A tin oxide-based composite target and a method for manufacturing the same

Abstract

The application belongs to the technical field of target materials, and particularly relates to a tin oxide-based composite target material and a preparation method thereof. The tin oxide-based composite target material provided by the application comprises tin oxide, doped oxide and sintering aid, the doped oxide is antimony pentoxide, vanadium pentoxide, nickel oxide and tungsten trioxide, and the sintering aid is magnesium oxide and yttrium oxide. The application uses antimony pentoxide, vanadium pentoxide, nickel oxide and tungsten trioxide as the doped oxide, effectively improves the electrical and optical properties of the target material; uses magnesium oxide and yttrium oxide as the sintering aid, refines the grains, and improves the density and mechanical properties of the target material; uses the sol-gel method to realize atomic-level mixing of part of elements, then uses the high-energy ball milling method to realize atomic-level doping, reduces the distribution deviation of the elements in the matrix, uses the discharge plasma furnace to realize sintering, and reduces the volatilization loss of the elements and the pore defects in the target material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of target materials, and particularly relates to a tin oxide-based composite target material and a preparation method thereof. BACKGROUND

[0002] With the progress of science and technology, the photovoltaic industry and the electronic information industry, as the medium of information transmission, play a decisive role in the development of science and technology, and the demand for transparent conductive films with high electrical conductivity and high visible light transmittance is also increasing day by day. Transparency and conductivity are two key factors for evaluating the performance of transparent conductive oxide films, so it is of great significance to develop low-cost, high-visible light transmittance and low-resistivity environmentally friendly transparent conductive films to promote the development of China's optoelectronic information industry.

[0003] At present, the transparent conductive film is mainly an indium tin oxide film, but the indium element is scarce and toxic, resulting in high cost of the transparent conductive film and environmental pollution, which limits its development and application. Therefore, it is urgent to develop a new type of non-toxic and environmentally friendly and low-cost material transparent conductive film. Tin oxide is a wide band gap semiconductor material, which has high light transmittance, good chemical stability and high temperature resistance, and has strong adhesion to inorganic materials. Tin oxide is low in cost, non-toxic and harmless, so it has broad prospects in the field of conductive films. The tin oxide film material has high light transmittance and low resistivity and high carrier concentration in the visible light range, but the conductivity of the tin oxide film material cannot be compared with that of the indium tin oxide film material, and it needs to be doped with other elements or compounded with other oxides to meet the demand for high-performance materials in the field of film preparation. The existing tin oxide-based composite target material still has the following problems: the chemical property difference and lattice matching degree of the doped element and tin oxide lead to compatibility problems, reducing the conductivity of the target material; the agglomeration of nano-powder and uneven mixing of powder during preparation lead to pores or density differences in the target material after forming, affecting the performance of the target material; the sintering temperature difference between the doped element and tin oxide is large, and the addition of sintering aids will reduce the purity of the target material, and the shrinkage rate difference is large during the sintering process of the target material.

[0004] The Chinese patent application file with the publication number CN118930250A discloses a preparation method of a tin antimony oxide ceramic target material, specifically: S1, mixing raw materials: uniformly mixing tin oxide powder, antimony oxide powder and additives to form a slurry; S2, ball milling process; S3, sand milling process; S4, spray granulation; S5, mold forming: through precisely controlled mold forming pressure and isostatic pressing time, a high-density and defect-free original target blank is obtained, and then through cold isostatic pressing with higher pressure, the uniformity and density of the blank are further improved. S6, debinding and sintering: through pre-debinding and final sintering, complete solidification forming and densification of the target blank are realized, and sintering in an oxygen atmosphere helps to improve the quality and performance of the product. However, the density difference between tin oxide and antimony oxide is large, and even after ball milling and sand milling, the components will still be stratified due to gravity settlement when mixed by wet method, causing the content of antimony element in the target blank to fluctuate by more than 1%, which will cause "conductive islands" in the subsequent sputtered film, affecting the performance of the film. In addition, antimony oxide will volatilize during sintering, forming vacancy defects in the target material, causing the conductivity of the target material to decrease. SUMMARY

[0005] In order to solve the technical problems of poor target material performance, doping element segregation and target material defects in the prior art, the present application provides a tin oxide-based composite target material and a preparation method thereof.

