TWI578336B - A carbon nanotube - polymer layered composite transparent flexible electrode and preparation method - Google Patents
A carbon nanotube - polymer layered composite transparent flexible electrode and preparation method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 103
- 239000002041 carbon nanotube Substances 0.000 title claims description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 70
- 239000002131 composite material Substances 0.000 title claims description 32
- 229920000642 polymer Polymers 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 claims description 29
- 239000002109 single walled nanotube Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 20
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000004528 spin coating Methods 0.000 claims description 16
- 239000002238 carbon nanotube film Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 13
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 13
- 229920001940 conductive polymer Polymers 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000007641 inkjet printing Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- SMNNDVUKAKPGDD-UHFFFAOYSA-N 2-butylbenzoic acid Chemical compound CCCCC1=CC=CC=C1C(O)=O SMNNDVUKAKPGDD-UHFFFAOYSA-N 0.000 claims description 5
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical group [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- JVQOASIPRRGMOS-UHFFFAOYSA-M dodecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[N+](C)(C)C JVQOASIPRRGMOS-UHFFFAOYSA-M 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 polyethylene terephthalate Polymers 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002079 double walled nanotube Substances 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims 3
- 229960002796 polystyrene sulfonate Drugs 0.000 claims 3
- 239000011970 polystyrene sulfonate Substances 0.000 claims 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 230000008961 swelling Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 22
- 238000002834 transmittance Methods 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 2
- PPNHCZHNVOCMHS-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCC[N+](C)(C)C PPNHCZHNVOCMHS-UHFFFAOYSA-M 0.000 description 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- JYMQFZFDRMIPGC-UHFFFAOYSA-N [C].C1=CC=CC2=CC=CC=C21 Chemical compound [C].C1=CC=CC2=CC=CC=C21 JYMQFZFDRMIPGC-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000008154 viscoelastic solution Substances 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. 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
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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
- 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
Description
本發明採用一種以碳奈米管為導電質，經旋塗工藝或噴墨列印工藝在聚對苯二甲酸乙二酯(以下簡稱PET)表面製備均勻網路結構的碳奈米管薄膜，然後在其表面旋塗或噴墨列印一層聚二氧乙基噻吩：聚苯乙烯磺酸(以下簡稱PEDOT：PSS)導電高分子，形成表面粗糙度小，導電性良好的碳奈米管-高分子層狀複合透明電極。 The invention adopts a carbon nanotube film prepared by using a carbon nanotube as a conductive material and preparing a uniform network structure on the surface of polyethylene terephthalate (hereinafter referred to as PET) by a spin coating process or an inkjet printing process. Then, a layer of polydioxyethyl thiophene: polystyrene sulfonic acid (hereinafter referred to as PEDOT: PSS) conductive polymer is spin-coated or ink-jet printed on the surface to form a carbon nanotube with small surface roughness and good conductivity - Polymer layered composite transparent electrode.
碳奈米管是一種具有典型的層狀中空結構特徵的碳材料，構成碳奈米管的管身由六邊形石墨碳環結構單元組成，是一種具有特殊結構(徑向尺寸為奈米量級，軸向尺寸為微米量級)的一維量子材料。它的管壁構成主要為數層到數十層的同軸圓管，層與層之間保持固定的距離，約為0.34nm，直徑一般為2~20nm。碳奈米管的碳原子的P電子形成大範圍的離域π鍵，因此共軛效應顯著。由於碳奈米管的結構與石墨的片層結構相同，具有很好的電學性能。為此碳奈米管作為一種電極材料在電子科學領域中受到較大的關注，其優勢在於作為透明電極材料優異的光電性能，超順排的碳奈米管以其優良的機械性能 可以紡絲拉膜，此外碳奈米管的耐環境腐蝕性能較強，不會受到環境的影響而降低。 The carbon nanotube is a carbon material with a typical layered hollow structure. The body of the carbon nanotube is composed of a hexagonal graphite carbon ring structural unit and has a special structure (the radial dimension is nanometer amount). One-dimensional quantum material with a grade of axial dimension on the order of microns. Its tube wall is composed of several layers to tens of layers of coaxial tubes, and the layer is kept at a fixed distance of about 0.34 nm, and the diameter is generally 2-20 nm. The P electrons of the carbon atoms of the carbon nanotubes form a wide range of delocalized π bonds, so the conjugation effect is remarkable. Since the structure of the carbon nanotubes is the same as that of graphite, it has good electrical properties. For this reason, carbon nanotubes have received much attention in the field of electronic science as an electrode material, and their advantages are excellent photoelectric properties as transparent electrode materials, and super-aligned carbon nanotubes with excellent mechanical properties. The film can be spun and the carbon nanotube tube has strong environmental corrosion resistance and is not affected by the environment.
