CN113604792B - Preparation method of diamond nano burr structure - Google Patents
Preparation method of diamond nano burr structure Download PDFInfo
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- CN113604792B CN113604792B CN202110687993.4A CN202110687993A CN113604792B CN 113604792 B CN113604792 B CN 113604792B CN 202110687993 A CN202110687993 A CN 202110687993A CN 113604792 B CN113604792 B CN 113604792B
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method of a diamond nano burr structure, which comprises the following steps: providing a substrate; forming a nanocrystalline diamond film on the substrate; and annealing the substrate with the nanocrystalline diamond film in an oxygen-containing atmosphere to obtain the diamond nano burr structure. The method can prepare the nanocrystalline diamond film with a nano-scale close-packed structure, the film has high growth rate, and the diamond nano burr structure with large length-diameter ratio and high density can be easily obtained by utilizing the film through the oxidation reaction with high selection ratio. The high selectivity of the oxidation reaction in the method of the invention results in a low diamond consumption. In addition, the method has simple equipment and process and can greatly reduce the processing cost.
Description
Technical Field
The invention relates to the field of diamond nano structures, in particular to a preparation method of a diamond nano burr structure.
Background
Diamond has a high refractive index, low absorption, and extremely high hardness, thermal conductivity, and corrosion resistance. The micro-nano structure of the diamond is beneficial to enhancing the material characteristics, and the diamond has excellent performance in the aspects of super-capacitors or electrochemical sewage treatment electrodes, field emission devices, ion filter sieves and the like. Diamond nanostructures include nanoporous films, nanocolumns, diamond foam, nanofabrics, and nanofiber films, among others. The diamond has high hardness and extremely strong chemical inertia, so the preparation of the micro-nano structure is difficult. At present, the preparation method of the diamond nano structure mainly comprises reactive ion etching and electrochemical corrosion. These production methods have disadvantages of low selectivity and large diamond consumption. Therefore, it is required to develop a method for preparing a diamond nanostructure having a high selectivity ratio and a small consumption of diamond.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a diamond nano burr structure, which has the advantages of high selection ratio, small diamond consumption, simple equipment and process and capability of greatly reducing the processing cost.
In order to achieve the above object, the present invention provides the following technical solutions.
A preparation method of a diamond nano burr structure comprises the following steps:
providing a substrate;
forming a nanocrystalline diamond film on the substrate; and
and annealing the substrate with the nanocrystalline diamond film in an oxygen-containing atmosphere to obtain the diamond nano burr structure.
Compared with the prior art, the invention achieves the following technical effects:
1. the method can prepare the nanocrystalline diamond film with a nano-scale close-packed structure, the film has high growth rate, and the diamond nano burr structure with large length-diameter ratio and high density can be easily obtained by utilizing the film through the oxidation reaction with high selection ratio.
2. The high selectivity of the oxidation reaction in the method of the invention results in a low diamond consumption.
3. The method has simple equipment and process and can greatly reduce the processing cost.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 and fig. 2 are schematic diagrams of structures obtained in each step in the preparation method provided in example 1 of the present invention.
Fig. 3 and 4 are scanning electron microscope images of the structure obtained at each step in the manufacturing method provided in example 1 of the present invention.
FIG. 5 is a scanning electron microscope photograph of the structure obtained in comparative example 1 of the present invention.
Description of the reference numerals
100 is a substrate, 200 is a nanocrystalline diamond film, 300 is a diamond phase nano-skeleton, 400 is non-diamond phase carbon, and 500 is diamond nano-burr.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. It should be understood that the description is illustrative only and is not intended to limit the scope of the present disclosure. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure.
Various structural schematics according to embodiments of the present disclosure are shown in the figures. The figures are not drawn to scale, wherein certain details are exaggerated and some details may be omitted for clarity of presentation. The shapes of various regions, layers, and relative sizes and positional relationships therebetween shown in the drawings are merely exemplary, and deviations may occur in practice due to manufacturing tolerances or technical limitations, and a person skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions, as actually required.