[0006] In order to achieve the above-mentioned purpose, the technical scheme of the present application is as follows:

[0007] A tin oxide-based composite target material, comprising tin oxide, doped oxide and sintering aid; the doped oxide comprises antimony pentoxide, vanadium pentoxide, nickel oxide and tungsten trioxide; the sintering aid comprises magnesium oxide and yttrium oxide.

[0008] Through the above technical scheme, the present application improves the electrical and optical performance of the target material through the synergistic effect of the multi-component doped oxide. Among them, antimony pentoxide, as the core doping element of the tin oxide-based target material, provides Sb 5+ which can efficiently replace Sn 4+ , effectively improving the conductivity of the target material; V 5+ provided by vanadium pentoxide can fill the local vacancies of Sb 5+ in the SnO2 lattice, reduce "conductive islands" and improve the uniformity of conductivity. At the same time, the V-O bond energy of vanadium pentoxide is high, which can enhance the high temperature resistance of the target material and avoid the attenuation of the conductivity caused by the volatilization of doping ions during high temperature sputtering; Ni 2+ provided by nickel oxide can replace Sn 4+ to form P-type doping (SnO2 is n-type), construct n-SnO2 / p-NiO heterojunction and enhance the absorption efficiency of ultraviolet light; W6+ Can be incorporated into SnO2 lattice to form impurity levels, improve the absorption rate of near-infrared light.

[0009] Mg provided by magnesium oxide 2+ Can be uniformly dispersed in the lattice gap of SnO2, buffer the difference of sintering shrinkage, reduce the lattice diffusion activation energy, reduce the sintering temperature, and significantly reduce Sb 5+ , V 5+ Evaporation of plasma; Y provided by yttrium oxide 3+ Form nanoscale precipitates at the grain boundary of SnO2, inhibit the excessive growth of grains, play a role in refining grains, reduce the problem that pores between grains cannot be filled during sintering, and improve the density and mechanical properties of the target material. As a sintering aid, magnesium oxide and yttrium oxide can solve the technical problems of ion evaporation and target defects of tin oxide-based target material through the systematic effects of low-temperature densification + grain refinement + stress relief.

[0010] Further, the molar ratio of the sum of tin elements in the tin oxide and the metal elements in the doped oxide is 1:(0.25-0.33); the molar ratio of antimony in the antimony pentoxide, vanadium in the vanadium pentoxide, nickel in the nickel oxide and tungsten in the tungsten trioxide is (9-11):(2-5):(4-7):(1-3).

[0011] Through the above technical scheme, the performance of the tin oxide-based target material is adjusted by adjusting the amount of the doped oxide and the molar ratio of the doped oxide. If the amount of antimony pentoxide and vanadium pentoxide is too low, the conductivity of the target material cannot meet the application standard, the doped elements are enriched in the local target material, resulting in a large difference in conductivity in different regions of the target material, and a large resistivity fluctuation during sputtering. If the amount of antimony pentoxide and vanadium pentoxide is too high, the excess doped elements cannot be incorporated into the lattice, resulting in the precipitation of a second phase or the destruction of the lattice structure, causing phase separation and lattice distortion, which affects the performance of the target material. If the amount of nickel oxide and tungsten trioxide is too low, the absorption rate of the target material to ultraviolet light and infrared light decreases, and if the amount is too high, it increases the lattice mismatch rate of SnO2, increases the risk of target cracking, and at the same time, the excess nickel oxide forms an insulating layer at the grain boundary, reducing the conductivity of the target material.

[0012] Further, the molar ratio of the tin oxide to the sintering aid is 1:(0.03-0.06); the molar ratio of the magnesium oxide and the yttrium oxide is (22-25):(13-16).

[0013] Through the above technical solution, this invention regulates the microstructure of tin oxide-based targets during sintering by adjusting the molar ratio of tin oxide to sintering aids and the molar ratio of magnesium oxide to yttrium oxide. Studies have found that if the amount of magnesium oxide and yttrium oxide is too low, the sintering temperature of the target is too high, which cannot reduce the loss of volatile elements such as antimony and vanadium. If the amount is too high, the excess magnesium oxide will form an insulating phase at the grain boundaries, and the excess yttrium oxide precipitates will accumulate, forming micro-defects and reducing the uniformity of the target.

