Preparation method and application of cerium-doped indium oxide evaporation target

By doping cerium and carbon powder, the strength and porosity problems of cerium-doped indium oxide evaporation targets were solved, and high-density and high-strength targets were prepared, which are suitable for photovoltaic cells and improve the coating quality and cell efficiency.

CN119774982BActive Publication Date: 2025-09-23ZHONGSHAN ZL ADVANCED MATERIALS TECHNOLOGY
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Patent Information

Application Number
CN202411828511.2
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-12-12
Publication Date
2025-09-23
Estimated Expiration
2044-12-12

AI Technical Summary

Technical Problem

The existing cerium-doped indium oxide evaporation target has uneven porosity during the preparation process, resulting in weak target strength and easy powder loss, which affects the coating quality and cost, and is difficult to apply to high-efficiency RPD coating.

Method used

By doping cerium and carbon powder, the porosity of the target is controlled, the strength of the target is improved, the relative density is prepared to be 59%-64%, the powder loss phenomenon is optimized, and the steps of mixed ball milling, degreasing, sintering and hydraulic forming are adopted.

Benefits of technology

It increases the resistivity and strength of the target material, improves the coating quality and uniformity, is suitable for RPD coating, and enhances the conversion efficiency and stability of photovoltaic cells.

✦ Generated by Eureka AI based on patent content.

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Abstract

The present invention provides a preparation method and application of a cerium-doped indium oxide evaporation target. Compared to existing ITO targets used for heterojunction and perovskite solar cells, the preparation method of the present invention improves the resistivity of the target by doping with cerium, resulting in a target with a relative density of 59% to 64%. Furthermore, by doping with carbon powder during mixing, the present invention achieves the effects of controlling the target porosity, increasing the target strength, and optimizing the target powder shedding phenomenon. The present invention also provides a transparent conductive oxide film and a photovoltaic solar cell containing the cerium-doped indium oxide evaporation target.
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Description

Technical Field

[0001] The present invention belongs to the technical field of magnetron sputtering target material preparation, and in particular relates to a preparation method and application of a cerium-doped indium oxide evaporation target material. Background Art

[0002] Under the current technological background, transparent conductive oxide (TCO) films have become a key material in the field of photovoltaic solar cells, especially in the production of high-efficiency solar cells. The reason why these films have received widespread attention is that while allowing sunlight to pass through, they can effectively collect light-generated charges, thereby improving the efficiency of solar energy conversion. Among the many coating methods, reactive pulsed magnetron sputtering (RPD) has received special attention due to its unique advantages such as higher deposition rate, better film quality, and higher target material utilization. In the field of photovoltaic solar cells, TCO films prepared by RPD can not only improve the photoelectric conversion efficiency of solar cells, but also reduce production costs, which is of great significance for achieving cost-effective solar cell products. Therefore, RPD technology shows broad application prospects in solar cell manufacturing and is one of the important directions of current and future solar cell technology research and development.

[0003] Unlike magnetron sputtering, the RPD process generally uses a target material with a porous structure with a relative density of about 60%. This is because during the RPD coating process, a target material with too high a density is prone to cracking, and a target material with too low a density is prone to splashing dust or structural collapse, making it impossible to obtain high-quality films.

[0004] Cerium-doped indium oxide (ICO) has more application advantages than ITO in photovoltaic cells due to its advantages such as ultra-high mobility and high film stability. Although ICO thin films have certain challenges in the complexity of the coating process, the excellent properties they display make it a direction worthy of further research and development. Compared with ITO targets, the ultra-high mobility of ICO targets provides a more ideal future for photovoltaic heterojunction cells and perovskite cells. However, the current preparation process of ICO evaporation targets has uneven porosity, which causes the target material itself to have weak strength, making the target material prone to large amounts of powder loss after sintering, causing chamber contamination during the coating process and increasing production costs. The film quality and uniformity are also difficult to control. Therefore, there is an urgent need to develop an ICO target preparation method that can improve the strength and porosity uniformity of the target material for evaporation. Summary of the Invention

[0005] The present invention aims to address at least one of the aforementioned technical problems existing in the prior art. To this end, the present invention provides a method for preparing a cerium-doped indium oxide evaporation target. Compared to existing ITO targets used in heterojunction and perovskite solar cells, the present invention improves the target's resistivity by doping it with cerium, resulting in a target with a relative density of 59%-64%. Furthermore, by doping it with carbon powder during mixing, the present invention controls the target's porosity, improves its strength, and mitigates target powder shedding.

