A titanium dioxide-zirconium composite target, its preparation method and application

Abstract

This invention discloses a titanium oxide-zirconia composite target, its preparation method, and its applications. The titanium oxide-zirconia composite target comprises the following raw materials in parts by weight: 60-80 parts titanium oxide; 20-40 parts zirconium oxide; and 0.5-3 parts cerium oxide or 0.1-1 parts tantalum oxide. By doping titanium oxide and zirconium oxide with specific amounts of cerium oxide or tantalum oxide, this invention effectively improves the grain size of the titanium oxide-zirconia composite target and reduces grain boundary defects. The oxide film obtained from the titanium oxide-zirconia composite target of this invention possesses high refractive index and a wide bandgap, with the bandgap increased to over 3.5 eV, expanding its application in deep ultraviolet optical devices. The doping of cerium oxide or tantalum oxide improves the crack resistance of the film, making it crack-free after bending.

Description

Technical Field

[0001] This invention relates to the field of target technology, and in particular to a titanium oxide-zirconium composite target, its preparation method, and its application. Background Technology

[0002] Zirconium titanate (TiO2-ZrO2) is widely used in antireflective coatings, high-reflectivity coatings, and flexible display protective layers due to its high refractive index, wide bandgap, and chemical stability. Zirconium titanate sputtering targets are commonly used as important sputtering sources for preparing optical thin films, high-dielectric-constant thin films, and other functional coatings. However, current Zirconium titanate sputtering targets suffer from several drawbacks. Firstly, their bandgap is insufficient, typically less than 3.2 eV, resulting in high absorption rates in the ultraviolet (UV) band, limiting their application in deep UV optics. Secondly, films formed using Zirconium titanate sputtering targets exhibit poor crack resistance, especially in flexible electronics, where cracking occurs when the bending radius of the flexible substrate exceeds 3 mm. Furthermore, the coarse grains of Zirconium titanate sputtering targets lead to particulate contamination during sputtering. Summary of the Invention

[0003] The present invention aims to solve at least one of the aforementioned technical problems existing in the prior art. Therefore, the object of the present invention is to provide a titanium oxide-zirconium composite target, its preparation method, and its application.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] In a first aspect, the present invention provides a titanium dioxide-zirconium composite target material comprising the following raw materials in parts by weight:

[0006] 60-80 parts of titanium dioxide;

[0007] 20-40 parts of zirconium oxide; and

[0008] 0.5 to 3 parts cerium oxide or 0.1 to 1 part tantalum oxide.

[0009] In this invention, the composition of titanium oxide and zirconium oxide ensures that the thin film formed by the composite target possesses high refractive index, light transmittance, and a wide bandgap. Meanwhile, cerium oxide or tantalum oxide effectively reduces grain size and increases the relative density of the target through grain boundary segregation-pinning effect and vacancy-assisted diffusion mechanism. Thus, during the sputtering formation of the thin film, cerium oxide or tantalum oxide induces the formation of a "nanocrystalline / amorphous structure," increasing the bandgap of the thin film through band engineering and enhancing its crack resistance through a stress buffer layer. Therefore, the high density and low defect characteristics of the composite target guarantee the compositional uniformity and low internal stress of the formed thin film.

[0010] In some embodiments of the present invention, the titanium dioxide-zirconium composite target material comprises the following raw materials in parts by weight:

[0011] 65-75 parts of titanium dioxide;

[0012] 25-35 parts of zirconium oxide; and

[0013] 0.5 to 2 parts cerium oxide or 0.1 to 0.8 parts tantalum oxide.

[0014] In some embodiments of the present invention, the content of titanium oxide that can achieve the purpose of the present invention is 65 to 75 parts by weight, such as 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, and 75 parts.

[0015] In some embodiments of the present invention, the zirconium oxide content that enables the present invention to achieve its purpose is 25 to 35 parts by weight, such as 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, and 35 parts.

[0016] In some embodiments of the present invention, the content of cerium oxide, calculated by weight, to achieve the purpose of the present invention is 0.5 to 2 parts, such as 0.5 parts, 0.6 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, and 2.0 parts. In the present invention, CeO2 is formed through grain boundary segregation (CeO2). x Zr 1-x O2 solid solution neutralizes oxygen vacancy defects and reduces grain boundary energy; simultaneously, it generates nano-sized Ce2Zr3O 10 Phase pinning of grain boundary migration (Zener pinning model) makes the grain size ≤12μm.

