A multi-doped tin oxide-based target material, a preparation method thereof and applications thereof

Abstract

The application discloses a kind of multi-doped tin oxide base target material and its preparation method and application.It relates to photovoltaic cell technical field.The above-mentioned tin oxide base target material includes the following mass ratio components: tin oxide, 95-98%;Zinc oxide, 1-3%;Antimony oxide, 0.5-1%;Cerium oxide, 0.5-1%.The tin oxide base target material of the application can play the role of sintering aid to the tin oxide base target material by doping zinc oxide;Doping cerium oxide promotes the growth of tin oxide lattice, and also produces a large number of electrons, greatly increases the conductivity of sintered body;Doping antimony oxide provides a large number of free electrons, effectively reduces the resistivity of tin oxide.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic cell technology, and in particular to a multi-doped tin oxide-based target material, its preparation method, and its application. Background Technology

[0002] Tin oxide (SnO2) is a direct interstitial semiconductor with a large optical band gap (approximately 3.5-4.0 eV). Under high-temperature sintering conditions, pure tin oxide typically does not melt but sublimates directly. Sublimation becomes significant above 1400°C, making it difficult to densify pure SnO2 through sintering, resulting in a porous, loose, and low-strength structure in the sintered body. However, tin oxide exhibits degenerate n-type semiconductor properties in the presence of interstellar tin or oxygen vacancies. Due to its good chemical stability, high visible light transmittance, and low resistivity, it is widely used in optoelectronic devices such as solar cells and gas sensors. Furthermore, due to its abundant reserves and relatively low price, tin oxide-based materials are often developed as alternatives to ITO materials.

[0003] In heterojunction solar cell technology, due to the poor lateral conductivity of microcrystalline silicon thin films, TCO thin films are often deposited on both sides using PVD (sputtering deposition) or RPD (evaporation deposition) methods to allow light transmission and current transport. However, each GW of heterojunction solar cells requires approximately 5 tons of indium. If production capacity expands to 100GW, global indium reserves (approximately 12,000 tons) will become a serious problem restricting the healthy development of heterojunction solar cells. Therefore, developing alternative materials to reduce dependence on indium has become extremely urgent. Tin oxide-based materials, due to their high reliability, are expected to find applications in heterojunction solar cells when used in combination with ITO.

[0004] The development of perovskite solar cell technology has also demonstrated a demand for tin oxide materials. Early perovskite solar cells used TiO2 as the electron transport layer, but it suffered from high UV absorption, poor stability, and low mobility. In contrast, SnO2 has a better bandgap match with the perovskite layer and possesses excellent properties such as high transmittance and high mobility, as well as good chemical stability and UV resistance. Therefore, SnO2 is currently widely used as an electron transport layer material in perovskite solar cells. With the advancement of perovskite solar cell industrialization, dry preparation processes (such as PVD and vapor deposition) are gradually replacing wet processes in the laboratory due to their advantages of good uniformity and ease of control, thus creating broader application demands for related target materials.

[0005] PVD sputtering typically employs a DC magnetron sputtering power supply, a method that is simple, reliable, stable, powerful, and has a fast deposition rate. The target material is placed in an electric field loop and sputtered onto the substrate by Ar ions bombarding it under magnetic field discharge. Therefore, the target material itself needs to have high density and low bulk resistivity. Existing technology discloses a method for preparing zinc oxide-doped tin oxide targets via high-temperature sintering in an atmosphere, resulting in fine grains and high density. However, this system has a high bulk resistivity, making it unsuitable for DC sputtering. Other existing technologies have optimized the density and resistivity of the target material through TiO2 modification doping, but there is still room for further improvement.

[0006] Therefore, there is an urgent need to develop a multi-doped tin oxide-based target material with good adaptability and excellent performance to solve the above problems. Summary of the Invention

[0007] The first technical problem to be solved by this invention is:

[0008] A tin oxide-based target material is provided.

[0009] The second technical problem to be solved by this invention is:

[0010] A method for preparing the tin oxide-based target is provided.

[0011] The third technical problem to be solved by this invention is:

[0012] Application of the tin oxide-based target material.

[0013] To solve the first technical problem, the technical solution adopted by the present invention is as follows:

[0014] A tin oxide-based target material comprises the following components in the following mass ratio:

[0015] Tin oxide, 95-98%;

[0016] Zinc oxide, 1-3%;

[0017] Antimony oxide, 0.5-1%;

[0018] Cerium oxide, 0.5-1%.

[0019] According to embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0020] The tin oxide-based target material of this invention, by doping with zinc oxide, can act as a sintering aid, suppress the volatilization of tin oxide at high temperatures, reduce internal porosity, and promote sintering densification. However, excessive zinc oxide doping can inhibit lattice growth during sintering and cause lattice distortion; therefore, the amount of cerium oxide doping must be controlled. Within the doping range defined in this application, ZnO and SnO2 react at high temperatures to form Zn2SnO4, filling the gaps between particles and greatly enhancing the sintering densification of the target material.

