CN104299681B - A kind of compound transparent electricity conductive film and preparation method thereof - Google Patents
A kind of compound transparent electricity conductive film and preparation method thereof Download PDFInfo
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- CN104299681B CN104299681B CN201410514149.1A CN201410514149A CN104299681B CN 104299681 B CN104299681 B CN 104299681B CN 201410514149 A CN201410514149 A CN 201410514149A CN 104299681 B CN104299681 B CN 104299681B
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Abstract
The invention discloses a kind of compound transparent electricity conductive film and preparation method thereof, wherein, compound transparent electricity conductive film includes metal nanometer line, silicon-containing nano granule and conductive sheet carbon simple substance；Wherein, each described metal nanometer line constitutes the conductive network of described compound transparent electricity conductive film；Some described silicon-containing nano granules are attracted to around each described metal nanometer line by intermolecular force, are used for disperseing each described metal nanometer line；Described conductive sheet carbon simple substance is used for being conductively connected each described metal nanometer line.This compound transparent electricity conductive film can be used as flexible transparent electrode, in photoelectric field extensive application such as solaode, touch screen, electroluminescent display, Electronic Paper, liquid crystal display, plasma display, electromagnetic shielding materials.
Description
Technical field
The present invention relates to transparent conductive film, in particular, a kind of compound transparent electricity conductive film and
Its preparation method.
Background technology
Transparent conductive film is a kind of one can conducted electricity and have high transparency rate in visible-range
Thin film, is mainly used in the window material of photoelectric device, wherein, photoelectric device such as LED, thin film solar
Battery etc..Tin indium oxide (ITO) thin film has that light transmission is good, resistivity is low, stable chemical nature
Advantage, current is most widely used.But the fragility of ito thin film is big, poor toughness, synthesis temperature
High poor with the associativity of flexible substrate, and the reserves of indium are limited, and price is rising steadily, this
A little shortcomings all limit it and further apply, and are badly in need of developing other substitution material.
CNT, Graphene and metal nanometer line, be respectively provided with good electric conductivity, leads transparent
There is good application prospect in conductive film field.But CNT and Graphene are respectively provided with higher connecing
Get an electric shock and hinder so that the electrical conductivity of thin-film material is relatively low.It addition, CNT and the quality pair of Graphene
Its electrical conductivity has appreciable impact, and the existence of various defects all can have a strong impact on the mobility of electronics, mesh
Before still can not realize the scale of high-quality CNT and Graphene and prepare.
Metal nanometer line has good electric conductivity, excellent light transmission, flexible resistance, for bendable
The realization of the folding flexible product such as light-emitting diode display, touch screen provides possibility.Compared with Graphene, high
The metal nanometer line of draw ratio can form the conductive network of UNICOM under relatively low content, therefore uses
The thin film of metal nanometer line has higher transmitance and cost advantage；There is as with high length-diameter ratio knot
The CNT of structure is compared, and the contact resistance between metal nanometer line is little, has more preferable electric conductivity.
Such as, silver is the metal that electric conductivity is best, has good chemical stability, has been developed at present
The preparation method of multiple nano silver wire, the industrial applications for nano silver wire provides the foundation.
But, metal nanometer line nesa coating, such as nano silver wire nesa coating, its light transmission
Rate and electric conductivity contradictory relation each other.The increase of nano silver wire content, contributes to constructing complete conduction
Network, improves the electric conductivity of thin film, but owing to nano silver wire is nontransparent, the increase gesture of its content
The decline of transmitance must be caused.As it is shown in figure 1, nano silver wire is due to its high specific surface area,
Easily reunite during application so that part nano wire can not give full play to its effect.
By the intermolecular force between regulation and control metal nanometer line, the dispersion of metal nanometer line can be improved
Performance.Prior art introduces in multidirectional system the macromolecule surfaces such as polyvinylpyrrolidone (PVP) live
Property agent dispersant is to regulate and control intermolecular force.But these surfactants can be by metal nano
Line is coated with wholly or in part so that the electric conductivity of metal nanometer line declines, and generally requires follow-up sintering
Process.
But, due to the existence of sintering circuit, on the one hand make it difficult to be similar to the low heat-resisting of PET
Property plastic base on form transparency electrode, on the other hand higher due to sintering temperature, metal nanometer line holds
Easy fracture.
Additionally, the metal nanowire thin-films prepared with methods such as spraying, silk screen printing, roller coat, spin coatings,
Such as nano silver wire nesa coating, the combination with substrate is insecure so that thin film is easy to fall off.Existing
Many organic adhesion layers that increase on substrate in technology, but, this adhesion layer is set, both added
The integral thickness of bright conducting film, reduces again the mobility of electronics.
Therefore, on the premise of utilizing metal nanometer line high conductivity, how to realize metal nanometer line
Effective dispersion, there is great using value and economic benefit, thus, it is necessary to research is a kind of new
Metal nanowire thin-films.
Summary of the invention
The technical problem to be solved is to provide a kind of new compound transparent electricity conductive film, it is possible to
Dispersion effective to metal nanometer line, constructs complete conductive network with less metal nanometer line, with joint
Save the cost of transparent conductive film；Also provide for the preparation method of this compound transparent electricity conductive film.
Technical scheme is as follows: the preparation method of a kind of compound transparent electricity conductive film, comprising:
By the most scattered silicon-containing nano particle solution, join in the most scattered metal nanometer line solution, obtain
Primary mixed solution；By the most scattered conductive sheet carbon simple substance solution, join the most scattered described at the beginning of
In level mixed solution, obtain pending mixed solution；By true for the most scattered described pending mixed solution
Empty sucking filtration, obtains the first filter paper of pending film and attachment thereof；Described first filter paper water-wet, will
First filter paper of the first substrate, pending film and attachment thereof, use the second filter paper of water-wet, the second lining
It is dried after the end is fixing；Respectively by described second substrate, described second filter paper and described pending membrance separation；
By described first substrate, it is placed in solvent with described first filter paper of water-wet and described pending film,
Dissolve described first filter paper；It is dried after described pending film is taken out with described first substrate；By described
Pending film separates with described first substrate, obtains described compound transparent electricity conductive film.
Preferably, the most scattered silicon-containing nano particle solution is joined the most scattered metal nanometer line molten
Before liquid, being also carried out metal nanometer line, after being centrifuged, ultrasonic disperse is in water.
