AU2020103599A4 - Preparation Method of CVD Graphene Planar Micro Super Capacitor - Google Patents
Preparation Method of CVD Graphene Planar Micro Super Capacitor Download PDFInfo
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- AU2020103599A4 AU2020103599A4 AU2020103599A AU2020103599A AU2020103599A4 AU 2020103599 A4 AU2020103599 A4 AU 2020103599A4 AU 2020103599 A AU2020103599 A AU 2020103599A AU 2020103599 A AU2020103599 A AU 2020103599A AU 2020103599 A4 AU2020103599 A4 AU 2020103599A4
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003990 capacitor Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 25
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 25
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 25
- 238000001259 photo etching Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002791 soaking Methods 0.000 claims description 20
- GZRQNURXIQGETR-UHFFFAOYSA-N methane;methyl 2-methylprop-2-enoate Chemical compound C.COC(=O)C(C)=C GZRQNURXIQGETR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000861 blow drying Methods 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 229920002120 photoresistant polymer Polymers 0.000 claims description 17
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 11
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- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
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- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000001020 plasma etching Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 102000020897 Formins Human genes 0.000 claims description 2
- 108091022623 Formins Proteins 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 229920006267 polyester film Polymers 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 230000010354 integration Effects 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
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- 239000007772 electrode material Substances 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 239000006262 metallic foam Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000001459 lithography Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000000059 patterning Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/40—Alkaline compositions for etching other metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F4/00—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of CVD graphene planar micro super
capacitor, which mainly solves the problems of large volume, small effective contact area
between an electrolyte and an electrode, and blocked charge transmission of the traditional
super capacitor. The realization scheme comprises the following steps of: pretreating catalytic
metal; preparing graphene on the pretreated metal by using a CVD method, and transferring
the graphene onto a target substrate by using polymethyl methacrylate; designing an interdigital
photoetching mask plate; depositing a metal current collector by using E-Beam equipment;
preparing a graphene microelectrode by using a photoetching process; and dripping gel
electrolyte on the surface of the graphene microelectrode to prepare a graphene planar micro
super capacitor. The graphene planar micro super capacitor prepared by the invention has the
advantages of small volume, high integration and flexibility, shortened transportation distance
for transferring charges, improved utilization area of electrode materials, reduced obstruction
of transferred charges in transportation, increased frequency response, and capability of being
used for wearable equipment.
1/7
Metal pretreatment
CVD method for preparing and transferring graphene
Mask plate for designing interdigital structure
E-Beam depositing metal current collector
Photoetching to form graphene
microelectrode
Graphene planar super capacitor prepared by dripping gel electrolyte
Figure I
Description
1/7
Metal pretreatment
CVD method for preparing and transferring graphene
Mask plate for designing interdigital structure
E-Beam depositing metal current collector
Photoetching to form graphene microelectrode
Graphene planar super capacitor prepared by dripping gel electrolyte
Figure I
Preparation Method of CVD Graphene Planar Micro Super Capacitor
[01] The invention belongs to the technical field of semiconductor devices, and particularly relates to a preparation method of a chemical vapor deposition CVD graphene planar micro super capacitor, which can be used for manufacturing a large integrated circuit.
[02] The super capacitor is an energy device with quick charge and discharge ability and long service life. In addition, the super capacitor has higher energy density and power density compared with the traditional battery, and is widely applied to various fields of equipment. The traditional super capacitor has a sandwich structure and consists of a positive electrode, a negative electrode, an electrode liquid, a diaphragm and the like.
[03] With the rapid development of microminiaturization, flexibility and integration electronic devices and systems, such as biological detection, distance control system, radio frequency detection and microelectromechanical system, the required energy self-supply system also needs to meet the characteristics of microminiaturization, flexibility and integration, and the energy devices are intended to be embedded into portable electronic devices. The traditional super capacitors have the defects of large volume, heavy mass, no bending and low power density, so that the application of the traditional super capacitors in the micro devices is limited. The development of super capacitors with characteristics of microminiaturization, flexibility and integration is very urgent. Compared with the traditional sandwich super capacitor, the planar micro super capacitor has the characteristic of two-dimensional integrated patterning and has the following advantages:
[04] (1) the distance between planarized electrodes is reduced, generally tens of microns to hundreds of microns, so that an electrolyte ion transport channel is greatly shortened; and meanwhile, because the microelectrode of the planar micro super capacitor provides a larger contact surface area, electrolyte ions are more easily transported in the electrodes, the utilization rate of the electrode surface area is greatly enhanced, the impedance of the device is reduced, the power density is improved, and a faster frequency reaction is achieved.