[0021] Cerium oxide, as a rare earth oxide, Ce 4+ The ionic radius is 0.092 nm, which is larger than that of Sn. 4+ The cerium oxide doping level (0.069nm) is much higher. At high temperatures, rare earth elements exhibit unique reactivity, unstable outer electrons, and a tendency to leak large amounts of electrons. This causes nearby oxygen atoms to detach when they replace tin ions, creating oxygen vacancies and promoting the growth of the tin oxide lattice. Simultaneously, a large number of electrons are generated, significantly increasing the conductivity of the sintered body. However, excessive doping can hinder lattice growth and cause lattice distortion; therefore, the amount of cerium oxide doped must be controlled.

[0022] Antimony oxide, as a classic SnO2-doped oxide, exists in solid solutions with +3 and +5 oxidation states. 5+ Replace Sn 4+ Afterward, it can provide a large number of free electrons, effectively reducing the resistivity of tin oxide, but it also generates a large number of lattice defects, resulting in reduced crystallinity and hindering grain growth. Therefore, too little antimony oxide doping helps reduce the resistivity of SnO2, but is not conducive to sintering densification; too much antimony oxide doping leads to excessively high resistivity, so the doping amount needs to be strictly controlled.

[0023] According to one embodiment of the present invention, the tin oxide-based target material comprises the following components in the following mass ratio:

[0024] Tin oxide, 97.1-98%;

[0025] Zinc oxide, 1-2%;

[0026] Antimony oxide, 0.5-1%;

[0027] Cerium oxide, 0.5-0.7%.

[0028] While ensuring a suitable density, by further limiting the mass ratio of the components in the tin oxide-based target, the resistivity can be reduced to 1.20 × 10⁻⁶. -3 Below Ω.

[0029] According to one embodiment of the present invention, the D50 of the tin oxide, zinc oxide, antimony oxide and cerium oxide are all less than or equal to 2 μm.

[0030] For tin oxide-based targets, the D50 value of the components is related to the microstructure of the sintered body, including particle size, porosity, and the degree of interparticle connectivity, which in turn affects the resistivity of the final target.

[0031] A suitable D50 value indicates a smaller average particle size in the raw material powder, which helps increase the contact area between particles during sintering, thereby promoting densification. Materials with higher densification levels have lower porosity because the gaps between particles are effectively filled during sintering, reducing voids and defects within the material. Reduced porosity generally leads to lower resistivity because there is less resistance in the current conduction path.

[0032] Similarly, a suitable D50 value also facilitates the formation of more sintered necks between particles, i.e., regions where particles are interconnected. These sintered necks not only help improve the mechanical strength of the target material but also provide a more continuous and less obstructed conduction path for electrons, thereby reducing resistivity.

[0033] Furthermore, a suitable D50 value contributes to the uniform distribution of dopants in the sintered body, resulting in a more uniform doping effect. Dopants, by substituting or forming solid solutions in the crystal lattice, can effectively modulate the electronic structure and defect concentration of the material, thereby affecting resistivity.

[0034] According to one embodiment of the present invention, the D50 of the tin oxide, zinc oxide, antimony oxide and cerium oxide are all less than or equal to 0.5 μm.

[0035] To solve the second technical problem, the technical solution adopted by the present invention is as follows:

[0036] A method for preparing the tin oxide-based target material includes the following steps:

[0037] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain tin oxide;

[0038] S2 mixes the tin oxide, zinc oxide, antimony oxide and cerium oxide, ball-mills and then spray-dries to obtain a mixed powder;

[0039] S3 The mixed powder is placed in a mold and pressed to obtain a blank. The blank is then degreased and sintered to obtain the tin oxide-based target material.

[0040] According to one embodiment of the present invention, in step S1, tin salt is dissolved in an alcohol solution, hydrolyzed, and then calcined to obtain high-purity tin oxide.

[0041] According to one embodiment of the present invention, in step S1, the purity of high-purity tin oxide is ≥99.99%.

[0042] According to one embodiment of the present invention, in step S1, the specific surface area (BET) of high-purity tin oxide is 15-25 m². 2 / g.

[0043] According to one embodiment of the present invention, in step S1, the high-purity tin oxide has a D50 ≤ 0.5 μm and a Dmax ≤ 5 μm.

[0044] According to one embodiment of the present invention, step S2 further includes the following steps: adding a binder and a plasticizer after ball milling, and then performing spray drying.

[0045] According to one embodiment of the present invention, in step S2, the purity of zinc oxide, antimony oxide and cerium oxide is ≥99.99%.

[0046] According to one embodiment of the present invention, in step S2, the BET of zinc oxide, antimony oxide, and cerium oxide is 10-25m. 2 / g.

[0047] According to one embodiment of the present invention, in step S2, the D50 of zinc oxide, antimony oxide and cerium oxide is ≤2μm and the Dmax is ≤10μm.