[0014] The present invention also provides a method for preparing the tin oxide-based composite target, comprising the following steps:

[0015] S1: Tetrabutyltin and vanadium acetylacetonate were added to an ethanol-water solution and stirred until homogeneous. Nickel nitrate was added, and the pH of the system was adjusted to 3.0-4.0. Citric acid and ethylene glycol were added, and the temperature was raised to 45-50℃. The mixture was stirred for 1.5-2 hours, dried at 50-60℃ for 40-48 hours, and then dried at 80-90℃ for 12-15 hours. The mixture was calcined, cooled, ground, and antimony pentoxide and tungsten trioxide were added to obtain mixed powder I.

[0016] S2: Mix the mixed powder I obtained in step S1 with the sintering aid, add triethanolamine aqueous solution and ball mill for 24-30 hours, then spray dry the ball mill slurry to obtain powder II;

[0017] S3: Calcine the powder II obtained in step S2 at 600-700℃ for 2 hours, cool it, spray it with polyethylene glycol for granulation, dry it, and then put it into a mold for isostatic pressing to obtain a green body.

[0018] S4: The green blank obtained in step S3 is placed in a spark plasma sintering furnace for sintering to obtain tin oxide-based composite target material.

[0019] Through the above technical solution, firstly, tetrabutyltin and vanadium acetylacetonate form a stable sol in an ethanol aqueous solution. Nickel nitrate achieves uniform dispersion through coordination with citric acid. The atomic-level dispersion of Sn, V, and Ni is achieved through the sol-gel method. Ethylene glycol, as a crosslinking agent, undergoes an esterification reaction with the carboxyl groups of citric acid, forming a stable three-dimensional network structure during the gelation process. This fixes the metal ions and ensures their uniform distribution, effectively avoiding the segregation of V and Ni in the tin oxide-based composite target. Secondly, after mixing with antimony pentoxide, tungsten trioxide, magnesium oxide, and yttrium oxide, high-energy ball milling is performed in a triethanolamine aqueous solution. This process uses mechanical force to break the tin oxide doped with vanadium pentoxide and nickel oxide, along with antimony pentoxide, tungsten trioxide, magnesium oxide, and yttrium oxide, to the nanoscale and form atomic-level doping. This effectively solves the problem of the difficulty in synchronously dispersing the dopant source during multi-element doping and reduces the distribution deviation of elements in the matrix. Secondly, spray drying of the ball-milled slurry effectively avoids component segregation during traditional drying-crushing processes. Pre-calcining the ball-milled powder (II) at 600-700℃ effectively removes residual organic components, significantly improving powder purity and preventing the formation of porosity defects during final sintering. Finally, sintering the isostatically pressed green body in a spark plasma furnace under a nitrogen atmosphere allows for rapid heating, significantly shortening the high-temperature dwell time and preventing element volatilization loss during sintering. Furthermore, high-pressure sintering significantly improves the density of the green body and reduces porosity defects within the target material.

[0020] Furthermore, in step S1, the mass percentage of the ethanol-water solution is 80%-90%; the molar ratio of citric acid to tetrabutyltin is (2.5-3):1; and the molar ratio of ethylene glycol to citric acid is 1:1.

[0021] Furthermore, the specific calcination process described in step S1 is as follows: Under an oxygen atmosphere, firstly, the temperature is increased to 300-350℃ at a heating rate of 1-2℃ / min and held for 2-3 hours; then, the temperature is increased to 500-600℃ at a heating rate of 2-3℃ / min and held for 2-2.5 hours; finally, the temperature is increased to 800-900℃ at a heating rate of 3-5℃ / min and held for 3-4 hours.

[0022] Through the above technical solutions, segmented calcination can effectively remove organic matter from powders, and a lower heating rate can avoid powder agglomeration caused by gases generated from the rapid decomposition of organic matter; sintering in an oxygen atmosphere can effectively suppress Sn. 4+ Restore to Sn 2+ It also promotes the formation of solid solutions of antimony pentoxide, vanadium pentoxide, tungsten trioxide and tin oxide, thereby reducing the lattice mismatch rate.