Preferably, described metal nanometer line includes metal simple-substance nano wire and/or metal alloy nanowires；
And/or, described silicon-containing nano granule includes nano level silicon grain, silica dioxide granule, carborundum
Grain and/or silicon nitride particle；And/or, described conductive sheet carbon simple substance includes Graphene or graphite flake；
And/or, described water is pure water.
Preferably, described preparation method comprises the following steps: by the most scattered nano silicon particles aqueous solution,
Join in the most scattered nano silver wire aqueous solution, obtain primary mixed solution, wherein, nano silver wire
It is 8:1～1:1 with the mass ratio of nano silicon particles；By the most scattered graphene aqueous solution, join and divide
In the described primary mixed solution dissipated, obtain pending mixed solution, wherein, nano silver wire and graphite
The mass ratio of alkene is 12:1～6:1；By the most scattered described pending mixed solution vacuum filtration,
To pending film and the first filter paper of attachment thereof, wherein, described first filter paper is cellulose mixture filter paper；
Described first filter paper water-wet, by the first filter paper, the use of the first substrate, pending film and attachment thereof
Being dried after second filter paper of water-wet, the second substrate are fixing, wherein, described second filter paper is nylon filter
Paper, the nano wire face of described pending film is just to described first substrate；First by described second substrate and institute
State the second filter paper to separate, then by described second filter paper and described pending membrance separation；By described first
Substrate, it is placed in organic solvent with described first filter paper of water-wet and described pending film, dissolves institute
State the first filter paper；Natural drying after described pending film is taken out with described first substrate；Treat described
Process film to separate with described first substrate, obtain described compound transparent electricity conductive film.
Preferably, described preparation method comprises the following steps: by the most scattered 0.5mg/mL silicon nanometer
Grain aqueous solution, joins in the most scattered 2mg/mL nano silver wire aqueous solution, obtains primary mixed solution,
Wherein, nano silver wire is 4:1 with the mass ratio of nano silicon particles；By the most scattered 1mg/g Graphene water
Solution, joins in the most scattered described primary mixed solution, obtains pending mixed solution, wherein,
Nano silver wire is 8:1 with the mass ratio of Graphene；By the most scattered described pending mixed solution vacuum
Sucking filtration, obtains the first filter paper of pending film and attachment thereof, wherein, described cellulose mixture filter paper
Aperture is 0.22 μm；Described first filter paper water-wet, by the first substrate, pending film and attachment thereof
The first filter paper, with the second filter paper of water-wet, the second substrate fixing after be dried, wherein, described the
Two filter paper are nylon filters, and the nano wire face of described pending film is just to described first substrate；First by institute
State the second substrate to separate with described second filter paper, then described second filter paper is divided with described pending film
From；By described first substrate, it is placed in acetone with described first filter paper of water-wet and described pending film
In solution, dissolve described first filter paper；Nature after described pending film is taken out with described first substrate
It is dried；Described pending film is separated with described first substrate, obtains described compound transparent electricity conductive film.
Preferably, described described pending film is separated with described first substrate, comprises the following steps:
Above described pending film, drip the acrylate being mixed with light trigger, make acrylate cover completely
Lid nano silver wire thin film, separates described pending film with described first substrate after ultra-violet curing, obtains
The described compound transparent electricity conductive film being attached on acrylate.
Preferably, described described pending film is separated with described first substrate, comprises the following steps:
Silicone rubber is covered, by described pending film and described first after heating cure above described pending film
Substrate separates, and obtains the described compound transparent electricity conductive film being attached on silicone rubber.
The another technical scheme of the present invention is as follows: a kind of compound transparent electricity conductive film, it includes that metal is received
Rice noodle, silicon-containing nano granule and conductive sheet carbon simple substance；Wherein, each described metal nanometer line constitutes institute
State the conductive network of compound transparent electricity conductive film；The surrounding of each described metal nanometer line adsorbs some respectively
Described silicon-containing nano granule, for each described metal nanometer line of scattering device；Described conductive sheet carbon list
Matter is used for being conductively connected each described metal nanometer line.
Preferably, described compound transparent electricity conductive film, use arbitrary above-mentioned preparation method to prepare.
Preferably, described metal nanometer line is nano silver wire, and described silicon-containing nano granule is silicon nanometer
Grain, described conductive sheet carbon simple substance includes Graphene or graphite flake.
Use above-mentioned each scheme, present invention achieves the effective dispersion to metal nanometer line, with less
Metal nanometer line constructs complete conductive network, thus saves the cost of transparent conductive film.This is saturating
Bright conductive film can be used as flexible transparent electrode, at solaode, touch screen, electroluminance display
The photoelectric fields such as device, Electronic Paper, liquid crystal display, plasma display, electromagnetic shielding material have
Extensively application.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that prior art nano silver wire is easily reunited；
Fig. 2 is that the nano silicon particles of one embodiment of the present of invention is adsorbed under the effect of Van der Waals force
Schematic diagram around nano silver wire；
Fig. 3 be one embodiment of the present of invention Graphene by each other not in contact with nano silver wire couple
Schematic diagram；
Fig. 4 is the schematic flow sheet of one embodiment of the present of invention.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with the accompanying drawings and specific embodiment, the present invention is carried out more
Detailed description.It should be noted that when element is expressed " being fixed on " another element, and it can
With directly on another element or one or more element placed in the middle can be there is therebetween.When one
Individual element is expressed " connection " another element, it can be directly to another element or
One or more element placed in the middle can be there is therebetween in person.Term " vertical " that this specification is used,
" level ", "left", "right" and similar statement are for illustrative purposes only.
Unless otherwise defined, this specification is used all of technology and scientific terminology with belong to this
The implication that bright those skilled in the art are generally understood that is identical.Saying in the present invention in this specification
Term used in bright book is intended merely to describe the purpose of specific embodiment, is not intended to limit this
Invention.The term "and/or" that this specification is used includes one or more relevant Listed Items
Arbitrary and all of combination.
