CN110629190A - Preparation method of sub-10 nanometer stable graphene quantum dots - Google Patents

Preparation method of sub-10 nanometer stable graphene quantum dots Download PDF

Info

Publication number
CN110629190A
CN110629190A CN201811497178.6A CN201811497178A CN110629190A CN 110629190 A CN110629190 A CN 110629190A CN 201811497178 A CN201811497178 A CN 201811497178A CN 110629190 A CN110629190 A CN 110629190A
Authority
CN
China
Prior art keywords
boron nitride
graphene quantum
nanometer
metal foil
quantum dots
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.)
Granted
Application number
CN201811497178.6A
Other languages
Chinese (zh)
Other versions
CN110629190B (en
Inventor
刘开辉
陈东学
乔瑞喜
俞大鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Peking University
Original Assignee
Peking University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Peking University filed Critical Peking University
Priority to CN201811497178.6A priority Critical patent/CN110629190B/en
Publication of CN110629190A publication Critical patent/CN110629190A/en
Application granted granted Critical
Publication of CN110629190B publication Critical patent/CN110629190B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/342—Boron nitride

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Plasma & Fusion (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a preparation method of a sub-10 nanometer stable graphene quantum dot, and relates to a preparation method of boron nitride, helium ion microscope processing and chemical vapor deposition growth of graphene. The method is mainly characterized in that boron nitride is placed on a metal foil substrate, sub-10 nanometer holes are etched on the boron nitride by using a helium ion microscope, and then graphene quantum dots are grown in the boron nitride nanometer holes by using a chemical vapor deposition method. The method provided by the invention solves the technical and scientific problems that the geometric dimension and the position of the graphene quantum dot cannot be effectively controlled and the stability is poor, and the helium ion processing assisted growth method realizes the preparation of the highly controllable sub-10 nanometer stable graphene quantum dot.