[0023] Furthermore, the mass percentage of the triethanolamine aqueous solution in step S2 is 0.3%-0.6%.

[0024] Furthermore, the ball milling in step S2 uses zirconia grinding balls with diameters of 1mm, 3mm, 5mm and 10mm, with a material-to-ball weight ratio of 1:3-6; the weight percentage of 1mm balls is 6%-10%, 3mm balls are 30%-50%, 5mm balls are 30%-40%, and 10mm balls are 10%-20%.

[0025] Furthermore, the isostatic pressing pressure in step S3 is 300-400 MPa, and the holding time is 10-15 min.

[0026] Furthermore, the specific sintering process described in step S4 is as follows: Under a nitrogen atmosphere, firstly, the temperature is increased to 500-600℃ at a heating rate of 100℃ / min, and the pressure is increased to 10-15MPa. The temperature is then held for sintering for 10-15min. Next, the temperature is increased to 900-1000℃ at a heating rate of 50℃ / min, and the pressure is increased to 30-40MPa. The temperature is then held for sintering for 20-30min. Finally, the temperature is increased to 1100-1200℃ at a heating rate of 50℃ / min, and the pressure is increased to 50MPa. The temperature is then held for sintering for 10-15min, and the furnace is cooled.

[0027] Through the above technical solutions, sintering at 500-600℃ can complete the decomposition and preliminary densification of organic matter in a short time, effectively removing residual polyethylene glycol in the green blank and avoiding porosity defects caused by high-temperature calcination. Sintering at 900-1000℃ can achieve the densification process of the green blank. Sintering under high pressure can effectively reduce oxide segregation and avoid abnormal grain growth. Sintering at 1100-1200℃ can achieve complete densification of the material. Through the step-by-step heating and pressurization process, the density of the tin oxide-based composite target is effectively guaranteed. In addition, the sintering process is carried out in a nitrogen atmosphere, which can effectively reduce the volatilization loss of volatile elements in the target material at high temperatures, ensure the consistency of target material performance, and avoid lattice defects.

[0028] Compared with the prior art, the tin oxide-based composite target and its preparation method provided by the present invention have the following technical advantages:

[0029] (1) The present invention uses antimony pentoxide, vanadium pentoxide, nickel oxide and tungsten trioxide as doped oxides of tin oxide-based composite target material, which effectively improves the electrical and optical properties of the target material;

[0030] (2) The present invention uses magnesium oxide and yttrium oxide as sintering aids, which can not only reduce the sintering temperature of tin oxide-based composite targets, but also refine the grains and improve the density and mechanical properties of the targets.

[0031] (3) The present invention uses the sol-gel method to achieve atomic-level mixing of some elements, and then uses the high-energy ball milling method to perform atomic-level doping to reduce the distribution deviation of elements in the matrix. The spark plasma furnace is used for sintering to reduce the volatilization loss of elements and the porosity defects inside the target material. Attached Figure Description

[0032] Figure 1 Here is a scanning electron microscope image of the composite target material prepared in Example 3;

[0033] Figure 2 This is a scanning electron microscope image of the composite target material prepared in Comparative Example 6. Detailed Implementation

[0034] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments. Those skilled in the art can make various modifications based on the fundamental principles of the present invention, but all modifications that do not depart from the fundamental principles of the present invention are within its scope.

[0035] Example 1

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

[0037] S1: Add 1 mol of tetrabutyltin and vanadium acetylacetonate to 150 mL of 80% ethanol aqueous solution, stir at 30℃ for 30 min, add nickel nitrate, stir for 30 min, adjust the pH of the system to 3.0, add 2.5 mol of citric acid and 2.5 mol of ethylene glycol, heat to 45℃, stir and react for 1.5 h, dry at 50℃ for 40 h, then dry at 80℃ for 12 h, calcine, cool, grind, add antimony pentoxide and tungsten trioxide to obtain mixed powder I;

[0038] The sum of the amounts of Sb in antimony pentoxide, V in vanadium acetylacetonate, Ni in nickel nitrate, and W in tungsten trioxide is 0.25 mol (molar ratio, Sb:V:Ni:W=9:2:4:1).

