Tin oxide-based target material as well as preparation method and application thereof

Abstract

The invention provides a tin oxide-based target material as well as a preparation method and application thereof. The tin oxide-based target material comprises tin oxide, niobium oxide and antimony oxide. The density and the conductivity of the tin oxide-based target material are optimized by utilizing the donor doping effect of niobium and the synergistic effect of antimony.

Description

Technical Field

[0001] This application relates to the field of functional ceramic materials technology, and in particular to a tin oxide-based target and its preparation method. Background Technology

[0002] As the photovoltaic industry accelerates its iteration towards high efficiency and low cost, the demand for indium-free TCO layers in heterojunction (HJT) solar cells is becoming increasingly urgent. The large-scale application of traditional indium tin oxide (ITO) sputtering targets is severely limited due to the scarcity and high price of indium resources and its environmental impact.

[0003] Tin oxide (SnO2) has become an ideal alternative material due to its abundant natural reserves, wide bandgap, and high visible light transmittance. However, intrinsic SnO2 suffers from drawbacks such as low carrier concentration, difficulty in sintering densification, and severe grain boundary scattering, making it difficult to meet the stringent requirements of DC sputtering processes for high conductivity, high density, and chemical stability of the target material.

[0004] Therefore, developing a tin oxide-based target material with high density, high conductivity, and chemical stability is an urgent problem to be solved in this field. Summary of the Invention

[0005] The present invention provides a tin oxide-based target material, which has higher density, conductivity and chemical stability.

[0006] The present invention also provides a method for preparing a tin oxide-based target material, which can prepare the above-mentioned tin oxide-based target material, and the process is simple and low in cost.

[0007] The present invention also provides a conductive thin film comprising the above-mentioned tin oxide-based target material, which has low resistivity and high visible light transmittance.

[0008] In a first aspect, the present invention provides a tin oxide-based target material, wherein the tin oxide-based target material includes tin oxide, niobium oxide and antimony oxide.

[0009] The tin oxide-based target material described above, wherein the atomic ratio of niobium oxide to antimony oxide in the tin oxide-based target material is (2-8):1.

[0010] The tin oxide-based target material described above, wherein the atomic ratio of tin oxide, niobium oxide and antimony oxide in the tin oxide-based target material is (95-97.5):(2-4):(0.5-1).

[0011] The tin oxide-based target material described above has a relative density greater than or equal to 99% and a resistivity less than or equal to 200 Ω·cm.

[0012] Secondly, the present invention provides a method for preparing the tin oxide-based target material as described above, comprising the following steps:

[0013] A slurry containing tin oxide, niobium oxide, and antimony oxide is spray-dried and granulated to obtain granulated powder.

[0014] The granulated powder is subjected to compression molding and cold isostatic pressing in sequence to obtain a green body.

[0015] The tin oxide-based target material is obtained by sequentially degreasing and calcining the raw blank.

[0016] In the preparation method described above, the slurry further includes a binder and / or a dispersant.

[0017] In the preparation method described above, the mass percentage of the dispersant in the slurry is 0.1~0.6%.

[0018] In the preparation method described above, the mass percentage of the binder in the slurry is 0.05~0.25%.

[0019] In the preparation method described above, the inlet air temperature of the spray drying granulation is 180-260℃, the outlet air temperature is 90-120℃, and the atomization speed is 14000-21000rpm.

[0020] And / or, the pressure of the compression molding process is 40~100MPa, and the holding time is 1~10min;

[0021] And / or, the pressure of the cold isostatic pressing treatment is 220-300 MPa, and the holding time is 5-20 min.

[0022] The preparation method described above, wherein the degreasing treatment includes: heating the green blank from room temperature to 200-800°C at a heating rate of 0.5-2°C / min, and holding at that temperature for 2-8 hours; and / or,

[0023] The calcination process includes heating the degreased green body to 1100-1600℃ at a heating rate of 1-5℃ / min and holding it at that temperature for 6-30 hours.

[0024] Thirdly, the present invention provides a conductive thin film, wherein the thin film includes the tin oxide-based target material described in the first aspect or the tin oxide-based target material prepared by the preparation method described in the second aspect.

[0025] The tin oxide-based target provided by this invention utilizes niobium (Nb) in the incorporation of tin oxide. 5+ ) and antimony (Sb 3+ Co-doping improves the performance of tin oxide-based targets. On the one hand, Nb... 5+By replacing Sn 4+ Lattice sites increase the concentration of free electrons, significantly improving carrier concentration and mobility, while reducing lattice distortion and grain boundary scattering, thus enhancing the material's density and stability. On the other hand, Sb... 3+ The introduction of Nb reduces the formation of Sn vacancies, lowers the carrier trap density, and enhances the weather resistance of the material. Simultaneously, through the charge compensation effect, Nb... 5+ and Sb 3+ The synergistic effect balances lattice stress and significantly improves the conductivity and light transmittance of the material. Detailed Implementation

[0026] Exemplary embodiments will now be described in detail. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this application. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this application as detailed in the appended claims.

[0027] In this application, the terms "first" and "second" are used for descriptive purposes only, to distinguish objects, such as substances, from one another, and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. For example, without departing from the scope of the embodiments of this application, "first XX" may also be referred to as "second XX," and similarly, "second XX" may also be referred to as "first XX." Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of that feature.

