CN105439126B - A kind of grade single crystal graphene preparation method - Google Patents
A kind of grade single crystal graphene preparation method Download PDFInfo
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- CN105439126B CN105439126B CN201410439978.8A CN201410439978A CN105439126B CN 105439126 B CN105439126 B CN 105439126B CN 201410439978 A CN201410439978 A CN 201410439978A CN 105439126 B CN105439126 B CN 105439126B
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Abstract
The invention belongs to advanced carbon material and semiconductor process technique field, more particularly to a kind of simplicity of large area single crystal graphene, stable preparation method, suitable for the preparation of grade single crystal graphene.The present invention is at 1000 DEG C with methane（CH4）It is that reducibility gas grows single crystal graphene using low-pressure chemical vapor deposition (LPCVD) method for carbon source, hydrogen.The present invention is ultrasonically treated without carrying out acetone, ethanol etc. to copper foil, it the preprocessing process such as need not be polished to copper foil using complicated electrochemical method, without the annealing process up to a few hours, high hydrogen flowing quantity, only need to take out the air in most reactor before heating and ensure there is no gas to be passed through in temperature-rise period, nucleation density of the graphene on copper foil can be greatly lowered by this convenient disposal method, and the single crystal graphene that opposite side distance reaches 1mm sizes need to can be only grown by the growth time of 23 hours.The scanned electron microscope of sample（SEM）, transmission electron microscope（TEM）, Raman spectrum analysis（Raman）Single crystal graphene is proved etc. means sign and there is the defects of less.
Description
Technical field
The invention belongs to advanced carbon material and semiconductor process technique field, more particularly to a kind of large area single crystal graphene
Simplicity, stable preparation method.
Background technology
Graphene be have between single layer of carbon atom with sp2 hybrid forms bonding and new, the advanced two dimension that is formed by connecting it is flat
Face nano material, cause graphene just because of this special bonding of graphene, connected mode and perfect two-dimensional characteristics
There is excellent performance in electricity, optics, calorifics, mechanics.Such as：The mechanical strength of graphene reaches as high as 130Gpa, and it is carried
Flow sub- migration rate and be up to 15000cmm-1·K-1, for more than 10 times of common silicon chip, and its thermal conductivity is up to 5000W
m-1·K-1, it is evident that the premium properties of graphene has larger advantage than with other same type materials.Therefore, graphene
It is expected to obtain in numerous areas such as high-performance nano device, composite, field emmision material, gas sensor and energy storages
Extensive use.
It is chemical vapor deposition that large area, which prepares the most popular method of graphene, at present（Chemical Vapor
Deposition）.Its general principle is：Using carbonaceous gas organic matter as growth precursors, it is aided with hydrogen and inert gas（Such as argon
Gas, helium, nitrogen etc.）, and with section transitions metal（Such as copper, iron, nickel, gold）As substrate, at a high temperature of 1000 DEG C, contain
Carbon organic gas is adsorbed onto metal surface under the intermolecular forces effect of metal and gas molecule, metal catalytic activity with
And a series of hydrocarbon active reaction intermediate for producing activation is gradually decomposed under high temperature action, these carbonaceous active intermediates afterwards
In metallic catalyst surfaces after the step such as dehydrogenation and ring formation, formed using the hexatomic ring of carbon as basic composition unit
Graphene.Large area and uniform single or multiple lift polycrystalline graphite alkene can be easily grown in this approach.But more spar
The presence of the black a large amount of crystal boundaries of alkene, causes graphene excellent in terms of the electricity such as electronic conductivity energy, thermal conductivity, optics, calorifics
Gesture is lowered, and single crystal graphene then reduces crystal boundary and influenceed to caused by graphene performance well, therefore growing large-area
Single crystal graphene just seem particularly significant.But the method for the growth single crystal graphene being currently known, need mostly very multiple
Miscellaneous pretreatment（Such as chemical polishing, electrochemical polish）, for a long time carry out in the annealing process of high hydrogen flowing quantity, growth course
Complicated gas conversion, or even transformed by designing some components copper sheet, and some growth method then need by
It is cumbersome, complicated up to a few hours growth of even tens of hours, technique.
Therefore, a kind of technique of single crystal graphene that is easy, stably preparing large area is sought for single crystal graphene
Using extremely important.
