CN116281969A - Red luminous graphene quantum dot and preparation method and application thereof - Google Patents
Red luminous graphene quantum dot and preparation method and application thereof Download PDFInfo
- Publication number
- CN116281969A CN116281969A CN202111527301.6A CN202111527301A CN116281969A CN 116281969 A CN116281969 A CN 116281969A CN 202111527301 A CN202111527301 A CN 202111527301A CN 116281969 A CN116281969 A CN 116281969A
- Authority
- CN
- China
- Prior art keywords
- graphene quantum
- quantum dot
- preparation
- quantum dots
- organic
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- 239000002096 quantum dot Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000010894 electron beam technology Methods 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 7
- 230000005284 excitation Effects 0.000 claims abstract description 7
- 239000005416 organic matter Substances 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 28
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000012798 spherical particle Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 claims description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 229960005489 paracetamol Drugs 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000005424 photoluminescence Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 24
- 238000010586 diagram Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 238000000799 fluorescence microscopy Methods 0.000 description 5
- 238000012634 optical imaging Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- 241000669618 Nothes Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000012632 fluorescent imaging Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of graphene quantum dots, which comprises the following steps: the organic matter containing benzene ring is used as carbon source, and is prepared by electron beam exposure and ice etching process at low temperature; the luminescent graphene quantum dot can emit red fluorescence under the excitation of blue light. The preparation method of the red luminous graphene quantum dot is a novel preparation method of fluorescent graphene quantum dots with high integration of flow, safe and nontoxic process raw materials, controllable micro-nano pattern structure and high resolution, and the graphene quantum dot with a more stable graphene six-membered ring structure is formed by directly exposing amorphous organic matters through high-energy electron beams so that molecules are ionized and crosslinked. The graphene quantum dot manufactured by the method has uniform size, photoluminescence red fluorescence characteristic and adjustable fluorescence intensity, and is expected to be widely applied in the field of fluorescent anti-counterfeiting marks.
Description
Technical Field
The invention belongs to the technical field of nano material and structure preparation and application, and particularly relates to a red luminescent graphene quantum dot and a preparation method and application thereof.
Background
The graphene quantum dots, as a new fluorescent nanomaterial, have great potential in photoelectric application and biomedicine due to high chemical stability, high biocompatibility, high environmental friendliness, simple synthesis route and adjustable photoluminescence characteristics.
The existing preparation method of the graphene quantum dot comprises two major types of 'top-down' and 'bottom-up'. The former cracks larger carbon structures into graphene quantum dots by chemical, electrochemical or physical methods, which are complex and uncontrollable and even cause environmental hazard. The latter refers to graphene quantum dots prepared by using smaller building blocks as precursors through a series of interaction forces, such as pyrolysis or carbonization of small organic molecules or gradual chemical fusion of small aromatic molecules, and the organic synthesis method is accurate and complex, and requires a plurality of steps to obtain large-size GQDs.
Patterning methods of graphene quantum dots currently include mixing them with a polymer matrix to pattern, or dispersing them in a solvent to form an ink for inkjet printing, which methods have low resolution, uncontrollable processes, and complex operations involving a variety of chemical reagents.
Disclosure of Invention
The invention provides a preparation method of graphene quantum dots, which is controllable, simple to operate, does not involve complex chemical solvents, and can be used for rapidly obtaining graphene quantum dot products with higher resolution.
The invention provides a graphene quantum dot product, which has a regular multi-layer graphite crystal structure, the size of the graphene quantum dot product is between 2 and 3nm, red fluorescence is emitted under the excitation of blue light, and the fluorescence intensity is adjustable.
The invention provides a graphene quantum dot anti-counterfeiting pattern, which has the same color of products with different exposure doses under a light mirror, but can display a fluorescent anti-counterfeiting pattern under a fluorescent microscope.
A preparation method of graphene quantum dots comprises the following steps: the organic matter containing benzene ring is used as carbon source, and is prepared by electron beam exposure and ice etching process at low temperature; the luminescent graphene quantum dot can emit red fluorescence under the excitation of blue light.
