CN102251231A - Preparation method for nano diamond film - Google Patents
Preparation method for nano diamond film Download PDFInfo
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- CN102251231A CN102251231A CN2011102176419A CN201110217641A CN102251231A CN 102251231 A CN102251231 A CN 102251231A CN 2011102176419 A CN2011102176419 A CN 2011102176419A CN 201110217641 A CN201110217641 A CN 201110217641A CN 102251231 A CN102251231 A CN 102251231A
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Abstract
The invention discloses a preparation method for a nano diamond film, comprising the following steps of: (1) carrying out assisted nuclear treatment on a substrate; (2) depositing a nano diamond film on the surface of the substrate; and (3) carrying out dehydration treatment on the nano diamond film: feeding the covered nano diamond film obtained in the step (2) in the oxygen atmosphere of 3-8kPar, heating the nano diamond film to be 100-300DEG C and keeping the temperature for 5-6 minutes. According to the preparation method disclosed by the invention, a hydrogenated layer on the surface of the nano diamond film is removed, so that the nano diamond film obtains higher and more stable electric conductivity and the application range of the nano diamond film is widened.
Description
Technical field
The present invention relates to the preparation method of nano-diamond film, particularly a kind of preparation method of nano-diamond film of stable conductivity.
Background technology
The diamond thin of unadulterated surface oxidation is nonconducting at normal temperatures, but by using different doped source and adulterating method that diamond thin is mixed, can make diamond thin become P type or N-type semiconductor, thereby can conduct electricity.This class film has kept unique characteristics such as the superelevation of diamond own is wear-resisting, high-melting-point simultaneously, is with a wide range of applications in fields such as preparation electrical contact, electrochemical electrode, high frequency field effect transistor, chemistry and biosensors.But because in the preparation process of diamond thin, diamond film surface can form hydride layer, the diamond film that has hydride layer can conduct electricity because of the electrochemical doping process in having the air of water vapour or in the aqueous solution, the redox couple that is water can exchange electronics with this quasi-diamond, even if make and do not use three races or pentels to mix to the diamond that has hydride layer, its surface also can have certain electric conductivity in air or in the aqueous solution.Yet because its mechanism has determined to have the diamond film resistance instability of hydride layer, usually change, limited its use because of the degree of drying of air or the variation of pH value.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of nano-diamond film of stable conductivity.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of nano-diamond film may further comprise the steps:
(1) assist forming core to handle to substrate;
(2) at substrate surface depositing nano diamond thin;
(3) nano-diamond film being carried out dehydrogenation handles.
Described step (3) is carried out the dehydrogenation processing to nano-diamond film, is specially:
Under the oxygen atmosphere that places 3～8kPar of the nano-diamond film that step (2) is obtained, and be heated to 100～300 ℃, keep 5min～60min.
Described nano-diamond film is the nano-diamond film of positive trivalent of heavy doping or positive pentad.
The attach most importance to nano-diamond film of doped with boron of described nano-diamond film.
Described step (2) is specially at substrate surface depositing nano diamond thin:
(2-1) substrate is placed the sample table of hot-wire chemical gas-phase deposition equipment; With the reactant gases thorough mixing, wherein the volume content of methane is 0.5～5% in the reactant gases, and the volume content of boric acid three formicesters is 1～4%, and surplus is a hydrogen;
(2-2) parameter of setting hot-wire chemical gas-phase deposition equipment: reaction pressure is 3～8KPar; The hot-wire temperature is 1500～2800 ℃; Underlayer temperature is 500～900 ℃, and the heated filament bias voltage is 10～50V; Bias voltage utmost point bias voltage is 0～100V; The sample table bias voltage is 0～400V; The described bias voltage utmost point be located at heated filament directly over;
(2-3) reactant gases is fed the deposit cavity of hot-wire chemical gas-phase deposition equipment, depositing time is 1～20h.
Described reactant gases comprises that also volume content is 30%～90% forming core assist gas.
Described forming core assist gas is Ar, N
2, O
2, H
2O, CO
2One of or arbitrary combination.
Described auxiliary forming core is handled and is specially: it is the diadust solution of solvent that substrate is put into the organic solvent, ultrasonic vibration 10～60min.
Described auxiliary forming core is handled and is specially: use with the diadust solution of organic solvent as solvent substrate is ground, the time is 1～20min.
Compared with prior art, the present invention has the following advantages and technique effect: the present invention is by finishing deposition back increase dehydrogenation treatment step, solved the diamond thin resistance instability that has hydride layer, the easy problem that changes with the variation of the degree of drying of air or pH value, after removing the hydride layer on nano-diamond film surface, nano-diamond film will obtain more stable specific conductivity, further enlarge the range of application of nano-diamond film.