然而，由於碳奈米管之間很強的凡德瓦作用力(~500eV/μm)和大的長徑比(>1000)，通常容易形成大的管束，難以分散，極大地制約了其優異光電性能的發揮和實際應用的開發。雖然碳奈米管超順排薄膜通過拉膜工藝製備的透明電極在觸控式螢幕上得以大面積應用(CN1016254665A)，但其表面電阻率較大(大於1000Ω/□)，透過率80%。相對於電阻要求更高高透明電極薄膜的電子器件來說，此類碳奈米管薄膜的功耗很大，會由於電極自身的熱效應影響器件的性能。 However, due to the strong van der Waals force (~500eV/μm) and the large aspect ratio (>1000) between the carbon nanotubes, it is easy to form a large tube bundle, which is difficult to disperse and greatly restricts its excellentness. The development of photoelectric performance and the development of practical applications. Although the transparent electrode prepared by the film-forming process of the carbon nanotube super-aligned film has been widely applied on the touch screen (CN1016254665A), its surface resistivity is large (greater than 1000 Ω/□) and the transmittance is 80%. Compared to electronic devices that require higher and higher transparent electrode films, such carbon nanotube films consume a lot of power and can affect the performance of the device due to the thermal effects of the electrodes themselves.
本發明立足於碳奈米管溶液的共混工藝在透明電極材料中的應用，提供一種高分散、黏度可調控的碳奈米管複合導電墨水，通過超聲波分散、機械攪拌、細胞粉碎等工藝方法複合技術，實現了碳奈米管與有機載體的均勻分散，製備的墨水穩定性和黏度可調控；該導電墨水通過旋塗工藝或噴墨列印工藝在PET表面製備均勻網路結構的碳奈米管薄膜，然後在其表面旋塗或噴墨列印一層PEDOT：PSS導電高分子，形成表面粗糙度小，導電性能良好的碳奈米管-高分子層狀複合透明電極。此層狀的碳奈米管-高分子複合透明柔性電極的表面電阻率可達到20-30Ω/□，光學透過率可達到80%以上。此層狀複合電極薄膜在觸控式螢幕、太陽能電池以及OLED等顯示器件所需的柔性透明電極方面具備良好的應用前景。 The invention is based on the application of the carbon nanotube tube solution blending process in the transparent electrode material, and provides a high-dispersion, viscosity-regulated carbon nanotube composite conductive ink, which is subjected to ultrasonic dispersion, mechanical stirring, cell pulverization and the like. The composite technology realizes the uniform dispersion of the carbon nanotubes and the organic carrier, and the prepared ink stability and viscosity can be controlled; the conductive ink is prepared by the spin coating process or the inkjet printing process on the PET surface to prepare a uniform network structure of carbon naphthalene The rice tube film is then spin-coated or ink-jet printed on the surface of a layer of PEDOT:PSS conductive polymer to form a carbon nanotube-polymer layer composite transparent electrode with small surface roughness and good electrical conductivity. The layered carbon nanotube-polymer composite transparent flexible electrode has a surface resistivity of 20-30 Ω/□ and an optical transmittance of 80% or more. The layered composite electrode film has a good application prospect in the flexible transparent electrodes required for display devices such as touch screens, solar cells, and OLEDs.
碳奈米管-高分子層狀複合透明柔性電極，其特徵在於：以PET表面為基底由裡至外依次分佈有碳奈米管層和導電高分子層，所述導電高分子層由混合的PEDOT：PSS高分子材料組成。 Carbon nanotube-polymer layered composite transparent flexible electrode, characterized in that a carbon nanotube layer and a conductive polymer layer are sequentially arranged from the inside to the outside of the PET surface, and the conductive polymer layer is mixed PEDOT: PSS polymer material composition.
所述碳奈米管層為單壁碳奈米管、多壁碳奈米管、雙壁碳奈米管以及改性的碳奈米管。 The carbon nanotube layer is a single-walled carbon nanotube, a multi-walled carbon nanotube, a double-walled carbon nanotube, and a modified carbon nanotube.
