CN110203912A - A kind of method that low molten carbon material surface ties up preparation two-dimensional graphene film layer surely - Google Patents
A kind of method that low molten carbon material surface ties up preparation two-dimensional graphene film layer surely Download PDFInfo
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Abstract
The invention discloses a kind of low molten carbon material surfaces tie up the method for preparing two-dimensional graphene film layer surely, method includes the following steps: one, low molten carbon material polished and cleaned；Two, the low molten carbon material after polishing and cleaning is subjected to vacuum annealing process；Three, chemical vapor deposition is carried out in the low molten carbon material surface after vacuum annealing process, then obtains two-dimensional graphene film layer in low molten carbon material surface.The present invention, as growth substrate, ties up preparation two-dimensional graphene film layer by the surface topography of the low molten carbon material of control and the realization of process parameters of chemical vapor deposition using low molten carbon material surely；The present invention uses CO2With high-purity porous graphite as carbon source, avoids existing C-H class gas and prepare the doping of protium caused by graphene film layer, improve the structural behaviour of graphene film layer；Preparation process of the present invention is simple, highly-safe, suitable for scale production, can produce the two-dimensional graphene film layer of high quality in low molten carbon material surface.
Description
Technical field
The present invention relates to technical field of film preparation, and in particular to the low molten carbon material surface of one kind ties up the two-dimentional graphite of preparation surely
The method of alkene film layer.
Background technique
Graphene is by sp2The material of the honeycomb two-dimension plane structure of the carbon atom arrangement composition of orbital hybridization, it is internal
Impurity and defect are few, have many excellent performances, pass it in materialogy, micro-nano technology, the energy, biomedicine and drug
Pass etc. is with important application prospects, it is considered to be a kind of future revolutionary material.
Chemical vapour deposition technique is one of production graphene film layer most efficient method, the graphene film of this method preparation
Layer has the characteristics that area is big and quality is high, in particular for molten carbon amounts less than 3 × 10-5The low molten carbon material of at%, such as copper,
Germanium or silicon, Yi Shixian active atoms of carbon promote active atoms of carbon forming core, are grown to graphene film layer in the absorption on its surface.But
Currently, the resistivity of the graphene film layer of preparation is still very high, such as document (the luminous journal 2013,34 (1) of peace nanmu, 45-
48.) it reports, in the graphene film layer that silicon face uses chemical vapour deposition technique to prepare 3 layers, the graphene film layer prepared
Resistivity be 3.729 × 10-6Ω·m.Also, the graphene film layer of chemical vapor deposition preparation mostly uses C-H class organic
Gas (such as CH4、C2H2、C2H6Deng) it is used as carbon source, to make to generate a certain amount of hydrogen in the preparation process of graphene film layer, this is not
It only influences whether the structural behaviour of graphene film layer, and is generated for industry and introduce security risk.In addition, graphene at this stage
Film layer preparation method is directed to the depositing behavior of active atoms of carbon, can't carry out accurately dimension control, is preparing two-dimentional graphite
When alkene film layer usually can it is too fast due to deposition rate, active atoms of carbon core forming speed is too fast, forming core site is excessive and lacks to work
Property carbon atom many reasons such as effective etching, cause two-dimensional graphene film layer to be changed into three-dimensional amorphous carbon film.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of low molten carbon material
The method that preparation two-dimensional graphene film layer is tieed up on surface surely, this method is with CO2It is low by controlling with high-purity porous graphite as carbon source
The surface topography of molten carbon material and the technological parameter of chemical vapor deposition, in low molten carbon material surface preparation two dimension after processing
Graphene film layer, obtained two-dimensional graphene film layer have excellent surface quality, structural behaviour and electrical property.