[0006] The present invention also provides a cerium-doped indium oxide evaporation target material.

[0007] The invention also provides a transparent conductive oxide film.

[0008] The present invention also provides a photovoltaic solar cell.

[0009] A first aspect of the present invention provides a method for preparing a cerium-doped indium oxide evaporation target, comprising the following steps:

[0010] S1: Mix nano-cerium oxide powder and nano-indium oxide powder and ball mill them. After granulation, the materials are divided into two parts: material A1 and material B1;

[0011] S2: adding water to the material B1, and performing compression molding and granulation to obtain material B2;

[0012] S3: heating the material A1 and the material B2 to degrease them separately, and then performing the first sintering on them after degreasing;

[0013] S4: ball milling the material A1 obtained after the first sintering to obtain material A2;

[0014] S5: dry-mixing the carbon powder with the material A2 to obtain a material C, homogenously mixing the material C with the material B2 processed in step S3, adding water to the mixture, and hydroforming the mixture to obtain a target blank;

[0015] S6: sintering the target material blank to obtain a blank, and cutting and polishing the blank to obtain the cerium-doped indium oxide evaporation target.

[0016] A technical solution of the present invention in a method for preparing a cerium-doped indium oxide evaporation target has at least the following beneficial effects:

[0017] Compared to existing ITO targets used in heterojunction and perovskite solar cells, this invention improves the resistivity of the target by doping it with cerium, resulting in a target with a relative density of 59%-64%. Furthermore, by doping it with carbon powder during mixing, this invention controls the target porosity, improves its strength, and mitigates target powder shedding.

[0018] The target material prepared by the present invention is applied to photovoltaic heterojunction cells and perovskite cells, is suitable for RPD coating, and can improve the conversion efficiency of the cells.

[0019] According to some embodiments of the present invention, in the preparation method of the present invention, the sum of the masses of nano-indium oxide powder, nano-cerium oxide powder and nano-carbon powder is 100%, wherein the mass of nano-indium oxide powder accounts for 94%-98%, the mass of nano-cerium oxide powder accounts for 1.5%-5%, and the mass of nano-carbon powder accounts for 0.5%-1%.

[0020] According to some embodiments of the present invention, in step S1, the D50 of the nano-cerium oxide powder is 30-50 nm.

[0021] According to some embodiments of the present invention, the D50 of the nano-indium oxide powder is 20-100 nm.

[0022] According to some embodiments of the present invention, in step S1, the mass ratio of material A1 to material B1 is 1:1 to 1.25.

[0023] According to some embodiments of the present invention, in step S3, the degreasing temperature is 600-650°C.

[0024] According to some embodiments of the present invention, the heating rate of the degreasing is 1.5°C / min-2°C / min.

[0025] According to some embodiments of the present invention, the degreasing holding time is 2-3 hours.

[0026] According to some embodiments of the present invention, the first sintering step includes: raising the temperature to 850-900°C at 0.5-1.5°C / min, keeping warm for 3-4 hours, then raising the temperature to 1350-1450°C at 0.5-1°C / min, keeping warm for 3-10 hours, and then naturally cooling to room temperature.

[0027] According to some embodiments of the present invention, the first sintering step includes: raising the temperature to 850-900°C at 1°C / min, keeping warm for 3.5 hours, then raising the temperature to 1350-1450°C at 0.5°C / min, keeping warm for 5 hours, and then naturally cooling to room temperature.

[0028] According to some embodiments of the present invention, in step S5, the hydraulic forming pressure is 10 MPa-20 MPa.

[0029] According to some embodiments of the present invention, in step S6, the step of sintering the green billet includes: heating the temperature to 600-650°C at a heating rate of 1.5°C / min-2°C / min for degreasing, keeping the temperature for 2-3 hours, heating the temperature to 850-900°C at a heating rate of 0.5-2°C / min, keeping the temperature for 3-4 hours, heating the temperature to 1400-1450°C at a heating rate of 0.5-1°C / min, keeping the temperature for 5-15 hours, and then naturally cooling to room temperature.

