 60g of zirconia balls were added to the ball mill jar according to a weight ratio of zirconia balls to powder of 3:1. The ball mill jar was installed on a planetary ball mill and milled at 360rpm for 6 hours. After milling, the slurry was transferred to an evaporating dish and dried in an 80℃ forced-air drying oven for 24 hours. The dried material was sieved through a 150-mesh sieve to obtain the target powder. The obtained powder is then placed in a muffle furnace, the temperature is set to 800℃, and it is pre-fired for 3 hours. The pre-fired powder is then ball-milled a second time, in the same manner as the first ball milling, and the same steps are followed to obtain the target powder.
[0020] Powder granulation: Take the above target powder, place it in an agate mortar, add 5% wt.% PVA and 5% wt.% PEG mixed solution, grind and mix thoroughly for 30 minutes, then put it in a forced-air drying oven to dry, and then pass it through a 150-mesh sieve to obtain granulated powder with good flowability.
[0021] Dry pressing: Pour the granulated powder into a cylindrical mold with an inner diameter of 50 mm, and press it for 3 minutes at a pressure of 200 MPa using a dry pressing machine to prepare a block blank. The relative density of the block blank is measured to be 58%.
[0022] Hot pressing sintering: The graphite mold containing the green blank is placed in a hot press furnace, sealed, and evacuated to 1×10-3 Pa. First, the temperature is raised to 600℃ at a heating rate of 3℃ / min and held for 3 hours for low-temperature degreasing; then, the temperature is raised to 1150℃ at a heating rate of 5℃ / min, nitrogen gas is introduced, and the temperature is held for 4 hours for high-temperature sintering. After cooling in the furnace, the ceramic target material is obtained.
[0023] Performance testing: The obtained product Zn 0.92 Ga 0.04 In 0.04 The Sb₂O₆ ceramic target was tested using a four-probe method. The sample surface must be flat and clean; otherwise, poor probe contact and voltage fluctuations will occur. The probes must be kept perpendicular to the sample surface with uniform spacing, avoiding probe tilting or spacing deviations. The measured resistivity was 1.5308 Ω·m.
[0024] Example 3:
[0025] Powder preparation: 4.4262g ZnO, 0.2038g Ga2O3, 0.1499g Sc2O3, and 15.2199g Sb2O3 in a molar ratio of 1:0.04:0.04:1.92 were weighed and mixed in a 500mL ball mill jar. 80mL anhydrous ethanol was added as a dispersant. 60g of zirconia balls were added to the ball mill jar according to a weight ratio of zirconia balls to powder of 3:1. The ball mill jar was installed on a planetary ball mill and milled at 360rpm for 6 hours. After milling, the slurry was transferred to an evaporating dish and dried in an 80℃ forced-air drying oven for 24 hours. The dried material was sieved through a 150-mesh sieve to obtain the target powder. The obtained powder is then placed in a muffle furnace, the temperature is set to 800℃, and it is pre-fired for 3 hours. The pre-fired powder is then ball-milled a second time, in the same manner as the first ball milling, and the same steps are followed to obtain the target powder.
[0026] Powder granulation: Take the above target powder, place it in an agate mortar, add 5% wt.% PVA and 5% wt.% PEG mixed solution, grind and mix thoroughly for 30 minutes, then put it in a forced-air drying oven to dry, and then pass it through a 150-mesh sieve to obtain granulated powder with good flowability.
[0027] Dry pressing: Pour the granulated powder into a cylindrical mold with an inner diameter of 50 mm, and press it for 3 minutes at a pressure of 200 MPa using a dry pressing machine to prepare a block blank. The relative density of the block blank is measured to be 54%.
[0028] Hot pressing sintering: The graphite mold containing the green blank is placed in a hot press furnace, sealed, and evacuated to 1×10-3 Pa. First, the temperature is raised to 600℃ at a heating rate of 3℃ / min and held for 3 hours for low-temperature degreasing; then, the temperature is raised to 1000℃ at a heating rate of 5℃ / min, nitrogen is introduced, and the temperature is held for 4 hours for high-temperature sintering. After cooling in the furnace, the ceramic target material is obtained.
[0029] Performance testing: The obtained product ZnGa 0.04 Sc 0.04 Sb 1.92 The O6 ceramic target was tested using a four-probe method. The sample surface must be flat and clean; otherwise, poor probe contact and voltage jumps will occur. The probes must be kept perpendicular to the sample surface with uniform spacing, avoiding probe tilting or spacing deviations. The measured resistivity was 8.1640 × 10⁻⁶. -1 Ω·m.
[0030] Example 4:
[0031] Powder preparation: 4.4095g ZnO, 0.2030g Ga₂O₃, 0.1504g In₂O₃, 0.0747g Sc₂O₃, and 15.1624g Sb₂O₃ in a molar ratio of 1:0.04:0.02:0.02:1.92 were weighed and mixed in a 500mL ball mill jar. 80mL anhydrous ethanol was added as a dispersant. 60g of zirconia balls were added to the ball mill jar at a weight ratio of 3:1 (zirconia balls to powder). The ball mill jar was mounted on a planetary ball mill and milled at 360rpm for 6 hours. After milling, the slurry was transferred to an evaporating dish and dried in an 80℃ forced-air drying oven for 24 hours. The dried material was sieved through a 150-mesh sieve to obtain the target powder. The obtained powder is then placed in a muffle furnace, the temperature is set to 800℃, and it is pre-fired for 3 hours. The pre-fired powder is then ball-milled a second time, in the same manner as the first ball milling, and the same steps are followed to obtain the target powder.