The content of the invention
Single crystal graphene method is complicated, cumbersome and the produced smaller present situation of single crystal graphene area for preparing at present, this
Invention provides a kind of method of simple, stable preparation large area single crystal graphene.This method is sunk using low pressure chemical phase
Product（LPCVD）Technology, using copper foil as growth substrate, methane is reacting precursor, and hydrogen is reducing gas, and polishing need to be only used before reaction
Liquid cleans to copper foil, and ensures not to be passed through any gas in temperature-rise period, annealed afterwards and 2-3 hours growth
Obtain the large area single crystal graphene that opposite side distance reaches 1mm.Specifically preparation method is：
A. the preparation of chemical polishing solution：8g solids FeCl is weighed with electronic balance3·6H2O, measured afterwards with graduated cylinder
10mLHCl solution and 100mL H2O is simultaneously stirred, dissolved；
B. copper sheet pre-processes：Copper sheet is taken out and is cut into 2cm × 2cm small pieces, is taken in appropriate polishing fluid and culture dish,
The copper sheet sheared is put into polishing fluid with tweezers and soaked, soak time then takes out between 25s-50s and uses deionization
Water soaks and flushed three times, and nitrogen dries up afterwards；
C. copper sheet is loaded：Pretreated copper sheet is placed on quartz plate and is pushed into a diameter of 1 inch of quartz ampoule
In, and quartz plate is pushed into quartz ampoule stage casing, it is placed in after quartz ampoule installs in heating furnace；
D., heating schedule is set：Temperature and the reaction time of each conversion zone are set in heating furnace sets panel；
E. vacuumize：Quartzy pipe end is connected on vavuum pump and vacuumized；
F., gas flow is set：The major-minor pressure-reducing valve of the steel cylinder equipped with argon gas, hydrogen is opened respectively, and opens gas stream
Gauge sets the hydrogen of temperature rise period and the volume flow of argon gas；
G. heat up：Starting heating furnace heating schedule makes quartz ampoule temperature be heated to certain temperature through certain time by room temperature,
And corresponding gas flow is set；
H. anneal：Adjust hydrogen flowing quantity annealing；
I. grow：Hydrogen and methane flow are adjusted respectively, react certain time；
J. cool down：After the completion of to be grown, quartz ampoule is carried away rapidly from reacting furnace and is positioned on support, close reacting furnace
And keep gas flow constant；
K. take out and preserve：After being cooled to room temperature, quartz ampoule end flange is closed, closes vavuum pump, until gas is by stone
Steel cylinder pressure-reducing valve and gas flowmeter are closed when English pipe inside is full of and quartz ampoule internal pressure reaches atmospheric pressure, takes out quartz plate
And reacted copper sheet is positioned in closed and drying receptacle and preserved.
Used in step a of the present invention reagent be the pure rank of analysis used in hydrogen purity be 99.999%, nitrogen used
Gas purity is 99.999%, and methane used is calibrating gas, and concentration 0.25%, blending gas is argon gas, and the useful water of institute is super
Pure deionized water and resistivity are 18.25 Ω cm.
Copper sheet model is Alfa Aesar in step b of the present invention, and #13382, thickness is 25 μm, and purity is
99.8%。
Copper sheet is placed in the middle part of heating furnace in step c of the present invention, close to heating furnace rear and front end inside quartz ampoule
It is slightly less than the Al of quartz tube equipped with two diameters2O3Pipe plug.
The step e pumpdown times of the present invention are 20 ~ 30min.
The heating-up time is 60 ~ 100min in step g of the present invention, and is not passed through any gas in temperature-rise period.
Reaction temperature is 980 ~ 1040 DEG C in step g of the present invention, and annealing temperature is 950 ~ 1040 DEG C.
Hydrogen flowing quantity is 15-30 sccm, annealing time 10-30min in step h of the present invention.
