CN103663437A - Graphene quantum dot prepared by virtue of magnetron sputtering technology - Google Patents
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 48
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Abstract
The invention relates to a method of preparing a graphene quantum dot. The method is mainly characterized by comprising the following steps: preparing a graphene mixed thin film by virtue of a radio-frequency magnetron sputtering technology; diluting by use of diluted hydrochloric acid; filtering and extracting by virtue of a dialysis membrane to obtain the graphene quantum dot with higher quantum yield. The method is very simple to operate and environment-friendly, and the quantum dot obtained is very high in quantum yield. The particle size of the graphene quantum dot can be adjusted by changing the target material mixing proportion and the sputtering power, so that the graphene quantum dot has potential for large-scale preparation and wide application prospect.
Description
Technical field
This invention relates to a kind of novel method of preparing graphene quantum dot, and adopting cheap Graphite Powder 99 and simple oxide is raw material, utilizes magnetron sputtering technique room temperature to prepare monodispersity good, and has the method for the graphene quantum dot of the characteristics of luminescence.
Background technology
Graphene (Graphene) is a kind of Novel carbon material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape crystalline structure.Since two-dimentional Graphene after successfully obtaining for 2004, caused the research boom of people to this novel material.This two-dimensional material has special electric property (as electronics mobility of quantum hall effect abnormal under good electroconductibility, normal temperature, superelevation etc.), and (face conductance is 3000wm to good heat conductance
-1k
-1) and higher physical strength (face intensity is 1060Gpa), broad stopband can be according to the features such as the random cutting of demand of its device, make its research in fields such as unit molecule gas detection, unicircuit, transparency conductive electrode, biological device, ultracapacitor and power electric couplers obtain new progress, there is important theoretical investigation and be worth and wide application prospect.
As up-to-date member's quantum dot in carbon family, made up to a great extent the defect of Graphene, become one of study hotspot recently.Graphene quantum dot is the another Novel Carbon Nanomaterials after soccerballene and carbon nanotube, he is that size is less than 10nm and has the spherical fluorescent carbon nano particle of good dispersion, it not only has the fluorescence quantum yield comparing favourably with conventional semiconductors quantum dot (as CdS, CdSe and nucleocapsid structure thereof), and there is excellent biocompatibility, asepsis environment-protecting is easy to the advantages such as surface-functionalized.The graphene quantum dot that has quantum size has from blue light to the ruddiness continuous fluorescence characteristics of luminescence, and good stability, resistance to bleaching, without features such as optical flares.
Current preparation method has multiple, but can be divided into generally two large classes and from the bottom to top from top to bottom.From organism, to obtain thin small and scattered graphene quantum dot by means such as chemical oxidation, microwave treatment, organic charings from bottom to up, the raw material of selecting due to these class methods is Nonrenewable energy resources and needs strict treatment process, so the popularization that is unfavorable for accomplishing scale production; Class methods are to utilize arc-over, laser and electrochemical means directly from the carbon material of bulk or carbon nanotube, to obtain from top to bottom, these class methods often need strict experiment condition or the special energy, cost is high, and the fluorescence quantum yield of acquisition graphene quantum dot is less.
Through the existing retrieval of preparing graphene quantum dot technology is found, be conventionally divided into physical preparation method and chemical synthesis process.The method that the people such as Pan use hydro-thermal to shear micron order graphene sheet layer has first been prepared the graphene quantum dot of different size.The people such as Li use the method that electrochemistry is cut out to prepare size homogeneous, monodispersed graphene quantum dot.The people such as Liu use the technology of chemical stripping graphene oxide, then utilize hydrazine hydrate reduction to obtain the graphene quantum dot of hyperfluorescenceZeng Yongminggaoyingguang.The people such as Dong utilize the chemical synthesis process of pyrolysis citric acid to prepare the graphene quantum dot that is of a size of 15nm, have also observed the phenomenon of graphene quantum dot photoluminescence.Graphene quantum dot prepared by aforesaid method, the fluorescence of graphene quantum dot own is very poor, need to as (PEG1500N, Edamine, oleyl amine etc.), further process by organism, just can obtain the good graphene quantum dot of fluorescence.Technical information through inquiry this area, has not yet to see the novel method of utilizing radiofrequency magnetron sputtering technology (RF Magnetron Sputtering) to prepare graphene quantum dot.
Summary of the invention
The object of the present invention is to provide a kind of radiofrequency magnetron sputtering technology to prepare the method for graphene quantum dot, it is starting material that the method be take the hybrid target of cheap graphite and simple oxide, have that cost is low, technique is simple, be easy to the advantages such as industrialization production, can obtain high-density, large ratio of height to width, size uniform, graphene quantum dot that controllability is good, realize by changing growth conditions utilization and had the radiofrequency magnetron sputtering technology of maturation process to prepare good quantum dot.