Description of drawings
Fig. 1 is the synoptic diagram of the heated filament vapor deposition apparatus of first embodiment use of the present invention.
Fig. 2 is preparation method's schema of first embodiment of the present invention.
Fig. 3 is the surface scan Electronic Speculum figure of the nano-diamond film of first embodiment preparation of the present invention.
Fig. 4 is the profile scanning Electronic Speculum figure of the nano-diamond film of first embodiment preparation of the present invention.
Fig. 5 is the nano-diamond film of first embodiment preparation of the present invention and the comparison diagram of the resistance of the nano-diamond film of handling without dehydrogenation, and wherein (1) is the nano-diamond film of handling without dehydrogenation; (2) be nano-diamond film after dehydrogenation is handled.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Present embodiment uses hot-wire chemical gas-phase deposition equipment to prepare nano-diamond film, as shown in Figure 1.Hot-wire chemical gas-phase deposition equipment comprises deposit cavity 8, sample table 7, heated filament 6 and the bias voltage utmost point 5; The top of deposit cavity 8 is provided with inlet mouth 3, and the below is provided with venting port 9; Described sample table 7 is positioned at the bottom of described deposit cavity 8, described heated filament 6 be positioned at described sample table 7 directly over, the described bias voltage utmost point 5 be positioned at described heated filament 6 directly over; Be connected with direct supply 1 between the described bias voltage utmost point 5 and the ground, be the bias voltage utmost point 5 biasings; Be connected with direct supply 2 between described heated filament 6 and the ground, for heated filament 6 adds direct-current biasing; Be connected with direct supply 4 between described sample table 7 and the ground, for sample table 7 adds direct-current biasing.
As shown in Figure 2, the preparation method of the nano-diamond film of present embodiment is as follows:
(1) assist forming core to handle to substrate: it is the diadust solution of solvent that substrate is put into the organic solvent, ultrasonic vibration 10min.
(2-1) substrate is placed the sample table of hot-wire chemical gas-phase deposition equipment; With the reactant gases thorough mixing, wherein the volume content of methane (carbon-source gas) is 0.5% in the reactant gases; Boric acid three formicesters (impurity gas) volume content is 1%; The volume content of helium (forming core assist gas) is 30%; Surplus is hydrogen (delivering gas);
(2-2) parameter of setting hot-wire chemical gas-phase deposition equipment: reaction pressure is 3KPar; The hot-wire temperature is 1500 ℃; Underlayer temperature is 500 ℃, and the heated filament bias voltage is 10V, and the bias voltage utmost point is biasing not; Sample table is biasing not;
(2-3) mixed gas is fed the deposit cavity of hot-wire chemical gas-phase deposition equipment, depositing time is 5h, and obtaining thickness is the nano-diamond film of 4 microns heavy doping boron.
(3) nano-diamond film is carried out dehydrogenation and handles, be specially:
Under the oxygen atmosphere that places 3kPar that is coated with nano-diamond film that step (2) is obtained, and be heated to 100 ℃, keep 5min.
The nano-diamond film surface topography that present embodiment obtains as shown in Figure 3, as shown in Figure 3, grain size is 250～400nm, uniform particles, quality of forming film is higher.
The nano-diamond film cross-section morphology that present embodiment obtains as shown in Figure 4, as shown in Figure 4, crystal grain is upwards growth behind the substrate forming core, intergranule forms dense structure, good uniformity.
Fig. 5 is the comparison diagram of the resistance of present embodiment nano-diamond film that obtains and the nano-diamond film of handling without dehydrogenation (all the other preparation processes and present embodiment are together).As seen from the figure, than the nano-diamond film of handling without dehydrogenation, the nano-diamond film of handling through dehydrogenation is along with the variation rangeability of clamping time is very little, and stability is higher, and has littler resistivity.
(1) assist forming core to handle to substrate: it is the diadust solution of solvent that substrate is put into the organic solvent, ultrasonic vibration 60min.
(2-1) substrate is placed the sample table of hot-wire chemical gas-phase deposition equipment; With the reactant gases thorough mixing, wherein the volume content of methane (carbon-source gas) is 5% in the reactant gases; Boric acid three formicesters (impurity gas) volume content is 4%; The volume content of helium (forming core assist gas) is 60%; Surplus is hydrogen (delivering gas);
(2-2) parameter of setting hot-wire chemical gas-phase deposition equipment: reaction pressure is 8KPar; The hot-wire temperature is 2800 ℃; Underlayer temperature is 900 ℃, heated filament bias voltage 50V, bias voltage utmost point biasing 100V; Sample table biasing 400V;
(2-3) mixed gas is fed the deposit cavity of hot-wire chemical gas-phase deposition equipment, depositing time is 20h, and obtaining thickness is the nano-diamond film of 15 microns heavy doping boron.
