CN106601382B - A kind of preparation method of flexible transparent conducting film - Google Patents
A kind of preparation method of flexible transparent conducting film Download PDFInfo
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- CN106601382B CN106601382B CN201611157354.2A CN201611157354A CN106601382B CN 106601382 B CN106601382 B CN 106601382B CN 201611157354 A CN201611157354 A CN 201611157354A CN 106601382 B CN106601382 B CN 106601382B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 238000004026 adhesive bonding Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 104
- 239000010408 film Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- -1 fluororesin Polymers 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010129 solution processing Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000004425 Makrolon Substances 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005240 physical vapour deposition Methods 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 238000013007 heat curing Methods 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 8
- 239000002070 nanowire Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920005553 polystyrene-acrylate Polymers 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- H01B13/32—Filling or coating with impervious material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The invention discloses a kind of preparation methods of flexible transparent conductive film, are prepared including preparing composite conductive layers, water oxygen barrier layer deposition, flexible substrate are bonded and dissociation process.The invention also discloses flexible transparent conductive films, include flexible substrate, gluing layer, water oxygen barrier layer, composite conductive layers successively from the bottom to top；The composite conductive layers include transparent polymer support layer and electrically conducting transparent network from the bottom to top.The present invention realizes the preparation of the transparent conductive film with high conductivity and flat surface, and obtained flexible transparent conducting film has bend resistance.
Description
Technical field
The present invention relates to flexible electronic field, more particularly to a kind of preparation method of flexible transparent conducting film.
Background technology
It is required for using transparent electrode material in film photovoltaic cell, FPD, touch screen field, and at present using most
Extensive transparent electrode material is tin indium oxide (ITO), by indium oxide and tin oxide two oxides material under different proportion
Deposition obtains.Its visible light transmittance more than 90% requirement under, can still realize relatively low square resistance (10-100 Ω/
), thus with very superior electrical conductivity energy.But indium metal belongs to scarce resource, only 50,000 tons of indium reserves are estimated in the whole world, because
, with continuing to develop in opto-electronics, the price of ITO can rapidly rise with the rapid exploitation of indium for this.Although ITO exists
It is had excellent performance on tablet, but its film is more crisp, its performance can decline to a great extent after bending on flexible substrates, thus ITO is uncomfortable
It closes and makes flexible device.
In today that flexible electronic device is greatly developed, it would be desirable to develop a flexibility cheap, that production is easy and lead
Electric material as the replacement for substituting ITO simultaneously, is applied in flexible electronic field.
The approach for preparing transparent conductive film at present has：Transparent conductive oxide film, metallic mesh structural membrane, ultra-thin gold
Belong to film, inorganic/organic transparent conductive material film (such as nano silver wire, carbon nanotube, graphene, PEDOT:PSS).Wherein oxygen
Compound scheme all suffers from being not suitable for flexible the problem of using；Metallic mesh structure surface roughness is larger, and complex steps, photoetching
Cost is higher；Super thin metal film light transmittance can not get both with electric conductivity.And in photoelectric device, in OPV and OLED device, bottom
The surface smoothness of electrode is by extreme influence device performance, therefore, it is intended that the transparent electrode surface prepared is smooth enough
Smooth.Therefore we finally select inorganic/organic transparent conductive material as conductive layer, and by increasing polymer support
Layer package conductive layer, by the levelability of liquid polymer solution, obtains a smooth conductive surface after the dissociation, wherein
Conductive layer has been embedded to polymer superficial face, realizes the film with high conductivity and flat surface.
Invention content
In order to overcome the disadvantages mentioned above of the prior art, the purpose of the present invention is to provide a kind of flexible and transparent conductives with insufficient
The preparation method of film realizes the preparation of the transparent conductive film with high conductivity and flat surface.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of flexible transparent conducting film, includes the following steps：
(1) electrically conducting transparent network and transparent polymer support are coated successively by Solution processing techniques on temporary substrates
Layer, is heating and curing, obtains composite conductive layers；
The thickness of the polymeric support layer is 10nm~1000nm；
(2) the connate water oxygen barrier layer on transparent polymer support layer；
(3) flexible substrate is covered on water oxygen barrier layer；The visible light transmittance of the flexible substrate is more than 85%；
(4) flexible substrate, water oxygen barrier layer and composite conductive layers entirety from temporary substrates are removed, obtains flexible and transparent
Conductive film.
