CN103172061A - Method for growing large-area graphene on insulating substrate - Google Patents
Method for growing large-area graphene on insulating substrate Download PDFInfo
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- CN103172061A CN103172061A CN2013101304762A CN201310130476A CN103172061A CN 103172061 A CN103172061 A CN 103172061A CN 2013101304762 A CN2013101304762 A CN 2013101304762A CN 201310130476 A CN201310130476 A CN 201310130476A CN 103172061 A CN103172061 A CN 103172061A
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Abstract
The invention discloses a method for growing large-area graphene on an insulating substrate. According to the method, a growing substrate is taken as an insulating material, a copper foil is taken as a catalyst and a carbon source, nitrogen and protective gas are taken as source gases, and the large-area graphene is grown on the insulating substrate by adopting a two-step (low-pressure growth and high-pressure growth) chemical vapor deposition method and using the short-range catalytic effect of the copper coil through face-to-face contact of the insulating substrate and the copper foil. The method disclosed by the invention is simple in operation of the whole process and low in cost; and the sample preparation is very high in repeatability and is less interfered by external world. The prepared single-layer graphene can be made into a large-area circuit device by using an exposure method without needing a complex transfer technology.
Description
Technical field
The present invention relates to a kind of on insulating substrate the method for growing large-area Graphene.
Background technology
Owing to finding dirac electron energy band structure that Graphene is special and unusual fractional quantum hall effect, two professors of the Konstantin Novoselov of Univ Manchester UK and Andre Geim have obtained the Nobel Prize in physics of 2010.Under room temperature, carrier mobility and saturating speed high in Graphene make Graphene be expected to replace silicon materials to become the base mateiral of large-scale integrated circuit of future generation.Present stage, the heavy industrialization of Graphene used the growth aspect mainly be confined to Graphene.In recent years, the research of Graphene growth aspect, particularly large area deposition cheaply more and more are subject to domestic and international company, institute and the researchist's of colleges and universities extensive concern.
Although the Graphene that the rare mechanically peel method of preparation graphite that proposed in 2005 obtains has the highest quality of Graphene of present report, but the size of the Graphene that this method obtains has been subject to very serious restriction, generally only has the size of tens microns, and the cost of the Graphene of the method preparation and skills involved in the labour require very high, be only suitable in the research in laboratory and be unfavorable for industrialized extensive growth (K.S.Novoselov et al., Nature438,197.2005).2006, Walter de professor Heer of georgia ,u.s.a Polytechnics proposed ultrahigh vacuum(HHV) by the method (C.Berger et al., Science312,1191.2006) of thermally decomposed carbon SiClx extending and growing graphene.But the expensive price of substrate material silicon carbide, the expensive device of the needed ultrahigh vacuum(HHV) of growth conditions and high temperature, stable, uniform heating system have increased to a great extent the cost of scale operation, thereby have made heavy industrialization be subject to huge obstruction.2009, Rodney professor S.Ruoff in Texas ,Usa university Jane Austen branch school adopts the growth method-chemical gaseous phase depositing process that meets heavy industrialization, take methane and hydrogen as source of the gas, utilize the katalysis of Copper Foil to grow large-area Graphene individual layer (X.Li et al. on Copper Foil, Science324,1312.2009).But due to the electroconductibility of substrate, if make unicircuit, need to the Graphene of growth be shifted.And the technique of this transfer step is quite loaded down with trivial details and require very high to technology and the skill level that shifts personnel.The pollution that may introduce in transfer process simultaneously and the abundant residues of metal ion at the interface and organic macromolecule make the degradation of quality in practical devices of Graphene clearly.In view of complicacy and the uncontrollability of above-mentioned factor, use from heavy industrialization based on the Graphene of the chemical vapor deposition growth of metal catalytic effect and also have very long stretch to walk.
Therefore, on insulating substrate, utilize chemical gaseous phase depositing process on a large scale growing graphene have great importance in the application of large-scale integrated circuit industry and the research of ultrafast electronics for Graphene.
