CN105948526A - Method for preparing smooth graphene film by pulling method - Google Patents
Method for preparing smooth graphene film by pulling method Download PDFInfo
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- CN105948526A CN105948526A CN201610273422.5A CN201610273422A CN105948526A CN 105948526 A CN105948526 A CN 105948526A CN 201610273422 A CN201610273422 A CN 201610273422A CN 105948526 A CN105948526 A CN 105948526A
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- graphene oxide
- film
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- graphene
- glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a method for preparing a smooth graphene film by a pulling method. The method comprises the steps: adding graphene oxide into ultrapure water, and carrying out ultrasonic treatment, so as to prepare a uniform graphene oxide aqueous solution; pretreating a glass substrate by sequentially using a piranha solution and a toluene solution of 3-aminopropyl triethoxysilane; submerging the pretreated glass substrate into the prepared graphene oxide aqueous solution, and pulling out the glass substrate at a constant speed, so as to prepare a graphene oxide film; and carrying out reduction on the prepared graphene oxide film by using hydrazine hydrate steam, thereby preparing the graphene film. According to the method, the pulling technology used is simple in operation, low in cost and easy in control, and the prepared graphene film is smooth and uniform and is easily subjected to functional modification.
Description
Technical field
The invention belongs to field of nano material preparation, be specifically related to a kind of method preparing smooth graphene film with czochralski method.
Background technology
Graphene is current optimal two-dimension nano materials, is star the most dazzling in nano-carbon material field nearly ten years, and the two dimensional crystal structure of its uniqueness imparts the physicochemical characteristics of its a series of uniqueness.The thin film being made up of Graphene has the series of advantages such as chemical stability is good, transparency is high, electric conductivity is strong, mechanical strength is big, good biocompatibility, huge application prospect is had at the numerous areas such as photoelectric cell, tissue culture, the most successfully attract many research interest of association area, and the most progressively become study hotspot.
Under tempting Research Prospects, the multiple coating films modes such as vacuum filtration method, spin coating method, injection cladding process, chemical vapour deposition technique have been successfully applied to the preparation of graphene film, and prepared thin film can deposit or transfer to as in the various substrates such as glass, quartz, silicon chip, polyurethane.
But, currently to the research of graphite film also in the primary research stage, film plating process there is also that uniformity of film is poor, roughness is big, preparation cost is high, complicated process of preparation, is difficult to a series of defects such as industrialized production.
Lifting coating process equipment is simple, small investment, with low cost, be the good method making optics high performance membrane.Its basic procedure is for standing a period of time in substrate uniform descent is immersed in solution, more at the uniform velocity lifts out, and along with the volatilization of solvent is complete, matrix surface can gradually form the film of densification.Comparing other film plating process, the lifting plated film uniformity is high, film particles size uniformity, and activity is good, easy to operate, it is not necessary to evacuation, has and prepares the complex-shaped and ability of large area film, it is easy to accomplish industrialization.Though having in the industry some to use czochralski methods to prepare graphene film to attempt, but plate graphene film fold is more, roughness is relatively big, and related process needs to be optimized further.
Summary of the invention
It is an object of the invention to provide a kind of method preparing smooth graphene film with czochralski method.Present invention lifting used technical operation is simple, with low cost, easily controllable, and prepared graphene film is smooth, uniform and is prone to carry out functional modification.
The technical solution realizing the object of the invention is: a kind of method preparing smooth graphene film with czochralski method, comprises the following steps:
Step 1: the pretreatment of substrate of glass
Substrate of glass is placed in Piranha solution immersion, cleans with ultra-pure water with ethanol successively after taking-up；
Substrate of glass after cleaning is placed in pretreatment in the toluene solution of 3-aminopropyl triethoxysilane, cleans with ultra-pure water with toluene, ethanol successively after taking-up；
Step 2: the preparation of graphene oxide film
Czochralski method will be used to prepare graphene oxide film in the pretreated substrate of glass of step 1 immerses graphene oxide water solution；
Step 3: the preparation of graphene film
The substrate of glass that step 2 is covered with graphene oxide film uses hydrazine hydrate reduction to obtain described graphene film under vacuum environment.
