CN106920583B - A kind of transparent conductive film and its preparation method and application - Google Patents
A kind of transparent conductive film and its preparation method and application Download PDFInfo
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- CN106920583B CN106920583B CN201710073791.4A CN201710073791A CN106920583B CN 106920583 B CN106920583 B CN 106920583B CN 201710073791 A CN201710073791 A CN 201710073791A CN 106920583 B CN106920583 B CN 106920583B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The present invention relates to field of nanometer material technology, disclose a kind of transparent conductive film and its preparation method and application, transparent conductive film provided by the invention includes pretreating substrates and the conductive material that is deposited on the pretreating substrates, the static contact angle of the tightly packed formation irregular grid pattern of conductive material, the pretreating substrates is 10 70 °.Assembling of the preparation method of transparent conductive film provided by the invention using the fusion and conductive material of default template of the surface with the convex array being distributed in the way of forming irregular pattern and pretreated base material co- controlling micro-bubble in bubble template, finally forms irregular grid pattern on pretreating substrates.What scheme provided by the invention may be implemented that conductive particle on pretreating substrates arranges accurately controls, can be with large-area applications, and irregular grid pattern can be periodically Chong Die to avoid being generated with LCD black matrix, so that Moire fringe will not be generated.
Description
Technical field
The present invention relates to field of nanometer material technology, and in particular, to a kind of transparent conductive film and its preparation method and application.
Background technology
Transparent conductive film is one kind having high transparency in visible-range, and possesses the membrane electrode of satisfactory electrical conductivity
Material.Transparent conductive film has been widely used for the fields such as touch screen, display and photoelectric device at present, with consumer electronics
Product such as smart mobile phone, tablet computer and ultrabook are popularized, and demand of the market to high-performance electrode is huge.
Currently used transparent conductive film is ITO electro-conductive glass, and ITO electro-conductive glass has higher light transmittance and conductivity.
But rare earth metal indium is arrived involved in ITO electro-conductive glass preparation process, and the multiple working procedures such as exposure, development and etching is needed
Realize that patterning, factors above determine that ITO electro-conductive glass is at high price and environmental pollution is serious；In addition, ITO conduction glass
Glass matter is crisp frangible, and can not large area prepare, limit its scope of application.For novel transparent conductive film, as carbon nanotube,
The exploitation of graphene, metal nanometer line etc. accelerates the diversified process of transparent conductive film.But these novel transparent conductive films exist
On light transmittance and electric conductivity compared with commercial ITO electro-conductive glass, the shortcomings of there are property is unstable and contact resistance is high, and it is difficult
To realize patterning.
Currently, the method for preparing electrically conducting transparent grid includes print process, direct-reduction process and is assembled by templating, printing
Method and direct-reduction process can be in the metal grills of specific region formation rule, while reducing cost, it is suppressed that pollution；By template
The pattern electrode of controllable precise can be prepared by changing assembling, have the advantages of inexpensive, rapid and low stain.But existing side
Transparent conductive metal grid made from method is typically all the network of rule, and Moire fringe phenomenon is constrained again with rule mesh
The application of the transparent electrode of lattice structure.Moire fringe phenomenon is caused by being repeated cyclically folded structures, is shown as light and dark
Striated structure, especially when the transparent electrode with regular grid structure is Chong Die with LCD black matrix, Moire fringe phenomenon will be tight
The display quality of display is reduced again.
Therefore, a kind of simple for process controllable there is an urgent need for developing, can large-area applications transparent conductive film preparation method, and
Transparent conductive film obtained does not generate Moire fringe phenomenon in application process.
Invention content
The purpose of the present invention is the applications of the transparent conductive film provided for the prior art there are Moire fringe phenomenon, and makes
Standby complex process, can not large-area applications defect, provide a kind of transparent conductive film, a kind of preparation method of transparent conductive film,
By the application of transparent conductive film and transparent conductive film that this method is prepared.
To achieve the goals above, the present invention provides a kind of transparent conductive film, and the transparent conductive film includes pretreatment base
Material and the conductive material being deposited on the pretreating substrates, the tightly packed formation irregular grid pattern of conductive material,
The static contact angle of the pretreating substrates is 10-70 °.
The present invention provides a kind of preparation methods of transparent conductive film, and this method comprises the following steps：
1) preparing surface has the default template of convex array, and the convex array is by the side for forming irregular pattern
Formula is distributed；
2) bubble with interlayer using the default template and pretreating substrates as lower substrate and upper substrate composition
Generation structure；
3) the conductive material assembles concentration containing micro-bubble is filled in the bubble formation system, and passes through micro-bubble
Fusion, formed patterning array of bubbles；
4) solvent in the conductive material assembles concentration is removed, conductive material patterns bubble battle array on pretreating substrates
It is classified as template assemblies, tightly packed formation irregular grid pattern；
5) default template is detached with pretreating substrates；
Wherein, the static contact angle of the pretreating substrates is 10-70 °.
The present invention also provides the transparent conductive films being prepared by the above method.
The present invention also provides application of the above-mentioned transparent conductive film in touch screen and display.
Through the above technical solutions, having the convex array being distributed in the way of forming irregular pattern using surface
Assembling of the fusion and conductive material of default template and pretreated base material co- controlling micro-bubble in bubble template,
Irregular grid pattern is finally formed on pretreating substrates.Scheme provided by the invention may be implemented conductive on pretreating substrates
Particle arrangement accurately controls, can be with large-area applications, and irregular grid pattern can generate week to avoid with LCD black matrix
Phase property is overlapped, to generate Moire fringe.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the signal of the silicon chip of cylindrical-array of the surface with the distribution of irregular hexagon in the embodiment of the present invention 1
Figure；
Fig. 2 is the distribution of conductive material on the pretreating substrates of the transparent conductive film S-1 obtained in the embodiment of the present invention 1
Schematic diagram；
Fig. 3 is the signal of the silicon chip of cylindrical-array of the surface with the distribution of irregular hexagon in the embodiment of the present invention 2
Figure；
Fig. 4 is the signal of the silicon chip of cylindrical-array of the surface with the distribution of irregular hexagon in the embodiment of the present invention 3
Figure.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of transparent conductive film, and the transparent conductive film includes pretreating substrates and is deposited on the pre- place
Manage base material on conductive material, the tightly packed formation irregular grid pattern of conductive material, the pretreating substrates it is quiet
State contact angle is 10-70 °.
