CN102492934B - A kind of device, method and gained graphene film of preparing graphene film - Google Patents
A kind of device, method and gained graphene film of preparing graphene film Download PDFInfo
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- CN102492934B CN102492934B CN201110442123.7A CN201110442123A CN102492934B CN 102492934 B CN102492934 B CN 102492934B CN 201110442123 A CN201110442123 A CN 201110442123A CN 102492934 B CN102492934 B CN 102492934B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000012010 growth Effects 0.000 claims abstract description 59
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 238000010924 continuous production Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 42
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000003139 buffering effect Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 13
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 33
- 238000010586 diagram Methods 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The present invention relates to a kind of by the device of chemical vapour deposition technique (CVD method) continuous production graphene film, it is mainly by Sample Room, boiler tube with go out specimen chamber and form, high growth temperature district of growth room will keep high growth temperature temperature always, need not wait for the process of heating and cooling, and solve the transmission problem of sample in high-temperature region, can carry out continual growth, thereby increase substantially the output of preparing graphene film by chemical vapour deposition (CVD) (CVD) method.
Description
Technical field
The present invention relates to a kind of apparatus and method of preparing graphene film, and the Graphene making is thinFilm. More specifically, relate to a kind of by continuous chemical vapour deposition technique (be called for short CVD method)Prepare the apparatus and method of graphene film, and the graphene film making.
Background technology
Graphene has excellent mechanics, calorifics, electricity and magnetic performance, is expected to receive in high-performanceMultiple fields such as rice electronic device, composite, energy storage obtain extensive use, become in recent yearsFor one of the focus of research.
The process of existing CVD method growing graphene film, as shown in Figure 1: first by tinsel1 under the protection of the environment of argon gas and hydrogen in approximately 1000 DEG C of the pre-heat treatment approximately 1.5 hours, then willIt is placed in circular quartz glass boiler tube 2 vitellariums, passes into methane 3, carries out carbon decomposition, growthTime is about 20-30 minute.
In the process of CVD method growing graphene film, before growth and after growth, need respectivelyOpening boiler tube puts into tinsel and takes out the Graphene sample of having grown. Now, boiler tube insideTo inevitably be exposed in atmosphere. For preventing that airborne oxygen from entering high temperature furnace pipe and being oxidizedGraphene sample also may be stained boiler tube inwall, and the temperature by the time of having to after every secondary growth is down to approximately 200DEG C time just can open boiler tube. Therefore,, while taking out sample, will have to wait at least 30 minutes at every turnTemperature fall time; And putting into after tinsel, close boiler tube and vacuumize, be warming up to again. at every turnApproximately 1000 DEG C, also will need more than 2 hours. Lifting/lowering temperature waiting process has a strong impact on for a long timeThe output of graphene film, cannot meet the demand of large-scale production.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of device of continuous production graphene film,It comprises the boiler tube of a both ends open, this both ends open respectively with an opening of a Sample RoomEnd is connected with an openend that goes out specimen chamber, and wherein the junction of boiler tube and Sample Room is provided withA valve and intake interface parts, boiler tube is provided with a valve with the junction that goes out specimen chamberWith the interface unit of giving vent to anger, and described Sample Room is also equipped with one and enters/give vent to anger interface unit(for air inlet or the interface unit of giving vent to anger) and an injection port, described in go out specimen chamber and be also equipped with oneIndividually enter/give vent to anger interface unit and an outlet.
In addition, the invention provides a kind of method of continuous production graphene film, comprise following stepRapid: (1) packs a base material sample in boiler tube, and to the whole system except Sample RoomVacuumize,
(2) in boiler tube, pass into protective gas,
(3) to boiler tube heating, to reaching growth temperature,
(4) to boiler tube and go out in specimen chamber to pass into growth gasses, make film growth,
(5) in growth, pack another same base material sample into Sample Room, andThis chamber is vacuumized,
(6) in Sample Room, pass into growth gasses, until identical with boiler tube internal gas pressure,
(7) after previous sample grown completes, by described another same base material sampleSend into boiler tube,
(8) the base material sample that makes to have grown enters out specimen chamber,
(9) from go out specimen chamber, shift out the base material sample of having grown, vacuumize going out specimen chamber afterwards,And again pass into same growth gasses, until identical with boiler tube internal gas pressure, and
(10) repeating step (5) is to (9).
