A multi-doped high-mobility ceramic target material, a preparation method and application thereof

Abstract

The application provides a multi-doped high-mobility ceramic target material and a preparation method and application thereof, and belongs to the technical field of ceramic materials. The application effectively provides extra electrons by introducing titanium oxide and gallium oxide as doped components, realizes the regulation of carrier concentration, and further improves the optical performance of the material. The doping of zirconium oxide can inhibit the excessive growth of crystal grains, refine the microstructure, and thus reduce the carrier scattering caused by the crystal boundary and defects. In addition, the introduction of cerium oxide effectively compensates for the lattice distortion caused by other doped elements, relieves internal stress, balances the lattice structure, and thus enhances the overall structural stability of the material. The synergistic effect of the multi-doped system introduced in the raw material can make the prepared ceramic target material have excellent characteristics such as high density, low resistivity and uniform composition distribution.

Description

Technical Field

[0001] This invention relates to the field of ceramic materials technology, and in particular to a multi-doped high-mobility ceramic target, its preparation method, and its application. Background Technology

[0002] Transparent conductive oxide thin films, possessing high visible light transmittance, excellent electrical conductivity, high infrared reflectivity, and strong ultraviolet absorption, have become indispensable key materials in solar cells and flat panel displays. An ideal transparent conductive oxide thin film material needs to maintain high conductivity (i.e., low resistivity) while achieving high transmittance (greater than 80%) in both the visible and infrared bands. Its overall performance depends primarily on the optimized design of material composition, crystal structure, and doping strategy. Among these materials, ITO (indium tin oxide) thin films, as a typical representative, not only exhibit excellent conductivity and high transmittance in the visible light region but also possess good corrosion resistance, environmental stability, mature large-area film deposition technology, and low cost, thus being widely used as a key basic material for solar cells and flat panel displays. However, with the continuous development of next-generation solar cell and display technologies, traditional ITO materials, limited by their low carrier mobility and insufficient infrared transmittance, are gradually becoming a bottleneck restricting further improvements in device performance.

[0003] Currently, some research has been conducted to improve the aforementioned properties. For example, related patents have proposed improving the mobility and optical properties of the target material through Ce unit doping. However, this method is difficult to achieve high density of the target material, and cannot guarantee the uniformity of the film composition and structure. Other related patents disclose the incorporation of components such as ytterbium oxide and scandium oxide into an indium oxide matrix to optimize the mobility and resistivity of the film. However, the effect of the doping element is relatively singular, which may limit further improvement in optical performance over a wider spectral range (especially the infrared band). Therefore, the improvement effect of single-element doping is relatively poor. To address the problems of single-element doping, research on composite doping has been conducted. For example, related patents prepare transparent conductive oxide films with high mobility by combining one or two metal oxides of nano-sized Ag, Cu, and Al with one or two metal oxides of wide bandgap elements Ti, Ga, and Zn, as well as one or two oxides of high-valence elements Zr, W, and Mo, with high-purity indium oxide in different proportions. However, the introduction of nano-sized metal oxides may form unnecessary light absorption centers or scattering sites in the film, impairing the transmittance in the visible light region, resulting in the inability to simultaneously achieve high light transmittance, high conductivity, and high mobility.

[0004] Therefore, how to obtain a ceramic target material that can prepare transparent conductive oxide thin films with high light transmittance, high conductivity and high mobility is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] The purpose of this invention is to provide a multi-doped high-mobility ceramic target, its preparation method, and its application. The multi-doped high-mobility ceramic target provided by this invention can be used to prepare transparent conductive oxide thin films that combine high light transmittance, high conductivity, and high mobility.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a multi-element doped high-mobility ceramic target, the raw materials of which include metal oxides, namely indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide; the mass ratio of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide is (97.2~99.5):(0.1~0.5):(0.1~0.8):(0.1~0.5):(0.1~1).

[0007] The present invention also provides a method for preparing the multi-doped high-mobility ceramic target described in the above technical solution, comprising the following steps: A mixed slurry is obtained by mixing metal oxide powder, dispersant, binder, defoamer and deionized water; the metal oxide powder is composed of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide. The mixed slurry is spray-granulated to obtain granulated powder; The granulated powder is subjected to cold pressing and cold isostatic pressing in sequence to obtain a ceramic body. The ceramic blank is sintered to obtain a multi-element doped high-mobility ceramic target.

