Multi-element doped tin oxide-based target material, preparation method therefor and use thereof

Abstract

The present application relates to the technical field of photovoltaic cells, and discloses a multi-element doped tin oxide-based target material, a preparation method therefor, and a use thereof. The described tin oxide-based target material comprises the following components by mass proportion: tin oxide, 95%-98%; zinc oxide, 1%-3%; antimony oxide, 0.5%-1%; cerium oxide, 0.5%-1%. In the tin oxide-based target material of the present application, the zinc oxide doping can promote sintering of the tin oxide-based target material; the cerium oxide doping promotes the growth of tin oxide lattices, and also generates a large number of electrons, which greatly increases the conductivity of a sintered body; the antimony oxide doping provides a large number of free electrons, effectively reducing the resistivity of the tin oxide.

Description

A multi-element doped tin oxide-based target material and its preparation method and application Technical Field

[0001] The present application relates to the field of photovoltaic cell technology, and in particular to a multi-element doped tin oxide-based target material and a preparation method and application thereof. Background Art

[0002] Tin oxide (SnO2) is a direct-gap semiconductor with a large optical band gap (approximately 3.5eV-4.0eV). Under high-temperature sintering conditions, pure tin oxide usually does not melt, but directly sublimates. When the temperature exceeds 1400°C, the sublimation phenomenon is significant, which makes it difficult for pure SnO2 to be densified through the sintering process, resulting in a porous, loose and low-strength structure of the sintered body. However, tin oxide exhibits degenerate n-type semiconductor properties in the presence of tin interstitials 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. In addition, due to its abundant reserves and relatively low price, tin oxide-based materials are often developed to replace ITO materials.

[0003] In heterojunction battery technology, due to the poor lateral conductivity of microcrystalline silicon thin films, TCO films are often deposited on both sides through PVD (sputtering coating) or RPD (evaporation coating) to transmit light and transmit current. However, each GW heterojunction battery requires about 5 tons of indium. If the production capacity is expanded to 100GW, the global indium reserves (about 12,000 tons) will become a serious problem restricting the healthy development of heterojunction batteries. Therefore, it has become urgent to develop alternative materials and reduce dependence on indium. Tin oxide-based materials are expected to find applications in heterojunction batteries by being used in combination with ITO due to their high reliability.

[0004] The development of perovskite battery technology also shows the demand for tin oxide materials. Early perovskite batteries used TiO2 as the electron transport layer, but TiO2 has high UV absorption, poor stability, and low mobility. In contrast, SnO2 is more compatible with the energy band of the perovskite layer, and has excellent properties of high transmittance and high mobility, as well as good chemical stability and UV resistance. Therefore, SnO2 is currently widely used as the electron transport layer material for perovskite batteries. With the advancement of the industrialization of perovskite batteries, dry preparation processes (such as PVD, evaporation, etc.) have gradually replaced laboratory wet processes due to their advantages of good uniformity and easy control, and have put forward broader application demands for related target materials.

[0005] PVD sputtering coating usually uses a DC magnetron power supply, which is simple and reliable, stable in operation, high in power and fast in deposition rate. The target material is in the electric field loop, and the required material is sputtered onto the substrate by the bombardment of Ar ions under magnetic field discharge. Therefore, the target material itself needs to have a high density and a low bulk resistivity. There is a prior art that discloses a method for preparing zinc oxide-doped tin oxide target material by atmosphere high-temperature sintering method, which has fine grains and high density. However, the bulk resistivity of the target material of this system is relatively high, and it is not suitable for sputtering method with DC power supply. There is also prior art that optimizes the density and resistivity of the target material by modifying TiO2 doping, but there is still room for further improvement.

[0006] Based on this, there is an urgent need to develop a multi-doped tin oxide-based target 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 application is:

[0008] Provided is a tin oxide-based target material.

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

[0010] Provided is a method for preparing the tin oxide-based target material.

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

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

[0013] In order to solve the first technical problem, the technical solution adopted in this application is:

[0014] A tin oxide-based target material comprises the following components in the following mass ratios: tin oxide, 95%-98%; zinc oxide, 1%-3%; antimony oxide, 0.5%-1%; and cerium oxide, 0.5%-1%.