[0032] Powder granulation: Take the above target powder, place it in an agate mortar, add 5% wt.% PVA and 5% wt.% PEG mixed solution, grind and mix thoroughly for 30 minutes, then put it in a forced-air drying oven to dry, and then pass it through a 150-mesh sieve to obtain granulated powder with good flowability.
[0033] Dry pressing: Pour the granulated powder into a cylindrical mold with an inner diameter of 50 mm, and press it for 3 minutes at a pressure of 200 MPa using a dry pressing machine to prepare a block blank. The relative density of the block blank is measured to be 54%.
[0034] Hot pressing sintering: The graphite mold containing the green blank is placed in a hot press furnace, sealed, and evacuated to 1×10-3 Pa. First, the temperature is raised to 600℃ at a heating rate of 3℃ / min and held for 3 hours for low-temperature degreasing; then, the temperature is raised to 1000℃ at a heating rate of 5℃ / min, nitrogen is introduced, and the temperature is held for 4 hours for high-temperature sintering. After cooling in the furnace, the ceramic target material is obtained.
[0035] Performance testing: The obtained product ZnGa 0.04 In 0.02 Sc 0.02 Sb 1.92 The O6 ceramic target was tested using a four-probe method. The sample surface must be flat and clean; otherwise, poor probe contact and voltage jumps will occur. The probes must be kept perpendicular to the sample surface with uniform spacing, avoiding probe tilting or spacing deviations. The resistivity after hot-pressing and sintering was measured to be 7.1435 × 10⁻⁶. -1 Ω·m.
Claims
1. A conductive oxide ceramic target material, characterized by, The chemical formula of the ceramic target is Zn 0.92 Ga 0.08 Sb2O6, Zn 0.92 Ga 0.04 In 0.04 Sb2O6, ZnGa 0.04 Sc 0.04 Sb 1.92 O6 or ZnGa 0.04 In 0.02 Sc 0.02 Sb 1.92 O6.
2. A method of producing a conductive oxide ceramic target material, characterized by, The method comprises the following steps: (1) Put ZnO, Ga2O3, Sb2O3 components with a molar ratio of 0.92:0.08:2, ZnO, Ga2O3, In2O3, Sb2O3 components with a molar ratio of 0.92:0.04:0.04:2, ZnO, Ga2O3, Sc2O3, Sb2O3 components with a molar ratio of 1:0.04:0.04:1.92 or ZnO, Ga2O3, In2O3, Sc2O3, Sb2O3 components with a molar ratio of 1:0.04:0.02:0.02:1.92 respectively into a ball mill jar as raw materials, add anhydrous ethanol as a dispersant, and add zirconia balls to the ball mill jar according to a weight ratio of zirconia balls to powder of 3:1; install the ball mill jar on a planetary ball mill, and ball mill at a speed of 360 rpm for 6 hours; after the ball milling is completed, transfer the slurry to an evaporation dish, place the evaporation dish in a forced air drying oven, dry the material after drying, sieve the material after drying with a 150-mesh sieve to obtain target material powder; and then put the obtained powder into a muffle furnace, set the temperature to 800 DEG C, pre-burn the powder for 3 hours, and then secondarily ball mill the pre-burned powder, which is consistent with the first ball milling condition, and then go through the same subsequent steps to obtain target material powder; (2) Take the target material powder, put it into an agate mortar, add a 5%wt.% PVA and 5%wt.% PEG mixed solution, grind and mix for 30 minutes, then put it into a forced air drying oven, dry it, and then sieve it with a 150-mesh sieve to obtain granulated powder with good fluidity; (3) Pour the granulated powder into a cylindrical mold with a set inner diameter, use a dry pressing machine to press the granulated powder under a pressure of 200 MPa for 3 minutes to prepare a bulk green body. (4) Place the graphite mold containing the blank into a hot press furnace, seal it, and evacuate it to 1×10⁻³ Pa. First, heat the mold to 600℃ at a heating rate of 3℃ / min and hold it at that temperature for 3 hours for low-temperature degreasing. Then, heat the mold to 1000~1150℃ at a heating rate of 5℃ / min, introduce nitrogen gas, and hold it at that temperature for 4 hours for high-temperature sintering. After cooling in the furnace, the resulting graphite molds have the chemical formula Zn. 0.92 Ga 0.08 Sb₂O₆, Zn 0.92 Ga 0.04 In 0.04 Sb₂O₆, ZnGa 0.04 Sc 0.040.04 Sb 1.92 O6 or ZnGa 0.04 In 0.02 Sc 0.02 Sb 1.92 O6 ceramic target material.