Oxide target material, oxide film, preparation method and application thereof

Abstract

The present invention discloses an oxide target material, an oxide film, and a preparation method and application thereof. The oxide target material of the present invention contains In2O3, SnO2 and ZnO, wherein, in terms of atomic molar ratio, In:Sn:Zn=9.7711:(A+N):N; wherein, 0<N<4.386, 0.3<A≤1.2, and the density of the oxide target material is greater than 99%. The oxide target material of the present invention has high density, uniform color, and will not form nodules after continuous use. The oxide film prepared by using the oxide target material of the present invention has low surface roughness, good conductivity and light transmittance, and has wide application value.

Description

Technical Field

[0001] The present invention relates to the technical field of oxide semiconductor materials, and in particular to an oxide target material, an oxide film, and a preparation method and application thereof. Background Art

[0002] With the development of heterojunction solar cells, thin-film solar cells, and LED chips, improving the properties of TCO conductive films is an eternal theme, among which improving the contact properties between the film and the substrate and the metal electrode is one of the most important key points. In related technologies, the work function matching of the gold-semiconductor contact is crucial. For heterojunction solar cells, without reducing the conductivity of the TCO film, improving the contact properties between the TCO film and amorphous silicon or microcrystalline silicon, metal electrode silver or copper electrode can make narrower grid lines, and can effectively increase the light transmission area and reduce the metal content of the metal electrode. Therefore, it is a good option for both reducing costs and improving efficiency. There are similar requirements for thin-film solar cells. For LED chips, in the TCO film that contacts the P pole with the gold electrode, improving the contact properties to improve the transport of carriers is the key to improving brightness.

[0003] Indium tin oxide (ITO) target is an N-type semiconductor material formed by solid dissolving tin dioxide in indium trioxide. It has excellent conductivity and transparency and is widely used in the preparation of TCO conductive films. However, due to the large grain size of the indium tin oxide target during film formation, the film surface is rough, which greatly limits the contact between the film and amorphous silicon or metal electrodes. In related technologies, some doping elements (such as Ti) are usually added to the target, but in practice, the addition of these doping elements can easily lead to a decrease in conductivity and transmittance.

[0004] Therefore, it is necessary to develop an oxide target material with high density, low surface roughness of the oxide film made with the target material, and excellent electrical conductivity and light transmittance. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes an oxide target material with high density, and the oxide film prepared by using the target material has low surface roughness and excellent electrical conductivity and light transmittance.

[0006] The present invention also provides an oxide film.

[0007] The invention also provides a method for preparing the oxide film.

[0008] The present invention also proposes an application of the above oxide target material or oxide film in preparing the P pole of a heterojunction solar cell.

[0009] In a first aspect of the present invention, an oxide target is provided, comprising In2O3, SnO2 and ZnO, wherein, in terms of atomic molar ratio, In:Sn:Zn=9.7711:(A+N):N;

[0010] Among them, 0<N<4.386, 0.3<A≤1.2;

[0011] The density of the oxide target is greater than 99%.

[0012] The oxide target material according to the embodiment of the present invention has at least the following beneficial effects: the oxide target material provided by the present invention has a high relative density (greater than 99%) and uniform color, and the target surface is smooth and free of nodules after continuous use.

[0013] The present invention dopes a certain amount of zinc oxide and tin oxide into an indium tin oxide target. Since the indium lattice vacancies formed by the doping of tin atoms can be additionally doped with zinc atoms of equal atomic mole, and the same atomic mole of zinc and tin atoms, one hole formed and one electron formed, do not affect the carrier concentration of the film, so the conductivity of the film is not greatly affected. Doping zinc oxide in the indium tin oxide target and increasing the total doping amount of tin oxide can effectively refine the grains of the deposited film, thereby reducing the surface roughness of the film.

[0014] According to some embodiments of the present invention, A satisfies 0.3053≤A≤1.0;

[0015] Preferably, N satisfies 0<N<4.386.

