CN105152165A - Method of directly synthesizing large-area graphene oxide based on plasma-enhanced chemical vapor deposition - Google Patents
Method of directly synthesizing large-area graphene oxide based on plasma-enhanced chemical vapor deposition Download PDFInfo
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- CN105152165A CN105152165A CN201510548830.2A CN201510548830A CN105152165A CN 105152165 A CN105152165 A CN 105152165A CN 201510548830 A CN201510548830 A CN 201510548830A CN 105152165 A CN105152165 A CN 105152165A
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Abstract
The invention belongs to the technical field of material science, and particularly relates to a method of directly synthesizing large-area graphene oxide based on plasma-enhanced chemical vapor deposition. The method comprises the following specific steps of pretreating a substrate; growing graphene oxide on the substrate by using a plasma-enhanced chemical vapor deposition system; after the growth is ended, taking out the graphene oxide, wherein the key point of synthesis is introduction and control of oxide atoms. The method disclosed by the invention is short in reaction time and low in reaction temperature; in addition, oxygen content of the graphene oxide is controllable. Compared with existing graphene oxide synthesized by a chemical method, the graphene oxide synthesized by the method disclosed by the invention has the characteristics of large size and good uniformity in size, and can be applied to the fields of gas detection, photoelectric devices and the like.
Description
Technical field
The invention belongs to materials science field, be specifically related to a kind of method of directly synthesizing big area graphene oxide based on plasma chemistry enhancing vapour deposition.
Background technology
Graphene is a kind of material with having splendid electricity, mechanics, thermal property, be considered to future microelectronics industry base mateiral.Graphene oxide is the derivative of Graphene, is constructed containing oxygen group by scion grafting Sauerstoffatom, hydroxyl, carboxyl, carbonyl etc. on Graphene lattice carbon.Compared with Graphene, graphene oxide is due to the oxy radical containing polarity, and the absorption for molecule is better, therefore can be used as gas or liquid sensor.In addition, due to the effect of polar group, minute sized graphene oxide in the solution can the orderly laminate structure of spontaneous formation, can be used for the filtration of solution.In addition, by the graphene oxide contact be oxidized in various degree, contact surface can form heterojunction, can be used to make all kinds of photoelectric device.
At present, in graphene oxide application process, the most key link is the preparation of graphene oxide composite material.The method preparing graphene oxide be most widely used now be improvement Hummer method (ModifiedHummer ' sMethod, come from: DanielaC.Marcanoetal, ImprovedSynthesisofGrapheneOxide,
aCSNanovol.4No.8pp.4806-4814,2010).The ultimate principle of this method utilizes strong oxidizer to be graphene oxide by graphite oxidation.But the long reaction time needed for this method, and the graphene oxide obtained is merely the small pieces of micro-meter scale.This application for graphene oxide is very disadvantageous.
The human hairs such as Chung understand a kind of method obtaining larger area graphene oxide.First they prepare Graphene by CVD, and then prepared Graphene is transferred on required substrate, finally carry out oxide treatment with ozone plasma to Graphene to obtain graphene oxide and (come from: MinGyunChungetal, HighlysensitiveNO
2gassensorbasedonozonetreatedgraphene, SensorsandActuatorsB166 – 167 (2012) 172 – 176).This method overcomes the prepared undersized shortcoming of graphene oxide in improvement Hummer method, but its shortcoming also clearly: the synthesis of graphene oxide need divide 2 steps to carry out, long reaction time; And when utilizing ozone plasma to process Graphene, once condition controls bad, Graphene local can be etched away, and forms cavity, destroys the integrity of graphene oxide film.
Summary of the invention
The object of the present invention is to provide a kind of reaction times short, temperature of reaction is low, and the method for the controlled direct synthesis big area graphene oxide of the oxygen level of graphene oxide.This application tool for graphene oxide is from now on of great significance.
The method of direct synthesis big area graphene oxide provided by the invention, strengthen vapour deposition process based on plasma chemistry, concrete steps are as follows:
Step 1.1: pre-treatment is carried out to substrate;
Step 1.2: at Grown graphene oxide;
Step 1.3: after growth terminates, graphene oxide is taken out.
