CN104843681A - Macroscopic quantity preparation method of dimension-ontrollable graphene quantum dots - Google Patents
Macroscopic quantity preparation method of dimension-ontrollable graphene quantum dots Download PDFInfo
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Abstract
The invention discloses a macroscopic quantity preparation method of dimension-ontrollable graphene quantum dots. The method comprises the following steps: 1, depositing a catalyst metal film on a substrate; 2, etching the metal film to prepare a nanometer graphical metal catalyst; 3, placing the substrate in a chemical vapor deposition reaction chamber, and introducing a carbon source and a reducing gas at a high temperature to prepare graphene quantum dots on the nanometer metal catalyst; and 4, cooling in reducing atmosphere until room temperature, taking out the substrate, and placing the substrate in a nanometer metal etching solution to obtain the quantum dots suspending in the solution. A CVD (chemical vapor deposition) process is used to prepare the graphene quantum dots in order to realize the macroscopic quantity preparation of the quantum dots; and an etching process is adopted to obtain the nanometer graphical metal as the catalyst, and the dimension of the catalyst is controlled to realize accurate controllability of the dimension of the graphene quantum dots, so the yield is improved, and the cost is reduced.
Description
Technical field
The present invention relates to a kind of graphene preparation method, particularly relate to a kind of graphene quantum dot preparation method, be applied to quantum dot synthesis technical field.
Background technology
Graphene quantum dot (Graphene quantum dot) is the nano material of accurate zero dimension, and the motion of its internal electron in all directions is all limited to, so quantum confinement effect is remarkable especially, has the character of many uniquenesses.Graphene quantum dot has important potential application in fields such as biology, medical science, material, semiconductor devices.Can monomolecular sensor be realized, also may expedite the emergence of subminiature transistor or the chip communication utilizing semiconductor laser to carry out and be used for making chemical sensor, solar cell, medical imaging apparatus or nanoscale circuit etc.
The synthetic method of graphene quantum dot is mainly divided into two large classes: from top to bottom and bottom-to-top method.Bottom-to-top method is, by the method for physics or chemistry, large-sized graphene platelet is cut into undersized graphene quantum dot, comprises hydrothermal method, electrochemical method and chemical method and peels off the methods such as carbon fiber; Bottom-to-top method prepares graphene quantum dot as precursor by series of chemical using small molecules, mainly contains ultrasonic method and microwave method, solution chemical method.The method that other is comparatively special, as electron beam lithography and ruthenium catalysis soccerballene open cage method, required harsh preparation condition limits the popularization of these methods to a great extent.Therefore, a kind of simple graphene quantum dot preparation in macroscopic quantity method is found extremely urgent.
Summary of the invention
In order to solve prior art problem, the object of the invention is to the deficiency overcoming prior art existence, a kind of preparation in macroscopic quantity method of controlled dimensions graphene quantum dot is provided, the etching commonly used by industry realizes the preparation of nano patterning metal catalyst, continue to use classical CVD and prepare graphene quantum dot, preparation is simple, and can be controlled the size of graphene quantum dot by the adjustment degree of graphical size, improve productive rate, reduce cost.
Create object for reaching foregoing invention, the present invention adopts following technical proposals:
A preparation in macroscopic quantity method for controlled dimensions graphene quantum dot, comprises the steps:
A. prepare metallic film at the deposition on substrate metal catalyst of cleaning, the thickness of metallic film is less than 50 nanometers; Metal catalyst preferably adopts the alloy nano particle of any one metal in copper, nickel, platinum and gold or any several metal; The deposition method preparing described metallic film is preferably thermal evaporation, magnetron sputtering or electron beam evaporation method; Described substrate is preferably sapphire, silicon chip GaN epitaxy sheet, silicon chip, sheet glass, alumina wafer, tin indium oxide sheet, mixes fluorine oxidation zinc metal sheet or flexible substrate;
B. be etched in the metallic film prepared in described step a, obtained nano patterned metal catalyst particles, the characteristic dimension of obtained patterned metal granules of catalyst is less than 60nm; The shape of the described nano patterned metal catalyst particles of preparation is preferably any one or any one the combination in right cylinder, square, rectangular parallelepiped, tetrahedron, terrace with edge and round platform;
C. substrate is placed in chemical vapor deposition reaction chamber, carbon source and reducing gas is passed under 300-1100 DEG C of condition, on the metallic catalyst particle prepared in described step b, load generates graphene quantum dot, and the graphene quantum dot prepared by control has the monatomic graphite linings of 1-3 layer; Described carbon source adopts gaseous carbon sources, specifically preferably adopts methane, acetylene or ethene; Or carbon source adopts solid carbon source, specifically preferably adopts urea, grass or biscuit; Or carbon source at least preferably adopts stupid liquid carbon source; Chemical gas-phase deposition system preferably adopts hot CVD stove, PECVD stove or microwave-assisted CVD stove; Chemical gas-phase deposition system preferably also includes preheating oven;
