CN110517809A - A kind of transparent graphene conductive film, preparation method and application - Google Patents
A kind of transparent graphene conductive film, preparation method and application Download PDFInfo
- Publication number
- CN110517809A CN110517809A CN201910870735.2A CN201910870735A CN110517809A CN 110517809 A CN110517809 A CN 110517809A CN 201910870735 A CN201910870735 A CN 201910870735A CN 110517809 A CN110517809 A CN 110517809A
- Authority
- CN
- China
- Prior art keywords
- layer
- graphene
- conductive film
- silica gel
- transparent conductive
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 246
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010410 layer Substances 0.000 claims abstract description 228
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000000741 silica gel Substances 0.000 claims abstract description 107
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 107
- 239000000758 substrate Substances 0.000 claims abstract description 82
- 230000003287 optical effect Effects 0.000 claims abstract description 46
- 239000012790 adhesive layer Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 45
- 238000005530 etching Methods 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 23
- -1 graphite alkene Chemical class 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- 239000011888 foil Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 5
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 2
- 239000004568 cement Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 23
- 230000003749 cleanliness Effects 0.000 abstract description 10
- 239000003990 capacitor Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 195
- 239000003292 glue Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 230000035699 permeability Effects 0.000 description 17
- 239000011889 copper foil Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 238000010030 laminating Methods 0.000 description 11
- 238000002848 electrochemical method Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000000411 transmission spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- YWKKLBATUCJUHI-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(C)=CC=1)C1=CC=CC=C1 YWKKLBATUCJUHI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明涉及导电薄膜生产技术领域，尤其涉及一种石墨烯透明导电薄膜、其制备方法及应用。本发明提供了一种石墨烯透明导电薄膜，包括：柔性基底；在所述柔性基底的一面复合高透硅胶层；在所述高透硅胶层上复合石墨烯薄膜层；在所述柔性基底的另一面复合OCA光学胶层。本发明提供的石墨烯透明导电薄膜的清洁度和表面平整度较优，同时，可以保持较好的完整性和优异的光电性能，透光率较优。适用于柔性电容器、传感器、触摸屏、太阳能电池和有机发光二极管等器件的制备。实验表明，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率不超过630ohm/sq，石墨烯薄膜层结构完整、表面光滑平整、干净、无残留。
The invention relates to the technical field of conductive film production, in particular to a graphene transparent conductive film, its preparation method and application. The invention provides a graphene transparent conductive film, comprising: a flexible substrate; a high-permeability silica gel layer is compounded on one side of the flexible substrate; a graphene film layer is compounded on the high-permeability silica gel layer; The other side is compounded with OCA optical adhesive layer. The graphene transparent conductive film provided by the invention has better cleanliness and surface smoothness, and at the same time, can maintain better integrity and excellent photoelectric properties, and has better light transmittance. It is suitable for the preparation of devices such as flexible capacitors, sensors, touch screens, solar cells and organic light-emitting diodes. Experiments show that in the graphene transparent conductive film, the surface resistivity of the graphene film layer does not exceed 630 ohm/sq, and the structure of the graphene film layer is complete, the surface is smooth, clean and free of residue.
Description
技术领域technical field
本发明涉及导电薄膜生产技术领域，尤其涉及一种石墨烯透明导电薄膜、其制备方法及应用。The invention relates to the technical field of conductive film production, in particular to a graphene transparent conductive film, its preparation method and application.
背景技术Background technique
石墨烯(Graphene)具有优异的透光、导电、导热和力学性能，作为新一代透明导电薄膜，可广泛地用于传感器、电容器、触摸屏、太阳能电池、有机发光二极管和传感器等领域。目前，化学气相沉积(CVD)法是制备大面积石墨烯薄膜的主要方法，但石墨烯通常在金属箔(铜、铂、镍等)基体上生长，为实现其表征和应用，需要将其转移到其它基体(硅片、玻璃片、塑料等)上。然而，已有的卷对卷(Rollto Roll)、机械剥离等转移过程容易造成石墨烯破损，严重影响转移后石墨烯的性能。利用转移介质的方法，能够减少这种破损，但目前使用的转移介质通常是聚甲基丙烯酸甲酯(PMMA)、聚二甲基硅氧烷(PDMS)等高分子树脂，与石墨烯的相互作用强、不易在溶剂中溶解，即使用大量的有机溶剂进行清洗，在石墨烯表面仍有大量的残留，不仅降低石墨烯的光电性能，还大大增加了石墨烯的表面粗糙度，阻碍了其在光电器件等领域中的应用。Graphene has excellent light transmission, electrical conductivity, thermal conductivity and mechanical properties. As a new generation of transparent conductive film, it can be widely used in the fields of sensors, capacitors, touch screens, solar cells, organic light-emitting diodes and sensors. At present, the chemical vapor deposition (CVD) method is the main method for preparing large-area graphene films, but graphene is usually grown on a metal foil (copper, platinum, nickel, etc.) onto other substrates (silicon, glass, plastic, etc.). However, existing transfer processes such as roll-to-roll (Roll-to-Roll) and mechanical exfoliation are prone to damage to graphene, which seriously affects the properties of graphene after transfer. The method of using transfer media can reduce this damage, but the transfer media currently used are usually polymer resins such as polymethyl methacrylate (PMMA) and polydimethylsiloxane (PDMS), and the interaction with graphene It has a strong effect and is not easy to dissolve in solvents. Even if a large amount of organic solvent is used for cleaning, there will still be a large amount of residue on the surface of graphene, which not only reduces the photoelectric performance of graphene, but also greatly increases the surface roughness of graphene, hindering it. Applications in optoelectronic devices and other fields.
发明内容Contents of the invention
有鉴于此，本发明要解决的技术问题在于提供一种石墨烯透明导电薄膜、其制备方法及应用，本发明提供的石墨烯透明导电薄膜的清洁度和表面平整度较优，同时，可以保持较好的完整性和优异的光电性能。In view of this, the technical problem to be solved in the present invention is to provide a graphene transparent conductive film, its preparation method and application, the cleanliness and surface smoothness of the graphene transparent conductive film provided by the present invention are better, and at the same time, can maintain Better integrity and excellent photoelectric properties.
本发明提供了一种石墨烯透明导电薄膜，包括：The invention provides a graphene transparent conductive film, comprising:
柔性基底；flexible substrate;
在所述柔性基底的一面复合高透硅胶层；A high-permeability silicone layer is compounded on one side of the flexible substrate;
在所述高透硅胶层上复合石墨烯薄膜层；Composite graphene thin film layer on described highly permeable silica gel layer;
在所述柔性基底的另一面复合OCA光学胶层。An OCA optical adhesive layer is compounded on the other side of the flexible substrate.
优选的，所述柔性基底的组分选自聚对苯二甲酸乙二醇酯、聚酰亚胺和聚萘二甲酸乙二醇酯中的一种或几种。Preferably, the components of the flexible substrate are selected from one or more of polyethylene terephthalate, polyimide and polyethylene naphthalate.
优选的，所述高透硅胶层的厚度为30nm～1000μm；Preferably, the thickness of the highly transparent silica gel layer is 30nm-1000μm;
所述柔性基底的厚度为10～300μm；The thickness of the flexible substrate is 10-300 μm;
所述OCA光学胶层的厚度为30nm～1000μm。The thickness of the OCA optical adhesive layer is 30 nm˜1000 μm.
本发明还提供了一种石墨烯透明导电薄膜的制备方法，包括以下步骤：The present invention also provides a kind of preparation method of graphene transparent conductive film, comprises the following steps:
A)采用化学气相沉积法在金属箔的上表面生长石墨烯薄膜，得到石墨烯薄膜层；在柔性基底的一面涂布高透硅胶，得到高透硅胶层/柔性基底复合层；A) using chemical vapor deposition to grow a graphene film on the upper surface of the metal foil to obtain a graphene film layer; coating a high-permeability silica gel on one side of the flexible substrate to obtain a high-permeability silica gel layer/flexible substrate composite layer;
B)将所述高透硅胶层与所述石墨烯薄膜层贴合，进行加压，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；B) laminating the high-permeability silica gel layer and the graphene film layer, and pressurizing to obtain a graphene film layer/high-permeability silica gel layer/flexible substrate composite layer;
C)在所述柔性基底的另一面涂布OCA光学胶，得到OCA光学胶层；C) coating OCA optical adhesive on the other side of the flexible substrate to obtain an OCA optical adhesive layer;
D)通过刻蚀法或电化学法去除所述金属箔，得到石墨烯复合体，经清洗和干燥后，得到石墨烯透明导电薄膜。D) removing the metal foil by an etching method or an electrochemical method to obtain a graphene composite body, and obtaining a graphene transparent conductive film after cleaning and drying.