[0028] In this application, references to "an embodiment," "an example," or "an example" mean that a specific feature, structure, or characteristic described in connection with that embodiment, example, or example is included in at least one embodiment of the invention. Therefore, the phrases "an embodiment," "an example," "an example," "an example," or "an example" appearing in various places throughout the specification do not necessarily refer to the same embodiment or example. Furthermore, specific features, structures, or characteristics can be combined in one or more embodiments or examples in any suitable combination and / or sub-combination.

[0029] Existing tin oxide-based targets suffer from insufficient intrinsic conductivity and difficulty in sintering densification. The inventors discovered in their research that doping tin oxide-based targets with other metal elements can optimize the density and conductivity of tin oxide-based targets, providing key material support for the production of indium-free or low-indium heterojunction batteries.

[0030] Therefore, the present invention provides the following solution:

[0031] In a first aspect, the present invention provides a tin oxide-based target material, which includes tin oxide, niobium oxide and antimony oxide.

[0032] This invention utilizes niobium (Nb) 5+ ) and antimony (Sb 3+ The co-doping strategy, utilizing a dual donor-acceptor synergistic mechanism, significantly enhances the performance of tin oxide-based targets. Firstly, niobium ions (Nb)... 5+ ) replaced the lattice position of tin (Sn) 4+ Each niobium atom doped with niobium contributes one free electron (Nb 5+ → Sn 4+ + e - This significantly increased the carrier concentration, reaching over 2 × 10⁻⁶. 20 cm -3 This doping not only improves the conductivity of the material, but also because the ionic radius of niobium ions is similar to that of tin ions (Sn). 4+ The niobium (0.69 Å) is very well matched, resulting in small lattice distortion, which reduces grain boundary scattering and improves carrier mobility to greater than 28 cm² / (V•s). In addition, niobium doping also inhibits the decomposition of SnO2 at high temperatures and promotes a diffusion-dominated sintering mechanism, thereby improving the density of the material.

[0033] Based on this, antimony ions (Sb 3+ The introduction of antimony ions further optimizes the material's properties. Antimony ions preferentially occupy tin sites, reducing the formation of tin vacancies and thus lowering the carrier trap density. This change not only improves the film's weather resistance but also enhances its performance through the acceptance of antimony (Sb). 3+ ) and donor niobium (Nb) 5+ The charge compensation effect between the crystals effectively balances the stress in the lattice. This charge compensation effect plays a crucial role in improving the conductivity of the material, reducing the resistivity to less than 10⁻⁶. 5 mΩ•cm. Simultaneously, this synergistic effect also improves the material's light transmittance, reaching over 83%.

[0034] By employing a co-doping strategy with niobium and antimony, this invention not only solves the problems of low carrier concentration, severe grain boundary scattering, and difficulty in sintering densification in traditional tin oxide materials, but also achieves significant improvements in conductivity, light transmittance, and chemical stability.

[0035] Furthermore, in tin oxide-based targets, when the atomic ratio of niobium oxide to antimony oxide is (2-8):1, the relative density of the tin oxide-based target can be further increased and the resistivity of the tin oxide-based target can be reduced.

[0036] In tin oxide-based targets, an atomic ratio of tin oxide, niobium oxide, and antimony oxide of (95-97.5):(2-4):(0.5-1) provides optimal conductivity and stability, making it suitable for manufacturing high-performance electronic devices. In some embodiments, inductively coupled plasma atomic ratios (ICP-ARP) can be used to measure the atomic ratio of tin oxide, niobium oxide, and antimony oxide in the tin oxide-based target.

[0037] Furthermore, when the relative density of the tin oxide-based target is ≥99% and the resistivity is ≤200Ω·cm, the tin oxide-based target has higher density and better conductivity, making it suitable for widespread application.

[0038] Secondly, the present invention provides a method for preparing a tin oxide-based target material, comprising the following steps:

[0039] A slurry containing tin oxide, niobium oxide, and antimony oxide is spray-dried and granulated to obtain granulated powder.

[0040] The granulated powder is subjected to compression molding and cold isostatic pressing in sequence to obtain a green body.

[0041] The green blank was subjected to degreasing and calcination treatments in sequence to obtain tin oxide-based target material.

[0042] Specifically, a slurry comprising tin oxide, niobium oxide, and antimony oxide is spray-dried and granulated. The granulated powder is collected, mixed, and sieved to obtain large-particle tin oxide-based mixed granulated powder. Spray drying granulation effectively avoids particle agglomeration, reduces defects in the tin oxide-based target material, and improves its mechanical strength and conductivity. The granulated powder is first subjected to molding and cold isostatic pressing to obtain a uniform preform through dual molding. Then, the preform is sequentially degreased and calcined. During calcination, the formation of low-valence tin oxide is suppressed, and grain densification is promoted. The preparation method of this invention can obtain tin oxide-based targets with both density and conductivity. This preparation method not only simplifies the process flow but also improves the quality and performance of the target material, making it more reliable and efficient in practical applications.

[0043] In some embodiments of the present invention, in order to enable tin oxide, niobium oxide and antimony oxide in the slurry to bond tightly and improve the density of the tin oxide-based target, the slurry may also include a binder.