[0016] According to some embodiments of the present invention, A=1;

[0017] Preferably, the N satisfies 0.5≤N≤2.5, and further, the N satisfies 1.0≤N≤1.5.

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned oxide target, comprising the following steps:

[0019] Step S1: preparing an indium tin zinc oxide composite powder, wherein the atomic molar ratio of In, Sn and Zn in the indium tin zinc oxide composite powder is 9.7711: (A+N): N; wherein 0<N<4.386, 0.3<A≤1.2;

[0020] Step S2: spraying and granulating the indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles

[0021] Step S3: molding the indium tin zinc oxide composite particles, and obtaining a blank target material after cold isostatic pressing;

[0022] Step S4: degreasing and sintering the rough target material to obtain the oxide target material.

[0023] The method for preparing an oxide target according to an embodiment of the present invention has at least the following beneficial effects: the method for preparing an oxide target of the present invention is simple and low in cost, and the oxide target prepared by the method of the present invention has a high relative density and good color uniformity.

[0024] According to some embodiments of the present invention, in step S1, the specific preparation method of the indium tin zinc oxide composite powder includes: mixing an indium raw material solution, a tin raw material solution and a zinc raw material solution, adding a pH adjuster, adjusting the pH to 7.7 to 8.6 for reaction, and after the reaction is completed, separating the solid and the liquid, collecting the solid phase, drying the solid phase, and calcining to obtain the indium tin zinc oxide composite powder.

[0025] According to some embodiments of the present invention, the specific surface area of ​​the indium tin zinc oxide composite powder is 5m 2 / g to 20m 2 / g.

[0026] According to some embodiments of the present invention, the indium raw material solution includes at least one of indium sulfate, indium nitrate and indium chloride.

[0027] According to some embodiments of the present invention, the tin raw material solution includes at least one of tin sulfate, tin nitrate and tin chloride.

[0028] According to some embodiments of the present invention, the zinc raw material solution includes at least one of zinc sulfate, zinc nitrate and zinc chloride.

[0029] According to some embodiments of the present invention, the molar concentration of indium in the indium raw material solution is 0.05 mol / L to 0.3 mol / L.

[0030] According to some embodiments of the present invention, the molar concentration of tin in the tin raw material solution is 0.05 mol / L to 0.3 mol / L.

[0031] According to some embodiments of the present invention, the molar concentration of zinc in the zinc raw material solution is 0.05 mol / L to 0.3 mol / L.

[0032] According to some embodiments of the present invention, the pH adjuster is an inorganic base or a carbonate.

[0033] According to some embodiments of the present invention, the inorganic base is at least one of sodium hydroxide, potassium hydroxide, cesium hydroxide and ammonia monohydrate.

[0034] According to some embodiments of the present invention, the carbonate is at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate and cesium bicarbonate.

[0035] According to some embodiments of the present invention, the reaction temperature is 20°C to 45°C.

[0036] According to some embodiments of the present invention, the calcination temperature is 600°C to 1500°C.

[0037] According to some embodiments of the present invention, the calcination temperature is 600°C to 950°C.

[0038] According to some embodiments of the present invention, in step S2, the D 50 5μm~15μm.

[0039] According to some embodiments of the present invention, in step S3, the compression molding pressure is 0.1 MPa to 0.8 MPa;

[0040] Preferably, the compression molding pressure is 0.1 MPa to 0.5 MPa.

[0041] According to some embodiments of the present invention, in step S3, the pressure of the cold isostatic pressing is 150 MPa to 250 MPa.

[0042] According to some embodiments of the present invention, in step S4, the degreasing temperature is 400° C. to 700° C.;

[0043] According to some embodiments of the present invention, in step S4, the degreasing temperature rise rate is 0.5°C / min to 2°C / min.

[0044] According to some embodiments of the present invention, in step S4, the sintering temperature is 1000° C. to 1500° C.;

[0045] Preferably, the sintering temperature is 1200°C to 1400°C.