In order to solve the above technical problems, the present invention provides the low molten carbon material surface of one kind ties up preparation two-dimensional graphene film layer surely
Method, which is characterized in that method includes the following steps:
Step 1: the surface of low molten carbon material is polished step by step, then successively dilute hydrochloric acid solution, acetone soln and
It is cleaned by ultrasonic 10min~30min in ethanol solution respectively, then carries out drying and processing, the low molten carbon material refers to that molten carbon amounts is small
In 3 × 10-5The material of at%；
It is carried out very Step 2: the low molten carbon material obtained after drying processing in step 1 is placed in vacuum heat treatment furnace
Sky annealing；The condition of the vacuum annealing process is: vacuum heat treatment furnace being passed through high-purity Ar gas, reaches furnace pressure
0.001Pa~0.008Pa is then heated to 700 DEG C~1000 DEG C heat preservation 10min~30min；
Step 3: the low molten carbon material obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace
High-purity porous graphite is placed in air inlet side in vacuum atmosphere tube furnace boiler tube and carries out chemical gas by the middle position in boiler tube
It mutually deposits, then obtains two-dimensional graphene film layer in low molten carbon material surface；The condition of the chemical vapor deposition is: by vacuum
Atmosphere tube type furnace is passed through CO2, so that furnace pressure is reached 0.01Pa~0.06Pa, be then heated to 800 DEG C~1000 DEG C heat preservations
80min~180min.
Above-mentioned method, which is characterized in that low molten carbon material described in step 1 is copper, germanium or silicon.The low molten carbon material
Molten carbon amounts it is low, be conducive to the adsorption to active atoms of carbon, be conducive to active atoms of carbon forming core, be conducive to active atoms of carbon
Homoepitaxial is graphene film layer.
Above-mentioned method, which is characterized in that the mass fraction of dilute hydrochloric acid solution described in step 1 is 10%~20%, third
The mass fraction of ketone solution is 50%~65%, and the mass fraction of ethanol solution is 75%~99%.The dilute hydrochloric acid solution carries out
Pickling removes the oxidation film of low molten carbon material surface, and the acetone soln and ethanol solution remove pickling residue, remove low molten carbon
The greasy dirt and impurity of material surface guarantee that low molten carbon material surface is clean, dustless, are conducive to inhale the surface of active atoms of carbon
It is attached, be conducive to active atoms of carbon forming core, being conducive to active atoms of carbon homoepitaxial is graphene film layer, the dilute hydrochloric acid solution, third
There are also advantages cheap and easy to get for ketone solution and ethanol solution.
Above-mentioned method, which is characterized in that the quality purity of high-purity Ar gas described in step 2 is described greater than 99.999%
The heating rate and rate of temperature fall of vacuum annealing process are 3 DEG C/min~10 DEG C/min.The quality purity of the high-purity Ar gas is big
It in 99.999%, can be introduced to avoid impurity, improve graphene film quality, which is inert gas and sample table
Face does not chemically react, and has protective effect to sample, the heating rate and rate of temperature fall of the vacuum annealing process are 3
DEG C/min~10 DEG C/min, vacuum heat treatment furnace allow heating rate and rate of temperature fall within the scope of, be conducive to extend equipment
Service life.
Above-mentioned method, which is characterized in that the quality purity of high-purity porous graphite described in step 3 is greater than 99.999%,
The aperture of high-purity porous graphite is 1mm~20mm, and the heating rate and rate of temperature fall of the chemical vapor deposition are 5
DEG C/min~10 DEG C/min.The quality purity of high-purity porous graphite is greater than 99.999%, can introduce to avoid impurity, improves stone
The aperture of black alkene film quality, high-purity porous graphite is 1mm~20mm, is conducive to CO2Come into full contact with high-purity porous graphite simultaneously
Sufficiently reaction, the heating rate and rate of temperature fall of the chemical vapor deposition are 5 DEG C/min~10 DEG C/min, in vacuum atmosphere pipe
Within the scope of the heating rate and rate of temperature fall that formula furnace allows, it is conducive to extend the service life of equipment.
Above-mentioned method, which is characterized in that CO described in step 32Quality purity be greater than 99.999%.The CO2Matter
It measures purity and is greater than 99.999%, can be introduced to avoid impurity, improve graphene film quality, the CO2Also cheap and easy to get is excellent
Point.