Preferably, the preparation method of the flexible transparent conducting film, it is further comprising the steps of：In temporary substrates and transparent
Release layer is deposited between conductive network.
Preferably, the release layer is prepared using physical sputtering, chemical vapor deposition or Solution processing techniques；It uses
Material is silicon nitride, and silica, molybdenum, aluminium is silver-colored, titanium, fluororesin solution, silicon resin solution, polyimide solution, poly- methyl-prop
One or more of e pioic acid methyl ester solution, polystyrene solution, polyvinylpyrrolidonesolution solution, poly-vinyl alcohol solution；
Preferably, prepared by the release layer or use following methods：
It is reacted using coupling agent, surfactant with temporary substrates surface, generates surface molecular decorative layer.
Preferably, the preparation method of the flexible transparent conducting film, it is further comprising the steps of：In water oxygen barrier layer and soft
Gluing layer is coated between property substrate.
Preferably, the Solution processing techniques described in step (1) be rotary coating, blade coating, slot coated, lifting apply
Cloth, letterpress, intaglio printing, silk-screen printing is roll-to-roll, one kind in inkjet printing.
Preferably, step (1) the transparent polymer support layer is by epoxy resin, fluororesin, silicon rubber, silicones, gathers
Any one in propylene, polyethylene or makrolon or polystyrene or polymethyl methacrylate is prepared；Or
Mixture or copolymer are formed by two or more in more than material or laminate is prepared.
Preferably, step (1) the electrically conducting transparent network be carbon nano tube dispersion liquid, graphene dispersing solution, silver paste, metal
Nano wire, the one or more in nano dot dispersion liquid.
Preferably, the water oxygen barrier layer described in step (2) is single-layer or multi-layer inorganic thin film；
The inorganic thin film thickness is 10nm~1000nm, by Al2O3, Si3N4, SiO2, TiO2, MgO, ZrO2, in ZnO
More than one materials are prepared by plasma activated chemical vapour deposition or physical vapour deposition (PVD)；
Water oxygen barrier layer water vapor transmittance is less than 5x10-5g/m2Day, OTR oxygen transmission rate are less than 1x10-3cm3/m2·
day。
Preferably, the gluing layer pastes method using dry film or solution processing method is prepared；The material used for PSA or
OCA。
Preferably, step (3) described flexible substrate is by polyethylene terephthalate, cyclic olefin polymer, polyamides
Imines, makrolon, polyolefin, polyether-ketone, fluororesin, a kind of material preparation in silicones form；Or by more than material
Two or more formation mixture or copolymer or laminate be prepared；
Preferably, step (1) the temporary substrates thickness is 0.3mm~2.5mm, is glass, stainless steel, the silicon of hard
Piece, plastic plate.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) present invention uses supporting layer of the ultra-thin polymer material as composite conductive layers.Simultaneously ultra-thin compound
Water oxygen barrier layer is introduced on conductive layer, the composite conductive layers of surfacing can be obtained, facilitates subsequent thin film photoelectric device
It prepares；Meanwhile conductive layer has been embedded to polymer superficial face, realizes the film with high conductivity and flat surface.
(2) after the present invention makes barrier layer on composite conductive layers, while the steam oxygen of blocking front diffusion, by
In the very thin thickness (only hundreds of nm magnitudes) of composite conductive layers, the expansion of lateral water oxygen molecule can be greatly prolonged or is breaking at
Channel is dissipated, obtains better water oxygen barriering effect.
(3) flexible transparent conducting film of the invention can protect the water oxygen from substrate to corrode, and extend organic electronic device
Service life makes flexible conductive film have more practicability.
