CN102492934A - Apparatus and method used for preparing graphene, and obtained graphene - Google Patents
Apparatus and method used for preparing graphene, and obtained graphene Download PDFInfo
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- CN102492934A CN102492934A CN2011104421237A CN201110442123A CN102492934A CN 102492934 A CN102492934 A CN 102492934A CN 2011104421237 A CN2011104421237 A CN 2011104421237A CN 201110442123 A CN201110442123 A CN 201110442123A CN 102492934 A CN102492934 A CN 102492934A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims description 43
- 238000001816 cooling Methods 0.000 claims description 30
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 46
- 230000008569 process Effects 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 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
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009997 thermal pre-treatment Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
The invention relates to an apparatus used for continuously preparing graphene through a chemical vapor deposition (CVD) method. The apparatus is mainly composed of a sample feeding chamber, a furnace tube, and a sample discharging chamber. A high growing temperature is maintained in a growing zone in a growing chamber. No temperature increasing or reducing procedure is required, and a transmission problem of a sample in a high-temperature zone is solved. Growing can be continuously carried out, such that the yield of graphene prepared with the CVD method is greatly improved.
Description
Technical field
The present invention relates to a kind of apparatus and method that prepare graphene film, and the graphene film that makes.More specifically, relate to a kind of apparatus and method through successive chemical Vapor deposition process (being called for short the CVD method) preparation graphene film, and the graphene film that makes.
Background technology
Graphene has excellent mechanics, calorifics, electricity and magnetic performance, is expected to obtain widespread use in a plurality of fields such as high-performance nano electron device, matrix material, store energy, becomes one of focus of research in recent years.
The process of existing C VD method growth graphene film; As shown in Figure 1: earlier with tinsel 1 under the protection environment of argon gas and hydrogen in about 1.5 hours of about 1000 ℃ of thermal pretreatment; Be placed on then in circular silica glass boiler tube 2 vitellariums; Feed methane 3, carry out carbon and decompose, growth time is about 20-30 minute.
In the process of CVD method growth graphene film, before growth and after the growth, need open boiler tube respectively and put into tinsel and take out the good Graphene sample of having grown.At this moment, boiler tube inside will be exposed in the atmosphere inevitably.For preventing that airborne oxygen from getting into high temperature furnace pipe graphene oxide sample and possibly stain the boiler tube inwall, have to after each growth just can open boiler tube when temperature is reduced to about 200 ℃ by the time.Therefore, when taking out sample, will have to wait at least 30 minutes temperature fall time at every turn; And at every turn after putting into tinsel, close boiler tube and vacuumize, be warming up to again about 1000 ℃, also need be more than 2 hours.Lifting/lowering temperature wait process has had a strong impact on the output of graphene film for a long time, can't satisfy requirement of large-scale production.
Summary of the invention
To above-mentioned technical problem; The invention provides a kind of device of continuous preparation graphene film; It comprises the boiler tube of a both ends open; This both ends open is connected with an opening end that goes out specimen chamber with an opening end of a Sample Room respectively, and wherein the junction of boiler tube and Sample Room is provided with a valve and intake interface parts, and boiler tube is provided with a valve and the interface unit of giving vent to anger with the junction that goes out specimen chamber; And said Sample Room also is equipped with one and advances/give vent to anger interface unit (interface unit that is used for air inlet or gives vent to anger) and an injection port, saidly goes out specimen chamber and also is equipped with one and advances/give vent to anger interface unit and an outlet.
In addition, the invention provides a kind of continuous method for preparing graphene film, may further comprise the steps: (1) the base material sample of in boiler tube, packing into, and the whole system except that Sample Room vacuumized,
(2) in boiler tube, feed shielding gas,
(3) to boiler tube heating, to reaching growth temperature,
(4) to boiler tube with go out to feed growth gasses in the specimen chamber, make film growth,
(5) in growth, the base material sample that another is the same Sample Room of packing into, and this chamber vacuumized,
(6) in Sample Room, feed growth gasses, until identical with the boiler tube internal gas pressure,
(7) after previous sample grown is accomplished, said another same base material sample is sent into boiler tube,
(8) good base material sample gets into out specimen chamber to make growth,
(9) from go out specimen chamber, shift out the good base material sample of growth, vacuumize going out specimen chamber afterwards, and feed same growth gasses once more, until identical with the boiler tube internal gas pressure and
(10) repeating step (5) is to (9).
