CN113526498A - Preparation method of patterned graphene and manufacturing method of biosensor - Google Patents
Preparation method of patterned graphene and manufacturing method of biosensor Download PDFInfo
- Publication number
- CN113526498A CN113526498A CN202110638584.5A CN202110638584A CN113526498A CN 113526498 A CN113526498 A CN 113526498A CN 202110638584 A CN202110638584 A CN 202110638584A CN 113526498 A CN113526498 A CN 113526498A
- Authority
- CN
- China
- Prior art keywords
- graphene
- photoresist
- patterned
- film
- copper foil
- 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.)
- Pending
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 209
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 154
- 239000011889 copper foil Substances 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000059 patterning Methods 0.000 claims abstract description 26
- 238000005530 etching Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229920002799 BoPET Polymers 0.000 claims description 24
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000004528 spin coating Methods 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 6
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- 229910002601 GaN Inorganic materials 0.000 claims description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 230000037303 wrinkles Effects 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 32
- 238000012546 transfer Methods 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001259 photo etching Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 241000700605 Viruses Species 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000233 ultraviolet lithography 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
- C01B32/194—After-treatment
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
Abstract
The invention relates to the technical field of graphene preparation, in particular to a preparation method of patterned graphene and a manufacturing method of a biosensor. The preparation method of the patterned graphene comprises the following steps: coating photoresist on one side of a copper foil on which graphene grows, curing and forming to complete patterning of the photoresist, etching the graphene according to the patterned photoresist to complete patterning of the graphene, attaching a flexible film serving as a supporting layer to the surface of the photoresist, placing a sample in etching liquid to etch and remove the copper foil, attaching the sample from which the copper foil is removed to a substrate by the graphene side, and removing the flexible film and the photoresist layer. The graphene transferred by the method has no wrinkle or damage. The invention also provides a manufacturing method of the biosensor.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a preparation method of patterned graphene and a manufacturing method of a biosensor.
Background
In recent years, the graphene film batch preparation technology is rapidly developed, and the technology is developed from the first millimeter-scale single crystal graphene to the current meter-scale single crystal graphene, so that support is provided for graphene related application. The bulk preparation of graphene is usually performed on copper foil, and the application of graphene often requires transferring graphene from copper foil to other substrates and patterning. Since graphene has only the thickness of atomic scale and is easily damaged in the transfer process, how to efficiently transfer large-area and patterned graphene is a key technical problem for the application and development of graphene.
The common graphene transfer methods mainly utilize PMMA transfer and photoresist transfer. In the process of transferring by utilizing PMMA, the graphene cannot be directly patterned, and the graphene can be transferred firstly and then patterned on a substrate with the graphene, so that the steps are complex and the efficiency is low. When the graphene is transferred through the photoresist, the photoresist is thin, an additional supporting layer does not exist during transfer, the photoresist/graphene needs to be fished up by manually removing corrosive liquid, the operation capability of an operator is tested very easily in the step, efficient transfer is difficult to realize, the photoetching treatment is also carried out after the graphene is transferred to the substrate, the transferred graphene is prone to wrinkling and breakage, and the method is difficult to realize transfer of the graphene to the flexible substrate. In addition, after the copper foil is corroded, the photoresist is used as a supporting layer and a photoetching layer, and the subsequent photoetching success rate is low due to the multiple actions of the etching liquid and the cleaning liquid on the photoresist. Therefore, technology breakthroughs are still needed for lossless and efficient transfer of large-area patterned graphene.
Disclosure of Invention
Based on the method, the invention provides a preparation method of patterned graphene. Researches show that the transfer efficiency and the photoetching success rate of the method are high, and the transferred graphene is free from wrinkles or damages.
A preparation method of patterned graphene comprises the following steps:
coating photoresist on one side of a copper foil on which graphene grows, and completing patterning of the photoresist after curing and forming;
etching the graphene according to the patterned photoresist to complete the patterning of the graphene;
sticking a flexible film serving as a supporting layer on the surface of the photoresist, and placing a sample in etching liquid to etch and remove the copper foil;
and attaching the sample with the copper foil removed to a substrate by using the graphene side, and removing the flexible film and the photoresist layer.
Optionally, in the preparation method of the patterned graphene, the flexible film is a PET film, a PI film, a TPU film, a PP film, a PVC film, a CPP film, an OPP film, a BOPP film, an MOPP film, or a PE film.
Optionally, in the method for preparing patterned graphene, the substrate is a silicon wafer, a silicon carbide substrate, a gallium nitride substrate, a PVA substrate, a PET substrate, a PI substrate, or a PDMS substrate.