[0015] According to the embodiments of the present application, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0016] The tin oxide-based target material of the present application, by doping with zinc oxide, can play a role in sintering the tin oxide-based target material, inhibit the volatilization of tin oxide at high temperatures, reduce internal pores, and promote sintering densification. However, when zinc oxide is doped too much, it will prevent the growth of the lattice during sintering and form lattice distortion, so the doping amount of tin oxide must be controlled. Within the doping range specified in this application, ZnO and SnO2 react at high temperatures to form Zn2SnO4, filling the gaps between the particles and greatly enhancing the sintering densification of the target material.

[0017] Cerium oxide as rare earth oxide, Ce 4+ The ionic radius is 0.092nm, which is smaller than Sn 4+ The nanostructured tin oxide (0.069nm) is much larger. At high temperatures, rare earth elements exhibit uniquely active properties, unstable outer electrons, and the tendency to release large quantities of electrons. When replacing tin ions, these elements dissociate from adjacent oxygen atoms, forming oxygen vacancies. This promotes the growth of the tin oxide lattice and generates a large number of electrons, significantly increasing the electrical conductivity of the sintered body. However, excessive doping with cerium oxide can inhibit lattice growth and cause lattice distortion, so the doping level must be controlled.

[0018] Antimony oxide is a classic SnO2 doped oxide, which exists in solid solution with +3 and +5 valences. 5+ Replace Sn 4+ Afterwards, it can provide a large number of free electrons, effectively reducing the resistivity of tin oxide, but it also produces a large number of lattice defects, resulting in a decrease in crystallinity and hindering grain growth. Therefore, too little antimony oxide doping can help reduce the resistivity of SnO2, but is not conducive to sintering densification; too much antimony oxide doping leads to excessively high resistivity, so the antimony oxide doping amount needs to be strictly controlled.

[0019] According to one embodiment of the present application, the tin oxide-based target material includes the following components in the following mass ratios: tin oxide, 97.1%-98%; zinc oxide, 1%-2%; antimony oxide, 0.5%-1%; cerium oxide, 0.5%-0.7%.

[0020] Under the condition of ensuring qualified 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 -3 Ω or less.

[0021] According to one embodiment of the present application, D50 of the tin oxide, zinc oxide, antimony oxide, and cerium oxide are all less than or equal to 2 μm.

[0022] For tin oxide-based targets, the D50 value of the component is related to the microstructure of the sintered body, including particle size, porosity and the degree of connection between particles, which in turn affects the resistivity of the final target.

[0023] 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 sintering densification. Densified materials 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 are fewer obstacles in the current conduction path.

[0024] Similarly, a suitable D50 value is also conducive to the formation of more sintering necks between particles, that is, the areas where particles are connected to each other. These sintering 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.

[0025] In addition, a suitable D50 value helps to evenly distribute the dopant in the sintered body, making the doping effect more uniform. Dopant can effectively adjust the electronic structure and defect concentration of the material by replacing or forming solid solutions in the crystal lattice, thereby affecting the resistivity.

[0026] According to one embodiment of the present application, D50 of the tin oxide, zinc oxide, antimony oxide, and cerium oxide are all less than or equal to 0.5 μm.

[0027] In order to solve the second technical problem, the technical solution adopted in this application is:

[0028] A method for preparing the tin oxide-based target material comprises the following steps:

[0029] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain tin oxide;

[0030] S2: mixing the tin oxide, zinc oxide, antimony oxide and cerium oxide, ball milling and spray drying to obtain a mixed powder;

[0031] S3: placing the mixed powder in a mold, pressing to obtain a green blank, degreasing and sintering the green blank to obtain the tin oxide-based target.

[0032] According to one embodiment of the present application, in step S1, a tin salt is dissolved in an alcohol solution, hydrolyzed, and then calcined to obtain high-purity tin oxide.

[0033] According to one embodiment of the present application, in step S1, the purity of the high-purity tin oxide is ≥99.99%.

[0034] According to one embodiment of the present application, in step S1, the specific surface area of ​​high-purity tin oxide is 15m 2 / g-25m 2 / g.

[0035] According to one embodiment of the present application, in step S1, the D50 of the high-purity tin oxide is ≤ 0.5 μm, and the Dmax is ≤ 5 μm.

[0036] According to one embodiment of the present application, step S2 further includes the following steps: adding a binder and a plasticizer after ball milling, and then spray drying.

[0037] According to one embodiment of the present application, in step S2, the purity of zinc oxide, antimony oxide and cerium oxide is ≥99.99%.

[0038] According to one embodiment of the present application, in step S2, the BET of zinc oxide, antimony oxide and cerium oxide is 10m 2 / g-25m 2 / g.

