CN1294293C - Auxiliary grid hot wire chemical vapor deposition process for preparing nano-diamond thin film - Google Patents
Auxiliary grid hot wire chemical vapor deposition process for preparing nano-diamond thin film Download PDFInfo
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- CN1294293C CN1294293C CNB2004100675713A CN200410067571A CN1294293C CN 1294293 C CN1294293 C CN 1294293C CN B2004100675713 A CNB2004100675713 A CN B2004100675713A CN 200410067571 A CN200410067571 A CN 200410067571A CN 1294293 C CN1294293 C CN 1294293C
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Abstract
The present invention relates to an auxiliary grid hot filament chemical vapor deposition process for preparing nanometer diamond films, which belongs to the technical field of plating. The process comprises: an auxiliary grid is additionally adopted on the basis of the hot filament chemical vapor deposition process for depositing diamond films; a diamond film is first deposited on the surface of the auxiliary grid in the initial stage of hot filament deposition, and then DC bias voltage is added between the auxiliary grid and the hot filament; the auxiliary grid performs negative, the diamond film on the surface of the auxiliary grid emits electrons to form DC discharge, wherein the auxiliary grid is bombarded by positive ions, the bombarded diamond atoms and atomic groups are sputtered onto a substrate and become drive points for nucleating and growing diamonds, the sputtering has keying function for the high density nucleation and the secondary nucleation of the diamonds on the substrate, and a nanometer diamond film is formed on the surface of the substrate by deposition. With the present invention, high nucleation density and high secondary nucleation speed rate in the growing process can be realized, nanometer diamond films can be obtained by growing, and the deposited films have high smoothness without finishing, which can meet the operation requirements.
Description
Technical field
What the present invention relates to is a kind of method for preparing nano-diamond film, specifically is a kind of auxiliary grid hot wire chemical vapor deposition process for preparing nano-diamond film, is used for the coating technology field.
Background technology
Along with the development and maturation of CVD depositing diamond film technology, the nano-diamond film coating technology becomes the new focus of CVD diamond film research field rapidly.Nano-diamond film crystal grain is very tiny, can reach several between tens nanometers, littler two more than the order of magnitude than conventional diamond thin, the surface is extremely smooth, surfaceness can be below Ra100nm, film friction coefficient is very little, only is 0.03～0.06, far below conventional diamond thin 0.2～1.1.The appearance of nano-diamond film makes that directly obtaining ganoid diamond thin on substrate material becomes possibility, the deposition of what is more important nano-diamond film on the complicated shape smooth substrates can need not post-processing technologies such as polishing, directly obtain extremely slick diamond film surface, fundamentally solve the problem that conventional CVD diamond thin can't be used in a lot of fields because of surface irregularity.The preparation method of conventional diamond thin comprises methods such as heated filament CVD, microwave plasma CVD and dc plasma jet CVD, is equally applicable to prepare nano-diamond film.
Find by prior art documents, people such as Y.E.Zhang are at " Diamond and RelatedMaterials " 2001, reported with methane CH in " The roles of argon addition in the hotfilament chemical vapor deposition system " (" diamond and associated materials ", " argon gas is added on the effect in the hot-wire chemical gas-phase deposition ") of delivering on the 10:1523-1527
4With hydrogen be source of the gas, adopt heated filament CVD method depositing nano diamond thin on the p type monocrystalline silicon piece of (100) orientation, in depositing system, need to add a large amount of argon Ars and strengthen secondary nucleation, the Nano diamond grain-size is 4～30nm.Adopt aforesaid method, before deposition, must adopt 0.5 μ m diadust to grind substrate is carried out the alligatoring pre-treatment, reach and strengthen the diamond thin nucleation density, therefore can influence the smooth slipperiness of film, in this case, but be difficult in the substrate surface deposition and obtain very slick nano-diamond membrane, and aforesaid method is to be research object with the silicon substrate material, for using extremely extensively WC-Co cemented carbide substrate material at tool and mould and wear resistant appliance field, owing to adopt the grinding alligatoring pretreatment process that destroys the substrate smooth surface and make it to produce a large amount of defectives, also do not occur suitable method at present at the very slick high-performance nano diamond thin of its surperficial directly deposition.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, propose a kind of auxiliary grid hot wire chemical vapor deposition process for preparing nano-diamond film.Substrate is even without the alligatoring milled processed through bortz powder before making its deposition, also can reach high forming core density, very high second nucleation speed is arranged in process of growth simultaneously, can growth obtain nano level diamond thin, the deposition rear film need not just can reach higher smooth finish by grinding and polishing, satisfies service requirements.