In the prior art, the clean dustless base material of the requirement due to transparent conductive film to light transmittance, selection, and this field
Or the static contact angle of conventional use of clean dustless base material is less than 10 ° or is more than 70 °, for example, conventional use of dry
The static contact angle of net quartz plate is generally less than 10 °, and the static contact angle of PDMS films is generally higher than 70 °.
In the present invention, static contact angle refers to the drop in horizontal substrate, the angle of gas-liquid interface and liquid-solid boundary.
The static contact angle is measured by Graph analysis method, is measured at ambient temperature by contact-angle measurement instrument.
The static contact angle of a preferred embodiment of the invention, the pretreating substrates is 55-65 °.This kind
Preferred embodiment has more suitable wettability, and then is more advantageous to the formation of irregular grid pattern, in addition, this is excellent
The static contact angle of choosing, which is more advantageous to, realizes the tightly packed of conductive particle, is more advantageous to the electric conductivity for increasing transparent conductive film.
In the present invention, to the pretreating substrates, there is no particular limitation, as long as pretreating substrates have above-mentioned static state
Contact angle, it is preferable that the pretreating substrates are colourless, and are had close to 100% in visible light 400-800nm
Light transmittance, i.e., it is almost nil to the absorption of light.
The preparation method of a preferred embodiment of the invention, the pretreating substrates includes：Optionally, by
One base material is contacted with silane coupling agent, then carries out plasma treatment or ultraviolet lighting processing, wherein the first base material is selected from
Rigid high transparency material or flexible transparent film, it is preferable that the first base material be selected from quartz plate, sheet glass, PMMA film,
At least one of PET film and PDMS films.
A preferred embodiment of the invention, when the first base material is selected from quartz plate and/or sheet glass, institute
The preparation method for stating pretreating substrates includes：The first base material is contacted with silane coupling agent, then carries out plasma treatment or purple
Outer photo-irradiation treatment；When the first base material is selected from least one of PMMA film, PET film and PDMS films, the pretreatment base
The preparation method of material includes：Plasma treatment or ultraviolet lighting processing are carried out to the first base material.
The present invention is preferably selected from perfluor siloxanes, dichloro silicon to optional wider range of the type of the silane coupling agent
At least one of oxygen alkane, vinylsiloxane, aminopropyl siloxane and dimethyl silicone polymer, further preferably perfluor silicon
Oxygen alkane and dichloro siloxanes.
There is no particular limitation for actual conditions of the present invention to the plasma treatment, the item of the preferably described plasma treatment
Part includes：Time is 5-60s, power 40-100W, it is further preferred that the time is 10-15s, power 70-90W.
There is no particular limitation to actual conditions that the ultraviolet lighting is handled by the present invention, the preferably described ultraviolet lighting processing
Condition include：Light application time is 12-20h, power 300-500W, it is further preferred that the time is 14-16h, power is
400-450W。
In the present invention, the average grain diameter of the conductive material can be 10-100nm, preferably 30-50nm.
It should be noted that the metal grill pattern (metal wire) that the prior art provides is mostly embedded, and in the present invention
The conductive material is attached on the pretreating substrates.
According to the present invention, the type of the conductive material is not particularly limited, can suitably be selected as needed, preferably
Ground, the conductive particle include nano particle, at least one of nano wire and polymer.
The nano particle can be monometallic nano particle, or alloy nanoparticle, the nano wire can be with
For monometallic nano wire, or alloy nano-wire.
A preferred embodiment of the invention, the nano particle and nano wire be each independently selected from platinum, gold,
At least one of silver, copper, palladium, cobalt and nickel.
Under preferable case, the monometallic nano particle is platinum, gold, silver, copper, palladium, cobalt or nano nickel particles；The alloy
Nano particle, which is selected from, contains silver alloy, for example, Ag-Cu alloy or silver-palladium alloy.
Under preferable case, the nano wire is selected from nano silver wire, copper nano-wire, Pt nanowires, nickel nano wire, gold-nickel and receives
At least one of rice noodles and gold-Pt nanowires.
Under preferable case, the polymer is selected from polythiophene (PT), Polyglycolic acid fibre (PEDOT), polyaniline
(PANI) and at least one of polyphenylacetylene (PPV).
There is no particular limitation to the irregular grid pattern by the present invention, as long as the irregular grid pattern makes
Moire fringe phenomenon is not generated when bright conductive film is applied in touch screen and display, it is preferable that the irregular grid
Pattern can be irregular polygon, it is further preferred that the irregular grid pattern is selected from irregular quadrilateral and not
At least one of regular hexagonal.
There is no particular limitation for line width of the present invention to irregular polygon, preferably 0.5-10 μm, further preferably
2-5μm.Using this kind of preferred embodiment, the invisible metal wire of naked eyes can be obtained, high conductivity is provided simultaneously with and (is less than 100
Ω/sq) and high transparency (being more than 80%).
In the present invention, the line width refers to the line thickness of irregular polygon, i.e. the lines of irregular polygon are wide
Range is spent between 0.5-10 μm.
The line width is measured by atomic force microscope (AFM) or scanning electron microscope (SEM).