[05] (2) the planarized micro super capacitor can be suitable for different substrates under different use conditions. For example, the capacitor may be integrated within the chip in conjunction with conventional silicon process technology or may be integrated into a flexible device for application to a wearable device.
[06] Graphene is a monoatomic two-dimensional carbon material. The theoretical specific capacitance can reach 550F/g, and the graphene has stable physical and chemical properties; due to the unique two-dimensional structure of the graphene and excellent inherent physical properties, such as high conductivity and large surface area, the graphene-based material has great potential in application to a super capacitor, and a large number of literature has reported that the graphene has been applied to the super capacitor.
[07] Chinese invention patent 201710398238.8 discloses graphene oxide raw solution, micro graphene electrode and their preparation method, and micro graphene super capacitor. In this patent application, a graphene oxide raw solution is used as the ink, and the positive and negative are printed by screen printing in the same plane. After reduction, a micro graphene super capacitor is obtained. This publicly disclosed reduced graphene oxide material incorporates functional groups due to the redox reaction during the preparation process, resulting in excessive graphene defects. The introduction of a binder in the graphene microelectrode preparation causes a serious decrease in the conductivity of graphene, which affected the performance of the micro super capacitor. Moreover, the patent uses screen printing technology, which does not achieve a true combination of energy devices and electronic devices.
[08] The purpose of the invention is provide a preparation method of CVD graphene planar micro super capacitor aiming at the defects of the prior art so as to avoid defects on graphene, improve the performance of the micro super capacitor and realize the combination of an energy device and an electronic device.
[09] The technical scheme of the invention comprises the following steps of: preparing large-area uniform graphene on catalytic metal by using a CVD method, and transferring the graphene to a required target substrate; depositing a metal current collector on the graphene by using E-Beam; copying a pattern of a mask plate on the graphene-loaded substrate by using a photoetching technology; and etching the graphene in an electrode gap part by using an oxygen plasma etching machine to prevent short circuit between polar plates; and manufacturing the super capacitor energy storage device with characteristics of microminiaturization and integration. The steps are as follows:
[010] (1) a pretreatment process of pressing and cleaning a catalytic metal substrate;
[011] (2) preparing graphene on the pretreated catalytic metal substrate by using a chemical vapor deposition (CVD) technology and transferring the graphene to a target substrate to obtain a sample with a graphene-target substrate structure;
[012] (3) designing a photoetching mask plate with an interdigital structure;
[013] (4) depositing a layer of metal current collector Au on a sample of the graphene-target substrate by using E-Beam equipment to obtain a sample with a current collector-graphene-target substrate structure;
[014] (5) photoetching a sample of the current collector-graphene-target substrate to obtain a graphene microelectrode;
[015] (5a) placing a sample of the current collector-graphene-target substrate on a spin coater, dripping photoresist, rotating for 60s at the rotating speed of 4000r/s, then placing the sample on a heating plate and drying for 90s at the temperature of 100 125 °C to obtain a sample with the structure of the photoresist-current collector graphene-target substrate, and exposing the sample for 3-5s by using a photoetching machine;
[016] (5b) putting a sample of the exposed photoresist-current collector graphene-target substrate into a developing solution for development for 30-60s, then putting the sample into deionized water for rinsing, and blow-drying with nitrogen to obtain an interdigital photoresist-current collector-graphene-target substrate sample;
[017] (5c) soaking a sample of the interdigital photoresist-current collector graphene-target substrate in a mixed solution of potassium iodide KI and iodine 12 to corrode and remove a gold layer which is not protected by the photoresist, wherein the corrosion time is 20-50s; then putting the sample into deionized water for rinsing for several times, and blow-drying with nitrogen;
[018] (5d) an oxygen plasma etching machine is used for etching graphene in an interdigital gap to prevent a positive electrode plate and a negative electrode plate from being short-circuited, the etching power is 200-500W, the oxygen flow rate is 100 300sccm, and the time is 2-15min, so that a graphene microelectrode sample with photoresist is obtained;
[019] (5e) soaking the graphene microelectrode sample with the photoresist in acetone solution to remove the photoresist, finally rinsing in absolute ethyl alcohol for min, rinsing in deionized water for 30min, and blow-drying with nitrogen to obtain the graphene microelectrode sample;
[020] And (6) dripping PVA gel electrolyte on the graphene microelectrode to prepare the graphene planar micro super capacitor.