[0039] According to one embodiment of the present application, in step S2, D50 of zinc oxide, antimony oxide and cerium oxide is ≤2 μm, and Dmax is ≤10 μm.

[0040] According to one embodiment of the present application, in step S2, the ball milling includes the following steps: first grinding with Φ0.60mm-Φ0.65mm grinding media for 8h-8.5h, and then grinding with Φ0.30mm-Φ0.35mm grinding media for 8h-8.5h.

[0041] According to one embodiment of the present application, in step S2, the mass ratio of the binder to the plasticizer is 0.4-2.5:0.1-2.

[0042] According to one embodiment of the present application, in step S2, the binder includes polyvinyl alcohol.

[0043] According to one embodiment of the present application, in step S2, the plasticizer includes polyethylene glycol.

[0044] According to one embodiment of the present application, in step S2, the specific surface area of ​​the mixed powder is 5m 2 / g-25m 2 / g.

[0045] According to one embodiment of the present application, in step S2, the bulk density of the mixed powder is 1.00 g / cm 3 -1.60g / cm 3 .

[0046] According to one embodiment of the present application, in step S2, the moisture content of the mixed powder is ≤1%.

[0047] According to one embodiment of the present application, in step S3, the degreasing temperature is 600°C-650°C, and the holding time during the degreasing process is 2h-3h.

[0048] According to one embodiment of the present application, in step S3, the sintering is a four-step sintering, including the following steps: first at 950℃-1000℃, keep warm for 8h-9h; then introduce oxygen, raise the temperature to 1200℃-1250℃, keep warm for 6h-8h; then raise the temperature to 1400℃-1450℃, keep warm for 10h-12h; then raise the temperature to 1500℃-1600℃, keep warm for 12h-14h.

[0049] According to one embodiment of the present application, in step S3, the sintering is a four-step sintering, including the following steps: first at 950°C, keep warm for 8 hours; then introduce oxygen, heat to 1200°C, keep warm for 6-8 hours; then heat to 1400°C, keep warm for 10-12 hours; then heat to 1500°C-1600°C, keep warm for 12-14 hours.

[0050] According to one embodiment of the present application, after the tin oxide-based target material is obtained in step S3, further fine processing can be performed, and the fine processing includes the following steps: placing the tin oxide-based target material on a lathe for grinding, using an 800-850 mesh grinding wheel for rough grinding, and processing for 8h-8.5h; using a 400-450 mesh grinding wheel for fine grinding, and processing for 8h-8.5h to obtain the finely processed tin oxide-based target material.

[0051] Another aspect of this application relates to the use of the tin oxide-based target in display panels or photovoltaic cells. This includes the tin oxide-based target described in the first embodiment. Because this application utilizes all of the technical solutions of the tin oxide-based target, it possesses at least all of the beneficial effects of the technical solutions of the aforementioned embodiments.

[0052] Other features and advantages of the present application will be set forth in the following description, and in part will be apparent from the description, or may be learned by practicing the present application. DETAILED DESCRIPTION

[0053] The terms "preferably," "more preferably," and the like in this application refer to embodiments of the present application that may 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 not applicable, nor is it intended to exclude other embodiments from the scope of this application.

[0054] 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 such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are understood to include any and all subranges subsumed therein.

[0055] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the embodiments described are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0056] Unless otherwise specified, the reagents, methods and equipment used in this application are conventional reagents, methods and equipment in this technical field.

[0057] For the tin oxide-based targets of Examples 1 to 15, D50 of tin oxide is ≤0.5 μm, and D50 of zinc oxide, antimony oxide, and cerium oxide are all ≤2 μm and ≥1 μm.

[0058] Example 1

[0059] A tin oxide-based target material comprises the following components in the following mass ratios: 95% tin oxide; 3% zinc oxide; 1% antimony oxide; and 1% cerium oxide.

[0060] The method for preparing a tin oxide-based target material comprises the following steps:

[0061] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0062] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 1.8% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 12m 2 / g, bulk density is 1.55g / cm 3 , moisture content ≤1%;

[0063] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0064] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0065] Example 2

[0066] The difference between Example 2 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0067] A tin oxide-based target material comprises the following components in the following mass ratios: tin oxide, 96%; zinc oxide, 2%; antimony oxide, 1%; and cerium oxide, 1%.

[0068] The method for preparing a tin oxide-based target material comprises the following steps:

[0069] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0070] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 10.5m 2 / g, bulk density is 1.35g / cm 3 , moisture content ≤1%;

[0071] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0072] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0073] Example 3

[0074] The difference between Example 3 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0075] A tin oxide-based target material comprises the following components in the following mass ratios: 96.5% tin oxide; 2% zinc oxide; 0.5% antimony oxide; and 1% cerium oxide.