As shown in Figure 4, one embodiment of the present of invention is, the preparation of a kind of compound transparent electricity conductive film
Method, it comprises the following steps: by the most scattered silicon-containing nano particle solution, join the most scattered
In metal nanometer line solution, obtain primary mixed solution；By the most scattered conductive sheet carbon simple substance solution,
Join in the most scattered described primary mixed solution, obtain pending mixed solution；By the most scattered
Described pending mixed solution vacuum filtration, obtains the first filter paper of pending film and attachment thereof；Described
First filter paper water-wet, by the first filter paper of the first substrate, pending film and attachment thereof, moistens with water
It is dried after wet the second filter paper, the second substrate are fixing, i.e. by the first substrate, with described in water-wet the
One filter paper and described pending film, with the second filter paper of water-wet, the second substrate fixing after be dried；
Respectively by described second substrate, described second filter paper and described pending membrance separation；By described first lining
The end, it is placed in solvent with described first filter paper of water-wet and described pending film, dissolves described first
Filter paper；It is dried after described pending film is taken out with described first substrate；By described pending film and institute
State the first substrate to separate；Compound transparent electricity conductive film can be prepared；This compound transparent electricity conductive film is
Metal nanometer line-silicon-containing nano granule-conductive sheet carbon simple substance membrane, metal nanometer line can be had by it
Effect dispersion, constructs complete conductive network with less metal nanometer line, to save transparent conductive film
Cost.Wherein, primary mixed solution is the most scattered silicon-containing nano particle solution, joins
In the most scattered metal nanometer line solution, obtained mixed solution；Pending mixed solution be by
The most scattered conductive sheet carbon simple substance solution, joins in the most scattered described primary mixed solution, institute
The mixed solution obtained；Pending film is the most scattered described pending mixed solution vacuum filtration,
Obtained film, common, it is attached on described first filter paper that vacuum filtration is used.
Such as, the preparation method of a kind of compound transparent electricity conductive film, it comprises the following steps.
By the most scattered silicon-containing nano particle solution, join in the most scattered metal nanometer line solution,
Obtain primary mixed solution；Such as, described solution can be regarded as suspension.Such as, silicon-containing nano
Grain solution be 0.3 to 1.0mg/mL, such as, silicon-containing nano particle solution is 0.3mg/mL, 0.4mg/mL,
0.5mg/mL, 0.6mg/mL, 0.7mg/mL, 0.8mg/mL, 0.9mg/mL or 1.0mg/mL；Preferably
, silicon-containing nano particle solution is 0.5mg/mL.And for example, metal nanometer line solution is 1 to 4mg/mL,
Such as, metal nanometer line solution be 1mg/mL, 1.4mg/mL, 1.9mg/mL, 2.6mg/mL, 3mg/mL,
3.5mg/mL, 3.9mg/mL or 4mg/mL；Preferably, metal nanometer line solution is 2mg/mL.Such as,
Silicon-containing nano particle solution is silicon-containing nano granule ethanol solution；Preferably, silicon-containing nano granule
Solution is silicon-containing nano granule aqueous solution；And for example, metal nanometer line solution is the anhydrous second of metal nanometer line
Alcoholic solution；Preferably, metal nanometer line solution is metal nanometer line aqueous solution.Preferably, described water
For pure water；Such as, described water is distilled water.Preferably, by molten for the most scattered silicon-containing nano granule
Before liquid joins the most scattered metal nanometer line solution, also metal nanometer line is carried out, centrifugal
After, ultrasonic disperse is in water.Such as, described metal nanometer line includes metal simple-substance nano wire and/or gold
Belong to alloy nano-wire；Such as, metal simple-substance nano wire includes nanowires of gold, nano silver wire, ferrum nanometer
Line, palladium nanometer wire, copper nano-wire, nickel nano wire and/or Pt nanowires；Preferably, metal simple-substance is received
Rice noodle is nano silver wire；And for example, metal alloy nanowires includes billon nano wire, silver alloy nanometer
Line, ferroalloy nano wire, palladium alloy nanowires, copper alloy nano wire, nickel alloy nano wire and/or platinum
Alloy nano-wire；Preferably, metal alloy nanowires is silver alloy nanowires.And/or, described siliceous
Nano-particle includes nano level silicon grain, silica dioxide granule, silicon-carbide particle and/or silicon nitride
Grain；Preferably, described silicon-containing nano granule is silicon grain.It should be noted that below portion is real
As a example by executing example employing nano silver wire and nano silicon particles, but the invention is not restricted to nano silver wire and receive with silicon
Rice grain.Preferably, described metal nanometer line is 8:1～1:1 with the mass ratio of described silicon-containing nano granule；
Such as, the mass ratio of described metal nanometer line and described silicon-containing nano granule be 8:1,7:1,6:1,5:1,
4:1,3:1,2:1 or 1:1；And for example, nano silver wire is 8:1～1:1 with the mass ratio of nano silicon particles；
Preferably, nano silver wire is 4:1 with the mass ratio of nano silicon particles.
By the most scattered conductive sheet carbon simple substance solution, join the most scattered described primary mixed solution
In, obtain pending mixed solution；Such as, described conductive sheet carbon simple substance solution can be regarded as suspendible
Liquid.And for example, described conductive sheet carbon simple substance solution is 0.5 to 3mg/g；Such as, described conductive sheet
Carbon simple substance solution is 0.5mg/g, 0.8mg/g, 1.2mg/g, 2.5mg/g or 3mg/g, it is preferred that
Described conductive sheet carbon simple substance solution is 1mg/g.Such as, described conductive sheet carbon simple substance includes Graphene
Or graphite flake；Such as, conductive sheet carbon simple substance solution is Graphene or graphite flake solution, it is preferred that
Conductive sheet carbon simple substance solution is Graphene or graphite flake aqueous solution；Preferably, described water is pure water；
Such as, described water is distilled water.Such as, described metal nanometer line and described conductive sheet carbon simple substance
Mass ratio is 12:1～6:1；Such as, described metal nanometer line and the matter of described conductive sheet carbon simple substance
Amount ratio is 12:1,11:1,10:1,9:1,8:1,7.5:1,7:1 or 6:1；Such as, silver nanoparticle
Line is 12:1～6:1 with the mass ratio of Graphene；Preferably, nano silver wire and the mass ratio of Graphene
Example is 8:1.
By the most scattered described pending mixed solution vacuum filtration, obtain pending film and attachment thereof
First filter paper；Preferably, employing dissolves in the filter paper of organic solvent as described first filter paper；Preferably
, described first filter paper is aqueous filter paper.Such as, described first filter paper is cellulose mixture filter paper.
