CN105174247A - Device and method for growing large-area graphene and graphene obtained therefrom - Google Patents
Device and method for growing large-area graphene and graphene obtained therefrom Download PDFInfo
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- CN105174247A CN105174247A CN201410240873.XA CN201410240873A CN105174247A CN 105174247 A CN105174247 A CN 105174247A CN 201410240873 A CN201410240873 A CN 201410240873A CN 105174247 A CN105174247 A CN 105174247A
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Abstract
The invention discloses a device and method for growing large-area graphene and graphene obtained therefrom. The device comprises a metal substrate, a roll quartz boat, a fixing device and a diffusion furnace, wherein at least one small hole is formed in each of two sides of the metal substrate; the fixing device comprises fixing wires; the fixing wires penetrate through the small holes at the two sides so as to fix the metal substrate on the roll quartz boat. The roll quartz boat is used as a copper foil bearing device, and a copper foil is assembled on the outer surface of the roll quartz boat and then is fixed through the fixing wires, so that the copper foil can be assembled in largest area and the graphene can be deposited in largest area; the copper foil is supported by the roll quartz boat all the time, so that folds are not produced during sample loading, deposition and sample taking, therefore, the area of the graphene sample produced through the device is larger than the area of an graphene sample produced industrially and an experimental sample in a laboratory (the largest area of the graphene sample is larger than 0.5 m<2>), the number of layers (1-3 layers) is uniform, the sheet resistance and the penetration rate are uniform, and the surface of the large-area graphene sample is smooth and flat without folds after being transferred.
Description
Technical field
The Graphene that the present invention relates to a kind of device of growing large-area Graphene, method and obtain thus.
Background technology
Along with making known of Nobel Prize in physics winner in 2010, Graphene (Graphene) also becomes the focus that everybody discusses.2004, An Deliehaimu and the Constantine Nuo Woxiaoluofu of Univ Manchester UK utilized normal tape successfully from graphite, to separate Graphene, and this material only has a carbon atom thick, were the thinnest known at present materials.It is not only one the thinnest in known materials, also very firmly soft; As simple substance, the speed that it at room temperature transmits electronics is all faster than known conductor.Graphene can be applied to the field of transistor, touch-screen, gene sequencing, is expected to help physicist to make new breakthroughs in quantum physics research field simultaneously, and its appearance causes global research boom.
In view of Graphene has many character being better than conventional material, have broad application prospects in theoretical basis research and nanoelectronics, therefore prepare big area, high quality, low defect Graphene be a matter of utmost importance urgently to be resolved hurrily.At present, the preparation method of Graphene mainly contains following four kinds:
1, graphite method peeled off by micromechanics: because graphite crystal is laminated structure, be with the faint combination of Van der Waals between each layer, and therefore micromechanics stripping graphite method mainly uses micromechanics external force to go out graphene film Rotating fields from graphite crystal sur-face peeling.It is low that the method has cost; sample quality is high, and the advantage that the sheet number of plies is controlled, shortcoming is difficult to accurately control size; repeatability is poor; yield poorly, efficiency is low, is difficult to the big area and the mass-producing preparation that realize Graphene; and it is longer to expend time in; size is less, namely only has about 0.1mm, so be only limitted to the application of the fundamental research aspect as laboratory.
2, graphite oxide reduction method: graphite oxide reduction method is under certain electrochemical conditions, utilize oxidizing reaction, the hydrophilic radicals such as epoxy group(ing), hydroxyl, carbonyl and carboxyl are introduced in graphite-structure, obtain graphite oxide, the methods such as the reduction of recycling reductive agent or thermal treatment, reduction-oxidation graphite obtains the method for Graphene.Graphite oxide reduction method is widely adopted due to its stability.But oxidising process can cause a large amount of textural defect, even if these defects can not be eliminated completely through 1100 DEG C of annealing, still have the residual of many hydroxyls, epoxy group(ing), carbonyl, carboxyl.The electronic structure change that defect causes makes Graphene transfer semi-conductor to by conductor, has a strong impact on the electric property of Graphene, constrains its application.