Summary of the invention
Order of the present invention be to provide a kind of on insulating substrate the method for growing large-area Graphene.
The present invention with insulating material as growth substrate; take Copper Foil as catalyzer; take carbon source (as methane), hydrogen and shielding gas (as rare gas element) as source of the gas; adopt the chemical gaseous phase depositing process of two-step approach (low-pressure growth and high pressure growth); contact by insulating substrate and the face-to-face of Copper Foil, utilize the short range catalytic effect of Copper Foil to grow large-area Graphene on insulating substrate.
Concrete grammar comprises the steps:
1) preparation of samples: insulating substrate and Copper Foil are cleaned, to remove organism and impurity metal ion; Make dielectric base and Copper Foil plane-plane contact after cleaning, obtain sample;
2) temperature rise period: the mixed gas that continues to pass into shielding gas and hydrogen in the reactor, simultaneously described sample is placed in described reactor, be heated to 1005-1030 ℃ (preferred 1020 ℃), and be incubated 10-30 minute (preferred 10 minutes);
3) the low-pressure growth stage: the temperature of keeping described reactor, and the pressure of regulating in described reactor is 100-120Pa (preferred 100Pa), then pass into simultaneously carbon source, shielding gas and hydrogen in described reactor, growing graphene 20-40 minute with this understanding (preferred 30 minutes);
4) the high pressure growth stage: the temperature of keeping described reactor, maintenance step 3) in, the flow of each gas is constant, regulate the interior pressure of described reactor to 400-500Pa (preferred 400Pa), growing graphene 50-70 minute with this understanding (preferred 60 minutes);
5) temperature-fall period: after growth finishes, reduce the temperature of described reactor to room temperature, take out sample, obtain being deposited on large-area Graphene on described insulating substrate; This process keeps the flow of pressure, carbon source, shielding gas constant, heightens the flow of hydrogen.
Wherein, the substrate that insulating substrate step 1) specifically can adopt following any one material to make: sapphire, quartz etc.Described Copper Foil is commercially produced product, and purity is more than 99.999%, and thickness can be 0.02 μ m-0.04 μ m.
Step 2) shielding gas described in can be rare gas element (as argon gas etc.), and its flow is 90-110sccm, specifically can be 100sccm; Hydrogen flowing quantity is 15-20sccm, specifically can be 20sccm.In the process of described intensification and insulation, the pressure in described reactor is 400Pa.
Step 3) carbon source described in specifically can be methane, ethene etc., and its flow is 1～5sccm, preferred 4～5sccm; Hydrogen flowing quantity is 0.4-0.8sccm, specifically can be 0.8sccm; Described shielding gas can be rare gas element (as argon gas etc.), and its flow is 90-110sccm, specifically can be 100sccm.
Reactor described in the present invention specifically can be high temperature process furnances.
The present invention combines the katalysis of Copper Foil and the substrate advantage of insulating substrate, grows large-area single-layer graphene on insulating substrate by chemical gaseous phase depositing process.
The present invention has following beneficial effect:
1) the inventive method can really realize the large-area Fast Growth of individual layer of Graphene on insulating substrate, rather than grows into nano level granular graphite alkene as the method for having reported;
2) single-layer graphene of the inventive method growth does not need loaded down with trivial details shifting process just can utilize exposure to make large-scale circuit devcie;
3) the whole process operation of the inventive method is simple, with low cost, and sample preparation repeatability is very high, is subjected to external interference little.
4) can Reusability up to a hundred times as the Copper Foil of catalyzer, reduced manufacturing cost.
Description of drawings
Fig. 1 is the experimental principle schematic diagram of the rare growth method of graphite provided by the invention, wherein, and (a) low-pressure growth stage, (b) high pressure growth stage.
Fig. 2 is the rare atomic force microscope pattern of graphite that utilizes method of the present invention to grow on (0001) surface sapphire; Wherein, (a) methane flow is 1sccm, and (b) methane flow is 3sccm, and (c) methane flow is 4sccm.