Finally, the present invention also provides a kind of graphene film of being prepared by the inventive method.
Use apparatus of the present invention and method, can continuous production graphene film, greatly improve itOutput, has met the requirement of CVD method large-scale production graphene film.
Brief description of the drawings
Fig. 1 is a schematic diagram of existing CVD method growing graphene film,
Fig. 2 is a schematic diagram of apparatus of the present invention,
Fig. 3 is a schematic diagram of base material sample,
Fig. 4 is the Sample Room profile of one embodiment of the invention,
Fig. 5 be one embodiment of the invention go out specimen chamber profile.
Detailed description of the invention
In the present invention, term used " sample " refers to the base for supporting graphene film growthThe base material sample of bottom material sample itself or band towing parts.
In literary composition, term used " growth gasses " or " growth gasses source " refer to for growing grapheneThe gas of film.
The invention provides a kind of device of continuous production graphene film, it comprises that two ends openMouthful boiler tube, this both ends open goes out specimen chamber with openend of a Sample Room and one respectivelyOpenend connects, and wherein the junction of boiler tube and Sample Room is provided with a valve and one and entersGas interface unit, boiler tube is provided with a valve and the interface portion of giving vent to anger with the junction that goes out specimen chamberPart, and described Sample Room is also equipped with one and enters/give vent to anger interface unit and an injection port, described inGoing out specimen chamber is also equipped with one and enters/give vent to anger interface unit and an outlet.
Fig. 2 is a schematic diagram of apparatus of the present invention. Below in conjunction with Fig. 2, apparatus of the present invention are carried outDescribe in detail.
As shown in Figure 2, this device comprises a boiler tube 14, and it is made up of exotic material, canQuartz glass or other melting temperatures higher than the material of 1100 DEG C, preferably quartz glass. This boiler tube14 mainly comprise a vitellarium (being high-temperature region) 3. Before vitellarium 3, preferably include onePreheating zone 2 (be positioned at vitellarium 3 before and be adjacent) and a buffering area 5 (are positioned at preheating zoneBefore 2 and be adjacent); After vitellarium 3, preferably include a cooling area 4 and (be positioned at growthAfter district 3 and be adjacent) and/or cooling zone 15 (after being positioned at cooling area 4 and with its phaseAdjacent). Wherein, preheating zone temperature is 400-600 DEG C, and vitellarium temperature is 900-1100 DEG C, coolingDistrict's temperature is that room temperature to the sample of having grown can be exposed to the temperature (being preferably room temperature) in atmosphere.The temperature control of preheating zone, vitellarium and cooling area all can be by conventional method for example by heater blockComplete with thermometric feedback circuit. For cooling zone 15, it can be the cooling or additional for example circulation of natureWater cooling.
Boiler tube 14 can be the various shapes such as cylindrical, cuboid, pref. cylindrical.
Can use heating and temperature controlling device 1 to heat to boiler tube 14, described heating and temperature controlling device is passableAny conventional equipment of realizing this object, for example electromagnetic induction heater.
Preferably, the length of boiler tube Zhong Ge district (except cooling zone) is equal to sample length or is sampleThe integral multiple of product length. The total length of boiler tube preferably equals the integral multiple of sample length.
Equal sample length a in the length of vitellarium 3, the total length of boiler tube 14 is mainCool time of the sample being completed by growth (refer to sample from vitellarium 3 out temperature be down to canBe exposed to the required time of temperature in atmosphere) decide with the ratio of graphene film growth time.If be n times of growth time cool time, as shown in Figure 2, cooling area 4 and cooling zone 15Length by the n that is at least sample length doubly, i.e. na; Add buffering area 5, preheating zone 2 and(its length is all at least length a), and now the total length of boiler tube 14 is at least sample in vitellarium 3(n+3) of product length times, i.e. (n+3) a.
Particularly, the not make-up machinery transmission device of boiler tube 14 inside of apparatus of the present invention, to keep awayExempt from inefficacy or the distortion of hot environment underdrive device, successively will but dependence pushes follow-up sampleSample above heads into out specimen chamber.