碳奈米管-高分子層狀複合透明柔性電極的製備方法，包括如下步驟：(1)製備碳奈米管導電墨水，所述導電墨水的組成為碳奈米管粉體0.03-1%，載體一0.2%-0.5%，載體二0.2%-0.5%，溶劑98%-99%，其中載體一為烷基化劑銨鹽，載體二為水溶性陰離子型酸性物質，所述溶劑為水；(2)將導電墨水採用旋塗工藝或噴墨列印工藝在PET表面製備均勻網路結構的碳奈米管薄膜，乾燥；(3)在乙醇或硝酸中浸泡，去離子水清洗，乾燥，形成碳奈米管層，(4)將PEDOT：PSS水溶液採用旋塗工藝或噴墨列印工藝附在碳奈米管層表面，形成導電高分子層，乾燥得層狀複合透明柔性電極。 The preparation method of the carbon nanotube-polymer layer composite transparent flexible electrode comprises the following steps: (1) preparing a carbon nanotube conductive ink, wherein the conductive ink has a composition of carbon nanotube tube 0.03-1%, The carrier is 0.2%-0.5%, the carrier is 0.2%-0.5%, and the solvent is 98%-99%, wherein the carrier one is an alkylating agent ammonium salt, the carrier two is a water-soluble anionic acidic substance, and the solvent is water; (2) Preparing a carbon nanotube film of uniform network structure on the surface of PET by spin coating process or inkjet printing process; (3) immersing in ethanol or nitric acid, washing with deionized water, drying, The carbon nanotube layer is formed, and (4) the PEDOT:PSS aqueous solution is attached to the surface of the carbon nanotube layer by a spin coating process or an inkjet printing process to form a conductive polymer layer, and dried to obtain a layered composite transparent flexible electrode.
所述烷基化劑銨鹽為十六烷基三甲基氫氧化銨，十二烷基三甲基氫氧化銨、十四烷基三甲基氫氧化銨、苄基三甲基氫氧化銨中的一種或幾種組合。 The alkylating agent ammonium salt is cetyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide One or several combinations.
所述水溶性陰離子型酸性物質為丁基苯甲酸(P-T)十二烷基苯磺酸、鄰苯二甲酸，對叔丁基苯甲酸，對羥基苯甲酸，β-苯丙烯酸、苯乙酸、水楊酸一種或幾種組合。 The water-soluble anionic acidic substance is butyl benzoic acid (PT) dodecylbenzenesulfonic acid, phthalic acid, p-tert-butylbenzoic acid, p-hydroxybenzoic acid, β-phenylacrylic acid, phenylacetic acid, water One or several combinations of salicylic acid.
所述PEDOT：PSS佔PEDOT：PSS水溶液的固含量1.0~1.7%。 The PEDOT:PSS accounts for 1.0 to 1.7% of the solid content of the PEDOT:PSS aqueous solution.
所述步驟(2)採用旋塗工藝，其轉速及時間：500rpm/30s，乾燥工藝：50℃/5min，表乾後，在120℃/10min，所述步驟(3)中的乾燥為常溫下 吹乾，所述步驟(4)採用旋塗工藝，其轉速及時間：1500rpm/30s，乾燥工藝：120℃/10min。 The step (2) adopts a spin coating process, the rotation speed and time: 500 rpm/30 s, the drying process: 50 ° C / 5 min, after the surface drying, at 120 ° C / 10 min, the drying in the step (3) is at normal temperature. Drying, the step (4) adopts a spin coating process, the rotation speed and time: 1500 rpm / 30 s, drying process: 120 ° C / 10 min.
所述碳奈米管導電墨水的製備方法為：(1)取部分溶劑將載體一、載體二製備成水溶液，(2)將純淨碳奈米管粉體材料分散於載體一的水溶液中，(3)再加入餘下溶劑，(4)在攪拌下滴加載體二的水溶液。 The preparation method of the carbon nanotube conductive ink is: (1) taking a part of a solvent to prepare a carrier 1 and a carrier 2 into an aqueous solution, and (2) dispersing the pure carbon nanotube powder material in an aqueous solution of the carrier 1 ( 3) The remaining solvent is further added, and (4) the aqueous solution of the bulk two is added dropwise with stirring.
所述步驟(2)、(3)採用超音波分散，所述步驟(4)採用磁力攪拌。 The steps (2) and (3) employ ultrasonic dispersion, and the step (4) employs magnetic stirring.