Optionally, in the preparation method of the patterned graphene, the photoresist is RZJ-304 positive photoresist or S1805 positive photoresist;
the coating mode of the photoresist is spin coating, and the thickness of the spin coating is 1-3 mu m;
the curing and forming mode of the photoresist is heating curing, and the heating temperature is 80-120 ℃.
Optionally, as in the above method for preparing patterned graphene, the method for removing the photoresist layer is wet photoresist removal.
Optionally, in the preparation method of patterned graphene, the solvent used in the wet photoresist stripping is at least one of acetone, isopropanol and ethanol.
Optionally, in the preparation method of patterned graphene, the etching solution is at least one of ammonium persulfate, potassium persulfate, and ferric chloride.
Optionally, in the method for preparing patterned graphene, after the copper foil is removed, a step of washing the sample in deionized water is further included.
Optionally, in the preparation method of the patterned graphene, the condition for laterally attaching the graphene to the substrate is heating and attaching, and the heating temperature is 80-120 ℃.
In one aspect of the present invention, there is also provided a method for manufacturing a biosensor, comprising the steps of:
patterning graphene using the method as described above;
coating photoresist on the graphene surface and exposing a pattern, and evaporating an electrode coating by an electron beam evaporation process;
and (4) carrying out a stripping process on the evaporated sample to manufacture the biosensor.
Has the advantages that:
according to the invention, the photoetching success rate is high by sequentially carrying out the patterning treatment on the photoresist and the graphene before the copper foil is etched, so that a complete graphene pattern can be obtained, and the lossless graphene can also be obtained after the transfer. And the photoresist is used only once in the whole transfer and patterning process, so that the problem of polymer macromolecule residue on the surface of the graphene caused by repeated use of the photoresist is avoided, and the performance of the graphene cannot be reduced.
In addition, in the process of transferring graphene, a flexible thin film with certain mechanical strength is used as a supporting layer to be combined with a photoresist layer to transfer graphene, so that on one hand, the graphene can be transferred to any substrate, even a flexible substrate, and the graphene can be patterned on the flexible substrate; on the other hand, what is more important is that the efficient and quick transfer can be ensured during the transfer, and the flexible film is not in contact with the graphene, so that the phenomenon that the graphene is folded and damaged in the transfer process is avoided, and the problem that the graphene is damaged when the flexible film is removed is also avoided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic process flow diagram of transferring patterned graphene in one embodiment of the present invention;
in the figure: 1-copper foil; 2-a graphene layer; 3-a photoresist layer; 4-a flexible film; 5-a substrate;
fig. 2 is an optical microscope image of patterned graphene transferred in one embodiment of the present invention;
fig. 3 is a diagram of patterned graphene transferred onto a flexible substrate in another embodiment of the invention;
FIG. 4 is an optical microscope photograph of graphene transferred in a comparative example of the present invention;
fig. 5 is an optical microscope image of graphene transferred in another comparative example of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
Description of the terms
The lift-off process is to obtain a patterned photoresist structure or a mask such as a metal mask by a photolithography process, plate a target coating on the mask by a plating process, and then obtain a target coating structure consistent with the pattern by dissolving the photoresist by a photoresist remover or mechanically removing the metal hard mask.
The invention provides a preparation method of patterned graphene, which comprises the following steps:
coating the photoresist on one side of the copper foil on which the graphene grows, and curing and forming to complete patterning of the photoresist;
etching the graphene according to the patterned photoresist to complete the patterning of the graphene;
sticking a flexible film serving as a supporting layer on the surface of the photoresist, and placing a sample in etching liquid to etch and remove the copper foil;
and (3) attaching the sample with the copper foil removed to the substrate in a graphene side mode, and removing the flexible thin film and the photoresist layer.
The photoetching success rate is high by the process of sequentially patterning the photoresist and the graphene before etching the copper foil, so that a complete graphene pattern can be obtained, and lossless graphene can be obtained after transfer.
In some embodiments, the flexible film is not limited, because the flexible film is used as the support layer in the present invention, and therefore, the selected flexible film needs to have a certain mechanical strength, including but not limited to PET film, PI film, TPU film, PP film, PVC film, CPP film, OPP film, BOPP film, MOPP film or PE film. Preferably, the flexible film is a PET film.
The graphene is transferred by selecting the flexible thin film with certain mechanical strength as the supporting layer, so that the graphene can be transferred to any substrate, even a flexible substrate, and the graphene can be patterned on the flexible substrate; on the other hand, what is more important is that the efficient and quick transfer can be ensured during the transfer, and the flexible film is not in contact with the graphene, so that the phenomenon that the graphene is folded and damaged in the transfer process is avoided, and the problem that the graphene is damaged when the flexible film is removed is also avoided.