In growth course, while transmission in boiler tube 14 for fear of sample, damage boiler tube 14 inWall can arrange a resistant to elevated temperatures sample and transmit track, in order to avoid sample straight in boiler tube 14Connect with boiler tube 14 and contact and rub. Sample transmits track material therefor and should be high temperature resistant, high machinery by forceThe material of degree, as carborundum etc.; Its shape is limited can carry sample and to make it be difficult for slippage, exampleAs having suitable radian or suitable roughness.
The two ends of boiler tube 14 go out specimen chamber 11 with a Sample Room 10 and one respectively and are connected, junctionBe provided with valve and gas interface unit. Preferably, described in be connected to flange and connect, furtherPreferably, described gas interface parts are connected on flange. In the embodiment of Fig. 2, concreteFor, between boiler tube 14 and Sample Room 10, be provided with a vacuum valve 9; With a band intake interfaceFlange 6 (be called for short inlet flange 6), in order to boiler tube 14 and the vacuum valve 9 of being tightly connected, hereinDescribed intake interface is in order to connect protective gas source or growth gasses source. Boiler tube 14 and go out specimen chamber 11Between be provided with a vacuum valve 8; With the give vent to anger flange 7 (abbreviation give vent to anger flange 7) of interface of a band,In order to boiler tube 14 and the vacuum valve 8 of being tightly connected, the interface of giving vent to anger described herein is in order to connect vavuum pump.
Due to Sample Room 10 with go out transmission device (if any), the vavuum pump in specimen chamber 11And the vibration producing when vacuum valve switch cause larger stress may to boiler tube 14, thus can energy lossBad boiler tube 14, therefore can be at boiler tube 14 and Sample Room 10, go out specimen chamber 11 junctions and respectively add oneSection flexible connection devices, as bellows.
Sample Room 10 is equipped with one and enters/give vent to anger interface 12, in order to connect growth gasses source, protectionGas source or vavuum pump, have outside change-over switch with switching gas circuit; With an injection port 21.
Go out specimen chamber 11 and be equipped with one and enter/give vent to anger interface 13, in order to connect growth gasses source, protectionGas source or vavuum pump, have outside change-over switch with switching gas circuit; With an outlet 41.
Sample Room 10 and vacuum valve 9 are preferably made up of exotic material, make can bear through preheatingThe temperature of sample, for example, be made up of stainless steel; Go out specimen chamber 11 and vacuum valve 8 by such material systemBecome: at least can bear and be cooled to the temperature that can be exposed to the sample in atmosphere, for example, by stainless steelMake; Described flange is made up of exotic material, as stainless steel.
To Sample Room 10 and the shape that goes out specimen chamber 11 without particular requirement, preferably with the shape phase of sampleSame or similar. Enter/give vent to anger interface 12 and 13 and can be positioned at the upper surface of respective compartments or closing of side surfaceSuitable position, is preferably placed at upper surface. Position and shape to injection port 21 and outlet 41 are equalWithout particular requirement, as long as can realize the object of dress sample and sampling, preferably lay respectively at Sample RoomWith the upper surface that goes out specimen chamber.
The described constituent material that enters/give vent to anger interface 12 and 13, injection port 21 and outlet 41 is preferredIdentical with the constituent material of its chamber separately (so far for repeating).
Use apparatus of the present invention, can continuous production graphene film, greatly improve its output,Meet the requirement of CVD method large-scale production graphene film.
In addition, the invention provides a kind of method of continuous production graphene film, comprise following stepRapid: (1) packs a base material sample in boiler tube, and to the whole system except Sample RoomVacuumize,
(2) in boiler tube, pass into protective gas,
(3) to boiler tube heating, to reaching growth temperature,
(4) to boiler tube and go out in specimen chamber to pass into growth gasses, make film growth,
(5) in growth, pack another same base material sample into Sample Room, andThis chamber is vacuumized,
(6) in Sample Room, pass into growth gasses, until identical with boiler tube internal gas pressure,
(7) after previous sample grown completes, by described another same base material sampleSend into boiler tube,
(8) the base material sample that makes to have grown enters out specimen chamber,
(9) from go out specimen chamber, shift out the base material sample of having grown, vacuumize going out specimen chamber afterwards,And again pass into same growth gasses, until identical with boiler tube internal gas pressure, and
(10) repeating step (5) is to (9).
