CN103663437B - Magnetron sputtering technique is utilized to prepare graphene quantum dot - Google Patents
Magnetron sputtering technique is utilized to prepare graphene quantum dot Download PDFInfo
- Publication number
- CN103663437B CN103663437B CN201310518141.8A CN201310518141A CN103663437B CN 103663437 B CN103663437 B CN 103663437B CN 201310518141 A CN201310518141 A CN 201310518141A CN 103663437 B CN103663437 B CN 103663437B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- graphene quantum
- magnetron sputtering
- target
- utilize
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 239000002096 quantum dot Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000001755 magnetron sputter deposition Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000004544 sputter deposition Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000502 dialysis Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 25
- 239000010439 graphite Substances 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000002189 fluorescence spectrum Methods 0.000 claims 1
- 239000011224 oxide ceramic Substances 0.000 claims 1
- 229910052574 oxide ceramic Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010884 ion-beam technique Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001659 ion-beam spectroscopy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- -1 bioluminescence Substances 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical group [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229950011333 edamine Drugs 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
The present invention relates to a kind of method preparing graphene quantum dot.The principal character of this method is: radiofrequency magnetron sputtering technology is prepared Graphene mixed film, filtered purify through diluted hydrochloric acid dissolution, dialysis membrane, obtains the graphene quantum dot with the sub-productive rate of higher amount.This method operation is very simple, and environmentally friendly, the quantum dot quantum productive rate obtained is very high, and graphene quantum dot grain size can be regulated by change target blending ratio and sputtering power, has extensive preparation potentiality and broad prospect of application.
Description
Technical field
This invention relates to a kind of novel method preparing graphene quantum dot, adopts cheap Graphite Powder 99 and simple oxide to be raw material, utilizes magnetron sputtering technique room temperature to prepare monodispersity good, and have the method for the graphene quantum dot of the characteristics of luminescence.
Background technology
Graphene (Graphene) is by a kind of Novel carbon material of monolayer carbon atom tightly packed one-tenth bi-dimensional cellular shape crystalline structure.After two-dimensional graphene successfully obtained in 2004, cause the research boom of people to this novel material.This two-dimensional material has special electric property (electron mobility etc. as quantum hall effect abnormal under good electroconductibility, normal temperature, superelevation), and (face conductance is 3000wm to good heat conductance
-1k
-1) and higher physical strength (face intensity is 1060Gpa), broad stopband can according to features such as the random cuttings of demand of its device, make it achieve new progress in the research in the fields such as monomolecular gases detection, unicircuit, transparency conductive electrode, biological devices, ultracapacitor and stress-electric coupling device, there is important theoretical investigation and be worth and wide application prospect.
As member's quantum dot up-to-date in carbon family, compensate for the defect of Graphene to a great extent, 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 compared 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 advantage such as surface-functionalized.The graphene quantum dot having 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 and from the bottom to top two large classes generally from top to bottom.From organism, obtain carefully small and scattered graphene quantum dot by means such as chemical oxidation, microwave treatment, organic charings from bottom to up, raw material due to such method selection is Nonrenewable energy resources and needs strict treatment process, so be unfavorable for popularization of accomplishing scale production; Class methods utilize arc-over, laser and electrochemical means directly to obtain from the carbon material of bulk or carbon nanotube from top to bottom, these class methods often need strict experiment condition or the special energy, cost is high, and the fluorescence quantum yield obtaining graphene quantum dot is less.
Through finding the existing retrieval preparing graphene quantum dot technology, be usually 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 prepared the graphene quantum dot of different size.The method that the people such as Li use electrochemistry to cut out has prepared size uniformity, 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 the Dong graphene quantum dot being of a size of 15nm that utilized the chemical synthesis process of pyrolysis citric acid to prepare, also been 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, needs to process further as (PEG1500N, Edamine, oleyl amine etc.) by organism, just can obtain the good graphene quantum dot of fluorescence.Through inquiring about the technical information of this area, have not yet to see the novel method utilizing radiofrequency magnetron sputtering technology (RFMagnetronSputtering) to prepare graphene quantum dot.
Summary of the invention
A kind of radiofrequency magnetron sputtering technology is the object of the present invention is to provide to prepare the method for graphene quantum dot, the method with the hybrid target of cheap graphite and simple oxide for starting material, have that cost is low, technique is simple, be easy to the advantages such as industrialization production, high-density, large ratio of height to width, size uniform, graphene quantum dot that controllability is good can be obtained, achieve and utilize have the radiofrequency magnetron sputtering technology of maturation process to prepare good quantum dot by changing growth conditions.