In some embodiments, the etching solution may be any solvent capable of corroding the copper foil, and may be at least one of ammonium persulfate, potassium persulfate, and ferric chloride, for example. Preferably, the etching liquid is ammonium persulfate. Etching the copper foil with ammonium persulfate can avoid introducing other new impurities during the etching process.
In some embodiments, the substrate may be any one of the substrates commonly used in the art, such as a silicon wafer, a silicon carbide substrate, or a gallium nitride substrate, and a flexible substrate, typically a flexible polymer substrate, including but not limited to a PVA substrate, a PET substrate, a PI substrate, or a PDMS substrate, may also be used.
In some embodiments, the positive photoresist used to make the exposed portions soluble in the developer may be RZJ-304 positive photoresist or S1805 positive photoresist.
In some embodiments, the method of removing the photoresist is a wet stripping.
In some embodiments, the solvent for wet stripping may be at least one of acetone, isopropanol, and ethanol. Preferably, the solvent is acetone and/or isopropanol.
In some embodiments, the specific step of removing the photoresist layer is to wash the sample in acetone at 50-70 ℃ for 10-15 min, and then wash the graphene surface with isopropanol or ethanol.
In some embodiments, the photoresist is coated by spin coating, the amount of the spin coating is 2 mL-6 mL, the initial rotation speed of the spin coating is 300 r/min-600 r/min for 4 s-8 s, the high rotation speed of the spin coating is 1000 r/min-6000 r/min for 20 s-70 s, and the thickness of the spin coating is 1 μm-3 μm;
in some embodiments, the photoresist is cured by heating at a temperature of 80-120 ℃.
In some embodiments, the specific step of patterning the photoresist comprises exposing the sample after the photoresist is cured to ultraviolet light and then developing the sample in a developing solution. Wherein the exposure time is 5 s-8 s, the exposure dosage is 8W-12W, the developing time is 50 s-70 s, and the developing solution is 3080 developing solution.
In some embodiments, the specific step of graphene patterning is bombarding the graphene surface with oxygen plasma. The graphene has been patterned before the photoresist is etched, thereby making the lithography success rate very high.
In some embodiments, the method further comprises the step of washing the sample after removing the copper foil in deionized water.
In some embodiments, the graphene side is attached to the substrate by heating at a temperature of 80 ℃ to 120 ℃.
In one aspect of the present invention, there is also provided a method for manufacturing a biosensor, comprising the steps of:
patterning graphene using the method as described above;
coating photoresist on the graphene surface and exposing a pattern, and evaporating an electrode coating by an electron beam evaporation process;
and (4) carrying out a stripping process on the evaporated sample to manufacture the biosensor.
In some embodiments, the stripping process removes the photoresist using a stripping solution, wherein the stripping solution is commonly used in the art, and may be, for example, ethanol and/or acetone.
In some embodiments, the electrode in the electrode coating is not particularly limited, and is based on an electrode commonly used in the art, and may be, for example, Ti — Au, Cr — Au, or the like. Preferably, the electrode is Ti-Au, wherein the thickness of the Ti electrode is 8 nm-12 nm, and the thickness of the Au electrode is 85 nm-95 nm. Preferably, the Ti electrode has a thickness of 10nm and the Au electrode has a thickness of 90 nm.
In another aspect of the present invention, there is further provided a biosensor prepared as described above.
It should be noted that the biosensor prepared in the present invention has similar performance and use as a general biosensor, and can be used for virus detection, for example. The detection principle is that whether viruses exist or not is detected through the change of the electrical property of the graphene.
The method for preparing the patterned graphene, the biosensor and the method for manufacturing the same according to the present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1 preparation of patterned graphite
Fig. 1 is a schematic flow chart of transferring large-area patterned graphene in this embodiment, in which the photoresist layer 3 is RZJ-304 positive photoresist layer, the flexible substrate 4 is a PET film, and the substrate 5 is a silicon wafer.