[0008] Preferably, the D50 of the indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide is independently less than or equal to 0.5 μm.

[0009] Preferably, the dispersant accounts for 0.1-1.0% of the mass of the metal oxide powder; the binder accounts for 0.1-10% of the mass of the metal oxide powder; the defoamer accounts for 0.1-0.5% of the mass of the metal oxide powder; and the deionized water accounts for 40-70% of the mass of the metal oxide powder.

[0010] Preferably, the solids in the mixed slurry have a D50 of less than or equal to 0.2 μm and a D90 of less than or equal to 0.6 μm.

[0011] Preferably, the pressure of the cold pressing treatment is 20~40MPa; the holding time of the cold pressing treatment is 1~3min.

[0012] Preferably, the pressure of the cold isostatic pressing treatment is 200~300MPa; the holding time of the cold isostatic pressing treatment is 1~60min.

[0013] Preferably, the sintering process includes sequential degreasing sintering, low-temperature sintering, and high-temperature sintering; The heating rate for the degreasing sintering is 0.1~5℃ / min; the degreasing sintering temperature is 600~750℃; and the holding time for the degreasing sintering is 5~10h. The heating rate from degreasing sintering to low-temperature sintering is 0.1~5℃ / min; the temperature of low-temperature sintering is 1200~1300℃; and the holding time of low-temperature sintering is 5~10h. The heating rate from low-temperature sintering to high-temperature sintering is 0.1~5℃ / min; the high-temperature sintering temperature is 1300~1500℃, and the holding time for high-temperature sintering is 12~36h.

[0014] Preferably, when the sintering temperature is below 650°C, the sintering atmosphere is air; when the sintering temperature is above 650°C, the sintering atmosphere is oxygen.

[0015] The present invention also provides the application of the multi-doped high-mobility ceramic target described in the above technical solution or the multi-doped high-mobility ceramic target prepared by the preparation method described in the above technical solution in the fields of display semiconductor devices, integrated semiconductor devices, LEDs or photovoltaic solar cells.

[0016] This invention provides a multi-component doped high-mobility ceramic target, prepared from metal oxides including indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide; the mass ratio of indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide is (97.2~99.5):(0.1~0.5):(0.1~0.8):(0.1~0.5):(0.1~1). The ceramic target provided by this invention effectively provides additional electrons by introducing titanium oxide (TiO2) and gallium oxide (Ga2O3) as dopants, achieving control over carrier concentration; simultaneously, based on their high bandgap characteristics, the optical properties of the conductive oxide thin film prepared from the ceramic target are further improved; the doping of zirconium oxide (ZrO2) can suppress excessive grain growth and refine the microstructure, thereby reducing carrier scattering caused by grain boundaries and defects; furthermore, the introduction of cerium oxide (CeO2) utilizes the large ionic radius of Ce... 4+This invention effectively compensates for lattice distortion caused by other doping elements, alleviates internal stress, and balances the lattice structure, thereby enhancing the overall structural stability of conductive oxide films prepared from ceramic targets. By introducing a multi-doped system into the raw materials, this invention enables the prepared ceramic targets to possess excellent properties such as high density, low resistivity, and uniform composition distribution. Transparent conductive films prepared based on this ceramic target exhibit high mobility, low resistivity, and excellent light transmittance, showing broad application prospects in the field of optoelectronics. Detailed Implementation

[0017] This invention provides a multi-element doped high-mobility ceramic target, the raw materials of which include metal oxides, namely indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide; the mass ratio of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide is (97.2~99.5):(0.1~0.5):(0.1~0.8):(0.1~0.5):(0.1~1).

[0018] The raw materials for preparing the multi-doped high-mobility ceramic target of the present invention include metal oxides.

