CN105174247B - A kind of device of growing large-area Graphene, method and thus obtained Graphene - Google Patents
A kind of device of growing large-area Graphene, method and thus obtained Graphene Download PDFInfo
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- CN105174247B CN105174247B CN201410240873.XA CN201410240873A CN105174247B CN 105174247 B CN105174247 B CN 105174247B CN 201410240873 A CN201410240873 A CN 201410240873A CN 105174247 B CN105174247 B CN 105174247B
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Abstract
The invention discloses a kind of device of growing large-area Graphene, method and thus obtained Graphene, device includes metal substrate, scroll quartz boat, fixing device and diffusion furnace；The both sides of metal substrate are each provided with least one aperture；The fixing device includes fixing silk, and the fixed silk is fixed on metal substrate on scroll quartz boat through both sides aperture.The present invention is used as Copper Foil bogey using roll quartz boat, Copper Foil is assembled in scroll quartz boat outer surface, then only fixed with fixed silk, the assembling Copper Foil and deposited graphite alkene of energy maximum area, and support as Copper Foil has scroll quartz boat to give all the time, when sample, deposition, sampling is filled all without generation fold, therefore not only area is much larger compared with industrialized production and laboratory experiment sample (can accomplish more than 0.5m2), the number of plies uniform (1～3 layer), sheet resistance and transmitance it is uniform, and so large-area graphene turns the smooth corrugationless in surface after sample.
Description
Technical field
The present invention relates to a kind of device of growing large-area Graphene, method and thus obtained Graphene.
Background technology
With making known for Nobel Prize in physics winner in 2010, Graphene (Graphene) also becomes Jiao of everybody discussion
Point.2004, the An Deliehaimu and Constantine Nuo Woxiao love of Univ Manchester UK using normal tape into
Graphene is separated from graphite, this material only has a carbon atom thickness, is the most thin material being currently known work(.It is not
Only it is most thin one kind in known materials, it is also very firmly soft；Used as simple substance, it transmits the speed ratio of electronics at room temperature
Known conductor is all fast.Graphene can apply to the field of transistor, touch screen, gene sequencing, while being expected to help physicss
Family makes new breakthroughs in quantum physicses research field, and its appearance causes global research boom.
In view of Graphene has many property better than conventional material, have in theoretical basis research and nanoelectronics wide
Wealthy application prospect, therefore preparation large area, high-quality, the Graphene of low defect are a matters of utmost importance urgently to be resolved hurrily.Mesh
Before, the preparation method of Graphene mainly has following four：
1st, micromechanics peels off graphite method：Because graphite crystal is lamellar structure, it is micro- with Van der Waals between each layer
Weak combination, therefore micromechanics stripping graphite method mainly goes out graphene sheet layer from graphite crystal sur-face peeling using micromechanics external force
Structure.The method has low cost, and sample quality is high, and the controllable advantage of the piece number of plies, has the disadvantage to be difficult precise control size, weight
Renaturation is poor, yields poorly, and efficiency is low, it is difficult to realize the large area and prepare with scale of Graphene, and the consuming time is longer, size
It is less, i.e. only 0.1mm or so, so the application being only limitted in terms of the fundamental research as laboratory.
2nd, graphite oxide reducing process：Graphite oxide reducing process is under certain electrochemical conditions, using oxidation reaction, by ring
The hydrophilic radicals such as epoxide, hydroxyl, carbonyl and carboxyl are introduced in graphite-structure, obtain graphite oxide, recycle reducing agent reduction
Or the method such as heat treatment, the method that reduction-oxidation graphite obtains Graphene.Graphite oxide reducing process is wide due to its stability
General employing.However, oxidizing process can cause substantial amounts of fault of construction, even if the 1100 DEG C of annealing of these defects Jing can not quilt completely
Eliminate, still have the residual of many hydroxyls, epoxy radicals, carbonyl, carboxyl.Electronic structure change caused by defect makes Graphene by conductor
Switch to quasiconductor, have a strong impact on the electric property of Graphene, constrain its application.