所述純淨碳奈米管粉體的製備方法為：將碳奈米管在甲醇中超音波分散成懸濁液，再將碳奈米管懸濁液放入UV光清洗機中照射，離心，得碳奈米管粉體；將此粉體加入到濃HNO3與過硫酸銨的混合水溶液中，磁子攪拌，120℃下回流反應5h，離心，用去離子水反復離心沖洗至中性，乾燥得純淨碳奈米管粉體。 The method for preparing the pure carbon nanotube powder is: dispersing the carbon nanotube in a supersonic wave into a suspension in methanol, and then placing the carbon nanotube suspension in a UV light cleaning machine, and centrifuging, and obtaining Carbon nanotube powder; the powder is added to a mixed aqueous solution of concentrated HNO 3 and ammonium persulfate, the magnet is stirred, refluxed at 120 ° C for 5 h, centrifuged, and repeatedly centrifuged with deionized water to neutral, dry Pure carbon nanotube powder is obtained.
所述純淨碳奈米管粉體的製備方法為：將碳奈米管在有機溶劑分散成懸濁液，靜置溶脹，離心，清洗；再加入到濃硝酸中，120℃下反應4h，離心，清洗至中性，乾燥得純淨碳奈米管粉體。 The pure carbon nanotube powder is prepared by dispersing the carbon nanotube into a suspension in an organic solvent, allowing it to swell, centrifuging, and washing; adding to concentrated nitric acid, reacting at 120 ° C for 4 h, and centrifuging. Clean to neutral, dry and pure carbon nanotube powder.
本發明碳奈米管-高分子層狀複合透明柔性電極的製備方法如下： The preparation method of the carbon nanotube-polymer layer composite transparent flexible electrode of the invention is as follows:
1)該複合導電墨水的一種製備方法說明 1) Description of a preparation method of the composite conductive ink
一種高分散碳奈米管複合導電墨水，由下列成分及其重量百分含量組成：1、純淨碳奈米管粉體 0.03-1%，2、載體一 0.2%-0.5%， 3、載體二 0.2%-0.5%，4、溶劑 98%-99%，碳奈米管粉體種類可以是單壁碳奈米管、多壁碳奈米管、雙壁碳奈米管以及改性的碳奈米管。 A highly dispersed carbon nanotube composite conductive ink consisting of the following components and their weight percentages: 1. pure carbon nanotube powder 0.03-1%, 2, carrier one 0.2%-0.5%, 3, carrier two 0.2% -0.5%, 4, solvent 98% -99%, carbon nanotube powder type can be single-walled carbon nanotubes, multi-wall carbon nanotubes, double-walled carbon nanotubes and Sexual carbon nanotubes.
載體一：烷基化劑銨鹽的水溶液，如十六烷基三甲基氫氧化銨，十二烷基三甲基氫氧化銨、十四烷基三甲基氫氧化銨、苄基三甲基氫氧化銨等有機堿水溶液。 Carrier 1: An aqueous solution of an alkylating agent ammonium salt, such as cetyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, benzyltrimethyl An aqueous solution of an organic hydrazine such as ammonium hydroxide.
載體二：為水溶性陰離子表面活性劑如：丁基苯甲酸(P-T)十二烷基苯磺酸、鄰苯二甲酸，對叔丁基苯甲酸對羥基苯甲酸，β-苯丙烯酸、苯乙酸、水楊酸等的水溶液。 Carrier 2: a water-soluble anionic surfactant such as: butyl benzoic acid (PT) dodecylbenzene sulfonic acid, phthalic acid, p-tert-butylbenzoic acid p-hydroxybenzoic acid, β -phenylacrylic acid, phenylacetic acid An aqueous solution of salicylic acid or the like.
當載體一和載體二以一定濃度混合時，會形成一種黏度可調的粘彈態的溶液體系。本發明採用其黏度可調特性來分散高濃度的碳奈米管，並且粘態的分散體系易於成膜。載體一和載體二混合後形成的分散體系的黏度在10-20Pa.s時，可有效分散碳奈米管。成膜後的載體容易在乙醇容易中脫附，在經過進一步水洗後在膜層表面殘留很少。 When the carrier 1 and the carrier 2 are mixed at a certain concentration, a viscoelastic solution system with an adjustable viscosity is formed. The invention adopts its viscosity-adjustable property to disperse a high-concentration carbon nanotube, and the viscous dispersion is easy to form a film. When the viscosity of the dispersion formed by mixing the carrier 1 and the carrier 2 is 10-20 Pa.s, the carbon nanotubes can be effectively dispersed. The film-forming carrier is easily desorbed in ethanol easily, and remains little on the surface of the film layer after further water washing.