[0044] The present invention does not impose any particular limitation on the adhesive, and any adhesive commonly used in the art can be used. For example, the adhesive may include polyvinyl alcohol.

[0045] In some embodiments, the mass percentage of binder in the slurry can be 0.05 to 0.25%.

[0046] For example, the mass percentage of the adhesive can be any value or a range of both of 0.05%, 0.1%, 0.15%, 0.2%, and 0.25%.

[0047] The binder content mentioned above can effectively improve the bonding force between tin oxide, niobium oxide and antimony oxide particles, enhance the mechanical strength and molding performance of the slurry, and thus help to prepare a dense and uniform tin oxide-based target. Within this range, it can also avoid the increase in porosity caused by excessive binder or the generation of residues during the calcination process, thereby maintaining the high conductivity and purity of the tin oxide-based target.

[0048] In some embodiments of the present invention, in order to improve the dispersion uniformity of the slurry, suppress the formation of low-valence tin oxide and promote grain densification, and promote the densification of tin oxide-based target materials, the slurry may also include a dispersant.

[0049] This invention does not specifically limit the dispersant; it can be any dispersant commonly used in the art. Exemplarily, the dispersant includes one or more of sodium dodecylbenzenesulfonate, polyethylene glycol, polyacrylic acid, and polyvinylpyrrolidone.

[0050] In one specific embodiment, the mass percentage of dispersant in the slurry is 0.1~0.6%.

[0051] For example, the mass percentage of dispersant in the slurry can be any value or a range of both of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, and 0.6%.

[0052] The dispersant content mentioned above can effectively reduce the agglomeration of niobium oxide, antimony oxide, and tin oxide particles, resulting in uniform dispersion of the slurry and improving the density of the tin oxide-based target material.

[0053] The tin oxide, niobium oxide, and antimony oxide of this invention can be tin oxide, niobium oxide, and antimony oxide commonly used in the art, respectively. In some embodiments, the purity of tin oxide, niobium oxide, and antimony oxide can all be ≥99.99%.

[0054] In some implementations, when the D50 of tin oxide is ≤8 μm, the BET is 5~18 μm. 2 / g;

[0055] And / or, niobium oxide has a D50 ≤ 8 μm and a BET of 5~18 μm. 2 / g;

[0056] And / or, antimony oxide has a D50 ≤ 8 μm and a BET of 5~18 μm. 2 At a density of / g, tin oxide-based targets with higher density and better electrical conductivity can be formed.

[0057] In one specific embodiment, the inlet air temperature of the spray drying granulation is 180-260℃, the outlet air temperature is 90-120℃, and the atomizer speed is 14000-21000 rpm.

[0058] For example, the inlet air temperature can be any value or a range of both of the following: 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, and 260°C.

[0059] For example, the outlet air temperature can be any value or a range of two of the following: 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, and 120°C.

[0060] For example, the atomizer speed can be any value or a range of both of the following: 14,000 rpm, 15,000 rpm, 16,000 rpm, 17,000 rpm, 18,000 rpm, 19,000 rpm, 20,000 rpm, 21,000 rpm.

[0061] The inlet and outlet air temperatures of the spray drying granulation process can quickly evaporate the moisture in the slurry, forming uniform particles, thereby improving the material's flowability and processability. The atomizer speed ensures fine atomization of the slurry, resulting in uniform particle size, which in turn improves the density and consistency of the tin oxide-based target material.

[0062] In some embodiments, the present invention can first mold the granulated powder obtained by spray drying into an intermediate preform, and then further vacuum package it and put it into a cold isostatic press for cold isostatic pressing to obtain the preform.

[0063] In one specific embodiment, the molding pressure is 40~100MPa, and the holding time is 1~10min.

[0064] For example, the compression molding pressure can be any value of 40MPa, 50MPa, 60MPa, 70MPa, 80MPa, 90MPa, 100MPa or a range of both.

[0065] For example, the holding time can be any value or a range of both of the following: 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min.

[0066] The pressure and holding time of the above-mentioned molding process can produce intermediate blanks with high density and uniformity, which is beneficial to subsequent operations. Furthermore, by adjusting the holding time to between 1 and 10 minutes, sufficient contact and bonding between tin oxide, niobium oxide and antimony oxide particles can be ensured, reducing porosity and internal defects. This helps to optimize the mechanical strength and conductivity of the tin oxide-based target material, while avoiding cracking or deformation of the intermediate blank due to excessive pressing.

[0067] In some implementations, the pressure during cold isostatic pressing is 220-300 MPa, and the holding time is 5-20 min.

[0068] For example, the cold isostatic pressure can be any value or a range of two of the following: 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, and 300 MPa.

[0069] For example, the holding time can be any value or a range of both of the following: 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min, 20 min.

[0070] The pressure and holding time of the above-mentioned cold isostatic pressing process can produce a green blank with excellent density and uniformity, which can ensure that the pressure applied to the intermediate green blank in all directions is consistent, effectively reduce the porosity of the green blank, enhance the electrical conductivity and wear resistance of the green blank, and thus improve the mechanical strength and structural integrity of the tin oxide-based target material.