The method comprises the following specific steps:
1) as shown in (a) and (b) of fig. 1, RZJ-304 positive photoresist is firstly spin-coated at a rotation speed of 500r/min for 5s, and then spin-coated at 3000r/min for 60s onto the copper foil 1 on which the graphene layer 2 has been grown, wherein the spin-coating thickness is 1.6 μm, and the spin-coating amount is 4mL, so as to form a photoresist layer 3-graphene layer 2-copper foil 1 structure. Then placing the photoresist layer 3-graphene layer 2-copper foil 1 on a heating plate at 100 ℃ for heating and baking to solidify the photoresist layer 3;
2) as shown in fig. 1 (c), the photoresist layer 3-graphene layer 2-copper foil 1 was placed on an ultraviolet lithography machine and exposed for 6s with an exposure dose of 10W. Then, the exposed photoresist layer 3-graphene layer 2-copper foil 1 is placed into 3080 developing solution for development for 60s, and patterning of the photoresist is completed to form a patterned photoresist layer 3-graphene layer 2-copper foil 1 structure;
3) as shown in fig. 1 (d), the patterned photoresist layer 3-graphene layer 2-copper foil 1 is placed in a plasma cleaning machine, oxygen plasma is used to bombard the surface of graphene, so as to complete the patterning of graphene, and a patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 structure is formed;
4) as shown in fig. 1 (e), a PET film is attached to the surface of the patterned photoresist layer 3, and is pressed by a glass plate to be tightly attached to the patterned photoresist layer 3, so as to form a PET film-patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 structure;
5) as shown in fig. 1 (f), the PET film-patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 is placed in an ammonium persulfate solution with a concentration of 0.1mol/L to be etched for 2h to remove the copper foil 1 to form a PET film-patterned photoresist layer 3-patterned graphene layer 2 structure, and after the structure is placed in deionized water to be cleaned, the deionized water remained on the surface of the patterned graphene layer 2 is dried by a nitrogen gun;
6) as shown in fig. 1 (g), the patterned graphene layer 2 in the PET film-patterned photoresist layer 3-patterned graphene layer 2 structure is bonded to a cleaned silicon wafer, and then heated on a heating plate at 100 ℃ for 30min to be tightly bonded, so as to form a PET film-patterned photoresist layer 3-patterned graphene layer 2-silicon wafer structure;
7) as shown in fig. 1 (h) and (i), the PET film in step 6) is removed, the patterned photoresist layer 3-patterned graphene layer 2-silicon wafer is placed in acetone at 70 ℃ for cleaning for 10min to remove the patterned photoresist layer 3, and then the patterned photoresist layer 2 is taken out and washed with isopropanol to remove the residual acetone, so that the patterned graphene is obtained by transfer.
As shown in fig. 2, the patterned graphene surface obtained by transferring in this example was found to be flat and free from wrinkles and breakage by observing the patterned graphene surface prepared as described above through an optical microscope.
Example 2 preparation of patterned graphite
The preparation method of example 2 is substantially the same as that of example 1 except that: the substrate 5 is a PDMS flexible substrate. In this embodiment, the photoresist layer 3 is a RZJ-304 positive photoresist layer, the flexible substrate 4 is a PET film, and the substrate 5 is a PDMS flexible substrate. The method comprises the following specific steps:
1) the RZJ-304 positive photoresist is firstly spin-coated for 5s at the rotating speed of 500r/min, then spin-coated for 60s at 3000r/min to the copper foil 1 on which the graphene layer 2 grows, the spin-coating thickness is 1.6 mu m, and the spin-coating amount is 4mL, so that the photoresist layer 3-graphene layer 2-copper foil 1 structure is formed. Then placing the photoresist layer 3-graphene layer 2-copper foil 1 on a heating plate at 100 ℃ for heating and baking to solidify the photoresist layer 3;
2) and placing the photoresist layer 3-graphene layer 2-copper foil 1 on an ultraviolet photoetching machine for exposure for 6s, wherein the exposure dosage is 10W. Then, the exposed photoresist layer 3-graphene layer 2-copper foil 1 is placed into 3080 developing solution for development for 60s, and patterning of the photoresist is completed to form a patterned photoresist layer 3-graphene layer 2-copper foil 1 structure;
3) placing the patterned photoresist layer 3-graphene layer 2-copper foil 1 in a plasma cleaning machine, bombarding the surface of graphene by using oxygen plasma to complete the patterning of the graphene, and forming a patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 structure;
4) attaching a PET film to the surface of the patterned photoresist layer 3, and pressing the PET film and the patterned photoresist layer by using a glass plate to enable the PET film and the patterned photoresist layer 3 to be tightly attached to form a PET film-patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 structure;
5) placing the PET film-patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 into ammonium persulfate solution with the concentration of 0.1mol/L for etching for 2h to remove the copper foil 1 to form a PET film-patterned photoresist layer 3-patterned graphene layer 2 structure, placing the PET film-patterned photoresist layer 3-patterned graphene layer 2 structure into deionized water for cleaning, and then drying the residual deionized water on the surface of the patterned graphene layer 2 by using a nitrogen gun;
6) attaching the patterned graphene layer 2 in the PET film-patterned photoresist layer 3-patterned graphene layer 2 structure to a cleaned PDMS flexible substrate, and then heating the attached substrate on a heating plate at 100 ℃ for 30min to attach the substrate tightly, so as to form a PET film-patterned photoresist layer 3-patterned graphene layer 2-PDMS flexible substrate structure;
7) uncovering the PET film in the step 6), placing the patterned photoresist layer 3-patterned graphene layer 2-PDMS flexible substrate in acetone at 70 ℃ for cleaning for 10min to remove the patterned photoresist layer 3, taking out the patterned photoresist layer and washing the surface of the patterned graphene layer 2 with isopropanol to remove residual acetone, and transferring to obtain the patterned graphene.