Hydrogen flowing quantity is 20-75 sccm in step i of the present invention, and methane flow is 5-40 sccm, and growth time is
2-3 h。
The characteristics of invention and have the beneficial effect that：
1. the present invention uses low-pressure chemical vapor deposition（LPCVD）Technology, using copper foil as growth substrate, before methane is reaction
Body, hydrogen are reducing gas.Copper foil need to only be cleaned, and ensure that any gas is not passed through in temperature-rise period causes copper sheet
Surface reaches a certain degree of passivation, so reaches the purpose that can greatly reduce nucleation density of the graphene on copper foil,
Annealed afterwards and 2-3 hours growth can obtain the large area single crystal graphene that opposite side distance reaches 1mm.It is 2. of the invention simple
It is easy to operate, handled without prolonged ultrasonic cleaning, complicated electrochemical polishing process, and the high hydrogen stream up to a few hours
Annealing process under amount, and process stabilizing, repeatability height, production cost are low, the single crystal graphene size prepared is big and equal
It is even, it is adapted to commercial application.
Brief description of the drawings
Fig. 1 is the single crystal graphene microphoto of the large area to be grown out using the present invention.
Fig. 2 is the graphite Raman spectrogram grown using the present invention.
Fig. 3 is the transmission electron micrograph of the single crystal graphene to be grown out using the present invention.
Embodiment
The invention provides a kind of simplicity of large area single crystal graphene, stable preparation method, below in conjunction with the accompanying drawings and have
The present invention is further elaborated body embodiment.
Embodiment 1
Large area single crystal graphene is prepared, its specific implementation step is as follows：
1. weigh 8g solids FeCl with electronic balance3·6H2O, measure 10mLHCl solution and 100mL with graduated cylinder afterwards
H2O is simultaneously stirred, and is ultrasonically treated 10 min.
2. copper sheet is taken out and is cut into the cm of 2 cm × 2 small pieces, take appropriate polishing fluid with culture dish, will with tweezers
The copper sheet sheared, which is put into polishing fluid, to be soaked, and soak time 25s-50s, is then taken out and is soaked and rinsed with deionized water
Three times, nitrogen dries up afterwards.
3. pretreated copper sheet is placed on quartz plate, then quartz plate is pushed into a diameter of 1 inch of quartz
Guan Zhong, quartz plate is located at quartz ampoule stage casing and ensure that copper sheet is located in the middle part of quartz ampoule, by quartz after quartz ampoule installs
Pipe is placed in heating furnace.
4. temperature and the reaction time of each conversion zone are set in heating furnace sets panel.
Vacuumized 5. quartzy pipe end is connected on vavuum pump.
6. opening the major-minor pressure-reducing valve of the steel cylinder equipped with argon gas, hydrogen respectively, and open gas flowmeter and heating rank is set
The hydrogen of section and the volume flow of argon gas.
Quartz ampoule temperature is heated to 1000 DEG C by 60min by room temperature 7. starting heating furnace heating schedule, and phase is set
Corresponding gas flow.
8. regulation hydrogen flowing quantity is 15sccm, anneal 20min at being 1000 DEG C in temperature.
9. adjusting respectively, hydrogen flowing quantity is 50sccm and methane flow is 20sccm, reaction time 2.5h.
10. after the completion of to be grown, quartz ampoule being carried away rapidly from reacting furnace and is positioned on support, close reacting furnace and protect
It is constant to hold gas flow.
11. take out and preserve：After being cooled to room temperature, quartz ampoule end flange is closed, closes vavuum pump, until gas will
Steel cylinder pressure-reducing valve and gas flowmeter are closed when quartz ampoule inside is full of and quartz ampoule internal pressure reaches atmospheric pressure, takes out quartz
Piece and reacted copper sheet is positioned in closed and drying receptacle preserves.
