CN112779517B - Preparation method of self-supporting nanocone diamond - Google Patents

Preparation method of self-supporting nanocone diamond Download PDF

Info

Publication number
CN112779517B
CN112779517B CN202011578907.8A CN202011578907A CN112779517B CN 112779517 B CN112779517 B CN 112779517B CN 202011578907 A CN202011578907 A CN 202011578907A CN 112779517 B CN112779517 B CN 112779517B
Authority
CN
China
Prior art keywords
diamond
substrate
self
preparation
supporting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011578907.8A
Other languages
Chinese (zh)
Other versions
CN112779517A (en
Inventor
袁晓溪
杨峰
曾旭
李楠
张文颖
李宏
郭明
冯悦姝
李美萱
杨璐赫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin Teachers Institute of Engineering and Technology
Original Assignee
Jilin Teachers Institute of Engineering and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin Teachers Institute of Engineering and Technology filed Critical Jilin Teachers Institute of Engineering and Technology
Priority to CN202011578907.8A priority Critical patent/CN112779517B/en
Publication of CN112779517A publication Critical patent/CN112779517A/en
Application granted granted Critical
Publication of CN112779517B publication Critical patent/CN112779517B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/274—Diamond only using microwave discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment

Abstract

The invention discloses a preparation method of a self-supporting nanocone diamond, and belongs to the technical field of diamond nanostructures and preparation thereof. First with high CH4And H2Introducing nitrogen gas for doping according to the flow ratio, and growing a diamond and non-diamond mixed phase to form a diamond inverted cone; readjust low CH4And H2Growing a diamond phase according to the flow ratio; and removing the substrate, annealing at high temperature in air and etching away the non-diamond phase to prepare the self-supporting nanocone diamond. The invention passes different CHs4And H2The flow rate ratio deposition growth and the introduction of nitrogen are beneficial to the growth of 100-face crystal orientation to form inverted cone, the high-density nano-cone diamond is prepared, and the surface area of the diamond film is greatly increased; compared with a top-down mask method or a plasma etching method, the preparation method and the preparation processSimple and convenient for large-scale preparation.