As shown in fig. 3, the patterned graphene transferred by the method of this embodiment has a smooth surface and is free from wrinkles and damages.
EXAMPLE 3 preparation of biosensor
In this embodiment, the photoresist layer 3 is RZJ-304 positive photoresist layer, the flexible substrate 4 is a PET film, and the substrate 5 is a silicon wafer.
1) The RZJ-304 positive photoresist is firstly spin-coated for 5s at the rotating speed of 500r/min, then spin-coated for 60s at 3000r/min to the copper foil 1 on which the graphene layer 2 grows, the spin-coating thickness is 1.6 mu m, and the spin-coating amount is 4mL, so that the photoresist layer 3-graphene layer 2-copper foil 1 structure is formed. Then placing the photoresist layer 3-graphene layer 2-copper foil 1 on a heating plate at 100 ℃ for heating and baking to solidify the photoresist layer 3;
2) and placing the photoresist layer 3-graphene layer 2-copper foil 1 on an ultraviolet photoetching machine for exposure for 6s, wherein the exposure dosage is 10W. Then, the exposed photoresist layer 3-graphene layer 2-copper foil 1 is placed into 3080 developing solution for development for 60s, and patterning of the photoresist is completed to form a patterned photoresist layer 3-graphene layer 2-copper foil 1 structure;
3) placing the patterned photoresist layer 3-graphene layer 2-copper foil 1 in a plasma cleaning machine, bombarding the surface of graphene by using oxygen plasma to complete the patterning of the graphene, and forming a patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 structure;
4) attaching a PET film to the surface of the patterned photoresist layer 3, and pressing the PET film and the patterned photoresist layer by using a glass plate to enable the PET film and the patterned photoresist layer 3 to be tightly attached to form a PET film-patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 structure;
5) placing the PET film-patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 into ammonium persulfate solution with the concentration of 0.1mol/L for etching for 2h to remove the copper foil 1 to form a PET film-patterned photoresist layer 3-patterned graphene layer 2 structure, placing the PET film-patterned photoresist layer 3-patterned graphene layer 2 structure into deionized water for cleaning, and then drying the residual deionized water on the surface of the patterned graphene layer 2 by using a nitrogen gun;
6) after the patterned graphene layer 2 in the structure of the PET film-patterned photoresist layer 3-patterned graphene layer 2 is attached to a cleaned silicon wafer, the cleaned silicon wafer is placed on a heating plate at 100 ℃ to be heated for 30min so as to be tightly attached to the cleaned silicon wafer, and the structure of the PET film-patterned photoresist layer 3-patterned graphene layer 2-silicon wafer is formed;
7) uncovering the PET film in the step 6), placing the patterned photoresist layer 3-patterned graphene layer 2-silicon wafer in acetone at 70 ℃ for cleaning for 10min to remove the patterned photoresist layer 3, taking out and washing the surface of the patterned graphene layer 2 with isopropanol to remove residual acetone, thus obtaining the patterned graphene layer 2-silicon wafer;
8) and (3) spin-coating photoresist on the patterned graphene layer 2 in the step 7) and exposing to obtain an electrode pattern, and then evaporating a Ti electrode with the thickness of 10nm and an Au electrode with the thickness of 90nm by using an electron beam evaporation process. And after the evaporation is finished, putting the graphene into acetone for stripping (lift-off) to obtain the graphene biosensor.