Description

Preparation method of sub-10 nanometer stable graphene quantum dots
Technical Field
The invention relates to a preparation method of a sub-10 nanometer stable graphene quantum dot.
Background
The graphene is two-dimensional honeycomb-shaped single-atomic-layer graphite consisting of carbon atoms, and the graphene quantum dots are graphene fragments with three dimensions reaching the nanometer level. Graphene is a zero-band-gap semi-metal material, and graphene quantum dots, especially sub-10 nm graphene quantum dots, can not only open the band gap of graphene, but also find that interesting quantum phenomena such as kliney tunneling, valley splitting and the like exist. These phenomena further open up a large application space for graphene quantum dots, such as graphene quantum dot LED display screens, quantum computing and the like, and can even be used for treating Parkinson's disease. However, the graphene quantum dots, especially the sub-10 nm graphene quantum dots, have a large proportion of edge atoms, the existence of edge atom dangling bonds renders the graphene quantum dots not very stable under a common environment, and the phenomenon of edge reconstruction or adsorption of other chemical molecules frequently occurs to cause quantum dots to deteriorate. For graphene quantum dots, quantum size and stability appear to be two conflicting properties. Hexagonal boron nitride is a cellular atomic layered material with very small lattice difference (1.7%) similar to graphene structure. Nevertheless, properties of hexagonal boron nitride and graphene are very different, for example, boron nitride is an insulator and graphene is a semimetal. These properties make the horizontal heterojunction of graphene and boron nitride more promising for maintaining graphene quantum dot stability. However, the size of the current horizontal heterojunction of graphene and boron nitride is generally over 100 nanometers, and the size is far from the scale of quantum graphene.
Helium ion microscopy is an emerging technology that allows simultaneous characterization of the surface structure and surface processing of samples. Firstly, helium ions are heavier than electrons, so that the layered material can be rapidly processed; second, helium ions are much lighter than gallium ions, resulting in higher process resolution than Focused Ion Beams (FIBs).
Disclosure of Invention
The invention provides a method for growing graphene quantum dots by CVD assisted by a helium ion microscope for the first time.
A method for growing graphene quantum dots by CVD assisted by a helium ion microscope comprises the following steps of firstly, paving boron nitride on a substrate, usually a metal foil; secondly, etching through the layered boron nitride by using a helium ion microscope to form a nano hole; and then growing graphene in the holes by using a chemical vapor deposition method to form a graphene boron nitride heterojunction.
Preferably, the substrate is not subjected to any surface treatment, i.e. substrates obtained from open commercial sources are used directly in the process without any surface pretreatment.
Preferably, the method comprises the steps of:
placing the boron nitride on a metal foil substrate, wherein the boron nitride can be obtained by peeling off boron nitride crystals by hands, and can also be grown on the substrate by other methods such as chemical vapor deposition and the like;
placing the metal foil with the boron nitride in a helium ion microscope, and etching sub-10 nanometer holes on the boron nitride by using helium ions;
after etching, putting the substrate into a chemical vapor deposition furnace to grow graphene;
and fourthly, after the growth is finished, cooling to room temperature to obtain the sub-10 nanometer graphene quantum dots with controllable height.
Preferably, the method comprises the steps of:
(one), boron nitride is placed or grown on the metal foil without any surface treatment. The boron nitride can be from a hand-tearing stripping method or from other methods such as chemical vapor deposition growth and the like;
placing the film into a helium ion microscope cavity, and etching holes by helium ions, wherein the dosage of the helium ion beams is more than 0.5pA and the time is different from 0.1s to 20 s;
thirdly, placing the etched boron nitride sample with the nanometer holes into a furnace for chemical vapor deposition, and introducing argon (Ar) and hydrogen (H)2) Gas with the flow rate of 20-500sccm and 2-50sccm respectively, heating to 500-1200 ℃, introducing a carbon source, keeping for 5-20min, annealing for 30-100 min, turning off a heating power supply after growth is finished, stopping introducing the carbon source, and introducing Ar and H2Naturally cooling to room temperature for protecting gas.
Preferably, the substrate is a metal foil and alloys thereof (Cu, Au, Ni, Pt, Ni/Cu alloy, Ni/Pt alloy, Cu/Pt, etc.).
Preferably, the carbon source in step three comprises solid (polyethylene, polystyrene, polymethyl methacrylate, etc.), liquid vapor (ethanol, benzoic acid, benzene, toluene, etc.) and gas (methane, ethylene, acetylene, etc.).
Preferably, the heating, annealing and growth processes in the third step can be performed under normal pressure or low pressure.
Preferably, the amount of the carbon source in step three may be any value under the condition that the growth of graphene is not affected.
