CN-117684142-B - Tantalum-based boron doped diamond semiconductor composite coating material and preparation method and application thereof

CN117684142BCN 117684142 BCN117684142 BCN 117684142BCN-117684142-B

Abstract

The invention discloses a tantalum-based boron-doped diamond semiconductor composite coating material, a preparation method and application thereof, wherein the tantalum-based boron-doped diamond semiconductor composite coating material consists of a tantalum substrate, a Ta-B compound gradient transition layer arranged on the surface of the tantalum substrate and a gradient boron-doped diamond semiconductor layer arranged on the surface of the Ta-B compound gradient transition layer, and the Ta-B compound gradient transition layer is increased in a gradient manner from bottom to top; the gradient boron doped diamond semiconductor layer is reduced in a gradient manner from bottom to top, and Ta element doping is further contained in the gradient boron doped diamond semiconductor layer. The composite coating material provided by the invention has good film-based bonding performance, excellent conductivity, high stability and good electrochemical performance.

Inventors

WANG JIAN
SHI HAIPING
SHI SHUAI
SHI YINGJIE
SHI ZHEN
WU SHUIPING
MA FENG
LUO HAO
WANG BAOFENG

Assignees

湖南新锋科技有限公司

Dates

Publication Date: 20260505
Application Date: 20231228

Claims (10)