优选的，步骤B)中，所述加压的压力为0.1～20MPa，所述加压的时间为1s～30h。Preferably, in step B), the pressurization pressure is 0.1-20 MPa, and the pressurization time is 1s-30h.
优选的，步骤D)中，所述刻蚀法采用的刻蚀液为盐酸与双氧水的混合溶液、氯化铁的水溶液和过硫酸铵的水溶液中的一种。Preferably, in step D), the etching solution used in the etching method is one of a mixed solution of hydrochloric acid and hydrogen peroxide, an aqueous solution of ferric chloride and an aqueous solution of ammonium persulfate.
优选的，所述刻蚀液的浓度为0.1～10mol/L；Preferably, the concentration of the etching solution is 0.1-10 mol/L;
所述盐酸与双氧水的体积比为1～9：1～9。The volume ratio of the hydrochloric acid to the hydrogen peroxide is 1-9:1-9.
优选的，步骤D)中，所述电化学法采用的电解液包括硫酸溶液、盐酸溶液、硝酸溶液、甲磺酸的水溶液、柠檬酸的水溶液、氢氧化钠的水溶液、氢氧化钾的水溶液、氯化钠的水溶液和氯化钾的水溶液中的一种；Preferably, in step D), the electrolytic solution used in the electrochemical method includes sulfuric acid solution, hydrochloric acid solution, nitric acid solution, methanesulfonic acid aqueous solution, citric acid aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, One of the aqueous solution of sodium chloride and the aqueous solution of potassium chloride;
所述电解液的浓度为0.1～10mol/L。The concentration of the electrolyte is 0.1-10 mol/L.
优选的，步骤D)中，所述清洗采用的清洗剂为去离子水。Preferably, in step D), the cleaning agent used in the cleaning is deionized water.
本发明还提供了一种上文所述的石墨烯透明导电薄膜或上文所述的制备方法制备的石墨烯透明导电薄膜作为光电器件的透明电极的应用。The present invention also provides an application of the above-mentioned graphene transparent conductive film or the graphene transparent conductive film prepared by the above-mentioned preparation method as a transparent electrode of a photoelectric device.
本发明提供了一种石墨烯透明导电薄膜，包括：柔性基底；在所述柔性基底的一面复合高透硅胶层；在所述高透硅胶层上复合石墨烯薄膜层；在所述柔性基底的另一面复合OCA光学胶层。本发明提供的石墨烯透明导电薄膜的清洁度和表面平整度较优，同时，可以保持较好的完整性和优异的光电性能，透光率较优。适用于柔性电容器、传感器、触摸屏、太阳能电池和有机发光二极管等器件的制备。The invention provides a graphene transparent conductive film, comprising: a flexible substrate; a high-permeability silica gel layer is compounded on one side of the flexible substrate; a graphene film layer is compounded on the high-permeability silica gel layer; The other side is compounded with OCA optical adhesive layer. The graphene transparent conductive film provided by the invention has better cleanliness and surface smoothness, and at the same time, can maintain better integrity and excellent photoelectric properties, and has better light transmittance. It is suitable for the preparation of devices such as flexible capacitors, sensors, touch screens, solar cells and organic light-emitting diodes.
本发明还提供了一种石墨烯透明导电薄膜的制备方法，包括以下步骤：A)采用化学气相沉积法在金属箔的上表面生长石墨烯薄膜，得到石墨烯薄膜层；在柔性基底的一面涂布高透硅胶，得到高透硅胶层/柔性基底复合层；B)将所述高透硅胶层与所述石墨烯薄膜层贴合，进行加压，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；C)在所述柔性基底的另一面涂布OCA光学胶，得到OCA光学胶层；D)通过刻蚀法或电化学法去除所述金属箔，得到石墨烯复合体，经清洗和干燥后，得到石墨烯透明导电薄膜。本发明以高透硅胶层为转移介质，在实现石墨烯薄膜层完整无损转移的同时，石墨烯薄膜层的表面光滑平整，无颗粒残留，具有更高的清洁度，最终制得的石墨烯透明导电薄膜的清洁度和表面平整度较优，同时，可以保持较好的完整性和优异的光电性能，透光率较优。另外，高透硅胶层具有自动排气泡的功能，贴合方法简便。本发明提供的制备方法可以制备大面积、高性能的透明导电薄膜，对于石墨烯的应用具有重要的意义。The present invention also provides a method for preparing a graphene transparent conductive film, comprising the following steps: A) using chemical vapor deposition to grow a graphene film on the upper surface of a metal foil to obtain a graphene film layer; Fabric high-permeability silica gel to obtain a high-permeability silica gel layer/flexible substrate composite layer; B) attach the high-permeability silica gel layer to the graphene film layer and pressurize to obtain a graphene film layer/high-permeability silica gel layer/ Flexible substrate composite layer; C) coating OCA optical adhesive on the other side of the flexible substrate to obtain an OCA optical adhesive layer; D) removing the metal foil by etching or electrochemical methods to obtain a graphene composite, After washing and drying, a graphene transparent conductive film is obtained. The invention uses a high-permeability silica gel layer as the transfer medium, and while realizing the complete and non-destructive transfer of the graphene film layer, the surface of the graphene film layer is smooth and flat, has no particle residue, and has a higher degree of cleanliness, and the finally obtained graphene is transparent The cleanliness and surface smoothness of the conductive film are better, and at the same time, it can maintain better integrity and excellent photoelectric performance, and the light transmittance is better. In addition, the high-permeability silicone layer has the function of automatically releasing air bubbles, and the bonding method is simple. The preparation method provided by the invention can prepare a large-area, high-performance transparent conductive film, which is of great significance for the application of graphene.
实验结果表明，本发明制备的石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率不超过630ohm/sq，石墨烯透明导电薄膜的电阻率较小；石墨烯薄膜层结构完整、表面光滑平整、干净、无残留。The experimental results show that in the graphene transparent conductive film prepared by the present invention, the surface resistivity of the graphene film layer is no more than 630ohm/sq, and the resistivity of the graphene transparent conductive film is less; the graphene film layer structure is complete and the surface is smooth and flat , clean and residue-free.
以本发明的石墨烯透明导电薄膜为透明电极制备的OLED器件，发光面积为0.4mm2；电压为5V时，绿光OLED器件的亮度可以达到8000cd m-2。以本发明的石墨烯透明导电薄膜为透明电极制备的有机太阳能电池的光电转化效率不小于3.6％。The OLED device prepared by using the graphene transparent conductive film of the present invention as a transparent electrode has a luminous area of 0.4mm 2 ; when the voltage is 5V, the brightness of the green OLED device can reach 8000cd m -2 . The photoelectric conversion efficiency of the organic solar cell prepared by using the graphene transparent conductive film of the present invention as a transparent electrode is not less than 3.6%.
附图说明Description of drawings
图1为本发明的一个实施例提供的石墨烯透明导电薄膜的结构示意图；Fig. 1 is the structural representation of the graphene transparent conductive film that an embodiment of the present invention provides;
图2为本发明实施例1的石墨烯透明导电薄膜的石墨烯薄膜层的原子力显微镜图；Fig. 2 is the atomic force microscope figure of the graphene film layer of the graphene transparent conductive film of the embodiment of the present invention 1;
图3为本发明实施例1的石墨烯透明导电薄膜的石墨烯薄膜层的扫描电子显微镜图；Fig. 3 is the scanning electron microscope figure of the graphene film layer of the graphene transparent conductive film of the embodiment of the present invention 1;
图4为本发明实施例1的石墨烯透明导电薄膜的石墨烯薄膜层的可见光透射光谱图。4 is a visible light transmission spectrum diagram of the graphene film layer of the graphene transparent conductive film of Example 1 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明提供了一种石墨烯透明导电薄膜，包括：The invention provides a graphene transparent conductive film, comprising:
柔性基底；flexible substrate;
在所述柔性基底的一面复合高透硅胶层；A high-permeability silicone layer is compounded on one side of the flexible substrate;
在所述高透硅胶层上复合石墨烯薄膜层；Composite graphene thin film layer on described highly permeable silica gel layer;
在所述柔性基底的另一面复合OCA光学胶层。An OCA optical adhesive layer is compounded on the other side of the flexible substrate.
所述石墨烯透明导电薄膜的结构如图1所示。图1为本发明的一个实施例提供的石墨烯透明导电薄膜的结构示意图。The structure of the graphene transparent conductive film is shown in Figure 1. Fig. 1 is a schematic structural diagram of a graphene transparent conductive film provided by an embodiment of the present invention.