(4) present invention process is simple, uses the solution processing technology of low cost.
Description of the drawings
Fig. 1 is the schematic diagram of the preparation method step (1) of the flexible transparent conducting film of the embodiment of the present invention 1.
Fig. 2 is the schematic diagram of the preparation method step (2) of the flexible transparent conducting film of the embodiment of the present invention 1.
Fig. 3 is the schematic diagram of the preparation method step (3) of the flexible transparent conducting film of the embodiment of the present invention 1.
Fig. 4 is the schematic diagram of the preparation method step (4) of the flexible transparent conducting film of the embodiment of the present invention 1.
Fig. 5 is the schematic diagram of the preparation method step (5) of the flexible transparent conducting film of the embodiment of the present invention 1.
Fig. 6 is the schematic diagram of the preparation method step (6) of the flexible transparent conducting film of the embodiment of the present invention 1.
Fig. 7 is the schematic diagram of the preparation method step (7) of the flexible transparent conducting film of the embodiment of the present invention 1.
Fig. 8 is the schematic diagram of the preparation method step (8) of the flexible transparent conducting film of the embodiment of the present invention 1.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
The preparation method of the flexible transparent conducting film of the present embodiment, includes the following steps：
(1) on cleaned glass substrate 00, depositing a layer thickness with the mode of chemical vapor deposition (CVD) first is
The SiN of 100nmXInorganic thin film is as release layer 01, as shown in Figure 1；
(2) spin coating nano silver wire dispersion liquid on the release layer 01 prepared in step (1), obtains one layer of uniform nano silver wire
Conductive layer 02, as shown in Figure 2；
(3) on nano silver wire conductive layer, by the use of the method for spin coating prepare a layer thickness be 20 μm PDMS coatings as
Polymeric support layer 03, and 1h is stood in room temperature environment, 1h is then toasted in 120 DEG C of baking oven, as shown in Figure 3；
(4) on PDMS film the Al that a layer thickness is 100nm is deposited with the mode of atomic layer deposition (ALD)2O3Film is made
For water oxygen barrier layer 04, as shown in Figure 4；
(5) the PSA laminating layers 05 that a layer thickness is 50um are bonded on water oxygen barrier layer 04, as shown in Figure 5；
(6) it is bonded the PET film that a layer thickness is 120um again by PSA and is used as flexible substrate layer 06, as shown in Figure 6；
(7) it is flexible substrate layer, water oxygen barrier layer, polymeric support layer, nano silver wire conductive layer is whole slowly from glass
Substrate dissociates, as shown in Figure 7；
(8) preparation process for coming to complete flexible transparent conducting film, obtained flexible transparent conducting film are inverted after dissociating
As shown in Figure 8.Include flexible substrate layer 06, PSA laminating layers 05, Al successively from the bottom to top2O3Film 04, composite conductive layers；It is described
Composite conductive layers include polymeric support layer 03 and nano silver wire conductive layer 02 from the bottom to top.
Nanowire Quality percentage is 0.1-5% in step (1) the nano silver wire dispersion liquid, and the length of nano silver wire exists
Between 1-100 μm, the diameter of nano silver wire is in 10-150nm.
The visible ray mean transmissivity of final transparent conductive film is more than 85%, and sheet resistance is 50 Ω/, and membrane stress is less than
50MPa, under 25 DEG C of -40% humidity environment, water oxygen transmitance is less than 5x10-5g/m2·day。
Embodiment 2
The preparation method of the flexible transparent conducting film of the present embodiment, includes the following steps：
(1) on cleaned glass substrate, first by the method for slot coated, a strata imide membrane is prepared, as
Release layer；
(2) on release layer, one layer of copper nano-wire conductive layer is prepared using the mode of blade coating；
(3) then on copper nano-wire, spin coating a layer thickness be the CYTOP coatings of 10um as polymeric support layer,
And toast 2h in 80 DEG C of baking ovens；
(4) and then on CYTOP films the mode of ALD is used, prepares the Al that a layer thickness is 100nm2O3/ MgO layer is folded thin
Film is as water oxygen barrier layer, wherein Al2O3With MgO film alternating deposit, Al2O3It is 50 ratios with the ratio between the deposition cycle number of MgO
10；
(5) then in Al2O3Coating thickness is the PSA laminating layers of 50um on film；
(6) the PEN films that a layer thickness is 100um are bonded on water oxygen barrier layer by PSA again and are used as flexible substrate layer；
(7) PEN films are slowly dissociated from glass substrate；
(8) preparation for coming to complete flexible transparent conducting film is inverted after dissociating；Include flexible substrate successively from the bottom to top
Layer, PSA laminating layers, water oxygen barrier layer, composite conductive layers；The composite conductive layers include CYTOP supporting layers and copper from the bottom to top
Nano wire conductive layer.
