CN105439126A - Simple preparation method of millimeter level monocrystalline graphene - Google Patents
Simple preparation method of millimeter level monocrystalline graphene Download PDFInfo
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Abstract
The invention belongs to the technical field of advanced carbon materials and semiconductor technologies, and especially relates to a simple and stable preparation method of large-area monocrystalline graphene. The method is suitable for preparing millimeter level monocrystalline graphene. The method is characterized in that the monocrystalline graphene is prepared through a low pressure chemical vapor deposition technology at 1000DEG C by using methane (CH4) as a carbon source and hydrogen as a reducing gas. Acetone or ethanol ultrasonic treatment of copper foil is not needed, polishing and other pretreatment processes of the copper foil by adopting a complex electrochemical process are not needed, a several-hours and high-hydrogen flow annealing process is not needed, and only complete extraction of air in a reactor and guaranteeing of no introduction of gases in the heating process are needed, so the simple treatment method greatly reduces the nucleating density of graphene on the copper foil, and realizes growth of the monocrystalline graphene with the opposite side distance reaching 1mm in 2-3h. Results of scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectrum analysis of a sample prove that the sample is the monocrystalline graphene and has few defects.
Description
Technical field
The invention belongs to advanced carbon material and semiconductor process techniques field, particularly a kind of easy, stable preparation method of big area single crystal graphene.
Background technology
Graphene has between monolayer carbon atom to become key with sp2 hybrid form and novel, the advanced two dimensional surface nano material be formed by connecting, and makes Graphene have excellent performance at electricity, optics, calorifics, mechanics just because of this special Cheng Jian of Graphene, mode of connection and perfect two-dimensional characteristics.Such as: the physical strength of Graphene reaches as high as 130Gpa, its carrier mobility speed is up to 15000cmm
-1k
-1, be more than 10 times of common silicon chip, and its thermal conductivity is up to 5000Wm
-1k
-1, clearly, the premium properties of Graphene has larger advantage than with other materials of the same type.Therefore, Graphene is expected to obtain widespread use at numerous areas such as high-performance nano device, matrix material, field emmision material, gas sensor and energy storage.
It is chemical vapour deposition (ChemicalVaporDeposition) that current big area prepares the most popular method of Graphene.Its ultimate principle is: with carbonaceous gas organism for growth precursors, be aided with hydrogen and rare gas element (as argon gas, helium, nitrogen etc.), and with section transitions metal (as copper, iron, nickel, gold etc.) as substrate, under the high temperature of 1000 DEG C, carbonaceous organic material gas is adsorbed onto metallic surface under effort between metal and gas molecule, the hydrocarbon active reaction intermediate producing a series of activation is decomposed gradually under the catalytic activity and high temperature action of metal, afterwards these carbonaceous active intermediates at metallic catalyst surfaces after the step such as dehydrogenation and ring formation, form the Graphene being basic composition unit with the six-ring of carbon.Big area can be grown easily in this approach and uniform single or multiple lift polycrystalline graphite alkene.But the existence of a large amount of crystal boundary of polycrystalline graphite alkene, the advantage of Graphene in electricity, optics, the calorifics such as electronic conduction performance, thermal conductivity is caused to be lowered, single crystal graphene then well reduces the impact that crystal boundary causes Graphene performance, and therefore the single crystal graphene of growing large-area just seems very important.But, the method of growing single-crystal Graphene known at present, complicated gas conversion is carried out in the annealing process of the very complicated pre-treatment (as chemical rightenning, electrochemical etching etc.) of most needs, long-time high hydrogen flowing quantity, process of growth, even by some components of design, copper sheet is transformed, and some growth method then needs through the reach a few hours growth of even tens of hours, technique is loaded down with trivial details, complicated.
Therefore, a kind of easy, stable technique preparing large-area single crystal graphene is sought extremely important for the application of single crystal graphene.
