CN105810757A - Transparent conductive film electrode for intelligent light adjusting film and manufacturing method thereof - Google Patents
Transparent conductive film electrode for intelligent light adjusting film and manufacturing method thereof Download PDFInfo
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Classifications
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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
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Abstract
The invention discloses a transparent conductive film electrode for an intelligent light adjusting film and a manufacturing method thereof, as well as the relevant intelligent light adjusting film and a manufacturing method thereof. The transparent conductive film electrode is a graphene/ embedded metal grid composite transparent conductive film electrode, embedded metal grids are integrally embedded into a flexible substrate, and the upper surface of the embedded metal grids is in contact with a graphene layer. The intelligent light adjusting film is composed of two staggered graphene/ embedded metal grid composite transparent conductive film electrodes and a light adjusting layer sandwiched between the electrodes, wherein the light adjusting unit is doped with a spacer, and leading-out electrodes are distributed at the staggered position. The graphene/ embedded metal grid composite transparent conductive film can solve the problems of low conductivity of the traditional single graphene transparent conductive film and device failure caused by high metal grids in the traditional composite film, and thus can be applied to large-sized intelligent light adjusting film devices.
Description
Technical field:
The present invention relates to a kind of transparent conductive film, intelligent light modulation film and preparation method thereof, particularly a kind of transparent conductive film electrode for intelligent light modulation film and preparation method thereof, and relevant intelligent light modulation film and preparation method thereof.
Background technology:
Intelligent light modulation film is the photoelectric device that a kind of input by the signal of telecommunication changes its optical parametric such as light transmittance, mist degree.It is often used in the fields such as external wall, house property decoration, vehicle glass, automobile rearview mirror, projection curtain wall, office space, public entertainment facility.Smart window on the most typically application building of intelligent light modulation film, intelligent light modulation film by sticking, the mode such as clamping is combined with building glass, by to input electrical signal on intelligent light modulation film thus regulating from the incident light intensity of glass forms, and then reach energy-conservation purpose.
Usual intelligent dimming membrane module, is be made up of the light regulating course of two transparency conductive electrode material layers and middle clamping.The electrode material being widely used at present is tin indium oxide ITO electrode, and its basic structure is one layer of ITO conductive material of attachment in transparent substrates.But intelligent light modulation film is still difficult to commercially spread at present, reason is in that the core as intelligent light modulation film and transparent conductive electrode material there is also problems: one, the main component indium of ITO is scarce resource and expensive, the cost of raw material is higher, it is impossible to large-area applications is in construction material；Two, the processing of ITO conductive layer is realized by the method such as sputtering, evaporation mostly, not only energy consumption is high and also waste of raw materials seriously, cause that its technique manufacturing cost is very high；Three, ITO is a kind of oxide semiconductor material, and fragility is big, it is difficult to realize bending, the function such as folding, serious hinders its further application in smart window technology；Four, the reflectance of ITO is higher, and easily because illumination causes xanthochromia when preserving.
And emerging ITO substitution material Graphene is as a kind of Two-dimensional Carbon nano material, its thickness only has 0.34 nanometer, and it is almost fully transparent, only absorbs the light of 2.3%；Under room temperature, its electron mobility is more than 15000cm2/ Vs, and resistivity about 10-8Ω m, lower than copper or silver, it is the minimum material of current resistivity.Graphene transparency conductive electrode material has possessed the unrivaled advantage of ITO and performance, and carbon is extremely abundant in nature so that the cost of raw material of Graphene is also quite cheap.In theory, Graphene is to substitute ITO preferred plan.
But, transparent graphene conductive film is not but successfully applied in intelligent light modulation film field.One main cause is that current transparent graphene conductive film complicated process of preparation, lattice defect are many, and its higher surface resistance will produce serious pressure drop in larger-size intelligent light modulation film products application, cause the problems such as response time prolongation, cut-in voltage become greatly, variable color is uneven, energy consumption is higher.Thereby producing numerous composite conductive thin film to improve electric conductivity, mode the most frequently used at present is the composite construction adopting metal grill with Graphene.But it is applied on intelligent light modulation film and has serious drawback after metal mesh structure and Graphene compound, because metal mesh structure can be extra increase local height, being applied in increase light modulation film device breakdown probability on intelligent light modulation film causes the decline of product yield.Conventional screen mode of printing, inkjet printing mode standby metal grill, its grid height is commonly greater than 1 micron, require in more fine light modulation film structure at some, such as the thickness of whole light regulating course is less than 2 microns, so first, the metal grill of two electrodes is easy to contact with each other, and causes punch through.