在碳奈米管薄膜表面旋塗或噴墨列印一層PEDOT：PSS導電高分子，形成表面粗糙度小，導電性良好的碳奈米管-高分子層狀複合透明電極。PEDOT：PSS兩者的含量比可以根據需要調整(己有市售產品)。此層狀的碳奈米管-高分子複合透明柔性電極的表面電阻率可達到20-30Ω/□，光學透過率可達到80%以上。此層狀複合電極薄膜在觸控式螢幕、太陽能電池以及OLED等顯示器件所需的柔性透明電極方面具備良好的應用前景。 A layer of PEDOT:PSS conductive polymer is printed on the surface of the carbon nanotube film by spin coating or ink jetting to form a carbon nanotube-polymer layer composite transparent electrode having small surface roughness and good electrical conductivity. The content ratio of both PEDOT:PSS can be adjusted as needed (commercially available products). The layered carbon nanotube-polymer composite transparent flexible electrode has a surface resistivity of 20-30 Ω/□ and an optical transmittance of 80% or more. The layered composite electrode film has a good application prospect in the flexible transparent electrodes required for display devices such as touch screens, solar cells, and OLEDs.
圖1 是單壁碳奈米管(SWCNT)形貌，其中A，B為不同純化工藝的SEM圖像；圖2 是純單壁碳奈米管薄膜的SEM圖像，其中A，B，C為不同放大倍數圖像；圖3 是純單壁碳奈米管薄膜的AFM表面形貌圖像；以及圖4 是碳奈米管-高分子層狀複合透明柔性電極表面形貌圖像的AFM照片。 Figure 1 is a single-walled carbon nanotube (SWCNT) morphology, where A and B are SEM images of different purification processes; Figure 2 is an SEM image of a pure single-walled carbon nanotube film, where A, B, C Figure 3 is an AFM surface topography image of a pure single-walled carbon nanotube film; and Figure 4 is an AFM of a carbon nanotube-polymer layered composite transparent flexible electrode surface topography image. photo.
下面結合實施例對本發明作進一步的詳細說明。 The present invention will be further described in detail below with reference to the embodiments.
實施例1 Example 1
1)單壁碳奈米管的純化：0.05g的單壁碳奈米管(SWCNT)在20ml甲醇中超音波分散20min後形成SWNT懸濁液。將此SWCNT懸濁液放入UV光清洗機中處理40min，得到SWCNT粉體；取20ml的去離子水放入單口燒瓶中，再加入10ml的濃HNO3(68wt%)，加入5wt%過硫酸銨(APS)水溶液，混合均勻後加入提純過的SWCNT粉體，磁子攪拌，120℃下回流反應5h。去離子水反復離心沖洗(7000rpm，10min)3次，得到純化後的單壁碳奈米管(參見圖1)。 1) Purification of single-walled carbon nanotubes: 0.05 g of single-walled carbon nanotubes (SWCNTs) were ultrasonically dispersed in 20 ml of methanol for 20 min to form a SWNT suspension. The SWCNT suspension was placed in a UV light washer for 40 min to obtain SWCNT powder; 20 ml of deionized water was placed in a single-mouth flask, and 10 ml of concentrated HNO 3 (68 wt%) was added, and 5 wt% of persulfuric acid was added. The ammonium (APS) aqueous solution was uniformly mixed, and then the purified SWCNT powder was added, and the magnetic particles were stirred, and refluxed at 120 ° C for 5 hours. The deionized water was repeatedly centrifuged (7000 rpm, 10 min) three times to obtain a purified single-walled carbon nanotube (see Fig. 1).
2)將純化後的單壁碳奈米管分散在0.05M的3ml十六烷基三甲基氫氧化銨(CTAOH)中，再加入16ml水，經超音波分散15min。在此混合體系在磁力攪拌的條件下逐步滴加0.45M丁基苯甲酸0.15-0.2ml，形成高分散的黏度可調的碳奈米分散體系，其黏度在10-20Pa.s內可調。 2) The purified single-walled carbon nanotubes were dispersed in 0.05 M of 3 ml of cetyltrimethylammonium hydroxide (CTAOH), and 16 ml of water was added thereto, and ultrasonically dispersed for 15 minutes. In this mixed system, 0.15-0.2 ml of 0.45 M butyl benzoate was gradually added under the condition of magnetic stirring to form a highly dispersed carbon nano-dispersion system with adjustable viscosity, and the viscosity was adjustable within 10-20 Pa.s.