The resolution of transparent conductive film provided by the invention is not more than 5 μm, and light transmittance is more than 85%, and sheet resistivity is less than 100
Ω/sq.What conductive material was arranged on transparent conductive film realization pretreating substrates provided by the invention accurately controls, can be with large area
Using, and irregular grid pattern can be periodically Chong Die to avoid being generated with LCD black matrix, to which More's item will not be generated
Line.
The present invention also provides a kind of preparation methods of transparent conductive film, and this method comprises the following steps：
1) preparing surface has the default template of convex array, and the convex array is by the side for forming irregular pattern
Formula is distributed；
2) bubble with interlayer using the default template and pretreating substrates as lower substrate and upper substrate composition
Generation structure；
3) the conductive material assembles concentration containing micro-bubble is filled in the bubble formation system, and passes through micro-bubble
Fusion, formed patterning array of bubbles；
4) solvent in the conductive material assembles concentration is removed, conductive material patterns bubble battle array on pretreating substrates
Template assemblies are classified as, tightly packed continuous arrangement forms irregular grid pattern；
5) default template is detached with pretreating substrates；
Wherein, the static contact angle of the pretreating substrates is 10-70 °.
According to the present invention, in the bubble formation system the step of conductive material assembles concentration of the filling containing micro-bubble
In, after micro-bubble can be generated in conductive material assembles concentration, the conductive material assembles concentration containing micro-bubble is filled into
It, can also be after conductive material assembles concentration be filled into the bubble formation system, then in conduction in the bubble formation system
Micro-bubble is formed in material assembles concentration.
According to the present invention, the production method of the micro-bubble in the conductive material assembles concentration containing micro-bubble does not have
It is special to limit, specifically, it can be generated by physical method or chemical method.
Can be various methods commonly used in the art as the physical method for generating the micro-bubble, including but
It is not limited by interruption injection air and forms micro-bubble, such as can be fluid focus method or supercritical ultrasonics technology.
In the present invention, fluid focus method is formed by small gas by injecting separate air into conductive material assembles concentration
Bubble.This method is well known in the art, and for its actual conditions, there is no particular limitation, and item well known in the art may be used
Part.In addition, supercritical ultrasonics technology is also well known in the art, for its actual conditions, also there is no particular limitation, and ability may be used
Condition well known to domain.
As the chemical method for generating the micro-bubble, there is no particular limitation, can be the change that can generate gas
Learn reaction method.In the case of preferred, the chemical method is selected from hydrogen peroxide, the catalytic decomposition of carbamide peroxide, boron hydrogen
The acidolysis reaction of the hydrolysis of compound, the acidolysis reaction of carbonate and bicarbonate it is one or more.Wherein, boron hydride
Hydrolysis be in acid condition borohydride hydrolytic generate hydrogen reaction, the boron hydride can be selected from boron hydrogen
Change one or more in sodium, potassium borohydride, magnesium borohydride and calcium borohydride, preferably sodium borohydride；The carbonate can be with
For sodium carbonate and/or potassium carbonate, the bicarbonate can be sodium bicarbonate and/or saleratus.
Can be selected from metal nanoparticle, amount as the catalyst that above-mentioned hydrogen peroxide, carbamide peroxide are catalytically decomposed
It is one or more in sub- point (such as carbon, cadmium quantum dot) and bromide ion.
In addition, for the ease of the speed that control is reacted, the formation irregular grid pattern more stablized, it is preferable that described
Chemical reaction is the chemical reaction that solid and liquid reactions generate gas, is specifically as follows sodium borohydride and is generated with acid solution reaction
Hydrogen, hydrogen peroxide or carbamide peroxide decompose under catalyst (such as Nano silver grain) effect and generate oxygen.
According to the present invention, in the bubble formation system the step of conductive material assembles concentration of the filling containing micro-bubble
In, if physical method is selected to generate micro-bubble, after generating micro-bubble preferably in the conductive material assembles concentration, will contain
There is the conductive material assembles concentration of micro-bubble to be filled into the bubble formation system；If chemical method is selected to generate small gas
Bubble, preferably after the conductive material assembles concentration is filled into the bubble formation system, then is chemically reacted and is led described
Micro-bubble is formed in electric material assembles concentration.
According to the present invention, the conductive material assembles concentration includes conductive material and solvent.
A preferred embodiment of the invention, the conductive material are evenly dispersed and non-agglomerated.
In order to preferably complete the assembling of conductive material, the content of the conductive material in the conductive material assembles concentration is
0.1-60 weight %, preferably 0.1-30 weight %, more preferably 8-15 weight %.
The selection of the conductive material is as described above, and details are not described herein.
Solvent of the present invention can be various solvents commonly used in the art, it is preferable that the solvent be selected from
Water, methanol, ethyl alcohol, acetone, ethylene glycol, isopropanol, diethylene glycol (DEG), ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, second two
Alcohol phenylate, ethylene glycol benzyl oxide, furfuryl alcohol, diethylene glycol methyl ether, diethylene glycol ether, butyl carbitol, triethylene glycol methyl ether, diacetone alcohol,
Tridecanol, tetradecyl alchohol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, dimethylbenzene, bicyclohexyl, ring
At least one of hexane, n-butanol, butanone, repefral and D-sorbite.
According to the present invention, ruptured in fusion process to avoid bubble to reduce surface tension, it is preferable that described
Conductive material assembles concentration includes conductive material, solvent and surfactant.
Can be various surfactants commonly used in the art as the surfactant, it is preferable that described
Surfactant is selected from anion surfactant, cationic surfactant, zwitterionic surfactant and nonionic
At least one of surfactant.Specifically, the anion surfactant can be selected from sodium dodecyl benzenylsulfonate,
It is one or more in lauryl sodium sulfate and stearic acid；The cationic surfactant can be quaternary ammonium compound；Institute
It can be selected from amino acid type amphoteric ionic surface active agent, betaine type amphoteric ion surface to state zwitterionic surfactant
It is one or more in activating agent, polyacrylamide and lecithin；The nonionic surfactant can be selected from aliphatic acid
Sorb is smooth, one or more in fatty glyceride and polysorbate.