3rd, extending and growing graphene on silicon carbide substrates：The core of the method is to locate completing surface to SiC substrate in advance
After reason, using properties of the Si with the saturated vapor pressure higher than C, more than 1100 DEG C of high temperature and true less than the superelevation of 10-6Pa
Under empty condition, Si atoms take the lead in from substrate surface distilling, and remaining C atoms are reconstructed into graphene layer.Prepared by epitaxial growth method
Graphene shows the characteristics such as higher carrier mobility, thus shows outstanding electrical properties, but due to SiC crystal table
Face structure is complex, it is difficult to obtain the homogeneous Graphene of large area, thickness.
4th, the chemical vapour deposition technique of metal substrate：The method prepares the mechanism of grapheme material, at 800～1200 DEG C
High-temperature gas under the conditions of, hydrocarbon gas etc. through with catalysis activity transiting metal surface when, in metal surface
Dehydrogenation, the carbon atom absorption of residual ionization state bond together to form graphene-structured with sp2 at metal surface, cooling.The method is
One of relatively effective method of larger area, high-quality graphene is prepared in recent years, and can be with existing semiconductor manufacturing
Process compatible.But this kind of method still suffers from following defect under technique conventional at present：(1), the Graphene area of growth is less,
Usually 2-12 inches；(2), then the number of plies is uneven for the Graphene sample of the larger area of production, and general 1～10 layer has；(3)、
Although production small area Graphene is more uniform due to deposition rate, sheet resistance and transmitance are all in higher level.But Graphene sample
It is bigger that area does, and due to gas and the difference of temperature, difference is bigger everywhere to cause sheet resistance and transmitance surface, is unfavorable for criticizing
Amount production；(4), larger area Copper Foil substrate is all relatively difficult on dress sample and sampling, and after annealing, Copper Foil hardness drastically can decline,
Such as can not fit very well in assembling, Copper Foil can occur Folding Deformation, this can bring serious impact to techniques such as rotors afterwards,
The quality of graphene product is affected greatly.
The content of the invention
First purpose of the present invention is to provide a kind of device for growing large-area Graphene.
The technical scheme for realizing first purpose of the invention is：A kind of device of growing large-area Graphene, including metal
Substrate, scroll quartz boat, fixing device and diffusion furnace；The both sides of metal substrate are each provided with least one aperture；The fixation
Device includes fixing silk, and the fixed silk is fixed on metal substrate on scroll quartz boat through both sides aperture.
The fixing device also includes tying up bar for what is fixed metal substrate two ends and scroll quartz boat.
The device of the growing large-area Graphene also includes air inlet pipe；Venthole is evenly distributed with the air inlet pipe；
The air inlet pipe is straight tube or arranges around scroll quartz boat.
Second object of the present invention is to provide and a kind of easy to implement can grow that large area, thickness is homogeneous, performance is good
Growing large-area Graphene method.
The technical scheme for realizing second purpose of the invention is a kind of method of growing large-area Graphene, including following step
Suddenly：
Step one：Prepare metal substrate；The acetone of deionized water and purity not less than 99.7% is carried out to copper foil surface
Comprehensively clean, and dry；Fixed silk in the step 2 is copper free wire.
Step 2：By metal substrate dress sample on the outer surface of scroll quartz boat；At least one is beaten metal substrate both sides are each
Individual aperture, is fixed on metal substrate on scroll quartz boat through both sides aperture with fixed silk, after being fixed with fixed silk, then in gold
Bind bar in category substrate two ends.