The present invention is achieved by the following technical solutions, the present invention is on the basis of heated filament CVD depositing diamond film, increase a kind of auxiliary grid, auxiliary grid deposits the initial stage at heated filament, deposit one deck diamond thin in advance, between grid and heated filament, add direct-current biasing then, reach very high second nucleation speed, guarantee growth and obtain nano level diamond thin with this method.Grid is for negative, the diamond thin of gate surface is an emitting electrons and form direct-current discharge, wherein positive ion will bombard grid, the diamond atom and the atom group that are bombarded will splash on the substrate, become diamond nucleation and growth drive point, sputter has played keying action to adamantine high-density forming core and second nucleation on the substrate, and the substrate surface deposition obtains nano-diamond film.
Below the inventive method is further described, concrete steps are as follows:
(1) substrate (silicon, Wimet WC-Co etc.) after chemical treatment, need not adopt roughening treatment, directly places the CVD equipment reaction chamber.
(2) driving source adopts heated filament (vertical pulling tantalum wire or tungsten filament), near heated filament, auxiliary grid is set, and auxiliary grid can be used the graphite bar, also can be with tungsten filament or molybdenum filament.The relative position of auxiliary grid and heated filament is relevant with the shape of substrate.When substrate is flush type, grid can place heated filament above or below, when substrate when being cylindric (as drill bit, milling cutter etc.), grid can be parallel with heated filament.
(3) (pressure 1～6KPa for example under suitable heated filament CVD processing condition, total gas flow rate 400～800ml/min, acetone/hydrogen volume is than being 1-3%, hot-wire temperature 2000-2400 ℃), because grid and heated filament distance are very near, through about 1 hour, deposit one deck diamond thin in gate surface.
(4) between grid and heated filament, add direct-current biasing (grid is for negative), produce direct-current discharge, form direct-current plasma, because this diamond thin has negative electron affinity, gate surface reaches the high temperature more than 800 ℃ again, even under the low gaseous tension of number KPa, but grid is emitting electrons also, and positive ion will bombard grid, is bombarded the diamond atom and the atom group of getting off and will splash on the substrate, become substrate diamond thin nucleation drive point, be easy to nucleation.Under the triple role of d.c. sputtering, direct-current plasma and heated filament CVD, can reach high forming core density (10
11～10
12/ cm
2) and secondary nucleation speed, on substrate, grow high-quality nano-diamond film.
The invention has the beneficial effects as follows: do not damaging as far as possible under original substrate surface smooth finish prerequisite, by auxiliary grid is set, auxiliary grid after depositing one deck diamond thin under the heated filament effect in advance, between grid and heated filament, apply direct-current biasing, positive ion will bombard the diamond film of gate surface, in CVD growth deposition process, gate surface is in diamond film growth and by in the homeostasis process of sputter, sputter has played keying action to adamantine high-density forming core and second nucleation on the substrate, guaranteed the growth of nano-diamond film, finally reach at slick substrate surface, acquisition can be satisfied the purpose of the ultra-smooth nano-diamond film of sticking power requirement.
Description of drawings
Fig. 1 embodiment of the invention auxiliary grid heated filament CVD device synoptic diagram
Fig. 2 embodiment of the invention planar substrate heated filament and auxiliary grid relative position synoptic diagram
Fig. 3 embodiment of the invention cylindrical specimen heated filament, grid and substrate relative position synoptic diagram
Embodiment
In order to handle technical solution of the present invention better, be example with the flush type substrate below, be described further in conjunction with auxiliary heated filament CVD device and coating detected result.Fig. 1 is an auxiliary grid heated filament CVD device synoptic diagram, wherein 1 is reaction chamber, 2 is reaction gas inlet, 3 is heated filament (one group of parallel heated filament of vertical pulling), 4 is auxiliary grid (one group of parallel graphite bar), residing plane of heated filament and the residing plane of grid are parallel to each other, but as shown in Figure 2, heated filament 2 trends are vertical mutually with gate bar 3 trends, 5 is sample (flush type substrate), 6 is the sample support platform, and it can rotate, can cool off again, 7 is that (heated filament connects positive pole to adjustable power of direct current, grid connects negative pole), 8 is heater supply, it can make the hot-wire temperature be increased to 2000～2400 ℃, and 9 is vacuum and Pneumatic controller, comprises mechanical pump, variable valve, vacuumometer and tensimeter etc.With the difference of general heated filament CVD be to have increased auxiliary grid.This auxiliary grid and heated filament lean on nearerly (5～10 millimeters), and after moving for some time (being called the pre-deposition stage) under the heated filament CVD of the routine processing condition, its surface can deposit certain thickness diamond thin.Because diamond thin has negative electron affinity, when its temperature reaches more than 800 ℃ (being depositing temperature just), even residing gaseous tension is up to number KPa, also be easy to emitting electrons, if at this moment apply a direct current bias voltage (grid is for negative), can produce direct-current discharge, and positive ion will bombard grid, its surperficial diamond thin is carried out sputter, splash to the drive point that diamond atom on the substrate and atom group become forming core or second nucleation, to satisfy Nano diamond forming core and required forming core density and the speed of growth.Under the triple role of d.c. sputtering, direct-current plasma and heated filament CVD,, grow certain thickness gem grade diamond film on the substrate through a few hours.In process of growth, the diamond film of gate surface is in growth and by in the running balance of sputter, and sputter has play a part crucial for the forming core and the second nucleation speed that improve on the substrate.In addition, the d.c. sputtering effect also helps reducing substrate film depositing temperature and internal stress, can still keep higher growth velocity under low underlayer temperature.