The invention uses helium ion microscope to etch the boron nitride on the metal foil until the boron nitride is etched out of the nanometer hole. In the subsequent chemical vapor deposition process, the metal foil can be used as a catalyst and a growth substrate, and graphene quantum dots are grown in a furnace. The method provided by the invention solves the technical problems that the graphene quantum dots cannot be effectively controlled and are very unstable, and realizes the highly controllable and very stable sub-10 nanometer graphene quantum dots.
The invention has the advantages that:
1. the invention selects the metal foil as the growth substrate, does not need to carry out complex surface pretreatment on the substrate, greatly simplifies the growth process, shortens the growth period and greatly reduces the preparation cost;
2. according to the method, the graphene quantum dots are grown by helium ion-assisted processing, so that the height of the graphene quantum dots is controllable;
3. compared with commercial graphene quantum dots, the graphene quantum dots prepared by the method have very good stability;
4. the method is simple and effective, has stable performance, and is beneficial to the practical application of the graphene quantum dots.
Drawings
Fig. 1 is a flow chart of graphene quantum dot growth and a microscope image of a helium ion microscope after punching holes in boron nitride.
FIG. 2 is a microscope image of a helium ion microscope after drilling a sub-10 nm hole in boron nitride.
Fig. 3 is a representation of graphene quantum dots grown in hand-torn exfoliated boron nitride nanopores, a raman spectrum (a), and a representation of quantum dot atomic structures (b).
Fig. 4 is a representation of the chemical vapor deposition method for growing graphene quantum dots in boron nitride nanopores, and a raman spectrum (a) and a graphene moire fringe (b) of the graphene quantum dots grown on the boron nitride nanopores by the chemical vapor deposition method.
Fig. 5 shows the change of the raman spectrum of the graphene quantum dot invented by the present patent after baking for 100 days at 100 ℃.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are conventional unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The first implementation mode comprises the following steps: method for stripping boron nitride nano-pore grown graphene quantum dots
This embodiment was carried out in the apparatus shown in fig. 1, where bulk boron nitride was hand-peeled off with tape to a small layer of boron nitride on top of the metal foil, and the following procedure was followed:
firstly, manually peeling off a few layers of boron nitride from the bulk boron nitride on the metal foil by using an adhesive tape, and putting the metal foil into a chemical vapor deposition device for annealing (the step is mainly to remove adhesive residue of the adhesive tape). Introduction of Ar/H2500/10sccm, the operating pressure is atmospheric (i.e., one atmosphere or about 1 × 10)5Pa), then starting to heat up, wherein the heating process lasts for 50-70 min, stopping heating after the temperature reaches 1000 ℃, and naturally cooling to room temperature;
secondly, taking out a sample, placing the sample into a helium ion microscope cavity, etching nano holes with different sizes on boron nitride by using a helium ion beam, and selecting the dosage and etching time according to the state of an instrument;
thirdly, after the etching is finished, putting the sample into a chemical vapor deposition furnace, extracting the air in the furnace to a vacuum state, starting to introduce Ar/H2 gas of 50/2sccm, and adjusting H2The flow rate is 0.2-50sccm, the temperature rise process lasts for 45-70 min, and the temperature rises to 850-100 DEGAfter 0 ℃ CH is opened4Gas, CH4The flow rate is 0.5-10 sccm, the Ar flow rate is kept unchanged, and the growth time is 1-10 min;
fourthly, after the growth is finished, the heating power supply is closed, and the CH is stopped being introduced4Gas with Ar and H2And naturally cooling the carbon nanotube to room temperature for protecting the gas, and embedding the graphene quantum dots into the boron nitride nanopores to complete the preparation of the highly controllable quantum dots.
It should be noted that: the working pressure in the above method may be low pressure or normal pressure, i.e. one atmosphere or about 1X 105Pa。
The embodiment has the following beneficial effects:
1. in the embodiment, the easily-obtained metal foil is used as the catalyst and the growth substrate, and the graphene quantum dots can be obtained at a lower temperature.
2. The embodiment takes common metal foil as a substrate, does not need other special treatment, and reduces the growth cost.
3. The growth duration of the embodiment is only 1-10 min, the growth period is short, and the time and the cost are saved.
4. The graphene quantum dots grown by the method are highly controllable in geometric parameter, good in stability and good in application prospect in future electronics.
The beneficial effects of the invention are verified by the following tests:
test one: the verification of the preparation method of the sub-10 nanometer stable graphene quantum dot in the test is carried out according to the following steps:
firstly, placing the grown graphene quantum dots under a Raman spectrometer for characterization, and comparing the graphene quantum dots with Raman spectra of graphene and boron nitride;