According to the present invention, the bubble formation system is closed or open.The bubble formation system closed and
Opening refers to that the side of the bubble formation system is closed or open.When the bubble formation system is closed, liquid
It cannot be volatilized by the side of bubble formation system；When the bubble formation system is open, liquid can pass through bubble
It volatilizees the side of generation structure.Specifically, in order to ensure to remove the dissolving agent process in the conductive material assembles concentration it is smooth into
Row, in this step, the bubble formation system are preferably open.
According to method provided by the invention, the preparation of the pretreating substrates and property are as described above, no longer superfluous herein
It states.
According to the present invention, there is the default template of convex array to be obtained by being etched on the second base material on the surface
It arrives, second base material is selected from least one of silicon chip, aluminium flake, copper sheet, PDMS films, PET film, PMMA film and PVMS films.
According to the present invention, there is no particular limitation for the generation type of default template of the surface with convex array,
It can be selected according to specific second substrate material.When the second base material is silicon chip, aluminium flake or copper sheet, ability can be taken
The etching technique that domain routinely uses prepares irregular grid pattern；When the second base material is PDMS films, PET film, PMMA film or PVMS
When film, soft etching technology may be used and carry out preparing irregular grid pattern.This may be used in the step of specific etching and condition
The conventional use of mode in field carries out, and forms the required convex array being distributed in the way of forming irregular pattern i.e.
Can, details are not described herein.
According to the present invention, to the distribution of the convex array, there is no particular limitation, as long as irregular.It needs
It is noted that the method that provides through the invention preset convex array is presented in template irregular pattern with it is obtained at
The irregular grid pattern having in product transparent conductive film is almost the same, and the convex array in the default template is constituted not
The selection of regular pattern is as described in irregular grid pattern in transparent conductive film above, and details are not described herein.
In the case of preferred, the convex array is columnar arrays, it is further preferred that the convex array is by column
Irregular quadrilateral is formed at intervals in shape array and/or the mode of irregular hexagon is distributed, it is further preferred that the column
Shape array is selected from least one of cylindrical-array, cylindroid array and polyhedron pillar array structure.
The present invention has the surface size of the convex array of the default template of convex array not special
It limits, the patterning array of bubbles can be formed.The single pattern dimension that columnar arrays are formed in pattern structure
When smaller, can the column only be set on each vertex of pattern, the patterning array of bubbles can be precisely formed；And
When the single pattern dimension that columnar arrays are formed in pattern structure is larger, the column, difference figure only are set on the vertex of pattern
Bubble in case, which is easy to happen fusion, causes patterning array of bubbles that cannot be precisely formed, at this point, can be arranged on same side
Multiple columns, and control the distance of adjacent column, you can form good patterning array of bubbles.
In the present invention, the radius of the column is defined as the maximum distance of the lateral surface of the centre distance column of column, the column
Spacing be defined as the distance between the centers of circle of two adjacent columns.According to the present invention, in order to form more regular patterning
Array of bubbles, 5-50 μm of the height of the column in the columnar arrays structure, preferably 15-25 μm, the spacing of the column is 5-60 μ
The radius of m, preferably 10-60 μm, the column in the columnar arrays structure are 1-20 μm, preferably 5-10 μm.Also, the present invention
Inventor find that the spacing of the column is not more than 60 μm by further investigation, the height of the column between 20-40 μm,
Patterning array of bubbles can be more accurately controlled.
In the present invention, the default template and pretreating substrates have interlayer respectively as lower substrate and upper substrate composition
The thickness of interlayer of bubble formation system can be selected according to the height of column, for example, can be 15-25 μm.
According to the present invention, in order to be stably formed patterning array of bubbles, the conductive material group containing micro-bubble
The volume fraction for filling bubble in liquid is 40-90%, preferably 60-90%, more preferably 75-90%.The ruler of the micro-bubble
It is very little that there is no particular limitation, in the case of preferred, a diameter of 0.1-150 μm of the micro-bubble, and preferably 10-100 μm, more
Preferably 10-60 μm.Here, the volume fraction of bubble refers to 25 in the conductive material assembles concentration containing micro-bubble
DEG C, under conditions of 1 standard atmospheric pressure, gas volume accounts for the ratio of gas and the total volume of conductive material assembles concentration.It is micro- generating
In the physical method of minute bubbles, gas volume here refers to the gas volume injected by physical method；It is small generating
In the chemical method of bubble, gas volume here refers to the gas volume that chemical reaction generates.Calculate the volume point of bubble
When number, it is assumed that solubility of the gas in conductive material assembles concentration is zero.
In the present invention, the fusion of the bubble, the alternatively referred to as growth and differentiation of bubble, refer to bubble due to size not
One, interface curvature radius is different, and internal pressure is different, internal gas different solubility, what minute bubbles were gradually merged by air pocket
Process.
According to the present invention, the speed of the fusion process of the micro-bubble can be controlled by temperature, and specific temperature can
With appropriate selection as needed, it is specifically as follows 5-50 DEG C, preferably 10-30 DEG C.It, can be with as the specific method for adjusting temperature
Environment temperature is reduced using mixture of ice and water.
In the present invention, the process of the solvent in the removal conductive material assembles concentration refers to that solvent passes through volatilization
Etc. modes, the process that solvent is removed from bubble formation system.The conductive material is on pretreating substrates to pattern bubble
Array is the volatilization that template assemblies refer to solvent, the mistake that conductive material is precipitated and deposits and assemble between bubble and bubble
Journey.The speed of the assembling process can be controlled by temperature, specific temperature, can suitably be selected, specifically may be used as needed
Think 5-50 DEG C, preferably 20-30 DEG C.