[0030] According to some embodiments of the present invention, in step S6, the diameter of the target material after cutting and polishing may be 30 mm, and the height may be 40 mm.

[0031] The second aspect of the present invention provides a cerium-doped indium oxide evaporation target, which is prepared by the preparation method of the first aspect of the present invention.

[0032] One of the technical solutions of the present invention regarding the cerium-doped indium oxide evaporation target material has at least the following beneficial effects:

[0033] Improve resistivity: Doping with cerium significantly increases the resistivity of the target material, which helps to optimize the electrical performance of photovoltaic cells.

[0034] Enhanced strength: By doping with carbon powder, the strength of the target material is improved, which reduces the powder loss during use and increases the service life of the target material.

[0035] Optimizing porosity: Regulating the porosity of the target material helps improve the uniformity and deposition quality of the material during the evaporation process, thereby enhancing the performance of photovoltaic devices.

[0036] Wide applicability: This target is suitable for RPD coating and can be effectively used in photovoltaic heterojunction cells and perovskite cells to improve the conversion efficiency of the cells.

[0037] Simple and efficient preparation: Compared with traditional preparation methods, the method of the present invention simplifies the production process, improves the consistency and repeatability of the target material, and meets the requirements of industrial production.

[0038] Through these advantages, the target material of the present invention can exert greater performance improvement potential in the photovoltaic field.

[0039] The third aspect of the present invention provides a transparent conductive oxide film, which is prepared from the cerium-doped indium oxide evaporation target material of the second aspect of the present invention.

[0040] One of the technical solutions of the present invention regarding the transparent conductive oxide film has at least the following beneficial effects:

[0041] Excellent electrical conductivity: Cerium-doped targets improve the electrical conductivity of thin films and enhance their conductive properties in electronic devices.

[0042] High light transmittance: The film maintains good transparency and is suitable for use in optoelectronic applications such as solar cells and displays.

[0043] Thermal stability: Cerium doping enhances the thermal stability of the film, enabling it to maintain excellent performance under high temperature conditions.

[0044] Excellent mechanical properties: The strength and toughness of the film are improved, reducing peeling and damage during use.

[0045] Oxidation resistance: Cerium doping improves the corrosion resistance of the film, helping to extend its service life and stability.

[0046] A fourth aspect of the present invention provides a photovoltaic solar cell comprising the transparent conductive oxide thin film according to the third aspect of the present invention.

[0047] One of the technical solutions of the present invention regarding photovoltaic solar cells has at least the following beneficial effects:

[0048] Improve conversion efficiency: Excellent conductivity and high light transmittance enhance the photoelectric conversion efficiency, making the battery more efficient in absorbing light energy.

[0049] Improved stability: The thermal stability and oxidation resistance of the film enhance the reliability and durability of the battery under various environmental conditions.

[0050] Weight reduction: Transparent conductive films are generally lighter than traditional conductive materials, which helps reduce the weight of the entire battery and facilitates installation and use.

[0051] Cost reduction: By optimizing material properties, it is possible to reduce the need for expensive materials, thereby reducing overall production costs.

[0052] Wide applicability: Suitable for various types of photovoltaic applications, such as heterojunction cells and perovskite cells, broadening the application range of batteries. DETAILED DESCRIPTION

[0053] The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0054] In a first aspect, some embodiments of the present invention provide a method for preparing a cerium-doped indium oxide evaporation target, comprising the following steps:

[0055] S1: Mix nano-cerium oxide powder and nano-indium oxide powder and ball mill them. After granulation, the materials are divided into two parts: material A1 and material B1;

[0056] S2: Add water to material B1 and perform compression granulation to obtain material B2;

[0057] S3: heating and degreasing material A1 and material B2 respectively, and then performing the first sintering after degreasing;

[0058] S4: ball milling the material A1 obtained after the first sintering to obtain material A2;

[0059] S5: Dry-mixing the carbon powder with material A2 to obtain material C, homogenously mixing material C with material B2 processed in step S3, adding water to the mixture, and hydroforming to obtain a target blank;

[0060] S6: Sintering the target blank to obtain a blank, and cutting and polishing the blank to obtain a cerium-doped indium oxide evaporation target.