[0048] According to one embodiment of the present invention, in step S2, the ball milling includes the following steps: first grinding with Φ0.60-0.65mm grinding media for 8-8.5h, and then grinding with Φ0.30-0.35mm grinding media for 8-8.5h.

[0049] According to one embodiment of the present invention, in step S2, the mass ratio of the binder to the plasticizer is 0.4-2.5:0.1-2.

[0050] According to one embodiment of the present invention, in step S2, the adhesive comprises polyvinyl alcohol.

[0051] According to one embodiment of the present invention, in step S2, the plasticizer includes polyethylene glycol.

[0052] According to one embodiment of the present invention, in step S2, the specific surface area of ​​the mixed powder is 5-25 m². 2 / g.

[0053] According to one embodiment of the present invention, in step S2, the loose density of the mixed powder is 1.00-1.60 g / cm³. 3 .

[0054] According to one embodiment of the present invention, in step S2, the moisture content of the mixed powder is ≤1%.

[0055] According to one embodiment of the present invention, in step S3, the degreasing temperature is 600-650℃, and the heat preservation time during the degreasing process is 2-3 hours.

[0056] According to one embodiment of the present invention, in step S3, the sintering is a four-step sintering process, including the following steps: first, holding at 950-100℃ for 8-9 hours; then introducing oxygen and raising the temperature to 1200-1250℃ for 6-8 hours; then raising the temperature to 1400-1450℃ for 10-12 hours; and then raising the temperature to 1500℃-1600℃ for 12-14 hours.

[0057] According to one embodiment of the present invention, in step S3, the sintering is a four-step sintering, including the following steps: first, holding at 950°C for 8 hours; then introducing oxygen and raising the temperature to 1200°C, holding for 6-8 hours; then raising the temperature to 1400°C and holding for 10-12 hours; then raising the temperature to 1500°C-1600°C and holding for 12-14 hours.

[0058] According to one embodiment of the present invention, after obtaining the tin oxide-based target material in step S3, further finishing can be performed. The finishing process includes the following steps: placing the tin oxide-based target material into a lathe for grinding, using an 800-850 mesh grinding wheel for rough grinding for 8-8.5 hours, and using a 400-450 mesh grinding wheel for fine grinding for 8-8.5 hours to obtain the finished tin oxide-based target material.

[0059] Another aspect of the present invention relates to the application of the tin oxide-based target in display panels or photovoltaic cells. This includes the tin oxide-based target as described in the first aspect embodiment above. Since this application employs all the technical solutions of the aforementioned tin oxide-based target, it possesses at least all the beneficial effects brought about by the technical solutions of the above embodiments.

[0060] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Detailed Implementation

[0061] The terms "preferred," "more preferably," etc., used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0062] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0063] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of the present invention.

[0064] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0065] The tin oxide-based targets in Examples 1-15 have a D50 ≤ 0.5 μm for tin oxide, and a D50 ≤ 2 μm and ≥ 1 μm for zinc oxide, antimony oxide and cerium oxide.

[0066] Example 1

[0067] A tin oxide-based target material comprises the following components in the following mass ratio:

[0068] Tin oxide, 95%;

[0069] Zinc oxide, 3%;

[0070] Antimony oxide, 1%;

[0071] Cerium oxide, 1%.

[0072] A method for preparing tin oxide-based target materials includes the following steps:

[0073] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0074] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 1.8% of the total mass of the metal oxide components, and the plasticizer accounts for 0.5%. The specific surface area of ​​the mixed powder is measured to be 12 m². 2 / g, its loose density is 1.55g / cm³ 3 Moisture content ≤1%;

[0075] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0076] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0077] Example 2

[0078] The difference between Example 2 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0079] A tin oxide-based target material comprises the following components in the following mass ratio:

[0080] Tin oxide, 96%;

[0081] Zinc oxide, 2%;

[0082] Antimony oxide, 1%;

[0083] Cerium oxide, 1%.

[0084] A method for preparing tin oxide-based target materials includes the following steps:

[0085] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0086] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2% of the total mass of the metal oxide components, and the plasticizer accounts for 0.5% of the total mass of the metal oxide components. The specific surface area of ​​the mixed powder is measured to be 10.5 m². 2 / g, its loose density is 1.35g / cm³ 3Moisture content ≤1%;

[0087] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0088] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0089] Example 3

[0090] The difference between Example 3 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0091] A tin oxide-based target material comprises the following components in the following mass ratio:

[0092] Tin oxide, 96.5%;

[0093] Zinc oxide, 2%;

[0094] Antimony oxide, 0.5%;

[0095] Cerium oxide, 1%.