[0019] In this invention, the metal oxide includes indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide. In this invention, the mass ratio of indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide is (97.2~99.5):(0.1~0.5):(0.1~0.8):(0.1~0.5):(0.1~1). As an embodiment of the present invention, the mass ratio of indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide can be (97.5~99.6):(0.2~0.4):(0.2~0.7):(0.2~0.4):(0.5~1), or (98~99.6):(0.2~0.3):(0.3~0.6):(0.2~0.3):(0.5~0.8) or (98.5~99):(0.2~0.3):(0.3~0.6):(0.2~0.3):(0.6~0.7). By introducing the synergistic effect of a multi-component doping system into the raw materials, the present invention enables the prepared ceramic target material to possess excellent properties such as high density, low resistivity, and uniform composition distribution. Based on this target material, transparent conductive films exhibiting high mobility, low resistivity, and excellent light transmittance can be prepared.

[0020] The present invention also provides a method for preparing the multi-doped high-mobility ceramic target described in the above technical solution, comprising the following steps: A mixed slurry is obtained by mixing metal oxide powder, dispersant, binder, defoamer and deionized water; the metal oxide powder is composed of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide. The mixed slurry is spray-granulated to obtain granulated powder; The granulated powder is subjected to cold pressing and cold isostatic pressing in sequence to obtain a ceramic body. The ceramic blank is sintered to obtain a multi-element doped high-mobility ceramic target.

[0021] Unless otherwise specified, all raw materials used in this invention are commercially available products well known to those skilled in the art.

[0022] This invention involves mixing metal oxide powder, dispersant, binder, defoamer, and deionized water to obtain a mixed slurry.

[0023] In this invention, the metal oxide powder is composed of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide.

[0024] In this invention, the D50 of indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide is preferably less than or equal to 0.5 μm. When the D50 of indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide is controlled within the above range, the metal oxide powder is a nanoparticle, which promotes uniform mixing of the metal oxide powder at the nanoscale, and is more conducive to obtaining a dense and uniform ceramic target material.

[0025] In this invention, the dispersant is preferably an acidic dispersant; more specifically, the acidic dispersant is preferably ammonium polyacrylate. By adding a dispersant, this invention promotes the uniform dispersion of metal oxides in the mixed slurry.

[0026] In this invention, the dispersant preferably accounts for 0.1 to 1.0% of the mass of the metal oxide powder; as an embodiment of this invention, the dispersant can account for 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1.0% of the mass of the metal oxide powder.

[0027] In this invention, the binder preferably includes one or more of polyvinyl alcohol, polyethylene, polypropylene, and polyvinyl chloride, more preferably polyvinyl alcohol. This invention, by adding a binder, can bond various metal oxides, which is more conducive to granulation.

[0028] In this invention, the binder preferably accounts for 0.1 to 10% of the mass of the metal oxide powder; as an embodiment of this invention, the binder can account for 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% of the mass of the metal oxide powder.

[0029] In this invention, the defoamer is preferably a fatty acid-based defoamer, and the fatty acid-based defoamer is preferably polyacrylate. This invention eliminates bubbles generated during mixing by adding a defoamer.

[0030] In this invention, the defoamer preferably accounts for 0.1 to 0.5% of the mass of the metal oxide powder; as an embodiment of this invention, the defoamer can account for 0.1%, 0.2%, 0.3%, 0.4%, or 0.5% of the mass of the metal oxide powder.

[0031] In this invention, the deionized water content of the metal oxide powder is preferably 40-70% by mass; as an embodiment of this invention, the deionized water content of the metal oxide powder can be 40%, 45%, 50%, 55%, 60%, 65% or 70% by mass.

[0032] In this invention, the mixing process preferably includes: mixing indium oxide, titanium oxide, zirconium oxide, gallium oxide, cerium oxide, dispersant, binder, defoamer and deionized water, and then ball milling to obtain a mixed slurry.

[0033] In this invention, the ball milling speed is preferably 2000-3000 rpm, more preferably 2500-3000 rpm; the ball milling time is preferably 1-10 h, more preferably 2-5 h; the ball-to-material ratio is preferably 1:1-2, more preferably 1:1-1.5; the grinding balls used in the ball milling preferably include small balls, medium balls, and large balls, and the mass ratio of the small balls, medium balls, and large balls is preferably (1-5):(1-5):(1-5), more preferably (2-4):(2-4):(2-4). In an embodiment of this invention, the diameter of the small balls can be 0.1 mm, the diameter of the medium balls can be 0.3 mm, and the diameter of the large balls can be 0.6 mm. In an embodiment of this invention, the ball milling can be carried out in a sand mill. This invention, through ball milling, enables the solid particles in the mixed slurry to have a small particle size and narrow distribution, thereby giving the ceramic green body a more uniform microstructure and higher sintering density. In this invention, the solids in the mixed slurry preferably have a D50 of less than or equal to 0.2 μm and a D90 of less than or equal to 0.6 μm.