Claims (6)
1. a kind of preparation method of grade single crystal graphene, it is characterised in that this method uses low-pressure chemical vapor deposition skill
Art, using copper foil as growth substrate, methane is reacting precursor, and hydrogen is reducing gas, only need to be clear to copper foil with polishing fluid before reaction
Wash, and ensure not to be passed through gas in temperature-rise period, annealed afterwards and 2 ~ 3 hours growths obtain opposite side distance up to 1mm's
Large area single crystal graphene, including step are as follows：
A. the preparation of chemical polishing solution：8g solids FeCl is weighed with electronic balance3·6H2O, measure 10mL with graduated cylinder afterwards
HCl solution and 100mL H2O is simultaneously stirred, dissolved；
B. copper sheet pre-processes：Copper sheet is taken out and is cut into 2cm × 2cm small pieces, takes appropriate polishing fluid with culture dish, using tweezer
The copper sheet sheared is put into polishing fluid by son to be soaked, and soak time then takes out and soaked with deionized water between 25s-50s
Steep and flush three times, nitrogen dries up afterwards；
C. copper sheet is loaded：Pretreated copper sheet is placed on quartz plate and is pushed into a diameter of 1 inch of quartz ampoule, and
Quartz plate is pushed into quartz ampoule stage casing, is placed in after quartz ampoule installs in heating furnace；
D., heating schedule is set：Temperature and the reaction time of each conversion zone are set in heating furnace sets panel；
E. vacuumize：Quartzy pipe end is connected on vavuum pump and vacuumized；
F., gas flow is set：The major-minor pressure-reducing valve of the steel cylinder equipped with argon gas, hydrogen is opened respectively, and opens gas flowmeter
The hydrogen of temperature rise period and the volume flow of argon gas are set；
G. heat up：Starting heating furnace heating schedule makes quartz ampoule temperature be heated to certain temperature through certain time by room temperature, and sets
Put corresponding gas flow；
H. anneal：Adjust hydrogen flowing quantity annealing；
I. grow：Hydrogen and methane flow are adjusted respectively, react certain time；
J. cool down：After the completion of to be grown, quartz ampoule is carried away rapidly from reacting furnace and is positioned on support, closed reacting furnace and protect
It is constant to hold gas flow；
K. take out and preserve：After being cooled to room temperature, quartz ampoule end flange is closed, closes vavuum pump, until gas is by quartz ampoule
Steel cylinder pressure-reducing valve and gas flowmeter are closed when inside is full of and quartz ampoule internal pressure reaches atmospheric pressure, taking-up quartz plate simultaneously will
Reacted copper sheet is positioned in closed and drying receptacle and preserved.
2. according to the preparation method of the grade single crystal graphene described in claims 1, it is characterised in that：In temperature-rise period
Gas is not passed through, and the heating-up time is 60 ~ 100 min.
3. according to the preparation method of the grade single crystal graphene described in claims 1, it is characterised in that：Taken out before heating true
It is 20 ~ 30 min between space-time.
4. according to the preparation method of the grade single crystal graphene described in claims 1, it is characterised in that：Methane used is mark
Quasi- gas, concentration 0.25%, blending gas are argon gas.
5. according to the preparation method of the grade single crystal graphene described in claims 1, it is characterised in that：Reaction and annealing temperature
Degree is between 980 ~ 1040 DEG C, and annealing process hydrogen flowing quantity is 15 ~ 30 sccm, and annealing time is 10 ~ 30min.
6. according to the preparation method of the grade single crystal graphene described in claims 1, it is characterised in that：Hydrogen in growth course
Throughput is 20 ~ 75 sccm, and methane flow is 5 ~ 40 sccm, and growth time is 2 ~ 3 h.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106283179A (en) * | 2016-07-25 | 2017-01-04 | 福建师范大学 | A kind of preparation method of grade monolayer single crystal graphene |
| CN106698408B (en) * | 2016-12-30 | 2019-09-10 | 武汉理工大学 | A kind of concave structure single crystal graphene and preparation method thereof |
| CN108441951A (en) * | 2018-04-28 | 2018-08-24 | 华中科技大学 | A kind of method of quick preparation large-size monocrystal graphene |
| CN108423659B (en) * | 2018-05-30 | 2019-02-26 | 绍兴文理学院 | A kind of preparation method of the grade single layer single crystal graphene based on polycrystalline copper foil |
| CN114657635B (en) * | 2022-03-22 | 2023-05-26 | 西南交通大学 | Method for rapidly preparing monocrystalline graphene |
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| KR20100090580A (en) * | 2009-02-06 | 2010-08-16 | 에이비씨상사 주식회사 | Method of maufacturing graphene material |
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Patent Citations (4)
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| KR20100090580A (en) * | 2009-02-06 | 2010-08-16 | 에이비씨상사 주식회사 | Method of maufacturing graphene material |
| CN103668447A (en) * | 2012-09-01 | 2014-03-26 | 董国材 | Preparation device and preparation method for preparing same or similar lattice orientation graphene |
| CN103086370A (en) * | 2013-01-22 | 2013-05-08 | 东北大学 | Method for preparing graphene strip by adopting low-temperature chemical vapour deposition |
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