The diameter range of step (2) described copper nano-wire is in 10-200nm.The mass percent of copper nano-wire solution is
0.1%-10%, diameter range is in 10-500nm.
The visible ray mean transmissivity of final transparent conductive film is more than 85%, and sheet resistance is 30 Ω/, and membrane stress is less than
50MPa, under 25 DEG C of -40% humidity environment, water oxygen transmitance is less than 5x10-5g/m2·day。
The release layer of the present embodiment can also use physical sputtering, chemical vapor deposition or other Solution processing techniques systems
It is standby；The material used mainly includes：Silicon nitride, silica, molybdenum, aluminium, silver, titanium, fluororesin solution, silicon resin solution, polyamides
Imide liquor, polymethyl methacrylate solution, polystyrene solution, polyvinylpyrrolidonesolution solution, in poly-vinyl alcohol solution
More than one.The release layer can also use following methods to prepare：Use coupling agent, surfactant and temporary substrates table
Face is reacted, and generates surface molecular decorative layer.
The processing method of the composite conductive layers of the present embodiment can also be blade coating, and slot coated lifts coating, relief printing plate print
Brush, intaglio printing, silk-screen printing is roll-to-roll, one kind in inkjet printing.The transparent polymer support layer of the present embodiment is by epoxy
Resin, fluororesin, silicon rubber, silicones, polypropylene, polyethylene or makrolon or polystyrene or polymethylacrylic acid
Any one in methyl esters is prepared；Or form mixture or copolymer or lamination by two or more in more than material
Object is prepared.
The transparent polymer support layer of the present embodiment can also be by epoxy resin, fluororesin, silicon rubber, silicones, and poly- third
Any one in alkene, polyethylene or makrolon or polystyrene or polymethyl methacrylate is prepared；Or by
Two or more formation mixtures or copolymer or laminate in more than material are prepared.
The electrically conducting transparent network of the present embodiment is carbon nanotube (CNT) dispersion liquid, and graphene (Graphene) dispersion liquid is silver-colored
One or more of slurry, metal nanometer line, nano dot dispersion liquid.The major metal material of metal nanometer line or nano dot for silver,
Copper, aluminium composition simple substance or account for the alloy material of main component.
The water oxygen barrier layer of the present embodiment can be single-layer or multi-layer inorganic thin film；The inorganic thin film thickness for 10nm~
1000nm, can be by Al2O3, Si3N4, SiO2, TiO2, MgO, ZrO2, one or more of ZnO material passes through plasma chemistry gas
Mutually deposition or physical vapour deposition (PVD) are prepared.
The gluing layer can be used that dry film pastes method or solution processing method is prepared；The material used for PSA or
OCA。
The flexible substrate of the present embodiment is can also be by polyethylene terephthalate, cyclic olefin polymer, polyamides Asia
Amine, makrolon, polyolefin, polyether-ketone, fluororesin, a kind of material preparation in silicones form；Or by more than material
The mixture or copolymer or laminate of two or more formation are prepared, it is seen that light transmission rate is more than 85%.