Step 3：The scroll quartz boat comprising metal substrate of step 2 is put in diffusion furnace and is deposited；
Here can adopt two ways, and one kind is two step sedimentations：A, expanding furnace pressure is extracted into into below 100pa,
Pressurize 30 minutes, it is ensured that after diffusion furnace vacuum system is stable, leads to argon into diffusion furnace to normal pressure；This process is repeated twice, argon
Throughput is 1000sccm；B, diffusion furnace is warming up to 950～1050 DEG C, in temperature-rise period, adopts argon and hydrogen shield, should
During lead to the flow of argon and hydrogen and be respectively 500～2000sccm and 500～1000sccm, after reaching target temperature, close
Close argon and hydrogen；C, diffusion furnace vacuum is extracted into into 1～100pa, hydrogen and hydrocarbon gas or liquid are then passed through into diffusion furnace
Body carbon source, deposits 10～20min at this temperature and pressure；D, closing hydrogen and hydrocarbon gas or liquid carbon source, by diffusion furnace
Vacuum is extracted into 1～100pa, is then shut off air pump；Hydrogen and hydrocarbon gas or liquid carbon source are passed through into diffusion furnace, until pressure
Power closes all gas after being increased to 1.1～1.5Kpa；3～10min is deposited at this temperature and pressure；E, deposition process terminate
Afterwards, reacted residual gas in diffusion furnace is pumped immediately, and cooling down is lowered the temperature under argon and hydrogen shield, argon flow amount
1000sccm, hydrogen flowing quantity are 100～200sccm.C walks the purity of hydrogen and hydrocarbon gas or liquid carbon source in walking with d
99.999%；In c steps, the flow of hydrocarbon gas or liquid carbon source is 400～600sccm, and hydrogen flowing quantity is 20～40sccm；D is walked
The flow of middle hydrocarbon gas or liquid carbon source is 100～200sccm, and hydrogen flowing quantity is 100～200sccm.
Another kind is three step sedimentations：A, expanding furnace pressure is extracted into below 100pa, pressurize 30 minutes, it is ensured that diffusion
After stove vacuum system is stable, lead to argon into diffusion furnace to normal pressure；This process is repeated twice, and argon flow amount is 1000sccm；；b、
Diffusion furnace is warming up to into 950～1050 DEG C, argon and hydrogen shield in temperature-rise period, is adopted, should during lead to argon and hydrogen
Flow is respectively 500～2000sccm and 500～1000sccm, after reaching target temperature, closes argon and hydrogen；C, will diffusion
Stove vacuum is extracted into 1～100pa, is then passed through hydrogen and hydrocarbon gas or liquid carbon source into diffusion furnace, in the temperature and pressure
10～20min of lower deposition；D, diffusion furnace vacuum is extracted into into 1～100pa, be then passed through into diffusion furnace hydrogen and hydrocarbon gas or
Liquid carbon source, deposits 5～10min at this temperature and pressure；E, closing hydrogen and hydrocarbon gas or liquid carbon source, by diffusion furnace
Vacuum is extracted into 1～100pa, is then shut off air pump；Hydrogen and hydrocarbon gas or liquid carbon source are passed through into diffusion furnace, until pressure
Power closes all gas after being increased to 1.1～1.5Kpa；3～10min is deposited at this temperature and pressure；F, deposition process terminate
Afterwards, reacted residual gas in diffusion furnace is pumped immediately, is lowered the temperature under argon and hydrogen shield, argon flow amount 1000sccm,
Hydrogen flowing quantity is 100～200sccm；C walks the purity of hydrogen and hydrocarbon gas or liquid carbon source in walking with d steps and e
99.999%；In c steps, the flow of hydrocarbon gas or liquid carbon source is 400～600sccm, and hydrogen flowing quantity is 20～40sccm；D is walked
The flow of middle hydrocarbon gas or liquid carbon source is 40～60sccm, and hydrogen flowing quantity is 20～40sccm；Hydrocarbon gas or liquid in e steps
The flow of body carbon source is 100～200sccm, and hydrogen flowing quantity is 100～200sccm.
Step 4：Cooling, sampling.After cooling, bar and fixed silk are tied up in severing, and the bar of tying up for holding severing tangentially will be raw
The metal substrate of long Graphene is transferred on acrylic board.
Third object of the present invention is to provide the uniform Graphene of a kind of corrugationless, the number of plies.
The technical scheme for realizing third object of the present invention is, using aforesaid device and preparation method, so as to obtain
Without this week, the uniform large-area Graphene of the number of plies.
