CN103760722B - A kind of intelligent light modulation film using Graphene as transparency conductive electrode and preparation method thereof - Google Patents

A kind of intelligent light modulation film using Graphene as transparency conductive electrode and preparation method thereof Download PDF

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CN103760722B
CN103760722B CN201410011014.3A CN201410011014A CN103760722B CN 103760722 B CN103760722 B CN 103760722B CN 201410011014 A CN201410011014 A CN 201410011014A CN 103760722 B CN103760722 B CN 103760722B
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graphene
light modulation
film
modulation film
intelligent light
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CN103760722A (en
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赵文军
徐和平
邱玉锐
谭化兵
李慧峰
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Changzhou sixth element Semiconductor Co.,Ltd.
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WUXI GEFEI ELECTRONIC FILM TECHNOLOGY CO LTD
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Abstract

The invention discloses a kind of intelligent light modulation film using Graphene as transparency conductive electrode, using the graphene film of upper and lower both sides as conductive electrode, liquid crystal mixed material is sandwiched in centre, it is attached with transparent base in the outside of the graphene film of upper and lower both sides, form the structure of transparent base/Graphene/liquid crystal/Graphene/transparent base, wherein, the edge of upper and lower graphene film is respectively equipped with one or more electrode lead-out structure, is connected with external drive power supply.The present invention is based on the intelligent light modulation film of Graphene electrodes, ITO(tin indium oxide is substituted using one graphene film) as the intelligent dimming membrane structure of electrode, and the deriving structure of the conductive electrode in actual applications invented for the feature of Graphene, not only effectively reduce the cost of intelligent light modulation film, and it is substantially reduced cost of manufacture, technique is simple, and the cost of more existing intelligent light modulation film decreases more than 30%.