1. A tantalum-based boron-doped diamond semiconductor composite coating material is characterized by comprising a tantalum substrate, a Ta-B compound gradient transition layer arranged on the surface of the tantalum substrate and a gradient boron-doped diamond semiconductor layer arranged on the surface of the Ta-B compound gradient transition layer, wherein the Ta-B compound gradient transition layer is increased in a gradient manner from bottom to top, the gradient boron-doped diamond semiconductor layer is decreased in a gradient manner from bottom to top, and the gradient boron-doped diamond semiconductor layer further contains Ta element doping.
2. The tantalum-based boron-doped diamond semiconductor composite coating material of claim 1, wherein the composition of the top end of the Ta-B compound gradient transition layer is at least one selected from the group consisting of TaB/Ta 3 B 4 complex phase, taB/Ta 3 B 4 /TaB 2 complex phase, taB/TaB 2 complex phase, taB single phase, ta 3 B 4 single phase and TaB 2 single phase; the thickness of the Ta-B compound gradient transition layer is 5-100 mu m.
3. The tantalum-based boron-doped diamond semiconductor composite coating material of claim 1, wherein the gradient boron-doped diamond semiconductor layer sequentially comprises a boron-doped diamond bottom layer, a boron-doped diamond middle layer and a boron-doped diamond top layer from bottom to top, wherein the boron-doped diamond bottom layer adopts uniform boron content, B/C is 46666-60000ppm in terms of atomic ratio, the boron-doped diamond top layer adopts uniform boron content, B/C is 26666-40000ppm in terms of atomic ratio, and the boron content in the boron-doped diamond middle layer linearly decreases from bottom to top, and the boron content of the boron-doped diamond bottom layer linearly decreases to the boron content of the boron-doped diamond top layer with the maximum boron content of the boron-doped diamond bottom layer as the maximum value; The gradient boron doped diamond semiconductor layer is uniformly deposited on the surface of the Ta-B compound gradient transition layer by a chemical vapor deposition method, and the thickness of the gradient boron doped diamond semiconductor layer is 1 mu m-2mm; The boron-doped diamond semiconductor layer contains TaC or Ta 2 C, and the atomic percentage of tantalum in the boron-doped diamond semiconductor layer is 2% -15%.
4. The method of claim 1, wherein the tantalum in the tantalum matrix is selected from pure Ta or Ta alloys; the tantalum matrix has a structure of one of zero dimension, one dimension, two dimensions and three dimensions; the surface of the tantalum matrix is provided with a micro-nano structure.
5. The method for preparing the tantalum-based boron-doped diamond semiconductor composite coating material according to any one of claims 1 to 4, wherein boron doping is carried out on the surface of a tantalum substrate to obtain a Ta-B compound gradient transition layer, then the tantalum substrate containing the Ta-B compound gradient transition layer is placed in a hot wire chemical vapor deposition furnace, a tantalum wire is placed in front of the hot wire, boron-containing gas is introduced, and the gradient boron-doped diamond semiconductor layer is grown through chemical vapor deposition to obtain the tantalum-based boron-doped diamond semiconductor composite coating material.
6. The method for preparing the tantalum-based boron-doped diamond semiconductor composite coating material of claim 5, wherein the gradient transition layer of the Ta-B compound is obtained by performing boron doping on the surface of the tantalum substrate by a magnetron sputtering method or high temperature heat treatment.
7. The method for preparing the tantalum-based boron-doped diamond semiconductor composite coating material according to claim 6, wherein the magnetron sputtering process is as follows: Performing multi-target magnetron sputtering on a Ta substrate by using a Ta target and a B target with purity of more than or equal to 99.99%, wherein the sputtering parameters of the multi-target magnetron sputtering are that the sputtering power of the Ta target is 30-90W, the sputtering power of the B target is 100-300W, the working air pressure is 0.2-3Pa, the distance between the substrate and the target is 5-12 cm, and the sputtering time is 90-180 min; Or (b) The method comprises the steps of placing a Ta substrate in a B-containing atmosphere for direct-current magnetron sputtering, wherein during the direct-current magnetron sputtering, a Ta target or a TaB target with the purity of more than or equal to 99.99 percent is adopted, the distance between the substrate and the target is 5-12cm, the working air pressure is 0.2-3Pa, the sputtering power is 40-200W, and the sputtering time is 5-100min; And after the magnetron sputtering is finished, carrying out low-temperature heat treatment on the tantalum substrate containing the Ta-B compound gradient transition layer, wherein the temperature of the low-temperature heat treatment is 500-1100 ℃, the time of the low-temperature heat treatment is 1-6h, the air pressure is 8-25kPa, and the atmosphere of the low-temperature heat treatment is an inactive atmosphere.
8. The method for preparing the tantalum-based boron-doped diamond semiconductor composite coating material according to claim 6, wherein the high-temperature heat treatment process is characterized in that a Ta substrate is placed in a B-rich atmosphere, B-doped salt or solid B powder to be subjected to high-temperature heat treatment, the temperature of the high-temperature heat treatment is 1000-2000 ℃, the time of the high-temperature heat treatment is 1-20h, the working air pressure is 2-10kPa, and the high-temperature heat treatment atmosphere is an inactive atmosphere.
9. The method for preparing the tantalum-based boron-doped diamond semiconductor composite coating material according to claim 5, wherein the process of growing the gradient boron-doped diamond semiconductor layer by chemical vapor deposition is characterized in that a tantalum substrate containing a Ta-B compound gradient transition layer is placed in a chemical vapor deposition furnace, hydrogen, boron-containing gas and carbon-containing gas are introduced, the mass flow percentage of the boron-containing gas in the furnace is controlled to be 0.069% -0.0884% at first, the boron-doped diamond bottom layer is obtained, then the boron doping concentration is reduced in a linear decreasing mode until the mass flow percentage of the boron-containing gas in the furnace is 0.03968% -0.0593%, the boron-doped diamond transition layer is obtained, the mass flow percentage of the boron-containing gas in the furnace is controlled to be 0.03968% -0.0593%, and the boron-doped diamond top layer is obtained by redeposition, and the gradient boron-doped diamond semiconductor layer is obtained; The carbon-containing gas accounts for 0.5-10.0% of the total gas mass flow in the furnace, the deposition temperature of the boron doped diamond is 600-1000 ℃, the air pressure is 10 3 -10 4 Pa, and the deposition time is 3-20h; The tantalum wire is placed in front of the hot wire in the chemical vapor deposition furnace, the purity of the tantalum wire is more than or equal to 99.95%, the diameter of the Ta wire is 0.15-0.6 mm, and the length of the Ta wire is 10-100 mm.
10. The method of claim 1-4, wherein the tantalum-based boron-doped diamond semiconductor composite coating material is applied to one of semiconductor devices, electrochemical oxidation, electrochemical synthesis, and electrochemical analysis.