For above-mentioned technical problem, it would be highly desirable to provide a kind of new composite conductive thin film, solve that conventional graphite alkene conductivity is low, the problem such as metal grill height causes in conventional composite thin film component failure.
Summary of the invention:
For solving above-mentioned technical problem, especially solve that conventional graphite alkene conductivity is low, the problem such as the higher component failure caused of metal grill height in conventional composite thin film.The invention provides a kind of novel for intelligent light modulation film transparent conductive film electrode and preparation method thereof, provide a kind of intelligent dimming membrane module adopting above-mentioned electrode to make the preparation method disclosing this device simultaneously.
First, the invention provides a kind of for intelligent light modulation film transparent conductive film electrode, described transparent conductive film is Graphene/embedded metal grid compound transparent electricity conductive film electrode, it is characterised in that described electrode at least includes graphene layer, transparent substrates and embedded metal grid；Optionally, described electrode also includes functional layer, told functional layer be in reflecting layer, protective layer, antireflection layer, anti-dazzle photosphere, barrier layer, tack coat any one or multiple；Described embedded metal grid entirety embeds flexible substrate and its upper surface contacts with graphene layer.
Metal grill is a kind of important inorganic conductive material, and described metal grill includes but not limited to: the block metal grill of the arbitrarily biphase or biphase above alloying metal grid of Pt grid, Pd grid, Ag grid, Au grid, Cu grid, Sn grid, Pt/Pd/Ag/Au/Cu/Sn or aforementioned metal grid.
Metal mesh structure prepared by traditional silk screen printing and inkjet printing can be extra increase electrode local height, cause the increase of electrochromic device breakdown probability, the decline of product yield.Such as: as it is shown in figure 1, the thickness of whole light regulating course 2 microns, the height of the metal grill 111 in the first electrode 11 is 1 micron, and the height of the metal grill 121 in the second electrode 12 is also 1 micron, then first, and two electrode contacts will cause puncturing of electrode.
In the embodiment of some reality, metal grill is often embedded in substrate, and to prevent local height protruding, the mode that this structure fallen in can be imprinted with completes.Such as, such as the schematic cross-section of the transparent conductive film of Fig. 2 Graphene/embedding metal grill compound shown, in transparent conductive film 13, metal grill 133 is embedded in substrate, graphene layer 132 is laid in substrate, and graphene layer produces directly to contact with metal grill surface.This preferred structure is more suitable in electrochromic device to apply.
Generally, metal grill pattern is the pattern of rule so that it is scattering own is also inconspicuous, and prior impact also comes from its impact on light transmittance.In the transparent conductive film application that some are high-end, for instance Mobile phone touch control screen, if adopting metal grill, require that it is invisible, then the live width of metal grill is at least less than 5 microns.And in the dimming ratio field that light transmittance requirement is not high, generally the dimensional requirement of metal grill not being had too strict restriction, metal grill size Selection requires to may is that 100nm≤live width≤1mm, line-spacing >=500nm.In some embodiments, metal grill can be macroscopic, can as the dark stricture of vagina decoration of one, for instance the intelligent light modulation film of application in the rear seat windscreen of automobile.
In actual embodiment, metal grill needs physically better performance (such as: tensile property, light transmittance etc.), the metal grill pattern that can select is generally not vertical square or rectangular lattice, but can select that there is the two-dimensional pattern that more complicated periodicity repeats, Fig. 3 illustrates the two-dimensional pattern of some nonrestrictive complex periodic repetition and includes: hexagon, rhombus, cross structure or pentagon.
Described transparent substrates is selected from flexible substrate or rigid substrate, it is preferably flexible substrate, described flexible substrate includes: polymer includes Merlon, silica gel, polrvinyl chloride, polyethylene terephthalate, polystyrene, polymethylacrylic acid, glass resin, polypropylene, fluoropolymer, polyimides, polyamide, polyether-ether-ketone resin, polynorbornene, polyester, polyvinyl, acrylonitrile-butadiene-styrene copolymer, the copolymer of above-mentioned polymer, block copolymer or mixture.