[0071] In one specific embodiment, the degreasing treatment includes: heating the green blank from room temperature to 200-800°C at a heating rate of 0.5-2°C / min, and holding it at that temperature for 2-8 hours.

[0072] In some implementations, the degreasing process is carried out in an air atmosphere.

[0073] For example, the heating rate of the degreasing process can be any value or a range of both of 0.5℃ / min, 1℃ / min, 1.5℃ / min, 2℃ / min.

[0074] For example, the degreasing temperature may be any value or a range of two of the following: 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, and 800°C.

[0075] For example, the degreasing treatment holding time can be any value of 2h, 3h, 4h, 5h, 6h, 7h, 8h or a range of both.

[0076] The aforementioned degreasing treatment ensures the thorough removal of binders and other organic matter, reducing potential defects during sintering. The slow heating rate helps prevent thermal stress and crack formation within the tin oxide-based target. Controlling the temperature and holding time of the degreasing treatment further improves the density and purity of the tin oxide-based target, enhancing its mechanical strength and electrical conductivity, thus ensuring high quality and consistency.

[0077] In some implementations, the degreasing process is a gradient degreasing process, which is a process of dividing the entire heating process into multiple temperature ranges (gradients) with specific heating rates and holding times to remove the organic binders in the green body as completely and cleanly as possible.

[0078] In one specific embodiment, the calcination process includes: heating the degreased green blank to 1100-1600°C at a heating rate of 1-5°C / min and holding it at that temperature for 6-30 hours.

[0079] For example, the heating rate of the calcination treatment can be any value of 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, or a range of both.

[0080] For example, the calcination temperature can be any value or a range of both of 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, and 1600°C.

[0081] For example, the holding time for calcination treatment can be any value or a range of two of the following: 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, and 30h.

[0082] The parameters of the aforementioned calcination treatment ensure that the degreased green blank is fully sintered, promoting the formation of crystalline phases. The slow heating rate helps reduce internal thermal stress and crack formation in the tin oxide-based target, improving its structural integrity. The high-temperature holding stage promotes the diffusion and densification between tin oxide, niobium oxide, and antimony oxide particles, enhancing the mechanical strength and electrical conductivity of the tin oxide-based target.

[0083] In some embodiments, the calcination process can be carried out in oxygen, which helps to optimize the oxidation state and chemical stability of the tin oxide-based target.

[0084] In some embodiments, tin oxide-based targets can be prepared by a method including the following steps:

[0085] First, tin oxide, niobium oxide, and antimony oxide are mixed and stirred in deionized water with a dispersant added. This ensures the uniform distribution of each component and improves the uniformity and performance stability of the final tin oxide-based target. Second, sieving and grinding steps are used to further refine the slurry particles, which can optimize the microstructure of the tin oxide-based target and help improve its density and conductivity. Then, a binder is added and thoroughly stirred to obtain a slurry. The uniformity of the green blank is improved by spray drying granulation, molding, and cold isostatic pressing. Finally, degreasing and calcination are performed to suppress the formation of low-valence tin oxide and promote grain densification, achieving a preparation method that synergistically optimizes the density and conductivity of the target.

[0086] In some embodiments, tin oxide, niobium oxide and antimony oxide can be mixed to obtain a mixed powder, and then the mixed powder can be added to deionized water containing a dispersant to obtain a first intermediate slurry with a solid content of 40-60%.

[0087] For example, the solid content of the first intermediate slurry can be any value or a range of two of the following: 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, and 60%.

[0088] When the solid content of the first intermediate slurry meets the above range, it helps to achieve good particle packing and densification of oxide, niobium oxide and antimony oxide in the subsequent molding process, further optimizing the uniformity and stability of the slurry, thereby improving the density and conductivity of the tin oxide-based target material.

[0089] In some embodiments, the first intermediate slurry can be sieved and ground to obtain a second intermediate slurry. The grinding time is 0.5 to 2 hours, the grinding medium is zirconia beads with a diameter of 0.2-0.35 mm, and the particle size distribution D50 of the second intermediate slurry is 0.20 to 0.24 μm.

[0090] For example, the grinding time can be any value of 0.5h, 1h, 1.5h, 2h or a range of both.

[0091] For example, the diameter of the abrasive media zirconia beads can be any value or a range of both of the following: 0.2 mm, 0.21 mm, 0.22 mm, 0.23 mm, 0.24 mm, 0.25 mm, 0.26 mm, 0.27 mm, 0.28 mm, 0.29 mm, 0.3 mm, 0.31 mm, 0.32 mm, 0.33 mm, 0.34 mm, 0.35 mm.

[0092] The grinding time and the diameter of the zirconia beads used in the grinding media can effectively control the particle size distribution of the second intermediate slurry, so that the D50 of the second intermediate slurry reaches 0.20~0.24μm. This helps to improve the uniformity and stability of the slurry, thereby enhancing the density and conductivity of the tin oxide-based target, while reducing defects in the tin oxide-based target and improving the overall quality and performance consistency of the tin oxide-based target.

[0093] In some embodiments, after calcination, cooling can be performed to obtain tin oxide-based targets. The cooling includes: a first stage of cooling to 1000-1280°C at a rate of 2-10°C / min, and a second stage of furnace cooling to obtain tin oxide-based targets.