Preferably, in described step 1, Piranha solution be by 98wt% concentrated sulphuric acid and 30wt% hydrogen peroxide by volume for the mixed solution of 7:3 ~ 3:1；Soak time is 0.5 ~ 4 hour.
Preferably, in described step 1, in the toluene solution of 3-aminopropyl triethoxysilane, the volumetric concentration of 3-aminopropyl triethoxysilane is 3%；Pretreatment time is 0.5 hour.
Preferably, in described step 2, the concentration of graphene oxide water solution is 0.1 ~ 2.0
mg/ml；Pull rate is 200 ~ 700nm/s.
Preferably, in described step 3, the recovery time is 24 ~ 72 hours.
Compared with prior art, present invention have the advantage that
(1) present invention lifting used technical operation is simple, with low cost, easily controllable.
(2) present invention plate graphene film is smooth, uniform.
(3) present invention is prone to plated graphene film is carried out functional modification.
(4) appearance of graphenic surface fold can be controlled by the simple pull rate that adjusts on the basis of the present invention.
Accompanying drawing explanation
Fig. 1 is the atomic force microscope figure not using the graphene oxide film obtained by czochralski process in comparative example.
Fig. 2 is the atomic force microscope figure of the graphene oxide film obtained by the embodiment of the present invention 1.
Specific implementation method
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Comparative example
(1) weighing 0.02 gram of graphene oxide to be dissolved in 20 milliliters of ultra-pure waters, supersound process obtains the graphene oxide water solution of uniform 1.0 milligrams every milliliter for 2 hours.
(2) measure the concentrated sulphuric acid of 21 milliliter 98% and the hydrogen peroxide of 9 milliliter 30% is formulated as Piranha solution, glass slide is inserted wherein etching and, after 2 hours, cleans with ultra-pure water with ethanol successively after taking-up.
(3) measure the toluene of 29 milliliters and the 3-aminopropyl triethoxysilane of 1 milliliter is joined for solution, the microscope slide after Piranha solution etches is inserted and wherein processes 30 minutes, clean with ultra-pure water with toluene, ethanol successively after taking-up.
(4) microscope slide after pretreated is inserted in prepared graphene oxide solution, take out and dry after soaking 5 hours.
(5) inserting in glass evacuated exsiccator by the substrate of glass being coated with graphene oxide film, instill evacuation after 2 ~ 3 hydrazine hydrates, reductase 12 took out after 4 hours.
In this example, the atomic force microscope figure of gained graphene oxide film is shown in Fig. 1.
Embodiment
1
(1) weighing 0.02 gram of graphene oxide to be dissolved in 20 milliliters of ultra-pure waters, supersound process obtains the graphene oxide water solution of uniform 1.0 milligrams every milliliter for 2 hours.
(2) measure the concentrated sulphuric acid of 21 milliliter 98% and the hydrogen peroxide of 9 milliliter 30% is formulated as Piranha solution, glass slide is inserted wherein etching and, after 2 hours, cleans with ultra-pure water with ethanol successively after taking-up.
(3) measure the toluene of 29 milliliters and the 3-aminopropyl triethoxysilane of 1 milliliter is joined for solution, the microscope slide after Piranha solution etches is inserted and wherein processes 30 minutes, clean with ultra-pure water with toluene, ethanol successively after taking-up.
(4) with the microscope slide after pretreated as substrate, in prepared graphene oxide solution, using the method for lifting plated film to prepare graphene oxide film, it is that 500 nanometers are per second that pull rate controls.
(5) inserting in glass evacuated exsiccator by the substrate of glass being coated with graphene oxide film, instill evacuation after 2 ~ 3 hydrazine hydrates, reductase 12 took out after 4 hours.
In this example, the atomic force microscope figure of gained graphene oxide film is shown in Fig. 2.