The principle that the present invention is achieved is：General quartz pipe size will not be very big, and other shapes quartz member is unfavorable
In assembling large-area graphene film.And on the one hand scroll quartz boat does not result in the fold of Copper Foil, separately because its coil configuration
On the one hand assembling large area Copper Foil is also caused to be possibly realized.For example in the quartz ampoule of same thickness, the copper that slab construction can be assembled
Paper tinsel area is much smaller than scroll quartz boat；And common quartz boat, just holds without supporting in the middle part of Copper Foil when large-area Copper Foil is assembled
Easily sink to producing fold, the final quality for affecting Graphene.Device used in the present invention and dress sample and sampling method, scroll
Quartz boat can be supported well to Copper Foil one, during dress sample in the case where guaranteeing that Copper Foil fixation will not fall off, as far as possible greatly
The effective area that ensure that Graphene deposition substrate Copper Foil.During sampling, due to the Copper Foil area for growing graphene film it is big, no
Fold cut is not produced as small area Copper Foil so easily takes out.
After employing above-mentioned technical proposal, the present invention has following beneficial effect：(1) present invention innovatively utilizes roll
Quartz boat is used as Copper Foil bogey, and Copper Foil is assembled in scroll quartz boat outer surface, is then only fixed with fixed silk, can be most
Large-area assembling Copper Foil and deposited graphite alkene, and support as Copper Foil has scroll quartz boat to give all the time, in dress sample, sink
All without producing fold when product, sampling, therefore not only area is much larger compared with industrialized production and laboratory experiment sample (can do
To more than 0.5m2), the number of plies uniform (1～3 layer), sheet resistance and transmitance it is uniform, and so large-area graphene turns surface after sample
Smooth corrugationless, thus simultaneously solve Graphene preparation facilitiess in prior art cannot produce the consistent number of plies, sheet resistance and
The problem and prior art of the uniform large-area graphene sample of transmitance is filling sample, sampling, is turning for production large-area graphene
The problem of fold is also easy to produce during pressure.
(2) little pore is set in the air inlet pipe in device of the invention, so can more guarantees the air pressure in diffusion furnace
Uniformly, further increase the quality of Graphene.And air inlet pipe can be arranged around scroll quartz boat, pore is uniformly distributed,
So effect is more preferable.
(3), in the case where guaranteeing that Copper Foil fixation will not fall off, as big as possible ensure that stone to dress quadrat method of the invention
The effective area of black alkene deposition substrate Copper Foil, and sampling method farthest can ensure in such large-area Copper Foil from scroll
Fold is not produced when shifting on quartz boat.
(4) during large-area graphene film can cause the Graphene sample number of plies not to prepare using existing CVD technological parameters
Uniformly, sheet resistance transmitance is uneven, and the selected technological parameter of CVD of the present invention can further ensure that the graphite for preparing
The alkene thin film number of plies is uniform, and sheet resistance light transmittance is good.Selection especially with the technique and technological parameter of three steps deposition causes system
The deformation that technological reason causes Copper Foil to occur in standby rear Copper Foil soft or hard degree and preparation process is different and scroll quartz boat
Load unloading piece maneuver joint effect can then accomplish that outward appearance is more smooth, and quality is more preferable.
Description of the drawings
In order that present disclosure is easier to be clearly understood, below according to specific embodiment and accompanying drawing is combined, it is right
The present invention is described in further detail, wherein
Fig. 1 is the front schematic diagram that Copper Foil is fixed with scroll quartz boat of present invention deposition.
Fig. 2 is the surface topography (200 times) of the large-area graphene of the deposition of application examples of the present invention 2.Copper Foil is found out from the figure
The Graphene of surface deposition is continuous, flat smooth, zero defect.
Fig. 3 is the Raman spectrum of the Graphene that the present invention quotes the deposition of example 2.
It is numbered in accompanying drawing：
Metal substrate 1, aperture 11, scroll quartz boat 2, fixed silk 3, tie up bar 4.