[0039] The specific calcination process is as follows: Under an oxygen atmosphere, the temperature is first raised to 300℃ at a heating rate of 1℃ / min and held for 2 hours; then the temperature is raised to 500℃ at a heating rate of 2℃ / min and held for 2 hours; finally, the temperature is raised to 800℃ at a heating rate of 3℃ / min and held for 3 hours.

[0040] S2: Mix the mixed powder I obtained in step S1 with 0.03 mol of sintering aid, add 200 mL of 0.3% triethanolamine aqueous solution and ball mill for 24 h. Spray dry the ball mill slurry to obtain powder II.

[0041] The sintering aid is composed of magnesium oxide and yttrium oxide in a molar ratio of 22:13;

[0042] The ball milling was performed using zirconia grinding balls with diameters of 1mm, 3mm, 5mm, and 10mm, with a ball-to-material weight ratio of 1:3. The weight percentage of the 1mm balls was 6%, the 3mm balls were 50%, the 5mm balls were 34%, and the 10mm balls were 10%.

[0043] S3: Calcine the powder II obtained in step S2 at 600℃ for 2 hours (heating rate is 10℃ / min), cool it, spray in polyethylene glycol for granulation (the amount of polyethylene glycol sprayed is 1.2% of the mass of powder II), dry it, and then put it into a mold for isostatic pressing. The isostatic pressing pressure is 300MPa and the holding time is 10min to obtain the green blank.

[0044] S4: The green blank obtained in step S3 is placed in a spark plasma sintering furnace for sintering to obtain tin oxide-based composite target material.

[0045] The specific sintering process is as follows: Under a nitrogen atmosphere, the temperature is first raised to 500℃ at a heating rate of 100℃ / min, pressurized to 10MPa, and sintered at that temperature for 10min. Then, the temperature is raised to 900℃ at a heating rate of 50℃ / min, pressurized to 30MPa, and sintered at that temperature for 20min. Finally, the temperature is raised to 1100℃ at a heating rate of 50℃ / min, pressurized to 50MPa, and sintered at that temperature for 10min, followed by furnace cooling.

[0046] Example 2

[0047] A method for preparing a tin oxide-based composite target includes the following steps:

[0048] S1: Add 1 mol of tetrabutyltin and vanadium acetylacetonate to 150 mL of 90% ethanol aqueous solution, stir at 30°C for 30 min, add nickel nitrate, stir for 30 min, adjust the pH of the system to 4.0, add 3 mol of citric acid and 3 mol of ethylene glycol, heat to 50°C, stir for 2 h, dry at 60°C for 48 h, then dry at 90°C for 15 h, calcine, cool, grind, add antimony pentoxide and tungsten trioxide to obtain mixed powder I;

[0049] The sum of the amounts of Sb in antimony pentoxide, V in vanadium acetylacetonate, Ni in nickel nitrate, and W in tungsten trioxide is 0.33 mol (molar ratio, Sb:V:Ni:W=11:5:7:3).

[0050] The specific calcination process is as follows: Under an oxygen atmosphere, the temperature is first raised to 350℃ at a heating rate of 2℃ / min and held for 3 hours; then the temperature is raised to 600℃ at a heating rate of 3℃ / min and held for 2.5 hours; finally, the temperature is raised to 900℃ at a heating rate of 5℃ / min and held for 4 hours.

[0051] S2: Mix the mixed powder I obtained in step S1 with 0.06 mol of sintering aid, add 200 mL of 0.6% triethanolamine aqueous solution and ball mill for 30 h. Spray dry the ball mill slurry to obtain powder II.

[0052] The sintering aid is composed of magnesium oxide and yttrium oxide in a molar ratio of 25:16;

[0053] The ball milling was carried out using zirconia grinding balls with diameters of 1mm, 3mm, 5mm, and 10mm, with a material-to-ball weight ratio of 1:6. The weight percentage of the 1mm balls was 10%, the 3mm balls 45%, the 5mm balls 30%, and the 10mm balls 15%.