Further, the substrate material described in step 1.1 is have the metal of catalysis characteristics or some is nonmetal.The described metal with catalysis characteristics mainly contains: copper, nickel, platinum, gold etc.; Describedly nonmetally to mainly contain: silicon, carbon, germanium etc.
Further, pre-treatment carried out to substrate mainly comprise following flow process described in step 1.1: ultrasonic cleaning, chemical rightenning, flushing, oven dry; Wherein, the solvent that described ultrasonic cleaning uses comprises acetone, Virahol, deionized water etc.; The polishing fluid that described chemical rightenning adopts can be ammonium persulfate solution etc.; The irrigation that described flushing adopts is deionized water; The temperature of described drying course is 50 DEG C-70 DEG C.
Further, the process of the growth of oxygen functionalized graphene described in step 1.2 mainly comprises the steps:
Step 1.2.1: substrate is loaded into plasma reinforced chemical vapor deposition system;
Step 1.2.2: pre-treatment;
Step 1.2.3: graphene oxide grows.
Further, the plasma reinforced chemical vapor deposition system described in step 1.2.1 mainly comprises airing system, vacuum system, furnace chamber, heating system and discharge system.The major function of described airing system is air feed in furnace chamber, and institute's supplied gas comprises carbon-source gas, reducing gas, current-carrying gas.The major function of described vacuum system is vacuumized by furnace chamber, and control the air pressure in furnace chamber.Described furnace chamber is the place of graphene oxide synthesis.The major function of described heating system is the temperature controlling furnace chamber.The major function of described discharge system is that the gas provided by airing system excites and ionizes, and produces all kinds of particles of synthesis needed for graphene oxide.
Further, described carbon-source gas can be the organism of the carbon containing such as methane, acetylene; Described reducing gas is hydrogen; Described current-carrying gas is argon gas.
Further, the preprocessing process described in step 1.2.2 comprises: open vacuum system furnace chamber is vacuumized, open heating system furnace chamber is heated to temperature required, open reducing gas continuing for some time.The main purpose of described preprocessing process utilizes reducing gas by the Reduction of Oxide on substrate at a certain temperature.Described temperature is depending on substrate material.
Further, the graphene oxide process of growth described in step 1.2.3 mainly comprises: utilize heating system to control in temperature of reaction by cavity temperature; Then in furnace chamber, pass into the carbon-source gas, reducing gas, the current-carrying gas that mix by a certain percentage; Open discharge system and continue one period of reaction times; Close carbon-source gas and electric discharge.Described temperature of reaction is 100 DEG C-700 DEG C; The power of the plasma body that described discharge system produces is 10-100W; The method of oxy radical introduced needed for graphene oxide synthesis has 3 kinds: (1) is introduced by the remnant oxygen in described carbon-source gas, reducing gas, current-carrying gas or water vapour, namely in described carbon-source gas, reducing gas, current-carrying gas the purity of at least one gas lower than 99.9%; (2) water vapour adsorbed by furnace chamber inwall is introduced, and the water vapour content in the reaction compartment namely caused because of furnace chamber inwall adsorb water vapor during graphene oxide building-up reactions is greater than 100ppm; (3) method of comprehensive (1) and (2); The blending ratio of described carbon-source gas, reducing gas, current-carrying gas is 1:(20-100): (100-200); In the graphene oxide generated, the ratio of carbon and oxygen element is by regulating the blending ratio of described reducing gas to change, or by regulating temperature of reaction to change.The described reaction times is 1-20 minute.
The crucial part of the inventive method is introducing and the control of Sauerstoffatom; The inventive method reaction times is short, and temperature of reaction is low, and the oxygen level of graphene oxide is controlled.Compared with the graphene oxide synthesized with existing chemical method, the graphene oxide of present method synthesis has size greatly, and the feature of good uniformity, can be used on the field such as gas detection, photoelectric device.
Accompanying drawing explanation
Fig. 1 plasma reinforced chemical vapor deposition system schematic diagram.
Fig. 2 cavity temperature-time variations schematic diagram.
The Raman spectrogram of graphene oxide synthesized by Fig. 3.