Fig. 3 is in the situation that methane flow is 5sccm, the atomic force microscope Tapping modeling that the graphite of (0001) surface sapphire substrate grown is rare (a, b), and Raman Characterization (c) and x-ray photoelectron spectroscopy characterize (d).
Fig. 4 is the electrical testing to the 1 μ m that grows on sapphire substrates * 2 rare bands of μ m graphite.
Embodiment
Below by specific embodiment, the inventive method is described, but the present invention is not limited to the growth of Graphene on the sapphire insulating substrate.
Experimental technique described in following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Embodiment 1, the extensive single-layer graphene of growing on (0001) surface sapphire substrate
1) with acetone to sapphire (Kyocera, Japan) and Copper Foil (Alfa Aesar, UK) carry out ultrasonic cleaning and remove organic substance residues, then with deionized water, they are carried out the impurity such as ultrasonic clear removal metal ion, then dry up rapidly sample with nitrogen gun.
2) (0001) surface sapphire is covered on Copper Foil, and make both close contacts.Then whole sample is pushed horizontal quartz tube stove central section.
3) with argon gas, the silica tube of whole tube furnace being carried out three times cleans in order to remove foreign gas residual in silica tube.
4) before the intensification beginning, pass into the argon gas of 100sccm and the hydrogen of 20sccm, by the valve of controlling mechanical pump, pressure is stabilized in 400Pa.Then in 50 minutes, tube furnace is raised to 1020 ℃, and is stabilized in 10 minutes stablizing with assurance silica tube warm area temperature distribution of this growth temperature.
5) before the growth beginning, the valve of driving the great machinery pump makes the interior pressure of tube furnace drop to 100Pa, then passes into the methane of 1-5sccm, and the flow of hydrogen is transferred to 0.8sccm from 20sccm.In this first step low-pressure growth stage, the time kept 30 minutes.
6) after said process finishes, turn down the valve of mechanical pump, make pressure be raised to the 400Pa left and right.This is the second step high pressure growth stage, and the time kept 60 minutes.The same step 5) of flow that keeps methane, argon gas and hydrogen in this step.
7) after process of growth finishes, close the tube furnace power supply, the flow of hydrogen recalled to 20sccm again, keep 6) in other conditions constant.Take out sample after naturally cooling to room temperature, be deposited on the big area single-layer graphene on (0001) surface sapphire.One-tenth-value thickness 1/10 by the Graphene of atomic force microscope gained is that it is single-layer graphene to 0.456nm as can be known.
Fig. 2 guarantees simultaneously that by the flow (from 1sccm to 4sccm) that changes methane other growth parameter(s) is constant.When the flow of methane was 1sccm, very low-density little Graphene island had appeared on sapphire surface.Along with the increase of methane flow, the density on Graphene island and their size are all increasing.These are shaped as the height on circular Graphene island the chances are 0.45nm.
Fig. 3 is located at 5sccm to the flow of methane, and growth temperature is located at 1020 degree, growing graphene under this specific condition.Fig. 3 (a) is the shape appearance figure of atomic force microscope tapping pattern, is (b) phase diagram of atomic force microscope tapping pattern.From phase diagram, can see that sapphire surface covers to have gone up about 92% Graphene, the size on each island is near one micron.(c) be the Raman spectrum curve of Graphene, can clearly find out three characteristic peaks of Graphene from the Raman spectrum, 1355cm
-1The D peak, 1612cm
-1G peak and 2692cm
-1The 2D peak.(d) be the x-ray photoelectron spectroscopy of Graphene, three centers are respectively at 284.8eV, and the peak of 285.8eV and 289.2eV is corresponding C-C sp respectively
2, three chemical bonds of C-H and COOH.
Fig. 4 is the electrical measurement data of Graphene, and along with the reduction of temperature, resistivity constantly increases, but can keep limited resistance value at low temperatures.We have also studied the IV characteristic of Graphene under differing temps, and the linearity of IV curve has remained to minimum temperature always, and the limited resistance meter under good ohm property and low temperature understands defective less in the Graphene of growth and higher quality.