3)將高分散的碳奈米管墨水採用旋塗工藝在PET薄膜上製備均勻的碳奈米管薄膜。工藝參數為：轉速及時間：500rpm/30s，烘乾工藝：50℃/5min，表乾後，在120℃/10min。 3) Prepare a uniform carbon nanotube film on the PET film by spin coating using a highly dispersed carbon nanotube ink. The process parameters are: speed and time: 500 rpm / 30 s, drying process: 50 ° C / 5 min, after surface drying, at 120 ° C / 10 min.
4)形成的碳奈米管薄膜在乙醇中常溫浸泡30min，用去離子水清洗乾淨，吹乾。在PET表面形成透過率為87%的碳奈米管薄膜，表面電阻率電阻為500Ω/□。其表面形貌見圖2和圖3。 4) The formed carbon nanotube film is immersed in ethanol at room temperature for 30 minutes, cleaned with deionized water, and dried. A carbon nanotube film having a transmittance of 87% was formed on the PET surface, and the surface resistivity resistance was 500 Ω/□. The surface topography is shown in Figures 2 and 3.
5)在碳奈米管表面旋塗PEDOT：PSS水溶液(市售產品，固含量1.0~1.7%)，其工藝參數為1500rpm/30s，烘乾工藝：120℃/10min。層狀碳奈米管高分子複合透明電極的表面形貌見圖4。 5) Spin-coated PEDOT:PSS aqueous solution (commercially available product, solid content 1.0~1.7%) on the surface of the carbon nanotube tube, the process parameter is 1500 rpm/30 s, and the drying process is 120 ° C/10 min. The surface morphology of the layered carbon nanotube polymer composite transparent electrode is shown in Fig. 4.
6)形成的碳奈米管/PEDOT：PSS層狀複合電極的光學透過率大於80%，表面電阻率為200Ω/□。 6) The formed carbon nanotube/PEDOT:PSS layered composite electrode has an optical transmittance of more than 80% and a surface resistivity of 200 Ω/□.
實施例2 Example 2
1)取0.05g SWCNT(加入到40ml苯甲酸乙酯溶劑中，超音波分散40min，靜置溶脹2天後，離心，再依次用乙醇，去離子水離心清洗。將溶脹後的SWCNT加入到30ml濃硝酸中，120℃下反應4h，取出後離心清洗多次至上清液基本澄清，達到離心溶液近中性。離心分離得到的單壁碳奈米管的粉體見圖1B。 1) Take 0.05g of SWCNT (added to 40ml of ethyl benzoate solvent, ultrasonically dispersed for 40min, allowed to swell for 2 days, centrifuged, and then centrifuged with deionized water in ethanol. Add swollen SWCNT to 30ml. In concentrated nitric acid, the reaction was carried out at 120 ° C for 4 h, and after centrifugation, it was centrifuged several times until the supernatant was substantially clarified, and the centrifugation solution was nearly neutral. The powder of the single-walled carbon nanotube obtained by centrifugation is shown in Fig. 1B.
2)將純化後的單壁碳奈米管分散在0.05M的3ml十二烷基三甲基氫氧化銨中，再加入18ml水，經超音波分散15min。在此混合體系在磁力攪拌的條件下逐步滴加0.3M鄰苯二甲酸0.1-0.2ml。形成高分散的黏度可調的碳奈米分散體系。其黏度在10-20Pa.s內可調。 2) The purified single-walled carbon nanotubes were dispersed in 0.05 M of 3 ml of dodecyltrimethylammonium hydroxide, and then added with 18 ml of water, and ultrasonically dispersed for 15 minutes. In this mixed system, 0.1-0.2 ml of 0.3 M phthalic acid was gradually added under the condition of magnetic stirring. A highly dispersed carbon nano-dispersion system with adjustable viscosity is formed. Its viscosity is adjustable within 10-20Pa.s.
3)將高分散的碳奈米管墨水採用旋塗工藝在PET薄膜上製備均勻的碳奈米管薄 膜。工藝參數為：轉速及時間：500rpm/30s，烘乾工藝：50℃/5min，表乾後，在120℃/10min。 3) Preparation of a uniform carbon nanotube tube on a PET film by spin coating using a highly dispersed carbon nanotube ink membrane. The process parameters are: speed and time: 500 rpm / 30 s, drying process: 50 ° C / 5 min, after surface drying, at 120 ° C / 10 min.