本发明提供的石墨烯透明导电薄膜包括柔性基底。在本发明的某些实施例中，所述柔性基底的组分选自聚对苯二甲酸乙二醇酯、聚酰亚胺和聚萘二甲酸乙二醇酯中的一种或几种。在本发明的某些实施例中，所述柔性基底的厚度为10～300μm。The graphene transparent conductive film provided by the invention includes a flexible substrate. In some embodiments of the present invention, the components of the flexible substrate are selected from one or more of polyethylene terephthalate, polyimide and polyethylene naphthalate. In some embodiments of the present invention, the flexible substrate has a thickness of 10-300 μm.
本发明提供的石墨烯透明导电薄膜还包括高透硅胶层。所述高透硅胶层复合在所述柔性基底的一面。在本发明的某些实施例中，所述高透硅胶层的透光率>90％。在本发明的某些实施例中，所述高透硅胶层的组分包括有机硅胶或无机硅胶。所述高透硅胶层中可以添加固化剂也可以不添加固化剂。在本发明的某些实施例中，所述高透硅胶层的组分为透光率>90％的有机硅胶或透光率>90％的无机硅胶。在本发明的某些实施例中，所述高透硅胶层的组分选自有机硅胶KL-9310B。The graphene transparent conductive film provided by the invention also includes a high-permeability silica gel layer. The high-permeability silica gel layer is compounded on one side of the flexible base. In some embodiments of the present invention, the light transmittance of the high-transmittance silica gel layer is >90%. In some embodiments of the present invention, the components of the high permeability silica gel layer include organic silica gel or inorganic silica gel. A curing agent may or may not be added to the high permeability silica gel layer. In some embodiments of the present invention, the composition of the highly transparent silica gel layer is organic silica gel with a light transmittance >90% or inorganic silica gel with a light transmittance >90%. In some embodiments of the present invention, the components of the high permeability silica gel layer are selected from organic silica gel KL-9310B.
在本发明的某些实施例中，所述高透硅胶层的厚度为30nm～1000μm。在某些实施例中，所述高透硅胶层的厚度为50nm～100μm。在某些实施例中，所述高透硅胶层的厚度为50μm或100μm。In some embodiments of the present invention, the thickness of the highly permeable silica gel layer is 30 nm˜1000 μm. In some embodiments, the thickness of the highly transparent silica gel layer is 50 nm˜100 μm. In some embodiments, the thickness of the highly transparent silica gel layer is 50 μm or 100 μm.
在本发明的某些实施例中，所述高透硅胶层复合在所述柔性基底的一面上的复合方式为涂覆。In some embodiments of the present invention, the way of compounding the high-permeability silicone layer on one side of the flexible substrate is coating.
本发明提供的石墨烯透明导电薄膜还包括石墨烯薄膜层。所述石墨烯薄膜层复合在所述高透硅胶层上。The graphene transparent conductive film provided by the invention also includes a graphene film layer. The graphene thin film layer is compounded on the high permeability silica gel layer.
所述石墨烯薄膜层可以为单层石墨烯薄膜或多层石墨烯薄膜。在本发明的某些实施例中，所述多层石墨烯薄膜的层数为2层、5层或3层。本发明的石墨烯透明导电薄膜中的石墨烯薄膜层表面光滑平整，无颗粒残留，具有较高的清洁度和表面平整度，这对于保持石墨烯透明导电薄膜优异的光电性能是非常重要的。The graphene film layer can be a single-layer graphene film or a multi-layer graphene film. In some embodiments of the present invention, the number of layers of the multilayer graphene film is 2 layers, 5 layers or 3 layers. The surface of the graphene film layer in the graphene transparent conductive film of the present invention is smooth and smooth, without particle residue, and has high cleanliness and surface smoothness, which is very important for maintaining the excellent photoelectric performance of the graphene transparent conductive film.
本发明对所述石墨烯薄膜层的厚度并无特殊的限制，可以根据实际需要选择相应的厚度。The present invention has no special limitation on the thickness of the graphene film layer, and the corresponding thickness can be selected according to actual needs.
在本发明的某些实施例中，所述石墨烯薄膜层复合在所述高透硅胶层上的复合方式为加压粘合。In some embodiments of the present invention, the composite method of the graphene thin film layer on the high permeability silica gel layer is pressure bonding.
本发明提供的石墨烯透明导电薄膜还包括OCA光学胶层。所述OCA光学胶层复合在所述柔性基底的另一面。所述OCA光学胶层的组分为OCA光学胶。在本发明的某些实施例中，所述OCA光学胶为深圳市光华士科技有限公司生产的OCA光学胶。The graphene transparent conductive film provided by the invention also includes an OCA optical adhesive layer. The OCA optical glue layer is compounded on the other side of the flexible substrate. A component of the OCA optical glue layer is OCA optical glue. In some embodiments of the present invention, the OCA optical glue is OCA optical glue produced by Shenzhen Guanghuashi Technology Co., Ltd.
在本发明的某些实施例中，所述OCA光学胶层的厚度为30nm～1000μm。In some embodiments of the present invention, the thickness of the OCA optical adhesive layer is 30 nm˜1000 μm.
在本发明的某些实施例中，所述OCA光学胶层复合在所述柔性基底的另一面上的复合方式为涂覆。In some embodiments of the present invention, the OCA optical adhesive layer is compounded on the other surface of the flexible substrate by coating.
在本发明的某些实施例中，在所述OCA光学胶层上复合有离型膜。所述离型膜用于保护OCA光学胶表面，转移时可以将离型膜去掉。In some embodiments of the present invention, a release film is compounded on the OCA optical adhesive layer. The release film is used to protect the surface of the OCA optical adhesive, and the release film can be removed during transfer.
本发明对所述离型膜的材质并无特殊的限制，可以为本领域技术人员熟知的离型膜材质。The present invention has no special limitation on the material of the release film, which may be a release film material well known to those skilled in the art.
本发明提供的石墨烯透明导电薄膜的清洁度和表面平整度较优，同时，可以保持较好的完整性和优异的光电性能。The graphene transparent conductive film provided by the invention has better cleanliness and surface smoothness, and at the same time, can maintain better integrity and excellent photoelectric performance.
本发明提供的石墨烯透明导电薄膜的透光率较优，透光率为80～97.5％。The graphene transparent conductive film provided by the invention has better light transmittance, and the light transmittance is 80-97.5%.
本发明还提供了一种上文所述的石墨烯透明导电薄膜的制备方法，包括以下步骤：The present invention also provides a kind of preparation method of above-mentioned graphene transparent conductive film, comprises the following steps:
A)采用化学气相沉积法在金属箔的上表面生长石墨烯薄膜，得到石墨烯薄膜层；在柔性基底的一面涂布高透硅胶，得到高透硅胶层/柔性基底复合层；A) using chemical vapor deposition to grow a graphene film on the upper surface of the metal foil to obtain a graphene film layer; coating a high-permeability silica gel on one side of the flexible substrate to obtain a high-permeability silica gel layer/flexible substrate composite layer;
B)将所述高透硅胶层与所述石墨烯薄膜层贴合，进行加压，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；B) laminating the high-permeability silica gel layer and the graphene film layer, and pressurizing to obtain a graphene film layer/high-permeability silica gel layer/flexible substrate composite layer;
C)在所述柔性基底的另一面涂布OCA光学胶，得到OCA光学胶层；C) coating OCA optical adhesive on the other side of the flexible substrate to obtain an OCA optical adhesive layer;
D)通过刻蚀法或电化学法去除所述金属箔，得到石墨烯复合体，经清洗和干燥后，得到石墨烯透明导电薄膜。D) removing the metal foil by an etching method or an electrochemical method to obtain a graphene composite body, and obtaining a graphene transparent conductive film after cleaning and drying.
本发明采用化学气相沉积法在金属箔的上表面生长石墨烯薄膜，得到石墨烯薄膜层。The invention adopts a chemical vapor deposition method to grow a graphene film on the upper surface of the metal foil to obtain a graphene film layer.
本发明对所述化学气相沉积法的具体步骤和参数并无特殊的限制，采用本领域技术人员熟知的化学气相沉积法在金属箔的上表面生长石墨烯薄膜即可。在本发明的某些实施例中，所述金属箔的材质包括Au、Cu、Ni、Pt或Ru。在本发明的某些实施例中，得到的石墨烯薄膜层可以为单层石墨烯薄膜或多层石墨烯薄膜。在本发明的某些实施例中，所述多层石墨烯薄膜的层数为2层、5层或3层。The present invention has no special restrictions on the specific steps and parameters of the chemical vapor deposition method, and the graphene film can be grown on the upper surface of the metal foil by using the chemical vapor deposition method well known to those skilled in the art. In some embodiments of the present invention, the material of the metal foil includes Au, Cu, Ni, Pt or Ru. In some embodiments of the present invention, the obtained graphene film layer may be a single-layer graphene film or a multi-layer graphene film. In some embodiments of the present invention, the number of layers of the multilayer graphene film is 2 layers, 5 layers or 3 layers.