In the present invention, it is preferred to further include being post-processed to the substance that step 4) obtains, after further preferably described
Processing is included annealing or is impregnated using sodium chloride and/or hydrochloric acid solution.
There is no particular limitation for condition of the present invention to the annealing, and the annealing is to promote melting between nano particle
Change, improve electric conductivity, therefore, the condition of annealing can be selected according to ordinary skill in the art means, preferably described to move back
The temperature of fire is 150-200 DEG C, and the time of annealing is 1-2h.
There is no particular limitation to the condition impregnated using sodium chloride and/or hydrochloric acid solution by the present invention, uses chlorination
Sodium and/or hydrochloric acid solution are impregnated also for the thawing promoted between nano particle, are improved electric conductivity and are therefore used sodium chloride
And/or hydrochloric acid solution immersion can be selected according to ordinary skill in the art means, the preferably described sodium chloride and/or hydrochloric acid
A concentration of 0.04-0.1mol/L of solution, preferably 0.05-0.06 mol/L, time 1-10min, preferably 2-4min.
The present invention also provides the transparent conductive films being prepared by the above method.
The present invention also provides application of the above-mentioned transparent conductive film in touch screen and display.
The present invention will be described in detail by way of examples below.
Embodiment 1
(1) preparation of pretreating substrates
Dichloro siloxanes is coated on sheet glass (static contact angle is 3 °), then carries out air plasma processing, processing
Condition includes：Time is 10s, power 90W, obtains the pretreated glass piece that static contact angle is 60 °；
(2) preparation of template is preset
The silicon chip for choosing 5cm × 5cm is gone out in the surface etch of silicon chip and is not advised using the method for conventional mask photoetching
The then cylindrical-array (as shown in Figure 1) of hexagonal array, there are three cylinders, wherein cylinder on each side of irregular hexagon
The cylindrical radius of array is 5 μm, and for the spacing between the adjacent column center of circle in 20-60 μ ms, the height of cylinder is 20 μm；
(3) preparation of array of bubbles is patterned
Prepare the ethanol solution of hydrogen peroxide, a concentration of 21mg/mL of hydrogen peroxide；Using neopelex,
It is 8%, dodecyl benzene sulfonic acid that the silver nano-grain that grain size is about 48nm prepares silver nano-grain mass content with deionized water
The silver nano-grain assembles concentration that the mass content of sodium is 8%；Then micro syringe is used to draw the ethyl alcohol of 25 μ l hydrogen peroxide
Solution is added drop-wise at the silicon chip surface center of cylindrical-array of the surface with irregular hexagonal array, and ethyl alcohol is allowed to be evaporated completely naturally
Finish, obtains to surface and be evenly distributed with the silicon chip of hydrogen peroxide；Separately the prepared silver nano-grain assembles concentrations of 50 μ l is taken to be added drop-wise to
Pretreated glass on piece is stated, the silicon chip lid that surface is evenly distributed with hydrogen peroxide is then had into silver nano-grain group to above-mentioned dropwise addition
The bubble formation system overturning for filling the pretreated glass on piece of liquid, and being formed, makes pretreated glass piece have positioned at surface
The top of the silicon chip of the cylindrical-array of irregular hexagonal array, silver nano-grain is reacted with hydrogen peroxide chemistry generates a large amount of gas
Bubble (volume fraction of bubble be 84%, a diameter of 10-40 μm), the steaming of the water between the fusion and bubble of promoting the circulation of qi of going forward side by side bubble
Hair, silver nano-grain are assembled in bubble intersection.Surface is had to the silicon chip of the cylindrical-array of irregular hexagonal array
It is detached with pretreated glass piece, i.e., obtains the irregular hexagonal array of silver nano-grain assembling on pretreated glass piece surface
Network (line width is about 2 μm)；
(4) it post-processes
There is the pretreated glass piece of the silver nano-grain of irregular hexagonal array to anneal surface, annealing conditions
Including：The temperature of annealing is 200 DEG C, and the time of annealing is 2h, obtains transparent conductive film S-1, the pretreatment of transparent conductive film S-1
On base material, conductive material distribution is as shown in Figure 2.
Embodiment 2
(1) preparation of pretreating substrates
Perfluor siloxanes is coated on sheet glass (static contact angle is 3 °), then carries out air plasma processing, processing
Condition includes：Time is 15s, power 70W, obtains the pretreated glass piece that static contact angle is 65 °；
(2) preparation of template is preset
The silicon chip for choosing 5cm × 5cm is gone out in the surface etch of silicon chip and is not advised using the method for conventional mask photoetching
The then cylindrical-array (as shown in Figure 3) of hexagonal array, there are three cylinders, wherein cylinder on each side of irregular hexagon
The cylindrical radius of array is 5 μm, and the spacing between the adjacent column center of circle is 20-60 μm, and the height of cylinder is 20 μm；
(3) preparation of array of bubbles is patterned
Prepare the ethanol solution of carbamide peroxide, a concentration of 30mg/mL of carbamide peroxide；Use dodecyl phenyl-hydrogen-sulfate
It is 15%, detergent alkylate that the silver nano-grain and deionized water that sodium, grain size are about 48nm, which prepare silver nano-grain mass content,
The silver nano-grain assembles concentration that the mass content of sodium sulphate is 0.05%；Then micro syringe is used to draw 25 μ l hydrogen peroxide
The ethanol solution of urea be added drop-wise to surface with irregular hexagonal array cylindrical-array silicon chip surface center at, allow ethyl alcohol from
So volatilization finishes, and obtains to surface and is evenly distributed with the silicon chip of carbamide peroxide；It is another to take the prepared silver nano-grain assemblings of 50 μ l
Drop is added to above-mentioned pretreated glass on piece, then has the silicon chip lid that surface is evenly distributed with carbamide peroxide to above-mentioned dropwise addition
The pretreated glass on piece of silver nano-grain assembles concentration, and the bubble formation system overturning formed, make pretreated glass piece
There is the top of the silicon chip of the cylindrical-array of irregular hexagonal array, silver nano-grain and carbamide peroxide chemistry positioned at surface
Reaction generates a large amount of bubbles (volume fraction of bubble be 75%, a diameter of 20-50 μm), the fusion of promoting the circulation of qi of going forward side by side bubble and bubble
Between water evaporation, silver nano-grain assembled in bubble intersection.Surface is had to the circle of irregular hexagonal array
The silicon chip of column array is detached with pretreated glass piece, i.e., obtains the irregular of silver nano-grain assembling on pretreated glass piece surface
The network of hexagonal array (line width is about 5 μm)；
(4) it post-processes
There is the pretreated glass piece of the silver nano-grain of irregular hexagonal array to anneal surface, annealing conditions
Including：The temperature of annealing is 200 DEG C, and the time of annealing is 1.5h, obtains transparent conductive film S-2.