Claims (5)
1. a method for preparing the big area Graphene on insulating substrate, adopt chemical Vapor deposition process to be prepared, and comprises the steps:
1) insulating substrate and Copper Foil are cleaned, make insulating substrate and Copper Foil plane-plane contact after cleaning, obtain sample;
2) continue to pass into the mixed gas of shielding gas and hydrogen in the reactor, simultaneously described sample is placed in described reactor, be heated to 1005-1030 ℃, and insulation 10-30 minute;
3) keep the temperature of described reactor, and the pressure of regulating in described reactor is 100-120Pa, then passes into simultaneously carbon source, shielding gas and hydrogen in described reactor, growing graphene 20-40 minute with this understanding;
4) keep the temperature of described reactor, keep step 3) described in the flow of carbon source, shielding gas and hydrogen constant, regulates the interior pressure of described reactor to 400-500Pa, growing graphene 50-70 minute with this understanding;
5) after growth finishes, reduce the temperature of described reactor to room temperature, take out sample, obtain being deposited on large-area Graphene on described insulating substrate.
2. method according to claim 1, is characterized in that: step 1) described in the insulating substrate substrate that adopts following any one material to make: sapphire and quartz; The thickness of described Copper Foil is 0.02 μ m-0.04 μ m.
3. method according to claim 1 and 2, is characterized in that: step 2) described in shielding gas be rare gas element, its flow is 90-110sccm; Hydrogen flowing quantity is 15-20sccm;
In the process of described intensification and insulation, the pressure in described reactor is 400Pa.
4. the described method of any one according to claim 1-3, is characterized in that: step 3) described in carbon source be methane or ethene, its flow is 1～5sccm, preferred 4～5sccm; Hydrogen flowing quantity is 0.4-0.8sccm; Described shielding gas is rare gas element, and its flow is 90-110sccm.
5. the described method of any one according to claim 1-4, it is characterized in that: described Graphene is single-layer graphene.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588199A (en) * | 2013-11-21 | 2014-02-19 | 上海理工大学 | Method for preparing graphene membrane material through in-site metal catalytic decomposition and transfer |
| CN103754864A (en) * | 2014-01-02 | 2014-04-30 | 上海理工大学 | Preparation method of graphene film |
| CN104045079A (en) * | 2014-06-25 | 2014-09-17 | 无锡格菲电子薄膜科技有限公司 | Method for epitaxially growing graphene on sapphire/epitaxial metal interface |
| CN104562195A (en) * | 2013-10-21 | 2015-04-29 | 中国科学院上海微***与信息技术研究所 | Method for growing graphene |
| CN104973589A (en) * | 2014-04-11 | 2015-10-14 | 中国科学院上海硅酸盐研究所 | High-density, high-electric-conductive and high-heat-conductive graphene material grown through two-step method and preparation method thereof |
| CN105800602A (en) * | 2016-03-07 | 2016-07-27 | 华东师范大学 | Method for directly growing graphene on insulating substrate through remote catalysis of copper particle |
| WO2016149934A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院上海微***与信息技术研究所 | Growing method for graphene |
| CN106835260A (en) * | 2017-01-12 | 2017-06-13 | 北京大学 | The preparation method of oversize multilayer single crystal graphene and large size single crystal corronil |
| CN107032331A (en) * | 2017-04-26 | 2017-08-11 | 江苏科技大学 | A kind of graphene preparation method based on dielectric base |
| CN107452841A (en) * | 2017-09-04 | 2017-12-08 | 湘能华磊光电股份有限公司 | LED epitaxial growth methods based on graphene |
| CN107604338A (en) * | 2017-09-11 | 2018-01-19 | 信阳师范学院 | The method for preparing large area bilayer graphene film on an insulating substrate |