本发明中，在柔性基底的一面涂布高透硅胶，得到高透硅胶层/柔性基底复合层。In the present invention, high-permeability silica gel is coated on one side of the flexible substrate to obtain a high-permeability silica gel layer/flexible substrate composite layer.
本发明对所述柔性基底的来源并无特殊的限制，可以为一般市售的柔性基底或柔性衬底。在本发明的某些实施例中，所述柔性基底的组分选自聚对苯二甲酸乙二醇酯、聚酰亚胺和聚萘二甲酸乙二醇酯中的一种或几种。The present invention has no special limitation on the source of the flexible substrate, which may be a general commercially available flexible substrate or flexible substrate. In some embodiments of the present invention, the components of the flexible substrate are selected from one or more of polyethylene terephthalate, polyimide and polyethylene naphthalate.
在本发明的某些实施例中，所述高透硅胶的组分包括有机硅胶。所述高透硅胶中可以添加固化剂也可以不添加固化剂。在本发明的某些实施例中，所述高透硅胶的透光率>90％。在本发明的某些实施例中，所述高透硅胶为透光率>90％的有机硅胶。在本发明的某些实施例中，所述高透硅胶为有机硅胶KL-9310B。In some embodiments of the present invention, the components of the high permeability silica gel include organic silica gel. A curing agent may or may not be added to the high permeability silica gel. In some embodiments of the present invention, the light transmittance of the highly transparent silica gel is >90%. In some embodiments of the present invention, the highly transparent silica gel is an organic silica gel with a light transmittance >90%. In some embodiments of the present invention, the high permeability silica gel is organic silica gel KL-9310B.
得到高透硅胶层/柔性基底复合层后，将所述高透硅胶层/柔性基底复合层中的高透硅胶层与所述石墨烯薄膜层贴合，进行加压，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层。After obtaining the high-permeability silica gel layer/flexible substrate composite layer, the high-permeability silica gel layer in the high-permeability silica gel layer/flexible substrate composite layer is bonded to the graphene film layer, and pressurized to obtain the graphene film layer/ High permeability silicone layer/flexible substrate composite layer.
在本发明的某些实施例中，所述加压具体为：采用覆膜机的滚轴或压片机进行加压。In some embodiments of the present invention, the pressurization is specifically: using a roller of a laminating machine or a tablet press to perform pressurization.
在本发明的某些实施例中，所述加压的压力为0.1～20MPa；在某些实施例中，所述加压的压力为5～10MPa；在某些实施例中，所述加压的压力为10MPa。在本发明的某些实施例中，所述加压的时间为1s～30h；在某些实施例中，所述加压的时间为1s～10h；在某些实施例中，所述加压的时间为5h、8h。In some embodiments of the present invention, the pressurized pressure is 0.1-20MPa; in some embodiments, the pressurized pressure is 5-10MPa; in some embodiments, the pressurized The pressure is 10MPa. In some embodiments of the present invention, the pressurization time is 1s-30h; in some embodiments, the pressurization time is 1s-10h; in some embodiments, the pressurization The time is 5h, 8h.
经过加压后的高透硅胶层与所述石墨烯薄膜层紧密粘合在一起。The pressurized high-permeable silica gel layer is closely bonded to the graphene film layer.
得到石墨烯薄膜层/高透硅胶层/柔性基底复合层后，在所述柔性基底的另一面涂布OCA光学胶，得到OCA光学胶层。After obtaining the composite layer of graphene film layer/high-permeable silica gel layer/flexible substrate, OCA optical adhesive is coated on the other side of the flexible substrate to obtain an OCA optical adhesive layer.
在本发明的某些实施例中，所述OCA光学胶为深圳市光华士科技有限公司生产的OCA光学胶。In some embodiments of the present invention, the OCA optical glue is OCA optical glue produced by Shenzhen Guanghuashi Technology Co., Ltd.
得到OCA光学胶层后，通过刻蚀法或电化学法去除所述金属箔，得到石墨烯复合体，经清洗和干燥后，得到石墨烯透明导电薄膜。After the OCA optical adhesive layer is obtained, the metal foil is removed by an etching method or an electrochemical method to obtain a graphene composite, and after cleaning and drying, a graphene transparent conductive film is obtained.
在本发明的某些实施例中，所述刻蚀法采用的刻蚀液为盐酸与双氧水的混合溶液、氯化铁的水溶液和过硫酸铵的水溶液中的一种。在本发明的某些实施例中，所述刻蚀液的浓度为0.1～10mol/L。在某些实施例中，所述刻蚀液的浓度为0.5～5mol/L。在某些实施例中，所述刻蚀液的浓度为0.5mol/L、1mol/L、2mol/L或5mol/L。在本发明的某些实施例中，所述盐酸与双氧水的体积比为1～9：1～9。在某些实施例中，所述盐酸与双氧水的体积比为1：1。In some embodiments of the present invention, the etching solution used in the etching method is one of a mixed solution of hydrochloric acid and hydrogen peroxide, an aqueous solution of ferric chloride, and an aqueous solution of ammonium persulfate. In some embodiments of the present invention, the concentration of the etching solution is 0.1-10 mol/L. In some embodiments, the concentration of the etching solution is 0.5˜5 mol/L. In some embodiments, the concentration of the etching solution is 0.5 mol/L, 1 mol/L, 2 mol/L or 5 mol/L. In some embodiments of the present invention, the volume ratio of hydrochloric acid to hydrogen peroxide is 1-9:1-9. In some embodiments, the volume ratio of hydrochloric acid to hydrogen peroxide is 1:1.
在本发明的某些实施例中，所述电化学法为电化学鼓泡法。本发明对所述电化学鼓泡法的步骤和参数并无特殊的限制，采用本领域技术人员熟知的电化学鼓泡法即可。In some embodiments of the invention, the electrochemical method is an electrochemical bubbling method. The present invention has no special limitations on the steps and parameters of the electrochemical bubbling method, and the electrochemical bubbling method well known to those skilled in the art can be used.
在本发明的某些实施例中，所述电化学法采用的电解液包括无机酸的水溶液、有机酸的水溶液、碱的水溶液和盐的水溶液中的一种。在某些实施例中，所述电化学法采用的电解液包括硫酸溶液、盐酸溶液、硝酸溶液、甲磺酸的水溶液、柠檬酸的水溶液、氢氧化钠的水溶液、氢氧化钾的水溶液、氯化钠的水溶液和氯化钾的水溶液中的一种。在本发明的某些实施例中，所述电解液的浓度为0.1～10mol/L。在某些实施例中，所述电解液的浓度为1mol/L。In some embodiments of the present invention, the electrolytic solution used in the electrochemical method includes one of an aqueous solution of an inorganic acid, an aqueous organic acid, an aqueous alkali, and an aqueous salt. In some embodiments, the electrolytic solution used in the electrochemical method includes sulfuric acid solution, hydrochloric acid solution, nitric acid solution, methanesulfonic acid aqueous solution, citric acid aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, chlorine One of the aqueous solution of sodium chloride and the aqueous solution of potassium chloride. In some embodiments of the present invention, the concentration of the electrolyte is 0.1-10 mol/L. In some embodiments, the concentration of the electrolyte is 1 mol/L.
在本发明的某些实施例中，所述清洗采用的清洗剂为去离子水。本发明提供的制备方法中，所述清洗采用的清洗剂无需使用有机溶剂(比如：乙醇、乙醚、丙酮、洗板水、甲苯、二甲苯、柠檬烯、香蕉水、二硫化碳、二氯乙烷、松节油、石油醚、汽油)，因而，本发明提供的制备方法更为绿色环保，无污染。In some embodiments of the present invention, the cleaning agent used in the cleaning is deionized water. In the preparation method provided by the present invention, the cleaning agent used in the cleaning does not need to use organic solvents (such as: ethanol, ether, acetone, board washing water, toluene, xylene, limonene, banana water, carbon disulfide, dichloroethane, turpentine , petroleum ether, gasoline), thus, the preparation method provided by the invention is more green and environment-friendly, pollution-free.
在本发明的某些实施例中，所述干燥的方法为采用氮气枪吹干。In some embodiments of the present invention, the drying method is to blow dry with a nitrogen gun.