Summary of the invention
For preparing complicated, the loaded down with trivial details and less present situation of single crystal graphene area of producing of single crystal graphene method at present, the invention provides a kind of simple, stable method preparing big area single crystal graphene.The method adopts low-pressure chemical vapor deposition (LPCVD) technology, take Copper Foil as growth substrate, methane is reacting precursor, hydrogen is reducing gas, only need clean Copper Foil with polishing fluid before reaction, and ensure not pass into any gas in temperature-rise period, after can obtain opposite side distance from the big area single crystal graphene reaching 1mm through annealing and the growth of 2-3 hour.Concrete preparation method is:
A. the preparation of chemical brightening solution: take 8g solid FeCl with electronic balance
36H
2o, measures 10mlHCl solution and 100mlH with graduated cylinder afterwards
2o also carries out being uniformly mixed, dissolving;
B. copper sheet pre-treatment: copper sheet is taken out and is cut into the small pieces of 2cm × 2cm, get in appropriate polishing fluid and culture dish, with tweezers, the copper sheet sheared is put into polishing fluid and soak, soak time is between 25s-50s, then taking-up deionized water soaks and rinses three times, and nitrogen dries up afterwards;
C. copper sheet is loaded: being placed on by pretreated copper sheet on quartz plate and pushing diameter is in the silica tube of 1inch, and quartz plate is pushed into silica tube stage casing.Treating that silica tube installs is placed in process furnace;
D. heating schedule is set: the temperature and reaction times that arrange each conversion zone are set in panel at process furnace;
E. vacuumize: silica tube end is connected on vacuum pump and vacuumizes;
F. gas flow is set: open the major-minor reducing valve of steel cylinder that argon gas, hydrogen are housed respectively, and opens gas meter the hydrogen of temperature rise period and the volumetric flow rate of argon gas are set;
G. heat up: start process furnace heating schedule and make silica tube temperature from ambient be heated to certain temperature through certain hour, and corresponding gas flow is set;
H. anneal: regulate hydrogen flowing quantity annealing;
I. grow: regulate hydrogen and methane flow respectively, reaction certain hour;
J. cool: after growth completes, carried away from Reaktionsofen rapidly by silica tube and be positioned over support, off-response stove also keeps gas flow constant;
K. take out and preserve: after cool to room temperature, close silica tube end flange, close vacuum pump, until silica tube inside is full of by gas and silica tube internal pressure reaches normal atmosphere time close steel cylinder reducing valve and gas meter, take out quartz plate and also reacted copper sheet be positioned over airtight and preserve in drying receptacle.
In step a of the present invention to use reagent to be analytical pure rank hydrogen purity used be 99.999%, nitrogen gas purity used is 99.999%, and methane used is standard gas, and concentration is 0.25%, blending gas is argon gas, and useful water is ultra-pure deionized water and resistivity is 18.25 Ω cm.
In step b of the present invention, copper sheet model is AlfaAesar, #13382, and thickness is 25 μm, and purity is 99.8%.
Be placed in the middle part of process furnace by copper sheet in step c of the present invention, silica tube is inner is being equipped with near process furnace rear and front end the Al that two diameters are slightly less than quartz tube
2o
3pipe plug.
The step e pumpdown time of the present invention is 20 ~ 30min.
In step g of the present invention, the heating-up time is 60 ~ 100min, and does not pass into any gas in temperature-rise period.
In step g of the present invention, temperature of reaction is 980 ~ 1040 DEG C, and annealing temperature is 950 ~ 1040 DEG C.
In step h of the present invention, hydrogen flowing quantity is 15-30sccm, and annealing time is 10-30min.
In step I of the present invention, hydrogen flowing quantity is 20-75sccm, and methane flow is 5-40sccm, and growth time is 2-3h.
The present invention's feature of the present invention and beneficial effect are:
1. the present invention adopts low-pressure chemical vapor deposition (LPCVD) technology, take Copper Foil as growth substrate, and methane is reacting precursor, and hydrogen is reducing gas.Only need clean Copper Foil, and ensure that in temperature-rise period, do not pass into any gas makes the surperficial passivation acquired a certain degree of copper sheet, reach the object that can reduce the nucleation density of Graphene on Copper Foil greatly like this, after can obtain opposite side distance from the big area single crystal graphene reaching 1mm through annealing and the growth of 2-3 hour;
2. the present invention is simple to operation, without the need to long ultrasonic cleaning process, complicated electrochemical polishing process, and the annealing process under the high hydrogen flowing quantity reaching a few hours, and process stabilizing, repeatability is high, production cost is low, the single crystal graphene size prepared is large and even, is applicable to commercial application.
Accompanying drawing explanation
Fig. 1 is the large-area single crystal graphene Photomicrograph using the present invention to grow out.
Fig. 2 is the graphite Raman spectrogram using the present invention's growth.
Fig. 3 is the transmission electron micrograph of the single crystal graphene using the present invention to grow out.
Embodiment
The invention provides a kind of big area single crystal graphene easy, stablize preparation method, below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.