[0096] A method for preparing tin oxide-based target materials includes the following steps:

[0097] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0098] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2% of the total mass of the metal oxide components, and the plasticizer accounts for 1.5% of the total mass of the metal oxide components. The specific surface area of ​​the mixed powder is measured to be 15 m². 2 / g, its loose bulk density is 1.5g / cm³ 3 Moisture content ≤1%;

[0099] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 180MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0100] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0101] Example 4

[0102] The difference between Example 4 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0103] A tin oxide-based target material comprises the following components in the following mass ratio:

[0104] Tin oxide, 98%;

[0105] Zinc oxide, 1%;

[0106] Antimony oxide, 0.5%;

[0107] Cerium oxide, 0.5%.

[0108] A method for preparing tin oxide-based target materials includes the following steps:

[0109] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0110] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2.5% of the total mass of the metal oxide components, and the plasticizer accounts for 1.5%. The specific surface area of ​​the mixed powder is measured to be 20 m². 2 / g, its loose density is 1.60g / cm³ 3 Moisture content ≤1%;

[0111] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 175MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0112] S4 degreases the green blank at 600℃ for 3 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 8 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 12 hours. After holding, the temperature is increased to the maximum temperature of 1520℃ at a rate of 0.1℃ / min for 14 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0113] Example 5

[0114] The difference between Example 5 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0115] A tin oxide-based target material comprises the following components in the following mass ratio:

[0116] Tin oxide, 97%;

[0117] Zinc oxide, 1%;

[0118] Antimony oxide, 1%;

[0119] Cerium oxide, 1%.

[0120] A method for preparing tin oxide-based target materials includes the following steps:

[0121] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0122] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 0.8% of the total mass of the metal oxide components, and the plasticizer accounts for 0.15%. The specific surface area of ​​the mixed powder is measured to be 18.5 m². 2 / g, its loose density is 1.58g / cm³ 3 Moisture content ≤1%;

[0123] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 120MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0124] S4 degreases the green blank at 650℃ for 3 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 8 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 12 hours. After holding, the temperature is increased to the maximum temperature of 1600℃ at a rate of 0.1℃ / min for 14 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0125] Example 6

[0126] The difference between Example 6 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0127] A tin oxide-based target material comprises the following components in the following mass ratio:

[0128] Tin oxide, 96.5%;

[0129] Zinc oxide, 2.5%;

[0130] Antimony oxide, 0.5%;

[0131] Cerium oxide, 0.5%.

[0132] A method for preparing tin oxide-based target materials includes the following steps:

[0133] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0134] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 0.5% of the total mass of the metal oxide components, and the plasticizer accounts for 0.1%. The specific surface area of ​​the mixed powder is measured to be 7.5 m². 2 / g, its loose bulk density is 1.00g / cm³ 3 Moisture content ≤1%;

[0135] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0136] S4 degreases the green blank at 600℃ for 2 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1500℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0137] Example 7

[0138] The difference between Example 7 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0139] A tin oxide-based target material comprises the following components in the following mass ratio:

[0140] Tin oxide, 97%;

[0141] Zinc oxide, 2%;

[0142] Antimony oxide, 0.5%;

[0143] Cerium oxide, 0.5%.

[0144] A method for preparing tin oxide-based target materials includes the following steps:

[0145] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0146] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 0.85% of the total mass of the metal oxide components, and the plasticizer accounts for 0.15%. The specific surface area of ​​the mixed powder is measured to be 13.5 m². 2 / g, its loose density is 1.35g / cm³ 3 Moisture content ≤1%;

[0147] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 180MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0148] S4 degreases the green blank at a temperature of 630℃ for 2 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1565℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0149] Example 8

[0150] The difference between Example 8 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0151] A tin oxide-based target material comprises the following components in the following mass ratio:

[0152] Tin oxide, 97.5%;

[0153] Zinc oxide, 1%;

[0154] Antimony oxide, 0.5%;

[0155] Cerium oxide, 1%.

[0156] A method for preparing tin oxide-based target materials includes the following steps:

[0157] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0158] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2.5% of the total mass of the metal oxide components, and the plasticizer accounts for 0.18%. The specific surface area of ​​the mixed powder is measured to be 18.5 m². 2 / g, its loose density is 1.45g / cm³ 3 Moisture content ≤1%;

[0159] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 180MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0160] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 7 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 11 hours. After holding, the temperature is increased to the maximum temperature of 1520℃ at a rate of 0.1℃ / min for 13 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0161] Example 9

[0162] The difference between Example 9 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0163] A tin oxide-based target material comprises the following components in the following mass ratio:

[0164] Tin oxide, 96.7%;

[0165] Zinc oxide, 1.7%;

[0166] Antimony oxide, 0.8%;

[0167] Cerium oxide, 0.8%.

[0168] A method for preparing tin oxide-based target materials includes the following steps:

[0169] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0170] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 1.85% of the total mass of the metal oxide components, and the plasticizer accounts for 1.8% of the total mass of the metal oxide components. The specific surface area of ​​the mixed powder is measured to be 12.5 m². 2 / g, its loose density is 1.35g / cm³ 3 Moisture content ≤1%;

[0171] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0172] S4 degreases the green blank at 600℃ for 2 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0173] Example 10

[0174] The difference between Example 10 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0175] A tin oxide-based target material comprises the following components in the following mass ratio:

[0176] Tin oxide, 97%;

[0177] Zinc oxide, 1.8%;

[0178] Antimony oxide, 0.6%;

[0179] Cerium oxide, 0.6%.