At last, the present invention also provides a kind of graphene film by the inventive method preparation.
Use apparatus of the present invention and method, can prepare graphene film continuously, improved its output greatly, satisfied the requirement of CVD method scale operation graphene film.
Description of drawings
Fig. 1 is a synoptic diagram of existing CVD method growth graphene film,
Fig. 2 is a synoptic diagram of apparatus of the present invention,
Fig. 3 is a synoptic diagram of base material sample,
Fig. 4 is the Sample Room sectional view of one embodiment of the invention,
Fig. 5 goes out the specimen chamber sectional view for one embodiment of the invention.
Embodiment
In the present invention, used term " sample " is meant and is used to support the base material sample of graphene film growth itself or the base material sample of band towing parts.
Used term " growth gasses " or " growth gasses source " are meant the gas of the graphene film that is used to grow in the literary composition.
The invention provides a kind of device of continuous preparation graphene film; It comprises the boiler tube of a both ends open; This both ends open is connected with an opening end that goes out specimen chamber with an opening end of a Sample Room respectively; Wherein the junction of boiler tube and Sample Room is provided with a valve and intake interface parts; Boiler tube is provided with a valve and the interface unit of giving vent to anger with the junction that goes out specimen chamber, and said Sample Room also is equipped with one and advances/give vent to anger interface unit and an injection port, saidly goes out specimen chamber and also is equipped with one and advances/give vent to anger interface unit and an outlet.
Fig. 2 is a synoptic diagram of apparatus of the present invention.Below in conjunction with Fig. 2 apparatus of the present invention are elaborated.
As shown in Figure 2, this device comprises a boiler tube 14, and it is processed by high temperature material, can be that silica glass or other melting temperatures are higher than 1100 ℃ material, preferred silica glass.This boiler tube 14 mainly comprises a vitellarium (being the high-temperature zone) 3.Preferably include a preheating zone 2 (be positioned at before the vitellarium 3 and be adjacent) and a buffer zone 5 (be positioned at preheating zone 2 before and be adjacent) before 3 in the vitellarium; After vitellarium 3, preferably include a cooling area 4 (be positioned at after the vitellarium 3 and be adjacent) and/or cooling zone 15 (be positioned at after the cooling area 4 and be adjacent).Wherein, the preheating zone temperature is 400-600 ℃, and the vitellarium temperature is 900-1100 ℃, and the cooling area temperature is that the sample that room temperature is accomplished to growth can be exposed to the temperature (being preferably room temperature) in the atmosphere.The temperature control of preheating zone, vitellarium and cooling area all can for example be accomplished by heater block and thermometric reaction circuit through ordinary method.For cooling zone 15, can be naturally cooling or for example add the recirculated water cooling.
Can use heating and temperature controlling device 1 to heat to boiler tube 14, said heating and temperature controlling device can be any conventional equipment of realizing this purpose, for example electromagnetic induction heater.
Preferably, the length of boiler tube Zhong Ge district (except the cooling zone) is equal to sample length or is the integral multiple of sample length.The total length of boiler tube preferably equals the integral multiple of sample length.
Length in vitellarium 3 equals under the situation of sample length a, and the cooling time of the sample that the total length of boiler tube 14 is mainly accomplished by growth (be meant sample from the vitellarium the 3 back temperature of coming out reduce to the required time of temperature that can be exposed to the atmosphere), the ratio with the graphene film growth time decided.If be n times of growth time cooling time, then as shown in Figure 2, the length of cooling area 4 and cooling zone 15 will be at least n times of sample length, i.e. na; Add buffer zone 5, preheating zone 2 and vitellarium 3 (its length all is at least length a), this moment boiler tube 14 total length be at least sample length (n+3) doubly, i.e. (n+3) a.
Particularly, boiler tube 14 inside of apparatus of the present invention are the make-up machinery transmission mechanism not, to avoid the inefficacy or the distortion of hot environment underdrive device, one by one the sample of front is headed into out specimen chamber but dependence pushes follow-up sample.
In process of growth, the inwall of damage boiler tube 14 when transmitting in boiler tube 14 for fear of sample can be provided with a resistant to elevated temperatures sample and transmit track in boiler tube 14, directly contact and friction with boiler tube 14 in order to avoid sample.Sample transmits the track material therefor and should be material high temperature resistant, high mechanical strength, like silit etc.; Its shape is exceeded can carry sample and to make it be difficult for slippage, and suitable radian or suitable roughness for example can be arranged.