Preferably, the aperture of described cellulose mixture filter paper is that 0.20 μm is to 0.25 μm；Such as, described mixed
The aperture of condensating fiber element filter paper is 0.22 μm or 0.23 μm.
By the first substrate, with the first filter paper described in water-wet and described pending film, with water-wet
It is dried after second filter paper, the second substrate are fixing；Preferably, the nano wire face of described pending film is the most right
Described first substrate, in other words, the nano wire face of described pending film is just to described first filter paper, institute
State the first filter paper and the first substrate contacts.Preferably, described second filter paper is nylon filters.Such as,
Described second filter paper at least covers described pending film；Preferably, the shape, big of described second filter paper
Little and described pending film is identical.
Respectively by described second substrate, described second filter paper and described pending membrance separation；By described
One substrate, it is placed in solvent with described first filter paper of water-wet and described pending film, dissolves described
First filter paper；Such as, solvent is organic solvent, and such as, solvent is acetone or its solution.Wherein,
Nano silver wire/nano silicon particles/last sucking filtration of Graphene mixed solution is at the first filter paper, with the first filter paper
There is the strongest combination, even being peeled off when moistening, also resulting in nano silver wire/silicon
Rupturing of nano-particle/Graphene sucking filtration film.So needing last organic solvent to be dissolved.Therefore
First filter paper selects to be spontaneously wet out by water the aqueous phase filter membrane being dissolved by an organic solvent, as mixed cellulose ester is filtered
Film etc..
It is dried after described pending film is taken out with described first substrate；Such as, solvent is volatile
Solvent.Preferably, natural drying after described pending film being taken out with described first substrate.
Described pending film is separated with described first substrate；Such as, drip above described pending film
Add the acrylate being mixed with light trigger, make acrylate that nano silver wire thin film, ultraviolet are completely covered
After solidification, described pending film is separated with described first substrate.And for example, above described pending film
Cover silicone rubber, after heating cure, described pending film is separated with described first substrate.
Preferably, described preparation method comprises the following steps: by the most scattered nano silicon particles aqueous solution,
Join in the most scattered nano silver wire aqueous solution, obtain primary mixed solution, wherein, nano silver wire
It is 8:1～1:1 with the mass ratio of nano silicon particles；By the most scattered graphene aqueous solution, join and divide
In the described primary mixed solution dissipated, obtain pending mixed solution, wherein, nano silver wire and graphite
The mass ratio of alkene is 12:1～6:1；By the most scattered described pending mixed solution vacuum filtration,
To pending film and the first filter paper of attachment thereof, wherein, described first filter paper is cellulose mixture filter paper；
Described first filter paper water-wet, by the first filter paper, the use of the first substrate, pending film and attachment thereof
Being dried after second filter paper of water-wet, the second substrate are fixing, wherein, described second filter paper is nylon filter
Paper, the nano wire face of described pending film is just to described first substrate；First by described second substrate and institute
State the second filter paper to separate, then by described second filter paper and described pending membrance separation；By described first
Substrate, it is placed in organic solvent with described first filter paper of water-wet and described pending film, dissolves institute
State the first filter paper；Natural drying after described pending film is taken out with described first substrate；Treat described
Process film to separate with described first substrate.
One preferable example is that described preparation method comprises the following steps: by the most scattered 0.5mg/mL
Nano silicon particles aqueous solution, joins in the most scattered 2mg/mL nano silver wire aqueous solution, obtains primary
Mixed solution, wherein, nano silver wire is 4:1 with the mass ratio of nano silicon particles；By the most scattered 1mg/g
Graphene aqueous solution, joins in the most scattered described primary mixed solution, obtains pending mixing molten
Liquid, wherein, nano silver wire is 8:1 with the mass ratio of Graphene；By the most scattered described pending mixed
Close solution for vacuum sucking filtration, obtain the first filter paper of pending film and attachment thereof, wherein, described mixing fibre
The aperture of dimension element filter paper is 0.22 μm；Described first filter paper water-wet, by the first substrate, pending
Film and the first filter paper of attachment thereof, with the second filter paper of water-wet, the second substrate fixing after be dried, its
In, described second filter paper is nylon filters, and the nano wire face of described pending film is just to described first lining
The end；First described second substrate is separated with described second filter paper, then by described second filter paper with described
Pending membrance separation；By pending with described for described first filter paper of described first substrate, use water-wet
Film is placed in acetone soln, dissolves described first filter paper；By described pending film and described first substrate
Natural drying after taking-up；Described pending film is separated with described first substrate.Preferably, described general
Described pending film separates with described first substrate, comprises the following steps: above described pending film
Dropping has been mixed with the acrylate of light trigger, makes acrylate that nano silver wire thin film is completely covered, purple
After outer solidification, described pending film is separated with described first substrate；Or, it is preferred that described by institute
State pending film to separate with described first substrate, comprise the following steps: cover above described pending film
Lid silicone rubber, separates described pending film with described first substrate after heating cure.So prepare
Compound transparent electricity conductive film, it is possible to substrate strong bonded.
Another embodiment of the present invention is as follows: a kind of compound transparent electricity conductive film, it includes metal nano
Line, silicon-containing nano granule and conductive sheet carbon simple substance, i.e. metal nanometer line-silicon-containing nano granule-conduction
Lamellar carbon simple substance membrane；Wherein, each described metal nanometer line constitutes described compound transparent electricity conductive film
Conductive network；Some described silicon-containing nano granules are attracted to each described metal by intermolecular force and receive
Around rice noodle, it is used for disperseing each described metal nanometer line；Described conductive sheet carbon simple substance is used for conducting electricity
Connect each described metal nanometer line.Preferably, described metal nanometer line is nano silver wire, described siliceous
Nano-particle is nano silicon particles, and described conductive sheet carbon simple substance includes Graphene or graphite flake.So
Compound transparent electricity conductive film, it is possible to dispersion effective to metal nanometer line, with less metal nanometer line
Construct complete conductive network, to save the cost of transparent conductive film.
Such as, this compound transparent electricity conductive film includes nano silver wire, nano silicon particles and Graphene, i.e.
