CN-122013319-A - Two-dimensional non-layered metal oxide film growth method based on electrochemical driving passivation liquid metal printing and application thereof

Abstract

The invention discloses a two-dimensional non-layered metal oxide film growing method based on electrochemical driving passivation liquid metal printing and application thereof, the invention puts high-purity metal on a Al foil bearing high-purity metal substrate, heats the high-purity metal, removes oxide with impurities on the surface after the high-purity metal is melted and oxidized, exposes fresh liquid high-purity metal, the transfer substrate is used for touching the surface of the liquid high-purity metal to paste a metal oxide film, the liquid high-purity metal on the surface of the substrate is removed, and the ultrathin (the thickness is lower than 2 nm) large-area two-dimensional non-layered metal oxide film is obtained. The memristor provided by the invention has the switching ratio of >10 4 , the retention time of >10 4 s and the fatigue resistance of >10 4 cycles, the recognition precision of the neuromorphic encryption image is 98.6%, and a foundation is laid for a new-generation neuromorphic calculation chip.

Inventors

• TAN SHIJIA
• GENG DECHAO
• LI LIN
• ZHANG QING

Assignees

• 天津大学

Dates

Publication Date

20260512

Application Date

20260128

Priority Date

20250929

Claims (10)

1. 1. Placing high-purity metal on a high-purity metal bearing substrate, heating, melting and oxidizing the high-purity metal, removing oxide with impurities on the surface, exposing fresh liquid high-purity metal, lightly touching the surface of the liquid high-purity metal by using a transfer substrate to paste a metal oxide film, and removing the liquid high-purity metal on the surface of the transfer substrate to obtain the two-dimensional non-layered metal oxide film; the bearing high-purity metal substrate is an Al foil.
2. 2. The method for growing a two-dimensional non-layered metal oxide film based on electrochemical driving passivation liquid metal printing according to claim 1, wherein the high purity metal is selected from Bi, zn or In, and the purity is not lower than 99.99%.
3. 3. The method for growing a two-dimensional non-layered metal oxide film based on electrochemically driven passivation liquid metal printing according to claim 1, wherein the heating temperature is not lower than the melting point of the high-purity metal.
4. 4. The two-dimensional non-layered metal oxide thin film growth method based on electrochemically driven passivation liquid metal printing according to claim 2, wherein when the high purity metal is Bi, the heating temperature is 300-350 ℃; and/or, when the high-purity metal is Zn, the heating temperature is 400-450 ℃; and/or, when the high purity metal is In, the heating temperature is 200-250 ℃.
5. 5. The method for growing a two-dimensional non-layered metal oxide film based on electrochemically driven passivation liquid metal printing according to claim 1, characterized in that the high-purity metal-carrying substrate further comprises a polishing step before use.
6. 6. The method for growing a two-dimensional non-layered metal oxide film based on electrochemical driving passivation liquid metal printing according to claim 1, wherein the transfer substrate further comprises a pretreatment step of sequentially performing ultrasonic cleaning of ultrapure water, acetone, isopropanol and ethanol, nitrogen blow-drying, and oxygen plasma treatment before use.
7. 7. The method for growing a two-dimensional non-layered metal oxide thin film based on electrochemically driven passivation liquid metal printing according to claim 1, wherein the oxidation time is 1-30s.
8. 8. A two-dimensional non-layered metal oxide film prepared according to the preparation method of any one of claims 1 to 7.
9. 9. Use of the two-dimensional non-layered metal oxide thin film of claim 8 in the fabrication of memristors.
10. 10. A memristor prepared from the two-dimensional non-layered metal oxide thin film of claim 8.

Description

Two-dimensional non-layered metal oxide film growth method based on electrochemical driving passivation liquid metal printing and application thereof Technical Field The invention belongs to the technical field of two-dimensional non-layered materials and electronic devices, and particularly relates to a two-dimensional non-layered metal oxide film growth method based on electrochemical driving passivation liquid metal printing and application thereof. Background Two-dimensional (2D) metal oxides have broad application prospects in the fields of electronics, optoelectronics, energy storage and conversion, etc., thanks to their wide band gap, high dielectric constant, excellent mechanical flexibility and memristive properties. Among them, two-dimensional non-layered metal oxide thin films (NMOs) are an important subclass that overcome the structural limitations of conventional three-dimensional metal oxides and exhibit unique electronic structures, surface activity, and optical properties. A large number of unsaturated dangling bonds exist on the surface of the two-dimensional NMOs, so that the material is endowed with rich active sites. The characteristic enables the material to show extremely high activity in adsorption and catalytic reaction, and the performance of the material in catalytic and sensing application is remarkably improved. However, the high reactivity of these dangling bonds often results in undesirable chemical reactions or structural rearrangements during thinning of the material, thereby compromising the stability and performance of the material. This presents a key challenge for achieving further thickness reduction. In this context, researchers have explored a variety of synthetic methods to prepare two-dimensional NMOs. However, the operational challenges presented by the complexity of existing Chemical Vapor Deposition (CVD) processes continue to exist during development. On this basis, a Liquid Metal Printing (LMP) process is established. The liquid metal has an atomically flat surface, so that the liquid metal becomes an ideal natural platform for synthesizing two-dimensional materials. The atomic level flat surface and the ultra-high surface mobility facilitate the synthesis of ultra-thin, uniform oxide layers. However, most LMP methods to date require the synthesis of metal oxides in a glove box under an oxygen controlled environment (10-100 ppm), which brings about severe operating conditions. Therefore, providing a simple and environmentally compatible synthesis method for preparing large-area ultrathin two-dimensional NMOs, which effectively improves the performance of NMOs in the fields of electronic devices and the like, is a problem to be solved by those skilled in the art. Disclosure of Invention In order to solve the technical problems, the invention provides a two-dimensional non-layered metal oxide film growth method based on electrochemical driving passivation liquid metal printing and application thereof. The method provided by the invention has high controllability and repeatability, provides a high-efficiency technical means for preparing a large-area ultrathin two-dimensional non-layered metal oxide film material, and solves the technical problem that the non-layered metal oxide film is difficult to thin. The method is accurate in control and suitable for preparing the large-area ultrathin two-dimensional non-layered metal oxide film material. In order to achieve the above purpose, the present invention provides the following technical solutions: Placing high-purity metal on a high-purity metal bearing substrate, heating, melting and oxidizing the high-purity metal, removing oxide with impurities on the surface, exposing fresh liquid high-purity metal, lightly touching the surface of the liquid high-purity metal by using a transfer substrate to paste a metal oxide film, and removing the liquid high-purity metal on the surface of the transfer substrate to obtain the two-dimensional non-layered metal oxide film; the bearing high-purity metal substrate is an Al foil. When the high purity metal bearing substrate is an active metal Al foil, the liquid Bi contacts the Al foil, and the electrode potential of Al is significantly lower than Bi, resulting in Al spontaneously acting as an anode and preferentially undergoing oxidation reactions. At this time, bi is located in the cathode region, forming electrochemical coupling, driving the reaction path. The electrochemical passivation effect transfers the rate determining step of the oxidation reaction to the anodic dissolution process of Al. The mechanism effectively improves the overpotential of the Bi oxidation reaction, thereby reducing the oxidation rate of the liquid Bi and being capable of obtaining ultrathin (the thickness is lower than 2 nm) and large-area two-dimensional non-layered metal oxide films. Further, the high-purity metal is selected from Bi, zn or In, and the purity is not lower than 99.99%. Further, the