A preparation method of graphene quantum dots comprises the following specific steps:
(1) Placing a substrate in an electron microscope, cooling to a low temperature, and depositing organic gas on the substrate to form an organic ice film;
(2) Exposing the organic ice film in step (1) with an electron beam at a low temperature;
(3) And (3) removing the unexposed ice film in the step (2) to prepare the red luminescent graphene quantum dots.
In the step (1), the low temperature is 90K-130K. For example, 90K, 100K, 110K, 120K, 130K, and specific point values between the above values, are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values encompassed by the described ranges. The temperature is selected primarily based on the desublimation temperature of the organic material selected.
In the step (1), the main component of the base material is Pt, pd, al, au, ti, cr, V, W, ni, co, ge, si, ag, cu, mn, fe, ni, zn, cd, ge, sn, pb, sb, bi, si, ge, gaN, gaAs, gaP, inAs, znS, znSe, cdS, cdSe, znO, tiO 2 、TiN、MgO、CdO、Al 2 O 3 、SiO 2 、Si 3 N 4 InAs, inP, al, znO and ITO.
In the step (1), the organic matter is selected from any one or a combination of two or more of toluene, ethylbenzene, butylbenzene, xylene, trimethylbenzene, benzyl alcohol, phenethyl alcohol, benzoic acid, gallic acid, styrene, phenylmethane, phenylethane, phenylmethylamine, anisole, phenetole, benzaldehyde, phenol, acetaminophen, aniline, chlorobenzene, chlorotoluene, dichlorobenzene, iodobenzene, bromobenzene, bromostyrene and bromobenzoic acid; the ice film is a solid film formed after the gas is condensed.
In the step (1), the electron microscope is selected from one of a thermal field emission scanning electron microscope, an environmental scanning electron microscope, a transmission electron microscope, and a spherical aberration correction transmission electron microscope.
Preferably, in the step (2), the organic ice film in the step (1) is exposed according to a set pattern, so as to obtain the red luminescent graphene quantum dot with the micro-nano pattern structure.
The process of determining the exposure pattern in the step (2) includes the steps of:
(1) Designing a micro-nano pattern structure of the red luminescent graphene quantum dot;
(2) Calculating the electron beam exposure dose required for preparing the micro-nano pattern structure by utilizing the contrast curve (namely, the relation curve between the exposure dose and the residual thickness of the film after exposure; which can be obtained through a plurality of tests) of the amorphous organic film;
(3) And drawing a layout of the micro-nano pattern structure of the red luminescent graphene quantum dot, and finally converting the layout into a computer readable code to realize electron beam exposure dose control.
In the step (2), the electron energy ranges from 2keV to 30keV. For example, 2keV, 3keV, 4keV, 5keV, 6keV, 7keV, 8keV, 9keV, 10keV, 15keV, 20keV, 25keV, 30keV, and specific point values between the above values are limited in space and for the sake of brevity, the invention is not intended to exhaustively list the specific point values included in the range. Preferably 5keV to 15keV.
In the step (2), the electron beam exposure dose is preferably 0.1mC/cm 2 -60mC/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the As a further preferable aspect, the electron beam exposure dose is 0.2mC/cm 2 -50.5mC/cm 2 . For example 0.2mC/cm 2 、0.5mC/cm 2 、1mC/cm 2 、2mC/cm 2 、3mC/cm 2 、4mC/cm 2 、5mC/cm 2 、6mC/cm 2 、7mC/cm 2 、8mC/cm 2 、9mC/cm 2 、10mC/cm 2 、20mC/cm 2 、30mC/cm 2 、40mC/cm 2 、50mC/cm 2 And the particular values of points between the values recited above, are limited in space and for brevity, the invention is not intended to exhaustively enumerate the particular values of points within the range. . Scanning electron microscope can provide noThe electron beam bombards a specific area of the amorphous organic thin film to form a micro-nano pattern structure in the electron beam exposure process, the interaction of the high-energy electrons and the amorphous organic thin film can lead to ionization of substances, chain scission of organic molecular side groups can be generated, free radicals and dangling bonds are generated on benzene rings, when free dangling bonds on adjacent benzene rings are combined, crosslinking is generated, a more stable graphene six-membered ring structure is formed, and therefore red luminous graphene quantum dots are formed in an amorphous carbon matrix.