Described functional layer is used to regulate the physical chemistry function of transparency electrode or make certain physics chemical action between substrate and conductive layer; described functional layer is not essential, it is possible to be in protective layer, antireflection layer, anti-reflection layer, anti-dazzle photosphere, barrier layer, tack coat any one or multiple.
In the example embodiment of indefiniteness, Fig. 4 illustrates a layer flexible transparency conductive electrode, contains graphene layer 113, is embedded with the substrate 112 of metal grill.Further, multiple structure also includes being positioned at the functional layer 114 above conductive layer, is positioned at the functional layer 111 of the lower section of substrate.It is understood that these functional layers optically should have transparency.Functional layer 111,114 has various function, for instance reduces mist degree, reduce reflection, its cementation, shield, play barrier layer effect.A functional layer can have multi-functional in some cases, for instance anti-reflecting layer can simultaneously serve as the barrier layer intercepting extraneous steam entrance and is also used as the cover plate of protectiveness.
Secondly, the preparation method that the invention provides a kind of transparent conductive film electrode for intelligent light modulation film, it is characterised in that comprise the following steps:
S1, comprises the preparation of the transparent substrates of embedded metal grid
Substrate, coating curing glue on substrate are provided, then by grid masterplate and solidification glue pressure contact, carry out cured to solidifying glue, after solidification, masterplate is peeled off, substrate is formed groove；Filled conductive slurry in groove, removes unnecessary electrocondution slurry after full-filling, then solidified by electrocondution slurry, forms the transparent substrates including embedded metal grid；
S2, the preparation of graphene layer
Graphene dispersing solution is coated in the step S1 transparent substrates surface obtained, forms graphene layer by last handling process, it is thus achieved that for the Graphene/embedded metal grid compound transparent electricity conductive film electrode of intelligent light modulation film.
Again, present invention also offers a kind of intelligent light modulation film, it is characterized in that, set gradually from bottom to up: include Graphene/the first electrode unit of embedded metal grid compound transparent electricity conductive film electrode, light regulon, include the second electrode unit of Graphene/embedded metal grid compound transparent electricity conductive film electrode；Described first electrode unit and the second electrode unit become dislocation opposed；Dislocation distribution has extraction electrode；Light regulon embeds dunnage to prevent the first electrode unit, the second electrode unit from contacting；Whole device is encapsulated by encapsulating material；
With reference to Fig. 5 (a), in the example embodiment of indefiniteness, include three layers basic comprising unit from bottom to up successively, including Graphene/the first electrode unit 10 of embedded metal grid compound transparent electricity conductive film electrode, light regulon 2, include Graphene/embedded metal grid compound transparent electricity conductive film the second electrode unit 11.In a particular embodiment, Graphene/embedded metal grid compound transparent electricity conductive film electrode, can have identical structure and composition can also be different structures and composition, and they are not completely just right, but there is certain dislocation and be beneficial to arrange extraction electrode, the mode of dislocation both can be monolateral dislocation can also be bilateral dislocation, and monolateral dislocation can cause current electric fields skewness, the modes of emplacement more optimized is bilateral dislocation, as shown in Fig. 5 (b).In actual embodiment, each unit of above three elementary cell all can have multiple structure；Further, as shown in Fig. 5 (a) and (b), first electrode unit 10 comprises at least one extraction electrode 41 and is arranged in dislocation place, second electrode unit 11 also comprises at least one extraction electrode 42 and is arranged in dislocation place, the extraneous signal of telecommunication is at least first, two electrode units respectively select an extraction electrode to input, and the signal of telecommunication that the extraction electrode on same electrode unit receives is identical；Light regulon embeds dunnage 5 to prevent first, two electrode unit contacts；Whole device is finally encapsulated by encapsulating material 3.
Described light regulon includes: liquid crystal type light regulon, electrochromism light regulon or its combination.