[021] Compared with the prior art, the invention has the following advantages:
[022] 1) the invention utilizes a CVD method to prepare the graphene on the catalytic metal, and the prepared high-quality graphene has excellent performance and is beneficial to charge transmission and electrode surface rapid contact and transmission.
[023] 2) Compared with the traditional sandwich super capacitor, the graphene planar micro super capacitor prepared by the invention has the advantages that the volume is reduced; the planar interdigital design reduces the distance between the positive plate and the negative plate, so that the transmitted charge can be rapidly conducted and stored, the impedance of the device is reduced, the frequency response is increased, and the rapid charging and discharging capability of the micro super capacitor is further improved.
[024] 3) the invention manufactures the graphene planar micro super capacitor by utilizing a semiconductor photoetching process. The capacitor could combine with a traditional silicon electronic device, which could not only realize the integration of device energy driving, but also prepare the flexible graphene micro super capacitor that is suitable for wearable equipment based on the PET substrate.
[025] Figure 1 is a flowchart of the implementation of the invention;
[026] Figure 2 is an interdigital lithography mask layout according to the invention;
[027] Figure 3 is a schematic diagram of a graphene planar micro super capacitor prepared by the invention.
[028] The invention will now be described in detail with reference to the accompanying figures and specific embodiments, but the invention is not limited thereto. The experimental methods described in the following embodiments are conventional methods, if not specified, and the reagents and materials, if not specified, are commercially available.
[029] Referring to Figure 1, the invention provides the following three embodiments.
[030] Embodiment 1: manufacturing a graphene planar micro super capacitor based on a silicon dioxide substrate.
[031] Step 1, carrying out substrate pretreatment on the metal foam copper.
[032] la) selecting metal foam copper as a substrate for preparing graphene with CVD, and carrying out surface pretreatment on the metal foam copper, that is pressing foam copper thinner by using a tablet press, sequentially carrying out ultrasonic cleaning on the thinned foam copper by using deionized water, purified acetone and purified ethanol for a plurality of times, and then drying the thinned foam copper for later use;
[033] lb) soaking the thinned foam copper in 0.01M ammonium persulfate solution for 3 min to remove oxides on the surface of the copper, and washing the sample with deionized water for several times and blow-drying.
[034] Step 2, preparing and transferring graphene by a CVD method.
[035] 2a) placing the foamed copper into a tubular furnace, vacuumizing to below 1Pa, introducing H2with the flow rate of 10sccm into the furnace, and raising the temperature to the set temperature of 1030 °C;
[036] 2b) after reaching the set temperature of 1030 °C, keeping the gas flow rate unchanged, and annealing the metal for 30min;
[037] 2c) under the condition that the flow rate of hydrogen is kept at 10sccm and the preparing temperature is 1030 °C, 50sccm methane is introduced, and the graphene is prepared for 120min by a chemical vapor deposition method;
[038] 2d) taking out a foamed copper sample loaded with graphene after the graphene preparing reaction is finished; spin-coating polymethyl methacrylate PMMA on the surface of the sample; drying at 80 °C for 10 min to obtain the sample with the structure of PMMA-graphene-foamed copper;
[039] 2e) soaking a sample of PMMA-graphene-foamed copper in an ammonium persulfate solution with concentration of IM for more than 24 hours, and facing the PMMA upwards so that the acid solution completely corrodes the foamed copper substrate to obtain a sample with the structure of PMMA-graphene;
[040] 2f) taking out a PMMA-graphene sample from an acid solution, transferring the PMMA-graphene sample to deionized water for rinsing for a plurality of times, transferring the PMMA-graphene sample to a target substrate silicon dioxide sheet, and naturally airing the target substrate silicon dioxide sheet and the PMMA-graphene sample to obtain a sample with the structure of PMMA-graphene-silicon dioxide ;
[041] 2g) soaking a sample of PMMA-graphene- silicon dioxide in acetone to remove polymethyl methacrylate PMMA on the surface sufficiently to obtain a sample with the structure of graphene- silicon dioxide.
[042] And step 3, designing a mask plate with an interdigital structure.