Specific embodiment
See Fig. 1, the device of the growing large-area Graphene of the present embodiment includes metal substrate 1, scroll quartz boat 2, fixes
Device, air inlet pipe and diffusion furnace；The both sides of metal substrate 1 are each provided with least one aperture 11；Scroll quartz boat 2 is by two
Support angle is supported and is placed in diffusion furnace.Fixing device includes fixing silk 3 and ties up bar 4, and fixed silk 3 passes through both sides aperture 11 by metal
Substrate 1 is fixed on scroll quartz boat 2.Tie up bar 4 to fix 1 two ends of metal substrate and scroll quartz boat 2.Uniformly divide in air inlet pipe
It is furnished with venthole.
Comprised the following steps using the method for aforesaid device growing large-area Graphene：
Step one：Prepare metal substrate 1；It is not less than as metal substrate 1, deionized water and purity using Copper Foil
99.7% acetone is comprehensively cleaned to copper foil surface, and is dried；
Step 2：Metal substrate 1 is filled into sample on the outer surface of scroll quartz boat 2；Fixed silk 3 is copper free wire；In gold
1 both sides of category substrate are each to make a call at least one aperture 11, metal substrate 1 is fixed on scroll stone through both sides aperture 11 with fixed silk 3
On English boat 2；Bar 4 is bound at 1 two ends of metal substrate again, as shown in Figure 1.
Step 3：The scroll quartz boat 2 comprising metal substrate 1 of step 2 is put in diffusion furnace and is deposited；
A, expanding furnace pressure is extracted into below 100pa, pressurize 30 minutes, it is ensured that after diffusion furnace vacuum system is stable, to
Lead to argon in diffusion furnace to normal pressure；A step processes are repeated twice, and argon flow amount is 1000sccm；
B, diffusion furnace is warming up to 950～1050 DEG C；Argon and hydrogen shield are adopted in temperature-rise period, during being somebody's turn to do, leads to argon
The flow of gas and hydrogen is respectively 500～2000sccm and 500～1000sccm, after reaching target temperature, closes argon and hydrogen
Gas；
C, diffusion furnace vacuum is extracted into into 1～100pa, hydrogen and hydrocarbon gas or liquid carbon are then passed through into diffusion furnace
Source, deposits 10～20min at this temperature and pressure；The purity of hydrogen and hydrocarbon gas or liquid carbon source is 99.999%；Hydrocarbon
The flow of class gas or liquid carbon source is 400～600sccm, and hydrogen flowing quantity is 20～40sccm；
Diffusion furnace vacuum is extracted into 1～100pa by d, closing hydrogen and hydrocarbon gas or liquid carbon source, is then shut off pumping
Pump；Hydrogen and hydrocarbon gas or liquid carbon source are passed through into diffusion furnace, are closed after pressure rise to 1.1～1.5Kpa all
Gas；3～10min is deposited at this temperature and pressure；The purity of hydrogen and hydrocarbon gas or liquid carbon source is 99.999%；Hydrocarbon
The flow of class gas or liquid carbon source is 100～200sccm, and hydrogen flowing quantity is 100～200sccm；
After e, deposition process terminate, reacted residual gas in diffusion furnace is pumped immediately, under argon and hydrogen shield
Cooling down, argon flow amount 1000sccm, hydrogen flowing quantity are 100～200sccm.
Step 4：Cooling, sampling：After cooling, bar 4 and fixed silk 3 are tied up in severing, and hold severing ties up bar 4 tangentially
The metal substrate 1 of growth Graphene is transferred on acrylic board.