3, extending and growing graphene on silicon carbide substrates: the core of the method is after completing surface preparation to SiC substrate, Si is utilized to have the character of the saturated vapor pressure higher than C, be greater than 1100 DEG C of high temperature with under the UHV condition being less than 10-6Pa, Si atom takes the lead in from substrate surface distillation, and remaining C atom reconstructs graphene layer.Graphene prepared by epitaxial growth method shows the characteristics such as higher carrier mobility, thus shows outstanding electrical properties, but due to SiC crystal surface tissue comparatively complicated, be difficult to obtain the homogeneous Graphene of big area, thickness.
4, the chemical Vapor deposition process of metal substrate: the mechanism that the method prepares grapheme material is, under the high-temperature gas condition of 800 ~ 1200 DEG C, gaseous hydrocarbons etc. are through having the transiting metal surface of catalytic activity, in metallic surface dehydrogenation, the carbon atom of residual ionization state is adsorbed on metallic surface, forms graphene-structured during cooling with sp2 bonding.The method be prepare larger area in recent years, high-quality graphene compares one of effective means, and can be compatible with existing semiconductor fabrication process.But still there is following defect in this kind of method: the Graphene area of (1), growth is less, is generally 2-12 inch under technique conventional at present; (2), then the number of plies is uneven for the Graphene sample of larger area produced, and general 1 ~ 10 layer has; (3) although produce small area Graphene due to deposition rate comparatively even, sheet resistance and transmitance are all in higher level.But Graphene sample area do larger, due to the difference of gas and temperature, difference is larger everywhere to cause sheet resistance and transmitance surface, is unfavorable for batch production; (4), larger area Copper Foil substrate is all more difficult on dress sample and sampling, after annealing, Copper Foil hardness can sharply decline, as do not fitted very well in assembling, can Folding Deformation be there is in Copper Foil, this can bring serious impact to techniques such as rotors afterwards, greatly affects the quality of graphene product.
Summary of the invention
First object of the present invention is to provide a kind of device for growing large-area Graphene.
The technical scheme realizing the present invention's first object is: a kind of device of growing large-area Graphene, comprises metal substrate, scroll quartz boat, stationary installation and diffusion furnace; The both sides of metal substrate are respectively provided with at least one aperture; Described stationary installation comprises fixing silk, and metal substrate is fixed on scroll quartz boat through both sides aperture by described fixing silk.
Described stationary installation also comprises ties up bar for what fixed in metal substrate two ends and scroll quartz boat.
The device of described growing large-area Graphene also comprises inlet pipe; Described inlet pipe is evenly distributed with production well; Described inlet pipe is straight tube or arranges around scroll quartz boat.
The method of the growing large-area Graphene that second object of the present invention is to provide a kind ofly easy to implement can grow big area, thickness is homogeneous, performance is good.
The technical scheme realizing the present invention's second object is a kind of method of growing large-area Graphene, comprises the following steps:
Step one: prepare metal substrate; The acetone being not less than 99.7% by deionized water and purity is comprehensively cleaned copper foil surface, and dries; Fixing silk in described step 2 is copper free wire.
Step 2: metal substrate is filled sample on the outside surface of scroll quartz boat; Respectively on metal substrate both sides beat at least one aperture, through both sides aperture, metal substrate is fixed on scroll quartz boat with fixing silk, after fixing with fixing silk, then bind bar at metal substrate two ends.