本发明以高透硅胶层为转移介质，在实现石墨烯薄膜层完整无损转移的同时，石墨烯薄膜层的表面光滑平整，无颗粒残留，具有更高的清洁度，最终制得的石墨烯透明导电薄膜的清洁度和表面平整度较优，同时，可以保持较好的完整性和优异的光电性能，透光率较优。另外，高透硅胶层具有自动排气泡的功能，贴合方法简便。本发明提供的制备方法可以制备大面积、高性能的透明导电薄膜，成本较低，对于石墨烯的应用具有重要的意义。The invention uses a high-permeability silica gel layer as the transfer medium, and while realizing the complete and non-destructive transfer of the graphene film layer, the surface of the graphene film layer is smooth and flat, has no particle residue, and has a higher degree of cleanliness, and the finally obtained graphene is transparent The cleanliness and surface smoothness of the conductive film are better, and at the same time, it can maintain better integrity and excellent photoelectric performance, and the light transmittance is better. In addition, the high-permeability silicone layer has the function of automatically releasing air bubbles, and the bonding method is simple. The preparation method provided by the invention can prepare a large-area, high-performance transparent conductive film with low cost and is of great significance for the application of graphene.
本发明还提供了一种上文所述的石墨烯透明导电薄膜或上文所述的制备方法制备的石墨烯透明导电薄膜作为光电器件的透明电极的应用。本申请人研究发现，本发明制备的石墨烯透明导电薄膜的清洁度和表面平整度较优，同时，可以保持较好的完整性和优异的光电性能，透光率较优，因而，可以作为光电器件诸如电容器、传感器、触摸屏、太阳能电池(所述太阳能电池可以为有机太阳能电池或钙钛矿太阳能电池)和有机发光二极管的透明电极。因而，请求保护上文所述的石墨烯透明导电薄膜或上文所述的制备方法制备的石墨烯透明导电薄膜作为光电器件的透明电极的应用。The present invention also provides an application of the above-mentioned graphene transparent conductive film or the graphene transparent conductive film prepared by the above-mentioned preparation method as a transparent electrode of a photoelectric device. The applicant has found that the cleanliness and surface smoothness of the graphene transparent conductive film prepared by the present invention are better, and at the same time, it can maintain better integrity and excellent photoelectric performance, and the light transmittance is better. Therefore, it can be used as Transparent electrodes of optoelectronic devices such as capacitors, sensors, touch screens, solar cells (which may be organic solar cells or perovskite solar cells) and organic light emitting diodes. Therefore, the application of the above-mentioned graphene transparent conductive film or the graphene transparent conductive film prepared by the above-mentioned preparation method as a transparent electrode of an optoelectronic device is claimed.
为了进一步说明本发明，下面结合实施例对本发明提供的一种石墨烯透明导电薄膜、其制备方法及应用进行详细地描述，但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, a graphene transparent conductive film provided by the present invention, its preparation method and application are described in detail below in conjunction with examples, but they should not be understood as limiting the protection scope of the present invention.
以下实施例所用的原料均为一般市售。The raw materials used in the following examples are generally commercially available.
实施例1Example 1
采用化学气相沉积法在铜箔的上表面生长双层石墨烯薄膜，得到石墨烯薄膜层；A double-layer graphene film is grown on the upper surface of the copper foil by a chemical vapor deposition method to obtain a graphene film layer;
在组分为聚对苯二甲酸乙二醇酯的柔性基底的一面涂布有机硅胶KL-9310B，得到高透硅胶层/柔性基底复合层；所述高透硅胶层的厚度为50μm；Coating organic silica gel KL-9310B on one side of a flexible substrate composed of polyethylene terephthalate to obtain a high-permeability silica gel layer/flexible substrate composite layer; the thickness of the highly permeable silica gel layer is 50 μm;
将有机硅胶KL-9310B覆盖与所述石墨烯薄膜层贴合，采用覆膜机的滚轴进行加压，使得所述高透硅胶层与所述石墨烯薄膜层紧密粘合在一起，所述加压的压力为10MPa，所述加压的时间为5h，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；The organic silica gel KL-9310B is covered with the graphene film layer, and the roller of the laminating machine is used to pressurize, so that the high-permeability silica gel layer and the graphene film layer are tightly bonded together. The pressurized pressure is 10MPa, and the pressurized time is 5h to obtain a composite layer of graphene film layer/high permeability silica gel layer/flexible substrate;
在所述柔性基底的另一面涂布OCA光学胶(深圳市光华士科技有限公司生产)，得到OCA光学胶层；OCA optical glue (produced by Shenzhen Guanghuashi Technology Co., Ltd.) is coated on the other side of the flexible substrate to obtain an OCA optical glue layer;
通过刻蚀法去除所述铜箔，得到石墨烯复合体；所述刻蚀法采用的刻蚀液为浓度为0.5mol/L的氯化铁的水溶液；The copper foil is removed by an etching method to obtain a graphene composite; the etching solution used in the etching method is an aqueous solution of ferric chloride with a concentration of 0.5mol/L;
所述石墨烯复合体用去离子水清洗，并用氮气枪吹干，得到石墨烯透明导电薄膜。The graphene composite was cleaned with deionized water, and dried with a nitrogen gun to obtain a graphene transparent conductive film.
经检测，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率为260ohm/sq；石墨烯透明导电薄膜的透光率为95.1％。After testing, in the graphene transparent conductive film, the surface resistivity of the graphene film layer is 260 ohm/sq; the light transmittance of the graphene transparent conductive film is 95.1%.
将实施例1得到的石墨烯透明导电薄膜的石墨烯薄膜层采用原子力显微镜进行分析，结果如图2所示。图2为本发明实施例1的石墨烯透明导电薄膜的石墨烯薄膜层的原子力显微镜图。从图2中可以看出，石墨烯薄膜褶皱清晰可见，表面光滑平整、清洁无破损，无明显的大颗粒残留。The graphene film layer of the graphene transparent conductive film obtained in Example 1 was analyzed by an atomic force microscope, and the results are shown in FIG. 2 . 2 is an atomic force microscope image of the graphene film layer of the graphene transparent conductive film of Example 1 of the present invention. It can be seen from Figure 2 that the graphene film wrinkles are clearly visible, the surface is smooth and flat, clean and undamaged, and there is no obvious large particle residue.
将实施例1得到的石墨烯透明导电薄膜的石墨烯薄膜层采用扫描电子显微镜进行分析，结果如图3所示。图3为本发明实施例1的石墨烯透明导电薄膜的石墨烯薄膜层的扫描电子显微镜图。从图3可以清晰的看到石墨烯薄膜的褶皱，表面光滑平整，清洁无破损，无明显的大颗粒残留。The graphene film layer of the graphene transparent conductive film obtained in Example 1 is analyzed by scanning electron microscope, and the results are shown in FIG. 3 . 3 is a scanning electron microscope image of the graphene film layer of the graphene transparent conductive film of Example 1 of the present invention. From Figure 3, we can clearly see the wrinkles of the graphene film, the surface is smooth and flat, clean and undamaged, and there is no obvious residue of large particles.
将实施例1得到的石墨烯透明导电薄膜的石墨烯薄膜层进行可见光透射光谱分析，结果如图4所示。图4为本发明实施例1的石墨烯透明导电薄膜的石墨烯薄膜层的可见光透射光谱图。从图4中可以看出，石墨烯薄膜层在可见光范围内具有较高的透光率。The graphene thin film layer of the graphene transparent conductive film obtained in Example 1 is subjected to visible light transmission spectrum analysis, and the results are shown in Figure 4. 4 is a visible light transmission spectrum diagram of the graphene film layer of the graphene transparent conductive film of Example 1 of the present invention. It can be seen from Figure 4 that the graphene film layer has a high light transmittance in the visible light range.
实施例2Example 2
采用化学气相沉积法在铜箔的上表面生长单层石墨烯薄膜，得到石墨烯薄膜层；A single-layer graphene film is grown on the upper surface of the copper foil by a chemical vapor deposition method to obtain a graphene film layer;
在组分为聚萘二甲酸乙二醇酯的柔性基底的一面涂布有机硅胶KL-9310B，得到高透硅胶层/柔性基底复合层；所述高透硅胶层的厚度为100μm；Coating organic silica gel KL-9310B on one side of a flexible substrate whose component is polyethylene naphthalate, to obtain a high-permeability silica gel layer/flexible substrate composite layer; the thickness of the high-permeability silica gel layer is 100 μm;
将有机硅胶KL-9310B覆盖与所述石墨烯薄膜层贴合，采用覆膜机的滚轴进行加压，使得所述高透硅胶层与所述石墨烯薄膜层紧密粘合在一起，所述加压的压力为5MPa，所述加压的时间为8h，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；The organic silica gel KL-9310B is covered with the graphene film layer, and the roller of the laminating machine is used to pressurize, so that the high-permeability silica gel layer and the graphene film layer are tightly bonded together. The pressure of pressurization is 5MPa, and the time of described pressurization is 8h, obtains graphene film layer/high permeability silica gel layer/flexible substrate composite layer;
在所述柔性基底的另一面涂布OCA光学胶(深圳市光华士科技有限公司生产)，得到OCA光学胶层；OCA optical glue (produced by Shenzhen Guanghuashi Technology Co., Ltd.) is coated on the other side of the flexible substrate to obtain an OCA optical glue layer;
通过刻蚀法去除所述铜箔，得到石墨烯复合体；所述刻蚀法采用的刻蚀液为浓度为0.5mol/L的氯化铁的水溶液；The copper foil is removed by an etching method to obtain a graphene composite; the etching solution used in the etching method is an aqueous solution of ferric chloride with a concentration of 0.5mol/L;
所述石墨烯复合体用去离子水清洗，并用氮气枪吹干，得到石墨烯透明导电薄膜。The graphene composite was cleaned with deionized water, and dried with a nitrogen gun to obtain a graphene transparent conductive film.