Embodiment 1
Preparation big area single crystal graphene, its concrete implementation step is as follows:
1. take 8g solid FeCl with electronic balance
36H
2o, measures 10mlHCl solution and 100mlH with graduated cylinder afterwards
2o is also uniformly mixed, supersound process 10min;
2. copper sheet taken out and be cut into the small pieces of 2cm × 2cm, get in appropriate polishing fluid and culture dish, with tweezers, the copper sheet sheared is put into polishing fluid and soak, soak time is 25s-50s, then taking-up deionized water soaks and rinses three times, and nitrogen dries up afterwards;
3. be placed on quartz plate by pretreated copper sheet, then quartz plate being pushed diameter is in the silica tube of 1inch, makes quartz plate be positioned at silica tube stage casing and ensures that copper sheet is positioned in the middle part of silica tube.After silica tube installs, silica tube is placed in process furnace;
4. the temperature and reaction times that arrange each conversion zone are set in panel at process furnace;
5. silica tube end is connected on vacuum pump and vacuumizes;
6. open the major-minor reducing valve of steel cylinder that argon gas, hydrogen are housed respectively, and open gas meter the hydrogen of temperature rise period and the volumetric flow rate of argon gas are set;
7. starting process furnace heating schedule makes silica tube temperature from ambient be heated to 1000 DEG C through 60min, and arranges corresponding gas flow;
8. regulate hydrogen flowing quantity to be 15sccm, anneal 20min at temperature is 1000 DEG C;
9. regulating hydrogen flowing quantity to be 50sccm and methane flow is respectively 20sccm, and the reaction times is 2.5h;
10., after growth completes, carried away from Reaktionsofen rapidly by silica tube and be positioned over support, off-response stove also keeps gas flow constant;
11. take out and preserve: after cool to room temperature, close silica tube end flange, close vacuum pump, until silica tube inside is full of by gas and silica tube internal pressure reaches normal atmosphere time close steel cylinder reducing valve and gas meter, take out quartz plate and also reacted copper sheet be positioned over airtight and preserve in drying receptacle.
Claims (7)
1. the simple and convenient process for preparing of a grade single crystal graphene, it is characterized in that: the method adopts low-pressure chemical vapor deposition technology, take Copper Foil as growth substrate, methane is reacting precursor, hydrogen is reducing gas, only need clean Copper Foil with polishing fluid before reaction, and ensure not pass into any gas in temperature-rise period, after growth through annealing and 2-3 hour can obtain opposite side distance from the big area single crystal graphene reaching 1mm.
2. according to the simple and convenient process for preparing of the grade single crystal graphene described in claims 1, it is characterized in that: the present invention does not pass into any gas in temperature-rise period, and the heating-up time is 60 ~ 100min.
3. according to the simple and convenient process for preparing of the grade single crystal graphene described in claims 1, it is characterized in that: the present invention's methane used is standard gas, concentration is 0.25%, and blending gas is argon gas.
4. according to the simple and convenient process for preparing of the grade single crystal graphene described in claims 1, it is characterized in that: before heating, the pumpdown time is 20-30min.
5. according to the simple and convenient process for preparing of the grade single crystal graphene described in claims 1, it is characterized in that: reaction and annealing temperature are all between 980 ~ 1040 DEG C.
6. according to the simple and convenient process for preparing of the grade single crystal graphene described in claims 1, it is characterized in that: annealing process hydrogen flowing quantity is 15-30sccm, annealing time is 10-30min.
7. according to the simple and convenient process for preparing of the grade single crystal graphene described in claims 1, it is characterized in that: in process of growth, hydrogen flowing quantity is 20-75sccm, methane flow is 5-40sccm, and growth time is 2-3h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106698408A (en) * | 2016-12-30 | 2017-05-24 | 武汉理工大学 | Concave structure monocrystalline graphene and preparation method thereof |
| CN108423659A (en) * | 2018-05-30 | 2018-08-21 | 绍兴文理学院 | A kind of preparation method of the grade single layer single crystal graphene based on polycrystalline copper foil |
| 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 |
| CN114657635A (en) * | 2022-03-22 | 2022-06-24 | 西南交通大学 | Method for rapidly preparing single crystal graphene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100090580A (en) * | 2009-02-06 | 2010-08-16 | 에이비씨상사 주식회사 | Method of maufacturing graphene material |
| CN103086370A (en) * | 2013-01-22 | 2013-05-08 | 东北大学 | Method for preparing graphene strip by adopting low-temperature chemical vapour deposition |
| CN103213979A (en) * | 2013-05-10 | 2013-07-24 | 山西大同大学 | Method for preparing graphene by solvent-thermal process |
| CN103668447A (en) * | 2012-09-01 | 2014-03-26 | 董国材 | Preparation device and preparation method for preparing same or similar lattice orientation graphene |
-
2014
- 2014-09-01 CN CN201410439978.8A patent/CN105439126B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103213979A (en) * | 2013-05-10 | 2013-07-24 | 山西大同大学 | Method for preparing graphene by solvent-thermal process |
Non-Patent Citations (1)
| Title |
|---|
| SHANSHAN CHEN等: "Millimeter-Size Single-Crystal Graphene by Suppressing Evaporative Loss of Cu During Low Pressure Chemical Vapor Deposition", 《ADV. MATER》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106698408A (en) * | 2016-12-30 | 2017-05-24 | 武汉理工大学 | Concave structure monocrystalline 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 |
| CN108423659A (en) * | 2018-05-30 | 2018-08-21 | 绍兴文理学院 | A kind of preparation method of the grade single layer single crystal graphene based on polycrystalline copper foil |
| CN114657635A (en) * | 2022-03-22 | 2022-06-24 | 西南交通大学 | Method for rapidly preparing single crystal graphene |
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