4)形成的碳奈米管薄膜在濃硝酸常溫浸泡2min，用去離子水清洗乾淨，吹乾。在PET表面形成透過率為87%的碳奈米管薄膜，表面電阻率電阻為150-200Ω/□。其表面形貌見圖2和圖3。 4) The formed carbon nanotube film is immersed in concentrated nitric acid at room temperature for 2 minutes, cleaned with deionized water, and blown dry. A carbon nanotube film having a transmittance of 87% was formed on the PET surface, and the surface resistivity was 150-200 Ω/□. The surface topography is shown in Figures 2 and 3.
5)在碳奈米管表面旋塗PEDOT：PSS水溶液(市售產品，固含量1.0~1.7%)，其工藝參數為1500rpm/30s，烘乾工藝：120℃/10min。層狀碳奈米管高分子複合透明電極的表面形貌見圖4。 5) Spin-coated PEDOT:PSS aqueous solution (commercially available product, solid content 1.0~1.7%) on the surface of the carbon nanotube tube, the process parameter is 1500 rpm/30 s, and the drying process is 120 ° C/10 min. The surface morphology of the layered carbon nanotube polymer composite transparent electrode is shown in Fig. 4.
6)形成的碳奈米管/PEDOT：PSS層狀複合電極的光學透過率大於80%，表面電阻率為15-40Ω/□。 6) The formed carbon nanotube/PEDOT:PSS layered composite electrode has an optical transmittance of more than 80% and a surface resistivity of 15 to 40 Ω/□.
實施例3 Example 3
1)取0.05g SWCNT加入到40ml的二甲基甲酰胺(DMF)中，超音波分散40min，靜置溶脹48h後，離心，再依次用乙醇，去離子水離心清洗。將溶脹後的SWCNT加入到30ml濃硝酸中，120℃下反應4h，取出後離心清洗多次至上清液基本澄清，達到離心溶液近中性。離心分離得到的單壁碳奈米管的粉體，見圖1A。 1) 0.05 g of SWCNT was added to 40 ml of dimethylformamide (DMF), ultrasonically dispersed for 40 min, allowed to stand for 48 h, centrifuged, and then centrifuged with deionized water in ethanol. The swollen SWCNT was added to 30 ml of concentrated nitric acid, and reacted at 120 ° C for 4 h. After taking out, it was centrifuged several times until the supernatant was substantially clarified, and the centrifugation solution was nearly neutral. The powder of the single-walled carbon nanotube obtained by centrifugation is shown in Fig. 1A.
2)將純化後的單壁碳奈米管分散在0.05M的3ml苄基三甲基氫氧化銨中，再加入13ml水，經超音波分散15min。在此混合體系在磁力攪拌的條件下逐步滴加0.3M鄰苯二甲酸0.15-0.2ml，形成高分散的黏度可調的碳奈米分散體系，其黏度在10-20Pa.s內可調。 2) The purified single-walled carbon nanotubes were dispersed in 0.05 M of 3 ml of benzyltrimethylammonium hydroxide, and then added with 13 ml of water, and ultrasonically dispersed for 15 minutes. In this mixed system, 0.15-0.2 ml of 0.3M phthalic acid was gradually added under the condition of magnetic stirring to form a highly dispersed carbon nano-dispersion system with adjustable viscosity, and the viscosity was adjustable within 10-20 Pa.s.
3)將高分散的碳奈米管墨水採用旋塗工藝在PET薄膜上製備均勻的碳奈米管薄膜。工藝參數為：轉速及時間：500rpm/30s，烘乾工藝：50℃/5min，表乾後， 在120℃/10min。 3) Prepare a uniform carbon nanotube film on the PET film by spin coating using a highly dispersed carbon nanotube ink. The process parameters are: speed and time: 500 rpm / 30 s, drying process: 50 ° C / 5 min, after drying, At 120 ° C / 10 min.
4)形成的碳奈米管薄膜在濃硝酸常溫浸泡2min，用去離子水清洗乾淨，吹乾。在PET表面形成透過率為87%的碳奈米管薄膜，表面電阻率電阻為150-200Ω/□。其表面形貌見圖2和圖3。 4) The formed carbon nanotube film is immersed in concentrated nitric acid at room temperature for 2 minutes, cleaned with deionized water, and blown dry. A carbon nanotube film having a transmittance of 87% was formed on the PET surface, and the surface resistivity was 150-200 Ω/□. The surface topography is shown in Figures 2 and 3.
5)在碳奈米管表面旋塗PEDOT：PSS水溶液(市售產品，固含量1.0~1.7%)，其工藝參數為1500rpm/30s，烘乾工藝：120℃/10min。層狀碳奈米管高分子複合透明電極的表面形貌見圖4。 5) Spin-coated PEDOT:PSS aqueous solution (commercially available product, solid content 1.0~1.7%) on the surface of the carbon nanotube tube, the process parameter is 1500 rpm/30 s, and the drying process is 120 ° C/10 min. The surface morphology of the layered carbon nanotube polymer composite transparent electrode is shown in Fig. 4.