[0094] For example, the cooling rate in the first stage can be any value or a range of two of the following: 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, 10℃ / min.

[0095] For example, the first stage may cool down to any value or a range of both of the following: 1000°C, 1040°C, 1080°C, 1120°C, 1160°C, 1200°C, 1240°C, and 1280°C.

[0096] The segmented cooling described above helps to obtain high-density niobium-antimony co-doped tin oxide-based targets. By precisely controlling the cooling rate and temperature, the thermal stress and defects inside the tin oxide-based targets can be effectively reduced, thereby improving the structural integrity and conductivity of the tin oxide-based targets.

[0097] Thirdly, the present invention provides a conductive thin film, comprising a tin oxide-based target material of the first aspect or a tin oxide-based target material prepared by the preparation method of the second aspect.

[0098] The conductive thin film provided by this invention exhibits excellent conductivity due to the effective enhancement of carrier concentration and mobility through the co-doping of niobium and antimony in the tin oxide-based target. Secondly, the high light transmittance of the conductive film makes it ideal for application in optoelectronic devices such as solar cells and displays, thanks to the wide bandgap characteristics of the tin oxide-based target. Furthermore, the strictly controlled process parameters during fabrication, such as calcination and cooling conditions, ensure the high density and uniformity of the conductive film, reducing defects and interface scattering, thereby improving the mechanical strength and durability of the conductive film. These advantages make the conductive thin film of this invention promising for broad applications in the fields of electronics and optoelectronics.

[0099] Example 1

[0100] Step 1: Weigh tin oxide, niobium oxide, and antimony oxide powders according to an atomic ratio of 97.5:2:0.5 and mix them to form a total powder mixture. Add an equal mass of water and 0.2 parts by mass of polyacrylic acid (D134C) as a dispersant to the total powder mixture and stir until homogeneous to obtain the first intermediate slurry. Sieve the first intermediate slurry and pour it into a sand mill. Mill at 1800 r / min for 1.5 h. The slurry D50 is tested with a laser particle size analyzer and is ≤0.25 μm to obtain the second intermediate slurry. Add 0.1 parts by mass of polyvinyl alcohol (relative molecular mass 47000) as a binder to the second intermediate slurry and continue stirring for 0.5 h to mix it evenly to obtain the final slurry.

[0101] Step 2: Spray dry the obtained slurry with an inlet air temperature of 205℃, an outlet air temperature of 95℃, and an atomizer speed of 18000rpm. After mixing and sieving, granulated powder is obtained.

[0102] Step 3: Pour the granulated powder into a molding die and press it at 80MPa for 3 minutes to obtain an intermediate preform. Package the intermediate preform and send it into a cold isostatic press at 270MPa for 16 minutes to obtain a preform with higher density.

[0103] Step 4: In air, the blank is first heated to 600℃ at a rate of 0.5℃ / min and held for 6 hours to degrease the interior. Then, it is heated to 1550℃ at a rate of 1℃ / min and oxygen with a flow rate of 100L / min and a purity of 99.5% is introduced and held for 20 hours for calcination. After the calcination, it is cooled to 1100℃ at a rate of 2℃ / min and then cooled with the furnace to room temperature to obtain a high-density niobium-antimony co-doped tin oxide target blank.

[0104] Step 5: Perform wire cutting, grinding and other machining on the tin oxide-based target blank according to the specified dimensions of diameter φ=75mm and thickness 5mm to obtain the final high-density niobium-antimony co-doped tin oxide-based target material.

[0105] Example 2

[0106] Step 1: Weigh tin oxide, niobium oxide, and antimony oxide powders according to an atomic ratio of 97:2:1 and mix them to form a total powder mixture. Add an equal mass of water and 0.2 parts by mass of polyacrylic acid (D134C) as a dispersant to the total powder mixture and stir until homogeneous to obtain the first intermediate slurry. Sieve the first intermediate slurry and pour it into a sand mill. Mill at 1800 r / min for 1.5 h. Test the slurry with a laser particle size analyzer. If the slurry D50 is ≤ 0.25 μm, the second intermediate slurry is obtained. Add 0.1 parts by mass of polyvinyl alcohol as a binder to the second intermediate slurry and continue stirring for 0.5 h to mix it evenly to obtain the final slurry.

[0107] Step 2: Spray dry the obtained slurry 3 with an inlet air temperature of 205℃, an outlet air temperature of 95℃, and an atomizer speed of 18000rpm. After mixing and sieving, granulated powder is obtained.

[0108] Step 3: Weigh an appropriate amount of granulated powder and pour it into a molding die. Press the die at 80MPa for 3 minutes to obtain an intermediate preform. Package the intermediate preform and send it into a cold isostatic press at 270MPa for 16 minutes to obtain a preform with higher density.

[0109] Step 4: In air, the above-mentioned blank is first heated to 600℃ at a rate of 0.5℃ / min and held for 6 hours to degrease the inside of the blank. Then, it is heated to 1550℃ at a rate of 1℃ / min and oxygen with a flow rate of 100L / min and a purity of 99.5% is introduced and held for 20 hours for calcination. After the calcination is completed, it is cooled to 1100℃ at a rate of 2℃ / min and then cooled with the furnace until room temperature to obtain a high-density niobium-antimony co-doped tin oxide target blank.