Step 3: the scroll quartz boat comprising metal substrate of step 2 is put into diffusion furnace and deposits;
Can adopt in two ways at this, one is two step sedimentation: a, expanding furnace pressure is extracted into below 100pa, pressurize 30 minutes, and after guaranteeing that diffusion furnace vacuum system is stable, in diffusion furnace, logical argon gas is to normal pressure; This process repeats twice, and argon flow amount is 1000sccm; B, diffusion furnace is warming up to 950 ~ 1050 DEG C, adopts argon gas and hydrogen shield in temperature-rise period, in this process, the flow of logical argon gas and hydrogen is respectively 500 ~ 2000sccm and 500 ~ 1000sccm, after reaching target temperature, closes argon gas and hydrogen; C, diffusion furnace vacuum is extracted into 1 ~ 100pa, in diffusion furnace, then passes into hydrogen and hydrocarbon gas or liquid carbon source, deposit 10 ~ 20min at this temperature and pressure; D, closedown hydrogen and hydrocarbon gas or liquid carbon source, be extracted into 1 ~ 100pa by diffusion furnace vacuum, then close off-gas pump; Hydrogen and hydrocarbon gas or liquid carbon source is passed into, until pressure closes all gas after being elevated to 1.1 ~ 1.5Kpa in diffusion furnace; Deposit 3 ~ 10min at this temperature and pressure; After e, deposition process terminate, pump reacted entrap bubble in diffusion furnace immediately, cooling down, at argon gas and hydrogen shield borehole cooling, argon flow amount 1000sccm, hydrogen flowing quantity is 100 ~ 200sccm.Hydrogen during c step and d walk and the purity of hydrocarbon gas or liquid carbon source are 99.999%; In c step, the flow of hydrocarbon gas or liquid carbon source is 400 ~ 600sccm, and hydrogen flowing quantity is 20 ~ 40sccm; In d step, the flow of hydrocarbon gas or liquid carbon source is 100 ~ 200sccm, and hydrogen flowing quantity is 100 ~ 200sccm.
Another kind is three step sedimentation: a, expanding furnace pressure is extracted into below 100pa, pressurize 30 minutes, and after guaranteeing that diffusion furnace vacuum system is stable, in diffusion furnace, logical argon gas is to normal pressure; This process repeats twice, and argon flow amount is 1000sccm; ; B, diffusion furnace is warming up to 950 ~ 1050 DEG C, adopts argon gas and hydrogen shield in temperature-rise period, in this process, the flow of logical argon gas and hydrogen is respectively 500 ~ 2000sccm and 500 ~ 1000sccm, after reaching target temperature, closes argon gas and hydrogen; C, diffusion furnace vacuum is extracted into 1 ~ 100pa, in diffusion furnace, then passes into hydrogen and hydrocarbon gas or liquid carbon source, deposit 10 ~ 20min at this temperature and pressure; D, diffusion furnace vacuum is extracted into 1 ~ 100pa, in diffusion furnace, then passes into hydrogen and hydrocarbon gas or liquid carbon source, deposit 5 ~ 10min at this temperature and pressure; E, closedown hydrogen and hydrocarbon gas or liquid carbon source, be extracted into 1 ~ 100pa by diffusion furnace vacuum, then close off-gas pump; Hydrogen and hydrocarbon gas or liquid carbon source is passed into, until pressure closes all gas after being elevated to 1.1 ~ 1.5Kpa in diffusion furnace; Deposit 3 ~ 10min at this temperature and pressure; After f, deposition process terminate, pump reacted entrap bubble in diffusion furnace immediately, at argon gas and hydrogen shield borehole cooling, argon flow amount 1000sccm, hydrogen flowing quantity is 100 ~ 200sccm; Hydrogen during c step and d step and e walk and the purity of hydrocarbon gas or liquid carbon source are 99.999%; In c step, the flow of hydrocarbon gas or liquid carbon source is 400 ~ 600sccm, and hydrogen flowing quantity is 20 ~ 40sccm; In d step, the flow of hydrocarbon gas or liquid carbon source is 40 ~ 60sccm, and hydrogen flowing quantity is 20 ~ 40sccm; In e step, the flow of hydrocarbon gas or liquid carbon source is 100 ~ 200sccm, and hydrogen flowing quantity is 100 ~ 200sccm.
Step 4: cooling, sampling.After cooling, bar and fixing silk are tied up in severing, and the metal substrate of growing graphene is tangentially transferred on acrylic board by the bar of tying up holding severing.
3rd object of the present invention is to provide a kind of corrugationless, the uniform Graphene of the number of plies.
The technical scheme realizing the 3rd object of the present invention adopts aforesaid device and preparation method, thus obtain without this week, the uniform large-area Graphene of the number of plies.