When sample (substrate) is cylindrical shape (as drill bit, milling cutter etc.), as shown in Figure 3, heated filament 1, auxiliary grid 2 and sample 3 are parallel arrangement, and grid is between heated filament and substrate.Identical under the situation of other heated filament CVD equipment and processing condition and planar shaped substrate, can obtain the fine nano-diamond membrane at substrate surface equally.
Below be embodiments of the invention:
Be matrix specimen preparation nano-diamond film with silicon chip and inserted drill respectively.
(1) silicon chip sample
After 3 cun silicon chips are carried out conventional clean with the vitriol oil-hydrogen peroxide and diluted hydrofluoric acid etc. successively, just directly place on the sample support platform of reaction chamber shown in Figure 1 without the bortz powder milled processed, hot filament adopts the tantalum wire of 0.6 millimeter of 6 φ, and stretching with resistant to elevated temperatures spring.Grid adopts the graphite bar of 2.5 millimeters of 5 φ, and 5～6 millimeters of grid plane and filament interplanar spacings are with apart 8～10 millimeters of sample silicon chips.Only reaction chamber vacuumizes the back and feeds reactant gases hydrogen and acetone, and acetone/hydrogen ratio is 2%, reaction chamber total gas flow rate 400 ml/min, adjust gaseous tension to the 4KPa, the heating tantalum wire through 1 hour pre-deposition, can deposit one deck diamond thin to 2200 ℃ of temperature on gate surface.After finishing pre-deposition, adjust air pressure to 3KPa, between grid and heated filament, apply a direct current bias voltage (grid for negative, heated filament for just), bias current is 200～300 milliamperes, positive ion begins to bombard grid, the diamond atom and the atom group that splash on the substrate become the forming core drive point, under the triple role of d.c. sputtering, direct-current plasma and heated filament CVD, grew the nano-diamond film of thick about 2.5～3 μ m on the time substrate through 4 hour.
With atomic force microscope AFM, Raman spectrum, X-ray diffraction, surface profiler the sample of preparation is characterized.The nano-diamond film of AFM observation post preparation is evenly finer and close than conventional heated filament CVD method, and surfacing is smooth, and the average grain size in the film is 10nm.The Raman spectrum shows 1332cm
-1The diamond characteristic peak is obvious, and 1580cm
-1Near graphite peaks a little less than, illustrated that the nano-diamond film purity that obtains is very high; X-ray diffractogram presents two diamond characteristic peaks, but halfwidth increases than conventional diamond, and measuring specimen surface roughness with the surface step instrument is R
Max=22.9nm.。
(2) Wimet sample
Sample adopts high precision hard alloy bar YG6 (WC-Co6%) (φ 2mm), and the surface is through polished finish.Sample only soaks half an hour with dilute hydrochloric acid to be removed cobalt surface and not to grind alligatoring, before putting into depositing device with the acetone ultrasonic cleaning and apply adhesion promoters and dry up.As shown in Figure 3, heated filament adopts three Zhi Pai Tantalum silks (diameter 0.8mm), remains straight and upright horizontality with the stretching fixedly ， of high temperature resistant spring Shi Tantalum silk in whole deposition process, and sample is placed in the middle of two heated filaments, and parallel with heated filament.For guaranteeing the homogeneity of diamond nucleation on the smooth substrates, need careful heated filament and sample spacing and each the heated filament spacing adjusted.Heated filament is apart from the about 6mm of sample.Grid adopts the molybdenum bar of 1.5 millimeters of 4 φ, is spaced respectively in the middle of heated filament and sample, and parallel with heated filament, concrete deposition parameter is identical with silicon chip, the about 6h of depositing time.Carry out nano-diamond film structure and Performance Detection with scanning electron microscope (SEM), atomic force microscope (AFM), Raman spectrum (Raman) and X-ray diffraction (XRD), the granularity of film has been reduced to nanoscale, and (grain fineness number is 20～80nm), thick about 2.5～3 μ m, surfaceness R
a≤ 0.1 μ m.