[0110] Step 5: Perform wire cutting, grinding and other machining on the target blank according to the specified dimensions of diameter φ=75mm and thickness 5mm to obtain the final high-density niobium-antimony co-doped tin oxide-based target material.

[0111] Example 3

[0112] Step 1: Weigh out tin oxide, niobium oxide, and antimony oxide powders in an atomic ratio of 96.5:3:0.5 and mix them to form a general powder mixture. Add an equal mass of water and 0.2 parts by mass of polyacrylic acid (D134C) as a dispersant to the general powder mixture and stir until homogeneous to obtain the first intermediate slurry. Sieve the first intermediate slurry and pour it into a sand mill. Mill at 1800 r / min for 1.5 h. Test the slurry with a laser particle size analyzer. If the slurry D50 is ≤0.25 μm, the second intermediate slurry is obtained. Add 0.1 parts by mass of polyvinyl alcohol as a binder to the second intermediate slurry and continue stirring for 0.5 h to mix it evenly to obtain the final slurry.

[0113] Step 2: Spray dry the obtained slurry with an inlet air temperature of 205℃, an outlet air temperature of 95℃, and an atomizer speed of 18000rpm. After mixing and sieving, granulated powder is obtained.

[0114] Step 3: Weigh an appropriate amount of granulated powder and pour it into a molding die. Press the die at 80MPa for 3 minutes to obtain an intermediate preform. Package the intermediate preform and send it into a cold isostatic press at 270MPa for 16 minutes to obtain a preform with higher density.

[0115] Step 4: In air, the above-mentioned blank is first heated to 600℃ at a rate of 0.5℃ / min and held for 6 hours to degrease the inside of the blank. Then, it is heated to 1550℃ at a rate of 1℃ / min and oxygen with a flow rate of 100L / min and a purity of 99.5% is introduced and held for 20 hours for calcination. After the calcination is completed, it is cooled to 1100℃ at a rate of 2℃ / min and then cooled with the furnace until room temperature to obtain a high-density niobium-antimony co-doped tin oxide target blank.

[0116] Step 5: Perform wire cutting, grinding and other machining on the tin oxide-based target blank according to the specified dimensions of diameter φ=75mm and thickness 5mm to obtain the final high-density niobium-antimony co-doped tin oxide-based target material.

[0117] Example 4

[0118] Step 1: Weigh tin oxide, niobium oxide, and antimony oxide powders according to an atomic ratio of 96:3:1 and mix them to form a total powder mixture. Add an equal mass of water and 0.2 parts by mass of polyacrylic acid (D134C) as a dispersant to the total powder mixture and stir until homogeneous to obtain the first intermediate slurry. Sieve the first intermediate slurry and pour it into a sand mill. Mill at 1800 r / min for 1.5 h. Test the slurry with a laser particle size analyzer. If the slurry D50 is ≤ 0.25 μm, the second intermediate slurry is obtained. Add 0.1 parts by mass of polyvinyl alcohol as a binder to the second intermediate slurry and continue stirring for 0.5 h to mix it evenly to obtain the final slurry.

[0119] Step 2: Spray dry the obtained slurry with an inlet air temperature of 205℃, an outlet air temperature of 95℃, and an atomizer speed of 18000rpm. After mixing and sieving, granulated powder is obtained.

[0120] Step 3: Weigh an appropriate amount of granulated powder and pour it into a molding die. Press the die at 80MPa for 3 minutes to obtain an intermediate preform. Package the intermediate preform and send it into a cold isostatic press at 270MPa for 16 minutes to obtain a preform with higher density.

[0121] Step 4: In air, the blank is first heated to 600℃ at a rate of 0.5℃ / min and held for 6 hours to degrease the interior. Then, it is heated to 1550℃ at a rate of 1℃ / min and oxygen with a flow rate of 100L / min and a purity of 99.5% is introduced and held for 20 hours for calcination. After the calcination, it is cooled to 1100℃ at a rate of 2℃ / min and then cooled with the furnace to room temperature to obtain a high-density niobium-antimony co-doped tin oxide target blank.

[0122] Step 5: Perform wire cutting, grinding and other machining on the tin oxide-based target blank according to the specified dimensions of diameter φ=75mm and thickness 5mm to obtain the final high-density niobium-antimony co-doped tin oxide-based target material.

[0123] Example 5

[0124] Step 1: Weigh tin oxide, niobium oxide, and antimony oxide powders according to an atomic ratio of 95.5:4:0.5 and mix them to form a total powder mixture. Add an equal mass of water and 0.2 parts by mass of polyacrylic acid dispersant to the total powder mixture and stir until homogeneous to obtain the first intermediate slurry. Sieve the first intermediate slurry and pour it into a sand mill. Mill at 1800 r / min for 1.5 h. Test the slurry with a laser particle size analyzer. If the slurry D50 is ≤0.25 μm, the second intermediate slurry is obtained. Add 0.1 parts by mass of polyvinyl alcohol as a binder to the second intermediate slurry and continue stirring for 0.5 h to mix it evenly to obtain the final slurry.