[043] The required photoetching mask layout is drawn by utilizing L-Edit software, and the patterns comprise a single interdigital type shown in Figure 2(a), a parallel interdigital type shown in Figure 2(b), a series interdigital type shown in Figure 2(c), a ring type shown in Figure 2(d), a spiral type shown in Figure 2(e) and a sawtooth type shown in Figure 2(f); and the photoetching mask layout drawn in the embodiment is a single interdigital type shown in Figure 2(a), wherein the width of the interdigital type is 100um, the distance between the interdigital type is 50um, and the length of the interdigital type is 4.5mm.
[044] Step 4, depositing a current collector.
[045] The vacuum degree is kept to be less than or equal to 1*10-8 Torr, an E Beam device is used for depositing a layer of metal current collector Au with the thickness of 100 nm on a graphene-silicon dioxide sample, and the deposition rate is SA/, that the sample with the structure of gold-graphene-silicon dioxide is obtained.
[046] Step 5, photoetching.
[047] 5a) putting a sample of Au-graphene-silicon dioxide on a spin coater, dripping the positive glue BC13511, rotating the sample for 40s at the rotating speed of 4000r/s, then putting the sample on a heating plate, drying the sample for 90s at the temperature of 100 °C to obtain a sample with the structure of photoresist-gold graphene-silicon dioxide, and exposing the sample for 3s by using a photoetching machine;
[048] 5b) putting the exposed photoresist-gold-graphene-silicon dioxide sample into a developing solution for development for 30 seconds, then putting the sample into deionized water for rinsing, and blow-drying with nitrogen to obtain an interdigital photoresist-gold-graphene-silicon dioxide sample;
[049] 5c) soaking an interdigital photoresist-gold-graphene-silicon dioxide sample in a mixed solution of potassium iodide KI and iodine12 to corrode and remove an Au layer which is not protected by the photoresist, wherein the corrosion time is 20s; then putting the sample in the deionized water for rinsing for a plurality of times, and blow-drying with nitrogen;
[050] 5d) an oxygen plasma etching machine is used for etching graphene at an interdigital gap to prevent a positive electrode plate and a negative electrode plate from being short-circuited; the etching power is 200W, the oxygen flow is100sccm, and the time is 10min;
[051] 5e) soaking the graphene microelectrode sample with the photoresist in an acetone solution to remove the photoresist, and finally sequentially rinsing the sample in absolute ethyl alcohol for 30min, rinsing the sample in deionized water for 30min, and blow-drying the sample with nitrogen to obtain the graphene microelectrode sample based on the silicon dioxide substrate.
[052] And step 6, adding PVA-KOH gel electrolyte to prepare the super capacitor.
[053] 6a) dissolving 10 gKOH and 10 gPVA powder in 100 mL of deionized water to prepare an electrolyte mixed solution;
[054] 6b) placing the electrolyte mixed solution in a water bath heating box, setting the constant temperature of the water bath heating box to be 80 °C, and heating for 1 hour to obtain colorless and transparent PVA-KOH gel electrolyte;
[055] 6c) the PVA-KOH gel electrolyte is dripped on the surface of the graphene microelectrode sample for solidifying for 24 hours to obtain the graphene planar micro super capacitor based on the silicon dioxide substrate as shown in Figure 3.
[056] Embodiment 2: manufacturing a graphene planar micro super capacitor based on a PET substrate.
[057] Step 1, carrying out substrate pretreatment on the copper foil.
[058] 1.1) selecting a copper foil as a substrate for preparing graphene with CVD, performing pretreatment on the surface, that is pressing the substrate with a tablet press, sequentially using deionized water, purified acetone and purified ethanol for ultrasonic cleaning for a plurality of times, and then blow-drying the substrate for later use;
[059] 1.2) soaking the copper foil in 0.01M ammonium persulfate solution for 3min to remove the oxide on the surface of the copper, and washing the sample with deionized water for a plurality of times to blow dry.
[060] Step 2, preparing and transferring graphene by a CVD method.