Number in the figure: 101 is furnace chamber, 102 is discharge system, and 103 is airing system, and 104 is vacuum system, and 105 is heating system, and 106 is plasma body, and 107 is Copper Foil substrate.201 is pretreatment stage, and 202 is temperature-fall period, and 203 for starting growth phase, and 204 is cooling stages.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.
Figure 1 shows that the schematic diagram of the plasma reinforced chemical vapor deposition system that synthesis graphene oxide is used.In this example, we are 99.998% by purity, and thickness is that the Copper Foil of 25 μm is as substrate.
First the Copper Foil cut is put into acetone, ultrasonic cleaning 10 minutes.Clean with deionized water rinsing after taking-up, then put into dilute hydrochloric acid (5% mass concentration) immersion 10 minutes, to remove the oxide compound of copper foil surface.Afterwards Copper Foil is put into deionized water to rinse well, after the nitrogen with 99% dries up, put into the incubator of 70 DEG C, remove the moisture on surface further.The Copper Foil substrate 107 that Copper Foil after above-mentioned process just can synthesize as graphene oxide.
Plasma reinforced chemical vapor deposition system major constituents used by this example is furnace chamber 101, discharge system 102, airing system 103, vacuum system 104, heating system 105.During beginning, first Copper Foil substrate 107 is put into furnace chamber 101, then by vacuum system 104, furnace chamber is vacuumized.And then, in furnace chamber 101, passed into the hydrogen of 100sccm by airing system 103, open heating system 105 simultaneously and heat to furnace chamber.The time dependent situation of Heating temperature of heating system as shown in Figure 2.At pretreatment stage 201, the temperature in furnace chamber will rise to 1000 DEG C from room temperature, and keep 20 minutes.During this period of time, the oxide compound on Copper Foil substrate 107 is by hydrogen reducing; Meanwhile, under high temperature action, the planeness on Copper Foil substrate 107 surface can improve.Afterwards, temperature-fall period 202(about 100 minutes), the temperature in furnace chamber is down to the temperature of synthesis needed for graphene oxide, is 550 DEG C in this example.After cavity temperature arrives 550 DEG C, start to grow for 203 stages.Now, airing system provides the gas needed for reaction.Gaseous species in this example and flow are respectively: methane 2sccm, hydrogen 80sccm, argon gas 100sccm.Meanwhile, discharge system is started working, and produces plasma body 106 in furnace chamber.In this example, the power of plasma body is about 10W, and frequency is about 1.5MHz.Give methane molecule in furnace chamber in Fig. 2, methane electric discharge is dissociated the methyl molecule generated, and by the C of methyl molecule aggregation
2the concentration distribution situation of hydro carbons.Wherein, C
2hydro carbons is the essential substance forming graphene oxide lattice.It should be noted that C
2hydro carbons is only occurred by the place of heating in furnace chamber, and its reason is C
2hydro carbons only at high temperature generates, and its generation is very responsive to temperature.The time that growth phase 203 continues should determine according to cavity temperature, the gas station of airing system input and the power of electric discharge.In this example, the time growing 203 phase lasts is 5 minutes.After growth phase 203 terminates, methane gas is closed, turns off discharge system and heating system 105 simultaneously, enter cooling stages 204.Copper Foil substrate 107 just can take out after terminating by the stage 204 to be cooled from furnace chamber 101.
Figure 3 shows that the Raman spectrogram of grown graphene oxide.