[0076] The method for preparing a tin oxide-based target material comprises the following steps:

[0077] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0078] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 1.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 15m 2 / g, bulk density is 1.5g / cm 3 , moisture content ≤1%;

[0079] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 180 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0080] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0081] Example 4

[0082] The difference between Example 4 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0083] A tin oxide-based target material comprises the following components in the following mass ratios: 98% tin oxide; 1% zinc oxide; 0.5% antimony oxide; and 0.5% cerium oxide.

[0084] The method for preparing a tin oxide-based target material comprises the following steps:

[0085] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0086] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 1.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 20m 2 / g, bulk density is 1.60g / cm 3 , moisture content ≤1%;

[0087] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 175 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0088] S4: Degreasing the blank, the degreasing temperature is 600℃, and the holding time is 3h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 8h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 12h; after the holding is completed, the temperature is increased to a maximum temperature of 1520℃ at a heating rate of 0.1℃ / min, and the holding time is 14h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0089] Example 5

[0090] The difference between Example 5 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0091] A tin oxide-based target material comprises the following components in the following mass ratios: 97% tin oxide; 1% zinc oxide; 1% antimony oxide; and 1% cerium oxide.

[0092] The method for preparing a tin oxide-based target material comprises the following steps:

[0093] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0094] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 0.8% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.15% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 18.5m 2 / g, and the bulk density is 1.58g / cm 3 , moisture content ≤1%;

[0095] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, with a molding pressure of 120 MPa, and statically strengthening the target material green blank, and pressing to obtain a green blank;

[0096] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 3h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 8h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 12h; after the holding is completed, the temperature is increased to a maximum temperature of 1600℃ at a heating rate of 0.1℃ / min, and the holding time is 14h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0097] Example 6

[0098] The difference between Example 6 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0099] A tin oxide-based target material comprises the following components in the following mass ratios: 96.5% tin oxide; 2.5% zinc oxide; 0.5% antimony oxide; and 0.5% cerium oxide.

[0100] The method for preparing a tin oxide-based target material comprises the following steps:

[0101] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0102] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8 hours, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8 hours. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 0.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.1% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 7.5m 2 / g, bulk density is 1.00g / cm 3 , moisture content ≤1%;

[0103] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0104] S4: Degreasing the blank, the degreasing temperature is 600℃, and the holding time is 2h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1500℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0105] Example 7

[0106] The difference between Example 7 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0107] A tin oxide-based target material comprises the following components in the following mass ratios: tin oxide, 97%; zinc oxide, 2%; antimony oxide, 0.5%; and cerium oxide, 0.5%.

[0108] The method for preparing a tin oxide-based target material comprises the following steps:

[0109] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0110] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 0.85% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.15% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 13.5m 2 / g, bulk density is 1.35g / cm 3 , moisture content ≤1%;

[0111] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 180 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0112] S4: Degreasing the blank, the degreasing temperature is 630℃, and the holding time is 2h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1565℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0113] Example 8

[0114] The difference between Example 8 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0115] A tin oxide-based target material comprises the following components in the following mass ratios: 97.5% tin oxide; 1% zinc oxide; 0.5% antimony oxide; and 1% cerium oxide.

[0116] The method for preparing a tin oxide-based target material comprises the following steps:

[0117] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0118] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.18% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 18.5m 2 / g, bulk density is 1.45g / cm 3 , moisture content ≤1%;

[0119] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 180 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0120] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 7h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 11h; after the holding is completed, the temperature is increased to a maximum temperature of 1520℃ at a heating rate of 0.1℃ / min, and the holding time is 13h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0121] Example 9

[0122] The difference between Example 9 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0123] A tin oxide-based target material comprises the following components in the following mass ratios: 96.7% tin oxide; 1.7% zinc oxide; 0.8% antimony oxide; and 0.8% cerium oxide.

[0124] The method for preparing a tin oxide-based target material comprises the following steps:

[0125] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0126] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 1.85% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 1.8% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 12.5m 2 / g, bulk density is 1.35g / cm 3 , moisture content ≤1%;

[0127] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0128] S4: Degreasing the blank, the degreasing temperature is 600℃, and the holding time is 2h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0129] Example 10

[0130] The difference between Example 10 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0131] A tin oxide-based target material comprises the following components in the following mass ratios: tin oxide, 97%; zinc oxide, 1.8%; antimony oxide, 0.6%; and cerium oxide, 0.6%.