Below in conjunction with Fig. 2, the inventive method specific embodiments is described.
(1) place in 2,3 and 5 districts and install graphene film growth base material sample, soAfter vacuum valve 8 is opened, vacuum valve 9 cuts out, the inlet close of inlet flange 6, goes out specimen chamber11 close. Open the gas interface of the flange 7 of giving vent to anger, with vavuum pump by whole system (Sample Room 10Except) vacuumize, to vacuum be 10-3-10-5Holder.
(2) close the flange 7 of giving vent to anger, open the air inlet of inlet flange 6, interior logical to boiler tube 14Protective gas, as argon gas, hydrogen, nitrogen or their mist, until air pressure is atmospherePress, switch and give vent to anger flange 7 to UNICOM's atmosphere. Continue to pass into protective gas.
(3) boiler tube 14 is heated up. Boiler tube 14 generally can be divided into 3 districts, as shown in Figure 3,Be respectively preheating zone 2, vitellarium 3 and cooling area 4. Each length of an interval degree is a, each district temperatureGrowth conditions parameter (being the conditional parameter of required graphene film) by Graphene sample determines.The temperature of preheating zone 2 is generally 400-600 DEG C, and the temperature of vitellarium 3 is generally 900-1100 DEG C,The temperature of cooling area is generally room temperature to the sample of having grown, and can be exposed to temperature in atmosphere (excellentElect room temperature as). In addition, for example, for supporting the base material (Copper Foil) of graphene film growthThe length of sample is also a.
(4) temperature of vitellarium 3 reaches after film growth temperature, switches and gives vent to anger flange 7 to vacuumPump, passes into growth gasses by inlet flange 6, is generally the mist of argon gas, hydrogen and methane.The flowrate proportioning of concrete each gas is determined by the conditional parameter of required graphene film. Pass into growth gasAfter body half a minute, close vacuum pump valve, when boiler tube internal gas pressure rises to after atmospheric pressure, switch the method for giving vent to angerBlue 7 to UNICOM's atmosphere, closes vacuum valve 8. Then start growth, growth time is generally 5-30Minute (can regulate to control by atmosphere).
(5) when growth, open Sample Room 10, another is installed to Graphene growth baseThe sample of bottom material is put into Sample Room 10, afterwards, closes Sample Room 10, opens into/the interface of giving vent to anger12, rapid (being less than a growth cycle) is evacuated to 10 by Sample Room 10-3-10-5Holder.
Fig. 3 is a schematic diagram of Graphene growth base material sample. Wherein sample is by sampleDistrict 16 and towing parts 17 two parts compositions.
(6) switch into/the interface 12 of giving vent to anger, growth gasses is passed into Sample Room 10 until air pressure and stoveManage 14 internal gas pressures identical.
(7) after previous sample grown completes, (growth time of graphene film is generally 5-30Minute), open vacuum valve 9, a rear sample is sent in boiler tube 14, close afterwards vacuum valve9. After enter boiler tube 14 sample can successively the sample entering be pushed out to the direction of specimen chamber 11 above.
(8) once there be sample to arrive after vacuum valve 8, in (6) step, vacuum valve 9 is openedTime, open vacuum valve 8, allow the sample of the most close vacuum valve 8, there iing fresh sample from sample introductionWhen chamber 10 is pushed into boiler tube 14, by sample below, (left side is adjacent as shown in Figure 3Sample) automatically head into out specimen chamber 11, then close vacuum valve 8.
In addition, go out that specimen chamber 11 itself is also salable is connected with mechanically actuated bar (this operationBar is not necessarily), in the case, specimen chamber 11 drawn in out by sample by available this bar.
(9) open out specimen chamber 11, take out the sample of having grown, then close out specimen chamber, openEnter/give vent to anger interface 13, be evacuated to 10 to going out specimen chamber 11-3-10-5Holder. Then by same growthGas again passes into out specimen chamber 11 until air pressure is identical with the air pressure in boiler tube 14.
(10) process of repetition (5)-(9).
In above-mentioned embodiment, described base material can be metal, metal alloy, metallic carbideThing, carborundum, preferable alloy, further preferred Copper Foil.