Nano silver wire-nano silicon particles-graphene film, wherein, nano silver wire constitutes the conductive network of thin film；
Nano silicon particles plays peptizaiton, as in figure 2 it is shown, at Van der Waals force (i.e. intermolecular force)
It is attracted under effect around nano silver wire, is effectively improved the dispersion of nano silver wire；Graphene plays bridge
Beam effect, as it is shown on figure 3, by each other not in contact with nano silver wire couple, reduce electron transmission gesture
Build.Wherein, nano silicon particles can use SiO2, SiC, SiN replace；And/or, nano silver wire can use it
He replaces, such as copper nano-wire, nickel nano wire, corronil nano wire etc. by metal or alloy nano wire；
And/or, Graphene can replace with graphite flake or other conductive materials with laminated structure；So, adopt
Nano silver wire is disperseed, to have the graphite of the laminated structure of electric conductivity with nonconducting nano silicon particles
Alkene supplements the incomplete conductive network that nano silver wire is formed；Without adding the surfactants such as PVP,
Without sintering process, do not apply organic tack coat, do not affect electronics conduction and the transmitance of thin film,
Flexible substrate all can be prepared with the transparent conductive film on inflexibility substrate.
Preparation method described in connected applications any embodiment, it is preferred that described compound transparent electricity conductive film,
Preparation method described in any embodiment is used to prepare.
Continue with as a example by nano silver wire, nano silicon particles, Graphene, to the silver that the present invention relates to
The preparation method of the compound transparent electricity conductive film of nano wire-nano silicon particles-Graphene illustrates.
1, the surface of material processes.
With acetone, nano silver wire is carried out, is repeatedly centrifuged, when infrared spectrum shows nano silver wire table
After face has not had the group of the surfactants such as PVP, ultrasonic disperse is stand-by in distilled water.This enforcement
In example, the draw ratio of nano silver wire does not limits, putting down of the mean diameter nano silver wire to be less than of nano silicon particles
All diameters.Such as, the average diameter of nano silver wire is 100 nanometers, the mean diameter of nano silicon particles
It is 80 nanometers, and the maximum particle diameter of nano silicon particles is less than 100 nanometers.
2, the preparation of nano silver wire-nano silicon particles-Graphene mixed solution.
After will be dispersed in the ultrasonic 30min of the nano silicon particles in ethanol, it is slowly dropped to the most scattered
In nano silver wire aqueous solution or ethanol solution, magnetic agitation 10-20min, treat after ultrasonic 5-10min
With.Wherein the mass ratio of nano silver wire and nano silicon particles is between 8:1～1:1.Then will disperse
The mixed solution that the aqueous solution of good Graphene is slowly added dropwise to above-mentioned nano silver wire and nano silicon particles
In, stir 5-10min, ultrasonic 5-10min.Wherein nano silver wire exists with the mass ratio of Graphene
Between 12:1～6:1.
Such as, the ethanol solution of the nano silicon particles of the most scattered 0.5mg/mL is added drop-wise to
In the nano silver wire aqueous solution of scattered 2mg/mL or ethanol solution, magnetic agitation 10-20min,
After ultrasonic 5-10min stand-by.Wherein nano silver wire is 4:1 with the mass ratio of nano silicon particles.Then
The graphene aqueous solution of the most scattered 1mg/g is dropped to above-mentioned nano silver wire and nano silicon particles
In mixed solution, stir 5-10min, ultrasonic 5-10min.Wherein nano silver wire and the matter of Graphene
Amount ratio is 8:1.
3, the preparation of nano silver wire-nano silicon particles-graphene film.
After uniform for the mixed solution ultrasonic disperse of above-mentioned nano silver wire/nano silicon particles/Graphene,
The method using vacuum filtration, sucking filtration film forming, wherein filter paper used be diameter 50mm, aperture be 0.22
The water system filter paper 1 of μm, such as cellulose mixture filter paper.
Then being placed on a sheet glass by gained filter membrane, distilled water moistening, just to glass, is used in nano wire face.
An ordinary filter paper 2 that can be dissolved in water is covered above filter membrane, such as nylon filters, after distilled water moistening,
Place another sheet glass thereon, form sandwich structure, with binder clip, it is fixed up and down, be placed in
In temperature vacuum drying oven below 120 DEG C.Wherein, sheet glass can be with metal substrate such as copper sheet, plastics
Substrate such as PET replaces.Or, " sandwich structure " that binder clip is fixing is placed in less than 120 DEG C
Vacuum drying oven in, at available 120 DEG C, the mode of pressurization replaces.Such as, it is forced into 100kpa.
It is drawn off after being completely dried, takes off binder clip, separate two sheets, slowly take filter paper 2 off,
With the filter paper 1 on distilled water moistening bottom glass plate, it is placed in acetone soln immersion 15-30min, treats
After filter paper dissolves, taking-up, natural drying, obtain the nesa coating being attached on substrate.
The acrylate being mixed with light trigger is dripped above the nesa coating being attached on substrate,
Ultraviolet light irradiates a period of time, such as 30s or 35s etc., with cured acrylate；Then by
The polyacrylate of solidification separates with substrate, i.e. can obtain the nano silver wire-silicon being attached on acrylate
The compound transparent electricity conductive film of nano-particle-Graphene；Or, this step is mixed with the third of light trigger
Olefin(e) acid ester can replace with the silicone rubber being mixed with coupling agent, treats that silicone rubber is solid at the vacuum drying oven of 60-100 DEG C
Change.
Such as, drip above the nesa coating being attached on substrate and be mixed with the propylene of light trigger
Acid esters, makes acrylate that nano silver wire thin film is completely covered.Light trigger used is that phenyl is double
(2,4,6-trimethylbenzoyl) phosphine oxide, acrylate is 2-ethylhexyl acrylate, light
Initiator is 1:100 with the ratio of acrylate monomer, and ultraviolet irradiation 30s, by cured polypropylene
Acid esters separates with substrate, i.e. can obtain the nano silver wire-nano silicon particles-stone being attached on acrylate
The compound transparent electricity conductive film of ink alkene.The ultraviolet time is too short, and acrylate can be made not exclusively to be polymerized,
Affect the cementability of acrylate and nano silver wire；Ultraviolet overlong time can make the acrylic acid after polymerization
Ester yellowish, the impact transparency, such as, it is set according to the size of filter paper 1 the ultraviolet time.And for example,
The acrylate being mixed with light trigger in this step can substitute with double-component DOW CORNING 184 silicone rubber,
The vacuum drying oven of 60-100 DEG C treats that silicone rubber solidifies.