The low molten carbon material surface of the present invention ties up the principle of preparation two-dimensional graphene film layer surely: the present invention uses CO2With it is high-purity
Porous graphite is as carbon source, by CO2It is passed through vacuum atmosphere tube furnace, and is placed in air inlet one in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of side reacts in the high temperature environment, generates CO, and reaction equation is as follows: CO2The CO of+C → 2CO, generation are arrived
It reacts in the high temperature environment up to the middle position in vacuum atmosphere tube furnace boiler tube, generates active atoms of carbon, reaction equation is such as
Under: 2CO → C+CO2, the active atoms of carbon of generation forms two-dimensional graphene film in low molten carbon material surface absorption, forming core, growth
Layer.
Compared with the prior art, the present invention has the following advantages:
1, the realization of process parameters such as pressure, temperature and the soaking time for controlling chemical vapor deposition of the invention that pass through determine dimension
Two-dimensional graphene film layer is prepared, improves the surface quality of graphene film layer to improve the electrical property of graphene film layer；This
Invention, as growth substrate, the table of low molten carbon material is controlled by polishing, cleaning and vacuum annealing process using low molten carbon material
Face pattern easily realizes the adsorption to active atoms of carbon, promotes active atoms of carbon forming core, is grown to two-dimensional graphene film layer.
2, the present invention uses CO2With high-purity porous graphite as carbon source, avoids existing C-H class gas and prepare graphene film
The doping of protium caused by layer, improves the purity of graphene film layer, to improve electrical property, avoids in actual production
The generation of hydrogen, improves the structural behaviour of graphene film layer, improves the safety assurance in production process, eliminate industry
The security risk of production, reduces production cost, is advantageously implemented large-scale production.
3, preparation process of the present invention is simple, it is easy to accomplish, it is highly-safe, it is suitable for scale production.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Fig. 1 is the Raman spectrogram for the two-dimensional graphene film layer that the embodiment of the present invention 1 is prepared in T1 red copper surface.
Fig. 2 is the volt-ampere curve figure for the two-dimensional graphene film layer that the embodiment of the present invention 1 is prepared in T1 red copper surface.
Specific embodiment
Embodiment 1
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the T1 red copper of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to T1 red copper point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 10%, mass fraction are 50% are 75% point
Not Chao Shengqingxi 10min, then carry out drying and processing；
Vacuum is carried out Step 2: the T1 red copper obtained after drying processing in step 1 is placed in vacuum heat treatment furnace
Annealing；The condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through the Ar that quality purity is greater than 99.999%
Gas makes furnace pressure reach 0.008Pa, is then heated to 700 DEG C of heat preservation 30min, the heating rate of the vacuum annealing process and
Rate of temperature fall is 3 DEG C/min；
Step 3: the T1 red copper obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 1mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer in T1 red copper surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.06Pa, be then heated to
1000 DEG C of heat preservation 80min, the heating rate and rate of temperature fall of the chemical vapor deposition are 5 DEG C/min.
Fig. 1 is the Raman spectrogram of two-dimensional graphene film layer that the present embodiment is prepared in T1 red copper surface, can be with from Fig. 1
Find out, graphene film layer manufactured in the present embodiment has tri- characteristic peaks of D, G and 2D, is respectively belonging to: the peak D (1350cm-1) be
Graphene carbon nuclear carbon atom sp2The stretching vibration peak of key represents the defect level of graphene；The peak G (1580cm-1) it is graphite
Sp in olefinic carbon ring and carbochain2The stretching vibration peak of key；The peak 2D (2690cm-1) be graphene characteristic peak, graphite can be reacted
The number of plies of alkene can illustrate that manufactured in the present embodiment is really graphene film layer by three above characteristic peak, high by the peak 2D half
The wide and its ratio I with the peak G2D/IG=5203.49/5826.02=0.89 can determine graphene film layer manufactured in the present embodiment
Between 2 layers to 5 layers.