Embodiment 3
(1) preparation of pretreating substrates
Perfluor siloxanes is coated on sheet glass (static contact angle is 5 °), ultraviolet lighting processing is then carried out, handles item
Part includes：14h is irradiated under 400W, obtains the pretreated glass piece that static contact angle is 55 °；
(2) preparation of template is preset
The silicon chip for choosing 5cm × 5cm is gone out in the surface etch of silicon chip and is not advised using the method for conventional mask photoetching
The then cylindrical-array (as shown in Figure 4) of hexagonal array, there are three cylinders, wherein cylinder on each side of irregular hexagon
The cylindrical radius of array is 5 μm, and the spacing between the adjacent column center of circle is 20-60 μm, and the height of cylinder is 20 μm；
(3) preparation of array of bubbles is patterned
Prepare the ethanol solution of carbamide peroxide, a concentration of 30mg/mL of carbamide peroxide；Use dodecyl phenyl-hydrogen-sulfate
It is 15%, detergent alkylate that the silver nano-grain and deionized water that sodium, grain size are about 48nm, which prepare silver nano-grain mass content,
The silver nano-grain assembles concentration that the mass content of sodium sulphate is 0.05%；Then micro syringe is used to draw 25 μ l hydrogen peroxide
The ethanol solution of urea be added drop-wise to surface with irregular hexagonal array cylindrical-array silicon chip surface center at, allow ethyl alcohol from
So volatilization finishes, and obtains to surface and is evenly distributed with the silicon chip of carbamide peroxide；It is another to take the prepared silver nano-grain assemblings of 50 μ l
Drop is added to above-mentioned pretreated glass on piece, then has the silicon chip lid that surface is evenly distributed with carbamide peroxide to above-mentioned dropwise addition
The pretreated glass on piece of silver nano-grain assembles concentration, and the bubble formation system overturning formed, make pretreated glass piece
There is the top of the silicon chip of the cylindrical-array of irregular hexagonal array, silver nano-grain and carbamide peroxide chemistry positioned at surface
Reaction generates a large amount of bubbles (volume fraction of bubble be 75%, a diameter of 20-60 μm), the fusion of promoting the circulation of qi of going forward side by side bubble and bubble
Between water evaporation, silver nano-grain assembled in bubble intersection.Surface is had to the circle of irregular hexagonal array
The silicon chip of column array is detached with pretreated glass piece, i.e., obtains the irregular of silver nano-grain assembling on pretreated glass piece surface
The network of hexagonal array (line width is about 5 μm)；
(4) it post-processes
There is the pretreated glass piece of the silver nano-grain of irregular hexagonal array to anneal surface, annealing conditions
Including：The temperature of annealing is 150 DEG C, and the time of annealing is 2h, obtains transparent conductive film S-3.
Embodiment 4
(1) preparation of pretreating substrates
By PDMS films that thickness is 0.5mm, (static contact angle is 109 °, is purchased from Dowcoring (DOW CORNING) company, article No.
184) to carry out air plasma processing, time 60s, power 80W obtain the pretreatment PDMS that static contact angle is 60 °
Film；
(2) preparation of template is preset
The preparation method that template is preset with embodiment 3 is identical；
(3) preparation of array of bubbles is patterned
Prepare the ethanol solution of carbamide peroxide, a concentration of 21mg/mL of carbamide peroxide；Use dodecyl phenyl-hydrogen-sulfate
It is 15%, detergent alkylate that the silver nano-grain and deionized water that sodium, grain size are about 48nm, which prepare silver nano-grain mass content,
The silver nano-grain assembles concentration that the mass content of sodium sulphate is 0.05%；Then micro syringe is used to draw 25 μ l hydrogen peroxide
The ethanol solution of urea be added drop-wise to surface with irregular hexagonal array cylindrical-array silicon chip surface center at, allow ethyl alcohol from
So volatilization finishes, and obtains to surface and is evenly distributed with the silicon chip of carbamide peroxide；It is another to take the prepared silver nano-grain assemblings of 50 μ l
Drop is added on above-mentioned pretreatment PDMS films, then has the silicon chip lid that surface is evenly distributed with carbamide peroxide to above-mentioned dropwise addition
On the pretreatment PDMS films of silver nano-grain assembles concentration, and the bubble formation system overturning formed, make pretreatment PDMS films
There is the top of the silicon chip of the cylindrical-array of irregular hexagonal array, silver nano-grain and carbamide peroxide chemistry positioned at surface
Reaction generates a large amount of bubbles (volume fraction of bubble be 80%, a diameter of 20-60 μm), the fusion of promoting the circulation of qi of going forward side by side bubble and bubble
Between water evaporation, silver nano-grain assembled in bubble intersection.Surface is had to the circle of irregular hexagonal array
The silicon chip of column array and pretreatment PDMS UF membranes, i.e., obtain the irregular of silver nano-grain assembling in pretreatment PDMS film surfaces
The network of hexagonal array (line width is about 5 μm)；
(4) it post-processes
There is the pretreatment PDMS films of the silver nano-grain of irregular hexagonal array to be soaked in surface a concentration of
2min in the sodium-chloride water solution of 0.06mol/L obtains transparent conductive film S-4.
