Nickel-based composite oxide sputtering target material and preparation method thereof, and preparation method of nickel-based composite oxide film

Abstract

The invention provides a nickel-based composite oxide sputtering target material and a preparation method thereof, and a preparation method of a nickel-based composite oxide film, and particularly relates to the technical field of nickel-based composite oxides. According to the nickel-based composite oxide sputtering target material provided by the invention, the doped metal oxide exists in the form of a nickel oxide solid solution, and in the nickel-based composite oxide sputtering target material, the content of nickel oxide is 80-99 mol%, the content of nickel is 0.5-10 mol%, and the content of the doped metal oxide is 0.5-10 mol%. According to the nickel-based composite oxide sputtering target material prepared by the preparation method disclosed by the invention, the defect concentration is increased and the conductivity is improved by doping the metal oxide and introducing nickel vacancies; metal nickel is used as an electronic conductive carrier, a conductive network is constructed in a nickel oxide target material, the conductivity of the target material is improved, nickel is used as a sintering aid, the sintering temperature can be reduced, and the sintering relative density can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of nickel-based composite oxides, and in particular relates to a nickel-based composite oxide sputtering target material and a preparation method thereof, and a preparation method of a nickel-based composite oxide film. Background Art

[0002] The role of the perovskite hole transport layer in a perovskite solar cell is to efficiently transport holes and block electron migration. Its characteristics must have appropriate energy level matching with the perovskite, high hole mobility, good light transmittance, etc. Common perovskite cell hole transport materials include nickel oxide, cuprous thiocyanate, copper oxide, molybdenum oxide, etc. Among them, nickel oxide, a wide bandgap semiconductor material, has a stable crystal structure and excellent transmittance in the near-ultraviolet and visible light ranges. The intrinsic point defect in nickel oxide - nickel vacancies, can make nickel oxide exhibit the characteristics of a p-type semiconductor. As a perovskite cell hole transport layer, it can make the perovskite cell have good light and thermal stability and a long service life.

[0003] However, the concentration of nickel vacancies in nickel oxide sintered at high temperature is low, resulting in low intrinsic conductivity of the sintered target, causing the Fermi level of the intrinsic nickel oxide to mismatch with the perovskite photon absorption layer, increasing the energy level offset of the nickel oxide-perovskite contact interface, weakening the built-in electric field strength, and insufficient hole transport capacity; the lower conductivity and mismatched energy levels cause holes to accumulate at the perovskite interface, increasing the probability of carrier recombination, and adversely affecting the photoelectric conversion efficiency of the perovskite cell. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a nickel-based composite oxide sputtering target material and a preparation method thereof, and a preparation method of a nickel-based composite oxide thin film. The nickel-based composite oxide sputtering target material prepared by the present invention has a high nickel vacancy concentration, strong conductivity, low resistivity, and high density. The nickel oxide thin film formed by sputtering thereof is used as a hole transport layer, which can meet the requirements of different perovskite materials for the energy level structure of the hole transport layer and improve the photoelectric conversion efficiency of the perovskite cell.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] The present invention provides a nickel-based composite oxide sputtering target material, wherein the nickel-based composite oxide sputtering target material comprises nickel oxide, nickel and a doped metal oxide;

[0007] The doped metal oxide exists in the form of a nickel oxide solid solution;

[0008] The nickel-based composite oxide sputtering target has a nickel oxide content of 80-99 mol %, a nickel content of 0.5-10 mol %, and a doped metal oxide content of 0.5-10 mol %.

[0009] Preferably, the doped metal in the doped metal oxide includes at least one of Li, Na, Mg, Al, Ca, Ti, V, Mn, Fe, Co, Cu, Zn, Ga, Sr, Y, Nb, Mo, Ag, In, Sn and Ta.

[0010] Preferably, the relative density of the nickel-based composite oxide sputtering target is 95-99.5%.