Fig. 2 is the volt-ampere curve figure of two-dimensional graphene film layer that the present embodiment is prepared in T1 red copper surface, can be with from Fig. 2
Find out, the volt-ampere curve of graphene film layer manufactured in the present embodiment is the straight line of single slope, it may be said that bright the present embodiment preparation
Graphene thicknesses of layers it is uniform, smooth, and the quality of film layer is good, passes through and calculates graphene film layer manufactured in the present embodiment
Resistivity be 7.0 × 10-7Ω·m。
Embodiment 2
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the T1 red copper of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to T1 red copper point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 20%, mass fraction are 65% are 99% point
Not Chao Shengqingxi 15min, then carry out drying and processing；
Step 2: the T1 red copper obtained after drying processing in step 1 is placed in vacuum heat treatment furnace, carry out true
Sky annealing, the condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through quality purity greater than 99.999%
Ar gas, makes furnace pressure reach 0.001Pa, is then heated to 1000 DEG C of heat preservation 10min, the heating rate of the vacuum annealing process
It is 8 DEG C/min with rate of temperature fall；
Step 3: the T1 red copper obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 20mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer in T1 red copper surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.01Pa, be then heated to
800 DEG C of heat preservation 180min, the heating rate and rate of temperature fall of the chemical vapor deposition are 8 DEG C/min.
Graphene film layer manufactured in the present embodiment is detected between 2 layers to 5 layers, resistivity is 3.0 × 10-7Ω·m。
Embodiment 3
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the T1 red copper of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to T1 red copper point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 15%, mass fraction are 60% are 80% point
Not Chao Shengqingxi 30min, then carry out drying and processing；
Vacuum is carried out Step 2: the T1 red copper obtained after drying processing in step 1 is placed in vacuum heat treatment furnace
Annealing, the condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through the Ar that quality purity is greater than 99.999%
Gas makes furnace pressure reach 0.005Pa, is then heated to 800 DEG C of heat preservation 20min, the heating rate of the vacuum annealing process and
Rate of temperature fall is 10 DEG C/min；
Step 3: the T1 red copper obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 10mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer in T1 red copper surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.03Pa, be then heated to
900 DEG C of heat preservation 120min, the heating rate and rate of temperature fall of the chemical vapor deposition are 10 DEG C/min.
Graphene film layer manufactured in the present embodiment is detected between 2 layers to 5 layers, resistivity is 4.5 × 10-7Ω·m。
Embodiment 4
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the monocrystalline germanium of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to monocrystalline germanium point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 10%, mass fraction are 50% are 75% point
Not Chao Shengqingxi 10min, then carry out drying and processing；
Vacuum is carried out Step 2: the monocrystalline germanium obtained after drying processing in step 1 is placed in vacuum heat treatment furnace
Annealing；The condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through the Ar that quality purity is greater than 99.999%
Gas makes furnace pressure reach 0.008Pa, is then heated to 700 DEG C of heat preservation 30min, the heating rate of the vacuum annealing process and
Rate of temperature fall is 3 DEG C/min；
Step 3: the monocrystalline germanium obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 1mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer on monocrystalline germanium surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.06Pa, be then heated to
1000 DEG C of heat preservation 80min, the heating rate and rate of temperature fall of the chemical vapor deposition are 5 DEG C/min.
Graphene film layer manufactured in the present embodiment is detected between 2 layers to 5 layers, resistivity is 6.0 × 10-7Ω·m。
Embodiment 5
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the monocrystalline germanium of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to monocrystalline germanium point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 20%, mass fraction are 65% are 99% point
Not Chao Shengqingxi 15min, then carry out drying and processing；
Step 2: the monocrystalline germanium obtained after drying processing in step 1 is placed in vacuum heat treatment furnace, carry out true
Sky annealing, the condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through quality purity greater than 99.999%
Ar gas, makes furnace pressure reach 0.001Pa, is then heated to 1000 DEG C of heat preservation 10min, the heating rate of the vacuum annealing process
It is 8 DEG C/min with rate of temperature fall；
Step 3: the monocrystalline germanium obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 20mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer on monocrystalline germanium surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.01Pa, be then heated to
800 DEG C of heat preservation 180min, the heating rate and rate of temperature fall of the chemical vapor deposition are 8 DEG C/min.