In the step (3), removing the unexposed ice film in the step (2) in a melting and removing mode; further, the natural rewarming melting removal is performed.
The transmission electron microscope shows that the synthesized graphene quantum dots are spherical particles, and the Raman spectrum and the X-ray photoelectron spectrum show that the surfaces of the graphene quantum dots contain a large number of oxygen-containing functional groups. Under the excitation of 473nm blue light, the graphene quantum dot can emit red fluorescence, the wavelength center of an emission band is located at about 630nm-650nm, and the intensity of an emission peak increases with the increase of the exposure dose of the electron beam.
According to the preparation method of the graphene quantum dot pattern with the anti-counterfeiting function, in the step (2), according to the set pattern, the amorphous organic ice film is exposed by using gradient doses exceeding saturation doses for different areas, so that the graphene quantum dot pattern with the anti-counterfeiting function is obtained.
In the invention, the "saturation dose" refers to the thickness of the organic ice film with a specific thickness, and when the ice film is exposed by using the electron beam dose exceeding the "saturation dose", the thickness of the product remained on the substrate is not increased any more; the minimum electron beam dose corresponding to the thickness of the product is the "saturation dose".
The obtained red luminous graphene quantum dots with the micro-nano pattern structure can realize the function of optical encryption anti-counterfeiting mark, and the gradient dosage exceeding the saturation dosage is used for exposing the amorphous organic ice film, so that the thickness of a product left on a substrate can not be further increased due to the increase of the exposure dosage exceeding the saturation dosage, the color of the product with different exposure dosages under the light mirror is the same, but the increase of the exposure dosage can continuously generate the graphene quantum dots, so that the fluorescence intensity of the product with different exposure dosages is continuously increased under a fluorescence microscope, and the purpose of manufacturing the optical encryption anti-counterfeiting mark is achieved.
The preparation method of the red luminescent graphene quantum dot with the micro-nano pattern structure comprises the steps of preparing the red luminescent carbon quantum dot with the micro-nano pattern structure on an organic amorphous film by using an ice etching process; the specific process steps comprise:
(1) And (3) placing a substrate in an electron microscope, cooling to a low temperature, and depositing gas on the substrate to form an ice film.
(2) Exposing the ice film in step (1) to electron beams at a low temperature.
(3) And (3) removing the unexposed ice film in the step (2) to prepare the red luminescent graphene quantum dot with the micro-nano pattern structure.
A graphene quantum dot is prepared by the preparation method according to any one of the technical schemes.
Preferably, the graphene quantum dots are spherical particles, and the scale of the particles is about 2nm-3 nm.
In the invention, the graphene quantum dots have a regular multi-layer graphite crystal structure.
An anti-counterfeiting pattern prepared by the preparation method according to any one of the technical schemes. The fluorescent anti-counterfeiting pattern can be obtained by the method of the invention, and the application of the fluorescent anti-counterfeiting pattern in fluorescent anti-counterfeiting is realized.
The preparation method of the red luminescent graphene quantum dot with the micro-nano pattern structure is a preparation method of the novel fluorescent graphene quantum dot with the advantages of high integration of flow, safe and nontoxic process raw materials, controllable micro-nano pattern structure and high resolution, and the preparation method of the graphene quantum dot used by the preparation method is obviously different from the existing preparation method of the graphene quantum dot, and the graphene quantum dot with the more stable graphene six-membered ring structure is formed by directly exposing amorphous organic matters through high-energy electron beams so that molecules are ionized and crosslinked. The graphene quantum dot manufactured by the method has uniform size, photoluminescence red fluorescence characteristic and adjustable fluorescence intensity, and is expected to be widely applied in the field of fluorescent anti-counterfeiting marks.