In order to achieve the above object, technical scheme of the present invention comprises the following steps:
(1) rf magnetron sputtering target used is the mixing target of graphite and simple oxide (Ga203, ZnO, Al203, CuO etc.), adopting high purity graphite and simple oxide powder is raw material, by mixing, grinding, sintering process prepare the hybrid ceramic target of different graphite ratios.Wherein graphite proportion is 2-90mol%;
(2) described glass substrate needs effects on surface in advance to process, concrete grammar: use successively acetone, alcohol, deionized water ultrasonic cleaning 8-12 minute, tentatively remove substrate surface organism and inorganics impurity, high pure nitrogen dries up; Adopt ion beam cleaning rifle to clean glass substrate surface, glass substrate is put into ion beam sputtering indoor, adopt the Ar+ that ion beam sputtering technology utilization ionizes out to clean glass substrate surface, further remove surface particle and impurity particle;
(3) adopt the grow film sample of different graphite blending ratios of radiofrequency magnetron sputtering technology in clean glass substrate.Glass substrate and hybrid ceramic target are put into magnetron sputtering equipment, to being mixed with the ceramic target of different graphite ratios, carry out sputter, at the film sample of deposition on glass 20-100nm;
(4) film sample of above-mentioned preparation is put into dilute hydrochloric acid solution, after Film Fractionation, utilizing molecular weight is that 1000 dialysis membrane filters out halogen.
Graphite and simple oxide (Ga that the described ceramic target starting material of step of the present invention (1) are purity 5N
2o
3, ZnO, Al
2o
3, CuO) powder, according to different content of graphite (2-90mol%), put into ball grinder after taking respectively and mix, powder total mass amounts to 80g; Treat that ball milling is complete, in mixed powder, add 2-5ml polyvinyl alcohol (PVA) fully to mix as adhesion agent; Under the pressure of 30-50MPa pressurize 3-5 minute by target compression moulding; Target sintering temperature parameter: per minute intensification 1-2 ℃, be warming up to 1000-1100 ℃, be incubated cooling naturally after 3-5 hour.
When the described ion beam cleaning rifle of step of the present invention (2) cleans glass surface, first glass substrate is put into ion beam chamber, after being extracted into high vacuum, pass into argon gas, heater current adds to 4A to tungsten filament preheating, after completing, preheating carries out pre-sputtering, its parameter is that beam intensity 8-12mA, sparking voltage are 60-80V, and operating air pressure is 4 * 10
-2pa; Sample is moved to corresponding target position after pre-sputtering completes glass substrate surface is cleaned, guarantee, under condition that pre-sputtering experiment condition is constant, substrate surface to be cleaned to 50-60 second,
Step of the present invention (3) is described while utilizing the film sample that rf magnetron sputtering prepares different graphite blending ratios, distance between ceramic target and glass substrate is 40-80mm, background air pressure is 1 * 10-4mTorr, passing into high-purity argon gas is sputter gas, operating pressure is 0.5-2mTorr, sputtering power is 20-100W, and growth time is 5-20 minute;
The described graphene quantum dot place dispersion agent of step of the present invention (4) is salt aqueous acid, and the dialysis membrane that is 1000 by molecular weight filters out the halogen in solution,
The critical nature of the important graphene quantum dot that the present invention is obtained is measured: do transmission electron microscope and detect.Result shows that graphene quantum dot is dispersion state, and the grain size of Graphene is mainly distributed in 8-12nm; The fluorescent emission nature examination of the graphene quantum dot that the present invention is obtained: the ultraviolet lamp that is 365nm with wavelength irradiates graphene quantum dot solution example, can obviously observe strong blue light; With spectrophotofluorometer, detect, result shows that graphene quantum dot has multiple VISIBLE LIGHT EMISSION characteristic.
Product prepared by preparation technology of the present invention and the method has the following advantages:
(1) monodispersity: the median size of graphene quantum dot prepared by the present invention is 10nm, and it is narrow that quantum dot is evenly distributed size;
(2) technique is simple: the relatively traditional quantum dot preparation technology of the present invention has advantages of simple to operate, and preparation process only relates to two operating process;
(3) quantum point grain diameter controllability: the median size of graphene quantum dot prepared by the present invention can be by regulating blending ratio and sputtering power to reach;
(4) be easy to batch production: because rf magnetron sputtering equipment can amplify according to the scale of suitability for industrialized production, so can be for industrial mass manufacture;
(5) preparation technology's environmental protection: the equal nontoxicity of simple oxide powder that the present invention uses, chemical reagent used is cheap, nontoxic hydrochloric acid dilute solution;
Therefore (6) the good characteristics of luminescence: graphene quantum dot prepared by the present invention has less size, and quantum confined effect is remarkable, sends the light of green glow or other colors in UV-light, purple light, blue-light excited lower meeting;
(7) have concurrently water-soluble: therefore Graphene dispersion agent of the present invention is salt aqueous acid, and these dispersion agents have the advantages that to dissolve each other with water, alcohol, ether etc., can be by graphene quantum dot of the present invention for water-soluble system.
Based on above advantage, by present method, obtain graphene quantum dot material, can be widely used in the aspects such as photoelectron, the bioluminescence in the fields such as physics, chemistry, biology, material, the research of matrix material and application.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the graphene quantum dot of preparation.
Fig. 2 is the fluorescence emission spectrogram of the graphene quantum dot of preparation.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited only to following embodiment.