D. the substrate attachment prepared in described step c being generated graphene quantum dot is cooled to room temperature in reducing atmosphere, take out substrate and be placed in nano metal etching liquid, after metal catalyst particles is dissolved completely, graphene quantum dot and substrate separation, obtain the graphene quantum dot be suspended in solution, again after separation and purification, i.e. obtained graphene quantum dot; Etching liquid preferably adopts any one or any one the mixed solution in hydrochloric acid, sulfuric acid, iron nitrate, ammonium persulphate, hydrofluoric acid, Glacial acetic acid and nitric acid, and etching technics is one or multi-channel etching.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the present invention by the characteristic dimension controlling nano patterned metal catalyst control graphene quantum dot size, simply controlled;
2. the present invention adopts CVD to realize the preparation in macroscopic quantity of graphene quantum dot, and productive rate is high, and cost is low;
3. present invention employs conventional etching technics, simple for process, be easy to promote, and have the space of further adjust size along with the development of lithographic technique.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation in macroscopic quantity method of preferred embodiment of the present invention controlled dimensions graphene quantum dot.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
In the present embodiment, see Fig. 1, the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot, comprises the steps:
A. on silicon chip after cleaning by copper that the method deposition 20nm of thermal evaporation is thick;
B. etch copper film, realizing spacing is 30nm, is of a size of the preparation of the patterned copper of 30*30nm;
C. step b gained substrate is placed in PECVD stove, to be evacuated in reaction chamber below pressure drop to 0.1 pascal, passing into methane flow is 10sccm, hydrogen 10sccm, be warming up to 500 DEG C, be incubated 10 minutes under pressure 200 pascal, cut off methane, under the condition that hydrogen flowing quantity is constant, be cooled to room temperature;
D. take out the combination of step c gained silicon chip/copper/graphene quantum dot, be placed in the iron nitrate solution that concentration is 0.1g/ml, after metal catalyst copper dissolves completely, separation and purification completes the preparation of graphene quantum dot.
In the present embodiment, adopt nano-nickel powder as the catalyzer of graphene quantum dot preparation in macroscopic quantity, adopt the nano patterned catalyzer of etching metallic film gained, the simple preparation in macroscopic quantity of graphene quantum dot at low temperature is achieved by PECVD, adopt etching technics to obtain nano patterned metal as catalyzer, realized the controllable precise of graphene quantum dot size by the size controlling catalyzer.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; multiple change can also be made according to the object of innovation and creation of the present invention; change, the modification made under all spirit according to technical solution of the present invention and principle, substitute, combination, to simplify; all should be the substitute mode of equivalence; as long as goal of the invention according to the invention; only otherwise deviate from know-why and the inventive concept of the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot of the present invention, all protection scope of the present invention is belonged to.
Claims (9)
1. a preparation in macroscopic quantity method for controlled dimensions graphene quantum dot, is characterized in that, comprise the steps:
A. prepare metallic film at the deposition on substrate metal catalyst of cleaning, the thickness of metallic film is less than 50 nanometers;
B. be etched in the metallic film prepared in described step a, obtained nano patterned metal catalyst particles, the characteristic dimension of obtained patterned metal granules of catalyst is less than 60nm;
C. substrate is placed in chemical vapor deposition reaction chamber, carbon source and reducing gas is passed under 300-1100 DEG C of condition, on the metallic catalyst particle prepared in described step b, load generates graphene quantum dot, and the graphene quantum dot prepared by control has the monatomic graphite linings of 1-3 layer;
D. the substrate attachment prepared in described step c being generated graphene quantum dot is cooled to room temperature in reducing atmosphere, take out substrate and be placed in nano metal etching liquid, after metal catalyst particles is dissolved completely, graphene quantum dot and substrate separation, obtain the graphene quantum dot be suspended in solution, again after separation and purification, i.e. obtained graphene quantum dot.
2. the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot according to claim 1, it is characterized in that: in described step b, the shape of the described nano patterned metal catalyst particles of preparation is any one or any one the combination in right cylinder, square, rectangular parallelepiped, tetrahedron, terrace with edge and round platform.
3. the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot according to claim 1 or 2, it is characterized in that: in described step a, any one metal in described metal catalyst employing copper, nickel, platinum and gold or the alloy nano particle of any several metal.
4. the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot according to claim 1 or 2, it is characterized in that: in described step a, the deposition method preparing described metallic film is thermal evaporation, magnetron sputtering or electron beam evaporation method.
5. the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot according to claim 1 or 2, it is characterized in that: in described step a, described substrate is sapphire, silicon chip GaN epitaxy sheet, silicon chip, sheet glass, alumina wafer, tin indium oxide sheet, mix fluorine oxidation zinc metal sheet or flexible substrate.