secondly, by contrast, Raman spectra can clearly see that a boron nitride region only has signals of boron nitride, a graphene region only has signals of graphene, a quantum dot region simultaneously has signals of graphene and boron nitride, and the graphene quantum dot signals are weaker than the graphene signals in strength;
and (2) test II: the verification of the preparation method of the sub-10 nanometer stable graphene quantum dot in the test is carried out according to the following steps:
firstly, transferring the successfully grown graphene quantum dots to a special copper net for a transmission electron microscope;
secondly, in a transmission electron microscope, a clear graphene atomic image can be seen in a boron nitride nanopore region, and finally, the success of preparing the sub-10-nanometer graphene quantum is further proved.
The second embodiment: method for growing graphene quantum dots in chemical vapor deposition boron nitride nanopores
This embodiment is carried out in the apparatus shown in fig. 1, growing boron nitride by chemical vapor deposition on top of a metal foil and is carried out as follows:
firstly, placing the metal foil in a chemical vapor deposition device. Introduction of Ar/H2500/5sccm, the operating pressure is atmospheric (i.e., one atmosphere or about 1 × 10)5Pa), then starting to heat up, wherein the heating process lasts for 50-70 min, and heating BH after the temperature reaches 1000 DEG C3-NH3Introducing boron source and nitrogen source, stopping heating BH after one hour3-NH3Naturally cooling to room temperature;
secondly, taking out a sample, placing the sample into a helium ion microscope cavity, etching nano holes with different sizes on boron nitride by using a helium ion beam, and selecting the dosage and etching time according to the state of an instrument;
thirdly, after the etching is finished, putting the sample into a chemical vapor deposition furnace, extracting the air in the furnace to a vacuum state, starting to introduce Ar/H2 gas of 50/2sccm, and adjusting H2The flow rate is 0.2-50sccm, the temperature rise process lasts for 45-70 min, and C is opened after the temperature rises to 850-1000 DEG C2H2Gas, C2H2The flow rate is 0.5-10 sccm, the Ar flow rate is kept unchanged, and the growth time is 1-10 min;
fourthly, after the growth is finished, the heating power supply is closed, and the C is stopped to be introduced2H2Gas with Ar and H2Naturally cooling to room temperature for protecting gas, embedding the graphene quantum dots into the boron nitride nanopores, and thus achieving highly controllable amountAnd (4) preparing the sub-dots.
The embodiment has the following beneficial effects:
1. in the embodiment, the easily-obtained metal foil is used as the catalyst and the growth substrate, and the graphene quantum dots can be obtained at a lower temperature.
2. The embodiment takes common metal foil as a substrate, does not need other special treatment, and reduces the growth cost.
3. The growth duration of the embodiment is only 1-10 min, the growth period is short, and the time and the cost are saved.
4. The graphene quantum dots grown by the method are highly controllable in geometric parameter, good in stability and good in application prospect in future electronics.
The beneficial effects of the invention are verified by the following tests:
test one: the verification of the preparation method of the sub-10 nanometer stable graphene quantum dot in the test is carried out according to the following steps:
firstly, placing the grown graphene quantum dots under a Raman spectrometer for characterization;
secondly, Raman spectrum can clearly see that the boron nitride region only has weak boron nitride signals, because the Raman signals of chemical vapor deposition single-layer boron nitride are weak, the region of the quantum dots has graphene signals, and the boron nitride signals are very weak and are covered;
and (2) test II: the verification of the preparation method of the sub-10 nanometer stable graphene quantum dot in the test is carried out according to the following steps:
firstly, transferring successfully grown graphene quantum dots to a special copper net for a transmission electron microscope, and paving a layer of single crystal graphene on the copper net in advance;
secondly, high-resolution imaging is carried out on the nanopore region, moire fringes formed by the laid graphene and the grown graphene can be seen, and existence of graphene quantum dots is proved.
The third embodiment is as follows: stability analysis of sub-10-nanometer graphene quantum dots
And (3) test III: the verification of the stability of the sub-10 nanometer stable graphene quantum dot in the test is carried out according to the following steps:
firstly, purchasing commercial graphene quantum dots as comparison;
secondly, testing the changes of the Raman spectrum and the fluorescence spectrum of the purchased graphene quantum dots baked at different temperatures and different times;
thirdly, testing the change of the Raman spectrum of the graphene quantum dots grown in the patent along with time;
fourthly, the comparison result shows that the purchased commercial graphene quantum dots are baked for 5 minutes at 100 ℃, the Raman spectrum disappears, and the fluorescence spectrum is seriously attenuated. After 10 minutes the fluorescence substantially disappeared. And the graphene quantum dots applied to the patent are baked for 100 days under the same conditions, and the Raman spectrum of the graphene is basically unchanged.