Description

Tantalum-based boron doped diamond semiconductor composite coating material and preparation method and application thereof Technical Field The invention relates to a tantalum-based boron doped diamond semiconductor composite coating material and a preparation method and application thereof, and belongs to the field of material preparation. Background Diamond has excellent physicochemical properties, hardness, molar density, thermal conductivity, acoustic velocity, and elastic modulus of diamond are the highest of known materials, and also has good corrosion resistance, light transmittance, heat resistance, and radiation resistance. Pure diamond has very high resistivity and is a good electrical insulator. Boron atoms are doped into the crystal structure of the diamond, so that the diamond can be converted into a semiconductor or even a conductor from an insulating material with the forbidden band width of 5.47eV, and the application range of the diamond is greatly expanded. Under the condition of low doping level, diamond shows semiconductor property, and the electron/hole mobility of diamond is high, so that the diamond is an ideal material for manufacturing high-temperature semiconductors and radiation-resistant semiconductors, and under the condition of high doping level, diamond shows semi-metal conductivity, so that the diamond is an ideal anode material in the fields of electrochemical synthesis, electrochemical oxidation, electrochemical analysis and the like. Boron Doped Diamond (BDD) coatings can be deposited on a variety of substrates by Chemical Vapor Deposition (CVD) techniques over a reasonable time scale and controlled doping levels. The Ta-based Boron Doped Diamond (BDD) material has extremely high oxygen evolution potential, good mechanical strength and conductivity, and is a good anode material in the electrochemical field. The stability of diamond on a substrate is directly affected by the high thermal stresses of the diamond and the substrate surface. Because of the large difference in thermal expansion coefficients between the diamond coating and the Ta substrate, cooling the system from high reaction temperatures to ambient temperature can cause large residual stresses, resulting in coating spalling. Disclosure of Invention Aiming at the defects of the prior art, the first aim of the invention is to provide a tantalum-based boron doped diamond semiconductor composite coating material with composite coating and high combination property and stability. The second aim of the invention is to provide a preparation method of the tantalum-based boron doped diamond semiconductor composite coating material. A third object of the present invention is to provide an application of a tantalum-based boron doped diamond semiconductor composite coating material. In order to achieve the above purpose, the present invention adopts the following technical scheme: The tantalum-based boron-doped diamond semiconductor composite coating material comprises a tantalum substrate, a Ta-B compound gradient transition layer arranged on the surface of the tantalum substrate and a gradient boron-doped diamond semiconductor layer arranged on the surface of the Ta-B compound gradient transition layer, wherein the Ta-B compound gradient transition layer is increased in a gradient manner from bottom to top, the gradient boron-doped diamond semiconductor layer is reduced in a gradient manner from bottom to top, and the gradient boron-doped diamond semiconductor layer further contains Ta element doping. According to the invention, the B-Ta compound gradient transition layer with linear gradient change is prepared at the interface between the BDD coating and the Ta substrate, and Ta element doping is carried out in the BDD coating, so that the chemical binding force of the BDD coating and the Ta substrate is increased, the residual stress is reduced, and the film-based binding performance and the service stability of the Ta-based BDD semiconductor composite coating material are greatly improved under the condition that other elements are not added. The invention relates to a tantalum-based boron doped diamond semiconductor composite coating material, wherein the top end of a Ta-B compound gradient transition layer is at least one selected from TaB/Ta 3B4 complex phase, taB/Ta 3B4/TaB2 complex phase, taB/TaB 2 complex phase, taB single phase, ta 3B4 single phase and TaB 2 single phase. In the invention, the gradient transition layer of the Ta-B compound gradually increases from bottom to top, the content of B in the bottom layer is lower, a TaB phase is preferentially formed, and the TaB is further combined with B to obtain Ta 3B4,Ta3B4 and then is further combined with B to obtain TaB 2. According to the invention, the Ta-B compound gradient transition layer is introduced, so that on one hand, the absorption of Ta to active C atoms is reduced, the nucleation rate of diamond is improved, meanwhile, taB and TaB 2 in the trans