[0125] Step 2: Spray dry the obtained slurry with an inlet air temperature of 205℃, an outlet air temperature of 95℃, and an atomizer speed of 18000rpm. After mixing and sieving, granulated powder is obtained.

[0126] Step 3: Weigh an appropriate amount of granulated powder and pour it into a molding die. Press the die at 80MPa for 3 minutes to obtain an intermediate preform. Package the intermediate preform and send it into a cold isostatic press at 270MPa for 16 minutes to obtain a preform with higher density.

[0127] Step 4: In air, the above-mentioned blank is first heated to 600℃ at a rate of 0.5℃ / min and held for 6 hours to degrease the inside of the blank. Then, it is heated to 1550℃ at a rate of 1℃ / min and oxygen with a flow rate of 100L / min and a purity of 99.5% is introduced and held for 20 hours for calcination. After the calcination is completed, it is cooled to 1100℃ at a rate of 2℃ / min and then cooled with the furnace until room temperature to obtain a high-density niobium-antimony co-doped tin oxide target blank.

[0128] Step 5: Perform wire cutting, grinding and other machining on the tin oxide-based target blank according to the specified dimensions of diameter φ=75mm and thickness 5mm to obtain the final high-density niobium-antimony co-doped tin oxide-based target material.

[0129] Example 6

[0130] Step 1: Weigh out tin oxide, niobium oxide, and antimony oxide powders according to an atomic ratio of 95:4:1, mix them to form a general mixture, and add an equal mass of water and 0.2 parts by mass of polyacrylic acid dispersant to the general mixture. Stir until homogeneous to obtain the first intermediate slurry. Sieve the first intermediate slurry and pour it into a sand mill. Mill at 1800 r / min for 1.5 h. Test the slurry with a laser particle size analyzer. If the slurry D50 is ≤ 0.25 μm, the second intermediate slurry is obtained. Add 0.1 parts by mass of polyvinyl alcohol as a binder to the second intermediate slurry and continue stirring for 0.5 h to mix it evenly to obtain the final slurry.

[0131] Step 2: Spray dry the obtained slurry with an inlet air temperature of 205℃, an outlet air temperature of 95℃, and an atomizer speed of 18000rpm. After mixing and sieving, granulated powder is obtained.

[0132] Step 3: Weigh an appropriate amount of granulated powder and pour it into a molding die. Press the die at 80MPa for 3 minutes to obtain an intermediate preform. Package the intermediate preform and send it into a cold isostatic press at 270MPa for 16 minutes to obtain a preform with higher density.

[0133] Step 4: In air, the above-mentioned blank is first heated to 600℃ at a rate of 0.5℃ / min and held for 6 hours to degrease the inside of the blank. Then, it is heated to 1550℃ at a rate of 1℃ / min and oxygen with a flow rate of 100L / min and a purity of 99.5% is introduced and held for 20 hours for calcination. After the calcination is completed, it is cooled to 1100℃ at a rate of 2℃ / min and then cooled with the furnace until room temperature to obtain a high-density niobium-antimony co-doped tin oxide target blank.

[0134] Step 5: Perform wire cutting, grinding and other machining on the tin oxide-based target blank according to the specified dimensions of diameter φ=75mm and thickness 5mm to obtain the final high-density niobium-antimony co-doped tin oxide-based target material.

[0135] Example 7

[0136] The difference between Example 7 and Example 1 is that in step 1, the atomic ratio of tin oxide, niobium oxide and antimony oxide is 97.5:1.5:1.

[0137] Example 8

[0138] The difference between Example 8 and Example 1 is that in step 1, the atomic ratio of tin oxide, niobium oxide and antimony oxide is 97.5:2.3:0.2.

[0139] Comparative Example 1

[0140] The difference between Comparative Example 1 and Example 1 is that in step 1, only tin oxide is used, and niobium oxide and antimony oxide are not present.

[0141] Comparative Example 2

[0142] The difference between Comparative Example 2 and Example 1 is that in step 1, the atomic ratio of tin oxide to niobium oxide is 98:2, and antimony oxide is not present.

[0143] Comparative Example 3

[0144] The difference between Comparative Example 3 and Example 1 is that in step 1, the atomic ratio of tin oxide to niobium oxide is 97:3, and antimony oxide is not present.

[0145] Comparative Example 4

[0146] The difference between Comparative Example 4 and Example 1 is that in step 1, the atomic ratio of tin oxide to niobium oxide is 96:4, and antimony oxide is not present.

[0147] Comparative Example 5

[0148] The difference between Comparative Example 5 and Example 1 is that in step 1, the atomic ratio of tin oxide to antimony oxide is 99.52:0.48, and niobium oxide is not present.

[0149] Comparative Example 6

[0150] The difference between Comparative Example 6 and Example 1 is that in step 1, the atomic ratio of tin oxide to antimony oxide is 99.03:0.97, and niobium oxide is not present.

[0151] Test case

[0152] 1. The weight (W) of the tin oxide-based target material in air was measured and recorded. air ) and apparent weight (W) when fully submerged in liquid (pure water) liquid The volume is calculated using buoyancy, and then the test density is obtained:

[0153] ρ 实测 =W air / (W) air -W liquid )

[0154] Relative density ρ=ρ 实测 / ρ 理论 *100%.