[0046] According to some embodiments of the present invention, in step S4, the heating rate of the sintering is 0.5°C / min to 5°C / min.

[0047] According to some embodiments of the present invention, in step S4, the sintering temperature reduction rate is 5°C / min to 10°C / min.

[0048] According to a third aspect of the present invention, an oxide thin film is provided, which is produced by the above-mentioned oxide target material through a sputtering deposition process or an evaporation deposition process.

[0049] The oxide thin film according to the embodiment of the present invention has at least the following beneficial effects: the oxide thin film made by using the oxide target material of the present invention has low surface roughness and good electrical conductivity and light transmittance.

[0050] In a fourth aspect of the present invention, a method for preparing the above-mentioned oxide thin film is provided, comprising installing the oxide target material on a magnetron sputtering target position, and then adjusting the vacuum in the magnetron sputtering chamber to less than 8×10 -4 Pa, and obtained after magnetron sputtering on the substrate;

[0051] Preferably, the atmosphere during the magnetron sputtering process is an argon atmosphere or a mixed atmosphere of argon and oxygen;

[0052] Preferably, the magnetic field strength on the target surface of the oxide target during the magnetron sputtering process is 300 Gs to 1000 Gs.

[0053] The method for preparing an oxide thin film according to an embodiment of the present invention has at least the following beneficial effects: the method for preparing an oxide thin film of the present invention is simple, and the deposited oxide thin film has low surface roughness and excellent electrical conductivity and light transmittance.

[0054] According to some embodiments of the present invention, when the oxide thin film is deposited on the substrate, a person skilled in the art may choose to heat the substrate as needed, and when the substrate is not heated, the deposited film layer is then annealed. The heating temperature or annealing temperature is 150 to 350°C, preferably, the heating temperature or annealing temperature is 150 to 250°C.

[0055] The method for preparing the oxide thin film of the present invention can obtain an oxide thin film with low surface roughness and good electrical conductivity and light transmittance regardless of whether the substrate is subjected to heating treatment during the deposition process.

[0056] According to some embodiments of the present invention, when the atmosphere in the magnetron sputtering process is a mixed atmosphere of argon and oxygen, the volume ratio is argon:oxygen=100:0-2.

[0057] According to some embodiments of the present invention, the sputtering gas pressure during the magnetron sputtering process is 0.05-1Pa.

[0058] According to some embodiments of the present invention, the magnetron sputtering may be DC magnetron sputtering, DC pulse magnetron sputtering, medium frequency magnetron sputtering or DC+RF magnetron sputtering.

[0059] According to some embodiments of the present invention, the power of the magnetron sputtering is 0.5w / cm 2 ~3.5w / cm 2 .

[0060] A fifth aspect of the present invention provides a use of the above-mentioned oxide target material or the above-mentioned oxide film in preparing the P pole of a heterojunction solar cell.

[0061] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:

[0063] Figure 1 This is the target surface condition of the indium tin zinc oxide target after sputtering in Example 4 of the present invention.

[0064] Figure 2 This is the target surface condition of the indium tin zinc oxide target after sputtering in Comparative Example 1 of the present invention.

[0065] Figure 3 This is the target surface condition of the indium tin zinc oxide target after sputtering in Comparative Example 2 of the present invention.

[0066] Figure 4 FIG. 4 is a phase diagram of indium tin oxide according to an embodiment of the present invention. DETAILED DESCRIPTION

[0067] The following will be combined with the embodiments to clearly and completely describe the concept of the present invention and the technical effects produced, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments 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.