[0017] In some embodiments of the present invention, the content of tantalum oxide that enables the present invention to achieve its purpose is 0.1 to 0.8 parts by weight, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8 parts.

[0018] In some embodiments of the present invention, the purity of the titanium oxide is ≥99.95% (3N5 grade).

[0019] In some embodiments of the present invention, the zirconium oxide has a purity of ≥99.95% (3N5 grade).

[0020] In some embodiments of the present invention, the purity of the cerium oxide is ≥99.95% (3N5 grade).

[0021] In some embodiments of the present invention, the purity of the tantalum oxide is ≥99.95% (3N5 grade).

[0022] In some embodiments of the present invention, the average particle size of the raw material is no more than 200 nm; for example, 50–200 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, and 200 nm. In the present invention, the average particle size of the raw material is measured using a laser particle size analyzer (dynamic light scattering).

[0023] In some embodiments of the present invention, the raw materials for preparation further include dispersants and / or binders.

[0024] In some embodiments of the present invention, the raw materials for preparation further include 0.1 to 5 parts of dispersant and 0.1 to 5 parts of binder.

[0025] In some embodiments of the present invention, the raw materials for preparation further include 0.3 to 2 parts of dispersant and 0.3 to 0.8 parts of binder.

[0026] In some embodiments of the present invention, the dispersant includes at least one of polyvinylpyrrolidone, polyacrylamide, polyethylene glycol, or hydrogenated nitrile rubber.

[0027] In some embodiments of the present invention, the ash content of the adhesive does not exceed 0.01 wt%; the adhesive includes at least one of polyvinyl alcohol, sodium polyacrylate, butyl rubber or cyanoacrylate; preferably, the ash content of the polyvinyl alcohol does not exceed 0.01 wt%.

[0028] In some embodiments of the present invention, the average grain size of the titanium dioxide-zirconia composite target does not exceed 12.0 μm, such as 1.0–12.0 μm, 8.0–12.0 μm, 8.5–11.5 μm, 9.0–12.0 μm, 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5.0 μm, 6.0 μm, 7.0 μm, 8.0 μm, 9.0 μm, 10.0 μm, 11.0 μm, and 12.0 μm. In the present invention, the average grain size of the target is determined using the cross-section method. In the present invention, the titanium dioxide-zirconia composite target with the above-mentioned average grain size can improve the transmittance and reduce the sheet resistance of the subsequently fabricated flexible oxide film.

[0029] In some embodiments of the present invention, the relative density of the titanium dioxide-zirconium composite target is 99.0% or higher; for example, 99.0% to 99.9%, such as 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, or 99.9%. In this invention, the density of the target material is measured using Archimedes' displacement method, and the relative density is the ratio of the actual density of the target material measured by the displacement method to the theoretical density.

[0030] In some embodiments of the present invention, the maximum and minimum surface resistivity Rs of different parts of the titanium dioxide-zirconium composite target satisfy the ratio relationship (Rs-Rd) / Rd≤10%, such as 3.0-10.0%, 10.0%, 9.0%, 8.0%, 7.0%, 6.0%, 5.0%, 4.0%, 3.0%, etc. In the present invention, the surface resistivity of the target is detected by four-probe surface scanning (9-point method).

[0031] A second aspect of the present invention provides a method for preparing the aforementioned titanium dioxide-zirconium composite target, comprising the following steps:

[0032] S1: The raw materials are ball-milled in water to obtain a slurry.

[0033] S2: Spray dry the slurry to obtain a mixed powder;

[0034] S3: The powder is shaped and sintered to obtain the titanium dioxide zirconium composite target.

[0035] In some embodiments of the present invention, the mass-to-volume ratio of the raw material to water is (3-8):1g / mL, such as (4-6):1g / mL or 5:1g / mL.

[0036] In some embodiments of the present invention, the rotational speed of the ball mill is 200-500 rpm, such as 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, or 500 rpm; the ball milling is performed using zirconia grinding beads; the average diameter of the zirconia grinding beads in the ball mill is 2-4 mm, such as 3 mm; and the ball-to-material ratio in the ball milling is (3-8):1, (4-6):1, or 5:1.

[0037] In some embodiments of the present invention, the average particle size of the slurry does not exceed 200 nm; such as 50-200 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm.