[0011] The present invention also provides a method for preparing the nickel-based composite oxide sputtering target described in the above technical solution, comprising the following steps:

[0012] Mixing nickel powder, nickel oxide powder, doped metal oxide powder and water and grinding them to obtain a mixed slurry;

[0013] The mixed slurry is spray-dried to obtain spherical granulated powder;

[0014] Pressing the spherical granulated powder into a shape to obtain a target blank;

[0015] The target material blank is subjected to segmented vacuum gradient sintering to obtain the nickel-based composite oxide sputtering target material.

[0016] Preferably, the segmented vacuum gradient sintering includes sequentially performing a first heating, a first vacuum sintering, a second heating and a second vacuum sintering, the temperature of the first vacuum sintering is 750-850°C; the temperature of the second vacuum sintering is 1250-1600°C.

[0017] Preferably, the vacuum pressure of the segmented vacuum gradient sintering is less than 0.1 Pa.

[0018] Preferably, the inlet temperature of the spray drying is 200-300°C, and the outlet temperature is 100-120°C;

[0019] The particle size D50 of the spherical granulated powder is 30 to 60 μm.

[0020] Preferably, the mass ratio of water to nickel oxide powder is 1 to 3:1.

[0021] The present invention also provides a method for preparing a nickel-based composite oxide film, comprising the following steps:

[0022] Sputtering the nickel-based composite oxide sputtering target prepared by the preparation method described in the above technical solution to obtain the nickel-based composite oxide thin film;

[0023] The sputtering pressure is 1-3 Pa, the oxygen partial pressure is 0.6-1.2 Pa, and the oxygen partial pressure is less than the sputtering pressure.

[0024] Preferably, the working power source of the sputtering is a radio frequency power source, and the power density of the sputtering is 1.5 to 2.5 W / cm 2 , sputtering vacuum degree <6.0×10 -4 Pa.

[0025] The invention provides a nickel-based composite oxide sputtering target, which comprises nickel oxide, nickel and doped metal oxide; the doped metal oxide exists in the form of nickel oxide solid solution; the content of nickel oxide in the nickel-based composite oxide sputtering target is 80-99 mol%, the content of nickel is 0.5-10 mol%, and the content of doped metal oxide is 0.5-10 mol%. The invention introduces nickel vacancies by doping metal oxides, increases defect concentration, and thus improves conductivity; the doped metal cations can regulate the energy level structure of nickel oxide to meet the requirements of different perovskite materials for the energy level structure of the hole transport layer, thereby improving the photoelectric conversion efficiency of the perovskite cell; metal nickel is dispersed in the nickel oxide target as an electronic conductive carrier, and a conductive network is constructed in the nickel oxide target to transmit electrons, thereby improving the conductivity of the target.

[0026] In addition, the melting point of nickel is 1453°C, and the melting point of nickel oxide is 1990°C. Nickel can act as a process sintering aid, reducing the sintering temperature of the target material and increasing the sintering density of the target material.

[0027] The nickel-based composite oxide sputtering target obtained by the present invention is in a nickel-rich and oxygen-deficient state through component regulation, thereby improving the conductivity of the target material, increasing the density of the target material, reducing the probability of abnormal discharge and sparking during target sputtering, reducing the impurity content and defects in the film, increasing the density and uniformity of the film, and thus improving the quality and performance of the film. At the same time, a higher sputtering rate can be provided during the sputtering process, shortening the production cycle and improving production efficiency.

[0028] The present invention also provides a method for preparing a nickel-based composite oxide thin film. When a nickel-based composite oxide target is used for magnetron sputtering film formation, the oxygen content of the film components is changed by adjusting the oxygen partial pressure in the sputtering environment, so that the nickel oxide is transformed from the nickel-rich and oxygen-deficient state of the target to the oxygen-rich and nickel-deficient state of the film, and the conductive mechanism is transformed from electron conduction to hole conduction, thereby meeting the use requirements of the hole transport layer of the perovskite battery.