(2) nano-diamond film is carried out dehydrogenation and handles, be specially:
Under the oxygen atmosphere that places 8kPar that is coated with nano-diamond film that step (2) is obtained, and be heated to 300 ℃, keep 60min.
(1) assist forming core to handle to substrate: it is the diadust solution of solvent that substrate is put into the organic solvent, ultrasonic vibration 40min.
(2-1) substrate is placed the sample table of hot-wire chemical gas-phase deposition equipment; With the reactant gases thorough mixing, wherein the volume content of methane (carbon-source gas) is 2% in the reactant gases; Boric acid three formicesters (impurity gas) volume content is 3%; The volume content of helium (forming core assist gas) is 90%; Surplus is hydrogen (delivering gas);
(2-2) parameter of setting hot-wire chemical gas-phase deposition equipment: reaction pressure is 6KPar; The hot-wire temperature is 2000 ℃; Underlayer temperature is 700 ℃, heated filament bias voltage 30V, bias voltage utmost point biasing 50V; Sample table biasing 200V;
(2-3) mixed gas is fed the deposit cavity of hot-wire chemical gas-phase deposition equipment, depositing time is 20h, and obtaining thickness is the nano-diamond film of 15 microns heavy doping boron.
(3) nano-diamond film is carried out dehydrogenation and handles, be specially:
Under the oxygen atmosphere that places 5kPar that is coated with nano-diamond film that step (2) is obtained, and be heated to 200 ℃, keep 30min.
Present embodiment is except that auxiliary forming core treatment step, and all the other steps are all identical with embodiment 1.
Described auxiliary forming core is treated to: use with the diadust solution of organic solvent as solvent substrate is ground, the time is 1min.
Present embodiment is except that auxiliary forming core treatment step, and all the other steps are all identical with embodiment 1.
Described auxiliary forming core is treated to: use with the diadust solution of organic solvent as solvent substrate is ground, the time is 20min.
Present embodiment is except that auxiliary forming core treatment step, and all the other steps are all identical with embodiment 1.
Described auxiliary forming core is treated to: use with the diadust solution of organic solvent as solvent substrate is ground, the time is 10min.
The foregoing description is a preferred implementation of the present invention, but embodiments of the present invention are not limited by the examples, and can be physical vapor deposition, liquid deposition or other film coating method as the deposition method of nano-diamond membrane; Carbon-source gas can be one of methyl alcohol, ethanol, acetone, acetylene, ethene, methane, ethane or arbitrary combination; Impurity gas can be for containing the gas of other positive trivalents or positive pentad; The forming core assist gas can be Ar, N
2, O
2, H
2O, CO
2One of or arbitrary combination; Delivering gas can be the isotope gas of hydrogen etc.; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify, and all should be the substitute mode of equivalence, is included within protection scope of the present invention.
Claims (9)
1. the preparation method of a nano-diamond film is characterized in that, may further comprise the steps:
(1) assist forming core to handle to substrate;
(2) at substrate surface depositing nano diamond thin;
(3) nano-diamond film being carried out dehydrogenation handles.
2. the preparation method of nano-diamond film according to claim 1 is characterized in that, described step (3) is carried out the dehydrogenation processing to nano-diamond film, is specially:
Under the oxygen atmosphere that places 3～8kPar of the nano-diamond film that step (2) is obtained, and be heated to 100～300 ℃, keep 5min～60min.
3. the preparation method of nano-diamond film according to claim 1 is characterized in that, described nano-diamond film is the nano-diamond film of positive trivalent of heavy doping or positive pentad.
4. the preparation method of nano-diamond film according to claim 3 is characterized in that, the attach most importance to nano-diamond film of doped with boron of described nano-diamond film.
5. the preparation method of nano-diamond film according to claim 4 is characterized in that, described step (2) is specially at substrate surface depositing nano diamond thin:
(2-1) substrate is placed the sample table of hot-wire chemical gas-phase deposition equipment; With the reactant gases thorough mixing, wherein the volume content of methane is 0.5～5% in the reactant gases, and the volume content of boric acid three formicesters is 1～4%, and surplus is a hydrogen;
(2-2) parameter of setting hot-wire chemical gas-phase deposition equipment: reaction pressure is 3～8KPar; The hot-wire temperature is 1500～2800 ℃; Underlayer temperature is 500～900 ℃, and the heated filament bias voltage is 10～50V; Bias voltage utmost point bias voltage is 0～100V; The sample table bias voltage is 0～400V; The described bias voltage utmost point be located at heated filament directly over;
(2-3) reactant gases is fed the deposit cavity of hot-wire chemical gas-phase deposition equipment, depositing time is 1～20h.