Wherein said boiler tube 14 as shown in Figure 2. This boiler tube is made up of exotic material, can be stoneEnglish glass or other melting temperatures be higher than the material of 1100 DEG C, preferably quartz glass. This boiler tube 14Mainly comprise a vitellarium (being high-temperature region) 3. Before vitellarium 3, preferably include a preheatingDistrict 2 (before being positioned at vitellarium 3 and be adjacent) and buffering area 5 (be positioned at preheating zone 2 itBefore and be adjacent); After vitellarium 3, preferably include a cooling area 4 and (be positioned at vitellarium 3Afterwards and be adjacent) and/or cooling zone 15 (after being positioned at cooling area 4 and be adjacent).Wherein, preheating zone temperature is 400-600 DEG C, and vitellarium temperature is 900-1100 DEG C, cooling area temperatureFor room temperature to the sample of having grown can be exposed to the temperature (being preferably room temperature) in atmosphere. PreheatingThe temperature control of district, vitellarium and cooling area all can be by conventional method for example by heater block and surveyTemperature feedback circuit completes. For cooling zone 15, it can be the cooling or additional for example recirculated water cooling of natureBut.
Boiler tube 14 can be the various shapes such as cylindrical, cuboid, pref. cylindrical.
Can use heating and temperature controlling device 1 to heat to boiler tube 14, described heating and temperature controlling device is passableAny conventional equipment of realizing this object, for example electromagnetic induction heater.
Preferably, the length of boiler tube Zhong Ge district (except cooling zone) is equal to sample length or is sampleThe integral multiple of product length. The total length of boiler tube preferably equals the integral multiple of sample length.
Equal sample length a in the length of vitellarium 3, the total length of boiler tube 14 is mainCool time of the sample being completed by growth (refer to sample from vitellarium 3 out temperature be down to canBe exposed to the required time of temperature in atmosphere) decide with the ratio of graphene film growth time.If be n times of growth time cool time, as shown in Figure 2, cooling area 4 and cooling zone 15Length by the n that is at least sample length doubly, i.e. na; Add buffering area 5, preheating zone 2 and(its length is all at least length a), and now the total length of boiler tube 14 is at least sample in vitellarium 3(n+3) of product length times, i.e. (n+3) a.
Particularly, the not make-up machinery transmission device of boiler tube 14 inside of apparatus of the present invention, to keep awayExempt from inefficacy or the distortion of hot environment underdrive device, successively will but dependence pushes follow-up sampleSample above heads into out specimen chamber.
In growth course, while transmission in boiler tube 14 for fear of sample, damage boiler tube 14 inWall can arrange a resistant to elevated temperatures sample and transmit track, in order to avoid sample straight in boiler tube 14Connect with boiler tube 14 and contact and rub. Sample transmits track material therefor and should be high temperature resistant, high machinery by forceThe material of degree, as carborundum etc.; Its shape is limited can carry sample and to make it be difficult for slippage, exampleAs having suitable radian or suitable roughness.
The two ends of boiler tube 14 go out specimen chamber 11 with a Sample Room 10 and one respectively and are connected, junctionBe provided with valve and gas interface unit. Preferably, described in be connected to flange and connect, furtherPreferably, described gas interface parts are connected on flange. In the embodiment of Fig. 2, concreteFor, between boiler tube 14 and Sample Room 10, be provided with a vacuum valve 9; With a band intake interfaceFlange 6 (be called for short inlet flange 6), in order to boiler tube 14 and the vacuum valve 9 of being tightly connected, hereinDescribed intake interface is in order to connect protective gas source or growth gasses source. Boiler tube 14 and go out specimen chamber 11Between be provided with a vacuum valve 8; With the give vent to anger flange 7 (abbreviation give vent to anger flange 7) of interface of a band,In order to boiler tube 14 and the vacuum valve 8 of being tightly connected, the interface of giving vent to anger described herein is in order to connect vavuum pump.
Due to Sample Room 10 with go out transmission device (if any), the vavuum pump in specimen chamber 11And the vibration producing when vacuum valve switch cause larger stress may to boiler tube 14, thus can energy lossBad boiler tube 14, therefore can be at boiler tube 14 and Sample Room 10, go out specimen chamber 11 junctions and respectively add oneSection flexible connection devices, as bellows.