6)形成的碳奈米管/PEDOT：PSS層狀複合電極的光學透過率大於80%，表面電阻率為20-45Ω/□。 6) The formed carbon nanotube/PEDOT:PSS layered composite electrode has an optical transmittance of more than 80% and a surface resistivity of 20 to 45 Ω/□.
本發明採用一種以碳奈米管導電質為主的高分散、黏度可控性好的碳奈米管複合導電墨水，經旋塗工藝或噴墨列印工藝在PET表面製備均勻網路結構的碳奈米管薄膜，然後在其表面旋塗或噴墨列印一層PEDOT：PSS導電高分子，形成表面粗糙度小，導電性良好的層狀碳奈米管高分子複合透明電極。此層狀的碳奈米管高分子複合透明柔性電極的表面電阻率可達到20-30Ω/□，光學透過率可達到80%以上。此層狀複合電極薄膜在觸控式螢幕、太陽能電池以及OLED等顯示器件所需的柔性透明電極方面具備良好的應用前景。 The invention adopts a high-dispersion, viscosity-controllable carbon nanotube composite conductive ink mainly composed of a carbon nanotube conductive material, and prepares a uniform network structure on the PET surface by a spin coating process or an inkjet printing process. The carbon nanotube film is then spin-coated or ink-jet printed on the surface of a layer of PEDOT:PSS conductive polymer to form a layered carbon nanotube polymer composite transparent electrode with small surface roughness and good electrical conductivity. The layered carbon nanotube polymer composite transparent flexible electrode has a surface resistivity of 20-30 Ω/□ and an optical transmittance of 80% or more. The layered composite electrode film has a good application prospect in the flexible transparent electrodes required for display devices such as touch screens, solar cells, and OLEDs.
本發明的複合導電墨水，其工藝可操作性強，可採用噴墨列印技術，旋塗技術以及配套的光刻技術，可實現在玻璃，透明晶體，透明陶瓷，高分子薄膜等表面製備碳奈米導電膜層，其膜層表面形貌如圖4所示。 The composite conductive ink of the invention has strong process operability, and can adopt the inkjet printing technology, the spin coating technology and the matching lithography technology, and can realize carbon preparation on the surface of glass, transparent crystal, transparent ceramic, polymer film and the like. The surface layer of the nano-conductive film layer is shown in Fig. 4.
碳奈米管分散液中，碳奈米管的分散性能良好，形成了單束網狀分散。碳奈米管在PET薄膜表面塗膜後，經過乙醇或HNO3浸泡，形成的碳奈米管薄膜為較為均一網狀連結。 In the carbon nanotube dispersion, the carbon nanotubes have good dispersion properties, forming a single bundle of network dispersion. After the carbon nanotube tube is coated on the surface of the PET film, it is immersed in ethanol or HNO 3 to form a relatively uniform network of carbon nanotube film.
碳奈米導電薄膜層性能檢測見表1：
本發明墨水形成的碳奈米透明導電膜層具有良好的導電性能和可見光範圍內光學透過率以及柔性。此層狀的碳奈米管高分子複合透明柔性電極的表面電阻率可達到20-30Ω/□，光學透過率可達到80%以上。相比國內外碳奈米導電高分子電極材料的性能，本發明所製備的碳奈米柔性電極材料性能處於領先的水準。參見表2。 The carbon nano-transparent conductive film layer formed by the ink of the invention has good electrical conductivity and optical transmittance and flexibility in the visible light range. The layered carbon nanotube polymer composite transparent flexible electrode has a surface resistivity of 20-30 Ω/□ and an optical transmittance of 80% or more. Compared with the performance of carbon nano-conductive polymer electrode materials at home and abroad, the performance of the carbon nano-flexible electrode material prepared by the invention is at a leading level. See Table 2.
本發明所研製的碳奈米管柔性電極墨水及其所製備的透明柔性導電薄膜在觸控式螢幕，太陽能電池以及OLED等顯示器件所需的柔性透明電極方面具備良好的應用前景。 The carbon nanotube flexible electrode ink developed by the invention and the transparent flexible conductive film prepared by the invention have good application prospects in the flexible transparent electrodes required for display devices such as touch screens, solar cells and OLEDs.
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