Six application examples are carried out below, and table one is the specific process parameter of three application examples using two step sedimentations：
Table one
| Application examples 1 | Application examples 2 | Application examples 3 | |
| Copper Foil size | 400x1000mm | 500x1000mm | 600x1200mm |
| B walks intensification 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 sedimentation 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 boosting goal pressures | 1.1Kpa | 1.3Kpa | 1.5Kpa |
| D walks sedimentation 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 |
Table two is the specific process parameter of three application examples using three step sedimentations：
Table two：
| Application examples 1 | Application examples 2 | Application examples 3 | |
| Copper Foil size | 400x1000mm | 500x1000mm | 600x1200mm |
| B walks intensification 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 sedimentation 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 sedimentation 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 boosting goal pressures | 1.1Kpa | 1.3Kpa | 1.5Kpa |
| E walks sedimentation 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, here does three comparative examples with existing vapour deposition process：
Comparative example 1：Scroll quartz boat, step deposition；
Comparative example 2：Scroll quartz boat, two steps deposition, parameter are different；
Comparative example 3：Quartzy swash plate, two steps deposition；
Table three：
| To example 1 | Comparative example 2 | Comparative example 3 | |
| Copper Foil size | 70x150mm | 140x150mm | 100x200mm |
| B walks intensification 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 sedimentation 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 |
To more than, six application examples and three comparative examples are detected, each testing result such as following table four：
Table four
From the contrast of table two, large-area graphene sample prepared by the method for the present invention is big, the number of plies is uniform, sheet resistance and
Transmitance is uniform, and after turning sample, the smooth corrugationless in surface is (such as Fig. 2 and Fig. 3, the microscope photograph and Raman spectrum of application examples 2
Further can confirm.
Particular embodiments described above, has been carried out to the purpose of the present invention, technical scheme and beneficial effect further in detail
Describe bright, the be should be understood that specific embodiment that the foregoing is only the present invention in detail, be not limited to the present invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of device of growing large-area Graphene, it is characterised in that：Including metal substrate (1), scroll quartz boat (2), consolidate
Determine device and diffusion furnace；The both sides of metal substrate (1) are each provided with least one aperture (11)；The fixing device includes fixing
Silk (3), the fixed silk (3) are fixed on metal substrate (1) on scroll quartz boat (2) through both sides aperture (11).
2. the device of a kind of growing large-area Graphene according to claim 1, it is characterised in that：The fixing device is also
Including for metal substrate (1) two ends and scroll quartz boat (2) fixed is tied up bar (4).
3. the device of a kind of growing large-area Graphene according to claim 2, it is characterised in that：Also include air inlet pipe；
Venthole is evenly distributed with the air inlet pipe (5)；The air inlet pipe is straight tube or arranges around scroll quartz boat (2).
4. a kind of method of growing large-area Graphene, it is characterised in that：It is using the device described in claim 3 including following
Step：
Step one：Prepare metal substrate (1)；
Step 2：By metal substrate (1) dress sample on scroll quartz boat (2) outer surface；Beat at least metal substrate (1) both sides are each
One aperture (11), is fixed on metal substrate (1) on scroll quartz boat (2) through both sides aperture (11) with fixed silk (3), then
Bar (4) is bound at metal substrate (1) two ends；
Step 3：The scroll quartz boat (2) comprising metal substrate (1) of step 2 is put in diffusion furnace and is deposited；
Step 4：Cooling, sampling.
5. a kind of method for producing large-area graphene according to claim 4, it is characterised in that the tool of the step 4
Body method is：After cooling, bar (4) and fixed silk (3) are tied up in severing, hold tying up bar (4) and tangentially growing graphite for severing
The metal substrate (1) of alkene is transferred on acrylic board；Metal substrate (1) in the step one is Copper Foil；Process to Copper Foil
Method is：The acetone of deionized water and purity not less than 99.7% is comprehensively cleaned to copper foil surface, and is dried；It is described
Fixed silk (3) in step 2 is copper free wire.
6. a kind of method for producing large-area graphene according to claim 5, it is characterised in that：The step 3 deposition
The concrete grammar of Graphene is：A, will diffusion furnace pressure be extracted into below 100pa, pressurize 30 minutes, it is ensured that diffusion furnace vacuum system
After system is stable, lead to argon into diffusion furnace to normal pressure；B, diffusion furnace is warming up to 950～1050 DEG C；C, diffusion furnace vacuum is taken out
To 1～100pa, then hydrogen and hydrocarbon gas or liquid carbon source are passed through into diffusion furnace, deposit 10 at this temperature and pressure
～20min；Diffusion furnace vacuum is extracted into 1～100pa by d, closing hydrogen and hydrocarbon gas or liquid carbon source, is then shut off pumping
Pump；Hydrogen and hydrocarbon gas or liquid carbon source are passed through into diffusion furnace, are closed after pressure rise to 1.1～1.5Kpa all
Gas；3～10min is deposited at this temperature and pressure；After e, deposition process terminate, pump immediately reacted residual in diffusion furnace
Stay gas, cooling down.