Described liquid crystal type light regulon is constituted by after liquid crystal and polymer mixed；Described liquid crystal is selected from: Terphenyls liquid crystal, acetylene bridged bond class liquid crystal, dicyclic hexane liquid crystal, Phenylcyclohexane class liquid crystal or its combination；Described polymeric material is selected from: epoxy resin, polyamide-based resin, polymethacrylate resin, phenolic resin, Merlon, polyester resin, acetate resins, Corvic, polystyrene resin, polyvinyl alcohol resin, polyallyl resin, polyphenylene sulfide, (methyl) acrylic resin, carbamic acid resin, melmac, alkyd resin, sulfone resinoid, imide resin, polyethersulfone resin, polyetherimide resin, vinyl pyrrolidone resin, cellulosic resin or its combination；
In actual embodiment, liquid crystal material and polymer need same refractive index, to ensure light transmission and the mist degree of whole nesa coating.The mixed crystal material of the models such as being difficult to due to single liquid crystal composition and refractive index polymer reaches good coupling, in the embodiment of some reality, the liquid crystal material of selection is generally mixed crystal material, for instance select 5CB, 7CB, 5PCH, 7PCH of Merck KGaA, E7.
Described electrochromism light regulon, at least includes the superposition of three-decker: ion storage, dielectric substrate, electrochromic layer；Described electrochromic layer includes organic electrochromic layers or inorganic electrochromic layer；
In electrochromism type light regulon, electrode unit needs for injecting electronics, hole in electrochromism light regulon.Optionally, described electrochromism light regulon also includes: one or more in potential barrier regulating course, transition zone, electronic barrier layer, hole blocking layer, cushion.
Such as in the embodiment of an indefiniteness, as shown in Figure 6, this electrochromic cells includes potential barrier regulating course 221, ion storage 222, dielectric substrate 223, electrochromic layer 224 from top to bottom successively；Potential barrier regulating course 225.
Described ion storage includes: V2O5、IrO2、PB、TiO2-CeO2；Described dielectric substrate includes liquid electrolyte, solid electrolyte, polymer dielectric, it is preferred to solid electrolyte and polymer dielectric；Described solid electrolyte, including MgF4、CaF2、ZrO2、CrO2、V2O5、LiF、TaO5、LiAlF4、α-LiWO4、LiNbO3、Li2O、B2O3、MgO、Al2O3、Li3PO4、Li2SO4、LiBO2、LiF、Li3N、LiTaO3Or its combination；Described polymer dielectric include polymeric substrate and in acids, Li+ salt, K+ salt, Na+ salt, the NH4+ salt any one or multiple；Described polymeric substrate includes PEI, PEO, PVA, PAAm, PAMPS, PVP, P2VP, PPO, PMMA, PAN, PVC, PEG, PPG, PTMC, PU, PA, PB, PPEGMA, PHEMA, NPG, PPG, PEPI, PVSA or its combination；Described inorganic electrochromic layer is selected from the oxide of transition metal, the hydrate of transition metal, the composite oxides of transition metal, the Compound Water compound of transition metal, Prussian-blue or its combination, it is preferably: the oxide of Pt, Ir, Os, Pd, Ru, Rh, W, Mo, V, Nb, Ti, the hydrate of Pt, Ir, Os, Pd, Ru, Rh, W, Mo, V, Nb, Ti, Prussian blue, Prussia is black, Prussian green, Prussia are white；Described organic electrochromic layers includes: purple sieve essence, conducting polymer, poly-metal complex, transition metal coordination complexes, the co-ordination complex of lanthanide series, metal phthalocyanine.
The preparation method that present invention also offers a kind of intelligent light modulation film, it is characterised in that comprise the steps: that (1) prepares two Graphenes/embedded metal grid compound transparent electricity conductive film electrode, respectively as the first electrode unit and the second electrode unit；(2) light regulon coating, it concretely comprises the following steps: each layer in light regulon is processed into the dispersion liquid or slurry that can apply, each layer in the first electrode unit of Graphene/embedded metal grid compound transparent electricity conductive film electrode and/or the second electrode unit surface coating light regulon of Graphene/embedded metal grid compound transparent electricity conductive film electrode, and in the layer of coating, embed dunnage；(3) assembling of intelligent dimming membrane module, the steps include: to be coated with the first electrode unit of each layer of light regulon and the second electrode unit carries out dislocation laminating, and is encapsulated by encapsulating material, then puts extraction electrode in dislocation distribution；Preferably, described dislocation is selected from monolateral dislocation or bilateral dislocation.