[0034] After obtaining the mixed slurry, the present invention performs spray granulation on the mixed slurry to obtain granulated powder.

[0035] This invention does not specifically limit the operation method of spray granulation; conventional spray granulation methods can be used. In this invention, the spray granulation temperature is preferably 100-200℃, more preferably 150-200℃. Preferably, the powder obtained from spray granulation is sieved to obtain granulated powder. In this invention, the D50 of the powder obtained from spray granulation is 30-50 μm. Sieving allows for control of the uniformity of the granulated powder particle size. In an embodiment of this invention, the sieve opening can be 120 mesh, and the D50 of the granulated powder obtained after sieving can be 38 μm.

[0036] After obtaining the granulated powder, the present invention performs cold pressing and cold isostatic pressing on the granulated powder in sequence to obtain a ceramic body.

[0037] In this invention, the pressure of the cold pressing process is preferably 20-40 MPa; the holding time of the cold pressing process is preferably 1-3 min. As an embodiment of this invention, the pressure of the cold pressing process can be 20 MPa, 22 MPa, 24 MPa, 26 MPa, 27.3 MPa, 28 MPa, 30 MPa, 32 MPa, 34 MPa, 36 MPa, 38 MPa, or 40 MPa; the holding time of the cold pressing process can be 1 min, 1.5 min, 2 min, 2.5 min, or 3 min. This invention enables rapid shaping of granulated powder through cold pressing.

[0038] In this invention, the pressure of the cold isostatic pressing treatment is preferably 200-300 MPa; the holding time of the cold isostatic pressing treatment is preferably 1-60 min. As an embodiment of this invention, the pressure of the cold isostatic pressing can be 200 MPa, 210 MPa, 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, or 300 MPa; the holding time of the cold isostatic pressing can be 1 min, 10 min, 20 min, 30 min, 40 min, 50 min, or 60 min. This invention enables the ceramic green body to be uniformly densified through cold isostatic pressing.

[0039] After obtaining the ceramic blank, the present invention performs sintering treatment on the ceramic blank to obtain a multi-element doped high-mobility ceramic target.

[0040] In this invention, the sintering process preferably includes degreasing sintering, low-temperature sintering and high-temperature sintering performed sequentially.

[0041] In this invention, the heating rate to the debinding sintering stage is preferably 0.1~5℃ / min; the debinding sintering temperature is preferably 600~750℃; and the holding time for debinding sintering is preferably 5~10h. As an embodiment of this invention, the heating rate to the debinding sintering stage can be 0.1℃ / min, 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, or 5℃ / min; the debinding sintering temperature can be 600℃, 650℃, 700℃, or 750℃; and the holding time for debinding sintering can be 5h, 6h, 7h, 8h, 9h, or 10h. This invention can remove organic additives such as binders from the ceramic body through debinding sintering.

[0042] In this invention, the heating rate from degreasing sintering to low-temperature sintering is preferably 0.1~5℃ / min; the low-temperature sintering temperature is preferably 1200~1300℃, and the holding time for low-temperature sintering is preferably 5~10h. As an embodiment of this invention, the heating rate to the low-temperature sintering can be 0.1℃ / min, 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, or 5℃ / min; the low-temperature sintering temperature can be 1200℃, 1250℃, 1260℃, or 1300℃; and the holding time for low-temperature sintering can be 5h, 6h, 7h, 8h, 9h, or 10h. This invention enables preliminary sintering, strengthens the green body, and facilitates the transition before sealing pores through low-temperature sintering.