Sample Room 10 is equipped with one and enters/give vent to anger interface 12, in order to connect growth gasses source, protectionGas source or vavuum pump, have outside change-over switch with switching gas circuit; With an injection port 21.
Go out specimen chamber 11 and be equipped with one and enter/give vent to anger interface 13, in order to connect growth gasses source, protectionGas source or vavuum pump, have outside change-over switch with switching gas circuit; With an outlet 41.
Sample Room 10 and vacuum valve 9 are preferably made up of exotic material, make can bear through preheatingThe temperature of sample, for example, be made up of stainless steel; Go out specimen chamber 11 and vacuum valve 8 by such material systemBecome: at least can bear and be cooled to the temperature that can be exposed to the sample in atmosphere, for example, by stainless steelMake; Described flange is made up of exotic material, as stainless steel.
To Sample Room 10 and the shape that goes out specimen chamber 11 without particular requirement, preferably with the shape phase of sampleSame or similar. Enter/give vent to anger interface 12 and 13 and can be positioned at the upper surface of respective compartments or closing of side surfaceSuitable position, is preferably placed at upper surface. Position and shape to injection port 21 and outlet 41 are equalWithout particular requirement, as long as can realize the object of dress sample and sampling, preferably lay respectively at Sample RoomWith the upper surface that goes out specimen chamber.
The described constituent material that enters/give vent to anger interface 12 and 13, injection port 21 and outlet 41 is preferredIdentical with the constituent material of its chamber separately
Fig. 4 has provided a kind of manual Sample Room profile. Wherein, in Sample Room 10, be provided with oneIndividual sample transmits track 27, extends to out specimen chamber always, this track and Sample Room via passage 2610 and go out specimen chamber 11 and be sealedly and fixedly connected. Sample is positioned over this rail in Sample Room through injection port 21Surface, road, by the observation of watch window 23, uses mechanically actuated bar with magnetic loop bar by samplePush boiler tube 14 via passage 26 from Sample Room 10. Described mechanically actuated bar comprises magnetic loop barThe magnetic sliding handle 30 of can 29 and magnetic loop bar. Between injection port 21 and Sample Room 10, haveGood sealing, for example, by resistant to elevated temperatures sealing ring (being optionally cooled with circulating water it)Seal. The surface of the locular wall 20 of Sample Room 10 is also with entering/give vent to anger interface 12, in order to connectGrowth gasses source, protective gas source or vavuum pump, have outside change-over switch with switching gas circuit. Air inletThe intake interface 32 of flange 6 is in order to connect growth gasses source or protective gas source.
As shown in Figure 4, the surface of the locular wall 20 of Sample Room 10 is also with entering/give vent to anger interface 12,,In order to connect growth gasses source, protective gas source or vavuum pump, there is outside change-over switch to switch gasRoad. The intake interface 32 of inlet flange 6 is in order to connect growth gasses source or protective gas source.
For the sample of having grown, except dependence mentioned above push follow-up sample successively will be aboveSample head into out outside specimen chamber, can also manually pull out it into specimen chamber.
Fig. 5 has provided a kind of manual specimen chamber profile that goes out. Grasp with the machinery of magnetic loop bar hereinMake the front end (with sample contact jaw) of bar for example, with hook (being made by stainless steel), by sightExamine the observation of window 43, with hooking towing parts 17, sample is passed along sample from boiler tube 14Pass track 27 and pull out specimen chamber 11 into via passage 46, then take out sample by outlet 41.Mechanically actuated bar described herein comprises the magnetic sliding handle of magnetic sheath rod seal shell 51 and magnetic loop bar52. The front end of mechanically actuated bar, except for hook, can be also any other gripper components.
As shown in Figure 5, go out the surface of locular wall 40 of specimen chamber 11 also with entering/give vent to anger interface 13, useTo connect growth gasses source, protective gas source or vavuum pump, there is outside change-over switch to remove switching gas circuit.Give vent to anger the interface 50 of giving vent to anger of flange 7 in order to connect growth gasses source or vavuum pump.