Drawings
Fig. 1 is a process route diagram of a preparation method of red luminescent graphene quantum dots with a micro-nano pattern structure;
fig. 2a is a schematic diagram of a method for preparing a red luminescent graphene quantum dot with a micro-nano pattern structure according to the present invention;
fig. 2b is a schematic diagram of a method for preparing a red luminescent graphene quantum dot with a micro-nano pattern structure according to the present invention;
fig. 2c is a schematic diagram of a method for preparing a red luminescent graphene quantum dot with a micro-nano pattern structure according to the present invention;
fig. 3 is a fluorescence imaging diagram of a graphene quantum dot micro-nano pattern structure in embodiment 1 of the present invention;
FIG. 4 is a fluorescence spectrum of graphene quantum dots in example 1 of the present invention;
fig. 5 is a transmission electron microscope TEM image of graphene quantum dots in example 1 of the present invention;
fig. 6 is a raman spectrum of graphene quantum dots in example 1 of the present invention;
FIG. 7 is a high resolution C1s state X-ray photoelectron spectrum of a graphene quantum dot of example 1 of the present invention;
FIG. 8 is a fluorescence imaging diagram of a graphene quantum dot micro-nano pattern structure in example 2 of the present invention;
fig. 9 is an optical imaging diagram of a graphene quantum dot micro-nano pattern structure in embodiment 2 of the present invention;
fig. 10 is a fluorescence imaging diagram of a fluorescent anti-counterfeit mark manufactured by graphene quantum dots in embodiment 3 of the present invention.
Fig. 11 is an optical imaging diagram of a fluorescent anti-counterfeit mark manufactured by graphene quantum dots in embodiment 3 of the present invention.
Detailed Description
As shown in fig. 1, a method for manufacturing red luminescent graphene quantum dots with micro-nano pattern structures based on low-temperature electron beam exposure (ice etching) includes the following steps: (1) vapor deposition; (2) electron beam exposure at low temperature; (3) rewarming;
example 1:
a manufacturing method of red luminescent graphene quantum dots with micro-nano pattern structures is disclosed, and the process is shown in fig. 2 a-2 c.
(1) In FIG. 2a, a single anisole vapor is deposited on a substrate at low temperature, during which the anisole vapor pressure drops by 20 millitorr per minute for a total of 300-800 millitorr, forming a uniform, dense amorphous anisole film;
(2) In FIG. 2b, an amorphous anisole film was exposed by electron beam exposure at low temperature (ice lithography) using an acceleration voltage of 5keV at an exposure dose of 0.2mC/cm 2 Gradient was increased to 10.1mC/cm 2 An exposure dose gradient of 0.1mC/cm 2 Manufacturing a square micro-nano pattern array structure with gradient dosage, wherein the size of each square is 10 μm by 10 μm, and the spacing of each square is 20 μm;
(3) In fig. 2c, the exposed thin film is naturally rewarmed, and red luminescent graphene quantum dots with square micro-nano pattern array structures are left on the substrate.
The fluorescence imaging graph (figure 3) and the fluorescence spectrum (figure 4) show that the red fluorescence intensity of the synthesized graphene quantum dots is controllable, and the red fluorescence intensity rises along with the rising of the exposure dose, which shows that the number of the synthesized graphene quantum dots also rises along with the rising of the dose, and the fluorescence emission peak is located at 630nm-650nm under the excitation of 473nm blue light. The optical microscope image shows that the color of the square micro-nano pattern structure of the synthesized graphene quantum dot also changes gradually along with the increase of the exposure dose, which shows that the height of the square micro-nano pattern structure rises gradually along with the increase of the exposure dose. The transmission electron microscope (figure 5) shows that the synthesized graphene quantum dots are spherical particles with the size of about 2-3 nanometers, and have uniform sizes and regular graphite crystal structures. Raman spectroscopy (fig. 6) and high resolution C1s state X-ray photoelectron spectroscopy (fig. 7) indicate that the synthesized graphene quantum dots contain a large number of defect states associated with oxygen-containing functional groups.