[0068] In the description of the present invention, the description with reference to the terms "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 schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0069] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0070] Example 1

[0071] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0072] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1+4):4, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution for reaction. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0073] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0074] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0075] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0076] The method for preparing the oxide film specifically includes:

[0077] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0078] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0079] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0080] Example 2

[0081] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0082] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1+3.5):3.5, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution for reaction. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction liquid is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0083] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0084] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0085] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0086] The method for preparing the oxide film specifically includes:

[0087] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0088] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0089] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0090] Example 3

[0091] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0092] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1+2.5):2.5, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution for reaction. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0093] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0094] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0095] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0096] The method for preparing the oxide film specifically includes:

[0097] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0098] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0099] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0100] Example 4

[0101] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0102] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1+1.5):1.5, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution for reaction. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction liquid is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0103] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0104] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0105] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0106] The method for preparing the oxide film specifically includes:

[0107] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0108] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0109] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0110] Example 5

[0111] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0112] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L, and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1+1):1, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution, and the reaction temperature is controlled at about 30°C. During the reaction process, the reaction liquid is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed, and freeze-dried; and calcined at 900°C for 1 hour to obtain an indium tin zinc oxide composite powder.

[0113] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0114] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0115] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0116] The method for preparing the oxide film specifically includes:

[0117] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0118] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0119] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0120] Example 6

[0121] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0122] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1+0.5):0.5, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution for reaction. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0123] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0124] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0125] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0126] The method for preparing the oxide film specifically includes:

[0127] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0128] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0129] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0130] Example 7

[0131] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0132] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1+0.3):0.3, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution for reaction. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0133] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0134] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0135] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0136] The method for preparing the oxide film specifically includes:

[0137] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0138] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0139] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0140] Example 8

[0141] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0142] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(0.8+1.5):1.5, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction liquid is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0143] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0144] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0145] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0146] The method for preparing the oxide film specifically includes:

[0147] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0148] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0149] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0150] Example 9

[0151] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0152] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(0.5+1.5):1.5, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0153] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0154] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0155] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0156] The method for preparing the oxide film specifically includes:

[0157] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0158] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0159] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0160] Example 10

[0161] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0162] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(0.3053+1.5):1.5, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0163] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0164] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0165] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0166] The method for preparing the oxide film specifically includes:

[0167] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0168] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0169] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0170] Embodiment 11

[0171] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0172] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(0.3053+4):4, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0173] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0174] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0175] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0176] The method for preparing the oxide film specifically includes:

[0177] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0178] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0179] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0180] Comparative Example 1

[0181] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0182] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1+4.386):4.386, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction liquid is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0183] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0184] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0185] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0186] The method for preparing the oxide film specifically includes:

[0187] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0188] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0189] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0190] Comparative Example 2

[0191] This embodiment is a method for preparing an oxide target and an oxide film, comprising the following steps:

[0192] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L, a tin chloride solution with a concentration of 0.2 mol / L and a zinc chloride solution with a concentration of 0.2 mol / L, and mix them according to an atomic molar ratio of In:Sn:Zn=9.7711:(1.22+1.5):1.5, and adjust the pH value to 8.3 by dropping a sodium hydroxide solution for reaction. The reaction temperature is controlled at about 30°C. During the reaction process, the reaction liquid is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed and freeze-dried; and calcined at 900°C for 1h to obtain an indium tin zinc oxide composite powder.

[0193] Step S2: spray granulate the above indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, D 50 is 10μm.

[0194] Step S3: molding the above-mentioned indium tin zinc oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0195] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0196] The method for preparing the oxide film specifically includes:

[0197] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0198] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0199] (3) Sputtering with a DC power supply of 0.75w / cm 2 , arcing was serious during the sputtering process and no samples were produced.

[0200] Comparative Example 3

[0201] This comparative example is a method for preparing an indium tin oxide target and an oxide film, comprising the following steps:

[0202] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L and a tin chloride solution with an atomic molar ratio of In:Sn=9.7711:1, adjust the pH value to 8.3 by dropping a sodium hydroxide solution, and control the reaction temperature at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed, and freeze-dried; and calcined at 900°C for 1 hour to obtain an indium tin oxide composite powder.

[0203] Step S2: spray granulate the above indium tin oxide composite powder to obtain indium tin oxide composite particles, D 50 is 10μm.