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, Al2O3, CuO etc.), high purity graphite and simple oxide powder is adopted to be raw material, by the hybrid ceramic target mixing, grind, sintering process prepares different graphite ratio.Wherein graphite proportion is 2-90mol%;
(2) described glass substrate needs effects on surface process in advance, concrete grammar: use acetone, alcohol, deionized water ultrasonic cleaning 8-12 minute successively, preliminary removing substrate surface organism and inorganic contaminants, and high pure nitrogen dries up; Adopt ion beam cleaning rifle cleaning glass substrate surface, glass substrate is put into ion beam sputtering indoor, employing ion beam sputtering technology utilizes the Ar+ ionized out to clean glass substrate surface, removing surface particle and impurity particle further;
(3) adopt radiofrequency magnetron sputtering technology in clean glass substrate, grow the film sample of different graphite blending ratio.Glass substrate and hybrid ceramic target are put into magnetron sputtering equipment, the ceramic target being mixed with different graphite ratio is sputtered, 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, utilize molecular weight be 1000 dialysis membrane halogen is filtered out.
The described ceramic target starting material of step of the present invention (1) are graphite and the simple oxide (Ga of purity 5N
2o
3, ZnO, Al
2o
3, CuO) powder, put into ball grinder after taking respectively according to different content of graphite (2-90mol%) and mix, powder total mass amounts to 80g; Treat that ball milling is complete, in mixed powder, add 2-5ml polyvinyl alcohol (PVA) fully 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 DEG C, is warming up to 1000-1100 DEG C, is incubated Temperature fall after 3-5 hour.
When ion beam cleaning rifle described in step of the present invention (2) cleans glass surface, first glass substrate is put into ion beam chamber, argon gas is passed into after being extracted into high vacuum, heater current adds to 4A to tungsten filament preheating, pre-sputtering is carried out after preheating completes, its parameter is beam intensity 8-12mA, sparking voltage is 60-80V, and operating air pressure is 4 × 10
-2pa; Sample is moved to corresponding target position after pre-sputtering completes to clean glass substrate surface, under ensureing the condition that pre-sputtering experiment condition is constant, is cleaned to substrate surface 50-60 second,
Step of the present invention (3) is described when utilizing rf magnetron sputtering to prepare the film sample of different graphite blending ratio, 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;
Graphene quantum dot place dispersion agent described in step of the present invention (4) is salt aqueous acid, and the dialysis membrane being 1000 by molecular weight filters out the halogen in solution,
The critical nature of the important graphene quantum dot that the present invention obtains is measured: do transmission electron microscope and detect.Result display graphene quantum dot is dispersion state, and the grain size of Graphene is mainly distributed in 8-12nm; Fluorescent emission nature examination to the graphene quantum dot that the present invention obtains: be that the ultraviolet lamp of 365nm irradiates graphene quantum dot solution example with wavelength, can obviously observe strong blue light; Detect with spectrophotofluorometer, 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 present invention is relatively traditional, and quantum dot preparation technology has advantage 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 reach by regulating blending ratio and sputtering power;
(4) batch production is easy to: because rf magnetron sputtering equipment can amplify according to the scale of suitability for industrialized production, so may be used 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;
(6) the excellent characteristics of luminescence: graphene quantum dot prepared by the present invention has less size, quantum confined effect is remarkable, therefore sends the light of green glow or other colors in UV-light, purple light, blue-light excited lower meeting;
(7) both water-soluble: graphene dispersion agent of the present invention is salt aqueous acid, these dispersion agents have the advantages that can dissolve each other with water, alcohol, ether etc., therefore graphene quantum dot of the present invention can be used in aqueous solution systems.
Based on above advantage, obtain graphene quantum dot material by present method, the aspect such as research and apply of the photoelectron in the fields such as physics, chemistry, biology, material, bioluminescence, matrix material can be widely used in.
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
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give 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) be m by quality
cthe powdered graphite of=0.24g and quality are m
othe ZnO powder mixing and ball milling (graphite 2mol%) of=79.76g, treats that ball milling is complete, adds 3ml polyvinyl alcohol (PVA) and 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 DEG C, is incubated 4 hours after being warming up to 1100 DEG C.