[0180] A method for preparing tin oxide-based target materials includes the following steps:

[0181] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0182] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2.5% of the total mass of the metal oxide components, and the plasticizer accounts for 0.15%. The specific surface area of ​​the mixed powder is measured to be 13.5 m². 2 / g, its loose density is 1.30g / cm³ 3 Moisture content ≤1%;

[0183] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 180MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0184] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 8 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 12 hours. After holding, the temperature is increased to the maximum temperature of 1560℃ at a rate of 0.1℃ / min for 14 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0185] Example 11

[0186] The difference between Example 11 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0187] A tin oxide-based target material comprises the following components in the following mass ratio:

[0188] Tin oxide, 97.1%;

[0189] Zinc oxide, 1.5%;

[0190] Antimony oxide, 0.7%;

[0191] Cerium oxide, 0.7%.

[0192] A method for preparing tin oxide-based target materials includes the following steps:

[0193] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0194] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2.5% of the total mass of the metal oxide components, and the plasticizer accounts for 0.18%. The specific surface area of ​​the mixed powder is measured to be 15.5 m². 2 / g, its loose bulk density is 1.35g / cm³. 3 Moisture content ≤1%;

[0195] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 175MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0196] S4 degreases the green blank at 600℃ for 2 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12.5 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0197] Example 12

[0198] The difference between Example 12 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0199] A tin oxide-based target material comprises the following components in the following mass ratio:

[0200] Tin oxide, 95.9%;

[0201] Zinc oxide, 2.5%;

[0202] Antimony oxide, 0.8%;

[0203] Cerium oxide, 0.8%.

[0204] A method for preparing tin oxide-based target materials includes the following steps:

[0205] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0206] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 1.5% of the total mass of the metal oxide components, and the plasticizer accounts for 1.8%. The specific surface area of ​​the mixed powder is measured to be 18.5 m². 2 / g, its loose density is 1.45g / cm³ 3 Moisture content ≤1%;

[0207] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 200MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0208] S4 degreases the green blank at 650℃ for 3 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 8 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 12 hours. After holding, the temperature is increased to the maximum temperature of 1500℃ at a rate of 0.1℃ / min for 14 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0209] Example 13

[0210] The difference between Example 13 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0211] A tin oxide-based target material comprises the following components in the following mass ratio:

[0212] Tin oxide, 97.4%;

[0213] Zinc oxide, 1%;

[0214] Antimony oxide, 0.8%;

[0215] Cerium oxide, 0.8%.

[0216] A method for preparing tin oxide-based target materials includes the following steps:

[0217] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0218] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2.5% of the total mass of the metal oxide components, and the plasticizer accounts for 2%. The specific surface area of ​​the mixed powder is measured to be 25 m². 2 / g, its loose density is 1.58g / cm³ 3 Moisture content ≤1%;

[0219] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 200MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0220] S4 degreases the green blank at 650℃ for 3 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 8 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 12 hours. After holding, the temperature is increased to the maximum temperature of 1600℃ at a rate of 0.1℃ / min for 14 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0221] Example 14

[0222] The difference between Example 14 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0223] A tin oxide-based target material comprises the following components in the following mass ratio:

[0224] Tin oxide, 95.5%;

[0225] Zinc oxide, 2.5%;

[0226] Antimony oxide, 1%;

[0227] Cerium oxide, 1%.

[0228] A method for preparing tin oxide-based target materials includes the following steps:

[0229] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0230] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2.5% of the total mass of the metal oxide components, and the plasticizer accounts for 1.8%. The specific surface area of ​​the mixed powder is measured to be 18 m². 2 / g, its loose density is 1.30g / cm³ 3 Moisture content ≤1%;

[0231] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 180MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0232] S4 degreases the green blank at 650℃ for 3 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 8 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1500℃ at a rate of 0.1℃ / min for 14 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0233] Example 15

[0234] The difference between Example 15 and Example 1 is that the mass percentage of the components in the tin oxide-based target is different.

[0235] A tin oxide-based target material comprises the following components in the following mass ratio:

[0236] Tin oxide, 95.2%;

[0237] Zinc oxide, 2.8%;

[0238] Antimony oxide, 1%;

[0239] Cerium oxide, 1%.

[0240] A method for preparing tin oxide-based target materials includes the following steps:

[0241] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0242] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 2.5% of the total mass of the metal oxide components, and the plasticizer accounts for 2%. The specific surface area of ​​the mixed powder is measured to be 23.5 m². 2 / g, its loose density is 1.60g / cm³ 3 Moisture content ≤1%;

[0243] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 200MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0244] S4 degreases the green blank at 600℃ for 2 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 8 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1550℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0245] Example 16

[0246] The difference between Example 16 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0247] A tin oxide-based target material comprises the following components in the following mass ratio:

[0248] Tin oxide, 95%;

[0249] Zinc oxide, 3%;

[0250] Antimony oxide, 1%;

[0251] Cerium oxide, 1%.