[0204] Step S3: molding the above-mentioned indium tin oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0205] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0206] The method for preparing the oxide film specifically includes:

[0207] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0208] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0209] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0210] Comparative Example 4

[0211] This comparative example is a method for preparing an indium tin oxide target and an oxide film, comprising the following steps:

[0212] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L and a tin chloride solution with an atomic molar ratio of In:Sn=9.7711:0.8, adjust the pH value to 8.3 by dropping a sodium hydroxide solution, and control the reaction temperature at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed, and freeze-dried; and calcined at 900°C for 1 hour to obtain an indium tin oxide composite powder.

[0213] Step S2: spray granulate the above indium tin oxide composite powder to obtain indium tin oxide composite particles, D 50 is 10μm.

[0214] Step S3: molding the above-mentioned indium tin oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0215] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0216] The method for preparing the oxide film specifically includes:

[0217] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0218] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0219] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0220] Comparative Example 5

[0221] This comparative example is a method for preparing an indium tin oxide target and an oxide film, comprising the following steps:

[0222] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L and a tin chloride solution with an atomic molar ratio of In:Sn=9.7711:0.5, adjust the pH value to 8.3 by dropping a sodium hydroxide solution, and control the reaction temperature at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed, and freeze-dried; and calcined at 900°C for 1 hour to obtain an indium tin oxide composite powder.

[0223] Step S2: spray granulate the above indium tin oxide composite powder to obtain indium tin oxide composite particles, D 50 is 10μm.

[0224] Step S3: molding the above-mentioned indium tin oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0225] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0226] The method for preparing the oxide film specifically includes:

[0227] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0228] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0229] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0230] Comparative Example 6

[0231] This comparative example is a method for preparing an indium tin oxide target and an oxide film, comprising the following steps:

[0232] Step S1: Mix an indium chloride solution with a concentration of 0.2 mol / L and a tin chloride solution with an atomic molar ratio of In:Sn=9.7711:0.3053, adjust the pH value to 8.3 by dropping a sodium hydroxide solution, and control the reaction temperature at about 30°C. During the reaction process, the reaction solution is subjected to a ball milling cycle. After the reaction is completed, the solid-liquid separation is performed; the solid phase is collected, washed, and freeze-dried; and calcined at 900°C for 1 hour to obtain an indium tin oxide composite powder.

[0233] Step S2: spray granulate the above indium tin oxide composite powder to obtain indium tin oxide composite particles, D 50 is 10μm.

[0234] Step S3: molding the above-mentioned indium tin oxide composite particles under the condition of 0.4 MPa, and obtaining a blank target material after cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200 MPa;

[0235] Step S4: Debind the above-mentioned blank target material at 650°C, and then sinter it at 1350°C to obtain the oxide target material; wherein, the heating rate of the debinding temperature is 1°C / min, and the temperature is raised to 650°C and maintained for 5 hours; the heating rate of sintering is 2°C / min; the temperature is raised to 1350°C and maintained for 6 hours, and the cooling rate after sintering is 7°C / min.

[0236] The method for preparing the oxide film specifically includes:

[0237] (1) The above oxide target material is processed into a target material for a magnetron sputtering device and installed on a magnetron sputtering target position, with a target surface magnetic field strength of about 500 Gs.

[0238] (2) Place the substrate in the magnetron sputtering chamber and evacuate the chamber until the vacuum degree is less than 8×10 -4 Pa, and heat the substrate to 170 ° C, introduce Ar gas (purity 99.99%) and oxygen (purity 99.99%), according to the volume ratio of Ar: O2 = 100: 0.2, the pressure of the vacuum chamber is about 0.25 Pa;

[0239] (3) Sputtering with a DC power supply of 0.75w / cm 2 Finally, a film layer with a deposition thickness of about 100 nm is obtained, namely an oxide thin film.