Claims (10)

1. A preparation method of sub-10 nanometer stable graphene quantum dots is characterized in that boron nitride is placed on a metal foil substrate, nanometer holes are etched in the boron nitride through a helium ion microscope, and the graphene quantum dots are grown in the nanometer holes through a chemical vapor deposition method.
2. The method of claim 1, wherein the metal foil is free of any surface treatment.
3. Method according to claim 1, characterized in that it comprises the following steps:
placing boron nitride on a metal foil substrate, placing the metal foil substrate into helium ion microscope equipment, and etching sub-10-nanometer holes on the boron nitride by using helium ion beams, wherein the dosage of the helium ion beams is more than 0.5pA and the time is different from 0.1s to 20 s;
putting the metal foil with the boron nitride nanometer holes into chemical vapor deposition equipment, introducing inert gas and H into the equipment (vacuumizing)2Gas, H2The flow rate is 2-50sccm, and then the temperature is raised;
thirdly, when the temperature rises to 900-1100 ℃, starting to introduce a gas source or a solid source required by growth for 1 s-60 min;
and fourthly, after the growth is finished, cooling to room temperature to obtain the sub-10 nanometer graphene quantum dots.
4. Method according to claim 1, characterized in that it comprises the following steps:
placing boron nitride on a metal foil substrate, placing the metal foil substrate into helium ion microscope equipment, and etching sub-10-nanometer holes on the boron nitride by using helium ion beams, wherein the dosage of the helium ion beams is more than 0.5pA and the time is different from 0.1s to 20 s;
secondly, putting the metal foil with the boron nitride nanometer holes into chemical vapor deposition equipment, vacuumizing, introducing Ar gas of 20-500sccm, and introducing H2Gas, H2The flow rate is 2-50sccm, and then the temperature is raised;
(III) after the annealing is finished, starting to introduce CH4Gas, CH4The flow rate is 0.5-50 sccm, and H is adjusted2The flow is 0.2-50sccm, the Ar flow is kept unchanged, and the growth time is 1 s-60 min;
(IV) after the growth is finished, closing the heating power supply and stopping introducing CH4Gas with Ar and H2And naturally cooling to room temperature to form sub-10 nanometer graphene quantum dots in the boron nitride nanopores as protective gas, thereby completing the preparation.
5. The method of claim 1, wherein the substrate is a metal foil (Cu, Au, Ni, Pt, etc.) or an alloy (CuNi alloy, CuPt alloy, AuCu alloy, AuNi alloy, etc.), but is not limited thereto.
6. The method of claim 1, wherein the boron nitride is hand-peel boron nitride and chemical vapor deposition boron nitride.
7. The method of claim 3, wherein step two may or may not be evacuated.
8. The method of claim 3, wherein the steps of raising the temperature, annealing and growing in the first, second and third steps are performed under low pressure or normal pressure.
9. The method as claimed in claim 3, wherein the carbon source in step three can be solid carbon source (polyethylene, polystyrene, polymethyl methacrylate, etc.), liquid carbon source (ethanol, benzoic acid, benzene, toluene, etc.) and gaseous carbon source (methane, ethylene, acetylene, etc.).
10. The method of claim 4, CH4The flow rate is 0.5 to 50sccm, and H with the flow rate of 0.2 to 50sccm is introduced2，CH4And H2The flow ratio is 0.01 to 100.
CN201811497178.6A 2018-12-07 2018-12-07 Preparation method of sub-10 nanometer stable graphene quantum dots Active CN110629190B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811497178.6A CN110629190B (en) 2018-12-07 2018-12-07 Preparation method of sub-10 nanometer stable graphene quantum dots

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811497178.6A CN110629190B (en) 2018-12-07 2018-12-07 Preparation method of sub-10 nanometer stable graphene quantum dots

Publications (2)

Publication Number Publication Date
CN110629190A true CN110629190A (en) 2019-12-31
CN110629190B CN110629190B (en) 2020-11-03

Family

ID=68968026

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811497178.6A Active CN110629190B (en) 2018-12-07 2018-12-07 Preparation method of sub-10 nanometer stable graphene quantum dots

Country Status (1)