经检测，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率为580ohm/sq，石墨烯薄膜层结构完整、表面光滑平整、干净、无残留；石墨烯透明导电薄膜的透光率为97.2％。After testing, in the graphene transparent conductive film, the surface resistivity of the graphene film layer is 580ohm/sq, the structure of the graphene film layer is complete, the surface is smooth and flat, clean, and has no residue; the light transmittance of the graphene transparent conductive film was 97.2%.
实施例3Example 3
采用化学气相沉积法在铜箔的上表面生长单层石墨烯薄膜，得到石墨烯薄膜层；A single-layer graphene film is grown on the upper surface of the copper foil by a chemical vapor deposition method to obtain a graphene film layer;
在组分为聚酰亚胺的柔性基底的一面涂布有机硅胶KL-9310B，得到高透硅胶层/柔性基底复合层；所述高透硅胶层的厚度为50μm；Coating organic silica gel KL-9310B on one side of the flexible substrate whose component is polyimide, to obtain a high-permeability silica gel layer/flexible substrate composite layer; the thickness of the highly permeable silica gel layer is 50 μm;
将有机硅胶KL-9310B覆盖与所述石墨烯薄膜层贴合，采用覆膜机的滚轴进行加压，使得所述高透硅胶层与所述石墨烯薄膜层紧密粘合在一起，所述加压的压力为10MPa，所述加压的时间为5h，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；The organic silica gel KL-9310B is covered with the graphene film layer, and the roller of the laminating machine is used to pressurize, so that the high-permeability silica gel layer and the graphene film layer are tightly bonded together. The pressurized pressure is 10MPa, and the pressurized time is 5h to obtain a composite layer of graphene film layer/high permeability silica gel layer/flexible substrate;
在所述柔性基底的另一面涂布OCA光学胶(深圳市光华士科技有限公司生产)，得到OCA光学胶层；OCA optical glue (produced by Shenzhen Guanghuashi Technology Co., Ltd.) is coated on the other side of the flexible substrate to obtain an OCA optical glue layer;
通过刻蚀法去除所述铜箔，得到石墨烯复合体；所述刻蚀法采用的刻蚀液为浓度为1mol/L的氯化铁的水溶液；The copper foil is removed by an etching method to obtain a graphene composite; the etching solution used in the etching method is an aqueous solution of ferric chloride with a concentration of 1mol/L;
所述石墨烯复合体用去离子水清洗，并用氮气枪吹干，得到石墨烯透明导电薄膜。The graphene composite was cleaned with deionized water, and dried with a nitrogen gun to obtain a graphene transparent conductive film.
经检测，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率为630ohm/sq，石墨烯薄膜层结构完整、表面光滑平整、干净、无残留；石墨烯透明导电薄膜的透光率为97.2％。After testing, in the graphene transparent conductive film, the surface resistivity of the graphene film layer is 630ohm/sq, the structure of the graphene film layer is complete, the surface is smooth and flat, clean, and no residue; the light transmittance of the graphene transparent conductive film was 97.2%.
实施例4Example 4
采用化学气相沉积法在铜箔的上表面生长单层石墨烯薄膜，得到石墨烯薄膜层；A single-layer graphene film is grown on the upper surface of the copper foil by a chemical vapor deposition method to obtain a graphene film layer;
在组分为聚对苯二甲酸乙二醇酯的柔性基底的一面涂布有机硅胶KL-9310B，得到高透硅胶层/柔性基底复合层；所述高透硅胶层的厚度为50μm；Coating organic silica gel KL-9310B on one side of a flexible substrate composed of polyethylene terephthalate to obtain a high-permeability silica gel layer/flexible substrate composite layer; the thickness of the highly permeable silica gel layer is 50 μm;
将有机硅胶KL-9310B覆盖与所述石墨烯薄膜层贴合，采用覆膜机的滚轴进行加压，使得所述高透硅胶层与所述石墨烯薄膜层紧密粘合在一起，所述加压的压力为10MPa，所述加压的时间为5h，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；The organic silica gel KL-9310B is covered with the graphene film layer, and the roller of the laminating machine is used to pressurize, so that the high-permeability silica gel layer and the graphene film layer are tightly bonded together. The pressurized pressure is 10MPa, and the pressurized time is 5h to obtain a composite layer of graphene film layer/high permeability silica gel layer/flexible substrate;
在所述柔性基底的另一面涂布OCA光学胶(深圳市光华士科技有限公司生产)，得到OCA光学胶层；OCA optical glue (produced by Shenzhen Guanghuashi Technology Co., Ltd.) is coated on the other side of the flexible substrate to obtain an OCA optical glue layer;
通过刻蚀法去除所述铜箔，得到石墨烯复合体；所述刻蚀法采用的刻蚀液为浓度为2mol/L的过硫酸铵的水溶液；The copper foil is removed by an etching method to obtain a graphene composite; the etching solution used in the etching method is an aqueous solution of ammonium persulfate with a concentration of 2mol/L;
所述石墨烯复合体用去离子水清洗，并用氮气枪吹干，得到石墨烯透明导电薄膜。The graphene composite was cleaned with deionized water, and dried with a nitrogen gun to obtain a graphene transparent conductive film.
经检测，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率为300ohm/sq，石墨烯薄膜层结构完整、表面光滑平整、干净、无残留；石墨烯透明导电薄膜的透光率为97.1％。After testing, in the graphene transparent conductive film, the surface resistivity of the graphene film layer is 300ohm/sq, the structure of the graphene film layer is complete, the surface is smooth and flat, clean, and has no residue; the light transmittance of the graphene transparent conductive film was 97.1%.
实施例5Example 5
采用化学气相沉积法在铜箔的上表面生长双层石墨烯薄膜，得到石墨烯薄膜层；A double-layer graphene film is grown on the upper surface of the copper foil by a chemical vapor deposition method to obtain a graphene film layer;
在组分为聚对苯二甲酸乙二醇酯的柔性基底的一面涂布有机硅胶KL-9310B，得到高透硅胶层/柔性基底复合层；所述高透硅胶层的厚度为50μm；Coating organic silica gel KL-9310B on one side of a flexible substrate composed of polyethylene terephthalate to obtain a high-permeable silica gel layer/flexible substrate composite layer; the thickness of the highly transparent silica gel layer is 50 μm;
将有机硅胶KL-9310B覆盖与所述石墨烯薄膜层贴合，采用覆膜机的滚轴进行加压，使得所述高透硅胶层与所述石墨烯薄膜层紧密粘合在一起，所述加压的压力为10MPa，所述加压的时间为5h，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；The organic silica gel KL-9310B is covered with the graphene film layer, and the roller of the laminating machine is used to pressurize, so that the high-permeability silica gel layer and the graphene film layer are tightly bonded together. The pressurized pressure is 10MPa, and the pressurized time is 5h to obtain a composite layer of graphene film layer/high permeability silica gel layer/flexible substrate;
在所述柔性基底的另一面涂布OCA光学胶(深圳市光华士科技有限公司生产)，得到OCA光学胶层；OCA optical glue (produced by Shenzhen Guanghuashi Technology Co., Ltd.) is coated on the other side of the flexible substrate to obtain an OCA optical glue layer;
通过刻蚀法去除所述铜箔，得到石墨烯复合体；所述刻蚀法采用的刻蚀液为浓度为1mol/L的过硫酸铵的水溶液；The copper foil is removed by an etching method to obtain a graphene composite; the etching solution used in the etching method is an aqueous solution of ammonium persulfate with a concentration of 1mol/L;
所述石墨烯复合体用去离子水清洗，并用氮气枪吹干，得到石墨烯透明导电薄膜。The graphene composite was cleaned with deionized water, and dried with a nitrogen gun to obtain a graphene transparent conductive film.
经检测，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率为200ohm/sq，石墨烯薄膜层结构完整、表面光滑平整、干净、无残留；石墨烯透明导电薄膜的透光率为95.2％。After testing, in the graphene transparent conductive film, the surface resistivity of the graphene film layer is 200ohm/sq, the structure of the graphene film layer is complete, the surface is smooth and flat, clean, and has no residue; the light transmittance of the graphene transparent conductive film was 95.2%.