So, the dispersity of nano silver wire can be effectively improved, construct completely with less nano silver wire
Conductive network, save transparent conductive film cost, improve the transmitance of thin film, heat conductivility,
Reduce the thermal coefficient of expansion of thin film, make be improved the service life of thin film.Such as, nano silicon particles
Having good heat conductivility, thermal conductivity is 191W/mK, is commonly used for conductive filler material, silicon grain
Introducing can improve the heat conductivility of thin film.Argent thermal coefficient of expansion at room temperature is at 19.5 μ
M/ (m DEG C) left and right, the thermal coefficient of expansion under silicon room temperature is in 2.5 μm/(m DEG C) left and right, the introducing of silicon grain
The thermal coefficient of expansion of thin film can be reduced, make be improved the service life of thin film.It addition, system of the present invention
Standby transparent conductive film and substrate, substrate have more preferable adhesion.
It is embodied as remaking to the present invention as a example by Graphene by nano silver wire, nano silicon particles below
Further description, but it is understood that, these examples be equally applicable to other metal nanometer lines,
Compound transparent electricity conductive film of silicon-containing nano granule and conductive sheet carbon simple substance and preparation method thereof.
Embodiment 1
Acetone is added to the nano silver wire being dispersed in aqueous solution or organic solution, is centrifuged the most extremely
Infrared spectrum display nano silver wire surface has not had the group of the surfactants such as PVP, and ultrasonic disperse exists
In distilled water stand-by.
Nano silicon particles is dispersed in distilled water, after ultrasonic 30min, is slowly added dropwise to being dispersed with silver
In the aqueous solution of nano wire, stir 5min, ultrasonic 5min；Such as, with 1 or every five seconds for example per second
The speed of 1, drops to be dispersed with the aqueous solution of nano silver wire by the most scattered nano silicon particles aqueous solution
In.
Then, in above-mentioned mixed solution, it is slowly added dropwise the aqueous solution being dispersed with Graphene, such as, with
1 or the speed of every five seconds for example 1 per second, drop to above-mentioned by the aqueous solution of the most scattered Graphene
In mixed solution；Then 5min, ultrasonic 10min are stirred；Wherein nano silver wire, nano silicon particles,
The mass ratio of Graphene is 12:2:1.
Above-mentioned mixed solution ultrasonic disperse is uniform, and vacuum filtration film forming, wherein filter paper used is mixing
Cellulosic filter paper.By gained filter membrane, be placed on a glass plate, wherein, nano wire face just to glass plate,
After distilled water moistening, above filter membrane, cover another sizable filter paper, after distilled water moistening,
Place another sheet glass thereon, be fixed with binder clip, be placed in the vacuum drying oven of 90 DEG C.1 is little
Take out time after, take off binder clip, separate two sheets, slowly take blank filter paper off, use distilled water
After moistening residue filter paper, it is placed in acetone soln immersion, after 15min, takes out, natural drying,
I.e. obtain adhering to the nesa coating of nano silver wire-nano silicon particles-Graphene on the glass sheet.
Embodiment 2
Acetone is added to the nano silver wire being dispersed in aqueous solution or organic solution, is centrifuged the most extremely
Infrared spectrum display nano silver wire surface has not had the group of the surfactants such as PVP, and ultrasonic disperse exists
In distilled water stand-by.Nano silicon particles is dispersed in distilled water, after ultrasonic 30min, is slowly added dropwise
To the aqueous solution being dispersed with nano silver wire, stir 5min, ultrasonic 5min；To above-mentioned mixed solution
In be slowly added dropwise the aqueous solution being dispersed with Graphene, stir 5min, ultrasonic 10min, wherein silver is received
Rice noodle, nano silicon particles, the mass ratio of Graphene are 12:6:1.By above-mentioned mixed solution ultrasonic disperse
Uniformly, vacuum filtration film forming, filter paper used is cellulose mixture filter paper.By gained filter membrane, it is placed in one
On copper sheet, wherein, nano wire face is just to copper sheet, after distilled water moistening, covers another above filter membrane
One sizable filter paper, after distilled water moistening, places a glass plate thereon, will with binder clip
It is fixed, and is placed in the vacuum drying oven of 90 DEG C, takes out after 1 hour, takes off binder clip, separates two panels glass
Glass sheet, slowly takes blank filter paper off, after distilled water moistening residue filter paper, is placed on acetone soln
Middle immersion, after 15min, takes out, natural drying, i.e. obtains the nano silver wire-silicon being attached on copper sheet
Nano-particle-graphene transparent conductive film.
Embodiment 3
Acetone is added to the nano silver wire being dispersed in aqueous solution or organic solution, is centrifuged the most extremely
Infrared spectrum display nano silver wire surface has not had the group of the surfactants such as PVP, and ultrasonic disperse exists
In distilled water stand-by.Nano silicon particles is dispersed in distilled water, after ultrasonic 30min, is slowly added dropwise
To the aqueous solution being dispersed with nano silver wire, stir 5min, ultrasonic 5min；In above-mentioned mixed solution
Be slowly added dropwise the aqueous solution being dispersed with Graphene, stir 5min, ultrasonic 10min, wherein nano silver wire,
Nano silicon particles, the mass ratio of Graphene are 12:2:1.Above-mentioned mixed solution ultrasonic disperse is uniform,
Vacuum filtration film forming, filter paper used is cellulose mixture filter paper.By gained filter membrane, it is placed in a PET base
On plate, wherein nano wire face is just to PET sheet, after distilled water moistening, covers another above filter membrane
Sizable filter paper, after distilled water moistening, places a PET sheet, thereon with binder clip by it
Fixing, it is placed in the vacuum drying oven of 90 DEG C, takes out after 1 hour, take off binder clip, separate two sheet glass
Sheet, slowly takes blank filter paper off, after distilled water moistening residue filter paper, is placed in acetone soln
Soak, after 15min, take out, natural drying, i.e. obtain the nano silver wire that is attached on pet substrate-
Nano silicon particles-graphene transparent conductive film.