[0043] In this invention, the heating rate from low-temperature sintering to high-temperature sintering is preferably 0.1~5℃ / min; the high-temperature sintering temperature is preferably 1300~1500℃; and the holding time for high-temperature sintering is preferably 12~36h. As an embodiment of this invention, the heating rate to the high-temperature sintering can be 0.1℃ / min, 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, or 5℃ / min; the high-temperature sintering temperature can be 1300℃, 1350℃, 1400℃, 1450℃, or 1500℃; and the holding time for high-temperature sintering can be 12h, 15h, 18h, 20h, 24h, 30h, or 36h. This invention enables the green body to shrink rapidly, become dense, and gradually spheroidize its pores through high-temperature sintering. It also allows for the extensive diffusion and fusion of particles within the green body, resulting in moderate grain growth and the formation of a stable microstructure.

[0044] In this invention, the temperature is preferably reduced to 1000°C at a rate of 1°C / min after high-temperature sintering, and then allowed to cool naturally to room temperature.

[0045] In this invention, when the sintering temperature is below 650°C, the sintering atmosphere is preferably air; when the sintering temperature is above 650°C, the sintering atmosphere is preferably oxygen. In this invention, when the sintering atmosphere is oxygen, the oxygen flow rate is preferably 2~20 L / min, more preferably 6~15 L / min. This invention improves sintering efficiency by controlling the sintering atmosphere.

[0046] The present invention preferably involves mechanically grinding, inspecting, and bonding the target material obtained from the sintering process to obtain a multi-element doped high-mobility ceramic target material. The present invention does not impose any particular limitation on the operation methods for the mechanical grinding, inspection, and bonding; conventional methods can be used.

[0047] This invention also provides the application of the multi-doped high-mobility ceramic target described in the above-described technical solutions, or the multi-doped high-mobility ceramic target prepared by the preparation method described in the above-described technical solutions, in the fields of display semiconductor devices, integrated semiconductor devices, LEDs, or photovoltaic solar cells. This invention does not impose any special limitations on the methods for these applications; any process well-known to those skilled in the art can be used.

[0048] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0049] Example 1 A method for preparing a multi-doped high-mobility ceramic target: Powders of indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide with a D50 < 0.5 μm were weighed in a mass ratio of 99.6%:0.1%:0.1%:0.1%:0.1% and placed in a sand mill jar. Simultaneously, using indium oxide, titanium oxide, zirconium oxide, gallium oxide, and cerium oxide as metal oxide powders, 50% deionized water (by mass of the metal oxide powder), 0.5% dispersant (ammonium polyacrylate), 5.5% binder (polyvinyl alcohol), and [other components] were added. A defoamer (polyacrylate) with a mass content of 0.1% by weight was mixed with a powder and then ball-milled in a sand mill at a speed of 2250 rpm. The ball-to-powder ratio was 1:1, and the milling media were zirconia balls, which included small, medium, and large balls. The diameter of the small balls was 0.1 mm, the diameter of the medium balls was 0.3 mm, and the diameter of the large balls was 0.6 mm. The mass ratio of the small, medium, and large balls was 1:1:1. The milling time was 5 hours to obtain a mixed slurry. The solids in the mixed slurry had a D50 of 0.15 μm and a D90 of 0.55 μm. After obtaining the mixed slurry, the mixed slurry is spray-granulated at 230°C to obtain powder (D50 is 30~50μm), and then passed through a 120-mesh sieve to obtain granulated powder (D50 is 38μm). The granulated powder was subjected to cold pressing at 27.3 MPa for 3 minutes, and then further subjected to cold isostatic pressing at 270 MPa for 25 minutes to obtain a ceramic green body. The ceramic blank was placed in a sintering furnace and sintered at 650°C with a heating rate of 1°C / min for debinding and holding for 10 hours; then sintered at 1200°C with a heating rate of 1°C for 6 hours; then sintered at 1380°C with a heating rate of 0.5°C / min for 24 hours; and finally cooled to 1000°C with a heating rate of 1°C / min, followed by natural cooling to room temperature to obtain a multi-element doped high-mobility ceramic target. During the sintering process, air was introduced below 650°C and oxygen was introduced above 650°C at a flow rate of 6 L / min. The target obtained after the sintering process was then mechanically polished, inspected, and bonded to obtain a multi-element doped high-mobility ceramic target.

[0050] Example 2 A method for preparing a multi-doped high-mobility ceramic target: The difference from Example 1 is that the powders of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide are weighed in a mass ratio of 99.5%:0.1%:0.1%:0.1%:0.2%, and the remaining steps and parameters are the same as in Example 1.