In step (1) ~ (3), the preparation of related to layer or metal grill, all adopt coating and printing process, be coated with including but not limited to: nano impression, spin coating, spraying, blade coating, rod, nick coating, slot die coating, lip mould are extrusion coated, comma coating, silk screen printing, grenadine printing, inkjet printing.
In step (1) ~ (3), the surface of required coating or printing before arbitrarily coating or printing operation, will through a series of pre-treatment, namely described surface can be initial substrates can also be the layer arbitrarily existed, and described pretreatment mode includes but not limited to: heat treatment, physically or chemically cleaning, UV ozone process, Plasma process, Corona discharge Treatment, pressure treatment or its combination.
In step (1) ~ (3), after arbitrarily coating or printing operation, will through a series of post processing with the layer of coating or printing, the mode of post processing typically includes, but not limited to: doping treatment, reduction treatment, UV process, cured, electron beam treatment, radiation treatment, heat treatment, physical cleaning, Chemical cleaning, UV ozone process, Plasma process, Corona discharge Treatment, pressure treatment or its combination.
By content described above, it will be recognized by those of ordinary skills, the method and system of the present invention can have other embodiments many.Below with reference to the present invention some embodiments more specifically and the experimental result providing support for these embodiments.But, applicant is it is to be noted, that herein below for illustrative purposes only, but not is intended to limit the present invention in any manner scope of the claims.
Accompanying drawing explanation
Fig. 1 common metal grid causes first, the schematic diagram of two electrode unit contacts
The schematic diagram of a kind of Graphene of Fig. 2/embedded metal grid transparent conductive film electrode
Fig. 3 complex periodic repeats two-dimensional pattern (a) hexagon, (b) rhombus, (c) cross structure, (d) pentagon
A kind of Graphene/embedded transparent conductive film comprising functional layer of Fig. 4
Fig. 5 one intelligent dimming membrane module (a) sectional view, (b) top view
A kind of light regulon comprising potential barrier regulating course of Fig. 6
The preparation flow of Fig. 7 embedded metal grid
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.In the examples below, transmitance is measured with ultraviolet/visible/near infrared spectrophotometer (PerkinElmerLambda950);Square resistance is measured with double; two electrical measurement four-point probe (Guangzhou four probe science and technology RTS-9);Film thickness scanning probe microscopy tests (DigitalInstrumentsDimension3100).
Embodiment 1:
Prepared by Graphene/embedded silver metal grid compound transparent electricity conductive film electrode
1. the preparation of embedded silver metal clathrum
PET(Japan Ai Ke AICA at 5cm*5cm, model HC2106) coating last layer UV solidifies polymethyl methacrylate (PMMA Xinguang S KA-HC-1) on substrate, then by the (self-control of grid masterplate, it is highly 10 μm, line-spacing is 1mm, live width is the grid of 50 μm, and shape is selected from shape shown in Fig. 3 (b)) it is placed on PMMA glue, then pass through ultra-violet curing.After solidification, masterplate is peeled off, further by scraper at groove part full-filling conductive silver paste (the cold stone in Suzhou, SNP-MM-03), recycle scraper after full-filling and strike off unnecessary silver slurry.Then the plate made is put in the baking oven of 150 DEG C, toast 30min.Its preparation flow is as shown in Figure 7.With reference to embedded metal grid prepared by the method, can effectively preventing first in follow-up intelligent dimming membrane module, two electrode units directly turn on.
2. the preparation of graphene layer
The PET being embedded with wire netting compartment step 1 obtained, puts into O2Plasma work station MarchPX250 process, setup parameter is 150W, 30 seconds, O2Air-flow: 80sccm, pressure: 350mTorr.Strengthen through this process rear surface, affinity.
Referenced patent " a kind of thin film containing Graphene/or graphene oxide and preparation method thereof; CN103043654A " utilizes its preparation method preparing example 2 to prepare graphene sol, this colloidal sol is dispersed in further N-methyl pyrrole in alkanone, after ultrasonic disperse 1h, obtaining homodisperse stable dispersions, wherein the concentration of Graphene is 0.5mg/ml.Taking this solution 1ml and drop on the PET being embedded with metal grill, then using diameter is that 0.2mm bar is pulled through solution with the speed of 150mm/s, forms graphene film.After solvent volatilization completely, being formed for graphene layer, the graphene layer formed directly contacts with the metal grill embedded.