[0038] In some embodiments of the present invention, the inlet temperature of the spray dryer is 150-300°C, such as 180-250°C or 200±10°C; the atomization pressure of the spray dryer is 0.1-0.3 MPa, such as 0.1-0.2 MPa or 0.15 MPa.

[0039] In some embodiments of the present invention, the average particle size of the mixed powder is 10–50 μm, such as 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, and 50 μm. In the present invention, controlling the average particle size of the powder within this range can significantly improve the flowability of the powder during molding.

[0040] In some embodiments of the present invention, the molding process employs cold isostatic pressing (CIP); the molding pressure is 100–200 MPa; the holding time is 5–10 min; and the molding density is at least 2.8 g / cm³. 3 For example, 2.8–3.5 g / cm³ 3 In this invention, cold isostatic pressing ensures uniform powder flow, reduces density gradient, and makes the flowability of spray-granulated powder greater than 60s / 50g; the above-mentioned molding pressure ensures that the initial density of the molded body is above 55%TD; and the above-mentioned holding time eliminates elastic aftereffects; the above-mentioned molding density lays the foundation for sintering densification.

[0041] In some embodiments of the present invention, the sintering is carried out in an oxygen atmosphere; the sintering temperature is 1100–1600°C; the sintering time is 40–80 h; and the heating rate during the sintering process is 0.3–1.5°C / min.

[0042] In some embodiments of the present invention, the sintering includes pre-sintering and re-sintering. In this invention, the two-step sintering process reduces energy consumption and improves raw material utilization.

[0043] In some embodiments of the present invention, the pre-sintering is performed at 1100–1300°C (e.g., 1200°C); the pre-sintering time is 40–48 h; the heating rate during the pre-sintering process is 0.3–0.6°C / min (e.g., 0.4–0.6°C / min); the pre-sintering includes heating to 1100–1300°C at a rate of 0.3–0.6°C / min in an oxygen atmosphere and holding at that temperature for 3–5 h (e.g., 4 h). In the present invention, the above-mentioned pre-sintering can eliminate the internal stress of the target material.

[0044] In some embodiments of the present invention, the re-sintering is carried out at 1400–1600°C (e.g., 1500°C); the re-sintering time is 30–40 h; the heating rate during the re-sintering process is 0.9–1.1°C / min (e.g., 1.0°C / min); the re-sintering includes heating to 1400–1600°C at 0.9–1.1°C / min in an oxygen atmosphere and holding at that temperature for 8–12 h (e.g., 9 h, 10 h, 11 h).

[0045] A third aspect of the present invention provides a flexible oxide film comprising a titanium dioxide-zirconium composite target.

[0046] In some embodiments of the present invention, the thickness of the flexible oxide film is 10 to 1000 nm, such as 100 to 500 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, and 500 nm.

[0047] In some embodiments of the present invention, the transmittance of the flexible oxide film is at least 95.0%, such as 95.0% to 99.0%, or 95.0%, 95.5%, 96.0%, 97.0%, 98.0%, and 99.0%. In this invention, the transmittance of the oxide film is measured by sputtering a 100nm thick oxide film onto a titanium dioxide-zirconia composite target using a magnetron sputtering machine, with a 10*10mm plastic substrate, using a dual-beam UV-Vis spectrophotometer.

[0048] In some embodiments of the present invention, the bandgap of the flexible oxide film is 3.40–3.80 eV; for example, 3.45–3.70 eV. In this invention, the film bandgap is determined by measuring the film absorption spectrum using a UV-Vis spectrophotometer and fitting it according to the Tauc formula.

[0049] (αhν) 2 =A(hν-E) g ),

[0050] Where α: absorption coefficient, unit: cm -1 ;

[0051] hν: Photon energy, unit: eV; h is Planck's constant, ν is the frequency of light;

[0052] E g Bandwidth, unit: eV;

[0053] A: This is a proportionality constant (related to the type of material transition), and its value is 10 for direct bandgap semiconductors. 4 ~10 5 cm -1 eV -1 .

[0054] In some embodiments of the present invention, the sheet resistance of the flexible oxide film is 10–20 Ω / sq, such as 10 Ω / sq, 11 Ω / sq, 12 Ω / sq, 13 Ω / sq, 14 Ω / sq, 15 Ω / sq, 16 Ω / sq, 17 Ω / sq, 18 Ω / sq, 19 Ω / sq, and 20 Ω / sq. In this invention, the sheet resistance of the film is measured using the four-probe method.