Comparative example 1
This comparative example differs from example 1 in that: the PET film is directly attached to the graphene layer 2 without a photoresist layer 3. In the comparative example, the flexible substrate 4 is a PET film, and the substrate 5 is a silicon wafer. The method comprises the following specific steps:
1) placing the copper foil 1 with the grown graphene layer 2 in a plasma cleaning machine, bombarding the surface of graphene by using oxygen plasma to complete the patterning of the graphene, and forming a patterned graphene layer 2-copper foil 1 structure;
2) attaching a PET film to the surface of the patterned graphene layer 2, and pressing the PET film and the patterned graphene layer 2-copper foil 1 by using a glass plate to enable the PET film and the patterned graphene layer 2-copper foil to be tightly attached to each other;
3) placing the PET film-patterned graphene layer 2-copper foil 1 into an ammonium persulfate solution with the concentration of 0.1mol/L for etching for 2h to remove the copper foil 1 to form a PET film-patterned graphene layer 2 structure, placing the PET film-patterned graphene layer 2 structure into deionized water for cleaning, and then blowing the deionized water remained on the surface of the patterned graphene layer 2 by using a nitrogen gun;
4) and (3) attaching the patterned graphene layer 2 in the PET film-patterned graphene layer 2 to a cleaned silicon wafer, then placing the silicon wafer on a heating plate at 100 ℃ for heating for 30min to attach tightly, and removing the PET film, namely transferring to obtain the patterned graphene.
As shown in fig. 4, the patterned graphene surface obtained by the contrast transfer was observed through an optical microscope, and it was found that the patterned graphene surface obtained by the contrast transfer was prone to wrinkles and breakage.
Comparative example 2
This comparative example was prepared substantially the same as example 1, except that: patterned graphene was prepared by photoresist transfer only, without a PET film. In this comparative example, the photoresist layer 3 was RZJ-304 positive photoresist layer, and the substrate 5 was a silicon wafer. The method comprises the following specific steps:
1) the RZJ-304 positive photoresist is firstly spin-coated for 5s at the rotating speed of 500r/min, then spin-coated for 60s at 3000r/min to the copper foil 1 on which the graphene layer 2 grows, the spin-coating thickness is 1.6 mu m, and the spin-coating amount is 4mL, so that the photoresist layer 3-graphene layer 2-copper foil 1 structure is formed. Then placing the photoresist layer 3-graphene layer 2-copper foil 1 on a heating plate at 100 ℃ for heating and baking to solidify the photoresist layer 3;
2) and placing the photoresist layer 3-graphene layer 2-copper foil 1 on an ultraviolet photoetching machine for exposure for 6s, wherein the exposure dosage is 10W. Then, the exposed photoresist layer 3-graphene layer 2-copper foil 1 is placed into 3080 developing solution for development for 60s, and patterning of the photoresist is completed to form a photoresist layer 3-graphene layer 2-copper foil 1 structure;
3) placing the patterned photoresist layer 3-graphene layer 2-copper foil 1 in a plasma cleaning machine, bombarding the surface of graphene by using oxygen plasma to complete the patterning of the graphene, and forming a patterned photoresist layer 3-patterned graphene layer 2-copper foil 1 structure;
4) placing the patterned photoresist layer 3-the patterned graphene layer 2-the copper foil 1 into ammonium persulfate solution with the concentration of 0.1mol/L to etch for 2h to remove the copper foil to form a patterned photoresist layer 3-the patterned graphene layer 2 structure, placing the patterned photoresist layer 3-the patterned graphene layer 2 structure into deionized water to be cleaned, and then drying the deionized water remained on the surface of the patterned graphene layer 2 by using a nitrogen gun;
5) after the patterned graphene layer 2 in the patterned photoresist layer 3-patterned graphene layer 2 is attached to a cleaned silicon wafer, the cleaned silicon wafer is placed on a heating plate at 100 ℃ to be heated for 30min so as to be tightly attached to the silicon wafer, and a patterned photoresist layer 3-patterned graphene layer 2-silicon wafer structure is formed;
6) and (3) placing the patterned photoresist layer 3-the patterned graphene layer 2-the silicon wafer in acetone at 70 ℃ for cleaning for 10min to remove the patterned photoresist layer 3, taking out and washing the surface of the patterned graphene layer 2 with isopropanol to remove residual acetone, namely transferring to obtain the patterned graphene.
As shown in fig. 5, the patterned graphene surface transferred by the method described in this comparative example showed more wrinkles and breakage.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of patterned graphene is characterized by comprising the following steps:
coating photoresist on one side of a copper foil on which graphene grows, and completing patterning of the photoresist after curing and forming;
etching the graphene according to the patterned photoresist to complete the patterning of the graphene;
sticking a flexible film serving as a supporting layer on the surface of the photoresist, and placing a sample in etching liquid to etch and remove the copper foil;
and attaching the sample with the copper foil removed to a substrate by using the graphene side, and removing the flexible film and the photoresist layer.
2. The method of claim 1, wherein the flexible film is a PET film, a PI film, a TPU film, a PP film, a PVC film, a CPP film, an OPP film, a BOPP film, a MOPP film, or a PE film.
3. The method of claim 1, wherein the substrate is a silicon wafer, a silicon carbide substrate, a gallium nitride substrate, a PVA substrate, a PET substrate, a PI substrate, or a PDMS substrate.