The temporary substrates thickness of the present embodiment can be 0.3mm~2.5mm, can also be stainless steel, silicon chip, plastic plate.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of flexible transparent conducting film, which is characterized in that include the following steps：
(1) electrically conducting transparent network and transparent polymer support layer are coated successively by Solution processing techniques on temporary substrates, is added
Heat cure obtains composite conductive layers；
The thickness of the polymeric support layer is 10nm~1000nm；
(2) the connate water oxygen barrier layer on transparent polymer support layer；
(3) flexible substrate is covered on water oxygen barrier layer；The visible light transmittance of the flexible substrate is more than 85%；
(4) flexible substrate, water oxygen barrier layer and composite conductive layers entirety from temporary substrates are removed, obtains flexible and transparent conductive
Film；
The preparation method of the flexible transparent conducting film is further comprising the steps of：Between temporary substrates and electrically conducting transparent network
Deposit release layer；Gluing layer is coated between water oxygen barrier layer and flexible substrate；
The water oxygen barrier layer water vapor transmittance is less than 5x10-5g/m2Day, OTR oxygen transmission rate are less than 1x10-3cm3/m2·
day。
2. the preparation method of flexible transparent conducting film according to claim 1, which is characterized in that the release layer uses object
It is prepared by reason sputtering, chemical vapor deposition or Solution processing techniques；The material used is silicon nitride, and silica, molybdenum, aluminium is silver-colored,
Titanium, fluororesin solution, silicon resin solution, polyimide solution, polymethyl methacrylate solution, polystyrene solution, poly- second
One or more of alkene pyrrolidone solution, poly-vinyl alcohol solution；
The release layer is prepared using following methods：
It is reacted using coupling agent, surfactant with temporary substrates surface, generates surface molecular decorative layer.
3. the preparation method of flexible transparent conducting film according to claim 1, which is characterized in that molten described in step (1)
Liquid processing method be rotary coating, blade coating, slot coated, lifting coating, letterpress, intaglio printing, silk-screen printing, volume
To rolling up, one kind in inkjet printing.
4. the preparation method of flexible transparent conducting film according to claim 1, which is characterized in that step (1) is described transparent
Polymeric support layer is by epoxy resin, fluororesin, silicon rubber, silicones, polypropylene, polyethylene or makrolon or polyphenyl second
Any one in alkene or polymethyl methacrylate is prepared；Or it is mixed by two or more being formed in more than material
It closes object or copolymer or laminate is prepared.
5. the preparation method of flexible transparent conducting film according to claim 1, which is characterized in that step (1) is described transparent
Conductive network is carbon nano tube dispersion liquid, graphene dispersing solution, the one or more in silver paste and metal nanometer line.
6. the preparation method of flexible transparent conducting film according to claim 1, which is characterized in that the water described in step (2)
Oxygen barrier layer is single-layer or multi-layer inorganic thin film；
The inorganic thin film thickness is 10nm~1000nm, by Al2O3, Si3N4, SiO2, TiO2, MgO, ZrO2, one kind in ZnO
More than material is prepared by plasma activated chemical vapour deposition or physical vapour deposition (PVD).
7. the preparation method of flexible transparent conducting film according to claim 1, which is characterized in that the gluing layer is using dry
Film pastes method or solution processing method is prepared；The material used is PSA or OCA.
8. the preparation method of flexible transparent conducting film according to claim 1, which is characterized in that step (3) described flexibility
Substrate is by polyethylene terephthalate, cyclic olefin polymer, polyimides, makrolon, polyolefin, polyether-ketone, fluorine
Resin, a kind of material preparation in silicones form；Or the two or more mixtures or copolymer formed by more than material
Or laminate is prepared；
Step (1) the temporary substrates thickness is 0.3mm~2.5mm, is glass, stainless steel, silicon chip, the plastic plate of hard.
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| CN113409992B (en) * | 2021-06-18 | 2022-08-05 | 江苏纳美达光电科技有限公司 | Flexible composite conductive film and preparation method and application thereof |
| CN114059348B (en) * | 2021-11-18 | 2023-03-14 | 兰州大学 | Flexible transparent heating film, flexible transparent thermotherapy sheet and preparation method |
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