The principle that the present invention is achieved is: general silica tube size can not be very large, and other shape quartz member are unfavorable for assembling large-area graphene film.And scroll quartz boat is because its scroll structure, the fold of Copper Foil can not be caused on the one hand, also make assembling big area Copper Foil become possibility on the other hand.Such as, in the silica tube of same thickness, the Copper Foil area that slab construction can be assembled is much smaller than scroll quartz boat; And common quartz boat is when assembling large-area Copper Foil, not supporting in the middle part of Copper Foil, just easily sinking to producing fold, finally affecting the quality of Graphene.Device used in the present invention and dress sample and sampling method, scroll quartz boat well supports to Copper Foil one, during dress sample when guarantee Copper Foil fix can not come off, the useful area that ensure that Graphene deposition substrate Copper Foil large as far as possible.During sampling, because the Copper Foil area of growing graphene film is large, so easily takes out unlike small area Copper Foil and do not produce fold cut.
After have employed technique scheme, the present invention has following useful effect: (1) the present invention innovatively utilizes roll quartz boat to be used as Copper Foil bogey, Copper Foil is assemblied in scroll quartz boat outside surface, then only fix with fixing silk, the assembling Copper Foil of energy maximum area and deposited graphite alkene, and have scroll quartz boat to support all the time due to Copper Foil, all can not produce fold when filling sample, deposition, sampling, therefore not only area compared with suitability for industrialized production with laboratory experiment sample is much larger (can accomplish to be greater than 0.5m
2), evenly (1 ~ 3 layer), sheet resistance and transmitance are even for the number of plies, and so large-area graphene turns the smooth corrugationless in sample rear surface, solve thus simultaneously Graphene preparation facilities in prior art cannot the problem of consistent, the sheet resistance of the production number of plies and the uniform large-area graphene sample of transmitance and prior art for production large-area graphene in dress sample, sampling, turn and press through the problem that Cheng Zhongyi produces fold.
(2) inlet pipe in device of the present invention arranges little pore, more can guarantee at diffusion furnace internal gas pressure even like this, further increase the quality of Graphene.And inlet pipe can be arranged around scroll quartz boat, pore is uniformly distributed, such better effects if.
(3) dress quadrat method of the present invention when guarantee Copper Foil fix can not come off, the useful area that ensure that Graphene deposition substrate Copper Foil large as far as possible, and sampling method can farthest ensure not produce fold when large-area Copper Foil like this shifts from scroll quartz boat.
(4) the Graphene sample number of plies can be caused when adopting existing CVD processing parameter to prepare large-area graphene film uneven, sheet resistance transmitance is uneven, and the processing parameter selected by CVD of the present invention can guarantee that the graphene film number of plies prepared is even further, sheet resistance transmittance is good.Particularly adopt the technique of three step depositions and the selection of processing parameter to make to prepare the deformation load unloading piece gimmick joint effect that is different and scroll quartz boat that in rear Copper Foil soft or hard degree and preparation process, technological reason makes Copper Foil occur and then can accomplish that outward appearance is more smooth, quality is better.
Accompanying drawing explanation
In order to make content of the present invention more easily be clearly understood, below according to specific embodiment also by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is that the present invention deposits front schematic diagram Copper Foil and scroll quartz boat fixed.
Fig. 2 is the surface topography (200 times) of the large-area graphene of application examples 2 of the present invention deposition.Find out that the Graphene that copper foil surface deposits is continuous, flat smooth, zero defect from this figure.
Fig. 3 is the Raman spectrum that the present invention quotes the Graphene that example 2 deposits.
Attached number in the figure is:
Metal substrate 1, aperture 11, scroll quartz boat 2, fixing silk 3, tie up bar 4.