[0252] Among them, tin oxide has a D50 of 1 μm, zinc oxide has a D50 of 2.5 μm, antimony oxide has a D50 of 1 μm, and cerium oxide has a D50 of 1.8 μm.

[0253] A method for preparing tin oxide-based target materials includes the following steps:

[0254] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0255] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 1.8% of the total mass of the metal oxide components, and the plasticizer accounts for 0.5%. The specific surface area of ​​the mixed powder is measured to be 12 m². 2 / g, its loose density is 1.55g / cm³3 Moisture content ≤1%;

[0256] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0257] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0258] Example 17

[0259] The difference between Example 17 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0260] A tin oxide-based target material comprises the following components in the following mass ratio:

[0261] Tin oxide, 95%;

[0262] Zinc oxide, 3%;

[0263] Antimony oxide, 1%;

[0264] Cerium oxide, 1%.

[0265] Among them, tin oxide has a D50 of 0.5 μm, zinc oxide has a D50 of 1.5 μm, antimony oxide has a D50 of 1 μm, and cerium oxide has a D50 of 4 μm.

[0266] A method for preparing tin oxide-based target materials includes the following steps:

[0267] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0268] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 1.8% of the total mass of the metal oxide components, and the plasticizer accounts for 0.5%. The specific surface area of ​​the mixed powder is measured to be 12 m². 2 / g, its loose density is 1.55g / cm³ 3 Moisture content ≤1%;

[0269] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0270] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0271] Example 18

[0272] The difference between Example 18 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0273] A tin oxide-based target material comprises the following components in the following mass ratio:

[0274] Tin oxide, 95%;

[0275] Zinc oxide, 3%;

[0276] Antimony oxide, 1%;

[0277] Cerium oxide, 1%.

[0278] Among them, tin oxide has a D50 of 0.4 μm, zinc oxide has a D50 of 2 μm, antimony oxide has a D50 of 4 μm, and cerium oxide has a D50 of 4 μm.

[0279] A method for preparing tin oxide-based target materials includes the following steps:

[0280] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0281] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 1.8% of the total mass of the metal oxide components, and the plasticizer accounts for 0.5%. The specific surface area of ​​the mixed powder is measured to be 12 m². 2 / g, its loose density is 1.55g / cm³ 3 Moisture content ≤1%;

[0282] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0283] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0284] Example 19

[0285] The difference between Example 19 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0286] A tin oxide-based target material comprises the following components in the following mass ratio:

[0287] Tin oxide, 95%;

[0288] Zinc oxide, 3%;

[0289] Antimony oxide, 1%;

[0290] Cerium oxide, 1%.

[0291] Among them, tin oxide has a D50 of 0.4 μm, zinc oxide has a D50 of 1 μm, antimony oxide has a D50 of 1 μm, and cerium oxide has a D50 of 0.8 μm.

[0292] A method for preparing tin oxide-based target materials includes the following steps:

[0293] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0294] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 1.8% of the total mass of the metal oxide components, and the plasticizer accounts for 0.5%. The specific surface area of ​​the mixed powder is measured to be 12 m². 2 / g, its loose density is 1.55g / cm³ 3 Moisture content ≤1%;

[0295] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0296] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0297] Example 20

[0298] The difference between Example 20 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0299] A tin oxide-based target material comprises the following components in the following mass ratio:

[0300] Tin oxide, 95%;

[0301] Zinc oxide, 3%;

[0302] Antimony oxide, 1%;

[0303] Cerium oxide, 1%.

[0304] The D50 of tin oxide is 0.5 μm, the D50 of zinc oxide is 0.5 μm, the D50 of antimony oxide is 0.5 μm, and the D50 of cerium oxide is 0.5 μm.

[0305] A method for preparing tin oxide-based target materials includes the following steps:

[0306] S1 dissolves tin salt in an alcohol solution, hydrolyzes it, and then calcines it to obtain high-purity tin oxide;

[0307] S2 is a mixture of high-purity tin oxide, zinc oxide, antimony oxide, and cerium oxide, which is then ball-milled. First, 0.60mm zirconium beads are used for milling at 600 rpm for 8 hours, followed by 0.30mm zirconium beads at 800 rpm for 8 hours. A binder (PVA) and a plasticizer (PEG) are added, followed by stirring and filtration. The mixture is then spray-dried to obtain a mixed powder. The binder accounts for 1.8% of the total mass of the metal oxide components, and the plasticizer accounts for 0.5%. The specific surface area of ​​the mixed powder is measured to be 12 m². 2 / g, its loose density is 1.55g / cm³ 3 Moisture content ≤1%;

[0308] S3 uses a rotating target mold to inject the mixed powder into the mold, uses WCIP molding, molding pressure of 150MPa, and static pressure strengthening of the target blank, and then presses it to obtain the blank.