Embodiment 2:
By the grid masterplate of step 1 in embodiment 1, parameter setting is for being highly 10 μm, and line-spacing is 0.5mm, and live width is the grid of 50 μm, and all the other steps are consistent with embodiment 1, prepares Graphene/embedded silver metal grid composite graphite alkene transparent conductive film electrode.
Embodiment 3:
By the grid masterplate of step 1 in embodiment 1, parameter setting is for being highly 10 μm, and line-spacing is 2mm, and live width is the grid of 50 μm, and all the other steps are consistent with embodiment 1, prepares Graphene/embedded silver metal grid compound transparent electricity conductive film electrode.
Embodiment 4:
Graphene dispersing solution concentration in step 2 in embodiment 1 is adjusted to 0.2mg/ml, and all the other steps are consistent with embodiment 1, prepare Graphene/embedded silver metal grid compound transparent electricity conductive film electrode.
Embodiment 5:
Graphene dispersing solution concentration in step 2 in embodiment 1 is adjusted to 0.8mg/ml, and all the other steps are consistent with embodiment 1, prepare Graphene/embedded silver metal grid compound transparent electricity conductive film electrode.
The performance parameter contrast of the Graphene that embodiment 1 ~ 5 obtains/embedded silver metal grid compound transparent electricity conductive film electrode, is shown in following table.
Embodiment 6:
The preparation of organic electrochromic device
1. the coating of the light regulon on the first electrode unit
Utilizing surrounding preparing device, on Graphene/embedded silver metal grid compound transparent electricity conductive film the first electrode unit, coating wet-film thickness is PEDOT/PSS (Zhuhai is triumphant is) material, then 60 DEG C dry 4 hours in thermal station of 50 microns.
2. the coating of the light regulon on the second electrode unit
2.12g lithium perchlorate is dissolved in 20ml propylene carbonate solvent；The polymethyl methacrylate weighing 2.265g again joins in solution, heats 6 hours 70 DEG C of oil baths, forms viscous liquid.Utilize bar to be coated on Graphene/embedded silver metal grid compound transparent electricity conductive film the second electrode unit, then sprinkle the glass microballoon of a little 100 microns of sizes.
3. assembly device
First electrode unit and the second electrode unit relative dislocation being placed, modes of emplacement is bilateral dislocation, again through pressure pressing, recycling epoxy glue bonding surrounding, is stained with bonding jumper at dislocation part adhesive conductive tape, makes device.
Embodiment 7:
The wet-film thickness of the PEDOT/PSS in embodiment 6 is made as 100 microns of thickness, and other process is consistent with embodiment 6, making devices.
Embodiment 8:
The wet-film thickness of the PEDOT/PSS in embodiment 6 is made as 150 microns of thickness, and other process is consistent with embodiment 6, making devices.
Embodiment 9:
The wet-film thickness of the PEDOT/PSS in embodiment 6 is made as 200 microns of thickness, and other process is consistent with embodiment 6, making devices.
Embodiment 6 ~ 9 is with Graphene/embedded silver metal grid composite graphite alkene transparent conductive film for electrode, and the device parameter performance of making contrasts, and sees following table.
Claims (10)
1. the transparent conductive film electrode for the accurate brilliant patterning of intelligent light modulation film, described transparent conductive film electrode is the brilliant pattern metal grid compound transparent electricity conductive film electrode of Graphene/standard, it is characterized in that, described electrode at least includes graphene layer, transparent substrates and quasi-crystalline substance pattern metal grid；Its pattern of described metal grill is the accurate brilliant pattern only having rotational symmetry without translational symmetry；Optionally, described electrode also includes functional layer, described functional layer be in reflecting layer, protective layer, antireflection layer, anti-dazzle photosphere, barrier layer, tack coat any one or multiple.
2. transparent conductive film electrode according to claim 1, it is characterised in that described accurate brilliant pattern metal grid entirety embeds flexible substrate and its upper surface contacts with graphene layer.
3. transparent conductive film electrode according to claim 1, it is characterized in that, described metal grill includes the block metal grill of Pt grid, Pd grid, Ag grid, Au grid, Cu grid, Sn grid, the arbitrarily biphase or biphase above alloying metal grid of Pt/Pd/Ag/Au/Cu/Sn or aforementioned metal grid；Preferably, described metal grill, 100nm≤live width≤1mm, line-spacing >=500nm.