[0029] The results of the examples show that the target relative density of the nickel-based composite oxide sputtering target prepared by the present invention is 95-99.5%, and the target resistivity is 3.89×10 -5 ~1.67×10 -2 Ω·cm, with high sintering density and good conductivity. The film made by sputtering target of nickel-based composite oxide has a carrier concentration of 2.71×10 18 ~4.14×10 19 / cm3, the film mobility is 0.62~1.26cm2 / V·s, and the film resistivity is 1.83×10 -2 ~2.92×10 -1 Ω·cm, and the film transmittance is 80~85.5%. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0031] Figure 1 XRD diagram of the nickel-based composite oxide target prepared in Example 1 and Comparative Examples 1-2;

[0032] Figure 2 This is a SEM image of the thin film obtained by sputtering the nickel-based composite oxide target prepared in Example 1. DETAILED DESCRIPTION

[0033] The present invention provides a nickel-based composite oxide sputtering target material, wherein the nickel-based composite oxide sputtering target material comprises nickel oxide, nickel and a doped metal oxide;

[0034] The doped metal oxide exists in the form of a nickel oxide solid solution;

[0035] The nickel-based composite oxide sputtering target has a nickel oxide content of 80-99 mol %, a nickel content of 0.5-10 mol %, and a doped metal oxide content of 0.5-10 mol %.

[0036] In the present invention, unless otherwise specified, the raw materials and equipment used are commercially available products well known in the art.

[0037] In the present invention, the nickel-based composite oxide sputtering target comprises nickel oxide, nickel and doped metal oxide.

[0038] In the present invention, the content of nickel oxide in the nickel-based composite oxide sputtering target is 80-99 mol%. In a specific embodiment, the content of nickel oxide in the nickel-based composite oxide sputtering target can be 80 mol%, 85 mol%, 88 mol%, 90 mol%, 92 mol%, 93 mol%, 94 mol% or 99 mol%.

[0039] In the present invention, the nickel content is 0.5-10 mol%. In a specific embodiment, the nickel content can be 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 5 mol% or 10 mol%.

[0040] In the present invention, the content of the doped metal oxide is 0.5-10 mol%. In a specific embodiment, the content of the doped metal oxide can be 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 5 mol% or 10 mol%. In the present invention, the doped metal oxide exists in the form of nickel oxide solid solution.

[0041] In the present invention, the doped metal in the doped metal oxide preferably includes at least one of Li, Na, Mg, Al, Ca, Ti, V, Mn, Fe, Co, Cu, Zn, Ga, Sr, Y, Nb, Mo, Ag, In, Sn and Ta.

[0042] In the present invention, the relative density of the nickel-based composite oxide sputtering target is preferably 95-99.5%. In a specific embodiment, the relative density of the nickel-based composite oxide sputtering target can be 95%, 95.8%, 97.7%, 98.1%, 98.3%, 98.6%, 98.9%, 99.4% or 99.5%.

[0043] The present invention introduces nickel vacancies by doping metal oxides, thereby increasing the defect concentration and improving the electrical conductivity. The doped metal cations can regulate the energy level structure of nickel oxide to meet the requirements of different perovskite materials for the energy level structure of the hole transport layer, thereby improving the photoelectric conversion efficiency of the perovskite cell. Metal nickel is dispersed in the nickel oxide target material as an electronic conductive carrier, and a conductive network is constructed in the nickel oxide target material to transmit electrons, thereby improving the electrical conductivity of the target material. The melting point of nickel is 1453° C., and the melting point of nickel oxide is 1990° C. Nickel can play the role of a process sintering aid, thereby reducing the sintering temperature of the target material and increasing the sintering density of the target material. Through the composition regulation, the obtained nickel-based composite oxide sputtering target material is in a nickel-rich oxygen-deficient state, thereby improving the electrical conductivity of the target material, increasing the density of the target material, and reducing the probability of abnormal discharge and sparking during the sputtering of the target material. During sputtering, the impurity content and defects in the film can be reduced, the compactness and uniformity of the film can be improved, thereby improving the quality and performance of the film. At the same time, a higher sputtering rate can be provided during the sputtering process, the production cycle can be shortened, and the production efficiency can be improved.

[0044] The present invention also provides a method for preparing the nickel-based composite oxide sputtering target described in the above technical solution, comprising the following steps:

[0045] Mixing nickel powder, nickel oxide powder, doped metal oxide powder and water and grinding them to obtain a mixed slurry;

[0046] The mixed slurry is spray-dried to obtain spherical granulated powder;

[0047] Pressing the spherical granulated powder into a shape to obtain a target blank;

[0048] The target material blank is subjected to segmented vacuum gradient sintering to obtain the nickel-based composite oxide sputtering target material.