The two ends of boiler tube 14 go out specimen chamber 11 and are connected with one with a Sample Room 10 respectively, and the junction is provided with valve and gas interface unit.Preferably, the said flange that is connected to connects, and further preferably, said gas interface parts are connected on the flange.In the embodiment of Fig. 2, be specially, be provided with a vacuum valve 9 between boiler tube 14 and the Sample Room 10; With a flange 6 (being called for short inlet flange 6) of bringing the gas interface into, in order to boiler tube 14 and the vacuum valve 9 of being tightly connected, intake interface described herein is in order to connect shielding gas source or growth gasses source.Boiler tube 14 and go out to be provided with a vacuum valve 8 between the specimen chamber 11; With a flange 7 of taking the gas interface out of (abbreviation give vent to anger flange 7), 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 vacuum pump.
Because the vibration that Sample Room 10 produces when going out transmission mechanism (if any) in the specimen chamber 11, vacuum pump and vacuum valve switch cause big stress possibly for boiler tube 14; Thereby possibly damage boiler tube 14; Therefore can boiler tube 14 with Sample Room 10, go out specimen chamber 11 junctions and respectively add one section soft coupling device, like corrugated tube.
Go out specimen chamber 11 and be equipped with one and advance/give vent to anger interface 13,, outside change-over switch is arranged with switching gas circuit in order to connect growth gasses source, shielding gas source or vacuum pump; With an outlet 41.
Saidly advance/ interface 12 and 13 of giving vent to anger, the constituent material of injection port 21 and outlet 41 preferably with the constituent material identical (so far being repetition) of its chamber separately.
Use apparatus of the present invention, can prepare graphene film continuously, improved its output greatly, satisfied the requirement of CVD method scale operation graphene film.
In addition, the invention provides a kind of continuous method for preparing graphene film, may further comprise the steps: (1) the base material sample of in boiler tube, packing into, and the whole system except that Sample Room vacuumized,
(2) in boiler tube, feed shielding gas,
(3) to boiler tube heating, to reaching growth temperature,
(4) to boiler tube with go out to feed growth gasses in the specimen chamber, make film growth,
(5) in growth, the base material sample that another is the same Sample Room of packing into, and this chamber vacuumized,
(6) in Sample Room, feed growth gasses, until identical with the boiler tube internal gas pressure,
(7) after previous sample grown is accomplished, said another same base material sample is sent into boiler tube,
(8) good base material sample gets into out specimen chamber to make growth,
(9) from go out specimen chamber, shift out the good base material sample of growth, vacuumize going out specimen chamber afterwards, and feed same growth gasses once more, until identical with the boiler tube internal gas pressure and
(10) repeating step (5) is to (9).
Below in conjunction with Fig. 2 a specific embodiments of the inventive method is described.
(1) placement installs the graphene film growth and uses the base material sample in 2,3 and 5 districts, then vacuum valve 8 is opened, and vacuum valve 9 cuts out, and the inlet close of inlet flange 6 goes out specimen chamber 11 and closes.Open the gas interface of the flange 7 of giving vent to anger, total system (except the Sample Room 10) vacuumized with vacuum pump, to vacuum tightness be 10
-3-10
-5Holder.
(2) close the flange 7 of giving vent to anger, open the inlet mouth of inlet flange 6, logical shielding gas like argon gas, hydrogen, nitrogen or their mixed gas, is a normal atmosphere until air pressure in boiler tube 14, switches flange 7 to the UNICOM atmosphere of giving vent to anger.Continue to feed shielding gas.
(3) boiler tube 14 is heated up.Boiler tube 14 generally can be divided into 3 districts, and is as shown in Figure 3, is respectively preheating zone 2, vitellarium 3 and cooling area 4.Each length of an interval degree is a, and each distinguishes growth conditions parameter (be the conditional parameter of the required graphene film) decision of temperature by the Graphene sample.The temperature of preheating zone 2 is generally 400-600 ℃, and the temperature of vitellarium 3 is generally 900-1100 ℃, and the sample that the temperature of cooling area is generally room temperature to growth completion can be exposed to the temperature (being preferably room temperature) in the atmosphere.In addition, the length that is used to support base material (for example Copper Foil) sample of graphene film growth also is a.