Description

A kind of intelligent light modulation film using Graphene as transparency conductive electrode and preparation method thereof
Technical field
The present invention relates to a kind of intelligent light modulation film.
Background technology
Intelligent glass, also known as electronic-control dimming glass, by automatically controlled realize glass transparent and opaque between conversion, be widely applied to house property decoration at present, vehicle glass, large area projection wall, office space, the field such as public entertainment facility.The conversion of the electric-controlled light-regulating of intelligent glass, is realized by intelligent light modulation film.As most crucial parts, intelligent light modulation film is as electrode by upper and lower two-layer transparent conductive film, and the composite material of the liquid crystal material being clipped in the middle and polymer is constituted.ITO(tin indium oxide in the market) be used as intelligent dimming membrane electrode uniquely can material selection, and ITO is expensive, and phosphide element reserves on earth are limited, but ITO is at electronic device, photoelectricity, and the domain requirement amount such as photovoltaic is increasing.So, the present invention relates to brand-new a kind of transparent conductive film material in intelligent glass field, cost is low, and light transmittance is adjustable (97.7%-10%), and electric conductivity is adjustable (square resistance is at 50-300 ohm/).
Existing exist following problem: one in the intelligent dimming membrane technology that ITO is transparency electrode, uses transparent thin film, and ITO is unique selection;Two, ITO is expensive, and the cost of raw material is too high, and phosphide element is more rare, and on the earth, storage is limited, and ITO market demand is increasing, so the price of ITO only can be more and more higher;Three, ito thin film is more crisp, and pliability is poor, bending more than 60 degree will fracture distress, cause component failure, so being unsuitable to apply to the occasion that flexibility requirements is higher;Four, the transmitance of ITO is low, and the restriction by sheet resistance can not arbitrarily regulate.
Graphene is as a kind of monolayer carbon atom two-dimensional network, and its thickness only has 0.34 nanometer, therefore can arbitrarily bend, its visible light transmissivity is 97.7%, theoretical conductivity is 10E8/S m, is have now been found that best electric conductor, is theoretically a kind of fabulous transparency conductive electrode material.But, due to the ultra-thin property of Graphene, in actual application process, there is very big difficulty with connecting of external power source system in Graphene electrodes, thus fails so far to be applied in intelligent dimming membrane technology grapheme material.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defect, it is provided that a kind of can arbitrarily bend, light transmittance can arbitrarily regulate and cost the is low intelligent light modulation film using Graphene as transparency conductive electrode;
The preparation method that it is a further object of the present invention to provide the above-mentioned intelligent light modulation film using Graphene as transparency conductive electrode.
The purpose of the present invention implements by the following technical programs:
A kind of intelligent light modulation film using Graphene as transparency conductive electrode, using the graphene film of upper and lower both sides as conductive electrode, liquid crystal mixed material is sandwiched in centre, it is attached with transparent base in the outside of the graphene film of upper and lower both sides, form the structure of transparent base/Graphene/liquid crystal/Graphene/transparent base, wherein, the edge of upper and lower graphene film is respectively equipped with one or more electrode lead-out structure, is connected with external drive power supply.
Further, described electrode lead-out structure is the conductive silver paste coated on graphene film or the metal fitted tightly with graphene film.
Preferably,
The thickness of described conductive silver paste is 100 nanometers ~ 200 microns;
Described metal is copper, and thickness is 10 ~ 200 microns;
Described upper/lower electrode deriving structure is positioned at same one side of intelligent light modulation film, or is positioned at both sides as required, and when described upper/lower electrode deriving structure is positioned at intelligent light modulation film same, upper/lower electrode deriving structure staggers up and down.
Further, described graphene film is constituted for one or more layers Graphene.
Further, described transparent base is clear glass, PET polyester film or is the composite construction adhering to clear glass outside PET polyester film.
The preparation method of the above-mentioned intelligent light modulation film using Graphene as transparency conductive electrode, comprises the steps:
1) Graphene grown is transferred on transparent base, form transparency conducting layer, as upper strata;
2) by coating method, the Graphene side of the transparency conducting layer obtained according to step 1) additionally arranges liquid crystal mixed material, during coating, reserves the region of one fixed width at the edge of transparency conducting layer, forms lower floor;
3) by the method for step 1) obtained upper strata covering step 2) the lower floor that obtains of method, form liquid crystal mixed material in centre, transparency conducting layer is in " sandwich " structure of both sides, light modulation film is formed after pressing or solidification, wherein, when covering lower floor on upper strata, reserve the marginal area not contacted with liquid crystal mixed material;
4) one layer of conductive silver paste is covered in the region reserved in the upper and lower coating or point, or bond layer of metal with conducting resinl, form electrode lead-out structure, and the position being not coated with conductive silver paste or bonding metal in described region is removed.
Preferably, when described step 1) prepares transparency conducting layer, adopt and repeatedly shift, increase the number of plies of Graphene.
Preferably, in described step 4), as required, on upper strata or lower floor, make multiple electrode lead-out structure respectively according to the method for step 4), and when described electrode lead-out structure is positioned at intelligent light modulation film same, make these electrode lead-out structure mutually stagger.
Beneficial effects of the present invention:
1, the present invention utilizes Graphene to have the light transmittance of excellence, electric conductivity and mechanical performance, the intelligent light modulation film that preparation is transparency conducting layer with Graphene, its visible light transmissivity (400-700 nanometer) is adjustable at 10%-97.7%, square resistance (ohm/): 50-300;
2, intelligent light modulation film of the present invention had both been usable on rigidity intelligent dimming glass, it is also possible to be used directly on the various curved surfaces that flexibility is required, and can be used for making various intelligent dimming glass, or is fabricated to flexible intelligent light modulation film, is used on various curved surface.According to specific requirement, any shape, any size, its pliability: ultra-thin can be made, be arbitrarily bent to 180 degree;
3, the present invention gives the Graphene electrode lead-out method as transparency conducting layer, overcome that Graphene is ultra-thin is difficult to external problem, safe and practical, easily operated, the structural design that its electrode is drawn, can be prevented effectively from contact short circuit, it is simple to install, it is beneficial to intelligent dimming glass and is used in different occasion, it is achieved have the ultrathin electrodes of grapheme material;
4, the present invention is based on the intelligent light modulation film of Graphene electrodes, ITO(tin indium oxide is substituted using one graphene film) as the intelligent dimming membrane structure of electrode, and the deriving structure of the conductive electrode in actual applications invented for the feature of Graphene, not only effectively reduce the cost of intelligent light modulation film, and it is substantially reduced cost of manufacture, technique is simple, and the cost of more existing intelligent light modulation film decreases more than 30%.
Accompanying drawing explanation
Accompanying drawing is for providing a further understanding of the present invention, and constitutes a part for description, is used for together with embodiments of the present invention explaining the present invention, is not intended that limitation of the present invention.In the accompanying drawings:
Fig. 1 is using Graphene as the intelligent light modulation film profile of transparency conductive electrode in the embodiment of the present invention 1;
Fig. 2 is using Graphene as the intelligent light modulation film perspective view of transparency conductive electrode in the embodiment of the present invention 1;
Fig. 3 is the intelligent light modulation film profile using Graphene as transparency conductive electrode in the embodiment of the present invention 2.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention.
Embodiment 1:
A kind of intelligent light modulation film using Graphene as transparency conductive electrode, with reference to Fig. 1-2, using the graphene film 2(width 2cm of upper and lower both sides, long 10cm) as conductive electrode, liquid crystal mixed material 1 is sandwiched in centre, described graphene film is that bilayer graphene is constituted, it is attached with PET polyester film 3 in the outside of the graphene film 2 of upper and lower both sides, form the structure of PET polyester film 3/ bilayer graphene 2/ liquid crystal 1/ bilayer graphene 2/PET polyester film 3, wherein, the edge of upper and lower graphene film 2 is respectively equipped with two electrode lead-out structure 4, is connected with external drive power supply.
Described electrode lead-out structure 4 is coat the conductive silver paste on graphene film, and thickness is 10 microns;
Described electrode lead-out structure staggers up and down.
Embodiment 2:
A kind of intelligent light modulation film using Graphene as transparency conductive electrode, with reference to Fig. 3, graphene film 2(width 2cm with upper and lower both sides, long 10cm) as conductive electrode, liquid crystal mixed material 1 is sandwiched in centre, described graphene film is that bilayer graphene is constituted, it is attached with PET polyester film 3 in the outside of the graphene film 2 of upper and lower both sides, the outside of PET polyester film 3 is attached with clear glass 5, form the structure of clear glass 5/PET polyester film 3/ bilayer graphene 2/ liquid crystal 1/ bilayer graphene 2/PET polyester film 3/ clear glass 5, wherein, the edge of upper and lower graphene film 2 is respectively equipped with two electrode lead-out structure 4, it is connected with external drive power supply.
Described electrode lead-out structure 4 is coat the conductive silver paste on graphene film, and thickness is 10 microns;
Described electrode lead-out structure staggers up and down.
Embodiment 3:
Using Graphene as the preparation method of the intelligent light modulation film of transparency conductive electrode, comprise the steps:
The first step, described Graphene is grown on Copper Foil by chemical gaseous phase depositing process;
Second step, is etched away copper by chemical etching method, then Graphene is transferred on different matrixes, such as glass or PET polyester film.By continuing transfer Graphene, it is possible to increasing the number of plies of Graphene, thus increasing the electric conductivity of graphene conductive layer, regulating its transmitance;
3rd step, by coating method, lays liquid crystal mixed material on the Graphene transparency conducting layer matrix that second step obtains.Owing to the thickness of graphene conductive layer is at 0.3-3 nanometer, conventionally expose conductive layer by stripping matrix material, conductive layer the method being directly connected to external drive power supply is inapplicable.Therefore, when coating of liquid crystalline composite material, Graphene transparency conducting layer reserves the region (such as 1 centimetre wide, and width size is according to practical situation) of one fixed width, only at all the other homogeneous area coating of liquid crystalline composite materials;
4th step, on the Graphene transparency conducting layer matrix scribbling liquid crystal mixed material that the 3rd step obtains (in for the purpose of, it is called " lower floor " matrix), add the Graphene transparency conducting layer matrix (being called " upper strata " matrix) that last layer is obtained by second step, forming a kind of liquid crystal mixed material in centre, transparency conducting layer is in " sandwich " structure of both sides.Notice that the electrode of " upper strata " matrix is when covering " lower floor " matrix, it is also desirable to the region leaving one fixed width does not cover liquid crystal mixed material, as shown in Figure 1 or 2.
5th step, the structure that the 4th step obtains is shaped to light modulation film after pressing and solidification (ultra-violet curing or heat cure);
6th step, the part not covered by liquid crystal material at " lower floor " matrix, according to practical situation, select subregion, coating or point cover one layer of conductive silver paste 10 microns thick, conductive silver paste can not contact with the Graphene of " upper strata " matrix, and the region that all the other are not coated with conductive silver paste (or metal) is cut.This conductive silver paste stated (or metal) is connected with external drive power supply as drawing.Electrode is drawn according to actual needs, can make one or several according to the method described above, has made 2 extractions as shown in Figure 2 on the Graphene electrodes layer of " lower floor " matrix.
7th step, on " upper strata " matrix, the process described according to above-mentioned 6th step is repeated, it should be noted that to stagger with conductive silver paste (or metal) region of " lower floor " in the region of applying conductive silver slurry (or metal), thus avoiding contact with short circuit.This states conductive silver paste (or metal) and is connected with external drive power supply as drawing.Corresponding " lower floor " matrix, makes one or more on the Graphene electrodes layer of " upper strata " matrix and draws.
Embodiment 4:
Using Graphene as the preparation method of the intelligent light modulation film of transparency conductive electrode, comprise the steps:
The first step, described Graphene is grown on Copper Foil by chemical gaseous phase depositing process;
Second step, is etched away copper by chemical etching method, then Graphene is transferred on different matrixes, such as glass or PET polyester film.By continuing transfer Graphene, it is possible to increasing the number of plies of Graphene, thus increasing the electric conductivity of graphene conductive layer, regulating its transmitance;
3rd step, by coating method, lays liquid crystal mixed material on the Graphene transparency conducting layer matrix that second step obtains.Owing to the thickness of graphene conductive layer is at 0.3-3 nanometer, conventionally expose conductive layer by stripping matrix material, conductive layer the method being directly connected to external drive power supply is inapplicable.Therefore, when coating of liquid crystalline composite material, Graphene transparency conducting layer reserves the region (such as 1 centimetre wide, and width size is according to practical situation) of one fixed width, only at all the other homogeneous area coating of liquid crystalline composite materials;
4th step, on the Graphene transparency conducting layer matrix scribbling liquid crystal mixed material that the 3rd step obtains (in for the purpose of, it is called " lower floor " matrix), add the Graphene transparency conducting layer matrix (being called " upper strata " matrix) that last layer is obtained by second step, forming a kind of liquid crystal mixed material in centre, transparency conducting layer is in " sandwich " structure of both sides.Notice that the electrode of " upper strata " matrix is when covering " lower floor " matrix, it is also desirable to the region leaving one fixed width does not cover liquid crystal mixed material, as shown in Figure 1 or 2.
5th step, the structure that the 4th step obtains is shaped to light modulation film after pressing and solidification (ultra-violet curing or heat cure);
6th step, the part not covered by liquid crystal material at " lower floor " matrix, according to practical situation, select subregion, directly with metal (the such as copper of the viscous last layer more than 10 microns of conducting resinl, but it is not limited to copper), person's metal can not contact with the Graphene of " upper strata " matrix, and the region that all the other are not coated with conductive silver paste (or metal) is cut.This conductive silver paste stated (or metal) is connected with external drive power supply as drawing.Electrode is drawn according to actual needs, can make one or several according to the method described above, has made 2 extractions as shown in Figure 2 on the Graphene electrodes layer of " lower floor " matrix.
7th step, on " upper strata " matrix, the process described according to above-mentioned 6th step is repeated, it should be noted that to stagger with conductive silver paste (or metal) region of " lower floor " in the region of applying conductive silver slurry (or metal), thus avoiding contact with short circuit.This states conductive silver paste (or metal) and is connected with external drive power supply as drawing.Corresponding " lower floor " matrix, makes one or more on the Graphene electrodes layer of " upper strata " matrix and draws.
The foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature carries out equivalent replacement.All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.

Claims (3)

1. one kind using Graphene as the preparation method of the intelligent light modulation film of transparency conductive electrode, it is characterised in that: comprise the steps:
1) Graphene grown is transferred on transparent base, form transparency conducting layer, as upper strata;
2) by coating method, the Graphene side of the transparency conducting layer obtained according to step 1) additionally arranges liquid crystal mixed material, during coating, reserves the region of one fixed width at the edge of transparency conducting layer, forms lower floor;
3) by the method for step 1) obtained upper strata covering step 2) the lower floor that obtains of method, form liquid crystal mixed material in centre, transparency conducting layer is in " sandwich " structure of both sides, light modulation film is formed after pressing or solidification, wherein, when covering lower floor on upper strata, reserve the marginal area not contacted with liquid crystal mixed material;
4) one layer of conductive silver paste is covered in the region reserved in the upper and lower coating or point, or bond layer of metal with conducting resinl, form electrode lead-out structure, and the position being not coated with conductive silver paste or bonding metal in described region is removed.
2. the preparation method of the intelligent light modulation film using Graphene as transparency conductive electrode according to claim 1, it is characterised in that: when described step 1) prepares transparency conducting layer, adopt and repeatedly shift, increase the number of plies of Graphene.
3. the preparation method of the intelligent light modulation film using Graphene as transparency conductive electrode according to claim 1, it is characterized in that: in described step 4), as required, on upper strata or lower floor, multiple electrode lead-out structure is made respectively according to the method for step 4), and when being positioned at time on one side, make these electrode lead-out structure mutually stagger.
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