[0132] The method for preparing a tin oxide-based target material comprises the following steps:

[0133] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0134] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.15% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 13.5m 2 / g, bulk density is 1.30g / cm 3 , moisture content ≤1%;

[0135] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 180 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0136] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 8h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 12h; after the holding is completed, the temperature is increased to a maximum temperature of 1560℃ at a heating rate of 0.1℃ / min, and the holding time is 14h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0137] Example 11

[0138] The difference between Example 11 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0139] A tin oxide-based target material comprises the following components in the following mass ratios: 97.1% tin oxide; 1.5% zinc oxide; 0.7% antimony oxide; and 0.7% cerium oxide.

[0140] The method for preparing a tin oxide-based target material comprises the following steps:

[0141] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0142] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8 hours, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8 hours. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.18% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 15.5m 2 / g, bulk density is 1.35g / cm 3 , moisture content ≤1%;

[0143] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 175 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0144] S4: Degreasing the blank, the degreasing temperature is 600℃, and the holding time is 2h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12.5h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0145] Example 12

[0146] The difference between Example 12 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0147] A tin oxide-based target material comprises the following components in the following mass ratios: 95.9% of tin oxide; 2.5% of zinc oxide; 0.8% of antimony oxide; and 0.8% of cerium oxide.

[0148] The method for preparing a tin oxide-based target material comprises the following steps:

[0149] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0150] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 1.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 1.8% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 18.5m 2 / g, bulk density is 1.45g / cm 3 , moisture content ≤1%;

[0151] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 200 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0152] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 3h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 8h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 12h; after the holding is completed, the temperature is increased to a maximum temperature of 1500℃ at a heating rate of 0.1℃ / min, and the holding time is 14h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0153] Example 13

[0154] The difference between Example 13 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0155] A tin oxide-based target material comprises the following components in the following mass ratios: 97.4% tin oxide; 1% zinc oxide; 0.8% antimony oxide; and 0.8% cerium oxide.

[0156] The method for preparing a tin oxide-based target material comprises the following steps:

[0157] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0158] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 2% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 25m 2 / g, and the bulk density is 1.58g / cm 3 , moisture content ≤1%;

[0159] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 200 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0160] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 3h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 8h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 12h; after the holding is completed, the temperature is increased to a maximum temperature of 1600℃ at a heating rate of 0.1℃ / min, and the holding time is 14h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0161] Example 14

[0162] The difference between Example 14 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0163] A tin oxide-based target material comprises the following components in the following mass ratios: 95.5% tin oxide; 2.5% zinc oxide; 1% antimony oxide; and 1% cerium oxide.

[0164] The method for preparing a tin oxide-based target material comprises the following steps:

[0165] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0166] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 1.8% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 18m 2 / g, bulk density is 1.30g / cm 3 , moisture content ≤1%;

[0167] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 180 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0168] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 3h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 8h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1500℃ at a heating rate of 0.1℃ / min, and the holding time is 14h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0169] Example 15

[0170] The difference between Example 15 and Example 1 is that the mass proportions of the components in the tin oxide-based target are different.

[0171] A tin oxide-based target material comprises the following components in the following mass ratios: 95.2% of tin oxide; 2.8% of zinc oxide; 1% of antimony oxide; and 1% of cerium oxide.

[0172] The method for preparing a tin oxide-based target material comprises the following steps:

[0173] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0174] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 2.5% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 2% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 23.5m 2 / g, bulk density is 1.60g / cm 3 , moisture content ≤1%;

[0175] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 200 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0176] S4: Degreasing the blank, the degreasing temperature is 600℃, and the holding time is 2h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 8h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1550℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0177] Example 16

[0178] The difference between Example 16 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0179] A tin oxide-based target material comprises the following components in the following mass ratios: 95% tin oxide; 3% zinc oxide; 1% antimony oxide; and 1% cerium oxide.

[0180] Among them, D50 of tin oxide is 1 μm, D50 of zinc oxide is 2.5 μm, D50 of antimony oxide is 1 μm, and D50 of cerium oxide is 1.8 μm.

[0181] The method for preparing a tin oxide-based target material comprises the following steps:

[0182] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0183] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 1.8% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 12m 2 / g, bulk density is 1.55g / cm 3 , moisture content ≤1%;

[0184] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0185] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0186] Example 17

[0187] The difference between Example 17 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0188] A tin oxide-based target material comprises the following components in the following mass ratios: 95% tin oxide; 3% zinc oxide; 1% antimony oxide; and 1% cerium oxide.