Example 2:
the manufacturing schematic diagram of the red luminescent graphene quantum dot with the micro-nano pattern structure is shown in fig. 2 a-2 c.
(1) In fig. 2a, a uniform dense amorphous anisole film is formed by depositing monomeric anisole with vapor on a substrate at low temperature;
(2) In FIG. 2b, an amorphous anisole film was exposed by electron beam exposure at low temperature (ice lithography) using an acceleration voltage of 5keV at an exposure dose of 10mC/cm 2 Gradient was increased to 50.5mC/cm 2 An exposure dose gradient of 0.1mC/cm 2 Manufacturing a square micro-nano pattern array structure with gradient dosage, wherein the size of each square is 10 μm by 10 μm, and the spacing of each square is 20 μm;
(3) In fig. 2c, the exposed thin film is naturally rewarmed, and red luminescent graphene quantum dots with square micro-nano pattern array structures are left on the substrate.
The fluorescence imaging diagram (fig. 8) and the optical imaging diagram (fig. 9) illustrate that the color of the graphene quantum dot with the square micro-nano pattern structure manufactured under the irradiation of the exposure dose exceeding the anisole saturation dose is not changed with the exposure dose any more under the optical microscope, which indicates that the height of the graphene quantum dot structure is not changed any more, but the fluorescence intensity is still increased with the increase of the exposure intensity.
Example 3:
the manufacturing schematic diagram of the red luminescent graphene quantum dot with the micro-nano pattern structure is shown in fig. 2 a-2 c.
(1) Depositing monomer anisole on a substrate at low temperature, wherein the vapor pressure of anisole is reduced by 300 millitorr in the deposition process, so that a uniform compact amorphous anisole film is formed;
(2) Exposing amorphous anisole film by electron beam exposure (ice etching) at low temperature with accelerating voltage of 5keV and exposure dose of 12mC/cm 2 ～20mC/cm 2 The "PAINT" micro-nano pattern was produced with a pattern side length of 33.6X19.36. Mu.m 2 ，
(3) And naturally rewarming the exposed film, and leaving red luminescent graphene quantum dots with a PAINT micro-nano pattern structure on the substrate.
The fluorescent imaging image (figure 10) and the optical imaging image (figure 11) show that the color of the PAINT micro-nano pattern under the light mirror is not different, the fluorescence intensity is increased along with the increase of the exposure dose, and the pattern has the fluorescent anti-counterfeiting mark effect.
Claims (10)
1. The preparation method of the graphene quantum dot is characterized by comprising the following steps of: the organic matter containing benzene ring is used as carbon source, and is prepared by electron beam exposure and ice etching process at low temperature; the luminescent graphene quantum dot can emit red fluorescence under the excitation of blue light.
2. The method for preparing graphene quantum dots according to claim 1, wherein the method comprises the following specific steps:
(1) Placing a substrate in an electron microscope, cooling to a low temperature, and depositing organic gas on the substrate to form an organic ice film;
(2) Exposing the organic ice film in step (1) with an electron beam at a low temperature;
(3) And (3) removing the unexposed ice film in the step (2) to prepare the red luminescent graphene quantum dots.
3. The method for preparing graphene quantum dots according to claim 2, wherein the organic ice film in the step (1) is exposed according to a set pattern in the step (2) to obtain the red luminescent graphene quantum dots with micro-nano pattern structures.