Description

Preparation method of self-supporting nanocone diamond
Technical Field
The invention belongs to the technical field of diamond nano structures and preparation thereof, and relates to a preparation method of a novel self-supporting nano-cone diamond.
Background
Diamond is a functional material with excellent performances such as super hardness, high thermal conductivity coefficient, chemical inertness, stability and the like. Nanostructures (e.g., nanotextures, nanowires, porous diamonds, etc.) for making diamond are useful in many areas of research. However, due to the extreme hardness and chemical inertness, it is not convenient to be able to alter the morphology of the diamond by machining or wet chemical etching.
The invention prepares a diamond film structure which combines the self-growth orientation of diamond to generate a self-supporting nano cone by a bottom-up method, thereby greatly increasing the surface area of the diamond film.
The prior art close to the present invention is a patent application entitled "a structural member with diamond-like array and method of making the same" entitled CN106835011B, the method of making the same by etching a diamond-like coating formed on a substrate. The structural member with the diamond-like carbon array can generate pressure on the cell wall of bacteria, puncture the cell wall of the bacteria to stretch the cell wall and finally dissolve the cell wall, so that the bacteria die, the formation of a biological film is effectively destroyed, and the structural member is endowed with remarkable antibacterial performance.
Disclosure of Invention
The invention aims to solve the technical problem that a diamond film structure of a self-supporting nano cone is generated by combining the self growth orientation of diamond by a bottom-up method, so that the surface area of the diamond film is greatly increased.
The specific technical scheme for preparing the nano-cone diamond film is as follows:
a preparation method of self-supporting nano-cone diamond, which takes a silicon wafer or a molybdenum sheet as a substrate and is characterized in that the silicon wafer or the molybdenum sheet is subjected to the processes of substrate pretreatment, microwave plasma chemical vapor deposition coating and high-temperature annealing,
the microwave plasma chemical vapor deposition coating is to place the pretreated substrate in the cavity of a Chemical Vapor Deposition (CVD) device, and CH is firstly used under the conditions that the microwave power is 350W and the pressure of the cavity is 8KPa4、H2And N2The flow ratio is 5-8: 100:0.5, a diamond and non-diamond mixed phase grows for 5 hours, and then N is closed2Flow, turn down CH4And H2Growing a diamond phase with the flow ratio of 1: 100;
the high-temperature annealing is to remove the substrate, then to anneal at 800 ℃ in the air, to etch away the non-diamond phase, to obtain the self-supporting nano-cone diamond.
The substrate pretreatment can be carried out according to a conventional method, or the substrate can be ground by using nano diamond powder, then the substrate is placed in a nano diamond suspension for ultrasonic treatment for 1-2 hours, finally the substrate is sequentially cleaned by using acetone, absolute ethyl alcohol and deionized water in an ultrasonic manner, and the substrate is taken out and dried by using nitrogen.
The substrate is removed, after the diamond phase grows on the silicon substrate, the silicon substrate is placed into a mixed solution of hydrofluoric acid and nitric acid to be soaked for more than 24 hours; after the chemical vapor deposition device is closed, the molybdenum substrate is rapidly cooled at the speed of 80 ℃/min, so that the molybdenum substrate is separated from the grown diamond and non-diamond mixed phase.
The Chemical Vapor Deposition (CVD) coating method of the invention is a Microwave Plasma (MPCVD) method, and can also be a Hot Filament (HFCVD), a hot cathode (DCCVD) method and the like. Polycrystalline films may be heteroepitaxially grown on a silicon, titanium, or like substrate, and the films may be undoped, or semiconductor doped.
High-temperature annealing and etching the non-diamond phase to form a high-density nano-cone structure, terminating surface oxygen, and terminating the surface hydrogen through chemical treatment.
The invention solves the technical problem of preparing the high-density nano tapered diamond film by combining diamond growth orientation from bottom to top. The self-supporting high-density nano-cone diamond is prepared by growing diamond and non-diamond phases together, introducing nitrogen to help to grow 100-face crystal orientation to form inverted cone, and etching off the non-diamond phases, and meanwhile, the surface of the nano-cone has a plurality of pit-type structures, which is the main content and important innovation point related by the invention. Compared with a mask method or a plasma etching method from top to bottom, the preparation method is simple in process and convenient for large-scale preparation. The research has important significance for the diamond nano-cone structure and the preparation field thereof.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a nanocone diamond structure.
FIG. 2 is a diagram of a nanocone diamond morphology at a high methane to hydrogen ratio. Wherein (B) is an enlarged view of (A).
FIG. 3 is a Cyclic Voltammetry (CV) curve for testing the specific surface areas of nanocone diamond and diamond film of example 1.
Detailed Description
The present application is described in further detail below with reference to the accompanying drawings and examples, which are intended to facilitate the understanding of the present application and are not intended to limit the same in any way.
Example 1: preparation of silicon chip substrate nano-cone diamond film
Selecting a silicon wafer with the size of 1cm multiplied by 1cm as a growth substrate, firstly cleaning the silicon wafer and removing surface pollutants. In order to improve the nucleation density in the growth process, the growth surface of the diamond film is put on emery paper containing diamond powder to be ground for 15-30 minutes, the emery film is put into alcohol containing diamond powder to be subjected to ultrasonic treatment for 1 hour, finally, the emery film is sequentially subjected to ultrasonic cleaning for 10 minutes through acetone, alcohol and deionized water, and the emery film is blown dry through nitrogen and then is put into a CVD reaction chamber to be deposited. The main growth parameters are: the gas flow rates of the hydrogen, the methane and the nitrogen are respectively 200sccm, 10sccm and 1sccm, the microwave power is 350W, the cavity gas pressure is 8KPa, the growth time is 5 hours, the mixed phase of diamond and non-diamond is obtained, and the film deposition thickness is about 20 μm. And (3) closing the nitrogen flow, adjusting the methane concentration to be low, wherein the gas flow of the hydrogen and the methane is respectively 200sccm and 2sccm, the microwave power is 350W, the cavity gas pressure is 8KPa, the growth time is 5 hours, the diamond phase is grown, and the film deposition thickness is about 4 mu m. And (3) placing the sample in a mixed solution of hydrofluoric acid and nitric acid for more than 24 hours, removing the silicon substrate, cleaning with deionized water, and drying with nitrogen. And placing the obtained film in a tube furnace, annealing at the high temperature of 800 ℃ for 20 minutes, etching away the non-diamond phase, and successfully preparing the self-supporting nano-cone diamond.
The preparation process is schematically shown in figure 1.
The scanning electron micrograph is shown in FIG. 2. The height of the nano-cone is 4-6 um, and the density of the nano-cone is 1.3 х 107cm-2. The surface of the nano-cone has a plurality of pit type grain boundary structures.
In the phase of high methane flow growth diamond and non-diamond, the main function of nitrogen is to facilitate the growth of the diamond (100) surface to form an inverted rectangular pyramid structure, and if nitrogen is not added, the pyramid structure of the invention cannot be grown.
To verify the actual area increase of the nanocone diamond compared to the growth surface diamond film, 0.1M Na was used2SO4The Cyclic Voltammetry (CV) curves of the nano-cone diamond and the diamond film are tested in the solution, as shown in figure 3, the scanning potential interval is-0.5-0.9V, the scanning speed is 0.1mV/s, the integral area/scanning speed of the CV curve is the electric quantity, and the effective area of the nano-cone diamond can be calculated to be about 8.6 times of that of the diamond film on the growth surface by transferring the electric quantity through coulombs, so that the nano-cone diamond is verified to have larger specific surface area.
Example 2: preparation of molybdenum substrate nano-cone diamond film
Selecting a molybdenum sheet with the size of 1cm multiplied by 1cm as a growth substrate, firstly cleaning the molybdenum sheet and removing surface pollutants. In order to improve the nucleation density in the growth process, the growth surface of the diamond film is put on emery paper containing diamond powder to be ground for 15-30 min, the emery film is put into alcohol containing diamond powder to be subjected to ultrasonic treatment for 2h, finally, the emery film is sequentially subjected to ultrasonic cleaning through acetone, alcohol and deionized water, and the emery film is blown dry through nitrogen and then is put into a CVD reaction chamber to be deposited. The main growth parameters are: the gas flow rates of the hydrogen, the methane and the nitrogen are respectively 200sccm, 16sccm and 1sccm, the microwave power is 350W, the cavity gas pressure is 8KPa, the time is 5 hours, the diamond and the non-diamond mixed phase grows, and the film deposition thickness is about 20 micrometers. And (3) closing the nitrogen flow, adjusting the methane concentration to be low, wherein the gas flow of the hydrogen and the methane is respectively 200sccm and 2sccm, the microwave power is 350W, the cavity gas pressure is 8KPa, the growth time is 5 hours, the diamond phase is grown, and the film deposition thickness is about 4 mu m. And when the CVD device is closed, the molybdenum substrate is removed in a rapid cooling mode, and the molybdenum sheet is easily separated from the diamond film due to the large difference between the heat conductivities of the molybdenum sheet and the diamond. In the molybdenum substrate of the embodiment, after the chemical vapor deposition device is closed, the temperature is rapidly reduced at the speed of 80 ℃/min, so that the molybdenum substrate is separated from the grown mixed phase of diamond and non-diamond. And placing the obtained self-supporting film in a tube furnace, annealing at the high temperature of 800 ℃ for 20 minutes, etching away the non-diamond phase, and successfully preparing the self-supporting nano-cone diamond.