[0189] Among them, D50 of tin oxide is 0.5 μm, D50 of zinc oxide is 1.5 μm, D50 of antimony oxide is 1 μm, and D50 of cerium oxide is 4 μm.

[0190] The method for preparing a tin oxide-based target material comprises the following steps:

[0191] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0192] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 1.8% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 12m 2 / g, bulk density is 1.55g / cm 3 , moisture content ≤1%;

[0193] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0194] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0195] Example 18

[0196] The difference between Example 18 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0197] A tin oxide-based target material comprises the following components in the following mass ratios: 95% tin oxide; 3% zinc oxide; 1% antimony oxide; and 1% cerium oxide.

[0198] Among them, D50 of tin oxide is 0.4 μm, D50 of zinc oxide is 2 μm, D50 of antimony oxide is 4 μm, and D50 of cerium oxide is 4 μm.

[0199] The method for preparing a tin oxide-based target material comprises the following steps:

[0200] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0201] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 1.8% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 12m 2 / g, bulk density is 1.55g / cm 3 , moisture content ≤1%;

[0202] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0203] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0204] Example 19

[0205] The difference between Example 19 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0206] A tin oxide-based target material comprises the following components in the following mass ratios: 95% tin oxide; 3% zinc oxide; 1% antimony oxide; and 1% cerium oxide.

[0207] Among them, D50 of tin oxide is 0.4 μm, D50 of zinc oxide is 1 μm, D50 of antimony oxide is 1 μm, and D50 of cerium oxide is 0.8 μm.

[0208] The method for preparing a tin oxide-based target material comprises the following steps:

[0209] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0210] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 1.8% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 12m 2 / g, bulk density is 1.55g / cm 3 , moisture content ≤1%;

[0211] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0212] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0213] Example 20

[0214] The difference between Example 20 and Example 1 is that the D50 of the components in the tin oxide-based target is different.

[0215] A tin oxide-based target material comprises the following components in the following mass ratios: 95% tin oxide; 3% zinc oxide; 1% antimony oxide; and 1% cerium oxide.

[0216] Among them, D50 of tin oxide is 0.5 μm, D50 of zinc oxide is 0.5 μm, D50 of antimony oxide is 0.5 μm, and D50 of cerium oxide is 0.5 μm.

[0217] The method for preparing a tin oxide-based target material comprises the following steps:

[0218] S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain high-purity tin oxide;

[0219] S2: The high-purity tin oxide, zinc oxide, antimony oxide and cerium oxide are mixed and ball milled. First, Φ0.60mm zirconium beads are used for grinding at a speed of 600rpm for 8h, and then Φ0.30mm zirconium beads are used for grinding at a speed of 800rpm for 8h. After adding a binder (PVA) and a plasticizer (PEG), the mixture is stirred and filtered, and spray-dried to obtain a mixed powder. Among them, the mass of the binder accounts for 1.8% of the total mass of the metal oxide component, and the mass of the plasticizer accounts for 0.5% of the total mass of the metal oxide component. The specific surface area of ​​the mixed powder is measured to be 12m 2 / g, bulk density is 1.55g / cm 3 , moisture content ≤1%;

[0220] S3: using a rotating target mold, injecting the mixed powder into the mold, using WCIP molding, molding pressure of 150 MPa, static pressure strengthening target blank, and pressing to obtain blank;

[0221] S4: Degreasing the blank, the degreasing temperature is 650℃, and the holding time is 2.5h; after degreasing is completed, the temperature is increased to 950℃ at a heating rate of 1℃ / min, and kept warm for 8h; after the holding is completed, oxygen is introduced, and the temperature is increased to 1200℃ at a heating rate of 0.5℃ / min, and the holding time is 6h; after the holding is completed, the temperature is increased to 1400℃ at a heating rate of 0.3℃ / min, and the holding time is 10h; after the holding is completed, the temperature is increased to a maximum temperature of 1580℃ at a heating rate of 0.1℃ / min, and the holding time is 12h; after the holding is completed, ventilation is stopped, and the temperature is cooled to room temperature at a rate of 1℃ / min to obtain the tin oxide-based target.

[0222] Comparative Example 1

[0223] The difference between Comparative Example 1 and Example 1 is that the tin oxide-based target material in Comparative Example 1 contains only tin oxide.