Claims (3)
1, a kind of auxiliary grid hot wire chemical vapor deposition process for preparing nano-diamond film, it is characterized in that, on the basis of heated filament CVD depositing diamond film, increase a kind of auxiliary grid, auxiliary grid deposits the initial stage at heated filament, deposit one deck diamond thin in advance, between grid and heated filament, add direct-current biasing then, grid is for negative, the diamond thin of gate surface is an emitting electrons and form direct-current discharge, and wherein positive ion will bombard grid, be bombarded the diamond atom and the atom group of getting off to splash on the substrate, become diamond nucleation and growth drive point, sputter is 10 to adamantine density on the substrate
11～10
12/ cm
2Forming core and second nucleation played keying action, substrate surface deposition obtains nano-diamond film.
2, the auxiliary grid hot wire chemical vapor deposition process of preparation nano-diamond film according to claim 1 is characterized in that, below by step it is further qualified:
(1) substrate directly places the CVD equipment reaction chamber after chemical treatment;
(2) driving source adopts heated filament, near heated filament, auxiliary grid is set, when substrate is flush type, grid place heated filament above or below, when substrate when being cylindric, grid is parallel with heated filament;
(3) under heated filament CVD processing condition,, deposit one deck diamond thin in gate surface through 1 hour;
(4) between grid and heated filament, add direct-current biasing, grid is for negative, produce direct-current discharge, form direct-current plasma, positive ion will bombard grid, be bombarded the diamond atom and the atom group of getting off and will splash on the substrate, become substrate diamond thin nucleation drive point, be easy to nucleation, under the triple role of d.c. sputtering, direct-current plasma and heated filament CVD, reach 10
11～10
12/ cm
2Forming core density and secondary nucleation speed, on substrate, grow nano-diamond film.
According to the auxiliary grid hot wire chemical vapor deposition process of claim 1 or 2 described preparation nano-diamond films, it is characterized in that 3, described auxiliary grid is the graphite bar, perhaps tungsten filament or molybdenum filament.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387752C (en) * | 2005-10-14 | 2008-05-14 | 南京航空航天大学 | System for continuous batch preparing diamond film |
| CN102435596A (en) * | 2011-09-08 | 2012-05-02 | 中国科学院研究生院 | Method and device for testing light emission spectrum in hot filament chemical vapor deposition |
| CN105603385B (en) * | 2016-01-15 | 2018-07-06 | 山西大学 | A kind of device and method for preparing diamond crystal thin-film material |
| CN105506577B (en) * | 2016-03-02 | 2018-01-23 | 安徽纯源镀膜科技有限公司 | A kind of ejector of DLC film ion source |
| CN106480424A (en) * | 2016-09-28 | 2017-03-08 | 同济大学 | A kind of temperature field compensation device being applied to HFCVD equipment |
| CN110629192A (en) * | 2018-06-25 | 2019-12-31 | 廊坊西波尔钻石技术有限公司 | Method and equipment for preparing artificial CVD diamond for jewelry |
| CN117305805A (en) * | 2023-09-27 | 2023-12-29 | 上海交通大学 | Nuclear fuel cladding modification method based on nano diamond coating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145712A (en) * | 1991-02-08 | 1992-09-08 | Center For Innovative Technology | Chemical deposition of diamond |
| JPH0585892A (en) * | 1991-07-31 | 1993-04-06 | Nec Corp | Diamond thin film and its production |
| CN1096548A (en) * | 1993-06-17 | 1994-12-21 | 上海交通大学 | The manufacture method of single crystal diamond diaphragm |
| CN1327084A (en) * | 2001-05-31 | 2001-12-19 | 上海交通大学 | Method for preparing wire drawing mold with diamond compoiste coating |
-
2004
- 2004-10-28 CN CNB2004100675713A patent/CN1294293C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145712A (en) * | 1991-02-08 | 1992-09-08 | Center For Innovative Technology | Chemical deposition of diamond |
| JPH0585892A (en) * | 1991-07-31 | 1993-04-06 | Nec Corp | Diamond thin film and its production |
| CN1096548A (en) * | 1993-06-17 | 1994-12-21 | 上海交通大学 | The manufacture method of single crystal diamond diaphragm |
| CN1327084A (en) * | 2001-05-31 | 2001-12-19 | 上海交通大学 | Method for preparing wire drawing mold with diamond compoiste coating |
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Effective date of registration: 20091127 Address after: No. 800, Dongchuan Road, Shanghai, Minhang District: 200240 Co-patentee after: Shanghai Jiaoyou Diamond Coating Co., Ltd. Patentee after: Shanghai Jiao Tong University Address before: No. 800, Dongchuan Road, Shanghai, Minhang District: 200240 Patentee before: Shanghai Jiao Tong University |