Claims (4)
1. directly synthesize a method for big area graphene oxide based on plasma chemistry enhancing vapour deposition, it is characterized in that concrete steps are as follows:
Step 1: pre-treatment is carried out to substrate;
Step 2: at Grown graphene oxide;
Step 3: after growth terminates, graphene oxide is taken out;
Wherein, described in step 2 in the flow process of Grown graphene oxide be:
(1) substrate is loaded into plasma reinforced chemical vapor deposition system;
(2) pre-treatment;
(3) graphene oxide growth;
Wherein, described plasma reinforced chemical vapor deposition system is primarily of airing system, vacuum system, furnace chamber, heating system, discharge system composition; Described airing system is mainly used in air feed in furnace chamber, and institute's supplied gas comprises carbon-source gas, reducing gas, current-carrying gas; Described vacuum system is mainly used in furnace chamber to vacuumize, and controls the air pressure in furnace chamber; Described furnace chamber is the place of graphene oxide synthesis; Described heating system is mainly used in the temperature controlling furnace chamber; The gas being mainly used in being provided by airing system of described discharge system excites and ionizes, and produces all kinds of particles of synthesis needed for graphene oxide;
Described pretreated process comprises: open vacuum system furnace chamber is vacuumized, open heating system furnace chamber is heated to temperature required, open reducing gas continuing for some time;
The flow process of described graphene oxide growth comprises: utilize heating system to control in temperature of reaction by cavity temperature; The carbon-source gas, reducing gas, the current-carrying gas that mix by a certain percentage is passed in furnace chamber; Open discharge system and continue one period of reaction times; Close carbon-source gas and electric discharge;
Described temperature of reaction is 100 DEG C-700 DEG C; The power of the plasma body that described discharge system produces is 10-100W; The method of oxy radical introduced needed for graphene oxide synthesis is: introduced by the remnant oxygen in described carbon-source gas, reducing gas, current-carrying gas or water vapour, namely in described carbon-source gas, reducing gas, current-carrying gas the purity of at least one gas lower than 99.9%; Or the water vapour to be adsorbed by furnace chamber inwall is introduced, the water vapour content in the reaction compartment namely caused because of furnace chamber inwall adsorb water vapor during graphene oxide building-up reactions is greater than 100ppm; The blending ratio of described carbon-source gas, reducing gas, current-carrying gas is 1:(20-100): (100-200); In the graphene oxide generated, the ratio of carbon and oxygen element is by regulating the blending ratio of described reducing gas to change, or by regulating temperature of reaction to change; Reaction times is 1-20 minute.
2. according to claim 1ly strengthen vapour deposition based on plasma chemistry and directly synthesize the method for big area graphene oxide, it is characterized in that the substrate material described in step 1 is have the metal of catalysis characteristics or some is nonmetal; The described metal choosing with catalysis characteristics: copper, nickel, platinum, gold, is describedly nonmetally selected from silicon, carbon, germanium.
3. according to claim 1ly strengthen vapour deposition based on plasma chemistry and directly synthesize the method for big area graphene oxide, it is characterized in that pretreated flow process is carried out to substrate be described in step 1: ultrasonic cleaning, chemical rightenning, flushing, oven dry; The solvent that described ultrasonic cleaning process uses is acetone, Virahol or deionized water; The polishing fluid that described chemical polishing process adopts is ammonium persulfate solution; The irrigation that described flushing process adopts is deionized water; The temperature of described drying course is 50 DEG C-70 DEG C.
4. method of directly synthesizing big area graphene oxide based on plasma chemistry enhancing vapour deposition according to claim 1, is characterized in that described carbon-source gas is methane or acetylene; Described reducing gas is hydrogen; Described current-carrying gas is argon gas.
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Cited By (3)
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| CN107215859A (en) * | 2017-07-01 | 2017-09-29 | 中国科学院兰州化学物理研究所 | A kind of method of PECVD synthesizing graphite alkene |
| CN108163846A (en) * | 2018-01-19 | 2018-06-15 | 复旦大学 | A kind of method of the chemical vapor deposition synthesizing graphite alkene of carbon oxide auxiliary |
| CN108502873A (en) * | 2018-06-26 | 2018-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of high quality, less defect, the preparation method of the uniform graphene of structure |
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| CN102502605A (en) * | 2011-11-09 | 2012-06-20 | 复旦大学 | Electrically-induced reduction method for degraded graphene oxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107215859A (en) * | 2017-07-01 | 2017-09-29 | 中国科学院兰州化学物理研究所 | A kind of method of PECVD synthesizing graphite alkene |
| CN108163846A (en) * | 2018-01-19 | 2018-06-15 | 复旦大学 | A kind of method of the chemical vapor deposition synthesizing graphite alkene of carbon oxide auxiliary |
| CN108502873A (en) * | 2018-06-26 | 2018-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of high quality, less defect, the preparation method of the uniform graphene of structure |
| CN108502873B (en) * | 2018-06-26 | 2021-06-29 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Preparation method of high-quality graphene with few defects and uniform structure |
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