Embodiment 4
Acetone is added to the nano silver wire being dispersed in aqueous solution or organic solution, is centrifuged the most extremely
Infrared spectrum display nano silver wire surface has not had the group of the surfactants such as PVP, and ultrasonic disperse exists
In distilled water stand-by.Nano silicon particles is dispersed in distilled water, after ultrasonic 30min, is slowly added dropwise
To the aqueous solution being dispersed with nano silver wire, stir 5min, ultrasonic 5min；To above-mentioned mixed solution
In be slowly added dropwise the aqueous solution being dispersed with Graphene, stir 10min, ultrasonic 10min, wherein silver is received
Rice noodle, nano silicon particles, the mass ratio of Graphene are 6:2:1.By equal for above-mentioned mixed solution ultrasonic disperse
Even, vacuum filtration film forming, filter paper used is cellulose mixture filter paper.By gained filter membrane, face down,
It is placed on a glass plate, and with after distilled water moistening, above filter membrane, covers a sizable filter paper,
And with after distilled water moistening, cover a sheet glass suitable with foregoing glass chip size thereon, by length
After tail folder is fixed, it is placed in the vacuum drying oven of 90 DEG C, is drawn off after 1.5h hour, take off length
Tail presss from both sides, and separates two sheets, slowly takes blank filter paper off, with on distilled water moistening bottom glass plate
After remaining filter paper, it is placed in acetone soln immersion 15min, after filter paper dissolves, takes out, from
The most dried, above thin film, drip the acrylate being mixed with light trigger, after ultraviolet irradiation 30s,
Cured polyacrylate is peeled off from glass substrate, i.e. can obtain being attached on acrylate
The flexible composite transparent conductive film of nano silver wire-nano silicon particles-Graphene.
Embodiment 5
Acetone is added to the nano silver wire being dispersed in aqueous solution or organic solution, is centrifuged the most extremely
Infrared spectrum display nano silver wire surface has not had the group of the surfactants such as PVP, and ultrasonic disperse exists
In distilled water stand-by.Nano silicon particles is dispersed in distilled water, after ultrasonic 30min, is slowly added dropwise
To the aqueous solution being dispersed with nano silver wire, stir 5min, ultrasonic 5min；In above-mentioned mixed solution
Be slowly added dropwise the aqueous solution being dispersed with Graphene, stir 5min, ultrasonic 10min, wherein nano silver wire,
Nano silicon particles, the mass ratio of Graphene are 9:3:1.Above-mentioned mixed solution ultrasonic disperse is uniform, very
Empty sucking filtration film forming, filter paper used is cellulose mixture filter paper.By gained filter membrane, face down, it is placed in
On one glass plate, and with after distilled water moistening, above filter membrane, cover a sizable filter paper, and
After distilled water moistening, cover a sheet glass suitable with foregoing glass chip size thereon, form three
Mingzhi's structure, and be fixed with binder clip, it is placed in the vacuum drying oven of 120 DEG C, is taken after 1 hour
Go out, take off binder clip, separate two sheets, slowly take blank filter paper off, at the bottom of distilled water moistening
On layer glass plate after remaining filter paper, it is placed in acetone soln immersion 15min, treats that filter paper dissolves
After, take out, after natural drying, above thin film, drip the silicone rubber being mixed with coupling agent, 100 DEG C
After placing 30min in vacuum drying oven, cured silicone rubber is peeled off from glass substrate,
Flexible composite transparent conductive thin to the nano silver wire-nano silicon particles-Graphene being attached on silicone rubber
Film.
After tested, each compound transparent electricity conductive film obtained by above-described embodiment, ensureing metal nano
Realize the effective dispersion to metal nanometer line while line high conductivity, and it has preferably knot with substrate
Make a concerted effort, can be effectively improved the dispersity of metal nanometer line, with less with substrate strong bonded
Metal nanometer line constructs complete conductive network, thus saves the cost of transparent conductive film, improves thoroughly
The transmitance of bright conductive film, heat conductivility, reduce the thermal coefficient of expansion of transparent conductive film, thus
Improve the service life of transparent conductive film, related data is as shown in the table.
| Conductive film | Square resistance | Transmitance | Heat conductivility | Thermal coefficient of expansion |
| Embodiment 1 | 86.7Ω | 88.3% | 0.34W/mK | 29μm/(m℃) |
| Embodiment 2 | 88.1Ω | 89.6% | 0.28W/mK | 18μm/(m℃) |
| Embodiment 3 | 86.0Ω | 88.1% | 0.31W/mK | 25μm/(m℃) |
| Embodiment 4 | 85.8Ω | 87.9% | 0.40W/mK | 30μm/(m℃) |
| Embodiment 5 | 83.3Ω | 87.7% | 0.51W/mK | 21μm/(m℃) |
Further, embodiments of the invention also include, each technical characteristic of the various embodiments described above, phase
Compound transparent electricity conductive film based on nano silver wire that combination is formed mutually and preparation method thereof, in flexible liner
The end, all can prepare with the transparent conductive film on inflexibility substrate, flexible substrate such as polyacrylate, silicon
Rubber etc., inflexibility substrate such as glass etc..This compound transparent electricity conductive film can be used as flexible transparent electrode,
At solaode, touch screen, electroluminescent display, Electronic Paper, liquid crystal display, plasma
The photoelectric field extensive application such as display, electromagnetic shielding material.
It should be noted that the description of the present invention and accompanying drawing thereof give the most real of the present invention
Execute example, but, the present invention can be realized by many different forms, however it is not limited to this specification
Described embodiment, these embodiments are not as the extra restriction to present invention, it is provided that these
The purpose of embodiment is to make the understanding to the disclosure more thorough comprehensively.Further, above-mentioned
Each technical characteristic continues to be mutually combined, and forms various embodiments the most enumerated above, is accordingly to be regarded as this
Speak frankly the scope that bright secretary carries；Further, for those of ordinary skills, can basis
Described above is improved or is converted, and all these modifications and variations all should belong to the appended power of the present invention
The protection domain that profit requires.