[0224] Comparative Example 2

[0225] The difference between Comparative Example 2 and Example 1 is that the tin oxide-based target material in Comparative Example 2 contains only 97% by mass of tin oxide and 3% by mass of zinc oxide.

[0226] Comparative Example 3

[0227] The difference between Comparative Example 3 and Example 1 is that the tin oxide-based target material of Comparative Example 3 contains only 97% by mass of tin oxide, 2.5% by mass of zinc oxide, and 0.5% by mass of cerium oxide.

[0228] Comparative Example 4

[0229] The difference between Comparative Example 4 and Example 1 is that the tin oxide-based target material of Comparative Example 4 contains only 97% by mass of tin oxide and 3% by mass of antimony oxide.

[0230] Comparative Example 5

[0231] The difference between Comparative Example 5 and Example 1 is that the tin oxide-based target material of Comparative Example 5 contains only 96% by mass of tin oxide, 3% by mass of zinc oxide, and 1% by mass of antimony oxide.

[0232] Comparative Example 6

[0233] The difference between Comparative Example 6 and Example 1 is that the tin oxide-based target material of Comparative Example 6 contains only 98% by mass of tin oxide, 1% by mass of cerium oxide, and 1% by mass of antimony oxide.

[0234] Comparative Example 7

[0235] The difference between Comparative Example 7 and Example 1 is that in the tin oxide-based target material of Comparative Example 7, the mass proportion of tin oxide is 95.2%, the mass proportion of zinc oxide is 3.5%, the mass proportion of antimony oxide is 0.5%, and the mass proportion of cerium oxide is 0.8%.

[0236] Comparative Example 8

[0237] The difference between Comparative Example 8 and Example 1 is that in the tin oxide-based target material of Comparative Example 8, the mass proportion of tin oxide is 94%, the mass proportion of zinc oxide is 3.5%, the mass proportion of antimony oxide is 1.5%, and the mass proportion of cerium oxide is 1%.

[0238] Comparative Example 9

[0239] The difference between Comparative Example 9 and Example 1 is that in the tin oxide-based target material of Comparative Example 9, the mass proportion of tin oxide is 98.5%, the mass proportion of zinc oxide is 0.5%, the mass proportion of antimony oxide is 0.5%, and the mass proportion of cerium oxide is 0.5%.

[0240] Comparative Example 10

[0241] The difference between Comparative Example 10 and Example 1 is that in the tin oxide-based target material of Comparative Example 10, the mass proportion of tin oxide is 95%, the mass proportion of zinc oxide is 2.5%, the mass proportion of antimony oxide is 1.5%, and the mass proportion of cerium oxide is 1%.

[0242] Comparative Example 11

[0243] The difference between Comparative Example 11 and Example 1 is that in the tin oxide-based target material of Comparative Example 11, the mass proportion of tin oxide is 96.3%, the mass proportion of zinc oxide is 2.5%, the mass proportion of antimony oxide is 0.2%, and the mass proportion of cerium oxide is 1%.

[0244] Comparative Example 12

[0245] The difference between Comparative Example 12 and Example 1 is that in the tin oxide-based target material of Comparative Example 12, the mass proportion of tin oxide is 96.8%, the mass proportion of zinc oxide is 2.5%, the mass proportion of antimony oxide is 0.5%, and the mass proportion of cerium oxide is 0.2%.

[0246] Comparative Example 13

[0247] The difference between Comparative Example 13 and Example 1 is that in the tin oxide-based target material of Comparative Example 13, the mass proportion of tin oxide is 95.5%, the mass proportion of zinc oxide is 2.5%, the mass proportion of antimony oxide is 0.5%, and the mass proportion of cerium oxide is 1.5%.

[0248] Performance testing:

[0249] The tin oxide-based targets obtained in Examples 1 to 20 and Comparative Examples 1 to 13 were subjected to performance tests, and the test results are shown in Table 1-2.