(4) after the temperature of vitellarium 3 reaches the film growth temperature, switch and give vent to anger flange 7, feed growth gasses, be generally the mixed gas of argon gas, hydrogen and methane by inlet flange 6 to vacuum pump.The flowrate proportioning of concrete each gas is by the conditional parameter decision of required graphene film.Feed growth gasses after half a minute, close the vacuum pump valve, after the boiler tube internal gas pressure rises to normal atmosphere, switch flange 7 to the UNICOM atmosphere of giving vent to anger, close vacuum valve 8.Begin growth then, growth time is generally 5-30 minute (can regulate through atmosphere and control).
When (5) growing, open Sample Room 10, another is installed the Graphene growth put into Sample Room 10 with the sample of base material, afterwards, close Sample Room 10, open into/give vent to anger interface 12, (less than a growth cycle) is evacuated to 10 with Sample Room 10 rapidly
-3-10
-5Holder.
Fig. 3 is the synoptic diagram of Graphene growth with the base material sample.Wherein sample is made up of sample area 16 and towing parts 17 two portions.
(6) switch/interface 12 of giving vent to anger, it is identical with boiler tube 14 internal gas pressures until air pressure that growth gasses is fed Sample Room 10.
(7) after previous sample grown is accomplished (growth time of graphene film was generally 5-30 minute), open vacuum valve 9, a back sample is sent in the boiler tube 14, close vacuum valve 9 afterwards.The sample that the sample of back entering boiler tube 14 can get into the front one by one pushed out the direction of specimen chamber 11 to.
(8) in case after having sample to arrive vacuum valve 8; When vacuum valve 9 is opened in (6) step; Open vacuum valve 8, let, fresh sample is being arranged when Sample Room 10 is pushed into boiler tube 14 near the sample of vacuum valve 8; Automatically headed into out specimen chamber 11 by the sample of back (sample that left side as shown in Figure 3 is adjacent), close vacuum valve 8 then.
In addition, go out the also salable power operation bar (this operating stick not necessarily) that is connected with of specimen chamber 11 itself, in the case, available this bar is drawn in out specimen chamber 11 with sample.
(9) open out specimen chamber 11, take out the good sample of growth, close out specimen chamber then, open into/give vent to anger interface 13, be evacuated to 10 going out specimen chamber 11
-3-10
-5Holder.It is identical with air pressure in the boiler tube 14 until air pressure then same growth gasses to be fed out specimen chamber 11 once more.
(10) process of repetition (5)-(9).
In the above-mentioned embodiment, said base material can be metal, metal alloy, metallic carbide, silit, preferable alloy, further preferred Copper Foil.
Wherein said boiler tube 14 is as shown in Figure 2.This boiler tube is processed by high temperature material, can be that silica glass or other melting temperatures are higher than 1100 ℃ material, preferred silica glass.This boiler tube 14 mainly comprises a vitellarium (being the high-temperature zone) 3.Preferably include a preheating zone 2 (be positioned at before the vitellarium 3 and be adjacent) and a buffer zone 5 (be positioned at preheating zone 2 before and be adjacent) before 3 in the vitellarium; After vitellarium 3, preferably include a cooling area 4 (be positioned at after the vitellarium 3 and be adjacent) and/or cooling zone 15 (be positioned at after the cooling area 4 and be adjacent).Wherein, the preheating zone temperature is 400-600 ℃, and the vitellarium temperature is 900-1100 ℃, and the cooling area temperature is that the sample that room temperature is accomplished to growth can be exposed to the temperature (being preferably room temperature) in the atmosphere.The temperature control of preheating zone, vitellarium and cooling area all can for example be accomplished by heater block and thermometric reaction circuit through ordinary method.For cooling zone 15, can be naturally cooling or for example add the recirculated water cooling.
Can use heating and temperature controlling device 1 to heat to boiler tube 14, said heating and temperature controlling device can be any conventional equipment of realizing this purpose, for example electromagnetic induction heater.
Preferably, the length of boiler tube Zhong Ge district (except the cooling zone) is equal to sample length or is the integral multiple of sample length.The total length of boiler tube preferably equals the integral multiple of sample length.