In the context of the present disclosure, when a layer/element is referred to as being "on" another layer/element, it can be directly on the other layer/element or intervening layers/elements may be present. In addition, if a layer/element is "on" another layer/element in one orientation, then that layer/element may be "under" the other layer/element when the orientation is reversed.
As described above, the present invention provides a method for preparing a diamond nanopunch structure, which includes the following steps.
Providing a substrate;
the substrate of the present invention may be diamond, silicon, gaN, siC, BN, ir, stainless steel, or the like. The silicon substrate includes an N-type or P-type silicon substrate. The substrate of the present invention can be directly purchased from the market. The substrate is first cleaned before it is used. The cleaning method of the present invention is not particularly limited, and a cleaning method commonly used in the art, such as wet cleaning, dry cleaning, cleaning using a chelating agent, ozone cleaning, or low-temperature spray cleaning, may be used. The wet cleaning may be an RCA cleaning process, and the dry cleaning may be a plasma dry cleaning.
After cleaning, the substrate surface is preferably pretreated to increase the nucleation density of the diamond. The pretreatment method of the present invention may be seed implantation, mechanical scraping, ultrasonic scraping, pulsed laser irradiation, ion implantation, pre-deposition of graphite, or pre-deposition of amorphous carbon, etc. In a preferred embodiment of the present invention, the pretreatment step is carried out by seeding, and specifically comprises: the substrate was placed in a suspension containing diamond nanoparticles and subjected to sonication. The suspension is a suspension of diamond nanoparticle powder with a diameter of 2nm or more in a solvent. The solvent may be water, absolute ethanol, toluene or other organic solvents. The ultrasound time is preferably 30min or more. After the implantation of the seed, the substrate is preferably cleaned and dried. For example, the substrate may be ultrasonically cleaned in anhydrous ethanol and blown dry with dry air or nitrogen.
And forming a nanocrystalline diamond film on the substrate.
The present invention forms a nanocrystalline diamond film on a substrate by Chemical Vapor Deposition (CVD). The chemical vapor deposition method is Microwave Plasma Chemical Vapor Deposition (MPCVD), radio Frequency Chemical Vapor Deposition (RFCVD), direct current arc chemical vapor deposition (DCCVD), hot wire chemical vapor deposition (HFCVD) or bias enhanced chemical vapor deposition. The nanocrystalline diamond film of the invention has a diamond phase nano skeleton structure which is densely and vertically arranged, and the skeleton is composed of non-diamond phase carbon. The nanocrystalline diamond film (with a special crystallographic structure) with the diamond phase nano framework structure which is densely and vertically arranged can be formed on the substrate by adjusting the process parameters of the chemical vapor deposition method, wherein the process parameters comprise working atmosphere, working air pressure, power, substrate temperature, hot wire temperature, bias voltage and the like. The growth process parameters of the nanocrystalline diamond film have an important influence on the formation of the nano burr structure.
In a preferred embodiment, the nanocrystalline diamond film is formed on the substrate by microwave plasma chemical vapor deposition. The growth process parameters of the nanocrystalline diamond film comprise: working atmosphere 20% CH 4 And 80% of H 2 The substrate temperature is 700 ℃, the microwave power is 1800W, and the working air pressure is 6kPa. CH in the preparation of nanocrystalline diamond films by microwave plasma chemical vapor deposition 4 As a carbon source, carbon groups resulting from dissociation thereof are deposited on a substrate, and H 2 Etching interaction ofBalancing constraints. The invention prepares the nanocrystalline diamond film with a nano-scale close packing structure by controlling the technological parameters of the microwave plasma chemical vapor deposition method, including working atmosphere, substrate temperature, microwave power and working air pressure, and can prepare the nano-diamond burr structure with large length-diameter ratio and high density based on the film.