[0055] In some embodiments of the present invention, the resistance change rate of the flexible oxide film after bending to a radius of 1.5 mm does not exceed 5%, such as 4%, 3%, 2%, or 1%. In the present invention, the resistance change rate after bending is measured using a four-probe sheet resistance meter.

[0056] In some embodiments of the present invention, the oxygen vacancy concentration of the oxide film does not exceed 1 × 10⁻⁶. 17 pcs / cm 3 ; such as 1×10 16 ~1×10 17 pcs / cm 3 In this invention, the oxygen vacancy concentration is determined by XPS testing.

[0057] In a fourth aspect, the present invention provides an optical device thin film comprising the aforementioned oxide thin film.

[0058] In some embodiments of the present invention, the optical device includes either an OLED or an optical lens.

[0059] A fifth aspect of the present invention provides an application of the aforementioned titanium dioxide-zirconium composite target, the aforementioned oxide thin film, and the aforementioned optical device thin film in the field of optoelectronic coating.

[0060] The beneficial effects of this invention are:

[0061] In this invention, doping a specific amount of cerium oxide or tantalum oxide into a specific ratio of titanium oxide and zirconium oxide can effectively increase the grain size of the titanium oxide-zirconium composite target (≤12μm) and reduce grain boundary defects in the target.

[0062] The oxide film obtained by the titanium dioxide-zirconium composite target of this invention has high refractive index, transmittance (>95%) and wide bandgap characteristics. The bandgap width is increased to more than 3.5 eV, which expands its application in deep ultraviolet optical devices (ultraviolet cutoff edge is 345 nm). The doping of cerium oxide or tantalum oxide improves the crack resistance of the film, making its resistivity change rate after bending small (<5%) and crack-free.

[0063] In the preparation process of the titanium dioxide-zirconium composite target of the present invention, if a two-step sintering method is adopted, energy consumption can be effectively reduced and the crack resistance and density of the target can be further improved. Attached Figure Description

[0064] Figure 1 This is a cross-sectional SEM image of the titanium dioxide zirconium target material in Example 1 of the present invention.

[0065] Figure 2 This is a cross-sectional SEM image of the titanium dioxide zirconium target material of Comparative Example 1 of this invention. Detailed Implementation

[0066] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments and comparative examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the test or experimental methods are conventional methods in the art.

[0067] Example 1

[0068] This embodiment prepares a titanium dioxide-zirconium composite target material, and the specific process is as follows:

[0069] The raw material composition of the titanium dioxide-zirconium composite target in this embodiment is as follows by weight: 70 parts titanium dioxide, 30 parts zirconium oxide, 1 part cerium oxide, 300 parts deionized water, 0.5 parts dispersant: polyvinylpyrrolidone, and 0.5 parts binder: polyvinyl alcohol with ash content ≤0.01%.

[0070] The preparation method of the titanium oxide-zirconium composite target is as follows:

[0071] S1: After mixing the components, ball mill them for 12 hours at a speed of 350 rpm, using 3 mm zirconia grinding beads and a ball-to-material ratio of 5:1, so that the particle size is below 200 nm, to obtain a mixed slurry;

[0072] S2: Spray dry the mixed slurry, setting the inlet temperature to 200℃ and the atomization pressure to 0.15MPa to obtain mixed powder with a particle size of 10-50μm;

[0073] S3: The mixed powder is heated to 1200℃ in an oxygen atmosphere at a rate of 0.5℃ / min and held for 4 hours; then heated to 1500℃ at a rate of 1℃ / min and held for 10 hours to obtain the titanium dioxide zirconium composite target.

[0074] The cross-sectional SEM image of the zirconium oxide target in this embodiment is shown below. Figure 1 As shown, the grain size is uniform (10.0±0.5μm), the grain boundaries are clear and free of pores, and the grain boundaries are well compacted.

[0075] Example 2

[0076] This embodiment prepares a titanium dioxide-zirconium composite target material, and the specific process is as follows:

[0077] The raw material composition of the titanium oxide-zirconium composite target in this embodiment is as follows by weight: 65 parts titanium oxide, 35 parts zirconium oxide, 0.5 parts tantalum oxide, 300 parts deionized water, 0.5 parts dispersant: polyvinylpyrrolidone, and 0.5 parts binder: polyvinyl alcohol with ash content ≤0.01%.