Embodiment 1: a kind of preparation method of graphene quantum dot comprises the following steps:
(1) by quality, be m
cthe powdered graphite of=0.24g and quality are m
othe ZnO powder mixing and ball milling of=79.76g (graphite 2mol%) is treated that ball milling is complete and is added 3ml polyvinyl alcohol (PVA) to stir as adhesion agent in mixed powder; Under the pressure of 40MPa, pressurize 4 minutes is by target compression moulding; Target sintering temperature parameter: per minute heats up 1.5 ℃, is incubated 4 hours after being warming up to 1100 ℃.
(2) treat to put into magnetron sputtering chamber after glass substrate is cleaned, the distance between ceramic target and glass substrate is 60mm, and background air pressure is 1 * 10
-4mTorr, passing into high-purity argon gas is sputter gas, and operating pressure is 0.5mTorr, and sputtering power is 40W, and growth time is 15 minutes.
The film sample of above-mentioned preparation is put into hydrochloric acid dilute solution, and after Film Fractionation, utilizing molecular weight is that 1000 dialysis membrane filters out halogen.
Embodiment 2: similar to Example 1, its difference is to change ZnO powder into Ga
2o
3.
Embodiment 3: similar to Example 1, its difference is to change ZnO powder into Al
2o
3.
Embodiment 4: similar to Example 1, its difference is to change ZnO powder into CuO.
Embodiment 5: similar to Example 1, its difference is to change the powdered graphite quality taking into 0.62g (graphite 5mol%).
Embodiment 6: similar to Example 1, its difference is to change the powdered graphite quality taking into 1.29g (graphite 10mol%).
Embodiment 7: similar to Example 1, its difference is to change the powdered graphite quality taking into 2.86g (graphite 20mol%).
Embodiment 8: similar to Example 1, its difference is to change the powdered graphite quality taking into 10.31g (graphite 50mol%).
Embodiment 9: similar to Example 1, its difference is to change the powdered graphite quality taking into 55.47g (graphite 70mol%).
Embodiment 10: similar to Example 1, its difference is to change the powdered graphite quality taking into 68.08g (graphite 90mol%).
Claims (4)
1. utilize radio frequency magnetron sputtering method to prepare a method for graphene quantum dot, comprise the following steps:
(1) graphite-oxide ceramics target is synthetic: by quality, be m
cthe powdered graphite of=0.24g and quality are m
othe ZnO powder mixing and ball milling of=79.76g (graphite 2mol%), treats that ball milling is complete, in mixed powder, adds 3ml polyvinyl alcohol (PVA) to stir as adhesion agent; Under the pressure of 40MPa, pressurize 4 minutes is by target compression moulding; Target sintering temperature parameter: per minute heats up 1.5 ℃, is incubated 4 hours after being warming up to 1100 ℃.
(2) preparation of graphene quantum dot: gained ceramic target in (1) is put into magnetron sputtering chamber, utilize high-purity argon gas to bombard target as sputter gas, the distance between ceramic target and glass substrate is 60mm, and background air pressure is 1 * 10
-4mTorr, operating pressure is 0.5mTorr, and sputtering power is 40W, and growth time is 15 minutes.Utilize transmission electron microscope (TEM) to observe the structural performance of the graphene quantum dot of preparation, utilize fluorescent spectrophotometer measuring fluorescence spectrum.
2. according to preparation method claimed in claim 1, it is characterized in that: oxide compound kind (ZnO) on-fixed in step (1) can be other simple oxide (Ga
2o
3, Al
2o
3, CuO).
3. according to preparation method claimed in claim 1, it is characterized in that: graphite blending ratio (2mol%) on-fixed in step (1), graphite proportion all can within the scope of 2-90mol%.
4. according to preparation method claimed in claim 1, it is characterized in that: sputtering power (40W) the on-fixed of target in step (2), sputtering power within the scope of 20-200W all can, by regulating sputtering power can regulate and control the size of quantum dot.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016045045A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene quantum dots |
| RU2753399C1 (en) * | 2020-11-26 | 2021-08-16 | Акционерное общество "Концерн "Созвездие" | Method for creating quantum dots for element base of radio engineering |
| CN113421778A (en) * | 2021-06-21 | 2021-09-21 | 青岛理工大学 | Flexible micro super capacitor and manufacturing method thereof |
| CN114506843A (en) * | 2022-02-25 | 2022-05-17 | 电子科技大学 | Method for rapidly preparing graphene film on non-metal substrate |
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2014
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Patent Citations (4)
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| JPS63210006A (en) * | 1987-02-25 | 1988-08-31 | Meidensha Electric Mfg Co Ltd | Formation of thin amorphous carbon film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016045045A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene quantum dots |
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| CN113421778A (en) * | 2021-06-21 | 2021-09-21 | 青岛理工大学 | Flexible micro super capacitor and manufacturing method thereof |
| CN113421778B (en) * | 2021-06-21 | 2022-10-21 | 青岛理工大学 | Flexible micro super capacitor and manufacturing method thereof |
| CN114506843A (en) * | 2022-02-25 | 2022-05-17 | 电子科技大学 | Method for rapidly preparing graphene film on non-metal substrate |
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