And annealing the substrate with the nanocrystalline diamond film in an oxygen-containing atmosphere to obtain the diamond nano burr structure.
The oxygen-containing atmosphere of the present invention may be an air atmosphere or a mixed atmosphere of oxygen and an inert gas. The mixed atmosphere may be a mixed atmosphere of oxygen and nitrogen, a mixed atmosphere of oxygen and argon, or a mixed atmosphere of oxygen and helium. Oxygen in an oxygen-containing atmosphere acts as an oxidant and, at elevated temperatures, can undergo an oxidation reaction with non-diamond phase carbon, thereby converting it to carbon dioxide or carbon monoxide for removal. The annealing temperature of the invention is above 400 ℃, and the annealing time is determined according to the annealing temperature and the required burr height. The annealing step can be performed in a variety of thermal processing equipment, including but not limited to muffle furnaces, ovens, and the like.
The preparation of the diamond nano burr structure with large length-diameter ratio requires anisotropic etching with high selection ratio, so the preparation difficulty is very high. The invention adopts an oxidation annealing method to remove the non-diamond phase carbon part in the nanocrystalline diamond film, thereby forming the diamond nano burr structure with large length-diameter ratio. Compared with the reactive ion etching technology, the method has the following advantages: the selection ratio is high, the consumption of the diamond is low, the equipment and the process are simple, and the processing cost can be greatly reduced. In addition, the method need not be limited to highly conductive doped diamond as with electrochemical etching techniques.
The diamond nano burr structure prepared by the method has the characteristics of large length-diameter ratio and high density. Specifically, the aspect ratio of the diamond nanoprobe is preferably more than 1, and the distribution density of the diamond nanoprobe on the substrate is 1.0X 10 9 cm -2 The above.
The invention will be further illustrated with reference to specific embodiments and the accompanying drawings.
Example 1
In a single-throw N type<100>On a monocrystalline silicon wafer 100, a nanocrystalline diamond film 200 with diamond phase nano-frameworks 300 arranged densely and vertically is grown by MPCVD, which comprises the following steps: (1) Putting the diamond nano-particle powder with the diameter of 50nm into a proper amount of absolute ethyl alcohol, and carrying out ultrasonic treatment for 1h; (2) Putting the cleaned monocrystalline silicon wafer into the suspension, and carrying out ultrasonic treatment for more than 30 min; (3) Sequentially putting the silicon chip into two cups of absolute ethyl alcohol for ultrasonic cleaning for 30s respectively; and (4) taking out the silicon chip and drying the silicon chip by dry air. (5) Putting a silicon wafer into MPCVD equipment, wherein the growth process parameters are as follows: working atmosphere 20% CH 4 And 80% of H 2 The substrate temperature is 700 ℃, the microwave power is 1800W, the working pressure is 6kPa, and the growth time is 3h, so that the structure shown in figure 1 is obtained, and the scanning electron microscope picture thereof is shown in figure 3.
Annealing to remove the non-diamond phase carbon 400 between the diamond phase nano-skeletons 300, the specific steps include: the single crystal silicon wafer 100 on which the nanocrystalline diamond film 200 has grown is placed in a quartz boat and pushed into a muffle furnace in an atmosphere of air at an annealing temperature of 550 ℃ for an annealing time of 150min to obtain the structure shown in fig. 2, and a scanning electron microscope image of the structure is shown in fig. 4. The average length of the diamond nano burr is about 180nm, the diameter is less than 10nm, namely the length-diameter ratio is more than 18, and the distribution density of the diamond nano burr on the substrate is 1.8 multiplied by 10 9 cm -2 This indicates that it has a large aspect ratio and a high density of structural features.
Comparative example 1
This comparative example was carried out as described in example 1, except that the working atmosphere was 20% CH 4 10% of H 2 And 70% argon at 800 deg.C with a power of 2100W and a working pressure of 8kPa. The resulting structure after annealing is shown in fig. 5, and it can be seen that no nanoprobe is formed.