Length in vitellarium 3 equals under the situation of sample length a, and the cooling time of the sample that the total length of boiler tube 14 is mainly accomplished by growth (be meant sample from the vitellarium the 3 back temperature of coming out reduce to the required time of temperature that can be exposed to the atmosphere), the ratio with the graphene film growth time decided.If be n times of growth time cooling time, then as shown in Figure 2, the length of cooling area 4 and cooling zone 15 will be at least n times of sample length, i.e. na; Add buffer zone 5, preheating zone 2 and vitellarium 3 (its length all is at least length a), this moment boiler tube 14 total length be at least sample length (n+3) doubly, i.e. (n+3) a.
Particularly, boiler tube 14 inside of apparatus of the present invention are the make-up machinery transmission mechanism not, to avoid the inefficacy or the distortion of hot environment underdrive device, one by one the sample of front is headed into out specimen chamber but dependence pushes follow-up sample.
In process of growth, the inwall of damage boiler tube 14 when transmitting in boiler tube 14 for fear of sample can be provided with a resistant to elevated temperatures sample and transmit track in boiler tube 14, directly contact and friction with boiler tube 14 in order to avoid sample.Sample transmits the track material therefor and should be material high temperature resistant, high mechanical strength, like silit etc.; Its shape is exceeded can carry sample and to make it be difficult for slippage, and suitable radian or suitable roughness for example can be arranged.
The two ends of boiler tube 14 go out specimen chamber 11 and are connected with one with a Sample Room 10 respectively, and the junction is provided with valve and gas interface unit.Preferably, the said flange that is connected to connects, and further preferably, said gas interface parts are connected on the flange.In the embodiment of Fig. 2, be specially, be provided with a vacuum valve 9 between boiler tube 14 and the Sample Room 10; With a flange 6 (being called for short inlet flange 6) of bringing the gas interface into, in order to boiler tube 14 and the vacuum valve 9 of being tightly connected, intake interface described herein is in order to connect shielding gas source or growth gasses source.Boiler tube 14 and go out to be provided with a vacuum valve 8 between the specimen chamber 11; With a flange 7 of taking the gas interface out of (abbreviation give vent to anger flange 7), 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 vacuum pump.
Because the vibration that Sample Room 10 produces when going out transmission mechanism (if any) in the specimen chamber 11, vacuum pump and vacuum valve switch cause big stress possibly for boiler tube 14; Thereby possibly damage boiler tube 14; Therefore can boiler tube 14 with Sample Room 10, go out specimen chamber 11 junctions and respectively add one section soft coupling device, like corrugated tube.
Go out specimen chamber 11 and be equipped with one and advance/give vent to anger interface 13,, outside change-over switch is arranged with switching gas circuit in order to connect growth gasses source, shielding gas source or vacuum pump; With an outlet 41.
Saidly advance/ interface 12 and 13 of giving vent to anger, preferably the constituent material with its chamber separately is identical for the constituent material of injection port 21 and outlet 41
Fig. 4 has provided a kind of manual Sample Room sectional view.Wherein, be provided with sample in the Sample Room 10 and transmit track 27, extend to out specimen chamber always via passage 26, this track is with Sample Room 10 and go out specimen chamber 11 and be sealedly and fixedly connected.Sample is positioned over this raceway surface in the Sample Room through injection port 21, by the observation of view port 23, with the power operation bar that has the magnetic loop bar sample is pushed the boiler tube 14 via passage 26 from Sample Room 10.Said power operation bar comprises the magnetic sliding handle 30 of magnetic loop bar sealed enclosure 29 and magnetic loop bar.Between injection port 21 and the Sample Room 10 good sealing property is arranged, for example seal through resistant to elevated temperatures sealing-ring (randomly it being cooled with circulating water).The surface of the locular wall 20 of Sample Room 10 also has into/gives vent to anger interface 12, in order to connect growth gasses source, shielding gas source or vacuum pump, outside change-over switch is arranged with switching gas circuit.The intake interface 32 of inlet flange 6 is in order to connect growth gasses source or shielding gas source.
As shown in Figure 4, the surface of the locular wall 20 of Sample Room 10 also has into/gives vent to anger interface 12,, in order to connect growth gasses source, shielding gas source or vacuum pump, outside change-over switch is arranged with switching gas circuit.The intake interface 32 of inlet flange 6 is in order to connect growth gasses source or shielding gas source.
For the good sample of growth, except that pushing follow-up sample, dependence mentioned above one by one the sample of front is headed into out the specimen chamber, can also manually pull out it into specimen chamber.