7. the method for a kind of growing large-area Graphene according to claim 6, it is characterised in that：The a of the step 3
Step process is repeated twice, and argon flow amount is 1000sccm；Argon and hydrogen is adopted to protect in temperature-rise period in the b steps of the step 3
Shield, the flow for leading to argon and hydrogen during being somebody's turn to do are respectively 500～2000sccm and 500～1000sccm, reach target temperature
Afterwards, argon and hydrogen are closed；The e lowers the temperature in walking under argon and hydrogen shield, argon flow amount 1000sccm, and hydrogen flowing quantity is
100～200sccm；The c of the step 3 walks the purity of hydrogen and hydrocarbon gas or liquid carbon source in walking with d
99.999%；In c steps, the flow of hydrocarbon gas or liquid carbon source is 400～600sccm, and hydrogen flowing quantity is 20～40sccm；D is walked
The flow of middle hydrocarbon gas or liquid carbon source is 100～200sccm, and hydrogen flowing quantity is 100～200sccm.
8. a kind of method for producing large-area graphene according to claim 5, it is characterised in that：The step 3 deposition
The concrete grammar of Graphene is：A, will diffusion furnace pressure be extracted into below 100pa, pressurize 30 minutes, it is ensured that diffusion furnace vacuum system
After system is stable, lead to argon into diffusion furnace to normal pressure；B, diffusion furnace is warming up to 950～1050 DEG C；C, diffusion furnace vacuum is taken out
To 1～100pa, then hydrogen and hydrocarbon gas or liquid carbon source are passed through into diffusion furnace, deposit 10 at this temperature and pressure
～20min；D, diffusion furnace vacuum is extracted into into 1～100pa, hydrogen and hydrocarbon gas or liquid carbon are then passed through into diffusion furnace
Source, deposits 5～10min at this temperature and pressure；E, closing hydrogen and hydrocarbon gas or liquid carbon source, diffusion furnace vacuum is taken out
To 1～100pa, air pump is then shut off；Hydrogen and hydrocarbon gas or liquid carbon source are passed through into diffusion furnace, until pressure rise
All gas are closed to after 1.1～1.5Kpa；3～10min is deposited at this temperature and pressure；After f, deposition process terminate, stand
Reacted residual gas, cooling down in diffusion furnace are pumped.
9. the method for a kind of growing large-area Graphene according to claim 8, it is characterised in that：The a of the step 3
Step process is repeated twice, and argon flow amount is 1000sccm；Argon and hydrogen is adopted to protect in temperature-rise period in the b steps of the step 3
Shield, the flow for leading to argon and hydrogen during being somebody's turn to do are respectively 500～2000sccm and 500～1000sccm, reach target temperature
Afterwards, argon and hydrogen are closed；The f lowers the temperature in walking under argon and hydrogen shield, argon flow amount 1000sccm, and hydrogen flowing quantity is
100～200sccm；The c steps of the step 3 and d walk the purity of hydrogen and hydrocarbon gas or liquid carbon source in walking with e
99.999%；In c steps, the flow of hydrocarbon gas or liquid carbon source is 400～600sccm, and hydrogen flowing quantity is 20～40sccm；D is walked
The flow of middle hydrocarbon gas or liquid carbon source is 40～60sccm, and hydrogen flowing quantity is 20～40sccm；Hydrocarbon gas or liquid in e steps
The flow of body carbon source is 100～200sccm, and hydrogen flowing quantity is 100～200sccm.
10. a kind of Graphene, it is characterised in that；It is prepared by the arbitrary described method of claim 4-9.
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