Claims (3)

1. A preparation method of self-supporting nano-cone diamond, which takes a silicon wafer or a molybdenum sheet as a substrate and is characterized in that the silicon wafer or the molybdenum sheet is subjected to the processes of substrate pretreatment, microwave plasma chemical vapor deposition coating and high-temperature annealing,
the microwave plasma chemical vapor deposition coating is to place the pretreated substrate in the cavity of a chemical vapor deposition device and use CH under the microwave power of 350W and the cavity pressure of 8KPa4、H2And N2The flow ratio is 5-8: 100:0.5, a diamond and non-diamond mixed phase grows for 5 hours, and then N is closed2Flow, turn down CH4And H2Growing a diamond phase with the flow ratio of 1: 100;
the high-temperature annealing is to remove the substrate, then to anneal at 800 ℃ in the air, to etch away the non-diamond phase, to obtain the self-supporting nano-cone diamond.
2. The method for preparing the self-supporting nanocone diamond according to claim 1, wherein the substrate pretreatment comprises the steps of grinding the substrate by using the nanodiamond powder, placing the ground substrate in a nanodiamond suspension for ultrasonic treatment for 1-2 hours, finally sequentially performing ultrasonic cleaning by using acetone, absolute ethyl alcohol and deionized water, taking out the cleaned substrate, and drying the cleaned substrate by using nitrogen.
3. The method for preparing the self-supporting nanocone diamond according to the claim 1 or 2, characterized in that the substrate is removed, and after the diamond phase grows, the silicon substrate is soaked in the mixed solution of hydrofluoric acid and nitric acid for more than 24 hours; after the chemical vapor deposition device is closed, the molybdenum substrate is rapidly cooled at the speed of 80 ℃/min, so that the molybdenum substrate is separated from the grown diamond and non-diamond mixed phase.
CN202011578907.8A 2020-12-28 2020-12-28 Preparation method of self-supporting nanocone diamond Active CN112779517B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011578907.8A CN112779517B (en) 2020-12-28 2020-12-28 Preparation method of self-supporting nanocone diamond

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011578907.8A CN112779517B (en) 2020-12-28 2020-12-28 Preparation method of self-supporting nanocone diamond

Publications (2)

Publication Number Publication Date
CN112779517A CN112779517A (en) 2021-05-11
CN112779517B true CN112779517B (en) 2022-07-01