[0049] The invention mixes nickel powder, nickel oxide powder, doped metal oxide powder and water, and grinds the mixture to obtain mixed slurry.

[0050] In the present invention, the mass ratio of water to nickel oxide powder is preferably 1 to 3:1. In a specific embodiment, the mass ratio of water to nickel oxide can be 1:1, 1.5:1, 2:1, 2.5:1 or 3:1.

[0051] In the present invention, the particle size D50 of the nickel oxide powder is preferably 0.1 to 5 μm. In a specific embodiment, the particle size D50 of the nickel oxide can be 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm. In the present invention, the purity of the nickel oxide is preferably >99.9%.

[0052] In the present invention, the particle size D50 of the nickel powder is preferably 0.1 to 5 μm. In a specific embodiment, the particle size D50 of the nickel can be 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm. In the present invention, the purity of the nickel is preferably >99.99%.

[0053] In the present invention, the particle size D50 of the doped metal oxide powder is preferably 0.1-2 μm. In a specific embodiment, the particle size D50 of the doped metal oxide powder may be 0.1 μm, 0.5 μm, 1 μm, 1.5 μm or 2 μm.

[0054] The present invention has no special requirements on the mixing method, and the commonly used technical means in the field can be adopted.

[0055] In the present invention, the sanding is preferably performed using a sand grinder, and the sanding rotation speed is preferably 2000-2500rpm. In a specific embodiment, the sanding rotation speed is preferably 2000rpm, 2200rpm or 2500rpm; the sanding time is preferably 1-3h. In a specific embodiment, the sanding time can be 1h, 2h or 3h.

[0056] After obtaining the mixed slurry, the present invention spray-dries the mixed slurry to obtain spherical granulated powder.

[0057] In the present invention, the inlet temperature of the spray drying is preferably 200-300°C. In a specific embodiment, the inlet temperature of the spray drying can be 200°C, 250°C or 300°C. The outlet temperature of the spray drying is preferably 100-120°C. In a specific embodiment, the outlet temperature of the spray drying can be 100°C, 110°C or 120°C.

[0058] In the present invention, the particle size D50 of the spherical granulated powder is preferably 30 to 60 μm. In a specific embodiment, the particle size D50 of the spherical granulated powder may be 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm or 60 μm.

[0059] After obtaining the spherical granulated powder, the present invention presses the spherical granulated powder into a shape to obtain a target blank.

[0060] In the present invention, the molding method is preferably at least one of compression molding, slip casting, cold isostatic pressing, hot pressing and hot isostatic pressing. In the present invention, when the molding method is cold isostatic pressing, the pressure of the cold isostatic pressing is preferably 250-350 MPa. In a specific embodiment, the pressure of the cold isostatic pressing can be 250 MPa, 300 MPa or 350 MPa; the time is preferably 1-3 hours. In a specific embodiment, the time can be 1 hour, 2 hours or 3 hours.

[0061] After obtaining the target material blank, the present invention performs segmented vacuum gradient sintering on the target material blank to obtain the nickel-based composite oxide sputtering target.

[0062] In the present invention, the segmented vacuum gradient sintering preferably includes a first heating, a first vacuum sintering, a second heating and a second vacuum sintering in sequence. The temperature of the first vacuum sintering is preferably 750-850°C. In a specific embodiment, the temperature of the first vacuum sintering may be 750°C, 800°C or 850°C; the first heating rate is preferably 1-3°C / min. In a specific embodiment, the first heating rate may be 1°C / min, 2°C / min or 3°C / min; the holding time of the first vacuum sintering is preferably 4-8h. In a specific embodiment, the holding time of the first vacuum sintering may be 4h, 6h or 8h.