[0309] S4 degreases the green blank at 650℃ for 2.5 hours. After degreasing, the temperature is increased to 950℃ at a rate of 1℃ / min and held for 8 hours. After holding, oxygen is introduced and the temperature is increased to 1200℃ at a rate of 0.5℃ / min for 6 hours. After holding, the temperature is increased to 1400℃ at a rate of 0.3℃ / min for 10 hours. After holding, the temperature is increased to the maximum temperature of 1580℃ at a rate of 0.1℃ / min for 12 hours. After holding, the gas supply is stopped and the temperature is reduced to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target material.

[0310] Comparative Example 1

[0311] The difference between Comparative Example 1 and Example 1 is that the tin oxide-based target of Comparative Example 1 contains only tin oxide.

[0312] Comparative Example 2

[0313] The difference between Comparative Example 2 and Example 1 is that the tin oxide-based target of Comparative Example 2 contains only 97% tin oxide and 3% zinc oxide by mass.

[0314] Comparative Example 3

[0315] The difference between Comparative Example 3 and Example 1 is that the tin oxide-based target of Comparative Example 3 contains only 97% tin oxide, 2.5% zinc oxide and 0.5% cerium oxide by mass.

[0316] Comparative Example 4

[0317] The difference between Comparative Example 4 and Example 1 is that the tin oxide-based target of Comparative Example 4 contains only 97% tin oxide and 3% antimony oxide by mass.

[0318] Comparative Example 5

[0319] The difference between Comparative Example 5 and Example 1 is that the tin oxide-based target of Comparative Example 5 contains only 96% tin oxide, 3% zinc oxide and 1% antimony oxide by mass.

[0320] Comparative Example 6

[0321] The difference between Comparative Example 6 and Example 1 is that the tin oxide-based target of Comparative Example 6 contains only 98% tin oxide, 1% cerium oxide and 1% antimony oxide by mass.

[0322] Comparative Example 7

[0323] The difference between Comparative Example 7 and Example 1 is that in the tin oxide-based target material of Comparative Example 7, the mass percentage of tin oxide is 95.2%, the mass percentage of zinc oxide is 3.5%, the mass percentage of antimony oxide is 0.5%, and the mass percentage of cerium oxide is 0.8%.

[0324] Comparative Example 8

[0325] The difference between Comparative Example 8 and Example 1 is that in the tin oxide-based target material of Comparative Example 8, the mass percentage of tin oxide is 94%, the mass percentage of zinc oxide is 3.5%, the mass percentage of antimony oxide is 1.5%, and the mass percentage of cerium oxide is 1%.

[0326] Comparative Example 9

[0327] The difference between Comparative Example 9 and Example 1 is that in the tin oxide-based target material of Comparative Example 9, the mass percentage of tin oxide is 98.5%, the mass percentage of zinc oxide is 0.5%, the mass percentage of antimony oxide is 0.5%, and the mass percentage of cerium oxide is 0.5%.

[0328] Comparative Example 10

[0329] The difference between Comparative Example 10 and Example 1 is that in the tin oxide-based target material of Comparative Example 10, the mass percentage of tin oxide is 95%, the mass percentage of zinc oxide is 2.5%, the mass percentage of antimony oxide is 1.5%, and the mass percentage of cerium oxide is 1%.

[0330] Comparative Example 11

[0331] The difference between Comparative Example 11 and Example 1 is that in the tin oxide-based target material of Comparative Example 11, the mass percentage of tin oxide is 96.3%, the mass percentage of zinc oxide is 2.5%, the mass percentage of antimony oxide is 0.2%, and the mass percentage of cerium oxide is 1%.

[0332] Comparative Example 12

[0333] The difference between Comparative Example 12 and Example 1 is that in the tin oxide-based target material of Comparative Example 12, the mass percentage of tin oxide is 96.8%, the mass percentage of zinc oxide is 2.5%, the mass percentage of antimony oxide is 0.5%, and the mass percentage of cerium oxide is 0.2%.

[0334] Comparative Example 13

[0335] The difference between Comparative Example 13 and Example 1 is that in the tin oxide-based target material of Comparative Example 13, the mass percentage of tin oxide is 95.5%, the mass percentage of zinc oxide is 2.5%, the mass percentage of antimony oxide is 0.5%, and the mass percentage of cerium oxide is 1.5%.

[0336] Performance testing:

[0337] The performance of the tin oxide-based targets obtained in Examples 1-20 and Comparative Examples 1-13 was tested, and the test results are shown in Tables 1-2.