Family

ID=75752895

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011578907.8A Active CN112779517B (en) 2020-12-28 2020-12-28 Preparation method of self-supporting nanocone diamond

Country Status (1)

Country Link
CN (1) CN112779517B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113628944B (en) * 2021-06-21 2022-11-04 北京大学 Method for preparing field electron emission cathode
CN113604792B (en) * 2021-06-21 2022-11-04 北京大学 Preparation method of diamond nano burr structure

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009153116A2 (en) * 2008-05-29 2009-12-23 Eesti Nanotehnoloogiate Arenduskeskuse As Diamond nano-tip and method for production thereof
CN108658037A (en) * 2018-04-27 2018-10-16 国家纳米科学中心 A kind of graphene functionalized nanometer pinpoint and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009153116A2 (en) * 2008-05-29 2009-12-23 Eesti Nanotehnoloogiate Arenduskeskuse As Diamond nano-tip and method for production thereof
CN108658037A (en) * 2018-04-27 2018-10-16 国家纳米科学中心 A kind of graphene functionalized nanometer pinpoint and preparation method thereof

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
"A study of high-quality freestanding diamond films grown by MPCVD";Ming Q. Ding et al.;《Applied Surface Science》;20120303;第5987-5991页 *
"Bottom-Up Synthesis of Single Crystal Diamond Pyramids Containing Germanium Vacancy Centers";Milad Nonahal et al.;《Advanced Quantum Technologies》;20211231;第1-6页 *
"Production of single crystal diamond needles by a combination of CVD growth and thermal oxidation";Alexander N. Obraztsov et al.;《Diamond & Related Materials》;20090509;第1289-1293页 *
"Single-crystal diamond microneedles shaped at growth stage";Aleksey A. Zolotukhin et al.;《Diamond & Related Materials》;20130913;第15-20页 *
"Single-Crystal Diamond Needle Fabrication Using Hot-Filament Chemical Vapor Deposition";Rinat Ismagilov et al.;《materials》;20210429;第1-9页 *
"Single-crystal diamond pyramids: synthesis and application for atomic force microscopy";Feruza T. Tuyakova et al.;《Nanophotonics》;20151124;第012517-1-012517-8页 *
脉冲激光沉积制备纳米材料研究进展;安宁宁等;《真空》;20101125(第06期);第10-14页 *
超纳米金刚石薄膜及其在MEMS上的应用研究进展;***等;《材料导报》;20080715(第07期);第1-4页 *

Also Published As

Publication number Publication date
CN112779517A (en) 2021-05-11

Similar Documents

Publication Publication Date Title
CN102102220B (en) Preparation method of graphene on diamond (111) surface
CN112779517B (en) Preparation method of self-supporting nanocone diamond
CN112430803B (en) Preparation method of self-supporting ultrathin diamond film
CN110416065B (en) Preparation method of molybdenum disulfide/tungsten diselenide vertical heterojunction
CN110863243B (en) Secondary epitaxial method for preparing high-quality diamond single crystal by adopting nano structure
CN112760612B (en) Preparation method of self-supporting nano-needle porous diamond
CN102103953B (en) Cold cathode field emission material epitaxially growing on silicon carbide substrate and method
CN110002504B (en) Preparation method of rhenium disulfide nanosheet
CN109824038A (en) A kind of efficient method for eliminating chemical vapour deposition technique graphene fold
CN111118471A (en) Preparation method of high-quality polycrystalline diamond film
CN107267954A (en) A kind of method that epitaxial growth prepares highly-oriented diamond nano-chip arrays material
CN109811328B (en) Preparation method of boron-doped diamond film
CN110257798A (en) A kind of ICP-CVD prepares the deposition method of amorphous carbon film
CN102560687A (en) Diamond nanometer pit array and preparation method thereof
CN110055589A (en) Large scale single layer hexagonal boron nitride monocrystalline or film and preparation method
CN107244666B (en) Method for growing large-domain graphene by taking hexagonal boron nitride as point seed crystal
CN109179422B (en) Preparation method of large-scale amorphous silicon particles
CN113604792B (en) Preparation method of diamond nano burr structure
CN111020692A (en) Porous Ta3N5Single crystal material and preparation method and application thereof
CN113628944B (en) Method for preparing field electron emission cathode
CN109881248A (en) Nitrogen sulphur codope n-type semiconductor diamond and preparation method thereof
RU2816687C1 (en) Silicon carbide film functional element of device and method of its manufacturing
CN113418904B (en) Surface-enhanced Raman scattering substrate and preparation method and application thereof
CN104593746B (en) One kind prepares 3C SiC nanometer plates, preparation method
TW201122143A (en) Method for forming smooth diamond thin film.

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant