CN105810758A - Quasicrystal patterning transparent film electrode used for intelligent light modulation film - Google Patents
Quasicrystal patterning transparent film electrode used for intelligent light modulation film Download PDFInfo
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Abstract
The invention discloses a quasicrystal patterning transparent film electrode used for an intelligent light modulation film and a preparation method for the same, and a related intelligent modulation film and a preparation method for the same. The quasicrystal patterning transparent film electrode is a graphene/ quasicrystal patterning metal mesh composite transparent conductive film electrode; the graphene/ quasicrystal patterning metal mesh composite transparent conductive film electrode consists of a substrate, a quasicrystal patterning metal mesh and a graphene layer; the intelligent light modulation films consists of two graphene/ quasicrystal patterning metal mesh composite transparent conductive film electrodes which are opposite in a staggermanner and a light ray modulation unit clamped between the two graphene/ quasicrystal patterning metal mesh composite transparent conductive film electrodes, wherein the light ray modulation layer is doped with a backing, the stagger portion is provided with a lead out electrode, and the device is packaged by a packaging material. The graphene/ quasicrystal patterning metal mesh composite transparent conductive film electrode can effectively eliminate the optical effect produced by the metal grid in the light modulation film and enables the light modulation film to be applied in the light modulation device having higher requirements.
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 light modulation film thus regulating from the incident light intensity of glass forms, and then reach energy-conservation purpose.
Usual intelligent electroluminescent light modulation film device, 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 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/ V s, 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 electrode is not but successfully applied in intelligent light modulation film field.The transparent graphene conductive film technology for preparing electrode that one main cause is current is complicated, lattice defect is many, and its higher surface resistance will produce serious pressure drop in larger-size 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 produce numerous composite conductive thin film electrode, to improve electric conductivity.Especially metal grill and Graphene compound are prepared the method for transparency conductive electrode and are most widely used, such as patent " transparency electrode and the grid mixed structure based on Graphene; CN103038835A " and " metal grill-graphene transparent electrode manufacture method and the manufacture method for touch screen thereof; CN103236320A " just illustrate the method preparing metal grill/Graphene transparency conductive electrode, but their method needs application evaporation or sputtering equipment, its production cost is extremely high, suitable for application in intelligent light modulation film field.Additionally the more important thing is, metal grill itself should have very big optical defect.Such as, for touch screen, the pattern of the metal grill in its contact panel is usually the patterns such as vertical network or rhombus and some have the pattern that two-dimensional and periodic repeats, the eclipsed form of the pixel in this fine regular pattern and display panels and to cutting slightly deviation, then there will be not row interference ripple.Same, in light modulation film device, need first, second two Graphene/metal grill combination electrode unit of use simultaneously, if the metal grill in two combination electrodes can not will produce some optical interference by accurate alignment, affect the optical property of light modulation film device.
Above-mentioned technical problem, it would be highly desirable to a kind of new composite conductive thin film is provided, can eliminate, while solution conventional graphite alkene conductivity is low, the optical interference that composite metal structures brings.
Summary of the invention:
For solving above-mentioned technical problem, especially solve that conventional graphite alkene conductivity is low, the problem such as metal mesh structure brings in conventional composite thin film optical interference.The invention provides a kind of novel for intelligent light modulation film accurate brilliant patterned 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 accurate brilliant patterned transparent conductive film electrode for intelligent light modulation film.
In existing metal grill technology, it is be applied on touch screen mostly, owing to the metal grill in touch screen needs to provide X, Y addressing function, has, so the image of its metal grill is all some, the pattern that two-dimension periodic is repeated.And in light modulation film product, Graphene composition metal grid does not provide addressing function, and it being to provide the function strengthening electric conductivity, its pattern can have wider array of selection face, and the metal grill of the brilliant patterning of irregular standard just provides probability for solution optical interference.
Transparent conductive film electrode of the present invention is the brilliant pattern metal grid compound transparent electricity conductive film electrode of Graphene/standard, it is characterised 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.
Described accurate brilliant pattern, is primarily referred to as two dimensional quasicrystal pattern, mainly includes but not limited to: 5 weights, 7 weights, 8 weights, 10 weights, 12 fold rotational symmetry patterns.
The selection of described quasi-crystallization pattern metal grid, it is possible to reach certain physical effect or aesthetic effect, the non-limiting example of some accurate brilliant patterns is shown in Fig. 1.Such as, accurate brilliant pattern is utilized to eliminate not train wave stricture of vagina.Again such as, in having ornamental intelligent light modulation film, accurate brilliant dark stricture of vagina has graceful decoration performance.
In the application of some reality, the membrane electrode of usual Graphene composition metal grid, it is necessary to select different accurate brilliant patterns, be beneficial to the carrier transport of upper/lower electrode.
In some embodiments, the intelligent light modulation film that dimming unit is very thin, necessarily require the metal grill height in the brilliant pattern metal grid transparent conductive film electrode of Graphene/standard to be at least less than the half of light regulating course thickness, lost efficacy to prevent first, second electrode unit contact from leading light modulation film.But metal mesh structure height prepared by traditional silk screen printing and inkjet printing is generally higher, can cause that the probability that electrochromic device punctures increases, the decline of product yield.Such as: as in figure 2 it is shown, the thickness of whole light regulating course 2 microns, the height of the metal grill 111 in upper electrode 11 is 1 micron, and the height of the metal grill 121 in bottom electrode 12 is also 1 micron, then first, second electrode contact will cause puncturing of electrode.Some preferred settling modes can select brilliant for standard pattern metal grid entirety to be embedded flexible substrate and keeps metal grill upper surface to contact with graphene layer.Such as, as it is shown on figure 3, in the transparent conductive film 13 of Graphene/standard brilliant patterning compound, accurate brilliant pattern metal grid 133 is embedded in substrate, and graphene layer 132 is laid in substrate.This preferred structure is more suitable in slim intelligent dimming membrane module to apply.
Described accurate brilliant pattern metal grid 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.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 smart window 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.
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.
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, above-mentioned polymer mixture.
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 accurate brilliant pattern metal grid.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 accurate brilliant patterned 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 accurate brilliant pattern metal grid
Substrate, coating curing glue on substrate are provided, then by standard brilliant patterning grid masterplate and solidification glue pressure contact, carry out cured to solidifying glue, after solidification, masterplate is peeled off, substrate is formed quasi-crystalline substance patterned groove；Filled conductive slurry in accurate brilliant patterned groove, removes unnecessary electrocondution slurry, is then solidified by electrocondution slurry after full-filling, form the transparent substrates comprising embedded accurate brilliant pattern 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 brilliant pattern metal grid compound transparent electricity conductive film electrode of Graphene/standard of intelligent light modulation film.
In the step S1 of the preparation method of described transparent conductive film electrode, the preparation method of accurate brilliant pattern metal grid is not limited to adopt the mode of nano impression, in the light modulation film device that some are not high to metal grill requirement for height, it is also possible to adopt the low cost such as silk screen printing printing or inkjet printing to prepare non-embedded accurate brilliant pattern metal grid.In embodiment 4 ~ 6, illustrate the method that three nonrestrictive silk screen printings prepare Graphene/non-embedded accurate brilliant pattern metal grid compound transparent electricity conductive film electrode.
Again, present invention also offers a kind of 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 Graphene/standard, light regulon, include the second electrode unit of Graphene/quasi-crystalline substance pattern 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；
Described dunnage is the necessary means preventing first, second electrode unit conducting, and its shape mostly is spherical, and diameter is typically larger than 2 ~ 100 microns, and its material can be Muscovitum microballon, glass microballoon, glass fibre or plastic particles.
Preferably, described encapsulating material is epoxy glue.
With reference to Fig. 1 (a), in the example embodiment of indefiniteness, include three layers basic comprising unit from bottom to up successively, including Graphene/standard brilliant first electrode unit 10 of pattern metal grid compound transparent electricity conductive film electrode, light regulon 2, include brilliant pattern metal grid compound transparent electricity conductive film the second electrode unit 11 of Graphene/standard.In a particular embodiment, the brilliant pattern metal grid compound transparent electricity conductive film electrode of Graphene/standard, 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 at least respectively selects an extraction electrode to input at first, second electrode unit, and the signal of telecommunication that the extraction electrode on same electrode unit receives is identical；Light regulon embeds dunnage 5 to prevent first, second electrode unit contact；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 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.
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.
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 the brilliant pattern metal grid compound transparent electricity conductive film electrode of two Graphenes/standard, 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 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 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 accurate brilliant pattern metal grid, 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
The metal grill of the quasi-crystalline substance patterning of Fig. 1.
Metal grill protruding for Fig. 2 causes the schematic diagram of first, second electrode contact.
The schematic diagram of the brilliant pattern metal grid transparent conductive film electrode of a kind of Graphene of Fig. 3/standard.
A kind of brilliant pattern metal grid transparent conductive film electrode of Graphene/standard 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 the embedded accurate brilliant pattern metal grid of Fig. 7.
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)；Metal grill height scanning electron microscope (Hitachi S-4800) measures.
Embodiment 1
Prepared by Graphene/embedded accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode
1. the preparation of embedded accurate brilliant patterning silver metal grid
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, the length of side is 1mm, live width is the grid of 50 μm, and shape is selected from pattern shown in Fig. 1 (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.
2. the preparation of graphene layer
The PET being embedded with accurate brilliant patterning silver metal clathrum 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 to drop on the PET being embedded with accurate brilliant pattern metal grid, 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 accurate brilliant pattern metal grid embedded.
Embodiment 2
By the grid masterplate of step 1 in embodiment 1, parameter setting is for being highly 10 μm, and the length of side is 0.5mm, and live width is the grid of 50 μm, all the other steps are consistent with embodiment 1, prepare Graphene/embedded accurate brilliant patterning 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 the length of side is 2mm, and live width is the grid of 50 μm, and all the other steps are consistent with embodiment 1, prepares Graphene/embedded accurate brilliant patterning 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 accurate brilliant patterning 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 accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode.
Embodiment 6
By the grid masterplate of step 1 in embodiment 1, with reference to the quasi-crystal mesh lattice of design shown in Fig. 1 (b), all the other steps are consistent with embodiment 1, prepare Graphene/embedded accurate brilliant patterning silver metal grid composite graphite alkene transparent conductive film electrode.
Embodiment 7
Prepared by Graphene/non-embedded accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode
1. the preparation of non-embedded accurate brilliant patterning silver metal grid
Silk-screen printing technique is adopted to clean up the PET(Japan Ai Ke AICA of 5cm*5cm, model HC2106) the upper quasicrystalline patterns printing required metal grill, concrete figure is referring to accompanying drawing 1(b), accurate brilliant pattern metal grid, live width is 25 microns, length of side 1mm.Adopting manually accurate screen printing table, order number is 150 orders, adopts conductive silver paste (the cold stone SNP-MM-03 in Suzhou) as ink for screen printing.First dry at normal temperatures after finishing printing, place in 150 DEG C of baking ovens and dry 15 minutes, namely non-embedded accurate brilliant patterning silver metal grid is obtained on the pet substrate, the Graphene obtained/non-embedded accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode is carried out SEM sign, and wherein the average height of metal grill is 29.7 microns.
2. the preparation of graphene layer
Step 1 obtains being printed with the PET of accurate brilliant patterning silver metal clathrum, 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 non-embedded accurate brilliant pattern metal grid.
The performance parameter contrast of the Graphene that embodiment 1 ~ 7 obtains/standard brilliant patterning silver metal grid compound transparent electricity conductive film electrode, is shown in following table.
Embodiment 8:
The preparation of organic electrochromic intelligent light modulation film
1. the coating of the light regulon on the first electrode unit
Select two Graphenes/embedded accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode of embodiment 1 and embodiment 6 preparation respectively as the first electrode unit and the second electrode unit.Utilize surrounding preparing device, on Graphene/embedded accurate brilliant patterning 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 accurate brilliant pattern metal grid compound transparent electricity conductive film the second electrode unit of Graphene/embedded silver, 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 9:
The wet-film thickness of the PEDOT/PSS in embodiment 8 is made as 100 microns of thickness, and other process is consistent with embodiment 8, making devices.
Embodiment 10:
The wet-film thickness of the PEDOT/PSS in embodiment 8 is made as 150 microns of thickness, and other process is consistent with embodiment 8, making devices.
Embodiment 11
The wet-film thickness of the PEDOT/PSS in embodiment 8 is made as 200 microns of thickness, and other process is consistent with embodiment 8, making devices.
Embodiment 12
Being replaced with by first, second electrode unit in embodiment 8, the Graphene of preparation/non-embedded accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode in embodiment 7, other process is consistent with embodiment 8, making devices.
Embodiment 8 ~ 12 is with Graphene/embedded accurate brilliant patterning silver metal grid composite graphite alkene transparent conductive film for electrode, and the device parameter performance of making contrasts, and sees following table.
Embodiment 13
Liquid crystal type intelligent dimming film preparation
Select the Graphene/embedded accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode of two identical embodiment 1 preparations respectively as the first electrode unit and the second electrode unit.
By epoxy resin: polyamide modified dose: epoxychloropropane (little molecular regulation refractive index) is in harmonious proportion according to the ratio of 4:1:3.2, add the liquid crystal compound (LC-Beijing Bayi Space LCD Materials Technology Co., Ltd.) of the identical refractive index of 70%, and the glass fiber powder of 2000 a small amount of orders, diameter be 3 μm as dunnage, it is sufficiently mixed stirring 3 hours when room temperature, is liquid crystal compound coating liquid.
Taking 3ml liquid crystal compound coating liquid, drop on the first electrode unit, then use bar to be pulled through coating liquid with the speed of 100mm/s, form one layer of uniform film at glass basic surface, the other end leaves the width of 1.5cm does not have coated with liquid crystal mixture coating liquid.Second electrode unit and this are then coated with the first electrode unit dislocation laminating of liquid crystal compound, and dislocation part is the part of uncoated liquid crystal compound.Put the electrodes in 150 DEG C of baking ovens, solidify 2h.
Placing above-mentioned solidification rear electrode to room temperature in the environment, be then clipped in the dislocation zone of two electrodes with two U-shaped clamping cleats of metals respectively, thus prepared by device.Prepared device, it is 80% that mist degree regulates excursion.
Comparative example 1
Liquid crystal type intelligent dimming film preparation
First, second electrode unit in embodiment 13 replaces with the Graphene of preparation in embodiment 7/non-embedded accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode, and other process is consistent with embodiment 13, making devices.This comparative example and embodiment 13 are contrasted, and owing to adopting Graphene/non-embedded accurate brilliant patterning silver metal grid compound transparent electricity conductive film electrode, device first, second electrode contact of making, cause that device cannot normal operation.
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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