In addition the Sample Room 10 of apparatus of the present invention and go out specimen chamber 11 and also can be designed as with machinery,Automatic transmission track, automatic vacuum valve gauge tap, automatic gas path switch and vavuum pump leaves automaticallyClose the function such as control, thereby only need load manually sample, other are opened as vacuum valve and vavuum pumpPass, gas circuit are switched, sample transmits track and controls by pre-set program. Machinery motorCan design in the atmospheric environment of outside, region of no pressure, by using dynamic seal ring from vacuum environment outsideControl the transmission device of vacuum environment inside, these design comparative maturity, no longer detailed at thisState.
Use the inventive method, can make vitellarium keep high growth temperature state always, thereby can connectContinue and prepare graphene film, significantly improved the output of CVD legal system for graphene film, metThe requirement of CVD method large-scale production graphene film.
Although describe the present invention with reference to particular, art technology peopleMember should be appreciated that, in the situation that not departing from purport of the present invention and scope, can be to described realityThe scheme of executing changes or improves, and the scope of the invention limits by appended claims.
Claims (8)
1. a device for continuous production graphene film, it comprises the stove of a both ends openPipe (14), this both ends open respectively with an openend of a Sample Room (10)Be connected with an openend that goes out specimen chamber (11), wherein boiler tube and Sample RoomJunction is provided with a valve (9) and intake interface parts (32), stovePipe is provided with a valve (8) and the interface portion of giving vent to anger with the junction that goes out specimen chamberPart (50), and described Sample Room (10) is also equipped with one and enters/give vent to anger interfaceParts (12) and an injection port (21), described in go out specimen chamber and be also equipped with one and enter/ the interface unit of giving vent to anger (13) and an outlet (41), wherein Sample Room (10)In be provided with sample and transmit track (27), extend to out via passage (26) alwaysSpecimen chamber, this track and Sample Room (10) and go out specimen chamber (11) and be sealedly and fixedly connected, sampleBe positioned over this raceway surface in Sample Room through injection port (21), by watch window (23)Observation, use mechanically actuated bar with magnetic loop bar by sample from Sample Room (10) warpPushed in boiler tube (14) by passage (26), described mechanically actuated bar comprises that magnetic loop bar is closeEnvelope shell (29) and the magnetic sliding handle (30) of magnetic loop bar, go out specimen chamber and have to be with and be magneticThe mechanically actuated bar of loop bar, its front end is with gripper components, by watch window (43)Observation, with gripper components hook towing parts (17) by sample from boiler tube (14)Transmit track (27) along sample and pull out specimen chamber (11) into via passage (46), then pass throughOutlet (41) takes out sample, and described mechanically actuated bar comprises outside magnetic sheath rod sealThe magnetic sliding handle (52) of shell (51) and magnetic loop bar, wherein boiler tube (14) comprises successivelyA buffering area, a preheating zone, a vitellarium and a cooling area, and eachSection length is equal to sample length or the integral multiple for sample length.
2. the device of claim 1, wherein said boiler tube (14) and Sample Room (10),The junction that goes out specimen chamber (11) respectively adds one section of flexible connection devices.
3. the device of claim 1, wherein said boiler tube (14) comprise a cooling area and/ or cooling zone, wherein cooling area is that room temperature to the sample of having grown can be exposed to greatlyTemperature in gas.
4. by the method for the device continuous production graphene film of claim 1, its bagDraw together following steps:
(1) use mechanically actuated bar with magnetic loop bar by a base material sample from enteringSpecimen chamber transmits track by sample and pushes in boiler tube via passage, and whole to except Sample RoomIndividual system vacuumizes,
(2) in boiler tube, pass into protective gas,
(3) to boiler tube heating, to reaching growth temperature,
(4) to boiler tube and go out in specimen chamber to pass into growth gasses, make film growth,
(5) in growth, pack another same base material sample into sample introductionChamber, and this chamber is vacuumized,
(6) in Sample Room, pass into growth gasses, until identical with boiler tube internal gas pressure,
(7) after previous sample grown completes, by described another same substrate materialMaterial sample is sent into boiler tube,
(8) the base material sample that makes to have grown enters out specimen chamber,
(9) from go out specimen chamber, shift out the base material sample of having grown, wherein by withThe mechanically actuated bar of magnetic loop bar, by the observation of watch window, with grabbing of its front endGet parts hook towing parts by sample from boiler tube along sample transmit track via passagePull out specimen chamber into, then take out sample by outlet, vacuumize going out specimen chamber afterwards,And again pass into same growth gasses, until identical with boiler tube internal gas pressure, and
(10) repeating step (5) is to (9),
Wherein, protective gas is argon gas, hydrogen, nitrogen or their mist, rawLong gas is the gaseous mixture of argon gas, hydrogen and methane,
Wherein vitellarium temperature is 900-1100 DEG C, and preheating zone temperature is 400-600 DEG C.