[0250] Table 1

[0251] As can be seen from Table 1, since Comparative Example 1 uses undoped pure tin oxide, under this sintering process, there are many pores between the grains, the prepared target material has low density, too high resistivity, and almost no conductive properties. Comparative Example 2 improves the sintering density through ZnO doping, but the resistivity is too high and cannot meet the requirements of DC sputtering coating. Comparative Example 3, based on Comparative Example 2, doped with CeO2, reduced the resistivity, but still needs to be further reduced. Comparative Example 4 only doped with Sb2O3, and the resistivity was significantly reduced, but the sintered body density was too low. Comparative Example 5 doped with ZnO and Sb2O3 simultaneously, improving the density and resistivity, but still needs further improvement. Comparative Example 6 doped with CeO2 and Sb2O3 simultaneously without ZnO doping, although the resistivity was reduced, the sintered body density was low. Comparative Example 7 doped with three oxides simultaneously, but the ZnO doping level was too high, resulting in large lattice distortion and cracking after sintering. Comparative Example 8 has a low ZnO doping ratio, resulting in a weak sintering effect and low density. Comparative Example 9 has an excessive amount of Sb2O3 doped, which reduces the compactness of the sintering and has a low density. Comparative Example 10 has an insufficient amount of Sb2O3 doped, resulting in an insufficient resistivity reduction effect. Comparative Example 11 has an insufficient amount of CeO2 doped, resulting in an insufficient resistivity reduction effect. Comparative Example 12 has a high CeO2 doping ratio, resulting in lattice distortion and cracking after sintering.

[0252] In Examples 1 to 15, through multi-element doping, the D50 of tin oxide is ≤ 0.5 μm, and the D50 of the three doped oxides is ≤ 2 μm and ≥ 1 μm. By precisely controlling the doping amounts of the three oxides, the sintered target material exhibits both high density and low bulk resistivity. The processed target material can be stably used for DC magnetron sputtering (PVD) coating.

[0253] Table 2

[0254] In Examples 16 to 18, the powder D50 was relatively high, resulting in varying degrees of reduction in target density and resistivity after sintering. In Example 19, the D50 of all three doped oxides was ≤1 μm, resulting in a slightly higher target density. In Example 20, the D50 of all three doped oxides was ≤0.5 μm, resulting in the optimal target density and resistivity.

[0255] The above are merely embodiments of the present application and are not intended to limit the scope of patent protection of the present application. Any equivalent transformations made using the contents of the present application specification, or directly or indirectly applied in related technical fields, are also included in the scope of patent protection of the present application.

Claims

1. A tin oxide-based target, characterized in that: The invention comprises the following components in the following mass ratios: tin oxide, 95%-98%; zinc oxide, 1%-3%; antimony oxide, 0.5%-1%; cerium oxide, 0.5%-1%.

2. The tin oxide-based target according to claim 1, wherein: The tin oxide-based target material comprises the following components in the following mass ratios: tin oxide, 97.1%-98%; zinc oxide, 1%-2%; antimony oxide, 0.5%-1%; Cerium oxide, 0.5%-0.7%.

3. The tin oxide-based target according to claim 1, wherein: The D50 of the tin oxide, zinc oxide, antimony oxide and cerium oxide are all less than or equal to 2 μm.

4. The tin oxide-based target according to claim 3, wherein: The D50 of the tin oxide, zinc oxide, antimony oxide and cerium oxide are all less than or equal to 0.5 μm.

5. A method for preparing the tin oxide-based target according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1: dissolving tin salt in alcohol solution, hydrolyzing and calcining to obtain tin oxide; S2: mixing the tin oxide, zinc oxide, antimony oxide and cerium oxide, ball milling and spray drying to obtain a mixed powder; S3: placing the mixed powder in a mold, pressing to obtain a green blank, degreasing and sintering the green blank to obtain the tin oxide-based target.

6. The method according to claim 5, characterized in that: In step S2, the ball milling includes the following steps: firstly grinding with a Φ0.60 mm-Φ0.65 mm grinding medium for 8 h-8.5 h, and then grinding with a Φ0.30 mm-Φ0.35 mm grinding medium for 8 h-8.5 h.

7. The method according to claim 5, characterized in that: In step S2, The method comprises the following steps: adding a binder and a plasticizer after ball milling, and then spray drying; the mass ratio of the binder to the plasticizer is 0.4-2.5:0.1-2.

8. The method according to claim 5, characterized in that: In step S3, the degreasing temperature is 600° C.-650° C., and the holding time during the degreasing process is 2 h-3 h.

9. The method according to claim 5, characterized in that: In step S3, the sintering is a four-step sintering, including the following steps: first at 950℃-1000℃, keep warm for 8h-9h; then introduce oxygen, raise the temperature to 1200℃-1250℃, keep warm for 6h-8h; then raise the temperature to 1400℃-1450℃, keep warm for 10h-12h; then raise the temperature to 1500℃-1600℃, keep warm for 12h-14h.

10. Use of the tin oxide-based target material according to any one of claims 1 to 4 in a display panel or a photovoltaic cell.

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