[0155] 2. Resistivity (Ω·cm) was obtained by measuring with a four-probe tester.

[0156] The relative density and resistivity of the tin oxide-based targets prepared in Examples 1-6 and Comparative Examples 1-6 were measured, and the test results are shown in Table 1:

[0157] Table 1

[0158]

[0159] As can be seen from the data in Table 1, the tin oxide-based target in the embodiments has both superior relative density and lower resistivity, indicating that by including tin oxide, niobium oxide and antimony oxide in the tin oxide-based target, the tin oxide-based target can have both superior relative density and lower resistivity.

[0160] As can be seen from Examples 1-6 and Examples 7-8, by further selecting the atomic ratio of niobium oxide to antimony oxide in the tin oxide-based target, a tin oxide-based target with both excellent relative density and low resistivity can be obtained, especially a tin oxide-based target with a relative density of over 99% and a resistivity of less than or equal to 200 Ω·cm.

[0161] Comparative Example 1 had the lowest relative density at only 93.25%, indicating that the pure tin oxide target without niobium and antimony doping had poor density. With increasing niobium doping, the relative densities of Comparative Examples 2 to 4 gradually increased, demonstrating that niobium doping has a positive effect on improving relative density. Regarding resistivity, in the examples, the resistivity decreased significantly with increasing niobium and antimony doping amounts. Example 6 had the lowest resistivity at only 0.03 × 10² Ω•cm, indicating that co-doping with niobium and antimony significantly improved conductivity. The resistivity of Comparative Example 1 was 6.37 × 10² Ω•cm, indicating that pure tin oxide had poor conductivity. The resistivity of Comparative Example 2 was 3.64 × 10³ Ω•cm, much higher than the other comparative examples and examples, indicating that doping with only a small amount of niobium was not effective in reducing resistivity. The resistivity of Comparative Examples 3 and 4 decreased, but remained higher than the examples, indicating that while increasing the niobium doping ratio helps reduce resistivity, the effect is not as significant as co-doping with niobium and antimony. Comparative Examples 5 and 6 were doped with antimony oxide only. It can be seen that although the doping of antimony oxide reduced the resistivity, the relative density dropped sharply, making it difficult to meet the performance requirements of the target material.

[0162] In summary, compared with single-element doping of niobium or antimony, the co-doping of niobium and antimony in this invention can significantly reduce resistivity while increasing the relative density of the target material under the synergistic effect of the two elements, thus optimizing the conductivity and compactness of the material. In particular, under a specific niobium-antimony ratio, it can improve the overall performance of tin oxide-based targets, enabling tin oxide-based targets to have both high compactness and low resistivity.

[0163] Other embodiments of this application will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of this application that follow the general principles of this application and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of this application are indicated by the following claims.

[0164] It should be understood that this application is not limited to the content already described above, and various modifications and changes can be made without departing from its scope. The scope of this application is limited only by the appended claims.

Claims

1. A tin oxide-based target material, characterized in that, The tin oxide-based target material includes tin oxide, niobium oxide, and antimony oxide.

2. The tin oxide-based target material according to claim 1, characterized in that, In the tin oxide-based target material, the atomic ratio of niobium oxide to antimony oxide is (2-8):

1.

3. The tin oxide-based target material according to claim 1 or 2, characterized in that, In the tin oxide-based target material, the atomic ratio of tin oxide, niobium oxide, and antimony oxide is (95 97.5):(2-4):(0.5 1); and / or, The tin oxide-based target has a relative density of ≥99% and a resistivity of ≤200Ω·cm.

4. A method for preparing a tin oxide-based target material according to any one of claims 1-3, characterized in that, Includes the following steps: A slurry containing tin oxide, niobium oxide, and antimony oxide is spray-dried and granulated to obtain granulated powder. The granulated powder is subjected to compression molding and cold isostatic pressing in sequence to obtain a green body. The tin oxide-based target material is obtained by sequentially degreasing and calcining the raw blank.

5. The preparation method according to claim 4, characterized in that, The slurry also includes binders and / or dispersants.

6. The preparation method according to claim 5, characterized in that, The mass percentage of dispersant in the slurry is 0.1-0.6%.

7. The preparation method according to claim 6, characterized in that, The binder in the slurry has a mass percentage content of 0.05~0.25%.

8. The preparation method according to any one of claims 4-7, characterized in that, The inlet air temperature of the spray drying granulation is 180-260℃, the outlet air temperature is 90-120℃, and the atomization speed is 14000-21000rpm. And / or, the pressure of the compression molding process is 40~100MPa, and the holding time is 1~10min; And / or, the pressure of the cold isostatic pressing treatment is 220-300 MPa, and the holding time is 5-20 min.

9. The preparation method according to any one of claims 4-8, characterized in that, The degreasing treatment includes: heating the raw blank from room temperature to 200-800°C at a heating rate of 0.5-2°C / min, and holding at that temperature for 2-8 hours; and / or, The calcination process includes heating the degreased green body to 1100-1600℃ at a heating rate of 1-5℃ / min and holding it at that temperature for 6-30 hours.

10. A conductive thin film, characterized in that, Includes the tin oxide-based target material according to any one of claims 1-3 or the tin oxide-based target material prepared by the preparation method according to any one of claims 4-9.

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