[0240] Test example

[0241] This test example tests the performance of the oxide targets and oxide films prepared in Examples 1 to 11 and Examples 1 to 6, respectively, wherein the performance test specifically includes:

[0242] (1) Relative density of oxide target: The density was measured by the Archimedean method, and the ratio (%) of the density to the reference density determined by the composition was calculated as the relative density.

[0243] (2) Oxide film thickness: measured using a step profiler manufactured by Bruker, model number Dektak150.

[0244] (3) Surface roughness of oxide film: measured using an atomic force microscope (AFM), manufactured by Seiko, model SPA400.

[0245] (4) Transmittance of oxide thin film layer: measured by ultraviolet-visible-infrared spectrophotometer. The manufacturer of ultraviolet-visible-infrared spectrophotometer is Shimadzu, and the model is UV-3600i.

[0246] (5) Oxide film resistivity: The resistivity is calculated based on the film thickness and square resistance. The square resistance is measured at room temperature using a four-probe resistance tester manufactured by Mitsubishi, model MCP-T360.

[0247] The specific conditions of the oxide targets prepared in Examples 1 to 11 of the present invention and Comparative Examples 1 to 6 are shown in Table 1:

[0248] Table 1: Statistics of oxide targets prepared in Examples 1 to 11 and Comparative Examples 1 to 6

[0249]

[0250]

[0251] It can be seen from Table 1 that the oxide target material obtained by using the atomic molar ratio of the present invention has a high relative density and good uniformity. Figure 1 As shown, from Figure 1 It can be seen that the sputtering track is smooth, free of nodules, and its color is uniform.

[0252] Compared with Examples 1 to 7, the Zn atomic molar ratio of Comparative Example 1 is too high, In:Sn:Zn=9.7711:5.3860:4.3860 in terms of atomic moles. The results show that although the oxide target prepared in Comparative Example 1 has a higher density, the oxide target cracks when sputtered by the same method as in Example 1. Specifically, Figure 2 shown.

[0253] Compared with Examples 4, 8 to 10, the molar ratio of Sn atoms in Comparative Example 2 is too high (i.e., the A value is too high). In terms of atomic moles, In:Sn:Zn=9.7711:2.7200:1.500. The results show that the density of the oxide target prepared in Comparative Example 2 is low. When sputtering by the same method as in Example 2, the oxide target has severe arcing and severe nodules on the target surface. Specifically, Figure 3 This is mainly because the amount of tin oxide dissolved in indium oxide in the indium tin oxide material is limited. According to the indium tin oxide phase diagram (as shown in Figure 4 As shown in the figure, the maximum solid solution amount is the atomic ratio of indium:tin = about 9.7711:1.

[0254] Furthermore, the oxide films prepared in Examples 1 to 11 of the present invention and Comparative Examples 1 to 6 were tested, and the test results are shown in Table 2.

[0255] Table 2: Statistics of oxide films obtained in Examples 1 to 11 and Comparative Examples 1 to 6

[0256]

[0257]

[0258] It can be seen from Table 2 that the oxide film made from the oxide target material obtained by the atomic molar ratio of the present invention has low surface roughness, high transmittance and low resistivity.

[0259] Among them, when comparative example 3 is compared with examples 1 to 7 (i.e. after adding Zn, and when A=1), it can be seen that when the atomic ratio of In:Sn in the base target is 9.7711:1, and then Sn and Zn are doped with equal atomic moles, under the premise that the conductivity of the film is not greatly affected, the surface roughness of the oxide film is significantly reduced with the increase of the atomic moles of doped Sn and Zn. This is mainly because the indium tin oxide target is doped with equal atomic moles of tin and zinc, and the indium lattice vacancies formed by the doping of tin atoms can be additionally doped with equal atomic moles of zinc atoms, while the same atomic moles of zinc and tin atoms, one hole formed, and one electron formed, do not affect the carrier concentration of the film, so it has little effect on the conductivity of the film. Doping zinc oxide into the indium tin oxide target and increasing the total doping amount of tin oxide can refine the grains of the deposited film, thereby reducing the surface roughness of the oxide film.