Graphene film layer manufactured in the present embodiment is detected between 2 layers to 5 layers, resistivity is 7.3 × 10-7Ω·m。
Embodiment 6
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the monocrystalline germanium of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to monocrystalline germanium point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 15%, mass fraction are 60% are 80% point
Not Chao Shengqingxi 30min, then carry out drying and processing；
Vacuum is carried out Step 2: the monocrystalline germanium obtained after drying processing in step 1 is placed in vacuum heat treatment furnace
Annealing, the condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through the Ar that quality purity is greater than 99.999%
Gas makes furnace pressure reach 0.005Pa, is then heated to 800 DEG C of heat preservation 20min, the heating rate of the vacuum annealing process and
Rate of temperature fall is 10 DEG C/min；
Step 3: the monocrystalline germanium obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 10mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer on monocrystalline germanium surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.03Pa, be then heated to
900 DEG C of heat preservation 120min, the heating rate and rate of temperature fall of the chemical vapor deposition are 10 DEG C/min.
Graphene film layer manufactured in the present embodiment is detected between 2 layers to 5 layers, resistivity is 7.5 × 10-7Ω·m。
Embodiment 7
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the monocrystalline silicon of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to monocrystalline silicon point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 10%, mass fraction are 50% are 75% point
Not Chao Shengqingxi 10min, then carry out drying and processing；
Vacuum is carried out Step 2: the monocrystalline silicon obtained after drying processing in step 1 is placed in vacuum heat treatment furnace
Annealing；The condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through the Ar that quality purity is greater than 99.999%
Gas makes furnace pressure reach 0.008Pa, is then heated to 700 DEG C of heat preservation 30min, the heating rate of the vacuum annealing process and
Rate of temperature fall is 3 DEG C/min；
Step 3: the monocrystalline silicon obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 1mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer in monocrystalline silicon surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.06Pa, be then heated to
1000 DEG C of heat preservation 80min, the heating rate and rate of temperature fall of the chemical vapor deposition are 5 DEG C/min.
Graphene film layer manufactured in the present embodiment is detected between 2 layers to 5 layers, resistivity is 7.0 × 10-7Ω·m。
Embodiment 8
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the monocrystalline silicon of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to monocrystalline silicon point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 20%, mass fraction are 65% are 99% point
Not Chao Shengqingxi 15min, then carry out drying and processing；
Step 2: the monocrystalline silicon obtained after drying processing in step 1 is placed in vacuum heat treatment furnace, carry out true
Sky annealing, the condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through quality purity greater than 99.999%
Ar gas, makes furnace pressure reach 0.001Pa, is then heated to 1000 DEG C of heat preservation 10min, the heating rate of the vacuum annealing process
It is 8 DEG C/min with rate of temperature fall；
Step 3: the monocrystalline silicon obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 20mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer in monocrystalline silicon surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.01Pa, be then heated to
800 DEG C of heat preservation 180min, the heating rate and rate of temperature fall of the chemical vapor deposition are 8 DEG C/min.