(2) put into magnetron sputtering chamber after treating glass substrate cleaning, 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, after Film Fractionation, utilize molecular weight be 1000 dialysis membrane halogen is filtered out.
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 taken into 0.62g (graphite 5mol%).
Embodiment 6: similar to Example 1, its difference is to change the powdered graphite quality taken into 1.29g (graphite 10mol%).
Embodiment 7: similar to Example 1, its difference is to change the powdered graphite quality taken into 2.86g (graphite 20mol%).
Embodiment 8: similar to Example 1, its difference is to change the powdered graphite quality taken into 10.31g (graphite 50mol%).
Embodiment 9: similar to Example 1, its difference is to change the powdered graphite quality taken into 55.47g (graphite 70mol%).
Embodiment 10: similar to Example 1, its difference is to change the powdered graphite quality taken into 68.08g (graphite 90mol%).
Claims (2)
1. utilize radio frequency magnetron sputtering method to prepare a method for graphene quantum dot, comprise the following steps:
(1) synthesis of graphite-oxide ceramics target: be m by quality
cthe powdered graphite of=0.24g and quality are m
othe ZnO powder mixing and ball milling of=79.76g, treats that ball milling is complete, adds 3ml polyvinyl alcohol (PVA) and 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 DEG C, is incubated 4 hours after being warming up to 1100 DEG C;
(2) preparation of graphene quantum dot: gained ceramic target in (1) is put into magnetron sputtering chamber, and 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; The magnetron sputtering sample prepared is put into dilute hydrochloric acid solution, after Film Fractionation, utilize molecular weight be 1000 dialysis membrane halogen is filtered out; 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 according to claim 1, it is characterized in that: in step (1), ZnO can by Ga
2o
3, Al
2o
3, CuO replace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518141.8A CN103663437B (en) | 2014-01-10 | 2014-01-10 | Magnetron sputtering technique is utilized to prepare graphene quantum dot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518141.8A CN103663437B (en) | 2014-01-10 | 2014-01-10 | Magnetron sputtering technique is utilized to prepare graphene quantum dot |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103663437A CN103663437A (en) | 2014-03-26 |
| CN103663437B true CN103663437B (en) | 2016-01-06 |
Family
ID=50302347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310518141.8A Active CN103663437B (en) | 2014-01-10 | 2014-01-10 | Magnetron sputtering technique is utilized to prepare graphene quantum dot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103663437B (en) |
Families Citing this family (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 |
| CN113421778B (en) * | 2021-06-21 | 2022-10-21 | 青岛理工大学 | Flexible micro super capacitor and manufacturing method thereof |
| CN114506843B (en) * | 2022-02-25 | 2023-06-13 | 电子科技大学 | Method for rapidly preparing graphene film on nonmetallic substrate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63210006A (en) * | 1987-02-25 | 1988-08-31 | Meidensha Electric Mfg Co Ltd | Formation of thin amorphous carbon film |
| JP3250768B2 (en) * | 1993-09-28 | 2002-01-28 | アルプス電気株式会社 | Method for forming diamond-like carbon film, method for manufacturing magnetic head, and method for manufacturing magnetic disk |
| CN101966987B (en) * | 2010-10-13 | 2012-10-03 | 重庆启越涌阳微电子科技发展有限公司 | Fractal graphene material with negative electron affinity as well as preparation method and application thereof |
| WO2013187652A1 (en) * | 2012-06-11 | 2013-12-19 | 서울대학교산학협력단 | Method for manufacturing graphene quantum dot using thermal plasma |
-
2014
- 2014-01-10 CN CN201310518141.8A patent/CN103663437B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103663437A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103663437B (en) | Magnetron sputtering technique is utilized to prepare graphene quantum dot | |
| Hinklin et al. | Transparent, polycrystalline upconverting nanoceramics: towards 3‐D displays | |
| JP5237557B2 (en) | Sputtering target and manufacturing method thereof | |
| JP5205696B2 (en) | Gallium oxide based sintered body and method for producing the same | |
| KR101349676B1 (en) | Indium zinc oxide based sputtering target and manufacturing method of the same | |