[0061] It should be noted that compared to existing ITO targets used in heterojunction and perovskite solar cells, the present invention improves the resistivity of the target material by doping it with cerium, resulting in a target material with a relative density of 59%-64%. Furthermore, by doping it with carbon powder during mixing, the present invention achieves the effects of controlling the target material's porosity, increasing its strength, and minimizing target material shedding.

[0062] The target material prepared by the present invention is applied to photovoltaic heterojunction cells and perovskite cells, is suitable for RPD coating, and can improve the conversion efficiency of the cells.

[0063] In combination with the first aspect, in some embodiments of the present invention, in the preparation method of the present invention, the mass proportion of nano-indium oxide powder is 94%-98%, the mass proportion of nano-cerium oxide powder is 1.5%-5%, and the mass proportion of nano-carbon powder is 0.5%-1%.

[0064] It should be noted that in step S1, the material is divided into two parts, material A1 and material B1, after granulation. The purpose is to obtain two powder precursors with different densities before the pre-sintering process. Material A1 is directly sintered without mold granulation, which is beneficial for subsequent ball milling to obtain powder particles with smaller particle size. Therefore, after granulation, the material is first divided into two parts, material A1 and material B1, water is added to material B1, and mold granulation is performed to obtain material B2. Then, material A1 and material B2 are heated and degreased separately. After degreasing, they are sintered for the first time respectively. Material A1 obtained after the first sintering is ball milled to obtain material A2, which is beneficial for obtaining powders of two particle sizes for mixing.

[0065] In combination with the first aspect, in some embodiments of the present invention, in step S1, the D50 of the nano-cerium oxide powder is 30-50 nm.

[0066] In combination with the first aspect, in some embodiments of the present invention, the D50 of the nano-indium oxide powder is 20-100 nm.

[0067] In combination with the first aspect, in some embodiments of the present invention, in step S1, the mass ratio of material A1 to material B1 is 1:1 to 1.25.

[0068] In combination with the first aspect, in some embodiments of the present invention, in step S3, the degreasing temperature is 600-650°C.

[0069] In combination with the first aspect, in some embodiments of the present invention, the heating rate of the degreasing step is 1.5° C. / min-2° C. / min.

[0070] In combination with the first aspect, in some embodiments of the present invention, the holding time of the degreasing step is 2-3 hours.

[0071] In combination with the first aspect, in some embodiments of the present invention, the first sintering step includes: raising the temperature to 850-900°C at 1°C / min, keeping warm for 3.5 hours, then raising the temperature to 1350-1450°C at 0.5°C / min, keeping warm for 5 hours, and then naturally cooling to room temperature.

[0072] In combination with the first aspect, in some embodiments of the present invention, in step S5, the molding pressure of the hydraulic molding is 10 MPa-20 MPa.

[0073] In combination with the first aspect, in some embodiments of the present invention, in step S6, the step of sintering the green billet includes: heating to 600-650°C at a heating rate of 1.5°C / min-2°C / min for degreasing, keeping warm for 2-3 hours, heating to 850-900°C at 1°C / min, keeping warm for 3.5 hours, heating to 1400-1450°C at 0.5°C / min, keeping warm for 10 hours, and then naturally cooling to room temperature.

[0074] In combination with the first aspect, in some embodiments of the present invention, in step S6, the diameter of the target material after cutting and polishing may be 30 mm, and the height may be 40 mm.

[0075] In a second aspect, some embodiments of the present invention provide a cerium-doped indium oxide evaporation target, which is prepared by the preparation method of the first aspect of the present invention.