[0078] The preparation method of the titanium oxide-zirconium composite target was carried out in accordance with Example 1.

[0079] Example 3

[0080] This embodiment prepares a titanium dioxide-zirconium composite target material, and the specific process is as follows:

[0081] The raw material composition of the titanium dioxide-zirconium composite target in this embodiment is as follows by weight: 75 parts titanium dioxide, 25 parts zirconium oxide, 2 parts cerium oxide, 300 parts deionized water, 0.5 parts dispersant: polyvinylpyrrolidone, and 0.5 parts binder: polyvinyl alcohol with ash content ≤0.01%.

[0082] The preparation method of the titanium oxide-zirconium composite target was carried out in accordance with Example 1.

[0083] Comparative Example 1

[0084] This comparative example prepared a titanium dioxide-zirconium composite target material, and the specific process is as follows:

[0085] The raw material composition of this comparative titanium oxide-zirconium composite target material, by weight, is as follows: 70 parts titanium oxide, 30 parts zirconium oxide, 300 parts deionized water, 0.5 parts dispersant: polyvinylpyrrolidone, and 0.5 parts binder: polyvinyl alcohol with ash content ≤0.01%.

[0086] The preparation method of the titanium oxide-zirconium composite target was carried out in accordance with Example 1.

[0087] The cross-sectional SEM image of this comparative titanium dioxide-zirconium composite target is shown below. Figure 2 As shown, the grains are coarse (30.1±1.2μm), with poor compactness between grain boundaries and numerous micropores.

[0088] Comparative Example 2

[0089] This comparative example prepared a titanium dioxide-zirconium composite target material, and the specific process is as follows:

[0090] The raw material composition of the titanium dioxide-zirconia composite target in this embodiment is as follows by weight: 50 parts titanium dioxide, 50 parts zirconia, 1 part cerium oxide, 300 parts deionized water, 0.5 parts dispersant: polyvinylpyrrolidone, and 0.5 parts binder: polyvinyl alcohol with ash content ≤0.01%.

[0091] The preparation method of the titanium oxide-zirconium composite target was carried out in accordance with Example 1.

[0092] Comparative Example 3

[0093] This comparative example prepared a titanium dioxide-zirconium composite target material, and the specific process is as follows:

[0094] The raw material composition of the titanium oxide-zirconium composite target in this embodiment is as follows by weight: 50 parts titanium oxide, 50 parts zirconium oxide, 1 part tantalum oxide, 300 parts deionized water, 0.5 parts dispersant: polyvinylpyrrolidone, and 0.5 parts binder: polyvinyl alcohol with ash content ≤0.01%.

[0095] The preparation method of the titanium oxide-zirconium composite target was carried out in accordance with Example 1.

[0096] Comparative Example 4

[0097] This comparative example prepared a titanium dioxide-zirconium composite target material, and the specific process is as follows:

[0098] The raw material composition of the titanium dioxide-zirconium composite target in this embodiment is as follows by weight: 70 parts titanium dioxide, 30 parts zirconium oxide, 4 parts cerium oxide, 300 parts deionized water, 0.5 parts dispersant: polyvinylpyrrolidone, and 0.5 parts binder: polyvinyl alcohol with ash content ≤0.01%.

[0099] The preparation method of the titanium oxide-zirconium composite target was carried out in accordance with Example 1.

[0100] Example 4

[0101] This embodiment prepares an oxide thin film, and the specific process is as follows:

[0102] The titanium dioxide-zirconium composite targets prepared in Examples 1-3 and Comparative Examples 1-4 were sputtered onto a 100×100mm (125μm thick) PET substrate using a magnetron sputtering process with Ar:O2 = 4:1, power 200W, and substrate temperature 80℃, respectively, to obtain oxide films of a certain thickness. The films corresponding to Examples 1-3 and Comparative Examples 1-4 are films 1 to 7, with thicknesses of 200nm, 150nm, 250nm, 200nm, 200nm, 200nm, and 200nm, respectively.

[0103] Experimental Example 1

[0104] This experimental example characterizes and tests the titanium dioxide-zirconium composite targets prepared in the examples and comparative examples. The specific process is as follows:

[0105] Grain size testing method: SEM image + cross-section method; Standard basis: ASTM E112;

[0106] Relative density testing method: A fully automatic individual density meter was used, according to GB / T 3850-2015 Method for determining the density of dense sintered metallic materials and cemented carbides.