| CN109368622A (en) * | 2018-11-27 | 2019-02-22 | 西安理工大学 | A method of preparing graphene in dielectric material substrate |
| CN110590173A (en) * | 2019-10-18 | 2019-12-20 | 北京大学 | Method for preparing graphene glass with assistance of metal nanoparticles, graphene glass and defogging glass |
| CN114920238A (en) * | 2022-05-31 | 2022-08-19 | 安徽碳华新材料科技有限公司 | Graphene-like material with insulating and heat conducting functions |
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| CN102849961A (en) * | 2011-07-01 | 2013-01-02 | 中央研究院 | Method for growing carbon film or inorganic material film on substrate |
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| CN102849961A (en) * | 2011-07-01 | 2013-01-02 | 中央研究院 | Method for growing carbon film or inorganic material film on substrate |
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| CN104562195A (en) * | 2013-10-21 | 2015-04-29 | 中国科学院上海微***与信息技术研究所 | Method for growing graphene |
| CN104562195B (en) * | 2013-10-21 | 2017-06-06 | 中国科学院上海微***与信息技术研究所 | The growing method of Graphene |
| CN103588199A (en) * | 2013-11-21 | 2014-02-19 | 上海理工大学 | Method for preparing graphene membrane material through in-site metal catalytic decomposition and transfer |
| CN103754864A (en) * | 2014-01-02 | 2014-04-30 | 上海理工大学 | Preparation method of graphene film |
| CN104973589A (en) * | 2014-04-11 | 2015-10-14 | 中国科学院上海硅酸盐研究所 | High-density, high-electric-conductive and high-heat-conductive graphene material grown through two-step method and preparation method thereof |
| CN104973589B (en) * | 2014-04-11 | 2017-02-15 | 中国科学院上海硅酸盐研究所 | High-density, high-electric-conductive and high-heat-conductive graphene material grown through two-step method and preparation method thereof |
| CN104045079A (en) * | 2014-06-25 | 2014-09-17 | 无锡格菲电子薄膜科技有限公司 | Method for epitaxially growing graphene on sapphire/epitaxial metal interface |
| WO2016149934A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院上海微***与信息技术研究所 | Growing method for graphene |
| CN105800602B (en) * | 2016-03-07 | 2018-02-27 | 华东师范大学 | Copper particle is remotely catalyzed the method for directly growing graphene on an insulating substrate |
| CN105800602A (en) * | 2016-03-07 | 2016-07-27 | 华东师范大学 | Method for directly growing graphene on insulating substrate through remote catalysis of copper particle |
| CN106835260A (en) * | 2017-01-12 | 2017-06-13 | 北京大学 | The preparation method of oversize multilayer single crystal graphene and large size single crystal corronil |
| CN106835260B (en) * | 2017-01-12 | 2019-01-29 | 北京大学 | The preparation method of oversize multilayer single crystal graphene and large size single crystal corronil |
| CN107032331A (en) * | 2017-04-26 | 2017-08-11 | 江苏科技大学 | A kind of graphene preparation method based on dielectric base |
| CN107452841A (en) * | 2017-09-04 | 2017-12-08 | 湘能华磊光电股份有限公司 | LED epitaxial growth methods based on graphene |
| CN107452841B (en) * | 2017-09-04 | 2019-07-09 | 湘能华磊光电股份有限公司 | LED epitaxial growth method based on graphene |
| CN107604338A (en) * | 2017-09-11 | 2018-01-19 | 信阳师范学院 | The method for preparing large area bilayer graphene film on an insulating substrate |
| CN107604338B (en) * | 2017-09-11 | 2019-06-25 | 信阳师范学院 | The method of large area bilayer graphene film is prepared on an insulating substrate |
| CN109368622A (en) * | 2018-11-27 | 2019-02-22 | 西安理工大学 | A method of preparing graphene in dielectric material substrate |
| CN110590173A (en) * | 2019-10-18 | 2019-12-20 | 北京大学 | Method for preparing graphene glass with assistance of metal nanoparticles, graphene glass and defogging glass |
| CN114920238A (en) * | 2022-05-31 | 2022-08-19 | 安徽碳华新材料科技有限公司 | Graphene-like material with insulating and heat conducting functions |
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Application publication date: 20130626 |