As can be seen from example 1 and comparative example 1, the growth process parameters of the nanocrystalline diamond film have an important influence on the formation of the nanophase burr structure.
While the invention has been described with reference to specific preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A preparation method of a diamond nano burr structure is characterized by comprising the following steps:
providing a substrate;
forming a nanocrystalline diamond film on the substrate; and
annealing the substrate with the nanocrystalline diamond film in an oxygen-containing atmosphere to obtain a diamond nano burr structure;
forming a nanocrystalline diamond film on the substrate by a chemical vapor deposition method;
the chemical vapor deposition method is a microwave plasma chemical vapor deposition method;
forming a nanocrystalline diamond film with a dense vertically-arranged diamond phase nano-skeleton structure on the substrate by adjusting the process parameters of a chemical vapor deposition method, wherein the process parameters comprise: working atmosphere 20% CH 4 And 80% of H 2 The substrate temperature is 700 ℃, the microwave power is 1800W, and the working air pressure is 6kPa;
the distribution density of the diamond nano-burrs on the substrate is 1.0 multiplied by 10 9 cm -2 The above.
2. The production method according to claim 1, wherein the diamond nanoprotrusions have a large aspect ratio.
3. A production method according to claim 1 or 2, characterized in that the substrate is diamond, silicon, gaN, siC, BN, ir, or stainless steel.
4. A production method according to claim 1 or 2, characterized in that, before the nanocrystalline diamond film is formed, the surface of the substrate is subjected to pretreatment of seeding, mechanical scraping, ultrasonic scraping, pulsed laser irradiation, ion implantation, pre-deposited graphite, or pre-deposited amorphous carbon.
5. The production method according to claim 1 or 2, wherein the oxygen-containing atmosphere is an air atmosphere or a mixed atmosphere of oxygen and an inert gas.
6. The production method according to claim 5, wherein the mixed atmosphere is a mixed atmosphere of oxygen and nitrogen, a mixed atmosphere of oxygen and argon, or a mixed atmosphere of oxygen and helium.
7. The production method according to claim 1 or 2, wherein the annealing temperature is 400 ℃ or higher.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02239191A (en) * | 1989-03-10 | 1990-09-21 | Idemitsu Petrochem Co Ltd | Multilayer diamond film and its production |
| CN1616708A (en) * | 2004-11-19 | 2005-05-18 | 中国科学院物理研究所 | Diamond cone tip and its making method |
| JP5552654B2 (en) * | 2008-08-06 | 2014-07-16 | 並木精密宝石株式会社 | Sharpened diamond-shaped diamond, cantilever for scanning probe microscope using the same, probe for photomask correction, electron beam source |
| CN102560687B (en) * | 2011-12-31 | 2014-10-08 | 吉林大学 | Diamond nanometer pit array and preparation method thereof |
| CN103193217B (en) * | 2013-03-12 | 2014-12-24 | 南京理工大学 | Method for preparing boron-doped diamond and carbon nanotube composite nanocone |
| CN104553124B (en) * | 2014-12-02 | 2017-05-03 | 中国科学院深圳先进技术研究院 | Diamond nano needle array composite material and preparation method and application thereof |
| CN107267954B (en) * | 2017-06-14 | 2020-02-14 | 哈尔滨工业大学深圳研究生院 | Method for preparing highly-oriented diamond nanosheet array material through epitaxial growth |
| CN112301423B (en) * | 2020-09-23 | 2021-11-05 | 中国科学院金属研究所 | Preparation method of one-dimensional diamond nanocone array material |
| CN112760612B (en) * | 2020-12-28 | 2022-07-01 | 吉林工程技术师范学院 | Preparation method of self-supporting nano-needle porous diamond |
| CN112779517B (en) * | 2020-12-28 | 2022-07-01 | 吉林工程技术师范学院 | Preparation method of self-supporting nanocone diamond |
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