[061] 2.1) putting the pretreated copper foil into a tubular furnace, vacuumizing to below IPa, introducing H2with the flow rate of 50sccm into the furnace, and heating to the set temperature of 1050 °C;
[062] 2.2) after reaching the set temperature of 1050 °C, keeping the gas flow rate unchanged, and annealing the metal for 10 min;
[063] 2.3) under the condition that the flow rate of hydrogen is kept at 50sccm and the growth temperature is 1050 °C, 250sccm of methane is introduced, and the graphene is prepared on the copper foil for 60min by a chemical vapor deposition method;
[064] 2.4) after the graphene preparing reaction is finished, and the gas flow is kept to be reduced to about room temperature, a copper foil sample loaded with graphene is taken out; polymethyl methacrylate PMMA is spin-coated on the surface of the sample, and is dried at 80 °C for 10 min to obtain the sample with the structure of PMMA-graphene-copper foil;
[065] 2.5) soaking a sample of PMMA-graphene-copper foil in an ammonium persulfate solution with the concentration of IM for more than 24 hours, and facing the polymethyl methacrylate PMMA upwards so that the acid solution completely corrodes the copper foil to obtain a sample with the structure of PMMA-graphene;
[066] 2.6) taking out a PMMA-graphene sample from an acid solution, transferring the PMMA-graphene sample to deionized water for rinsing for a plurality of times, transferring the PMMA-graphene sample to a high temperature resistant polyester film PET, and naturally airing the PET and the PMMA-graphene sample to obtain a sample with the structure of PMMA-graphene-PET;
[067] 2.7) soaking the PMMA-graphene-PET sample in acetone to fully remove the polymethyl methacrylate PMMA on the surface to obtain the sample with the structure of graphene-PET.
[068] And step 3, designing a mask plate with a ring structure.
[069] The required photoetching mask layout is drawn by utilizing L-Edit software, and the photoetching mask layout in the embodiment is in a ring shape as shown in Figure 2(d), wherein the width of the ring-shaped line is 250um, and the spacing is 100um.
[070] Step 4, depositing a current collector.
[071] And keeping the vacuum degree to be less than or equal to 1*10-8Torr, and depositing a layer of metal current collector Au with the thickness of 50nm on a graphene-silicon wafer sample by using E-Beam equipment under the process condition of evaporation rate is 2A/s to obtain the sample with the structure of gold-graphene PET.
[072] And step 5, photoetching.
[073] 5.1) placing an Au-graphene-PET sample on a spin coater, dripping positive glue, rotating for 40s at a rotating speed of 4000r/s, placing the Au-graphene-PET sample on a heating plate, drying the Au-graphene-PET sample at 110 °C for 90s to obtain a photoresist-gold-graphene-PET sample, and exposing the photoresist-gold graphene-PET sample for 3.5s by using a photoetching machine;
[074] 5.2) putting the exposed photoresist-gold-graphene-PET sample into a developing solution for development for 45s, then putting the sample into deionized water for rinsing, and blow-drying the sample with nitrogen to obtain a ring-shaped photoresist-gold-graphene-PET sample;
[075] 5.3) soaking a ring-shaped photoresist-gold-graphene-PET sample in a mixed solution of potassium iodide KI and iodine 12 to corrode for 30 seconds, removing a gold layer which are not protected by the photoresist, placing the sample in deionized water for rinsing for a plurality of times, and blow-drying with nitrogen;
[076] 5.4) an oxygen plasma etching machine is used for etching the graphene at the annular line gap to prevent a positive electrode plate and a negative electrode plate from being short-circuited; the etching power is 300W, the oxygen flow is 200sccm, and the time is 2min;
[077] 5.5) soaking the graphene microelectrode sample with the photoresist in an acetone solution to remove the photoresist, and finally sequentially rinsing in absolute ethyl alcohol for 30min, rinsing in deionized water for 30min, and blow-drying with nitrogen to obtain the graphene microelectrode sample based on the PET substrate.
[078] And step 6, adding PVA-H2SO4 gel electrolyte to prepare the super capacitor.
[079] 6.1) adding 10 gPVA powder into a beaker filled with 100 mL of deionized water, and dropwise adding 6 mL of concentrated H2SO4 with the mass fraction of 98% into the beaker to prepare a PVA-H2SO4 mixed solution;
[080] 6.2) placing PVA-H2SO4 mixed solution in a water bath heating box, setting the constant temperature of the water bath heating box to be 80 °C, and heating for 1 hour to obtain colorless and transparent PVA-H2SO4 gel electrolyte;
[081] 6.3) PVA-H2SO4 gel electrolyte is dripped on the surface of the graphene microelectrode sample for solidifying for 24 hours to obtain the graphene planar micro super capacitor based on the PET substrate as shown in Figure 3.