[0054] S3: Calcine the powder II obtained in step S2 at 700℃ for 2 hours (heating rate is 15℃ / min), cool it, spray in polyethylene glycol for granulation (the amount of polyethylene glycol sprayed is 1.2% of the mass of powder II), dry it, and then put it into a mold for isostatic pressing. The isostatic pressing pressure is 400MPa and the holding time is 15min to obtain the green blank.

[0055] S4: The green blank obtained in step S3 is placed in a spark plasma sintering furnace for sintering to obtain tin oxide-based composite target material.

[0056] The specific sintering process is as follows: Under a nitrogen atmosphere, the temperature is first raised to 600℃ at a heating rate of 100℃ / min, pressurized to 15MPa, and sintered at that temperature for 15min. Then, the temperature is raised to 1000℃ at a heating rate of 50℃ / min, pressurized to 40MPa, and sintered at that temperature for 30min. Finally, the temperature is raised to 1200℃ at a heating rate of 50℃ / min, pressurized to 50MPa, and sintered at that temperature for 15min, followed by furnace cooling.

[0057] Example 3

[0058] A method for preparing a tin oxide-based composite target includes the following steps:

[0059] S1: Add 1 mol of tetrabutyltin and vanadium acetylacetonate to 150 mL of 84% ethanol aqueous solution, stir at 30°C for 30 min, add nickel nitrate, stir for 30 min, adjust the pH of the system to 3.7, add 2.85 mol of citric acid and 2.85 mol of ethylene glycol, heat to 48°C, stir and react for 1.8 h, dry at 55°C for 45 h, then dry at 85°C for 14 h, calcine, cool, grind, add antimony pentoxide and tungsten trioxide to obtain mixed powder I;

[0060] The sum of the amounts of Sb in antimony pentoxide, V in vanadium acetylacetonate, Ni in nickel nitrate, and W in tungsten trioxide is 0.29 mol (molar ratio, Sb:V:Ni:W=10:4:5:2).

[0061] The specific calcination process is as follows: Under an oxygen atmosphere, the temperature is first raised to 340℃ at a heating rate of 1.5℃ / min and held for 2.2h; then the temperature is raised to 580℃ at a heating rate of 2.6℃ / min and held for 2.3h; finally, the temperature is raised to 880℃ at a heating rate of 4℃ / min and held for 3.2h.

[0062] S2: Mix the mixed powder I obtained in step S1 with 0.05 mol of sintering aid, add 200 mL of 0.5% triethanolamine aqueous solution and ball mill for 28 h. Spray dry the ball mill slurry to obtain powder II.

[0063] The sintering aid is composed of magnesium oxide and yttrium oxide in a molar ratio of 23:15;

[0064] The ball milling was carried out using zirconia grinding balls with diameters of 1mm, 3mm, 5mm, and 10mm, with a material-to-ball weight ratio of 1:5. The weight percentage of the 1mm balls was 8%, the 3mm balls were 40%, the 5mm balls were 32%, and the 10mm balls were 20%.

[0065] S3: Calcine the powder II obtained in step S2 at 680℃ for 2 hours (heating rate is 13℃ / min), cool it, spray in polyethylene glycol for granulation (the amount of polyethylene glycol sprayed is 1.2% of the mass of powder II), dry it, and then put it into a mold for isostatic pressing. The isostatic pressing pressure is 360MPa and the holding time is 14min to obtain the green blank.

[0066] S4: The green blank obtained in step S3 is placed in a spark plasma sintering furnace for sintering to obtain tin oxide-based composite target material.

[0067] The specific sintering process is as follows: Under a nitrogen atmosphere, the temperature is first raised to 580℃ at a heating rate of 100℃ / min, pressurized to 13MPa, and held for sintering for 12min. Then, the temperature is raised to 970℃ at a heating rate of 50℃ / min, pressurized to 36MPa, and held for sintering for 24min. Finally, the temperature is raised to 1150℃ at a heating rate of 50℃ / min, pressurized to 50MPa, and held for sintering for 13min, followed by furnace cooling.

[0068] Comparative Example 1

[0069] The preparation method of the composite target in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that an equal amount of antimony trioxide is used instead of antimony pentoxide in this comparative example.