[0107] The results are shown in Table 1.

[0108] Table 1

[0109]

[0110]

[0111] As can be seen from Table 1, after doping with cerium oxide, the band gap of Example 1 increased from 3.15 eV to 3.52 eV compared to Comparative Example 1.

[0112] Experimental Example 2

[0113] This experimental example characterizes and tests the oxide thin film prepared in Example 4. The specific process is as follows:

[0114] Sheet resistance was tested using an MCP-T700 four-probe resistivity tester.

[0115] Bandgap width: Tauc plot method;

[0116] Resistance change rate: Tested using a four-probe sheet resistance meter (Keithley 2400).

[0117] The bending test is performed according to IEC 62715-6-1, with a bending radius of 1.5 mm. The resistance change rate is measured after 1000 cycles.

[0118] The results are shown in Table 2.

[0119] Table 2

[0120]

[0121] Table 2 shows that the oxide films prepared in the examples have a transmittance exceeding 95%, which is superior to the films in the comparative examples, indicating that doping with cerium oxide or tantalum oxide can improve the optical properties of the films. In Comparative Example 1, no doping was observed, and the resistance increased dramatically after bending, demonstrating that doping with cerium oxide or tantalum oxide plays a crucial role in improving the crack resistance of the films. In Comparative Example 2, the excessive zirconium oxide content led to a decrease in film transmittance. Comparative Example 3 (Ti:Zr = 50:50) had a transmittance <93% due to excessive zirconium content. In Comparative Example 4 (CeO2 = 4%), excessive doping caused grain growth, resulting in a film resistance change rate >12%.

[0122] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A titanium dioxide-zirconium composite target, characterized in that: The preparation materials include the following parts by weight: 65-75 parts of titanium dioxide; 25-35 parts of zirconium oxide; and 0.5–2 parts cerium oxide or 0.1–0.8 parts tantalum oxide; The average particle size of the raw materials used in the preparation does not exceed 200 nm; The average grain size of the titanium dioxide-zirconium composite target is 8.0–12.0 μm.

2. The titanium dioxide-zirconium composite target according to claim 1, characterized in that: The average particle size of the raw materials used in the preparation is 50-190 nm.

3. The titanium dioxide-zirconium composite target according to claim 1, characterized in that: The average grain size of the titanium dioxide-zirconium composite target is 8.5–11.5 μm.

4. The titanium dioxide-zirconium composite target according to claim 1, characterized in that: The relative density of the titanium dioxide-zirconium composite target is above 99.0%.

5. The titanium dioxide-zirconium composite target according to claim 1, characterized in that: The raw materials used in the preparation also include dispersants and / or binders.

6. A method for preparing the titanium dioxide-zirconium composite target according to any one of claims 1 to 5, characterized in that: Includes the following steps: S1: The raw materials are ball-milled in water to obtain a slurry. S2: Spray dry the slurry to obtain a mixed powder; S3: The powder is shaped and sintered to obtain the titanium dioxide zirconium composite target.

7. The method for preparing the titanium dioxide-zirconium composite target according to claim 6, characterized in that: The sintering process satisfies at least one of the following conditions: (I) The sintering is carried out in an oxygen atmosphere; (II) The sintering temperature is 1100–1600℃; (III) The sintering time is 40-80 h; (IV) The heating rate during the sintering process is 0.3 to 1.5 °C / min.

8. A flexible oxide thin film, characterized in that: It includes the titanium dioxide-zirconium composite target material as described in any one of claims 1 to 5.

9. The flexible oxide film according to claim 8, characterized in that: The flexible oxide film satisfies at least one of the following conditions: (I) The transmittance of the flexible oxide film is at least 95.0%; (II) The bandgap of the flexible oxide film is 3.40–3.80 eV; (III) The sheet resistance of the flexible oxide film is 10 to 20 Ω / sq; (IV) The resistivity change rate of the flexible oxide film after bending to a radius of 1.5 mm does not exceed 5%; (V) The oxygen vacancy concentration of the flexible oxide film does not exceed 1×10⁻⁶. 17 pcs / cm 3 .

10. An optical device thin film comprising the flexible oxide thin film of claim 8 or 9.

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