[0063] In the present invention, the temperature of the second vacuum sintering is preferably 1250-1600°C. In a specific embodiment, the temperature of the second vacuum sintering may be 1250°C, 1300°C, 1350°C, 1400°C, 1450°C, 1500°C, 1550°C or 1600°C; the second heating rate is preferably 0.3-1°C / min. In a specific embodiment, the second heating rate may be 0.3°C / min, 0.5°C / min, 0.7°C / min or 1°C / min; the holding time of the second vacuum sintering is preferably 10-20h. In a specific embodiment, the holding time of the second vacuum sintering may be 10h, 12h, 15h, 18h or 20h.

[0064] In the present invention, the protective atmosphere during the segmented vacuum gradient sintering is preferably nitrogen.

[0065] In the present invention, the vacuum pressure of the segmented vacuum gradient sintering is preferably <0.1 Pa.

[0066] The present invention also provides a method for preparing a nickel-based composite oxide film, comprising the following steps:

[0067] Sputtering the nickel-based composite oxide sputtering target described in the above technical solution to obtain the nickel-based composite oxide film;

[0068] The sputtering pressure is 1-3 Pa, and the oxygen partial pressure is 0.6-1.2 Pa, and the oxygen partial pressure is lower than the sputtering pressure.

[0069] In the present invention, the sputtering pressure is preferably 1-3Pa, and in a specific embodiment, the sputtering pressure may be 1Pa, 2Pa or 5Pa; the oxygen partial pressure is preferably 0.6-1.2Pa, and in a specific embodiment, the oxygen partial pressure may be 0.6Pa, 0.8Pa, 1.0Pa or 1.2Pa.

[0070] In the present invention, the working power source of the sputtering is preferably a radio frequency power source, and the power density of the sputtering is preferably 1.5 to 2.5 W / cm 2 In a specific embodiment, the power density of the sputtering can be 1.5 W / cm 2 , 2W / cm 2 or 2.5W / cm 2 The sputtering vacuum is preferably <6.0×10 -4 Pa.

[0071] In the present invention, the film thickness of the nickel-based composite oxide thin film is preferably 20-30 nm. In a specific embodiment, the film thickness of the nickel-based composite oxide thin film may be 20 nm, 25 nm or 30 nm.

[0072] The present invention has no special requirements for the specific implementation of the sputtering, and an implementation known in the art can be adopted. Specifically, the nickel-based composite oxide sputtering target is bound to a copper back plate, placed in a magnetron sputtering coating machine, and a thin film is deposited on the glass.

[0073] The method for preparing the nickel-based composite oxide sputtering target provided by the present invention changes the oxygen content of the film components by adjusting the oxygen partial pressure in the sputtering environment, so that the nickel oxide is transformed from the nickel-rich and oxygen-deficient state of the target to the oxygen-rich and nickel-deficient state of the film, and the conductive mechanism is transformed from electron conduction to hole conduction, thereby meeting the use requirements of the hole transport layer of the perovskite battery.

[0074] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described in conjunction with specific embodiments below. The described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Any modification, equivalent replacement, improvement, etc. made to the implementation methods of the present invention based on the technical essence and general principles of the present invention without creative work should be within the scope of protection of the present invention.

[0075] Example 1

[0076] Nickel powder, nickel oxide powder and copper oxide powder were mixed in a molar ratio of 0.01:0.94:0.05, and pure water twice the mass of nickel oxide was added, and the mixture was transferred to a sand mill and sanded at 2200rpm for 2h to obtain a mixed slurry. Among them, the nickel powder D50 was 0.5μm, and the purity was greater than 99.99%, the nickel oxide powder D50 was 0.5μm, and the purity was greater than 99.9%, and the copper oxide powder D50 was 0.2μm, and the purity was greater than 99.95%. The mixed slurry was spray dried, and the inlet temperature was set to 250℃ and the outlet temperature was set to 105℃ to obtain a spherical granulated powder with a D50 of 45μm.

[0077] The spherical granulated powder is filled into the rubber sleeve, sealed after being fully filled, and cold isostatically pressed at 300 MPa for 2 hours to obtain a target blank. The target blank is sintered in a vacuum atmosphere sintering furnace with nitrogen as the protective atmosphere, heated to 800°C at 2°C / min, kept warm for 6 hours, then heated to 1350°C at 0.5°C / min, kept warm for 12 hours, and placed in a cooler to obtain a nickel-based composite oxide target.