Fig. 5 has provided a kind of manual specimen chamber sectional view that goes out.The front end (with the sample contact jaw) that has the power operation bar of magnetic loop bar here has hook (for example being processed by stainless steel); Observation by view port 43; From boiler tube 14, pull out sample into specimen chamber 11 via passage 46 with hooking towing parts 17, take out samples through outlet 41 then along sample transmission track 27.Power operation bar described herein comprises the magnetic sliding handle 52 of magnetic loop bar sealed enclosure 51 and magnetic loop bar.The front end of power operation bar also can be any other gripper components except that for the hook.
As shown in Figure 5, the surface that goes out the locular wall 40 of specimen chamber 11 also has into/gives vent to anger interface 13, in order to connect growth gasses source, shielding gas source or vacuum pump, has outside change-over switch to remove switching gas circuit.Give vent to anger the interface 50 of flange 7 in order to connect growth gasses source or vacuum pump.
In addition; The Sample Room 10 of apparatus of the present invention with go out specimen chamber 11 and also can be designed as and have machinery conveyor track, automatic vacuum valve trip switch, automatic gas path switch and functions such as vacuum pump automatic switch control automatically; Thereby only need load sample manually, other transmit track and control by pre-set program like vacuum valve and vacuum pump switch, gas circuit switching, sample.The machinery motor can design in the atmospheric environment of outside, vacuum zone, and through controlling the inner transmission mechanism of vacuum environment with dynamic seal ring from the vacuum environment outside, these design comparative maturity, are not described in detail in this.
Use the inventive method, can make the vitellarium keep the high growth temperature state always, thereby can prepare graphene film continuously, significantly improved the output that the CVD legal system is equipped with graphene film, satisfied the requirement of CVD method scale operation graphene film.
Though describe the present invention with reference to particular; But what those skilled in the art will recognize that is; Under the situation that does not depart from purport of the present invention and scope, can change or improve said embodiment, the scope of the invention limits through appended claims.
Claims (10)
1. continuous device of preparation graphene film; It comprises the boiler tube (14) of a both ends open; This both ends open is connected with an opening end that goes out specimen chamber (11) with an opening end of a Sample Room (10) respectively; Wherein the junction of boiler tube and Sample Room is provided with a valve (9) and intake interface parts (32); Boiler tube is provided with a valve (8) and the interface unit of giving vent to anger (50) with the junction that goes out specimen chamber, and said Sample Room (10) also is equipped with one and advances/give vent to anger an interface unit (12) and an injection port (21), saidly goes out specimen chamber and also is equipped with one and advances/give vent to anger an interface unit (13) and an outlet (41).
2. the device of claim 1 is provided with a sample and transmits track (27) in the wherein said boiler tube (14).
3. the device of claim 1, wherein said boiler tube (14) and Sample Room (10), the junction that goes out specimen chamber (11) respectively add one section soft coupling device.
4. the device of claim 1, wherein said boiler tube (14) comprises a buffer zone and/or a preheating zone.
5. the device of claim 1, wherein said boiler tube (14) comprises a cooling area and/or cooling zone.
6. method for preparing continuously graphene film, it may further comprise the steps:
(1) the base material sample of in boiler tube, packing into, and the whole system except that Sample Room vacuumized,
(2) in boiler tube, feed shielding gas,
(3) to boiler tube heating, to reaching growth temperature,
(4) to boiler tube with go out to feed growth gasses in the specimen chamber, make film growth,
(5) in growth, the base material sample that another is the same Sample Room of packing into, and this chamber vacuumized,
(6) in Sample Room, feed growth gasses, until identical with the boiler tube internal gas pressure,
(7) after previous sample grown is accomplished, said another same base material sample is sent into boiler tube,
(8) good base material sample gets into out specimen chamber to make growth,
(9) from go out specimen chamber, shift out the good base material sample of growth, vacuumize going out specimen chamber afterwards, and feed same growth gasses once more, until identical with the boiler tube internal gas pressure and
(10) repeating step (5) is to (9).
7. the method for claim 6, the base material sample that wherein said growth is good is headed into out specimen chamber by follow-up sample one by one.
8. the method for claim 6, wherein that said growth is good base material sample is manually pulled out specimen chamber into.
9. the method for claim 6, the degree of wherein said vacuum is 10
-3-10
-5Holder.