[0070] Comparative Example 2

[0071] The preparation method of the composite target in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that an equal amount of antimony pentoxide is used instead of tungsten trioxide in this comparative example.

[0072] Comparative Example 3

[0073] The preparation method of the composite target in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that the molar ratio of tin to the sum of the amounts of metal elements in the doped oxide in this comparative example is 1:1.

[0074] Comparative Example 4

[0075] The preparation method of the composite target in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that the molar ratio of tin oxide to sintering aid in this comparative example is 1:0.5.

[0076] Comparative Example 5

[0077] The preparation method of the composite target in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that the sintering aid in this comparative example is magnesium oxide.

[0078] Comparative Example 6

[0079] The preparation method of the composite target in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that in this comparative example, tin oxide, antimony pentoxide, vanadium pentoxide, nickel oxide, tungsten trioxide, magnesium oxide and yttrium oxide are directly mixed and ball-milled, and then the ball-milled slurry is spray-dried to obtain powder II.

[0080] Test case

[0081] Performance testing methods: Relative density: The relative density of the targets prepared in Examples 1-3 and Comparative Examples 1-6 was tested using the Archimedes displacement method; Resistivity: The resistivity of the targets prepared in Examples 1-3 and Comparative Examples 1-6 was tested using a four-probe resistivity meter; Absorbency: The absorbance was tested using an ultraviolet spectrophotometer with a wavelength range of 300-1500 nm. The absorbance data were recorded as the ultraviolet light absorbance at a wavelength of 350 nm and the near-infrared light absorbance at a wavelength of 1250 nm.

[0082] The experimental results are shown in Table 1.

[0083] Table 1 Performance Test Results

[0084]

[0085] As shown in Table 1, the tin oxide-based composite target provided by the present invention has a relative density of 99.75%-99.92%, a resistivity of 0.14-0.17 mΩ·cm, an absorption rate of 82.2%-84.1% for ultraviolet light, and an absorption rate of 21.3%-23.6% for near-infrared light.

[0086] Furthermore, the composite targets prepared in Example 3 and Comparative Example 6 were subjected to scanning electron microscopy tests, and the test results are shown in [Figure number missing]. Figure 1 and Figure 2 ,Depend on Figure 1 It can be seen that the target material prepared in Example 3 has no obvious pores and elemental segregation, and has a high density. Figure 2 It can be seen that there is obvious phase separation in the target material prepared in Comparative Example 6, and the dopant elements have segregated.

[0087] The above embodiments are merely illustrative of the present invention and are not intended to limit the invention. Those skilled in the art should not modify the above embodiments without departing from the spirit and scope of the present invention. All equivalent modifications or alterations made by those skilled in the art without departing from the technical concept of the present invention are still within the protection scope of the present invention.

Claims

1. A tin oxide-based composite target, characterized in that, The mixture comprises tin oxide, doped oxides, and sintering aids; the doped oxides include antimony pentoxide, vanadium pentoxide, nickel oxide, and tungsten trioxide; the sintering aids include magnesium oxide and yttrium oxide; the molar ratio of tin in the tin oxide to the sum of the amounts of metal elements in the doped oxide is 1:(0.25-0.33); the molar ratio of tin oxide to sintering aids is 1:(0.03-0.06). The preparation method of tin oxide-based composite target material includes the following steps: S1: Tetrabutyltin and vanadium acetylacetonate were added to an ethanol-water solution and stirred until homogeneous. Nickel nitrate was added, and the pH of the system was adjusted to 3.0-4.

0. Citric acid and ethylene glycol were added, and the temperature was raised to 45-50℃. The mixture was stirred for 1.5-2 hours, dried at 50-60℃ for 40-48 hours, and then dried at 80-90℃ for 12-15 hours. The mixture was calcined, cooled, ground, and antimony pentoxide and tungsten trioxide were added to obtain mixed powder I. S2: Mix the mixed powder I obtained in step S1 with the sintering aid, add triethanolamine aqueous solution and ball mill for 24-30 hours, then spray dry the ball mill slurry to obtain powder II; S3: Calcine the powder II obtained in step S2 at 600-700℃ for 2 hours, cool it, spray it with polyethylene glycol for granulation, dry it, and then put it into a mold for isostatic pressing to obtain a green body. S4: The green blank obtained in step S3 is placed in a spark plasma sintering furnace for sintering to obtain tin oxide-based composite target material.