[0078] The prepared nickel-based composite oxide target was bound to a copper backplane and placed in a magnetron sputtering coating machine. The working power source was a radio frequency power source. The sputtering power density was 2W / cm 2 , vacuum degree is less than 6.0×10 -4 Pa, sputtering pressure 2Pa, oxygen partial pressure 1Pa, a film with a thickness of 25nm was deposited on the glass to obtain a nickel-based composite oxide film.

[0079] Example 2

[0080] Nickel powder, nickel oxide powder and aluminum oxide powder were mixed in a molar ratio of 0.01:0.94:0.05. Other conditions were the same as those in Example 1.

[0081] Example 3

[0082] Nickel powder, nickel oxide powder and vanadium pentoxide powder were mixed in a molar ratio of 0.01:0.94:0.05. Other conditions were the same as those in Example 1.

[0083] Example 4

[0084] Nickel powder, nickel oxide powder and lithium oxide powder were mixed in a molar ratio of 0.01:0.94:0.05. Other conditions were the same as those in Example 1.

[0085] Example 5

[0086] Nickel powder, nickel oxide powder and copper oxide powder were mixed in a molar ratio of 0.02:0.93:0.05. Other conditions were the same as those in Example 1.

[0087] Example 6

[0088] Nickel powder, nickel oxide powder and copper oxide powder were mixed in a molar ratio of 0.05:0.9:0.05. Other conditions were the same as those in Example 1.

[0089] Example 7

[0090] When sintering in a vacuum atmosphere sintering furnace, the temperature was raised to 800° C. at 2° C. / min and kept at that temperature for 6 h, then raised to 1450° C. at 0.5° C. / min and kept at that temperature for 12 h. Other conditions were the same as those in Example 1.

[0091] Example 8

[0092] When sintering in a vacuum atmosphere sintering furnace, the temperature was raised to 800° C. at 2° C. / min and kept at that temperature for 6 h, then raised to 1550° C. at 0.5° C. / min and kept at that temperature for 12 h. Other conditions were the same as those in Example 1.

[0093] Comparative Example 1

[0094] Nickel oxide powder and pure water were mixed in a mass ratio of 1:2 and sand-milled. Other conditions were the same as those in Example 1.

[0095] Comparative Example 2

[0096] Nickel oxide powder and copper oxide powder were mixed at a molar ratio of 0.95:0.05. Other conditions were the same as those in Example 1.

[0097] Comparative Example 3

[0098] The oxygen partial pressure was 0 Pa, and other conditions were the same as those in Example 1.

[0099] Comparative Example 4

[0100] The oxygen partial pressure was 0.5 Pa, and other conditions were the same as those in Example 1.

[0101] The density test and resistivity test of the target materials obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were performed using the Archimedean drainage method test and the four-probe square resistance tester test. The transmittance of the films prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was tested in the 300 to 1400 nm band using a Cary5000 UV spectrophotometer; the films were cut into 15×15 mm squares, and then the resistivity, mobility, and carrier concentration of the films were tested using a CH-50 Hall effect instrument. The results are shown in Table 1.

[0102] Table 1 Density and resistivity of the targets prepared in Examples 1 to 5 and Comparative Examples 1 to 4, and transmittance, resistivity, mobility and carrier concentration of the films prepared from the targets

[0103]

[0104] As shown in Table 1, the conductivity of the pure nickel oxide target (Comparative Example 1) is extremely poor, with a resistivity of >10 6 Ω·cm, the resistivity of the targets prepared by adding nickel powder (Examples 1 to 8 and Comparative Examples 2 to 4) decreased significantly, reaching 10 -3 ~10 -2 Ω·cm, the conductivity of the target material is significantly improved; at the same time, the sintering density of the target material prepared by adding nickel powder is significantly improved. Comparative Examples 3 to 4 are sputtered under relatively low oxygen partial pressure conditions, and the deposited film contains a small amount of metallic nickel, so the resistivity is significantly reduced and the mobility is significantly improved, but the conductive mechanism is mainly electronic conduction, and the transmittance is low, so it cannot be used as a hole transport layer for perovskite batteries. By increasing the oxygen partial pressure to enhance the efficiency of reactive sputtering, the target material is transformed from a nickel-rich state to an oxygen-rich state of the film, and the conductive principle is transformed from electronic conduction to hole conduction, so as to meet the use requirements of the hole transport layer of the perovskite battery.