Graphene film layer manufactured in the present embodiment is detected between 2 layers to 5 layers, resistivity is 6.5 × 10-7Ω·m。
Embodiment 9
The preparation method of the graphene film layer of the present embodiment the following steps are included:
Step 1: using the monocrystalline silicon of 20mm × 20mm × 5mm (length × width x thickness) as low molten carbon material, to monocrystalline silicon point
Not Shi Yong 80#, 240#, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper polished step by step, then successively in quality
In the ethanol solution that the acetone soln and mass fraction that dilute hydrochloric acid solution that score is 15%, mass fraction are 60% are 80% point
Not Chao Shengqingxi 30min, then carry out drying and processing；
Vacuum is carried out Step 2: the monocrystalline silicon obtained after drying processing in step 1 is placed in vacuum heat treatment furnace
Annealing, the condition of the vacuum annealing process is: vacuum heat treatment furnace is passed through the Ar that quality purity is greater than 99.999%
Gas makes furnace pressure reach 0.005Pa, is then heated to 800 DEG C of heat preservation 20min, the heating rate of the vacuum annealing process and
Rate of temperature fall is 10 DEG C/min；
Step 3: the monocrystalline silicon obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite of average pore size 10mm is placed in air inlet side in vacuum atmosphere tube furnace boiler tube by interior middle position
Chemical vapor deposition is carried out, then obtains two-dimensional graphene film layer in monocrystalline silicon surface；The condition of the chemical vapor deposition is:
Vacuum atmosphere tube furnace is passed through the CO that quality purity is greater than 99.999%2, so that furnace pressure is reached 0.03Pa, be then heated to
900 DEG C of heat preservation 120min, the heating rate and rate of temperature fall of the chemical vapor deposition are 10 DEG C/min.
Graphene film layer manufactured in the present embodiment is detected between 2 layers to 5 layers, resistivity is 7.2 × 10-7Ω·m。
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (6)
1. a kind of low molten carbon material surface tie up the method for preparing two-dimensional graphene film layer surely, which is characterized in that this method include with
Lower step:
Step 1: the surface of low molten carbon material is polished step by step, then successively in dilute hydrochloric acid solution, acetone soln and ethyl alcohol
Be cleaned by ultrasonic 10min~30min in solution respectively, then carry out drying and processing, the low molten carbon material refer to molten carbon amounts less than 3 ×
10-5The material of at%；
It is moved back Step 2: the low molten carbon material obtained after drying processing in step 1 is placed in vacuum heat treatment furnace and carries out vacuum
Fire processing；The condition of the vacuum annealing process is: vacuum heat treatment furnace being passed through high-purity Ar gas, reaches furnace pressure
0.001Pa~0.008Pa is then heated to 700 DEG C~1000 DEG C heat preservation 10min~30min；
Step 3: the low molten carbon material obtained after vacuum annealing process in step 2 is placed in vacuum atmosphere tube furnace boiler tube
High-purity porous graphite is placed in air inlet side in vacuum atmosphere tube furnace boiler tube and carries out chemical vapor deposition by interior middle position
Product, then obtains two-dimensional graphene film layer in low molten carbon material surface；The condition of the chemical vapor deposition is: by vacuum atmosphere
Tube furnace is passed through CO2, so that furnace pressure is reached 0.01Pa~0.06Pa, be then heated to 800 DEG C~1000 DEG C heat preservation 80min~
180min。
2. the method that the low molten carbon material surface of one kind according to claim 1 ties up preparation two-dimensional graphene film layer surely, special
Sign is that low molten carbon material described in step 1 is copper, germanium or silicon.
3. the method that the low molten carbon material surface of one kind according to claim 1 ties up preparation two-dimensional graphene film layer surely, special
Sign is that the mass fraction of dilute hydrochloric acid solution described in step 1 is 10%~20%, and the mass fraction of acetone soln is 50%
~65%, the mass fraction of ethanol solution is 75%~99%.
4. the method that the low molten carbon material surface of one kind according to claim 1 ties up preparation two-dimensional graphene film layer surely, special
Sign is that the quality purity of high-purity Ar gas described in step 2 is greater than 99.999%, the heating rate of the vacuum annealing process
It is 3 DEG C/min~10 DEG C/min with rate of temperature fall.
5. the method that the low molten carbon material surface of one kind according to claim 1 ties up preparation two-dimensional graphene film layer surely, special
Sign is that the quality purity of high-purity porous graphite described in step 3 is greater than 99.999%, the aperture of high-purity porous graphite
For 1mm~20mm, the heating rate and rate of temperature fall of the chemical vapor deposition are 5 DEG C/min~10 DEG C/min.
6. the method that the low molten carbon material surface of one kind according to claim 1 ties up preparation two-dimensional graphene film layer surely, special
Sign is, CO described in step 32Quality purity be greater than 99.999%.
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