Country Link
CN (1) CN110629190B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113264520A (en) * 2021-04-28 2021-08-17 河南大学 Hyperbolic super surface based on graphene-boron nitride transverse heterojunction and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104944417A (en) * 2015-06-01 2015-09-30 中国科学院上海微系统与信息技术研究所 Preparation method of graphene-boron nitride heterojunction
CN107481871A (en) * 2017-09-08 2017-12-15 武汉理工大学 A kind of preparation method of graphene hexagonal boron nitride heterogeneous structure material
CN107502347A (en) * 2017-07-17 2017-12-22 江苏师范大学 A kind of preparation method for gram rank nitrogen-doped graphene quantum dot that can be used as fluorescent ink
KR20180072537A (en) * 2016-12-21 2018-06-29 건국대학교 글로컬산학협력단 Film comprising atomic layer and graphene quantum dot, Preparation Method thereof, and Food packing material using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104944417A (en) * 2015-06-01 2015-09-30 中国科学院上海微系统与信息技术研究所 Preparation method of graphene-boron nitride heterojunction
KR20180072537A (en) * 2016-12-21 2018-06-29 건국대학교 글로컬산학협력단 Film comprising atomic layer and graphene quantum dot, Preparation Method thereof, and Food packing material using the same
CN107502347A (en) * 2017-07-17 2017-12-22 江苏师范大学 A kind of preparation method for gram rank nitrogen-doped graphene quantum dot that can be used as fluorescent ink
CN107481871A (en) * 2017-09-08 2017-12-15 武汉理工大学 A kind of preparation method of graphene hexagonal boron nitride heterogeneous structure material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LU, GY ET AL: "Synthesis of High-Quality Graphene and Hexagonal Boron Nitride Monolayer In-Plane Heterostructure on Cu-Ni Alloy", 《ADVANCED SCIENCE》 *
NIMA KALHOR ET AL: "Sub-10<ce:hsp sp="0.25"/>nm patterning by", 《MICROELECTRONIC ENGINEERING》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113264520A (en) * 2021-04-28 2021-08-17 河南大学 Hyperbolic super surface based on graphene-boron nitride transverse heterojunction and preparation method and application thereof

Also Published As

Publication number Publication date
CN110629190B (en) 2020-11-03

Similar Documents

Publication Publication Date Title
Cao et al. Large-scale graphitic thin films synthesized on Ni and transferred to insulators: Structural and electronic properties
Liu et al. Chemical vapor deposition of large area few layer graphene on Si catalyzed with nickel films
US10184175B2 (en) Method for synthesizing multilayer graphene
US9845551B2 (en) Methods for production of single-crystal graphenes
US8470400B2 (en) Graphene synthesis by chemical vapor deposition
Baraton et al. Synthesis of few-layered graphene by ion implantation of carbon in nickel thin films
JP5662249B2 (en) Method for producing graphene
US8288190B2 (en) Methods of making heterojunction devices
US8932673B2 (en) Methods of fabricating large-area graphene
Norimatsu et al. Formation mechanism of graphene layers on SiC (000 1) in a high-pressure argon atmosphere
WO2011025045A1 (en) Graphene film and method for producing same
Mishra et al. Rapid and catalyst-free van der Waals epitaxy of graphene on hexagonal boron nitride
Ago et al. Patterned growth of graphene over epitaxial catalyst
TWI526559B (en) Process for forming carbon film or inorganic material film on substrate by physical vapor deposition
US20150292110A1 (en) Method for preparing graphene
US20140299975A1 (en) Method and Board for Growing High-Quality Graphene Layer Using High Pressure Annealing
Wu et al. A fast transfer-free synthesis of high-quality monolayer graphene on insulating substrates by a simple rapid thermal treatment
US20230012266A1 (en) Maskless patterning and control of graphene layers
Park et al. Quasi-free-standing graphene monolayer on a Ni crystal through spontaneous Na intercalation
CN110629190B (en) Preparation method of sub-10 nanometer stable graphene quantum dots
Sandin et al. Improved graphene growth in UHV: Pit-free surfaces by selective Si etching of SiC (0001)–Si with atomic hydrogen
Herrmann et al. Growth of h-BN on copper (110) in a LEEM
TW201434744A (en) Method for manufacturing graphene film and graphene channel of transistor
KR20160134369A (en) Process for preparing graphene
JP2019524620A (en) Method for preparing high quality graphene on the surface of silicon carbide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant