CN100447294C - Method and apparatus for growing thick nano diamond film - Google Patents
Method and apparatus for growing thick nano diamond film Download PDFInfo
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- CN100447294C CN100447294C CNB2006100390864A CN200610039086A CN100447294C CN 100447294 C CN100447294 C CN 100447294C CN B2006100390864 A CNB2006100390864 A CN B2006100390864A CN 200610039086 A CN200610039086 A CN 200610039086A CN 100447294 C CN100447294 C CN 100447294C
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- substrate
- bias voltage
- diffuser
- diamond film
- voltage
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002113 nanodiamond Substances 0.000 title claims description 18
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 17
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 16
- 239000010432 diamond Substances 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 230000006911 nucleation Effects 0.000 claims description 11
- 238000010899 nucleation Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000010903 primary nucleation Methods 0.000 abstract 1
- 238000010900 secondary nucleation Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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Abstract
The present invention relates to a method and a device for growing a thick nanometer diamond film, which belongs to the field of the growth of superhard materials. Mixed gases containing hydrogen, carbonaceous gases and inert gases enter a deposition chamber through a gas inlet device which is provided with a water cooling passage, and are sprayed to hot filaments and a substrate. Lower bias voltage which is a positive electrode corresponding to a substrate supporting table and upper bias voltage which is negative voltage corresponding to the gas inlet device are applied to a hot filament array to cause the deposition surface of the substrate to be nucleated. The lower bias voltage which is zero voltage or negative voltage is applied to the substrate supporting table, the upper bias voltage which is negative voltage corresponding to the gas inlet device is applied correspondingly to the hot filament array, and the diamond film is grown on the deposition surface of the substrate. When the existence, the magnitude and the space of the two kinds of bias voltage are controlled, the nucleating process and the growing process of diamond are carried out alternately, and the nucleating technology and the growing technology are carried out alternately to suppress the growth of grains. The present invention has the advantages of large primary nucleation density and secondary nucleation density, high growth speed and thick nanometer diamond film.
Description
One, technical field
The method of growing thick nano diamond film of the present invention belongs to superhard material growth field.
Two, background technology
Chinese patent CN1261927 has proposed with two bias voltage hot wire process growing diamond films.But there is following defective in this method: if temperature control is improper on the grid, can produce thereon and adhere to the not firm carbon film that contains, the fragment of these films may drop on heated filament or the substrate, influences growth of diamond and quality, diffuser and independently grid increased the complicacy of equipment; Adopt this method and apparatus thin nano-diamond membrane of can only growing in addition, can not growing thick nano diamond film, and thick nano diamond film has intensity height, remarkable advantage that wear resistance is good.
Three, summary of the invention
The invention provides a kind of method of growing thick nano diamond film, with growth pressure height, purity height, thick nano diamond film that wear resistance is good.
A kind of method of growing thick nano diamond film comprises following process: the substrate that will have a deposition surface is arranged on the substrate supports platform in the vapor deposition chamber, the deposition surface of substrate and and its diffuser of being separated by between be provided with heater array; It is indoor that the mixed gas that will contain hydrogen and carbonaceous gas flows into described vapour deposition through diffuser, and the heating heater array is to about 1800 ℃-2900 ℃ temperature range, and described substrate is heated in about 300 ℃-1100 ℃ temperature range; Make relative substrate supports platform of heater array and diffuser produce bias voltage respectively by two groups of direct supplys: when heater array is the following bias voltage of positive voltage with respect to the substrate supports platform, be the last bias voltage of negative voltage with respect to diffuser, the substrate deposition surface nucleation; When heater array is the last bias voltage of negative voltage with respect to diffuser, when being the following bias voltage of 0 voltage or negative voltage with respect to the substrate supports platform, the growth of substrate deposition surface diamond film.It is characterized in that, also comprise following process: also be mixed with rare gas element in mixed gas, making inert gas content shared volume ratio in mixed gas is 50%-99%; Described diffuser is carried out water-cooled, make mixed gas in inlet plenum and the exit be not decomposed, and the diffuser surface is not tied contain carbon film or tie the adeciduate carbon film that contains; Control following bias voltage between described substrate supports platform and the heated filament and the last bias voltage between heated filament and the diffuser, make nucleation and growth hocket, the growth of control diamond particles size.It is relatively good at 5-15 minute that nucleation and growth replace the timed interval.Can make diamond film speed fast like this, can control the diamond particles size again in the nano material characteristic range.
A kind of equipment of growing thick nano diamond film, comprise diffuser, substrate, be in the heater array between substrate and the diffuser, with two groups of direct supplys, wherein one group of direct supply makes the relative substrate supports platform of heater array produce down bias voltage, another group direct supply the relative diffuser of heater array to be produced go up bias voltage, when heater array is the following bias voltage of positive voltage with respect to the substrate supports platform, with respect to diffuser is the last bias voltage of negative voltage, the substrate deposition surface nucleation; When heater array is the last bias voltage of negative voltage with respect to diffuser, when being the following bias voltage of 0 voltage or negative voltage with respect to the substrate supports platform, the growth of substrate deposition surface diamond film.It is characterized in that: described diffuser comprises chamber and following chamber, last chamber is the mixed gas inlet chamber, the inlet that a mixed gas is arranged, following chamber is mixed gas uniformly distributing chamber, is separated by dividing plate between the chamber up and down, has many equally distributed apertures on the dividing plate, bottom, following chamber has many equally spaced long and narrow gas passages, have water-cooling channel between every adjacent gas passage, these water-cooling channels communicate, and a total water inlet and a total water outlet are arranged.
Four, description of drawings
Fig. 1 is a growing thick nano diamond film equipment synoptic diagram of the present invention.
Label title among Fig. 1: 1. diffuser, 2. heater array, 3. substrate, 4. diamond film, 5. reaction chamber bell jar, 6. the reaction chamber base plate 7. descends direct supply, 8. goes up direct supply, 9. goes up the chamber, 10. dividing plate, 11. times chambers, 12. water holes, 13. air inlet slits.
Five, embodiment
According to shown in Figure 1, the equipment of growing thick nano diamond film of the present invention comprise diffuser 1, substrate 3 and be in substrate 3 and diffuser 1 between heater array 2, also comprise direct supply 8 and following direct supply 7, last direct supply 8 provides the last bias voltage between heater array 2 and the diffuser 1; Following direct supply 7 provides the following bias voltage between heater array 2 and the substrate 3.Described diffuser 1 comprises chamber 9 and following chamber 11, last chamber 9 is the mixed gas inlet chamber, the inlet that a mixed gas is arranged, following chamber 11 is mixed gas uniformly distributing chamber, 11 of last chamber 9 and following chambers are separated by slim dividing plate 10, have many equally distributed apertures on the dividing plate 10,11 bottoms, following chamber have many equally spaced long and narrow air inlet slits 13.13 of every adjacent air inlet slits have water hole 12, and these water holes 12 are following mutually logical, and a total water inlet and a total water outlet are arranged.
Because the water-cooled effect in water hole 12 in the diffuser 1, making mixed gas reach the exit in inlet plenum is not decomposed, and diffuser 1 surface is not tied contain carbon film or tie the adeciduate carbon film that contains, make the impurity and the fragment of these generations be unlikely to fall in the nano-diamond membrane of growth, to have guaranteed the quality of nano-diamond membrane.
It is the following bias voltage of positive electrode that heater array is imposed with respect to the substrate supports platform, and is the last bias voltage of negative voltage with respect to diffuser, makes the substrate deposition surface nucleation; For the substrate supports platform is the following bias voltage of 0 voltage or negative voltage, and relatively heater array to impose with respect to diffuser be the last bias voltage of negative voltage, substrate deposition surface diamond film is grown.
If control bias voltage size between described substrate supports platform and the heated filament, have or not and the timed interval and heated filament and diffuser between the bias voltage size and the timed interval, make nucleation and growth hocket, can control the diamond particles size in scope with nano material characteristic.
The method of described growing thick nano diamond film of the present invention is described below in conjunction with a specific embodiment:
Support on the platform put into reaction chamber substrate through Si substrate after the polished and cleaned, in reaction chamber, feed Ar, H2, CH4 mixed gas 200SCCM, volume ratio is Ar: H2: CH4=85: 11: 4, diffuser is through water-cooled, make mixed gas not decompose in diffuser inside and exit surface, simultaneously, at the diffuser exit surface caducous carbon film that contains of not growing.Heater array is heated to 2200 ℃, and 500 ℃ of underlayer temperatures, heated filament and substrate distance 6mm, diffuser and heated filament add the relative heater array of 250V and form direct-current plasma for the anodal direct-current biasing apart from 35mm on the diffuser; Adding the relative heater array of 150V on the substrate is the direct-current biasing of negative pole, continues 10 minutes, and carbon-containing group nucleation on the substrate is removed this 150V negative bias and allowed nucleus growth ten minutes, hockets every ten minutes nucleation and growth then; Grow the thick nano-diamond membrane of 30 μ m after 5 hours.
The adding of vast scale argon gas makes grain refining.Its shared volume ratio in mixed gas can be 50%-99%.Except that using argon gas, use other rare gas elementes also passable.
Claims (2)
1. the method for a growing thick nano diamond film comprises following process:
(a) substrate that will have a deposition surface is arranged on the substrate supports platform in the vapor deposition chamber, the deposition surface of substrate and and its diffuser of being separated by between be provided with heater array;
(b) to flow into described vapour deposition through diffuser indoor for the mixed gas that will contain hydrogen and carbonaceous gas, and the heating heater array is to about 1800 ℃-2900 ℃ temperature range, and described substrate is heated in about 300 ℃-1100 ℃ temperature range;
(c) heater array being imposed with respect to the substrate supports platform is the following bias voltage of positive electrode, and is the last bias voltage of negative voltage with respect to diffuser, makes the substrate deposition surface nucleation;
(d) heater array is imposed the following bias voltage that relative substrate supports platform is 0 voltage or negative voltage, and be the last bias voltage of negative voltage, make the growth of substrate deposition surface diamond film with respect to diffuser;
It is characterized in that, also comprise following process:
(e) also be mixed with rare gas element in mixed gas, making inert gas content shared volume ratio in mixed gas is 50%-99%;
(f) described diffuser is carried out water-cooled, make mixed gas in inlet plenum and the exit be not decomposed, and the diffuser surface is not tied contain carbon film or tie the adeciduate carbon film that contains;
(g) following bias voltage between described substrate supports platform of control and the heated filament and the last bias voltage between heated filament and the diffuser make nucleation and growth hocket, and control diamond particles size is in the scope with nano material characteristic.
2. the method for growing thick nano diamond film according to claim 1 is characterized by: the timed interval that nucleation and growth hocket is 5～15 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100390864A CN100447294C (en) | 2006-03-27 | 2006-03-27 | Method and apparatus for growing thick nano diamond film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100390864A CN100447294C (en) | 2006-03-27 | 2006-03-27 | Method and apparatus for growing thick nano diamond film |
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| Publication Number | Publication Date |
|---|---|
| CN1827846A CN1827846A (en) | 2006-09-06 |
| CN100447294C true CN100447294C (en) | 2008-12-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100390864A Expired - Fee Related CN100447294C (en) | 2006-03-27 | 2006-03-27 | Method and apparatus for growing thick nano diamond film |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2940326B1 (en) * | 2008-12-19 | 2011-03-25 | Centre Nat Rech Scient | METHOD FOR MANUFACTURING DIAMOND COMPOSITE MATERIALS |
| CN103643218A (en) * | 2013-11-14 | 2014-03-19 | 中山市创科科研技术服务有限公司 | Simple apparatus for preparing diamond film |
| AT519217B1 (en) | 2016-10-04 | 2018-08-15 | Carboncompetence Gmbh | Apparatus and method for applying a carbon layer |
| CN110678573A (en) * | 2017-01-16 | 2020-01-10 | 持续能源解决有限公司 | Method and device for preventing desublimation in direct contact heat exchanger |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060316A (en) * | 1987-04-03 | 1992-04-15 | 富士通株式会社 | The method of vapor deposition of diamond and device |
| CN1021713C (en) * | 1988-04-08 | 1993-07-28 | 国际商业机器公司 | Method and apparatus for concurrent modification of an Index Tree in a transaction processing system |
| US5989511A (en) * | 1991-11-25 | 1999-11-23 | The University Of Chicago | Smooth diamond films as low friction, long wear surfaces |
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2006
- 2006-03-27 CN CNB2006100390864A patent/CN100447294C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060316A (en) * | 1987-04-03 | 1992-04-15 | 富士通株式会社 | The method of vapor deposition of diamond and device |
| CN1021713C (en) * | 1988-04-08 | 1993-07-28 | 国际商业机器公司 | Method and apparatus for concurrent modification of an Index Tree in a transaction processing system |
| US5989511A (en) * | 1991-11-25 | 1999-11-23 | The University Of Chicago | Smooth diamond films as low friction, long wear surfaces |
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| CN1827846A (en) | 2006-09-06 |
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