[0105] The target materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 were crushed, and the target phase composition was analyzed by XRD. Figure 1 As can be seen from the figure, no phase other than nickel oxide was detected in Comparative Example 1 and Comparative Example 2, indicating that the doped metal oxide was incorporated into the nickel oxide lattice in the form of a solid solution. Nickel oxide phase and metallic nickel phase were detected in Example 1, indicating that the nickel element in the target material exists in the form of nickel oxide and metallic nickel.

[0106] After the target material prepared in Example 1 was sputtered into a film, the film morphology was observed using SEM. Figure 2As can be seen from the figure, the nickel thin film prepared by using the nickel-based composite oxide target obtained in Example 1 has fine grains, an average grain size of <10 nm, a dense and uniform film distribution, and good film quality.

[0107] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A nickel-based composite oxide sputtering target, characterized in that: The nickel-based composite oxide sputtering target comprises nickel oxide, nickel and doped metal oxide; The doped metal oxide exists in the form of nickel oxide solid solution; The nickel-based composite oxide sputtering target has a nickel oxide content of 80-99 mol%, a nickel content of 0.5-10 mol%, and a doped metal oxide content of 0.5-10 mol%.

2. The nickel-based composite oxide sputtering target according to claim 1, wherein The doping metal in the doped metal oxide includes at least one of Li, Na, Mg, Al, Ca, Ti, V, Mn, Fe, Co, Cu, Zn, Ga, Sr, Y, Nb, Mo, Ag, In, Sn and Ta.

3. The nickel-based composite oxide sputtering target according to claim 1, wherein The relative density of the nickel-based composite oxide sputtering target is 95-99.5%.

4. The method for preparing a nickel-based composite oxide sputtering target according to any one of claims 1 to 3, characterized in that: The following steps are involved: Mixing nickel powder, nickel oxide powder, doped metal oxide powder and water and sand-grinding to obtain a mixed slurry; spray drying the mixed slurry to obtain spherical granulated powder; Pressing the spherical granulated powder into a shape to obtain a target blank; The target material blank is subjected to segmented vacuum gradient sintering to obtain the nickel-based composite oxide sputtering target material.

5. The preparation method according to claim 4, characterized in that The segmented vacuum gradient sintering includes sequentially performing a first heating, a first vacuum sintering, a second heating, and a second vacuum sintering. The temperature of the first vacuum sintering is 750-850° C.; the temperature of the second vacuum sintering is 1250-1600° C.

6. The preparation method according to claim 4, characterized in that The vacuum pressure of the segmented vacuum gradient sintering is less than 0.1 Pa.

7. The preparation method according to claim 4, characterized in that The inlet temperature of the spray drying is 200-300°C, and the outlet temperature is 100-120°C; The particle size D50 of the spherical granulated powder is 30 to 60 μm.

8. The preparation method according to claim 4, characterized in that The mass ratio of the water to the nickel oxide powder is 1 to 3:

1.

9. A method for preparing a nickel-based composite oxide film, characterized in that: The following steps are involved: Sputtering the nickel-based composite oxide sputtering target according to any one of claims 1 to 3 or the nickel-based composite oxide sputtering target prepared by the preparation method according to any one of claims 4 to 8 to obtain the nickel-based composite oxide thin film; The sputtering pressure is 1-3 Pa, the oxygen partial pressure is 0.6-1.2 Pa, and the oxygen partial pressure is smaller than the sputtering pressure.

10. The preparation method according to claim 9, characterized in that The working power source of the sputtering is a radio frequency power source, and the power density of the sputtering is 1.5 to 2.5 W / cm 2 , sputtering vacuum degree <6.0×10 -4 Pa.

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