2. The tin oxide-based composite target according to claim 1, characterized in that, The molar ratio of antimony in antimony pentoxide, vanadium in vanadium pentoxide, nickel in nickel oxide and tungsten in tungsten trioxide is (9-11):(2-5):(4-7):(1-3).

3. The tin oxide-based composite target according to claim 1, characterized in that, The molar ratio of magnesium oxide to yttrium oxide is (22-25):(13-16).

4. The method for preparing the tin oxide-based composite target according to any one of claims 1-3, characterized in that, Includes the following steps: S1: Tetrabutyltin and vanadium acetylacetonate were added to an ethanol-water solution and stirred until homogeneous. Nickel nitrate was added, and the pH of the system was adjusted to 3.0-4.

0. Citric acid and ethylene glycol were added, and the temperature was raised to 45-50℃. The mixture was stirred for 1.5-2 hours, dried at 50-60℃ for 40-48 hours, and then dried at 80-90℃ for 12-15 hours. The mixture was calcined, cooled, ground, and antimony pentoxide and tungsten trioxide were added to obtain mixed powder I. S2: Mix the mixed powder I obtained in step S1 with the sintering aid, add triethanolamine aqueous solution and ball mill for 24-30 hours, then spray dry the ball mill slurry to obtain powder II; S3: Calcine the powder II obtained in step S2 at 600-700℃ for 2 hours, cool it, spray it with polyethylene glycol for granulation, dry it, and then put it into a mold for isostatic pressing to obtain a green body. S4: The green blank obtained in step S3 is placed in a spark plasma sintering furnace for sintering to obtain tin oxide-based composite target material.

5. The method for preparing the tin oxide-based composite target according to claim 4, characterized in that, The mass percentage of the ethanol-water solution in step S1 is 80%-90%; the molar ratio of citric acid to tetrabutyltin is (2.5-3):1; and the molar ratio of ethylene glycol to citric acid is 1:

1.

6. The method for preparing the tin oxide-based composite target according to claim 4, characterized in that, The specific calcination process described in step S1 is as follows: Under an oxygen atmosphere, first, the temperature is increased to 300-350℃ at a heating rate of 1-2℃ / min and held for 2-3 hours; then, the temperature is increased to 500-600℃ at a heating rate of 2-3℃ / min and held for 2-2.5 hours; finally, the temperature is increased to 800-900℃ at a heating rate of 3-5℃ / min and held for 3-4 hours.

7. The method for preparing the tin oxide-based composite target according to claim 4, characterized in that, The mass percentage of the triethanolamine aqueous solution in step S2 is 0.3%-0.6%.

8. The method for preparing the tin oxide-based composite target according to claim 4, characterized in that, The ball milling in step S2 uses zirconia grinding balls with diameters of 1mm, 3mm, 5mm and 10mm, with a material-to-ball weight ratio of 1:3-6; the weight percentage of 1mm balls is 6%-10%, 3mm balls is 30%-50%, 5mm balls is 30%-40%, and 10mm balls is 10%-20%.

9. The method for preparing the tin oxide-based composite target according to claim 4, characterized in that, The isostatic pressing pressure in step S3 is 300-400 MPa, and the holding time is 10-15 min.

10. The method for preparing the tin oxide-based composite target according to claim 4, characterized in that, The specific sintering process described in step S4 is as follows: Under a nitrogen atmosphere, the temperature is first increased to 500-600℃ at a heating rate of 100℃ / min, and the pressure is increased to 10-15MPa. The temperature is then held for sintering for 10-15min. Next, the temperature is increased to 900-1000℃ at a heating rate of 50℃ / min, and the pressure is increased to 30-40MPa. The temperature is then held for sintering for 20-30min. Finally, the temperature is increased to 1100-1200℃ at a heating rate of 50℃ / min, and the pressure is increased to 50MPa. The temperature is then held for sintering for 10-15min, and the furnace is cooled.

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