[0076] The cerium-doped indium oxide evaporation target material of the present invention, doped with cerium element, significantly improves the resistivity of the target material, which helps to optimize the electrical performance of photovoltaic cells. By doping with carbon powder, the strength of the target material is improved, the powder loss phenomenon during use is reduced, and the service life of the target material is increased. By regulating the porosity of the target material, it helps to improve the uniformity and deposition quality of the material during the evaporation process, thereby improving the performance of photovoltaic equipment. Furthermore, the target material is suitable for RPD coating and can be effectively applied to photovoltaic heterojunction cells and perovskite cells to improve the conversion efficiency of the battery. Compared with traditional preparation methods, the method of the present invention simplifies the production process, improves the consistency and repeatability of the target material, and meets the requirements of industrial production. Through these advantages, the target material of the present invention can exert greater performance improvement potential in the photovoltaic field.

[0077] In a third aspect, some embodiments of the present invention provide a transparent conductive oxide film, which is prepared from the cerium-doped indium oxide evaporation target material of the second aspect of the present invention.

[0078] The transparent conductive oxide thin film of the present invention, doped with cerium in the target material, improves the film's conductivity and enhances its conductive properties in electronic devices. The film maintains good transparency, making it suitable for use in optoelectronic applications such as solar cells and displays. Cerium doping enhances the film's thermal stability, enabling it to maintain excellent performance even under high-temperature conditions. This improves the film's strength and toughness, reducing flaking and damage during use. Cerium doping also enhances the film's corrosion resistance, helping to extend its service life and stability.

[0079] In a fourth aspect, some embodiments of the present invention provide a photovoltaic solar cell comprising the transparent conductive oxide thin film according to the third aspect of the present invention.

[0080] The photovoltaic solar cell of the present invention has excellent electrical conductivity and high light transmittance, which enhances the photoelectric conversion efficiency and makes the cell more efficient in absorbing light energy. The thermal stability and oxidation resistance of the film improve the reliability and durability of the cell under various environmental conditions. Transparent conductive films are generally lighter than traditional conductive materials, which helps to reduce the weight of the entire cell and facilitates installation and use. Furthermore, by optimizing material properties, it is possible to reduce the demand for expensive materials, thereby reducing overall production costs. The photovoltaic solar cell of the present invention is suitable for various types of photovoltaic applications, such as heterojunction cells and perovskite cells, which broadens the application range of the cell.

[0081] The following will clearly and completely describe the concept and technical effects of the present invention in conjunction with the embodiments to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0082] In the description of the present invention, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the exemplary expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0083] Unless otherwise specified, "room temperature" in the present invention means 25°C±5°C.

[0084] Unless otherwise specified, “about” in the present invention means that the allowable error is within ±2%.

[0085] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0086] Example 1

[0087] A cerium-doped indium oxide evaporation target was prepared, and the specific steps were as follows:

[0088] S1: Mix nano-cerium oxide powder and nano-indium oxide powder and ball mill them. After granulation, the materials are divided into two parts: material A1 and material B1;

[0089] S2: adding water to the material B1, and performing compression molding and granulation to obtain material B2;

[0090] S3: heating the material A1 and the material B2 to degrease them separately, and then performing the first sintering on them after degreasing;

[0091] S4: ball milling the material A1 obtained after the first sintering to obtain material A2;

[0092] S5: dry-mixing the carbon powder with the material A2 to obtain a material C, homogenously mixing the material C with the material B2 processed in step S3, adding water to the mixture, and hydroforming the mixture to obtain a target blank;

[0093] S6: sintering the target material blank to obtain a blank, and cutting and polishing the blank to obtain the cerium-doped indium oxide evaporation target.

[0094] Among the preparation raw materials, the mass proportion of nano-indium oxide powder is 94%, the mass proportion of nano-cerium oxide powder is 5%, and the mass proportion of nano-carbon powder is 1%.

[0095] In step S1:

[0096] The D50 of nano-cerium oxide powder is 40 nm.

[0097] The D50 of the nano-indium oxide powder is 60 nm.

[0098] The mass ratio of material A1 to material B1 is 1:1.

[0099] In step S3:

[0100] The degreasing temperature is 630°C.

[0101] The heating rate of degreasing is 2℃ / min.

[0102] The holding time for degreasing is 2h.

[0103] The first sintering step includes: increasing the temperature to 900°C at 1°C / min, keeping the temperature for 3.5 hours, increasing the temperature to 1400°C at 0.5°C / min, keeping the temperature for 5 hours, and then naturally cooling to room temperature.