4. transparent conductive film electrode according to claim 1, it is characterized in that, described transparent substrates is selected from flexible substrate or rigid substrate, it is preferably flexible substrate, described flexible substrate includes: Merlon, silica gel, polrvinyl chloride, polyethylene terephthalate, polystyrene, polymethylacrylic acid, glass resin, polypropylene, fluoropolymer, polyimides, polyamide, polyether-ether-ketone resin, polynorbornene, polyester, polyvinyl, acrylonitrile-butadiene-styrene copolymer, the copolymer of above-mentioned polymer, the block copolymer of above-mentioned polymer, the mixture of above-mentioned polymer.
5. the preparation method for the transparent conductive film electrode of the accurate brilliant patterning for intelligent light modulation film as described in claim 1-4, it is characterized in that, comprise the following steps: (S1) includes the preparation of the transparent substrates of accurate brilliant pattern metal grid, substrate is provided, coating curing glue on substrate, then will have grid masterplate and the solidification glue pressure contact of accurate brilliant pattern, carry out cured to solidifying glue, after solidification, masterplate is peeled off, substrate is formed accurate brilliant patterned groove；Filled conductive slurry in groove, removes unnecessary electrocondution slurry after filling, then solidified by electrocondution slurry, forms the transparent substrates including embedded accurate brilliant pattern metal grid；(S2) preparation of graphene layer, is coated in graphene dispersing solution the transparent substrates surface that step (S1) obtains, forms graphene layer by last handling process, to obtain the brilliant pattern metal grid compound transparent electricity conductive film electrode of Graphene/standard.
6. the preparation method of intelligent light modulation film according to claim 5, it is characterised in that adopt silk screen printing, inkjet printing to prepare non-embedded accurate brilliant pattern metal grid in step S1.
7. an intelligent light modulation film, it is characterized in that, set gradually from bottom to up: include brilliant first electrode unit of pattern metal grid compound transparent electricity conductive film electrode of the Graphene according to claim 1-4/standard, light regulon, include the second electrode unit of the Graphene according to claim 1-4/quasi-crystalline substance pattern metal grid compound transparent electricity conductive film electrode；Accurate brilliant pattern metal lattice in described first electrode unit and the second electrode unit can be identical, it is also possible to is different；Described first electrode unit and the second electrode unit become dislocation opposed；Dislocation distribution has extraction electrode；Light regulon embeds dunnage to prevent the first electrode unit, the second electrode unit from contacting；Whole device is encapsulated by encapsulating material；Preferably, described dislocation is monolateral dislocation or bilateral dislocation.
8. intelligent light modulation film according to claim 7, it is characterised in that described light regulon includes: liquid crystal type light regulon, electrochromism light regulon or its combination.
9. intelligent light modulation film according to claim 8, it is characterised in that described electrochromism light regulon, at least includes the superposition of three-decker: ion storage, dielectric substrate, electrochromic layer；Described electrochromic layer includes organic electrochromic layers or inorganic electrochromic layer；Optionally, described electrochromism light regulon also includes: one or more in potential barrier regulating course, transition zone, electronic barrier layer, hole blocking layer, cushion.
10. the preparation method of the intelligent light modulation film as described in claim 7-9, it is characterised in that comprise the steps: that (1) prepares the brilliant pattern metal grid compound transparent electricity conductive film electrode of Graphene/standard；(2) light regulon coating, it concretely comprises the following steps: each layer in light regulon is processed into the dispersion liquid or slurry that can apply, each layer in the first electrode unit of the brilliant pattern metal grid compound transparent electricity conductive film electrode of Graphene/standard and/or the second electrode unit surface coating light regulon of the brilliant pattern metal grid compound transparent electricity conductive film electrode of Graphene/standard, and in the layer of coating, embed dunnage；(3) assembling of light modulation film device, the steps include: to be coated with the first electrode unit of each layer of light regulon and the second electrode unit carries out dislocation laminating, and is encapsulated by encapsulating material, then puts extraction electrode in dislocation distribution；Preferably, described dislocation is selected from monolateral dislocation or bilateral dislocation.
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