[082] Embodiment 3: manufacturing a graphene planar micro super capacitor based on a silicon wafer substrate.
[083] Step A, carrying out substrate pretreatment on the foamed nickel.
[084] The method comprises the following steps of: selecting foamed nickel as a substrate for preparing graphene with CVD, and carrying out surface pretreatment on the foamed nickel, that is pressing foamed nickel thinner by using a tablet press, sequentially carrying out ultrasonic cleaning for a plurality of times by using deionized water, purified acetone and purified ethanol, and blow-drying for later use; and then soaking the thinned foamed nickel in 0.01M ammonium persulfate solution for 3 minutes to remove the oxide on the surface of the copper, and washing the sample with deionized water for a plurality of times to blow dry.
[085] Step B, preparing and transferring graphene by a CVD method.
[086] Step 1, placing foamed nickel in a tubular furnace, vacuumizing to be lower than 1Pa, introducing H2 with the flow rate of 20sccm into the furnace, and heating to a set temperature of 950 °C; keeping the gas flow rate unchanged after the set temperature reaches 950 °C, and annealing the PMMA for 20min; introducing 100sccm methane under the condition that the hydrogen flow rate is kept at 20sccm and the growth temperature is 950 °C, and preparing graphene for 30min by using a chemical vapor deposition method; taking out a foamed nickel sample loaded with the graphene after the graphene preparing reaction is finished; polymethyl methacrylate PMMA is spin-coated on the surface of the sample, and is dried at 80 °C for 10 min to obtain the sample with the structure of PMMA-graphene- foamed nickel;
[087] Step 2, soaking a PMMA-graphene-foam nickel sample in a hydrochloric acid solution with concentration of 6M for more than 24 hours, and facing the polymethyl methacrylate PMMA upwards so that the acid solution completely corrodes the metal substrate to obtain a sample with the structure of PMMA-graphene;
[088] Step 3, taking out the PMMA-graphene sample from the acid solution, transferring the PMMA-graphene sample to deionized water for rinsing for a plurality of times, transferring the PMMA-graphene sample to a target substrate silicon wafer, and naturally airing the target substrate silicon wafer to obtain a sample with the structure of PMMA-graphene-silicon wafer;
[089] Step 4, soaking the sample of the PMMA-graphene-silicon wafer in acetone to fully remove the polymethyl methacrylate PMMA on the surface to obtain the sample with the structure of graphene-silicon wafer.
[090] Step C, designing a mask plate with a sawtooth-shaped structure, that is drawing a required photoetching mask layout by utilizing L-Edit software, wherein the photoetching mask layout drawn in the embodiment is sawtooth-shaped as shown in Figure 2(f); the width of a sawtooth finger terminal is 250um, and the distance between fingers is 50um.
[091] Step D, depositing a current collector, that is keeping the vacuum degree to be less than or equal to 1*10-8 Torr, and depositing a layer of metal current collector Au with the thickness of 80nm on a graphene-silicon wafer sample by using E-Beam equipment under the process condition that the evaporation rate is 3As to obtain the sample with the structure of gold-graphene-silicon wafer.
[092] Step E, photoetching.
[093] Step 1, placing an Au-graphene-silicon wafer sample on a spin coater, dripping negative glue, rotating for 60s at a rotating speed of 4000r/s, placing the Au graphene-silicon wafer sample on a heating plate, drying the Au-graphene-silicon wafer sample at 125 °C for 90s to obtain a sample with the structure of photoresist-gold graphene-silicon wafer, and exposing the sample for 5s by using a photoetching machine;
[094] Step 2, putting the exposed photoresist-gold-graphene-silicon chip sample into a developing solution for development for 60s, then putting the sample into deionized water for rinsing, and blow-drying with nitrogen to obtain a sawtooth-shaped photoresist-gold-graphene-silicon wafer sample;
[095] Step 3, soaking a sawtooth type photoresist-gold-graphene-PET sample in a mixed solution of potassium iodide KI and iodine 12 to corrode and remove a gold layer which is not protected by the photoresist, wherein the corrosion time is 50s; placing the sample in deionized water for rinsing for a plurality of times, and blow drying with nitrogen;
[096] Step 4, under the process conditions that the etching power is 500W and the oxygen flow is 300sccm, the graphene at the sawtooth gap is etched for 15min by using an oxygen plasma etching machine so as to prevent a positive electrode plate and a negative electrode plate from being short-circuited;
[097] Step 5, soaking the graphene microelectrode sample with the photoresist in an acetone solution to remove the photoresist, sequentially rinsing the sample in absolute ethyl alcohol for 30min, rinsing the sample in deionized water for 30min, and blow-drying the sample with nitrogen to obtain the graphene microelectrode sample based on the silicon wafer substrate.