[0260] Compared with Comparative Examples 3 to 6, it can be seen from Examples 1, 4, and 8 to 11 that the resistivity of the oxide thin film layer prepared by the indium tin oxide target gradually increases as the molar number of Sn atoms doped in the indium oxide decreases.

[0261] Comparing Comparative Examples 3 to 6 with the embodiments of the present invention, it can be seen that when Zn is not doped, the surface roughness of the obtained oxide film is high, while after a certain proportion of Zn is doped, the surface roughness of the obtained oxide film is significantly reduced.

[0262] In summary, the present invention is based on an indium tin oxide target material, and is simultaneously doped with tin and zinc in equal atomic molar numbers. It can effectively reduce the surface roughness of the film without having a significant effect on the conductivity of the film. It has a wide range of application value, and is particularly suitable for use in the P pole of a heterojunction solar cell and the P pole of an LED chip that require the oxide film to have sufficient conductivity and that the surface roughness of the oxide film is small.

[0263] The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. An oxide target material, characterized in that: Contains In2O3, SnO2 and ZnO, wherein, in terms of atomic molar ratio, In:Sn:Zn=9.7711:(A+N):N; Wherein, 0.3≤N<4.386, 0.3<A≤1.2; the density of the oxide target material is greater than 99%; The oxide target is prepared by the following preparation method: Step S1: mixing an indium raw material liquid, a tin raw material liquid and a zinc raw material liquid, adding a pH adjusting agent, adjusting the pH to 7.7-8.6 for reaction, separating the solid and the liquid after the reaction is completed, collecting the solid phase, drying the solid phase, and calcining at 600° C.-950° C. to obtain an indium oxide tin zinc composite powder; wherein the indium raw material liquid comprises at least one of indium sulfate, indium nitrate and indium chloride, the tin raw material liquid comprises at least one of tin sulfate, tin nitrate and tin chloride, and the zinc raw material liquid comprises at least one of zinc sulfate, zinc nitrate and zinc chloride; Step S2: spraying and granulating the indium tin zinc oxide composite powder to obtain indium tin zinc oxide composite particles, wherein the indium tin zinc oxide composite particles have a D 50 10μm~15μm; Step S3: molding the indium tin zinc oxide composite particles, and obtaining a blank target material after cold isostatic pressing; Step S4: degreasing the rough target material and then sintering it to obtain the oxide target material, wherein the degreasing temperature is 400° C. to 700° C.; and the sintering temperature is 1000° C. to 1350° C.

2. The oxide target according to claim 1, characterized in that When A=1, N satisfies 0.3≤N<4.

386.

3. The oxide target according to claim 1, characterized in that In step S1, the reaction temperature is 20°C to 45°C.

4. The oxide target according to claim 1, characterized in that In step S3, the compression molding pressure is 0.1 MPa to 0.8 MPa.

5. The oxide target according to claim 4, characterized in that The cold isostatic pressing pressure is 150Mpa~250Mpa.

6. An oxide thin film, characterized in that: The oxide target material according to any one of claims 1 to 5 is prepared by a sputtering deposition process or an evaporation deposition process.

7. A method for preparing an oxide thin film as claimed in claim 6, characterized in that: The method comprises installing the oxide target material on a magnetron sputtering target position, and then adjusting the vacuum in the magnetron sputtering chamber to less than 8×10 -4 Pa, and is obtained by magnetron sputtering on a substrate.

8. The preparation method according to claim 7, characterized in that: The atmosphere during the magnetron sputtering process is an argon atmosphere or a mixed atmosphere of argon and oxygen.

9. The preparation method according to claim 7, characterized in that: The magnetic field strength of the target surface of the oxide target during the magnetron sputtering process is 300Gs~1000Gs.

10. Use of the oxide target material according to any one of claims 1 to 5 or the oxide thin film according to claim 6 in preparing a P pole of a heterojunction solar cell.

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