[0051] Example 3 A method for preparing a multi-doped high-mobility ceramic target: The difference from Example 1 is that the powders of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide are weighed in a mass ratio of 99.2%:0.2%:0.2%:0.2%:0.2%, while the remaining steps and parameters are the same as in Example 1.

[0052] Example 4 A method for preparing a multi-doped high-mobility ceramic target: The difference from Example 1 is that the powders of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide are weighed in a mass ratio of 99.0%:0.2%:0.3%:0.2%:0.3%, while the remaining steps and parameters are the same as in Example 1.

[0053] Example 5 A method for preparing a multi-doped high-mobility ceramic target: The difference from Example 1 is that the powders of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide are weighed in a mass ratio of 98.8%:0.3%:0.3%:0.3%:0.3%, while the remaining steps and parameters are the same as in Example 1.

[0054] Example 6 A method for preparing a multi-doped high-mobility ceramic target: The difference from Example 1 is that the powders of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide are weighed in a mass ratio of 98.5%:0.3%:0.4%:0.3%:0.5%, and the remaining steps and parameters are the same as in Example 1.

[0055] Example 7 A method for preparing a multi-doped high-mobility ceramic target: The difference from Example 1 is that the powders of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide are weighed in a mass ratio of 98.0%:0.5%:0.5%:0.5%:0.5%, while the remaining steps and parameters are the same as in Example 1.

[0056] Comparative Example 1 A method for preparing a multi-doped high-mobility ceramic target: The difference from Example 1 is that the powders of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide are weighed in a mass ratio of 96.0%:1.0%:1.0%:1.0%:1.0%, while the remaining steps and parameters are the same as in Example 1.

[0057] Comparative Example 2 A method for preparing a multi-doped high-mobility ceramic target: The difference from Example 1 is that 99.0% indium oxide and 1.0% tin oxide were weighed, while the remaining steps and parameters were the same as in Example 1.

[0058] Test case Performance testing experiments: 1. Processing binding: After the target materials prepared in the above embodiments and comparative examples were processed according to the drawing dimensions, the target materials were bonded to the copper back target with indium and subjected to ultrasonic testing. No dark cracks were found. Then, subsequent coating tests were carried out.

[0059] 2. Coating test: Target density: The density of the prepared target was determined using the Archimedes displacement method.

[0060] Resistivity: The resistivity of the prepared target material was measured using a four-probe resistivity meter.

[0061] Bending strength: The prepared target material was measured using a universal testing machine.

[0062] After being ultrasonically cleaned with acetone, ethanol, and deionized water for 10-20 minutes and dried with nitrogen, the target materials prepared in the above embodiments and comparative examples were used to deposit the required thin film by magnetron sputtering. The deposition power was 180W, the sputtering pressure was 0.5Pa, the sputtering atmosphere was a mixed gas of H2 / O2, and the film thickness was 100nm.

[0063] Thin film mobility: The prepared thin film was tested using a Hall effect meter.

[0064] Thin film transmittance: The prepared thin film was tested using a UV spectrophotometer at wavelengths of 400~1400nm.

[0065] The performance test results of the targets prepared in each embodiment and comparative example, and the thin films prepared therefrom, are shown in Table 1.

[0066] Table 1 Performance test results of Examples 1-7 and Comparative Examples 1-2

[0067] As shown in Table 1, the ceramic target material prepared in this invention possesses high density and low resistivity, meeting the basic application requirements of magnetron sputtering. The correspondingly prepared transparent conductive film exhibits high carrier mobility and good light transmittance, meeting the photoelectric property requirements of high-performance transparent conductive films. In Examples 1-7, with the gradual increase of the total doping amount, the relative density of the target material increased from 98.5% to 99.6%, and the flexural strength also increased from 166 MPa to 188 MPa. This is mainly attributed to the introduction of doping components such as titanium oxide and zirconium oxide, which promote densification during sintering, inhibit abnormal grain growth, thereby refining the microstructure and enhancing the mechanical properties of the material. Simultaneously, the decrease in target resistivity is due to the presence of Ti... 4+ Ga 3+ Ce 4+ The additional electrons provided by doped ions effectively increase the carrier concentration. Regarding thin film performance, the improved mobility stems from two synergistic effects: firstly, the additional electrons introduced by doping optimize the carrier concentration; secondly, the doping of zirconium oxide and cerium oxide effectively compensates for lattice distortion, alleviates internal stress, and enhances lattice stability, thereby reducing the scattering of carriers by defects. Furthermore, the high bandgap of titanium oxide and gallium oxide widens the optical bandgap, reducing absorption in the visible light region; simultaneously, the densification of the microstructure and the optimization of the grain boundary structure also reduce light scattering losses, jointly contributing to a significant increase in thin film transmittance. In Comparative Example 1, further increasing the dopant content leads to a significant decrease in mobility, mainly due to the intensified local potential fluctuations caused by high-concentration doping and the enhanced Coulomb scattering between carriers and ionized impurities. In Comparative Example 2, single-element doping failed to achieve an effective improvement in mobility, indicating that the single-doping strategy has limitations in performance control.