[0104] In step S5:

[0105] The forming pressure of the hydroforming is 15 MPa.

[0106] In step S6:

[0107] The steps of sintering the green billet include: heating to 650°C at a heating rate of 2°C / min for debinding, keeping warm for 2 hours, heating to 870°C at a heating rate of 1°C / min, keeping warm for 3.5 hours, heating to 1400°C at a heating rate of 0.5°C / min, keeping warm for 10 hours, and then naturally cooling to room temperature.

[0108] The target material after cutting and polishing has a diameter of 30 mm and a height of 40 mm.

[0109] Example 2

[0110] A cerium-doped indium oxide evaporation target was prepared. The difference from Example 1 was that, in the preparation raw materials, the mass proportion of nano-indium oxide powder was 95%, the mass proportion of nano-cerium oxide powder was 4.25%, and the mass proportion of nano-carbon powder was 0.75%.

[0111] Example 3

[0112] A cerium-doped indium oxide evaporation target was prepared. The difference from Example 1 was that, in the preparation raw materials, the mass proportion of nano-indium oxide powder was 96%, the mass proportion of nano-cerium oxide powder was 3.5%, and the mass proportion of nano-carbon powder was 0.5%.

[0113] Example 4

[0114] A cerium-doped indium oxide evaporation target was prepared. The difference from Example 1 was that, in the preparation raw materials, the mass proportion of nano-indium oxide powder was 97%, the mass proportion of nano-cerium oxide powder was 2.5%, and the mass proportion of nano-carbon powder was 0.5%.

[0115] Example 5

[0116] A cerium-doped indium oxide evaporation target was prepared. The difference from Example 1 was that, in the preparation raw materials, the mass proportion of nano-indium oxide powder was 98%, the mass proportion of nano-cerium oxide powder was 1.5%, and the mass proportion of nano-carbon powder was 0.5%.

[0117] Comparative Example 1

[0118] A cerium-doped indium oxide evaporation target was prepared. The difference from Example 1 was that no nano-carbon powder was added to the preparation raw materials, the mass proportion of nano-indium oxide powder was 96%, and the mass proportion of nano-cerium oxide powder was 4%.

[0119] Comparative Example 2

[0120] A cerium-doped indium oxide evaporation target was prepared. The difference from Example 1 was that, in the preparation raw materials, the mass proportion of nano-indium oxide powder was 94.5%, the mass proportion of nano-cerium oxide powder was 3.5%, and the mass proportion of nano-carbon powder was 2%.

[0121] Comparative Example 3

[0122] A cerium-doped indium oxide evaporation target was prepared. The difference from Example 1 was that, in the preparation raw materials, the mass proportion of nano-indium oxide powder was 90%, the mass proportion of nano-cerium oxide powder was 9.5%, and the mass proportion of nano-carbon powder was 0.5%.

[0123] Performance Testing

[0124] The targets prepared in the examples and comparative examples were tested for powder loss, shrinkage, relative density, and resistivity. The results are shown in Table 1.

[0125] The test method for powder loss is: if there is powder residue after wiping the target surface with a dust-free cloth, the powder loss is more serious; if there is no powder residue on the surface without dust-free paper, the powder loss is mild.

[0126] The test method for shrinkage is: the volume of the target after sintering is divided by the volume before sintering.

[0127] The test method for relative density is the wax sealing method.

[0128] The test method for resistivity is: resistivity tester.

[0129] Table 1

[0130]

[0131]

[0132] In Example 1-5, the doping ratio of cerium oxide and carbon powder is adjusted compared with Comparative Example 1-3, wherein the mass proportion of indium oxide powder is 94%-98%, the mass proportion of nano-scale tungsten oxide powder is 1.5%-5%, and the mass proportion of nano-scale carbon powder is 0.5%-1%.

[0133] Carbon powder plays a role in controlling the porosity of the target material during the molding process, which greatly improves the molding strength compared to when no carbon powder is added. During the sintering process, the carbon powder is converted into carbon dioxide under the action of high temperature and oxygen atmosphere, thereby achieving the effect of controlling the porosity of the target material. Finally, with the appropriate cerium oxide doping ratio, the final sintering is to obtain a high-quality ICO target material for vapor deposition with a high-strength surface and controllable relative density.

