CN-121976159-A - High-density praseodymium-zinc co-doped tin oxide sputtering target material and preparation method thereof

Abstract

The invention relates to a high-density praseodymium-zinc co-doped tin oxide sputtering target material and a preparation method thereof, belonging to the technical field of high-performance transparent conductive oxide targets. In order to solve the technical bottlenecks that the existing antimony-doped or fluorine-doped tin oxide target material is insufficient in stability and single doping is difficult to realize high conductivity and high density simultaneously, the invention provides a method for carrying out collaborative co-doping by taking tin oxide as a matrix and adopting praseodymium and zinc. The praseodymium inhibits oxygen vacancies and improves intrinsic stability through the unique valence variation characteristics of the praseodymium, and the zinc is used as an efficient sintering aid to promote densification and finely regulate and control electrical properties. Through the cooperation of the two, the restriction relation between performance parameters is successfully broken, and the prepared target material has high relative density, low resistivity and excellent thermal stability and environmental stability. The target is particularly suitable for preparing high-performance transparent conductive films by magnetron sputtering, and has wide application prospects in the fields of flexible display, perovskite solar cells and the like.

Inventors

• LIU JIANXIONG
• LIANG YINGXIANG
• HU TING
• ZHANG BEIWEI
• WU SONGHUI
• HUANG ZUO
• MO BIN
• HUANG SHICHENG
• LU YINGDONG
• SONG CHUNHUA

Assignees

• 广西晶联光电材料有限责任公司

Dates

Publication Date

20260505

Application Date

20260108

Claims (6)

1. 1. A high-density praseodymium and zinc co-doped tin oxide sputtering target is characterized by comprising a tin oxide matrix, and doping elements praseodymium and zinc, wherein the doping amount of the praseodymium element is 0.5-5at% and the doping amount of the zinc element is 1-8at% based on the total mole number of metal cations.
2. 2. The high-density praseodymium-zinc co-doped tin oxide sputtering target according to claim 1, wherein the doping amount of praseodymium element is 1-3at% and the doping amount of zinc element is 2-5at% based on the total mole number of metal cations.
3. 3. The high-density praseodymium-zinc co-doped tin oxide sputtering target according to claim 1 or 2, wherein the relative density of the target is not lower than 98.5%, and the volume resistivity is not higher than 6.0×10 -3 Ω·cm.
4. 4. A method of preparing a high density praseodymium zinc co-doped tin oxide sputter target according to any one of claims 1 to 3, comprising the steps of: (a) Weighing a tin source, a praseodymium source and a zinc source according to the proportion, and performing wet ball milling and mixing to obtain uniform mixed slurry; (b) Drying the mixed slurry, and calcining for 2-6 hours in an air atmosphere at 800-1100 ℃ to obtain praseodymium-zinc co-doped tin oxide solid solution powder; (c) Adding a binder into the solid solution powder, granulating and sieving; (d) Compacting the granulated powder to obtain a biscuit; (e) And sintering the biscuit in an oxygen-containing atmosphere at 1250-1550 ℃ for 5-15 hours to obtain the praseodymium-zinc co-doped tin oxide sputtering target.
5. 5. The method for preparing a high-density praseodymium-zinc co-doped tin oxide sputtering target according to claim 4, wherein in the step (e), the sintering is performed in an atmosphere with an oxygen volume fraction of not less than 20%, and the sintering temperature is 1400-1500 ℃.
6. 6. The method of claim 4 or 5, wherein in step (a), the tin source, praseodymium source and zinc source are tin oxide, praseodymium oxide and zinc oxide.

Description

High-density praseodymium-zinc co-doped tin oxide sputtering target material and preparation method thereof Technical Field The invention belongs to the technical field of functional ceramic materials, and particularly relates to a transparent conductive oxide target material for a magnetron sputtering technology, in particular to a praseodymium-zinc co-doped tin oxide sputtering target material with high density, low resistance and excellent stability and a preparation method thereof. Background Tin oxide (SnO 2) is an important n-type wide bandgap semiconductor and is widely used as a raw material for transparent conductive oxide films due to its good optical transparency and chemical stability. Magnetron sputtering is the dominant technique for preparing such films, whose performance is highly dependent on the quality of the target. Currently, commercial tin oxide targets improve their conductivity mainly by doping with antimony or fluorine. However, these conventional techniques have inherent drawbacks: 1. Antimony doped tin oxide (ATO) is characterized in that Sb 5+ is easily reduced to Sb 3+ under long-term use or high-temperature environment, so that the concentration of carriers is reduced, the resistivity is increased, and the performance is unstable. 2. Fluorine doped tin oxide (FTO) is characterized in that fluorine element is easy to volatilize in the high-temperature preparation process, so that the components of the film deviate, the performance is uneven, and the film has certain corrosiveness to equipment. In addition, tin oxide itself has low sintering activity, and it is difficult to prepare a high-density target (> 98%). The low-density target material is easy to generate microparticles and knots during sputtering, and influences the film quality and the deposition rate. Zinc oxide (ZnO) is also used as a common dopant to improve the sintering properties of tin oxide. For example, chinese patent (CN 113563063B) discloses a highly dense fine-grained zinc oxide doped tin oxide ceramic target and a preparation method thereof, which effectively improves the compactness of the target by finely adjusting and controlling ball milling, sand milling and sintering processes. However, the technology of this patent focuses mainly on solving densification problems through physical process optimization and single element (Zn) doping, and its target phase is composed of SnO 2 and Zn 2SnO4, and does not intrinsically solve the core challenges of insufficient long-term stability of electrical properties faced by tin oxide-based targets, especially when replacing ATO targets. Single doping of zinc is difficult to inhibit the generation and migration of oxygen vacancies of tin oxide in service environment, which is a key factor causing attenuation degradation of conductivity. Therefore, there is an urgent need in the art for a novel tin oxide target that can simultaneously achieve high conductivity, high density, and excellent long-term stability, so as to break through the limitations of the prior art. Disclosure of Invention The invention aims to solve the technical problems of providing a high-density praseodymium-zinc co-doped tin oxide sputtering target and a preparation method thereof, wherein tin oxide is taken as a matrix, praseodymium and zinc are adopted for cooperative co-doping, praseodymium element inhibits oxygen vacancies and improves intrinsic stability through the unique valence variation characteristics of the praseodymium element, zinc element is taken as an efficient sintering aid to promote densification and finely regulate and control electrical properties, and the preparation of the high-density, low-resistance and high-stability tin oxide sputtering target is realized through the cooperation of the praseodymium element and the zinc element. The technical scheme for solving the technical problems is that the high-density praseodymium-zinc co-doped tin oxide sputtering target comprises a tin oxide matrix, and doped elements praseodymium and zinc, wherein the doping amount of the praseodymium element is 0.5-5at% and the doping amount of the zinc element is 1-8at% based on the total mole number of metal cations. Furthermore, based on the total mole number of metal cations, the doping amount of praseodymium is 1-3at% and the doping amount of zinc is 2-5at%. Further, the relative density of the target is not lower than 98.5%, and the volume resistivity is not higher than 6.0X10 -3 Ω cm. The preparation method of the high-density praseodymium-zinc co-doped tin oxide sputtering target material comprises the following steps: (a) Weighing a tin source, a praseodymium source and a zinc source according to the proportion, and performing wet ball milling and mixing to obtain uniform mixed slurry; (b) Drying the mixed slurry, and calcining for 2-6 hours in an air atmosphere at 800-1100 ℃ to obtain praseodymium-zinc co-doped tin oxide solid solution powder; (c) Adding a binder into the solid solut