[0068] This invention, through the rational design of a multi-component doping system and the control of its ratio, can systematically optimize the overall optoelectronic performance of high-mobility indium oxide-based targets and their thin films. With the moderate increase of the total dopant content and the formation of synergistic effects among the components, the material achieves significant improvements in terms of density, conductivity, mobility, and light transmittance.

[0069] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A multi-doped high-mobility ceramic target, characterized in that, The raw materials for preparation include metal oxides, including indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide; the mass ratio of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide is (98~99.6):(0.1~0.5):(0.1~0.8):(0.1~0.5):(0.1~1).

2. The method for preparing the multi-doped high-mobility ceramic target according to claim 1, characterized in that, Includes the following steps: A mixed slurry is obtained by mixing metal oxide powder, dispersant, binder, defoamer and deionized water; the metal oxide powder is composed of indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide. The mixed slurry is spray-granulated to obtain granulated powder; The granulated powder is subjected to cold pressing and cold isostatic pressing in sequence to obtain a ceramic body. The ceramic blank is sintered to obtain a multi-element doped high-mobility ceramic target.

3. The preparation method according to claim 2, characterized in that, The D50 of the indium oxide, titanium oxide, zirconium oxide, gallium oxide and cerium oxide are independently less than or equal to 0.5 μm.

4. The preparation method according to claim 2, characterized in that, The dispersant accounts for 0.1-1.0% of the mass of the metal oxide powder; the binder accounts for 0.1-10% of the mass of the metal oxide powder; the defoamer accounts for 0.1-0.5% of the mass of the metal oxide powder; and the deionized water accounts for 40-70% of the mass of the metal oxide powder.

5. The preparation method according to claim 2, characterized in that, The solids in the mixed slurry have a D50 of less than or equal to 0.2 μm and a D90 of less than or equal to 0.6 μm.

6. The preparation method according to claim 2, characterized in that, The pressure of the cold pressing process is 20~40MPa; the holding time of the cold pressing process is 1~3min.

7. The preparation method according to claim 6, characterized in that, The pressure of the cold isostatic pressing treatment is 200~300MPa; the holding time of the cold isostatic pressing treatment is 1~60min.

8. The preparation method according to claim 2, characterized in that, The sintering process includes sequential degreasing sintering, low-temperature sintering, and high-temperature sintering; The heating rate for the degreasing sintering is 0.1~5℃ / min; the degreasing sintering temperature is 600~750℃; and the holding time for the degreasing sintering is 5~10h. The heating rate from degreasing sintering to low-temperature sintering is 0.1~5℃ / min; the temperature of low-temperature sintering is 1200~1300℃; and the holding time of low-temperature sintering is 5~10h. The heating rate from low-temperature sintering to high-temperature sintering is 0.1~5℃ / min; the high-temperature sintering temperature is 1300~1500℃, and the holding time for high-temperature sintering is 12~36h.

9. The preparation method according to claim 8, characterized in that, When the sintering temperature is below 650°C, the sintering atmosphere is air; when the sintering temperature is above 650°C, the sintering atmosphere is oxygen.

10. The application of the multi-doped high-mobility ceramic target of claim 1 or the multi-doped high-mobility ceramic target prepared by any one of claims 2 to 9 in the fields of display semiconductor devices, integrated semiconductor devices, LEDs or photovoltaic solar cells.

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