Claims (13)
1. the preparation method of a compound transparent electricity conductive film, it is characterised in that including:
By the most scattered silicon-containing nano particle solution, join in the most scattered metal nanometer line solution,
Obtain primary mixed solution；
By the most scattered conductive sheet carbon simple substance solution, join the most scattered described primary mixed solution
In, obtain pending mixed solution；
By the most scattered described pending mixed solution vacuum filtration, obtain pending film and attachment thereof
First filter paper；
Described first filter paper water-wet, by the first filter paper of the first substrate, pending film and attachment thereof,
It is dried after fixing with the second filter paper of water-wet, the second substrate；
First described second substrate is separated with described second filter paper, then by described second filter paper with described
Pending membrance separation；
By described first substrate, it is placed in solvent with described first filter paper of water-wet and described pending film
In, dissolve described first filter paper；
It is dried after described pending film is taken out with described first substrate；
Described pending film is separated with described first substrate, obtains described compound transparent electricity conductive film.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that
Before the most scattered silicon-containing nano particle solution is joined the most scattered metal nanometer line solution, the most right
Metal nanometer line is carried out, and after being centrifuged, ultrasonic disperse is in water.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that
Described metal nanometer line includes metal simple-substance nano wire and/or metal alloy nanowires.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that
Described silicon-containing nano granule include nano level silicon grain, silica dioxide granule, silicon-carbide particle and/or
Silicon nitride particle.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that
Described conductive sheet carbon simple substance includes Graphene or graphite flake.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that
Described water is pure water.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that
Including:
By the most scattered nano silicon particles aqueous solution, join in the most scattered nano silver wire aqueous solution,
Obtaining primary mixed solution, wherein, nano silver wire is 8:1～1:1 with the mass ratio of nano silicon particles；
By the most scattered graphene aqueous solution, join in the most scattered described primary mixed solution,
To pending mixed solution, wherein, nano silver wire is 12:1～6:1 with the mass ratio of Graphene；
By the most scattered described pending mixed solution vacuum filtration, obtain pending film and attachment thereof
First filter paper, wherein, described first filter paper is cellulose mixture filter paper；
Described first filter paper water-wet, by the first filter paper of the first substrate, pending film and attachment thereof,
Being dried after fixing with the second filter paper of water-wet, the second substrate, wherein, described second filter paper is nylon
Filter paper, the nano wire face of described pending film is just to described first substrate；
First described second substrate is separated with described second filter paper, then by described second filter paper with described
Pending membrance separation；
By described first substrate, with described first filter paper of water-wet and described pending film, it is placed in
In machine solvent, dissolve described first filter paper；
Natural drying after described pending film is taken out with described first substrate；
Described pending film is separated with described first substrate, obtains described compound transparent electricity conductive film.
The preparation method of compound transparent electricity conductive film the most according to claim 7, it is characterised in that
Comprise the following steps:
By the most scattered 0.5mg/mL nano silicon particles aqueous solution, join the most scattered 2mg/mL silver
In nano wire aqueous solution, obtain primary mixed solution, wherein, nano silver wire and the matter of nano silicon particles
Amount ratio is 4:1；
By the most scattered 1mg/g graphene aqueous solution, join the most scattered described primary mixed solution
In, obtain pending mixed solution, wherein, nano silver wire is 8:1 with the mass ratio of Graphene；
By the most scattered described pending mixed solution vacuum filtration, obtain pending film and attachment thereof
First filter paper, wherein, the aperture of described cellulose mixture filter paper is 0.22 μm；
Described first filter paper water-wet, by the first filter paper of the first substrate, pending film and attachment thereof,
Being dried after fixing with the second filter paper of water-wet, the second substrate, wherein, described second filter paper is nylon
Filter paper, the nano wire face of described pending film is just to described first substrate；
First described second substrate is separated with described second filter paper, then by described second filter paper with described
Pending membrance separation；
By described first substrate, with described first filter paper of water-wet and described pending film, it is placed in third
In ketone solution, dissolve described first filter paper；
Natural drying after described pending film is taken out with described first substrate；
Described pending film is separated with described first substrate, obtains described compound transparent electricity conductive film.
The preparation method of compound transparent electricity conductive film the most according to claim 8, it is characterised in that
Described described pending film is separated with described first substrate, including: on described pending film, drip
Add the acrylate being mixed with light trigger, make acrylate that nano silver wire thin film, ultraviolet are completely covered
After solidification, described pending film is separated with described first substrate, obtains being attached on acrylate
Described compound transparent electricity conductive film.
The preparation method of compound transparent electricity conductive film the most according to claim 8, it is characterised in that
Described described pending film is separated with described first substrate, comprise the following steps: described pending
Cover silicone rubber above film, after heating cure, described pending film is separated with described first substrate,
To the described compound transparent electricity conductive film being attached on silicone rubber.
11. 1 kinds of compound transparent electricity conductive films, it is characterised in that include metal nanometer line, siliceous receive
Rice grain and conductive sheet carbon simple substance；Wherein,
Each described metal nanometer line constitutes the conductive network of described compound transparent electricity conductive film；
Some described silicon-containing nano granules are adsorbed respectively in the surrounding of each described metal nanometer line, are used for disperseing
Each described metal nanometer line is set；
Described conductive sheet carbon simple substance is used for being conductively connected each described metal nanometer line.
12. according to compound transparent electricity conductive film described in claim 11, it is characterised in that it uses
The preparation method of compound transparent electricity conductive film as described in claim 1 to 10 any one, prepares described
Compound transparent electricity conductive film.
13. according to compound transparent electricity conductive film described in claim 12, it is characterised in that described gold
Genus nano wire is nano silver wire, and described silicon-containing nano granule is nano silicon particles, described conductive sheet carbon
Simple substance includes Graphene or graphite flake.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5221088B2 (en) * | 2007-09-12 | 2013-06-26 | 株式会社クラレ | Transparent conductive film and method for producing the same |
| CN103219066A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Flexible conductive thin film compositing two-dimensional graphene and one-dimensional nanowire and preparation method thereof |
| CN103794265A (en) * | 2014-02-26 | 2014-05-14 | 无锡格菲电子薄膜科技有限公司 | Composite material of graphene and nanowires and preparation method thereof |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5221088B2 (en) * | 2007-09-12 | 2013-06-26 | 株式会社クラレ | Transparent conductive film and method for producing the same |
| CN103219066A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Flexible conductive thin film compositing two-dimensional graphene and one-dimensional nanowire and preparation method thereof |
| CN103794265A (en) * | 2014-02-26 | 2014-05-14 | 无锡格菲电子薄膜科技有限公司 | Composite material of graphene and nanowires and preparation method thereof |
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