6. the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot according to claim 1 or 2, is characterized in that: in described step c, and described carbon source adopts gaseous carbon sources, specifically adopts methane, acetylene or ethene; Or carbon source adopts solid carbon source, specifically adopts urea, grass or biscuit; Or carbon source at least adopts stupid liquid carbon source.
7. the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot according to claim 1 or 2, is characterized in that: in described step c, and chemical gas-phase deposition system adopts hot CVD stove, PECVD stove or microwave-assisted CVD stove.
8. the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot according to claim 7, is characterized in that: described chemical gas-phase deposition system also includes preheating oven.
9. the preparation in macroscopic quantity method of controlled dimensions graphene quantum dot according to claim 1 or 2, it is characterized in that: in described steps d, etching liquid adopts any one or any one the mixed solution in hydrochloric acid, sulfuric acid, iron nitrate, ammonium persulphate, hydrofluoric acid, Glacial acetic acid and nitric acid, and etching technics is one or multi-channel etching.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105568251A (en) * | 2016-01-06 | 2016-05-11 | 中国科学院物理研究所 | Method for growing graphene on insulating substrate |
| CN107012443A (en) * | 2017-04-16 | 2017-08-04 | 北京工业大学 | A kind of process of the graphical direct growth graphene of dielectric substrate |
| CN107098340A (en) * | 2017-06-16 | 2017-08-29 | 青岛河澄知识产权有限公司 | A kind of preparation method of graphene quantum dot dispersion |
| CN109824039A (en) * | 2019-03-26 | 2019-05-31 | 宁波大学 | A method of doped graphene is prepared using doped graphene quantum dot as nucleation point |
| WO2019130353A1 (en) | 2017-12-27 | 2019-07-04 | Log 9 Materials Scientific Private Limited | System and method for synthesis of graphene quantum dots |
| CN111470493A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Preparation method and application of graphene quantum dots |
| CN112517044A (en) * | 2020-12-22 | 2021-03-19 | 盐城工学院 | Carbon nitride quantum dot/oxide nanofiber composite photocatalytic material and preparation method thereof |
| CN113912050A (en) * | 2020-07-09 | 2022-01-11 | Tcl科技集团股份有限公司 | Graphene quantum dot and processing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910349A (en) * | 2014-03-13 | 2014-07-09 | 吉林大学 | Method of preparing nitrogen-doped oriented bamboo-like carbon nanotube/graphene composite metal oxide |
| CN103981507A (en) * | 2014-05-21 | 2014-08-13 | 电子科技大学 | Graphene preparation method |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910349A (en) * | 2014-03-13 | 2014-07-09 | 吉林大学 | Method of preparing nitrogen-doped oriented bamboo-like carbon nanotube/graphene composite metal oxide |
| CN103981507A (en) * | 2014-05-21 | 2014-08-13 | 电子科技大学 | Graphene preparation method |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568251A (en) * | 2016-01-06 | 2016-05-11 | 中国科学院物理研究所 | Method for growing graphene on insulating substrate |
| CN107012443A (en) * | 2017-04-16 | 2017-08-04 | 北京工业大学 | A kind of process of the graphical direct growth graphene of dielectric substrate |
| CN107012443B (en) * | 2017-04-16 | 2019-07-12 | 北京工业大学 | A kind of insulating substrate graphically directly grows the process of graphene |
| CN107098340A (en) * | 2017-06-16 | 2017-08-29 | 青岛河澄知识产权有限公司 | A kind of preparation method of graphene quantum dot dispersion |
| CN107098340B (en) * | 2017-06-16 | 2019-04-19 | 青岛大学 | A kind of preparation method of graphene quantum dot dispersion |
| WO2019130353A1 (en) | 2017-12-27 | 2019-07-04 | Log 9 Materials Scientific Private Limited | System and method for synthesis of graphene quantum dots |
| EP3732130A4 (en) * | 2017-12-27 | 2021-10-27 | Log 9 Materials Scientific Private Limited | System and method for synthesis of graphene quantum dots |
| CN109824039A (en) * | 2019-03-26 | 2019-05-31 | 宁波大学 | A method of doped graphene is prepared using doped graphene quantum dot as nucleation point |
| CN111470493A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Preparation method and application of graphene quantum dots |
| CN113912050A (en) * | 2020-07-09 | 2022-01-11 | Tcl科技集团股份有限公司 | Graphene quantum dot and processing method thereof |
| CN113912050B (en) * | 2020-07-09 | 2023-11-14 | Tcl科技集团股份有限公司 | Graphene quantum dot and processing method thereof |
| CN112517044A (en) * | 2020-12-22 | 2021-03-19 | 盐城工学院 | Carbon nitride quantum dot/oxide nanofiber composite photocatalytic material and preparation method thereof |
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