Embodiment 5
(1) preparation of pretreating substrates
It is identical as the preparation method of 4 pretreating substrates of embodiment；
(2) preparation of template is preset
The preparation method that template is preset with embodiment 1 is identical；
(3) preparation of array of bubbles is patterned
Prepare the ethanol solution of sodium borohydride, a concentration of 5mg/mL of sodium borohydride；Use concentrated hydrochloric acid, solid dodecyl
It is about 2 that the copper nano particles and deionized water that benzene sulfonic acid sodium salt, grain size are about 50nm, which prepare pH, and copper nano particles mass content is
2%, the copper nano particles assembles concentration that the mass content of neopelex is 15%；Then it is drawn using micro syringe
The ethanol solution of 15 μ l sodium borohydrides is added drop-wise to the silicon chip surface center of cylindrical-array of the surface with irregular hexagonal array
Place, allows ethyl alcohol to volatilize naturally and finishes, obtain to surface and be evenly distributed with the silicon chip of sodium borohydride；Separately take the prepared copper nanometers of 25 μ l
Particle assembling drop is added on above-mentioned pretreatment PDMS films, then surface is evenly distributed with to the silicon chip lid of sodium borohydride to above-mentioned
Dropwise addition has on the pretreatment PDMS films of copper nano particles assembles concentration, and the bubble formation system overturning formed, makes pretreatment
PDMS films are located at the top of the silicon chip of cylindrical-array of the surface with irregular hexagonal array, copper nano particles and sodium borohydride
Chemical reaction generates a large amount of bubbles (volume fraction of bubble be 80%, a diameter of 20-60 μm), the fusion of promoting the circulation of qi of going forward side by side bubble and
The evaporation of water between bubble, copper nano particles are assembled in bubble intersection.Surface had into irregular hexagonal array
Cylindrical-array silicon chip with pretreatment PDMS UF membranes, i.e., pretreatment PDMS film surfaces obtain copper nano particles assembling not
The network of regular hexagonal arrangement (line width is about 5 μm)；
(4) it post-processes
There is the pretreatment PDMS films of the copper nano particles of irregular hexagonal array to be soaked in surface a concentration of
2min in the sodium-chloride water solution of 0.06mol/L obtains transparent conductive film S-5.
Embodiment 6
(1) preparation of pretreating substrates
The PET film (static contact angle is 78 °, is purchased from toray, article No. T60S10H10) that thickness is 1mm is carried out
Air plasma processing, time 10s, power 60W obtain the pretreatment PET film that static contact angle is 60 °；
(2) preparation of template is preset
The quartz plate for choosing 5cm × 5cm is gone out using the method for conventional mask photoetching in the surface etch of quartz plate
The cylindrical-array (as shown in Figure 3) of irregular hexagonal array, on each side of irregular hexagon there are three cylinder, wherein
The cylindrical radius of cylindrical-array is 5 μm, and the spacing between the adjacent column center of circle is 20-60 μm, and the height of cylinder is 20 μm；
(3) preparation of array of bubbles is patterned
Prepare the ethanol solution of hydrogen peroxide, a concentration of 20.8mg/mL of hydrogen peroxide；Use dodecyl benzene sulfonic acid
It is 10%, detergent alkylate that the silver nano-grain and deionized water that sodium, grain size are about 48nm, which prepare silver nano-grain mass content,
The silver nano-grain assembles concentration that the mass content of sodium sulfonate is 10%；Then micro syringe is used to draw 25 μ l hydrogen peroxide
Ethanol solution is added drop-wise at the quartz plate centre of surface of cylindrical-array of the surface with irregular hexagonal array, makes ethyl alcohol natural
Volatilization finishes, and obtains to surface and is evenly distributed with the quartz plate of hydrogen peroxide；Separately take the prepared silver nano-grain assembles concentrations of 50 μ l
It is added drop-wise on above-mentioned pretreatment PET film, the quartz plate lid that surface is evenly distributed with hydrogen peroxide is then had into silver to above-mentioned dropwise addition
On the pretreatment PET film of nano particle assembles concentration, and the bubble formation system overturning formed, so that pretreatment PET film is located at
There is the top of the quartz plate of the cylindrical-array of irregular hexagonal array, silver nano-grain to be reacted with hydrogen peroxide chemistry on surface
A large amount of bubbles (volume fraction of bubble be 75%, a diameter of 20-60 μm) are generated, between the fusion and bubble of promoting the circulation of qi of going forward side by side bubble
Water evaporation, silver nano-grain assembled in bubble intersection.Surface is had to the cylindrical array of irregular hexagonal array
The quartz plate of row is detached with pretreatment PET film, i.e., obtains irregular six side of silver nano-grain assembling on pretreatment PET film surface
The network of shape arrangement (line width is about 3 μm)；
(4) it post-processes
There is the pretreatment PET film of the silver nano-grain of irregular hexagonal array to be soaked in surface a concentration of
2min in the HCl/water solution of 0.05mol/L, obtains transparent conductive film S-6.