4. The method of claim 1, wherein the photoresist is RZJ-304 positive photoresist or S1805 positive photoresist;
the coating mode of the photoresist is spin coating, and the thickness of the spin coating is 1-3 mu m;
the curing and forming mode of the photoresist is heating curing, and the heating temperature is 80-120 ℃.
5. The method for preparing patterned graphene according to claim 4, wherein the photoresist layer is removed by a wet stripping method.
6. The method according to claim 5, wherein the solvent used for wet stripping is at least one of acetone, isopropanol and ethanol.
7. The method according to claim 1 or 2, wherein the etching solution is at least one of ammonium persulfate, potassium persulfate, and ferric chloride.
8. The method for preparing patterned graphene according to any one of claims 1 to 6, further comprising a step of washing the sample after removing the copper foil in deionized water after removing the copper foil.
9. The method for preparing patterned graphene according to any one of claims 1 to 6, wherein the graphene is laterally attached to the substrate under a condition of heating and attaching, and the heating temperature is 80 ℃ to 120 ℃.
10. A method of manufacturing a biosensor, comprising the steps of:
patterning graphene using a method according to any one of claims 1 to 9;
coating photoresist on the graphene surface and exposing a pattern, and evaporating an electrode coating by an electron beam evaporation process;
and (4) carrying out a stripping process on the evaporated sample to manufacture the biosensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110638584.5A CN113526498A (en) | 2021-06-08 | 2021-06-08 | Preparation method of patterned graphene and manufacturing method of biosensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110638584.5A CN113526498A (en) | 2021-06-08 | 2021-06-08 | Preparation method of patterned graphene and manufacturing method of biosensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113526498A true CN113526498A (en) | 2021-10-22 |
Family
ID=78095746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110638584.5A Pending CN113526498A (en) | 2021-06-08 | 2021-06-08 | Preparation method of patterned graphene and manufacturing method of biosensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113526498A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114023848A (en) * | 2021-11-03 | 2022-02-08 | 广东工业大学 | Method for patterning two-dimensional semi-metal film and application thereof |
| CN114229838A (en) * | 2021-12-27 | 2022-03-25 | 松山湖材料实验室 | Graphene device, multilayer film, and manufacturing method and application thereof |
| WO2024045863A1 (en) * | 2022-08-30 | 2024-03-07 | 松山湖材料实验室 | Graphene biosensor and preparation method therefor |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060292A (en) * | 2009-11-12 | 2011-05-18 | 三星电子株式会社 | Methods of manufacturing and transferring larger-sized graphene |
| CN102479819A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院微电子研究所 | Field effect transistor (FET) and preparation method thereof |
| US20130098540A1 (en) * | 2011-10-24 | 2013-04-25 | Samsung Electronics Co., Ltd. | Graphene-transferring member, graphene transferrer, method of transferring graphene, and methods of fabricating graphene device by using the same |
| CN104166307A (en) * | 2014-08-14 | 2014-11-26 | 深圳市贝特瑞纳米科技有限公司 | Graphical method for graphene thin film, functional device and application of graphene thin film |
| CN105679678A (en) * | 2016-03-18 | 2016-06-15 | 武汉华星光电技术有限公司 | Preparation method for graphene thin film transistor |
| CN106185900A (en) * | 2016-07-12 | 2016-12-07 | 中国科学院上海微系统与信息技术研究所 | A kind of method shifting Graphene |
| CN106672956A (en) * | 2017-01-21 | 2017-05-17 | 德阳烯碳科技有限公司 | Large-scale graphene transferring method |
| CN107673326A (en) * | 2016-08-02 | 2018-02-09 | 福建新峰二维材料科技有限公司 | A kind of graphene transfer method |
| KR20180091569A (en) * | 2017-02-07 | 2018-08-16 | 주식회사 가온인터내셔널 | Method for manufacturing pattern using graphene |
| CN110174197A (en) * | 2019-05-28 | 2019-08-27 | 北京旭碳新材料科技有限公司 | Graphene-based piezoresistive pressure sensor and preparation method thereof |
| CN111661842A (en) * | 2020-05-15 | 2020-09-15 | 西安交通大学 | Operation method for transferring graphene |
-
2021
- 2021-06-08 CN CN202110638584.5A patent/CN113526498A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060292A (en) * | 2009-11-12 | 2011-05-18 | 三星电子株式会社 | Methods of manufacturing and transferring larger-sized graphene |
| CN102479819A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院微电子研究所 | Field effect transistor (FET) and preparation method thereof |