Embodiment
See Fig. 1, the device of the growing large-area Graphene of the present embodiment comprises metal substrate 1, scroll quartz boat 2, stationary installation, inlet pipe 5 and diffusion furnace; The both sides of metal substrate 1 are respectively provided with at least one aperture 11; Scroll quartz boat 2 is supported by two strut angles and is placed in diffusion furnace.Stationary installation comprises fixing silk 3 and ties up bar 4, and metal substrate 1 is fixed on scroll quartz boat 2 through both sides aperture 11 by fixing silk 3.Tie up bar 4 metal substrate 1 two ends and scroll quartz boat 2 are fixed.Inlet pipe 5 is evenly distributed with production well 51.
The method of aforesaid device growing large-area Graphene is adopted to comprise the following steps:
Step one: prepare metal substrate 1; Adopt Copper Foil as metal substrate 1, the acetone being not less than 99.7% by deionized water and purity is comprehensively cleaned copper foil surface, and dries;
Step 2: metal substrate 1 is filled sample on the outside surface of scroll quartz boat 2; Fixing silk 3 is copper free wire; Respectively on metal substrate 1 both sides beat at least one aperture 11, through both sides aperture 11, metal substrate 1 is fixed on scroll quartz boat 2 with fixing silk 3; Bar 4 is bound again, as shown in Figure 1 at metal substrate 1 two ends.
Step 3: the scroll quartz boat 2 comprising metal substrate 1 of step 2 is put into diffusion furnace and deposits;
A, expanding furnace pressure is extracted into below 100pa, pressurize 30 minutes, after guaranteeing that diffusion furnace vacuum system is stable, in diffusion furnace, logical argon gas is to normal pressure; A walks process and repeats twice, and argon flow amount is 1000sccm;
B, diffusion furnace is warming up to 950 ~ 1050 DEG C; Adopt argon gas and hydrogen shield in temperature-rise period, in this process, the flow of logical argon gas and hydrogen is respectively 500 ~ 2000sccm and 500 ~ 1000sccm, after reaching target temperature, closes argon gas and hydrogen;
C, diffusion furnace vacuum is extracted into 1 ~ 100pa, in diffusion furnace, then passes into hydrogen and hydrocarbon gas or liquid carbon source, deposit 10 ~ 20min at this temperature and pressure; The purity of hydrogen and hydrocarbon gas or liquid carbon source is 99.999%; The flow of hydrocarbon gas or liquid carbon source is 400 ~ 600sccm, and hydrogen flowing quantity is 20 ~ 40sccm;
D, closedown hydrogen and hydrocarbon gas or liquid carbon source, be extracted into 1 ~ 100pa by diffusion furnace vacuum, then close off-gas pump; Hydrogen and hydrocarbon gas or liquid carbon source is passed into, until pressure closes all gas after being elevated to 1.1 ~ 1.5Kpa in diffusion furnace; Deposit 3 ~ 10min at this temperature and pressure; The purity of hydrogen and hydrocarbon gas or liquid carbon source is 99.999%; The flow of hydrocarbon gas or liquid carbon source is 100 ~ 200sccm, and hydrogen flowing quantity is 100 ~ 200sccm;
After e, deposition process terminate, pump reacted entrap bubble in diffusion furnace immediately, in argon gas and the cooling of hydrogen shield borehole cooling, argon flow amount 1000sccm, hydrogen flowing quantity is 100 ~ 200sccm.
Step 4: cooling, sampling: after cooling, bar 4 and fixing silk 3 are tied up in severing, and the metal substrate 1 of growing graphene is tangentially transferred on acrylic board by the bar 4 of tying up holding severing.