In Fig. 1, the height relief of film surface is at more than 20nm, and there is a large amount of continuous print, " mountain range " shape fold of stereovision distinctness；In Fig. 2, the height relief of film surface is at about 10nm, and protuberance is the most discontinuous.Comparison diagram 1, Fig. 2 two width atomic force microscope figure understand, and czochralski process can substantially suppress the appearance of fold on thin film, improves the flatness of plated graphene oxide film.
Embodiment
2
(1) weighing 0.03 gram of graphene oxide to be dissolved in 20 milliliters of ultra-pure waters, supersound process obtains the graphene oxide water solution of uniform 1.5 milligrams every milliliter for 3 hours.
(2) measure the concentrated sulphuric acid of 21 milliliter 98% and the hydrogen peroxide of 9 milliliter 30% is formulated as Piranha solution, glass slide is inserted wherein etching and, after 2 hours, cleans with ultra-pure water with ethanol successively after taking-up.
(3) measure the toluene of 29 milliliters and the 3-aminopropyl triethoxysilane of 1 milliliter is joined for solution, the microscope slide after Piranha solution etches is inserted and wherein processes 30 minutes, clean with ultra-pure water with toluene, ethanol successively after taking-up.
(4) with the microscope slide after pretreated as substrate, in prepared graphene oxide solution, using the method for lifting plated film to prepare graphene oxide film, it is that 250 nanometers are per second that pull rate controls.
(5) substrate of glass being coated with graphene oxide film is inserted in glass evacuated exsiccator, instill evacuation after 2 ~ 3 hydrazine hydrates, take out after reducing 48 hours.
In this example, the atomic force microscope figure of gained graphene oxide film is similar to Fig. 2.
Embodiment
3
(1) weighing 0.01 gram of graphene oxide to be dissolved in 20 milliliters of ultra-pure waters, supersound process obtains the graphene oxide water solution of uniform 0.5 milligram every milliliter for 1 hour.
(2) measure the concentrated sulphuric acid of 21 milliliter 98% and the hydrogen peroxide of 9 milliliter 30% is formulated as Piranha solution, glass slide is inserted wherein etching and, after 2 hours, cleans with ultra-pure water with ethanol successively after taking-up.
(3) measure the toluene of 29 milliliters and the 3-aminopropyl triethoxysilane of 1 milliliter is joined for solution, the microscope slide after Piranha solution etches is inserted and wherein processes 30 minutes, clean with ultra-pure water with toluene, ethanol successively after taking-up.
(4) with the microscope slide after pretreated as substrate, in prepared graphene oxide solution, using the method for lifting plated film to prepare graphene oxide film, it is that 700 nanometers are per second that pull rate controls.
(5) inserting in glass evacuated exsiccator by the substrate of glass being coated with graphene oxide film, instill evacuation after 2 ~ 3 hydrazine hydrates, reductase 12 took out after 4 hours.
In this example, the atomic force microscope figure of gained graphene oxide film is similar to Fig. 2.
Claims (5)
1. the method preparing smooth graphene film with czochralski method, it is characterised in that comprise the following steps:
Step 1: the pretreatment of substrate of glass
Substrate of glass is placed in Piranha solution immersion, cleans with ultra-pure water with ethanol successively after taking-up；
Substrate of glass after cleaning is placed in pretreatment in the toluene solution of 3-aminopropyl triethoxysilane, cleans with ultra-pure water with toluene, ethanol successively after taking-up；
Step 2: the preparation of graphene oxide film
Czochralski method will be used to prepare graphene oxide film in the pretreated substrate of glass of step 1 immerses graphene oxide water solution；
Step 3: the preparation of graphene film
The substrate of glass that step 2 is covered with graphene oxide film uses hydrazine hydrate reduction to obtain described graphene film under vacuum environment.
2. the method as claimed in claim 1 preparing smooth graphene film with czochralski method, it is characterised in that in step 1, Piranha solution be by 98wt% concentrated sulphuric acid and 30wt% hydrogen peroxide by volume for the mixed solution of 7:3 ~ 3:1；Soak time is 0.5 ~ 4 hour.