实施例6Example 6
采用化学气相沉积法在铜箔的上表面生长5层石墨烯薄膜，得到石墨烯薄膜层；A 5-layer graphene film is grown on the upper surface of the copper foil by chemical vapor deposition to obtain a graphene film layer;
在组分为聚对苯二甲酸乙二醇酯的柔性基底的一面涂布有机硅胶KL-9310B，得到高透硅胶层/柔性基底复合层；所述高透硅胶层的厚度为50μm；Coating organic silica gel KL-9310B on one side of a flexible substrate composed of polyethylene terephthalate to obtain a high-permeability silica gel layer/flexible substrate composite layer; the thickness of the highly permeable silica gel layer is 50 μm;
将有机硅胶KL-9310B覆盖与所述石墨烯薄膜层贴合，采用覆膜机的滚轴进行加压，使得所述高透硅胶层与所述石墨烯薄膜层紧密粘合在一起，所述加压的压力为10MPa，所述加压的时间为5h，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；The organic silica gel KL-9310B is covered with the graphene film layer, and the roller of the laminating machine is used to pressurize, so that the high-permeability silica gel layer and the graphene film layer are tightly bonded together. The pressurized pressure is 10MPa, and the pressurized time is 5h to obtain a composite layer of graphene film layer/high permeability silica gel layer/flexible substrate;
在所述柔性基底的另一面涂布OCA光学胶(深圳市光华士科技有限公司生产)，得到OCA光学胶层；OCA optical glue (produced by Shenzhen Guanghuashi Technology Co., Ltd.) is coated on the other side of the flexible substrate to obtain an OCA optical glue layer;
通过刻蚀法去除所述铜箔，得到石墨烯复合体；所述刻蚀法采用的刻蚀液为浓度为1mol/L的过硫酸铵的水溶液；The copper foil is removed by an etching method to obtain a graphene composite; the etching solution used in the etching method is an aqueous solution of ammonium persulfate with a concentration of 1mol/L;
所述石墨烯复合体用去离子水清洗，并用氮气枪吹干，得到石墨烯透明导电薄膜。The graphene composite was cleaned with deionized water, and dried with a nitrogen gun to obtain a graphene transparent conductive film.
经检测，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率为50ohm/sq，石墨烯薄膜层结构完整、表面光滑平整、干净、无残留；石墨烯透明导电薄膜的透光率为85％。After testing, in the graphene transparent conductive film, the surface resistivity of the graphene film layer is 50ohm/sq, the structure of the graphene film layer is complete, the surface is smooth and flat, clean, and no residue; the light transmittance of the graphene transparent conductive film is 50 ohm/sq. 85%.
以本实施例制备的石墨烯透明导电薄膜为透明电极，制备了结构为：透明电极/三氧化钼/4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]/乙酰丙酮酸二(2-苯基吡啶)铱:4,4',4”-三(咔唑-9-基)三苯胺/乙酰丙酮酸二(2-苯基吡啶)铱:1,10-邻二氮杂菲/1,10-邻二氮杂菲/(锂/铝))的绿光OLED器件。经检测，所述绿光OLED器件的发光面积为0.4mm2；电压为5V时，绿光OLED器件的亮度可以达到8000cd m-2。Using the graphene transparent conductive film prepared in this example as a transparent electrode, the prepared structure is: transparent electrode/molybdenum trioxide/4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline ]/bis(2-phenylpyridine)iridium acetylacetonate: 4,4',4"-tris(carbazol-9-yl)triphenylamine/bis(2-phenylpyridine)iridium acetylacetonate: 1, 10-o-phenanthrene/1,10-o-phenanthrene/(lithium/aluminum)) green OLED device. After testing, the light-emitting area of the green OLED device is 0.4mm 2 ; the voltage is 5V , the brightness of the green OLED device can reach 8000cd m -2 .
实施例7Example 7
采用化学气相沉积法在铜箔的上表面生长3层石墨烯薄膜，得到石墨烯薄膜层；A three-layer graphene film is grown on the upper surface of the copper foil by chemical vapor deposition to obtain a graphene film layer;
在组分为聚对苯二甲酸乙二醇酯的柔性基底的一面涂布有机硅胶KL-9310B，得到高透硅胶层/柔性基底复合层；所述高透硅胶层的厚度为50μm；Coating organic silica gel KL-9310B on one side of a flexible substrate composed of polyethylene terephthalate to obtain a high-permeability silica gel layer/flexible substrate composite layer; the thickness of the highly permeable silica gel layer is 50 μm;
将有机硅胶KL-9310B覆盖与所述石墨烯薄膜层贴合，采用覆膜机的滚轴进行加压，使得所述高透硅胶层与所述石墨烯薄膜层紧密粘合在一起，所述加压的压力为10MPa，所述加压的时间为5h，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；The organic silica gel KL-9310B is covered with the graphene film layer, and the roller of the laminating machine is used to pressurize, so that the high-permeability silica gel layer and the graphene film layer are tightly bonded together. The pressurized pressure is 10MPa, and the pressurized time is 5h to obtain a composite layer of graphene film layer/high permeability silica gel layer/flexible substrate;
在所述柔性基底的另一面涂布OCA光学胶(深圳市光华士科技有限公司生产)，得到OCA光学胶层；OCA optical glue (produced by Shenzhen Guanghuashi Technology Co., Ltd.) is coated on the other side of the flexible substrate to obtain an OCA optical glue layer;
通过刻蚀法去除所述铜箔，得到石墨烯复合体；所述刻蚀法采用的刻蚀液为浓度为5mol/L的过硫酸铵的水溶液；The copper foil is removed by an etching method to obtain a graphene composite; the etching solution used in the etching method is an aqueous solution of ammonium persulfate with a concentration of 5 mol/L;
所述石墨烯复合体用去离子水清洗，并用氮气枪吹干，得到石墨烯透明导电薄膜。The graphene composite was cleaned with deionized water, and dried with a nitrogen gun to obtain a graphene transparent conductive film.
经检测，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率为70ohm/sq，石墨烯薄膜层结构完整、表面光滑平整、干净、无残留；石墨烯透明导电薄膜的透光率为93％。After testing, in the graphene transparent conductive film, the surface resistivity of the graphene film layer is 70ohm/sq, the structure of the graphene film layer is complete, the surface is smooth and flat, clean, and has no residue; the light transmittance of the graphene transparent conductive film 93%.
以本实施例制备的石墨烯透明导电薄膜为透明电极，制备了结构为：透明电极/聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸/聚-3己基噻吩/PCBM(/钙/铝)的有机太阳能电池。经检测，所述有机太阳能电池的光电转化效率为5.6％。With the graphene transparent conductive film prepared in this embodiment as a transparent electrode, the prepared structure is: transparent electrode/poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid/poly-3-hexylthiophene/PCBM(/ Ca/Al) organic solar cells. After testing, the photoelectric conversion efficiency of the organic solar cell is 5.6%.
实施例8Example 8
采用化学气相沉积法在铜箔的上表面生长单层石墨烯薄膜，得到石墨烯薄膜层；A single-layer graphene film is grown on the upper surface of the copper foil by a chemical vapor deposition method to obtain a graphene film layer;
在组分为聚对苯二甲酸乙二醇酯的柔性基底的一面涂布有机硅胶KL-9310B，得到高透硅胶层/柔性基底复合层；所述高透硅胶层的厚度为50μm；Coating organic silica gel KL-9310B on one side of a flexible substrate composed of polyethylene terephthalate to obtain a high-permeability silica gel layer/flexible substrate composite layer; the thickness of the highly permeable silica gel layer is 50 μm;
将有机硅胶KL-9310B覆盖与所述石墨烯薄膜层贴合，采用覆膜机的滚轴进行加压，使得所述高透硅胶层与所述石墨烯薄膜层紧密粘合在一起，所述加压的压力为10MPa，所述加压的时间为5h，得到石墨烯薄膜层/高透硅胶层/柔性基底复合层；The organic silica gel KL-9310B is covered with the graphene film layer, and the roller of the laminating machine is used to pressurize, so that the high-permeability silica gel layer and the graphene film layer are tightly bonded together. The pressurized pressure is 10MPa, and the pressurized time is 5h to obtain a composite layer of graphene film layer/high permeability silica gel layer/flexible substrate;
在所述柔性基底的另一面涂布OCA光学胶(深圳市光华士科技有限公司生产)，得到OCA光学胶层；OCA optical glue (produced by Shenzhen Guanghuashi Technology Co., Ltd.) is coated on the other side of the flexible substrate to obtain an OCA optical glue layer;
通过电化学法去除所述铜箔，得到石墨烯复合体；所述电化学法采用的电解液为浓度为1mol/L的氯化钠的水溶液；The copper foil is removed by an electrochemical method to obtain a graphene composite; the electrolyte used in the electrochemical method is an aqueous solution of sodium chloride with a concentration of 1mol/L;
所述石墨烯复合体用去离子水清洗，并用氮气枪吹干，得到石墨烯透明导电薄膜。The graphene composite was cleaned with deionized water, and dried with a nitrogen gun to obtain a graphene transparent conductive film.