4. The method for preparing graphene quantum dots according to claim 2, wherein the organic substance is any one or a combination of two or more of toluene, ethylbenzene, butylbenzene, xylene, trimethylbenzene, benzyl alcohol, phenethyl alcohol, benzoic acid, gallic acid, styrene, phenylmethane, phenylethane, phenylmethyl amine, anisole, phenetole, benzaldehyde, phenol, acetaminophen, aniline, chlorobenzene, chlorotoluene, dichlorobenzene, iodobenzene, bromobenzene, bromostyrene, bromobenzoic acid; the organic matter ice film is a solid film formed after the organic matter gas is condensed.
5. The method for preparing graphene quantum dots according to claim 2, wherein in the step (2), according to the set pattern, different doses exceeding the saturation dose are used for exposing the amorphous organic ice film to different regions to obtain the graphene quantum dot pattern with the anti-counterfeiting function.
6. A graphene quantum dot, characterized in that it is prepared by the preparation method of any one of claims 1 to 5.
7. The graphene quantum dot according to claim 6, wherein the graphene quantum dot is a spherical particle having a size of about 2nm to 3 nm.
8. The graphene quantum dot according to claim 6, wherein the graphene quantum dot has a regular multi-layered graphite crystal structure.
9. The graphene quantum dot according to claim 6, wherein the graphene quantum dot prepared by using an ice etching process under the excitation of 473nm blue light and different electron beam exposure doses can emit red light with adjustable fluorescence intensity, and the fluorescence emission peak is located at 630nm-650nm.
10. The graphene quantum dot anti-counterfeiting pattern is characterized by being prepared by the preparation method of claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111527301.6A CN116281969B (en) | 2021-12-14 | 2021-12-14 | Red luminous graphene quantum dot and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111527301.6A CN116281969B (en) | 2021-12-14 | 2021-12-14 | Red luminous graphene quantum dot and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116281969A true CN116281969A (en) | 2023-06-23 |
| CN116281969B CN116281969B (en) | 2024-07-05 |
Family
ID=86783806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111527301.6A Active CN116281969B (en) | 2021-12-14 | 2021-12-14 | Red luminous graphene quantum dot and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116281969B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607707A (en) * | 2009-06-27 | 2009-12-23 | 兰州大学 | Adopt electronic beam irradiation technology to prepare the method for Graphene |
| CN103833029A (en) * | 2014-01-10 | 2014-06-04 | 云南师范大学 | Preparation method of high-efficient multicolor-fluorescence water-soluble sulfur oxygen-codoped graphene quantum dot |
| US20190031906A1 (en) * | 2017-07-28 | 2019-01-31 | Samsung Electronics Co., Ltd. | Method of preparing graphene quantum dot, hardmask composition including the graphene quantum dot obtained by the method, method of forming pattern using the hardmask composition, and hardmask formed from the hardmask composition |
| CN110167877A (en) * | 2016-11-06 | 2019-08-23 | 威廉马歇莱思大学 | Manufacture the method for graphene and combinations thereof of induced with laser |
| CN111792622A (en) * | 2020-09-10 | 2020-10-20 | 西湖大学 | Water ice-based electron beam induced etching process |
| CN112925173A (en) * | 2021-01-28 | 2021-06-08 | 西湖大学 | Three-dimensional suspended nanostructure processing method based on ice etching |
| CN113321206A (en) * | 2021-06-02 | 2021-08-31 | 中北大学 | In-situ growth manufacturing method of graphene nano-strips through electron beam induction |
| US20210269711A1 (en) * | 2020-02-28 | 2021-09-02 | Texas Christian University | Near-infrared emissive graphene quantum dots method of manufacture and uses thereof |
| CN113717719A (en) * | 2021-09-09 | 2021-11-30 | 东南大学 | Multi-optical-property carbon dots, and preparation method and application thereof |
-
2021
- 2021-12-14 CN CN202111527301.6A patent/CN116281969B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607707A (en) * | 2009-06-27 | 2009-12-23 | 兰州大学 | Adopt electronic beam irradiation technology to prepare the method for Graphene |