[0338] Table 1

[0339]

[0340]

[0341] Table 1 shows that, since Comparative Example 1 was pure undoped tin oxide, the sintering process resulted in numerous pores between grains, leading to low target density, excessively high resistivity, and almost no conductivity. Comparative Example 2 improved sintering density through ZnO doping, but the high resistivity failed to meet the requirements of DC sputtering deposition. Comparative Example 3, based on Comparative Example 2, added CeO2, reducing resistivity, but further reduction is still needed. Comparative Example 4 only doped with Sb2O3, significantly reducing resistivity, but the sintered body density was too low. Comparative Example 5 simultaneously doped with ZnO and Sb2O3, improving both density and resistivity, but further improvement is still required. Comparative Example 6 simultaneously doped with CeO2 and Sb2O3, without ZnO, reducing resistivity but resulting in low density. Comparative Example 7 simultaneously doped with three oxides, but the excessive ZnO doping caused significant lattice distortion, leading to cracking after sintering. Comparative Example 8 had a low ZnO doping ratio, resulting in insignificant sintering aid and low density. Comparative Group 9 had excessive Sb₂O₃ doping, reducing sintering density and resulting in low density. Comparative Group 10 had insufficient Sb₂O₃ doping, leading to inadequate resistivity reduction. Comparative Group 11 had insufficient CeO₂ doping, resulting in inadequate resistivity reduction. Comparative Group 12 had a high CeO₂ doping ratio, causing lattice distortion and cracking after sintering.

[0342] Examples 1-15 show that through multi-component doping, the D50 of tin oxide is ≤0.5μm, and the D50 of the three doped oxides is ≤2μm and ≥1μm. By precisely controlling the doping amount of the three oxides, the sintered target material simultaneously exhibits excellent properties of high density and low bulk resistivity. The processed target material can be stably used for DC magnetron sputtering (PVD) coating.

[0343] Table 2

[0344]

[0345] In Examples 16-18, the D50 of the powder was relatively high, resulting in varying degrees of decrease in the density and resistivity of the sintered target material. In Example 19, the D50 of all three doped oxides was ≤1μm, and the target material density was slightly higher. In Example 20, the D50 of all three doped oxides was ≤0.5μm, resulting in the optimal target material density and resistivity.

[0346] The above are merely embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A tin oxide-based target material, characterized by: Consists of the following mass ratio of components: tin oxide, 97.1-98%; zinc oxide, 1-2%; antimony oxide, 0.5-1%; cerium oxide, 0.5-0.7%; The preparation method of the tin oxide-based target material has the following steps: S1 dissolving tin salt in alcohol solution, hydrolysis and calcination to obtain tin oxide; S2 mixing the tin oxide, zinc oxide, antimony oxide and cerium oxide, ball milling and then spray drying to obtain a mixed powder; S3 placing the mixed powder in a mold, pressing to obtain a green body, degreasing and sintering the green body to obtain the tin oxide-based target material; In step S2, the ball milling includes the following steps: first using Φ0.60-0.65mm grinding medium for 8-8.5h, and then using Φ0.30-0.35mm grinding medium for 8-8.5h; In step S3, the sintering is four-step sintering, including the following steps: first at 950-100℃, holding for 8-9h; then introducing oxygen, heating to 1200-1250℃, holding for 6-8h; then heating to 1400-1450℃, holding for 10-12h; and then heating to 1500℃-1600℃, holding for 12-14h.

2. The tin oxide-based target according to claim 1, characterized in that: The D50 of the tin oxide, zinc oxide, antimony oxide and cerium oxide is less than or equal to 2μm.

3. The tin oxide-based target according to claim 2, characterized in that: The D50 of the tin oxide, zinc oxide, antimony oxide and cerium oxide is less than or equal to 0.5μm.

4. A method of producing a tin oxide-based target according to any one of claims 1 to 3, characterized by: including the following steps: S1 dissolving tin salt in alcohol solution, hydrolysis and calcination to obtain tin oxide; S2 mixing the tin oxide, zinc oxide, antimony oxide and cerium oxide, ball milling and then spray drying to obtain a mixed powder; S3 placing the mixed powder in a mold, pressing to obtain a green body, degreasing and sintering the green body to obtain the tin oxide-based target material.

5. The method of claim 4, wherein: In step S2, the ball milling includes the following steps: first using Φ0.60-0.65mm grinding medium for 8-8.5h, and then using Φ0.30-0.35mm grinding medium for 8-8.5h.

6. The method of claim 4, wherein: In step S2, the mass ratio of the binder and plasticizer is 0.4-2.5:0.1-2.

7. The method of claim 4, wherein: In step S3, the temperature of the degreasing is 600-650℃, and the holding time during the degreasing process is 2-3h.

8. The method of claim 4, wherein: In step S3, the sintering is four-step sintering, including the following steps: first at 950-100℃, holding for 8-9h; then introducing oxygen, heating to 1200-1250℃, holding for 6-8h; then heating to 1400-1450℃, holding for 10-12h; and then heating to 1500℃-1600℃, holding for 12-14h.

9. Use of a tin oxide-based target material according to any one of claims 1 to 3 in a display panel or a photovoltaic cell.

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