经检测，所述石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率为500ohm/sq，石墨烯薄膜层结构完整、表面光滑平整、干净、无残留；石墨烯透明导电薄膜的透光率为97.5％。After testing, in the graphene transparent conductive film, the surface resistivity of the graphene film layer is 500ohm/sq, the structure of the graphene film layer is complete, the surface is smooth and flat, clean, and no residue; the light transmittance of the graphene transparent conductive film is 500 ohm/sq. was 97.5%.
以本实施例制备的石墨烯透明导电薄膜为透明电极，制备了结构为：透明电极/聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸/聚-3己基噻吩/PCBM(/钙/铝)的有机太阳能电池。经检测，所述有机太阳能电池的光电转化效率为3.6％。With the graphene transparent conductive film prepared in this embodiment as a transparent electrode, the prepared structure is: transparent electrode/poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid/poly-3-hexylthiophene/PCBM(/ Ca/Al) organic solar cells. After testing, the photoelectric conversion efficiency of the organic solar cell is 3.6%.
实验结果表明，本发明制备的石墨烯透明导电薄膜中，石墨烯薄膜层的表面电阻率不超过630ohm/sq，石墨烯透明导电薄膜的电阻率较小；石墨烯薄膜层结构完整、表面光滑平整、干净、无残留。石墨烯透明导电薄膜的透光率较优。The experimental results show that in the graphene transparent conductive film prepared by the present invention, the surface resistivity of the graphene film layer is no more than 630ohm/sq, and the resistivity of the graphene transparent conductive film is less; the graphene film layer structure is complete and the surface is smooth and flat , clean and residue-free. Graphene transparent conductive film has better light transmittance.
以本发明的石墨烯透明导电薄膜为透明电极制备的OLED器件，发光面积为0.4mm2；电压为5V时，绿光OLED器件的亮度可以达到8000cd m-2。以本发明的石墨烯透明导电薄膜为透明电极制备的有机太阳能电池的光电转化效率不小于3.6％。The OLED device prepared by using the graphene transparent conductive film of the present invention as a transparent electrode has a luminous area of 0.4mm 2 ; when the voltage is 5V, the brightness of the green OLED device can reach 8000cd m -2 . The photoelectric conversion efficiency of the organic solar cell prepared by using the graphene transparent conductive film of the present invention as a transparent electrode is not less than 3.6%.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910870735.2A CN110517809A (en) | 2019-09-16 | 2019-09-16 | A kind of transparent graphene conductive film, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910870735.2A CN110517809A (en) | 2019-09-16 | 2019-09-16 | A kind of transparent graphene conductive film, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110517809A true CN110517809A (en) | 2019-11-29 |
Family
ID=68632431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910870735.2A Pending CN110517809A (en) | 2019-09-16 | 2019-09-16 | A kind of transparent graphene conductive film, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110517809A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437176A (en) * | 2021-01-30 | 2021-09-24 | 宣城睿晖宣晟企业管理中心合伙企业(有限合伙) | Preparation method of heterojunction battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795619A (en) * | 2012-09-04 | 2012-11-28 | 南开大学 | Graphene thin film transferring method based on physical adsorption |
| CN104015463A (en) * | 2014-05-12 | 2014-09-03 | 中国科学院宁波材料技术与工程研究所 | Transfer method of graphene film |
| CN104129783A (en) * | 2014-08-04 | 2014-11-05 | 中国科学院金属研究所 | Low cost clean nondestructive transfer method of large area of graphene |
| CN104360778A (en) * | 2014-09-29 | 2015-02-18 | 常州二维碳素科技有限公司 | Graphene capacitive screen and manufacturing method thereof |
| CN106986334A (en) * | 2017-04-28 | 2017-07-28 | 宁波柔碳电子科技有限公司 | The transfer method and system of a kind of graphene film |
| KR20180108219A (en) * | 2017-03-24 | 2018-10-04 | 솔베이코리아 주식회사 | Hybrid electrode using graphene, preparing method of the same, and device including the same |
-
2019
- 2019-09-16 CN CN201910870735.2A patent/CN110517809A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795619A (en) * | 2012-09-04 | 2012-11-28 | 南开大学 | Graphene thin film transferring method based on physical adsorption |
| CN104015463A (en) * | 2014-05-12 | 2014-09-03 | 中国科学院宁波材料技术与工程研究所 | Transfer method of graphene film |
| CN104129783A (en) * | 2014-08-04 | 2014-11-05 | 中国科学院金属研究所 | Low cost clean nondestructive transfer method of large area of graphene |
| CN104360778A (en) * | 2014-09-29 | 2015-02-18 | 常州二维碳素科技有限公司 | Graphene capacitive screen and manufacturing method thereof |
| KR20180108219A (en) * | 2017-03-24 | 2018-10-04 | 솔베이코리아 주식회사 | Hybrid electrode using graphene, preparing method of the same, and device including the same |
| CN106986334A (en) * | 2017-04-28 | 2017-07-28 | 宁波柔碳电子科技有限公司 | The transfer method and system of a kind of graphene film |
Non-Patent Citations (1)
| Title |
|---|
| 王作智 等: "基于石墨烯透明导电薄膜的OLED 研究进展", 《表面技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437176A (en) * | 2021-01-30 | 2021-09-24 | 宣城睿晖宣晟企业管理中心合伙企业(有限合伙) | Preparation method of heterojunction battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107364851B (en) | A kind of method of rosin resin transfer graphene and the preparation and application of transparent graphene conductive film | |
| CN104129783B (en) | Low cost clean nondestructive transfer method of large area of graphene | |
| CN106601382B (en) | A kind of preparation method of flexible transparent conducting film | |
| CN105989911B (en) | A kind of graphene and metal nanometer line composite transparent conductive plastic film and preparation method and application | |
| CN104409177B (en) | Large-scale preparation method for stably-doped large-area graphene transparent conductive films | |
| CN104134752B (en) | Perovskite solar cell and preparation method for thermoplastic carbon counter electrode | |
| CN105590703B (en) | Can graphical three-dimensional grapheme/polyurethane flexible conductive film preparation method | |
| Li et al. | Transparent and self-supporting graphene films with wrinkled-graphene-wall-assembled opening polyhedron building blocks for high performance flexible/transparent supercapacitors | |
| CN103440896A (en) | Composite flexible transparent electrode of copper nanowires and poly (3, 4-ethylenedioxy group thiophene)-poly (styrene sulfoacid) and manufacturing method thereof | |
| CN106782769A (en) | Flexible and transparent conductive laminated film of low roughness low square resistance and preparation method thereof | |
| CN107112272A (en) | Multiple graphene layers to multiple target substrates direct transfer | |
| CN105869719A (en) | PET-graphene-AgNW (polyethylene terephthalate-graphene-Ag nanowire) composite transparent conducting film and preparation method thereof | |
| CN103426494A (en) | Conducting film combined by graphene and metal nanowires, preparing method thereof and application for preparing transparent conducting film | |
| CN102719877A (en) | Low-cost lossless transfer method of graphene | |
| CN102087886A (en) | Silver nanowire-based transparent conductive thin film and preparation method thereof | |
| CN110164717B (en) | Preparation method and energy storage application of pi-d conjugated Ni-HITP MOF conductive film | |
| CN112216419B (en) | A kind of flexible conductive film normal temperature and low pressure transfer method | |
| Kang et al. | Flexible and mechanically robust organic light-emitting diodes based on photopatternable silver nanowire electrodes | |
| CN107799236A (en) | A kind of Graphene electrodes fast preparation method | |
| CN103280541B (en) | A kind of process preparing flexible device and flexible substrate on CVD Graphene | |
| CN103943790A (en) | Graphene composite flexible transparent electrode and manufacturing method thereof | |
| CN105741979B (en) | The preparation method of Flexible graphene conductive film | |
| CN108982632A (en) | A kind of flexible electrode and preparation method thereof based on flower-like nanometer gold structure | |
| CN107098339A (en) | A kind of method for shifting graphene | |
| CN106563632A (en) | Low-temperature preparation method of metal nanowire transparent conducting thin film |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191129 |
|
| RJ01 | Rejection of invention patent application after publication |