| US20130098540A1 (en) * | 2011-10-24 | 2013-04-25 | Samsung Electronics Co., Ltd. | Graphene-transferring member, graphene transferrer, method of transferring graphene, and methods of fabricating graphene device by using the same |
| CN104166307A (en) * | 2014-08-14 | 2014-11-26 | 深圳市贝特瑞纳米科技有限公司 | Graphical method for graphene thin film, functional device and application of graphene thin film |
| CN105679678A (en) * | 2016-03-18 | 2016-06-15 | 武汉华星光电技术有限公司 | Preparation method for graphene thin film transistor |
| CN106185900A (en) * | 2016-07-12 | 2016-12-07 | 中国科学院上海微系统与信息技术研究所 | A kind of method shifting Graphene |
| CN107673326A (en) * | 2016-08-02 | 2018-02-09 | 福建新峰二维材料科技有限公司 | A kind of graphene transfer method |
| CN106672956A (en) * | 2017-01-21 | 2017-05-17 | 德阳烯碳科技有限公司 | Large-scale graphene transferring method |
| KR20180091569A (en) * | 2017-02-07 | 2018-08-16 | 주식회사 가온인터내셔널 | Method for manufacturing pattern using graphene |
| CN110174197A (en) * | 2019-05-28 | 2019-08-27 | 北京旭碳新材料科技有限公司 | Graphene-based piezoresistive pressure sensor and preparation method thereof |
| CN111661842A (en) * | 2020-05-15 | 2020-09-15 | 西安交通大学 | Operation method for transferring graphene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114023848A (en) * | 2021-11-03 | 2022-02-08 | 广东工业大学 | Method for patterning two-dimensional semi-metal film and application thereof |
| CN114229838A (en) * | 2021-12-27 | 2022-03-25 | 松山湖材料实验室 | Graphene device, multilayer film, and manufacturing method and application thereof |
| CN114229838B (en) * | 2021-12-27 | 2023-04-11 | 松山湖材料实验室 | Graphene device, multilayer film, and manufacturing method and application thereof |
| WO2024045863A1 (en) * | 2022-08-30 | 2024-03-07 | 松山湖材料实验室 | Graphene biosensor and preparation method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113526498A (en) | Preparation method of patterned graphene and manufacturing method of biosensor | |
| JP5492667B2 (en) | Nanoimprint resist and nanoimprint method | |
| US6391523B1 (en) | Fast drying thick film negative photoresist | |
| TWI534072B (en) | Method of producing substrate provided with nanostructure on surface thereof | |
| CN108389784B (en) | The preparation method of patterned metal layer | |
| JP2004513515A (en) | Amorphous carbon layer for improved adhesion of photoresist | |
| CN109801739A (en) | A kind of stretchable electrode of patterns of high precisionization and preparation method thereof | |
| JPH0259452B2 (en) | ||
| CN104483812A (en) | Method for preparing high-density flat pattern by using thermal development enhanced electron beam photoresist contrast ratio | |
| WO2022257923A1 (en) | Photolithography method based on bilayer photoresist | |
| KR100911183B1 (en) | Fabrication of flexible substrate employed a thin film of patterned carbon nano tube | |
| CN109300774A (en) | A kind of micron order contains the method for processing and the transfer of the graphene layer of metal electrode | |
| WO2009086184A1 (en) | Organo-metallic hybrid materials for micro- and nanofabrication | |
| TWI248138B (en) | Electronic device manufacture | |
| JPH09507966A (en) | Planarized novolac polymer films for microelectronic structures | |
| TWI379166B (en) | ||
| KR101789921B1 (en) | Method of manufacturing a nano thin-layer pattern structure | |
| JPH0128368B2 (en) | ||
| CN111158215A (en) | Method for carrying out photoetching by transferring graphene by using ultraviolet photoresist as supporting layer | |
| CN116313762A (en) | Transfer method of metal electrode | |
| CN115373215A (en) | Method for preparing film mask plate by adopting photoetching method and application thereof | |
| CN115440585A (en) | Metal nanostructure and ion beam etching processing method thereof | |
| US5755947A (en) | Adhesion enhancement for underplating problem | |
| CN110600538B (en) | Application of ionic gel in graphene transfer and preparation of graphene transistor, graphene transistor and preparation method of graphene transistor | |
| CN103496664A (en) | Method for manufacturing self-support polymer structure with large depth-width ratio |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221205 Address after: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000 Applicant after: Material Laboratory of Songshan Lake Applicant after: INSTITUTE OF PHYSICS, CHINESE ACADEMY OF SCIENCES Address before: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000 Applicant before: Material Laboratory of Songshan Lake |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211022 |