| CN103833029A (en) * | 2014-01-10 | 2014-06-04 | 云南师范大学 | Preparation method of high-efficient multicolor-fluorescence water-soluble sulfur oxygen-codoped graphene quantum dot |
| CN110167877A (en) * | 2016-11-06 | 2019-08-23 | 威廉马歇莱思大学 | Manufacture the method for graphene and combinations thereof of induced with laser |
| US20190031906A1 (en) * | 2017-07-28 | 2019-01-31 | Samsung Electronics Co., Ltd. | Method of preparing graphene quantum dot, hardmask composition including the graphene quantum dot obtained by the method, method of forming pattern using the hardmask composition, and hardmask formed from the hardmask composition |
| US20210269711A1 (en) * | 2020-02-28 | 2021-09-02 | Texas Christian University | Near-infrared emissive graphene quantum dots method of manufacture and uses thereof |
| CN111792622A (en) * | 2020-09-10 | 2020-10-20 | 西湖大学 | Water ice-based electron beam induced etching process |
| CN112925173A (en) * | 2021-01-28 | 2021-06-08 | 西湖大学 | Three-dimensional suspended nanostructure processing method based on ice etching |
| CN113321206A (en) * | 2021-06-02 | 2021-08-31 | 中北大学 | In-situ growth manufacturing method of graphene nano-strips through electron beam induction |
| CN113717719A (en) * | 2021-09-09 | 2021-11-30 | 东南大学 | Multi-optical-property carbon dots, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈炯枢;: "电子束在微/纳制造中的应用进展", 真空与低温, no. 01, 15 March 2007 (2007-03-15), pages 6 - 15 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116281969B (en) | 2024-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | High-resolution patterning of colloidal quantum dots via non-destructive, light-driven ligand crosslinking | |
| Cho et al. | Direct optical patterning of quantum dot light‐emitting diodes via in situ ligand exchange | |
| CN106444132B (en) | Self-emission type photosensitive resin composition, color filter manufactured therefrom, and image display device having the color filter | |
| KR101879016B1 (en) | Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same | |
| KR100904330B1 (en) | Method for pattern formation | |
| US6699642B2 (en) | Method of manufacturing triode carbon nanotube field emitter array | |
| CN111095044A (en) | Colored resin composition, colored film, color filter and liquid crystal display device | |
| Mikulics et al. | Nano-LED array fabrication suitable for future single photon lithography | |
| Fitz-Gerald et al. | Laser direct writing of phosphor screens for high-definition displays | |
| Li et al. | Projection lithography patterned high-resolution quantum dots/thiol-ene photo-polymer pixels for color down conversion | |
| JP2010538419A (en) | Manufacturing method of organic electronic device or optoelectronic device | |
| US7425392B2 (en) | Lithographic template and method of formation and use | |
| Guo et al. | Large‐scale horizontally aligned ZnO microrod arrays with controlled orientation, periodic distribution as building blocks for chip‐in piezo‐phototronic LEDs | |
| US20220352430A1 (en) | Micro light emitting diode array and manufacturing method thereof | |
| US20100015398A1 (en) | Substrate with Partition Pattern and Process for Producing the Same | |
| CN116281969B (en) | Red luminous graphene quantum dot and preparation method and application thereof | |
| JP2003504802A (en) | Method of manufacturing a field emission material and a field electron emitter comprising said material | |
| TW201243500A (en) | Negative photosensitive resin composition and coating film | |
| TW200925223A (en) | Ink composition and method of forming a pattern using the same | |
| CN107219725B (en) | Photosensitive resin composition, color filter and image display device manufactured using the same | |
| JP2006310131A (en) | Color conversion film | |
| JP2011505055A (en) | Cathode assembly including an ultraviolet blocking dielectric layer | |
| US7749556B2 (en) | Method for manufacturing field emission substrate | |
| TWI684613B (en) | Photosensitive resin composition, color filter and image display device produced using the same | |
| CN116096197A (en) | Quantum dot light emitting structure, photoinduced patterning method and application thereof |
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 |