Carry out six application examples below, table one is the concrete technology parameter of three application examples of employing two step sedimentation:
Table one
| Application examples 1 | Application examples 2 | Application examples 3 | |
| Copper Foil size | 400x1000mm | 500x1000mm | 600x1200mm |
| B step-up temperature target temperature | 950℃ | 1000℃ | 1050℃ |
| B walks argon flow amount | 500sccm | 1500sccm | 2000sccm |
| B walks hydrogen flowing quantity | 500sccm | 750sccm | 1000sccm |
| C walks diffusion furnace pressure | 1pa | 50pa | 100pa |
| C walks depositing time | 10min | 15min | 20min |
| C walks hydro carbons or carbon source flow | Methane 400sccm | Toluene 500sccm | Ethanol 600sccm |
| C walks hydrogen flowing quantity | 20sccm | 30sccm | 40sccm |
| D walks diffusion furnace pressure | 1pa | 50pa | 100pa |
| D step-up pressure goal pressure | 1.1Kpa | 1.3Kpa | 1.5Kpa |
| D walks depositing time | 3min | 7min | 10min |
| D walks hydro carbons or carbon source flow | Methane 100sccm | Toluene 150sccm | Ethanol 200sccm |
| D walks hydrogen flowing quantity | 100sccm | 150sccm | 200sccm |
| E walks hydrogen flowing quantity | 100sccm | 150sccm | 200sccm |
The concrete technology parameter of three application examples that table two is employing three step sedimentation:
Table two:
| Application examples 1 | Application examples 2 | Application examples 3 | |
| Copper Foil size | 400x1000mm | 500x1000mm | 600x1200mm |
| B step-up temperature target temperature | 950℃ | 1000℃ | 1050℃ |
| B walks argon flow amount | 500sccm | 1500sccm | 2000sccm |
| B walks hydrogen flowing quantity | 500sccm | 750sccm | 1000sccm |
| C walks diffusion furnace pressure | 1pa | 50pa | 100pa |
| C walks depositing time | 5min | 8min | 10min |
| C walks hydro carbons or carbon source flow | Methane 400sccm | Toluene 500sccm | Ethanol 600sccm |
| C walks hydrogen flowing quantity | 20sccm | 30sccm | 40sccm |
| D walks diffusion furnace pressure | 1pa | 50pa | 100pa |
| D walks depositing time | 5min | 7min | 10min |
| D walks hydro carbons or carbon source flow | Methane 40sccm | Toluene 50sccm | Ethanol 60sccm |
| D walks hydrogen flowing quantity | 20sccm | 30sccm | 40sccm |
| E walks diffusion furnace pressure | 1pa | 50pa | 100pa |
| E step-up pressure goal pressure | 1.1Kpa | 1.3Kpa | 1.5Kpa |
| E walks depositing time | 3min | 7min | 10min |
| E walks hydro carbons or carbon source flow | Methane 100sccm | Toluene 150sccm | Ethanol 200sccm |
| E walks hydrogen flowing quantity | 100sccm | 150sccm | 200sccm |
| F walks hydrogen flowing quantity | 100sccm | 150sccm | 200sccm |
For ease of contrast, do three comparative examples at this with existing vapour deposition process:
Comparative example 1: scroll quartz boat, a step deposition;
Comparative example 2: scroll quartz boat, two step depositions, parameter is different;
Comparative example 3: quartzy swash plate, two step depositions;
Table three:
| To example 1 | Comparative example 2 | Comparative example 3 | |
| Copper Foil size | 70x150mm | 140x150mm | 100x200mm |
| B step-up temperature target temperature | 1000℃ | 1000℃ | 1000℃ |
| B walks argon flow amount | 2000sccm | 1500sccm | 2000sccm |
| B walks hydrogen flowing quantity | 700sccm | 750sccm | 750sccm |
| C walks diffusion furnace pressure | 5pa | 5pa | 5pa |
| C walks depositing time | 5min | 10min | 12min |
| C walks hydro carbons or carbon source flow | Methane 50sccm | Methane 100sccm | Methane 150sccm |
| C walks hydrogen flowing quantity | 10sccm | 15sccm | 20sccm |
| E walks hydrogen flowing quantity | 100sccm | 100sccm | 100sccm |
Detect above six application examples and three comparative examples, each detected result is as following table four:
Table four
From the contrast of table two, large-area graphene sample prepared by method of the present invention is large, the number of plies evenly, sheet resistance and transmitance even, (as Fig. 2 and Fig. 3, the microscope photograph of application examples 2 and Raman spectrum can confirm further to turn the smooth corrugationless in sample rear surface.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a device for growing large-area Graphene, is characterized in that: comprise metal substrate (1), scroll quartz boat (2), stationary installation and diffusion furnace; The both sides of metal substrate (1) are respectively provided with at least one aperture (11); Described stationary installation comprises fixing silk (3), and metal substrate (1) is fixed on scroll quartz boat (2) through both sides aperture (11) by described fixing silk (3).
2. the device of a kind of growing large-area Graphene according to claim 1, is characterized in that: described stationary installation also comprises ties up bar (4) for what fixed in metal substrate (1) two ends and scroll quartz boat (2).
3. the device of a kind of growing large-area Graphene according to claim 2, is characterized in that: also comprise inlet pipe (5); Described inlet pipe (5) is evenly distributed with production well (51); Described inlet pipe (5) is arranged for straight tube or around scroll quartz boat (2).
4. a method for growing large-area Graphene, is characterized in that: adopt device according to claim 3, comprise the following steps:
Step one: prepare metal substrate (1);
Step 2: by metal substrate (1) dress sample on scroll quartz boat (2) outside surface; Respectively on metal substrate (1) both sides beat at least one aperture (11), through both sides aperture (11), metal substrate (1) is fixed on scroll quartz boat (2) with fixing silk (3), then binds bar (4) at metal substrate (1) two ends;
Step 3: the scroll quartz boat (2) comprising metal substrate (1) of step 2 is put into diffusion furnace and deposits;
Step 4: cooling, sampling.
5. a kind of method of producing large-area graphene according to claim 4, it is characterized in that the concrete grammar of described step 4 is: after cooling, bar (4) and fixing silk (3) are tied up in severing, and the metal substrate (1) of growing graphene is tangentially transferred on acrylic board by the bar (4) of tying up holding severing; Metal substrate (1) in described step one is Copper Foil; To the treatment process of Copper Foil be: the acetone being not less than 99.7% by deionized water and purity is comprehensively cleaned copper foil surface, and dries; Fixing silk (3) in described step 2 is copper free wire.
6. a kind of method of producing large-area graphene according to claim 5, it is characterized in that: the concrete grammar of described step 3 deposited graphite alkene is: a, expanding furnace pressure is extracted into below 100pa, pressurize 30 minutes, after guaranteeing that diffusion furnace vacuum system is stable, in diffusion furnace, logical argon gas is to normal pressure; B, diffusion furnace is warming up to 950 ~ 1050 DEG C; C, diffusion furnace vacuum is extracted into 1 ~ 100pa, in diffusion furnace, then passes into hydrogen and hydrocarbon gas or liquid carbon source, deposit 10 ~ 20min at this temperature and pressure; D, closedown hydrogen and hydrocarbon gas or liquid carbon source, be extracted into 1 ~ 100pa by diffusion furnace vacuum, then close off-gas pump; Hydrogen and hydrocarbon gas or liquid carbon source is passed into, until pressure closes all gas after being elevated to 1.1 ~ 1.5Kpa in diffusion furnace; Deposit 3 ~ 10min at this temperature and pressure; After e, deposition process terminate, pump reacted entrap bubble in diffusion furnace immediately, cooling down.
7. the method for a kind of growing large-area Graphene according to claim 6, is characterized in that: a of described step 3 walks process and repeats twice, and argon flow amount is 1000sccm; Adopt argon gas and hydrogen shield in temperature-rise period in the b step of described step 3, in this process, the flow of logical argon gas and hydrogen is respectively 500 ~ 2000sccm and 500 ~ 1000sccm, after reaching target temperature, closes argon gas and hydrogen; At argon gas and hydrogen shield borehole cooling in described e step, argon flow amount 1000sccm, hydrogen flowing quantity is 100 ~ 200sccm; Hydrogen during the c step of described step 3 and d walk and the purity of hydrocarbon gas or liquid carbon source are 99.999%; In c step, the flow of hydrocarbon gas or liquid carbon source is 400 ~ 600sccm, and hydrogen flowing quantity is 20 ~ 40sccm; In d step, the flow of hydrocarbon gas or liquid carbon source is 100 ~ 200sccm, and hydrogen flowing quantity is 100 ~ 200sccm.
8. a kind of method of producing large-area graphene according to claim 5, it is characterized in that: the concrete grammar of described step 3 deposited graphite alkene is: a, expanding furnace pressure is extracted into below 100pa, pressurize 30 minutes, after guaranteeing that diffusion furnace vacuum system is stable, in diffusion furnace, logical argon gas is to normal pressure; B, diffusion furnace is warming up to 950 ~ 1050 DEG C; C, diffusion furnace vacuum is extracted into 1 ~ 100pa, in diffusion furnace, then passes into hydrogen and hydrocarbon gas or liquid carbon source, deposit 10 ~ 20min at this temperature and pressure; D, diffusion furnace vacuum is extracted into 1 ~ 100pa, in diffusion furnace, then passes into hydrogen and hydrocarbon gas or liquid carbon source, deposit 5 ~ 10min at this temperature and pressure; E, closedown hydrogen and hydrocarbon gas or liquid carbon source, be extracted into 1 ~ 100pa by diffusion furnace vacuum, then close off-gas pump; Hydrogen and hydrocarbon gas or liquid carbon source is passed into, until pressure closes all gas after being elevated to 1.1 ~ 1.5Kpa in diffusion furnace; Deposit 3 ~ 10min at this temperature and pressure; After f, deposition process terminate, pump reacted entrap bubble in diffusion furnace immediately, cooling down.
9. the method for a kind of growing large-area Graphene according to claim 8, is characterized in that: a of described step 3 walks process and repeats twice, and argon flow amount is 1000sccm; Adopt argon gas and hydrogen shield in temperature-rise period in the b step of described step 3, in this process, the flow of logical argon gas and hydrogen is respectively 500 ~ 2000sccm and 500 ~ 1000sccm, after reaching target temperature, closes argon gas and hydrogen; At argon gas and hydrogen shield borehole cooling in described f step, argon flow amount 1000sccm, hydrogen flowing quantity is 100 ~ 200sccm; Hydrogen during the c step of described step 3 and d step and e walk and the purity of hydrocarbon gas or liquid carbon source are 99.999%; In c step, the flow of hydrocarbon gas or liquid carbon source is 400 ~ 600sccm, and hydrogen flowing quantity is 20 ~ 40sccm; In d step, the flow of hydrocarbon gas or liquid carbon source is 40 ~ 60sccm, and hydrogen flowing quantity is 20 ~ 40sccm; In e step, the flow of hydrocarbon gas or liquid carbon source is 100 ~ 200sccm, and hydrogen flowing quantity is 100 ~ 200sccm.
10. a Graphene, is characterized in that; Prepared by the arbitrary described method of claim 4-9 and obtain.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862253A (en) * | 2018-07-17 | 2018-11-23 | 云南大学 | A kind of graphene growth method based on multilayer and large-area graphene growth quartz boat |
| CN111936611A (en) * | 2017-12-19 | 2020-11-13 | J·比尔拉帕米尔斯 | Biogas equipment |
| CN114289420A (en) * | 2022-02-21 | 2022-04-08 | 常州二维碳素科技股份有限公司 | Method for removing carbon deposit on inner wall of air inlet pipe in CVD (chemical vapor deposition) grown graphene powder |
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| WO2013133803A1 (en) * | 2012-03-06 | 2013-09-12 | Empire Technology Development Llc | Graphene production |
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| CN111936611A (en) * | 2017-12-19 | 2020-11-13 | J·比尔拉帕米尔斯 | Biogas equipment |
| CN108862253A (en) * | 2018-07-17 | 2018-11-23 | 云南大学 | A kind of graphene growth method based on multilayer and large-area graphene growth quartz boat |
| CN114289420A (en) * | 2022-02-21 | 2022-04-08 | 常州二维碳素科技股份有限公司 | Method for removing carbon deposit on inner wall of air inlet pipe in CVD (chemical vapor deposition) grown graphene powder |
| CN114289420B (en) * | 2022-02-21 | 2023-09-01 | 常州二维碳素科技股份有限公司 | Method for removing carbon deposition on inner wall of air inlet pipe in CVD (chemical vapor deposition) grown graphene powder |
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