[0134] In Comparative Example 1, without adding carbon powder, the sintering shrinkage of the target material is too high and the relative density is too large, and it is not suitable for RPD coating.

[0135] In Comparative Example 2, the carbon powder doping ratio is too high, resulting in excessive porosity and too low relative density of the target after sintering, which ultimately causes the target to still suffer from severe powder loss and is not suitable for RPD coating.

[0136] In comparative example 3, excessive doping of cerium oxide nanoparticles resulted in excessive lattice distortion, causing the target to crack during sintering.

[0137] Examples 1-5 control the doping ratio to produce ICO targets with suitable shrinkage and relative density for vapor deposition. The sintered targets exhibit excellent resistivity and strength, and the processed vapor deposition targets are stable for RPD coating.

[0138] The present invention has been described in detail above with reference to the embodiments. However, the present invention is not limited to the above embodiments. Various changes can be made within the scope of knowledge possessed by ordinary technicians in the relevant technical field without departing from the spirit of the present invention.

Claims

1. A method for preparing a cerium-doped indium oxide evaporation target, characterized in that: The following steps are involved: S1: Mix nano-cerium oxide powder and nano-indium oxide powder and ball mill them. After granulation, the materials are divided into two parts: material A1 and material B1; S2: adding water to the material B1, and performing compression molding and granulation to obtain material B2; S3: heating the material A1 and the material B2 to degrease them separately, and then performing the first sintering on them after degreasing; S4: ball milling the material A1 obtained after the first sintering to obtain material A2; S5: dry-mixing the nano-carbon powder with the material A2 to obtain a material C, homogeneously mixing the material C with the material B2 processed in step S3, adding water to the mixture, and hydroforming the mixture to obtain a target blank; S6: sintering the target material blank in an oxygen atmosphere to obtain a blank, and cutting and polishing the blank to obtain the cerium-doped indium oxide evaporation target; Among the preparation raw materials, the mass proportion of nano-indium oxide powder is 94%-98%, the mass proportion of nano-cerium oxide powder is 1.5%-5%, and the mass proportion of nano-carbon powder is 0.5%-1%.

2. The preparation method according to claim 1, characterized in that In step S1, the D50 of the nano-cerium oxide powder is 30-50 nm; and / or the D50 of the nano-indium oxide powder is 20-100 nm.

3. The preparation method according to claim 1, characterized in that In step S1, the mass ratio of material A1 to material B1 is 1:1~1.

25.

4. The preparation method according to claim 1, characterized in that In step S3, the temperature of the degreasing is 600-650°C; and / or the heating rate of the degreasing is 1.5°C / min-2°C / min; and / or the holding time of the degreasing is 2-3h; And / or, the first sintering step includes: raising the temperature to 850-900°C at 0.5-1.5°C / min, keeping the temperature for 3-4 hours, then raising the temperature to 1350-1450°C at 0.5-1°C / min, keeping the temperature for 3-10 hours, and then naturally cooling to room temperature.

5. The preparation method according to claim 1, characterized in that In step S5, the molding pressure of the hydraulic molding is 10MPa-20MPa.

6. The preparation method according to claim 1, characterized in that In step S6, the step of sintering the green billet includes: heating the temperature to 600-650°C at a heating rate of 1.5°C / min-2°C / min for degreasing, keeping the temperature for 2-3 hours, heating the temperature to 850-900°C at a heating rate of 0.5-2°C / min, keeping the temperature for 3-4 hours, heating the temperature to 1400-1450°C at a heating rate of 0.5-1°C / min, keeping the temperature for 5-15 hours, and then naturally cooling to room temperature.

7. A cerium-doped indium oxide evaporation target, characterized in that: The method is prepared according to any one of claims 1 to 6.

8. A transparent conductive oxide film, characterized in that It is prepared from the cerium-doped indium oxide evaporation target material according to claim 7.

9. A photovoltaic solar cell, characterized in that The transparent conductive oxide film according to claim 8 is included.

Citation Information

Patent Citations

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