| CN101231431B (en) | Indium tin oxide target, method of manufacturing the same and transparent electrode manufactured by using the same | |
| US20130206590A1 (en) | Manufacture of High Density Indium Tin Oxide (ITO) Sputtering Target | |
| JP2013507526A (en) | Tin oxide ceramic sputtering target and method for producing the same | |
| JP2009144238A (en) | Indium tin oxide target, method for manufacturing the same, transparent conductive film of indium tin oxide, and method for manufacturing the same | |
| KR20080113054A (en) | Transparent conductive film and method for production thereof | |
| KR101941719B1 (en) | Sintered material, and process for producing same | |
| Shi et al. | Luminescence of Cr3+-doped ZnGa2O4 thin films deposited by pulsed laser ablation | |
| CN110425877A (en) | Ceramic post sintering device and ceramic post sintering method | |
| CN102586741B (en) | Preparation method of doped zinc oxide film | |
| CN101096594B (en) | Zinc oxide film transmitting blue light and purple light under room temperature and preparation method thereof | |
| Bae et al. | Photoluminescence characteristics of Li-doped Y2O3: Eu3+ thin film phosphors | |
| CN101476155A (en) | Electrochemical deposition preparation for Mg doped ZnO nano-wire | |
| CN109082631A (en) | A kind of Ga2O3Base transparent conducting film and preparation method thereof | |
| CN1818147A (en) | Production of luminescent film material with tunstite | |
| CN102796517B (en) | Nitrogenous magnesium silicate film, and preparation method and application thereof | |
| KR20100002984A (en) | Zinc oxide based sputtering target, method for mamufacturing the same and zinc oxide based thin film manufactured by using the same | |
| JP5979082B2 (en) | Vapor deposition tablet and manufacturing method thereof | |
| KR20180116293A (en) | Sn-Zn-O oxide sintered body and manufacturing method thereof | |
| CN110331367A (en) | A kind of preparation method of wolframic acid stannous film | |
| KR100704273B1 (en) | A method for sintering ITO using a microwave |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: QINGDAO UNIVERSITY Effective date: 20150518 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20150518 Address after: Songyuan road 266033 in Shandong Province, Qingdao high tech Industrial Development Zone, No. 17 Qingdao Industrial Technology Research Institute C C1 District 4 floor -1 Applicant after: QINGDAO HUAGAO ENERGY TECHNOLOGY CO.,LTD. Address before: 266033 a, room 133, 705 Liu Liu Road, Sifang District, Shandong, Qingdao Applicant before: QINGDAO HUAGAO ENERGY TECHNOLOGY CO.,LTD. Applicant before: Qingdao University |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: Jin hi tech Zone 266111 Shandong province Qingdao City Department of Road No. 1 building a layer of C2 Island Park Patentee after: QINGDAO HUAGAO GRAPHENE TECHNOLOGY Corp.,Ltd. Address before: 266111 Shandong city of Qingdao province Songyuan Qingdao high tech Industrial Development Zone, No. 17 Qingdao Road, Industrial Technology Research Institute C C1 District 4 floor -1 Patentee before: QINGDAO HUAGAO INK MATERIAL TECHNOLOGY Co.,Ltd. Address after: 266111 Shandong city of Qingdao province Songyuan Qingdao high tech Industrial Development Zone, No. 17 Qingdao Road, Industrial Technology Research Institute C C1 District 4 floor -1 Patentee after: QINGDAO HUAGAO INK MATERIAL TECHNOLOGY Co.,Ltd. Address before: Songyuan road 266033 in Shandong Province, Qingdao high tech Industrial Development Zone, No. 17 Qingdao Industrial Technology Research Institute C C1 District 4 floor -1 Patentee before: QINGDAO HUAGAO ENERGY TECHNOLOGY CO.,LTD. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Graphene quantum dot prepared by virtue of magnetron sputtering technology Effective date of registration: 20170918 Granted publication date: 20160106 Pledgee: Qingdao high tech Cci Capital Ltd. Pledgor: QINGDAO HUAGAO GRAPHENE TECHNOLOGY Corp.,Ltd. Registration number: 2017370010056 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20181113 Granted publication date: 20160106 Pledgee: Qingdao high tech Cci Capital Ltd. Pledgor: QINGDAO HUAGAO GRAPHENE TECHNOLOGY Corp.,Ltd. Registration number: 2017370010056 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Graphene quantum dot prepared by virtue of magnetron sputtering technology Effective date of registration: 20181123 Granted publication date: 20160106 Pledgee: Qingdao high tech Cci Capital Ltd. Pledgor: QINGDAO HUAGAO GRAPHENE TECHNOLOGY Corp.,Ltd. Registration number: 2018370010124 |