[098] Step F, adding PVA- H3PO4 gel electrolyte to prepare the graphene planar super capacitor.
[099] Step 1, adding 10 gPVA powder into a beaker filled with 100 mL of deionized water, and dropwise adding 6 mL of H3PO4 with the mass fraction of 85% into the beaker to prepare a PVA- H3PO4 mixed solution;
[0100] Step 2, placing PVA- H3PO4 mixed solution in a water bath heating box, setting the water bath heating box to have the constant temperature of80 °C, and heating for 1 hour to obtain colorless and transparent PVA- H3PO4 gel electrolyte;
[0101] Step 3, dripping PVA- H3PO4 gel electrolyte on the surface of the graphene microelectrode sample for solidifying for 24 hours to obtain the graphene planar micro super capacitor based on the silicon chip substrate, as shown in Figure 3.
[0102] The above-described embodiments are merely illustrative of several embodiments of the invention and are described in greater detail, but are not therefore to be construed as limiting the scope of the invention. It should be noted that variations and modifications may be made by those skilled in the art without departing from the spirit of the invention, such as catalytic metals used in the invention; in addition to copper foil, foam nickel, foam copper, nickel foil, copper-nickel alloys, and foam copper-nickel alloy are also used in particular embodiments, all of which are within the scope of the invention. The scope of protection of the invention is, therefore, to be determined by the appended claims.
[0103] Although the invention has been described with reference to specific examples, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms, in keeping with the broad principles and the spirit of the invention described herein.
[0104] The present invention and the described embodiments specifically include the best method known to the applicant of performing the invention. The present invention and the described preferred embodiments specifically include at least one feature that is industrially applicable
Claims (9)
1. A preparation method of CVD graphene planar micro super capacitor comprises the steps of:
(1) a pretreatment process of pressing and cleaning a catalytic metal substrate;
(2) preparing graphene on the pretreated catalytic metal substrate by using a chemical vapor deposition (CVD) technology and transferring the graphene to a target substrate to obtain a sample with a graphene-target substrate structure;
(3) designing a photoetching mask plate with an interdigital structure;
(4) depositing a layer of metal current collector Au on a sample of the graphene-target substrate by using E-Beam equipment to obtain a sample with a current collector-graphene-target substrate structure;
(5) photoetching a sample of the current collector-graphene-target substrate to obtain a graphene microelectrode;
(5a) placing a sample of the current collector-graphene-target substrate on a spin coater, dripping photoresist, rotating for 60s at the rotating speed of 4000r/s, then placing the sample on a heating plate and drying for 90s at the temperature of 100-125 °C to obtain a sample with the structure of the photoresist-current collector-graphene target substrate, and exposing the sample for 3-5s by using a photoetching machine;
(5b) putting a sample of the exposed photoresist-current collector-graphene target substrate into a developing solution for development for 30-60s, then putting the sample into deionized water for rinsing, and blow-drying with nitrogen to obtain an interdigital photoresist-current collector-graphene-target substrate sample;
(5c) soaking a sample of the interdigital photoresist-current collector graphene-target substrate in a mixed solution of potassium iodide KI and iodine 12 to corrode and remove a gold layer which is not protected by the photoresist, wherein the corrosion time is 20-50s; then putting the sample into deionized water for rinsing for several times, and blow-drying with nitrogen;
(5d) an oxygen plasma etching machine is used for etching graphene in an interdigital gap to prevent a positive electrode plate and a negative electrode plate from being short-circuited, the etching power is 200-500W, the oxygen flow rate is 100 300sccm, and the time is 2-15min, so that a graphene microelectrode sample with photoresist is obtained;
(5e) soaking the graphene microelectrode sample with the photoresist in acetone solution to remove the photoresist, finally rinsing in absolute ethyl alcohol for min, rinsing in deionized water for 30min, and blow-drying with nitrogen to obtain the graphene microelectrode sample;
(6) dripping PVA gel electrolyte on the graphene microelectrode to prepare the graphene planar micro super capacitor.