10. graphene film by each method preparation among the claim 6-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110442123.7A CN102492934B (en) | 2011-12-26 | 2011-12-26 | A kind of device, method and gained graphene film of preparing graphene film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110442123.7A CN102492934B (en) | 2011-12-26 | 2011-12-26 | A kind of device, method and gained graphene film of preparing graphene film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102492934A true CN102492934A (en) | 2012-06-13 |
| CN102492934B CN102492934B (en) | 2016-05-11 |
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| CN103151248A (en) * | 2013-03-07 | 2013-06-12 | 武汉电信器件有限公司 | Zinc diffusion device and diffusion method thereof in manufacturing of photoelectric detector |
| CN103435035A (en) * | 2013-08-20 | 2013-12-11 | 常州二维碳素科技有限公司 | Device and method for continuous preparing and transferring graphene |
| CN103449428A (en) * | 2013-09-10 | 2013-12-18 | 常州二维碳素科技有限公司 | Graphene growing device and method |
| CN103920423A (en) * | 2014-04-21 | 2014-07-16 | 厦门大学 | Vacuum chamber with visual growth process for preparing 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 |
| 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 |
| CN105088335A (en) * | 2014-05-09 | 2015-11-25 | 理想能源设备(上海)有限公司 | Device and growth method for growing graphene films |
| CN105293474A (en) * | 2014-08-01 | 2016-02-03 | 常州二维碳素科技股份有限公司 | Equipment for quickly preparing graphene and preparation method of graphene |
| CN106119806A (en) * | 2016-06-27 | 2016-11-16 | 重庆墨希科技有限公司 | A kind of continuous-flow type continuous Large-scale graphene film preparation device |
| CN109112499A (en) * | 2018-08-30 | 2019-01-01 | 郑州大工高新科技有限公司 | A kind of novel vapour deposition process prepares the process units of graphene |
| WO2020082343A1 (en) * | 2018-10-26 | 2020-04-30 | 丁海钊 | Apparatus for coating layer of graphene on outer portion of wire |
| CN111394712A (en) * | 2020-04-27 | 2020-07-10 | 青岛赛瑞达电子装备股份有限公司 | Double-layer quartz process chamber structure |
| 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 |
| CN114671710A (en) * | 2022-03-10 | 2022-06-28 | 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 |
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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 |
| CN103151248A (en) * | 2013-03-07 | 2013-06-12 | 武汉电信器件有限公司 | Zinc diffusion device and diffusion method thereof in manufacturing of photoelectric detector |
| CN103435035A (en) * | 2013-08-20 | 2013-12-11 | 常州二维碳素科技有限公司 | Device and method for continuous preparing and transferring graphene |
| 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 |
| CN103449428A (en) * | 2013-09-10 | 2013-12-18 | 常州二维碳素科技有限公司 | Graphene growing device and method |
| 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 |
| CN103920423A (en) * | 2014-04-21 | 2014-07-16 | 厦门大学 | Vacuum chamber with visual growth process for preparing graphene |
| 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 |
| CN105088335A (en) * | 2014-05-09 | 2015-11-25 | 理想能源设备(上海)有限公司 | Device and growth method for growing graphene films |
| 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 |
| CN105293474A (en) * | 2014-08-01 | 2016-02-03 | 常州二维碳素科技股份有限公司 | Equipment for quickly preparing graphene and preparation method of graphene |
| 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 |
| CN106119806A (en) * | 2016-06-27 | 2016-11-16 | 重庆墨希科技有限公司 | A kind of continuous-flow type continuous Large-scale graphene film preparation device |
| CN106119806B (en) * | 2016-06-27 | 2018-12-28 | 重庆墨希科技有限公司 | A kind of continuous Large-scale graphene film preparation device of continuous-flow type |
| CN109112499A (en) * | 2018-08-30 | 2019-01-01 | 郑州大工高新科技有限公司 | A kind of novel vapour deposition process prepares the process units of graphene |
| WO2020082343A1 (en) * | 2018-10-26 | 2020-04-30 | 丁海钊 | Apparatus for coating layer of graphene on outer portion of wire |
| CN111394712A (en) * | 2020-04-27 | 2020-07-10 | 青岛赛瑞达电子装备股份有限公司 | Double-layer quartz process chamber structure |
| 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 |
| CN114671710A (en) * | 2022-03-10 | 2022-06-28 | 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 |
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