6. the preparation method of nano-diamond film according to claim 5 is characterized in that, described reactant gases comprises that also volume content is 30%～90% forming core assist gas.
7. the preparation method of nano-diamond film according to claim 6 is characterized in that, described forming core assist gas is Ar, N
2, O
2, H
2O, CO
2One of or arbitrary combination.
8. the preparation method of nano-diamond film according to claim 1 is characterized in that, described auxiliary forming core is handled and is specially: it is the diadust solution of solvent that substrate is put into the organic solvent, ultrasonic vibration 10～60min.
9. the preparation method of nano-diamond film according to claim 1 is characterized in that, described auxiliary forming core is handled and is specially: use with the diadust solution of organic solvent as solvent substrate is ground, the time is 1～20min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862663A (en) * | 2015-05-14 | 2015-08-26 | 浙江工业大学 | Method for improving p-type conductivity of boron-doped nanocrystalline diamond film |
| CN106830205A (en) * | 2016-12-16 | 2017-06-13 | 大连理工大学 | A kind of preparation method of self-supporting boron-doped diamond catalysis material |
| CN107400871A (en) * | 2017-07-28 | 2017-11-28 | 西安交通大学 | A kind of preparation method of the diamond thin based on silicon substrate |
| CN110423994A (en) * | 2019-08-10 | 2019-11-08 | 上海妙壳新材料科技有限公司 | A kind of diamond-like coating moves back membrane treatment appts and its application method |
| CN111115625A (en) * | 2018-11-01 | 2020-05-08 | 深圳先进技术研究院 | Preparation method of doped diamond powder |
| WO2022095301A1 (en) * | 2020-11-06 | 2022-05-12 | 上海征世科技有限公司 | Diamond and preparation method and application thereof |
| CN115786874A (en) * | 2022-11-15 | 2023-03-14 | 南京大学 | A high-efficiency doping HFCVD equipment based on dual gas flow |
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| CN1261927A (en) * | 1997-07-07 | 2000-08-02 | Cvd金刚石公司 | Apparatus and method for nucleotion and deposition of diamond using hot-filament DC plasma |
| CN101481792A (en) * | 2008-01-08 | 2009-07-15 | 中国科学院物理研究所 | Preparation of boron doped diamond superconduction material |
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2011
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Patent Citations (2)
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| CN1261927A (en) * | 1997-07-07 | 2000-08-02 | Cvd金刚石公司 | Apparatus and method for nucleotion and deposition of diamond using hot-filament DC plasma |
| CN101481792A (en) * | 2008-01-08 | 2009-07-15 | 中国科学院物理研究所 | Preparation of boron doped diamond superconduction material |
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| C. JANY ET AL.: "Post-growth treatments and contact formation on CVD diamond films for electronic applications", 《DIAMOND AND RELATED MATERIALS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862663A (en) * | 2015-05-14 | 2015-08-26 | 浙江工业大学 | Method for improving p-type conductivity of boron-doped nanocrystalline diamond film |
| CN106830205A (en) * | 2016-12-16 | 2017-06-13 | 大连理工大学 | A kind of preparation method of self-supporting boron-doped diamond catalysis material |
| CN106830205B (en) * | 2016-12-16 | 2020-08-21 | 大连理工大学 | Preparation method of self-supporting boron-doped diamond catalytic material |
| CN107400871A (en) * | 2017-07-28 | 2017-11-28 | 西安交通大学 | A kind of preparation method of the diamond thin based on silicon substrate |
| CN111115625A (en) * | 2018-11-01 | 2020-05-08 | 深圳先进技术研究院 | Preparation method of doped diamond powder |
| CN110423994A (en) * | 2019-08-10 | 2019-11-08 | 上海妙壳新材料科技有限公司 | A kind of diamond-like coating moves back membrane treatment appts and its application method |
| WO2022095301A1 (en) * | 2020-11-06 | 2022-05-12 | 上海征世科技有限公司 | Diamond and preparation method and application thereof |
| CN115786874A (en) * | 2022-11-15 | 2023-03-14 | 南京大学 | A high-efficiency doping HFCVD equipment based on dual gas flow |
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Application publication date: 20111123 |