2. According to claim 1, the pretreatment process of pressing and cleaning the catalytic metal substrate in step (1) comprises the steps of:
(1) firstly, pressing a catalytic metal substrate by a tablet press, then sequentially using deionized water, purified acetone and purified absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and then blow-drying for later use;
(lb) soaking the thinned metal substrate in 0.01M ammonium persulfate solution for 5min to remove oxides on the surface of the metal, and washing the sample with deionized water for several times and blow-drying.
3. According to claim 1, preparing graphene on the pretreated catalytic metal substrate using a chemical vapor deposition CVD technique and transferring the graphene to a target substrate in the step (2), the steps are as follows:
(2a) putting the catalytic metal substrate into a tubular furnace, vacuumizing to below Pa, introducing H2 with the flow rate of 10-50sccm into the furnace, and raising the temperature to a set temperature of 950-1050 DEG C;
(2b) after the set temperature is reached, the gas flow rate is kept unchanged, and the catalytic metal substrate is annealed for 10 to 30 min;
(2c) after annealing treatment, introducing CH4 with the flow rate of 50 250sccm to preparing graphene for 30-120min on the basis of keeping the original gas flow rate unchanged;
(2d) taking out the catalytic metal substrate loaded with graphene after the graphene preparing reaction is finished; spin-coating polymethyl methacrylate PMMA on the surface of the catalytic metal substrate loaded with graphene, and drying at 80 °C for 10 min to obtain a sample with the structure of the PMMA-graphene-catalytic metal substrate;
(2e) soaking a sample of PMMA-graphene-catalytic metal substrate in an ammonium persulfate solution with the concentration of 1M or hydrochloric acid with the concentration of6M for more than 24 hours, and facing the polymethyl methacrylate PMMA upwards so that the acid solution completely corrodes the metal substrate to obtain a sample with the structure of PMMA-graphene;
(2f) taking out a PMMA-graphene sample from an acid solution, transferring the PMMA-graphene sample to deionized water for rinsing for a plurality of times, transferring the PMMA-graphene sample to a target substrate, and naturally airing the sample to obtain a sample with the structure of PMMA-graphene-target substrate;
(2g) soaking a sample of the PMMA-graphene-target substrate in acetone to sufficiently remove polymethyl methacrylate PMMA on the surface to obtain a sample with the structure of graphene-target substrate.
4. According to claim 1, the design of a photoetching mask plate with an interdigital structure in the step (3) is to draw the figures needed using the L-Edit software, wherein the figures comprising the single interdigital pattern, the parallel interdigital pattern, the series interdigital pattern, the ring shape, the spiral shape, and the sawtooth shape.
5. According to the method in claim 1, a layer of metal current collector Au deposited on a sample of the graphene-target substrate in step (4) with a thickness of - 100 nm, and the deposition rate is 1~31s.
6. According to the method in claim 1, the PVA gel electrolyte is dripping on the graphene microelectrode in step (6) to prepare the graphene planar micro super capacitor, and the method comprises the following steps:
(6a) selecting one of the following mixed solutions as an electrolyte mixed solution: dissolving 10 gKOH and 10 gPVA powder in 100 mL of deionized water to prepare a PVA-KOH mixed solution;
adding 10 gPVA powder into a beaker filled with 100 mL of deionized water, and dropwise adding 6 mL of concentrated H2SO4with the mass fraction of 98% into the beaker to prepare a PVA- H2SO4mixed solution;
Adding 10 gPVA powder into a beaker filled with 100 mL of deionized water, and dropwise adding 6 mL of H3PO4with the mass fraction of 85% into the beaker to prepare a PVA- H2SO4mixed solution;
(6b) placing the electrolyte mixed solution in a water bath heating box, setting the constant temperature of the water bath heating box to be 80°C, and heating for 1 hour to obtain colorless and transparent gel electrolyte;
And (6c) dripping gel electrolyte on the surface of the graphene microelectrode sample for solidifying for 24 hours to obtain the graphene planar micro super capacitor.
7. According to the method in claim 1, the catalytic metal in step (la)comprises nickel foil, copper foil, copper-nickel alloy, foamed nickel, foamed copper, and foamed copper-nickel alloy.
8. According to the method in claim 1, the target substrate in step (2) is a silicon wafer or a silicon dioxide wafer or a high temperature resistant polyester film PET.
9. According to the method in claim 1, the photoresist in step (5a) comprises a positive glue or a negative glue.
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