3. the method preparing smooth graphene film with czochralski method as claimed in claim 1, it is characterised in that in step 1, in the toluene solution of 3-aminopropyl triethoxysilane, the volumetric concentration of 3-aminopropyl triethoxysilane is 3%；Pretreatment time is 0.5 hour.
4. the method preparing smooth graphene film with czochralski method as claimed in claim 1, it is characterised in that in step 2, the concentration of graphene oxide water solution is 0.1 ~ 2.0 mg/ml；Pull rate is 200 ~ 700nm/s.
5. the method preparing smooth graphene film with czochralski method as claimed in claim 1, it is characterised in that in step 3, the recovery time is 24 ~ 72 hours.
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| CN201610273422.5A CN105948526A (en) | 2016-04-28 | 2016-04-28 | Method for preparing smooth graphene film by pulling method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107226719A (en) * | 2017-05-12 | 2017-10-03 | 华南理工大学 | The application of a kind of preparation method of graphene oxide membrane and its graphene oxide membrane of preparation in the dehydration of high concentration ethylene glycol solution |
| CN108314333A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of Electrostatic Absorption preparation method of Graphene glass |
| CN109022339A (en) * | 2017-06-08 | 2018-12-18 | 南京理工大学 | A kind of preparation method of the graphene film of surface modification orientated nano fibers |
| CN110027292A (en) * | 2019-04-23 | 2019-07-19 | 盐城师范学院 | A kind of preparation method of the antifog Graphene glass of waterproof |
| CN112939478A (en) * | 2021-01-14 | 2021-06-11 | 南昌大学 | Preparation method of porous film material for shielding terahertz waves |
| CN113336215A (en) * | 2020-03-02 | 2021-09-03 | 赵昆 | Preparation method and application of monodisperse hydrothermal carbon spheres |
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| CN102424532A (en) * | 2011-08-31 | 2012-04-25 | 燕山大学 | Preparation method for graphene transparent conductive film on glass substrate |
| CN102604714A (en) * | 2012-02-26 | 2012-07-25 | 南昌航空大学 | Method for preparing graphene lubrication film |
| CN103489532A (en) * | 2013-09-03 | 2014-01-01 | 东华大学 | Czochralski method for preparing graphene transparent conducting thin films |
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2016
- 2016-04-28 CN CN201610273422.5A patent/CN105948526A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424532A (en) * | 2011-08-31 | 2012-04-25 | 燕山大学 | Preparation method for graphene transparent conductive film on glass substrate |
| CN102604714A (en) * | 2012-02-26 | 2012-07-25 | 南昌航空大学 | Method for preparing graphene lubrication film |
| CN103489532A (en) * | 2013-09-03 | 2014-01-01 | 东华大学 | Czochralski method for preparing graphene transparent conducting thin films |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107226719A (en) * | 2017-05-12 | 2017-10-03 | 华南理工大学 | The application of a kind of preparation method of graphene oxide membrane and its graphene oxide membrane of preparation in the dehydration of high concentration ethylene glycol solution |
| CN107226719B (en) * | 2017-05-12 | 2021-01-19 | 华南理工大学 | Preparation method of graphene oxide film and application of graphene oxide film prepared by preparation method in dehydration of high-concentration glycol solution |
| CN109022339A (en) * | 2017-06-08 | 2018-12-18 | 南京理工大学 | A kind of preparation method of the graphene film of surface modification orientated nano fibers |
| CN109022339B (en) * | 2017-06-08 | 2021-05-07 | 南京理工大学 | Preparation method of graphene film with surface modified oriented nanofibers |
| CN108314333A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of Electrostatic Absorption preparation method of Graphene glass |
| CN110027292A (en) * | 2019-04-23 | 2019-07-19 | 盐城师范学院 | A kind of preparation method of the antifog Graphene glass of waterproof |
| CN113336215A (en) * | 2020-03-02 | 2021-09-03 | 赵昆 | Preparation method and application of monodisperse hydrothermal carbon spheres |
| CN112939478A (en) * | 2021-01-14 | 2021-06-11 | 南昌大学 | Preparation method of porous film material for shielding terahertz waves |
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Application publication date: 20160921 |