5. the method for claim 4, the good base material sample of wherein said growth successivelyHeaded into out specimen chamber by follow-up sample.
6. the method for claim 4, wherein by base material sample hand good described growthThe moving specimen chamber of pulling into out.
7. the method for claim 4, the degree of wherein said vacuum is 10-3-10-5Holder.
8. a graphene film of being prepared by the method for any one in claim 4-7.
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| CN103151248B (en) * | 2013-03-07 | 2016-04-20 | 武汉电信器件有限公司 | The disperser of zinc and method of diffusion thereof during a kind of photodetector makes |
| CN103435035B (en) * | 2013-08-20 | 2016-08-10 | 常州二维碳素科技股份有限公司 | A kind of continuous preparation and the device and method of transfer Graphene |
| CN103449428B (en) * | 2013-09-10 | 2015-11-25 | 常州二维碳素科技股份有限公司 | A kind of method of graphene growth device and growing graphene thereof |
| CN103920423B (en) * | 2014-04-21 | 2016-04-06 | 厦门大学 | The vacuum chamber prepared for Graphene that a kind of growth course is visual |
| CN105088335B (en) * | 2014-05-09 | 2018-01-05 | 理想能源设备(上海)有限公司 | A kind of device and its growing method for growing graphene film |
| CN103993297A (en) * | 2014-06-09 | 2014-08-20 | 中国科学院宁波材料技术与工程研究所 | Vapor deposition device for continuously and quickly growing graphene |
| CN103993296A (en) * | 2014-06-09 | 2014-08-20 | 中国科学院宁波材料技术与工程研究所 | Tube furnace based roll-to-roll vapor deposition device |
| CN105293474B (en) * | 2014-08-01 | 2018-01-09 | 常州二维碳素科技股份有限公司 | It is a kind of quickly to prepare equipment of graphene and preparation method thereof |
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| CN113186515A (en) * | 2021-05-19 | 2021-07-30 | 江苏微导纳米科技股份有限公司 | Process pipeline heating device |
| CN114671710B (en) * | 2022-03-10 | 2023-04-07 | 西北工业大学 | Double-period multilayer TaC/HfC ultrahigh-temperature ceramic anti-ablation coating and preparation method thereof |
| CN115367740A (en) * | 2022-08-18 | 2022-11-22 | 安徽贝意克智能科技有限公司 | Continuous preparation equipment and use method of vertical graphene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200535269A (en) * | 2004-04-26 | 2005-11-01 | Applied Films Gmbh & Co Kg | Method for coating substrates in inline installations |
| CN101285175A (en) * | 2008-05-29 | 2008-10-15 | 中国科学院化学研究所 | Process for preparing graphenes by chemical vapour deposition method |
| CN102191480A (en) * | 2010-03-03 | 2011-09-21 | 佳能安内华股份有限公司 | Vacuum processing apparatus and vacuum processing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328410C (en) * | 2004-10-19 | 2007-07-25 | 吉林大学 | Low-pressure metal organic chemical vapour phase depositing apparatus for zinc oxide and process thereof |
-
2011
- 2011-12-26 CN CN201110442123.7A patent/CN102492934B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200535269A (en) * | 2004-04-26 | 2005-11-01 | Applied Films Gmbh & Co Kg | Method for coating substrates in inline installations |
| CN101285175A (en) * | 2008-05-29 | 2008-10-15 | 中国科学院化学研究所 | Process for preparing graphenes by chemical vapour deposition method |
| CN102191480A (en) * | 2010-03-03 | 2011-09-21 | 佳能安内华股份有限公司 | Vacuum processing apparatus and vacuum processing method |
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