Embodiment 7
(1) preparation of pretreating substrates
The PET film (static contact angle is 75 °, is purchased from toray, article No. T60S10H10) that thickness is 1mm is carried out
Air plasma processing, time 10s, power 60W obtain the pretreatment PET film that static contact angle is 60 °；
(2) preparation of template is preset
The silicon chip for choosing 5cm × 5cm is gone out in the surface etch of silicon chip and is not advised using the method for conventional mask photoetching
The then cylindrical-array (as shown in Figure 3) of hexagonal array, there are three cylinders, wherein cylinder on each side of irregular hexagon
The cylindrical radius of array is 5 μm, and the spacing between the adjacent column center of circle is 40-60 μm, and the height of cylinder is 40 μm；
(3) preparation of array of bubbles is patterned
Prepare the ethanol solution of hydrogen peroxide, a concentration of 20.8mg/mL of hydrogen peroxide；Use dodecyl benzene sulfonic acid
It is 15%, detergent alkylate that the silver nano-grain and deionized water that sodium, grain size are about 48nm, which prepare silver nano-grain mass content,
The silver nano-grain assembles concentration that the mass content of sodium sulfonate is 0.05%；Then micro syringe is used to draw 25 μ l hydrogen peroxide
Ethanol solution be added drop-wise at the silicon chip surface center of cylindrical-array of the surface with irregular hexagonal array, make ethyl alcohol natural
Volatilization finishes, and obtains to surface and is evenly distributed with the silicon chip of hydrogen peroxide；It is another to take the prepared silver nano-grain assembling drops of 50 μ l
It is added on above-mentioned pretreatment PET film, the silicon chip lid that surface is evenly distributed with hydrogen peroxide is then had into silver nanoparticle to above-mentioned dropwise addition
On the pretreatment PET film of particle assembles concentration, and the bubble formation system overturning formed, so that pretreatment PET film is located at surface
The top of the silicon chip of cylindrical-array with irregular hexagonal array, it is big that silver nano-grain reacts generation with hydrogen peroxide chemistry
Bubble (volume fraction of bubble be 80%, a diameter of 20-60 μm) is measured, the water between the fusion and bubble of promoting the circulation of qi of going forward side by side bubble
Evaporation, silver nano-grain are assembled in bubble intersection.Surface is had to the silicon of the cylindrical-array of irregular hexagonal array
Piece is detached with pretreatment PET film, i.e., the irregular hexagonal array of silver nano-grain assembling is obtained on pretreatment PET film surface
Network (line width is about 5 μm)；
(4) it post-processes
There is the pretreatment PET film of the silver nano-grain of irregular hexagonal array to be soaked in surface a concentration of
2min in the HCl/water solution of 0.05mol/L, obtains transparent conductive film S-7.
Comparative example 1
Transparent conductive film is prepared according to the method for embodiment 1, unlike, in step (2), go out in the surface etch of silicon chip
The cylindrical-arrays of (140 × 90 μm) of rectangle arrangement, there are four cylinder in rectangular long side, between the adjacent column center of circle between
Away from being 46.7 μm；For short side there are three cylinder, the spacing between the adjacent column center of circle is 45 μm, the wherein cylindrical radius of cylindrical-array
It it is 5 μm, the height of cylinder is 20 μm, and transparent conductive film D-1 is made.
Comparative example 2
According to the method for embodiment 1, the difference is that, in step (2), go out regular hexagonal arrangement in the surface etch of silicon chip
Cylindrical-array, there are three cylinders on each side of regular hexagonal, and the wherein cylindrical radius of cylindrical-array is 5 μm, adjacent
Spacing between the cylinder center of circle is 44 μm, and the height of cylinder is 20 μm, and transparent conductive film D-2 is made.
Test example 1
The performance of the embodiment 1-7 and comparative example 1-2 transparent conductive films provided is tested, include mainly light transmittance and
Sheet resistivity and when being applied in touch screen and display, if generate Moire fringe.
Light transmittance refers to：Through the percentage of the luminous flux and its incident flux of transparent or semitransparent body, by ultraviolet
Visible light instrument measures under 550nm wavelength conditions, and acquired results are listed in table 1.
Sheet resistivity refers to：Measurement with uniform thickness film resistor is measured at ambient temperature by quadrupole probe,
Acquired results are listed in table 1.
Transparent conductive film is combined with Rectangular grid (140 × 90 μm of the parameter) structure with commercial LCD pixel size
Body is subsequently placed on the light microscope with CCD (photoelectric coupled device), with center rotate 10 degree, make transparent conductive film and
Rectangular grid is at 10 degree of rotation angle.In a transmissive mode, with the pattern of CCD shooting superpositions, test result is listed in table 1.
Table 1
| Light transmittance, % | Sheet resistivity, Ω/sq | Whether Moire fringe is generated | |
| Embodiment 1 | 90 | 33 | It is no |
| Embodiment 2 | 89 | 25 | It is no |
| Embodiment 3 | 87 | 27 | It is no |
| Embodiment 4 | 87 | 35 | It is no |
| Embodiment 5 | 85 | 110 | It is no |
| Embodiment 6 | 88 | 45 | It is no |
| Embodiment 7 | 85 | 30 | It is no |
| Comparative example 1 | 90 | 41 | It is |
| Comparative example 2 | 89 | 36 | It is |
As can be seen from the above table, after the present invention has default template and the pretreatment of irregular grid pattern using surface
Base material co- controlling micro-bubble assembling in bubble template of fusion and conductive material, finally on pretreating substrates
Irregular grid pattern is formed, there is the default template of other irregular polygon latticed grid patterns by preparing, can locate in advance
It manages and forms irregular polygon lattice on base material, above-described embodiment is only using irregular hexagon as example, but the present invention is simultaneously
It is without being limited thereto.
What scheme provided by the invention may be implemented that conductive material on pretreating substrates arranges accurately controls, can be with large area
Using, and irregular grid pattern can be periodically Chong Die to avoid being generated with LCD black matrix, to which More's item will not be generated
Line.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (28)
1. a kind of transparent conductive film, which is characterized in that the transparent conductive film includes pretreating substrates and is deposited on the pre- place
Manage base material on conductive material, the tightly packed formation irregular grid pattern of conductive material, the pretreating substrates it is quiet
State contact angle is 10-70 °.
2. transparent conductive film according to claim 1, wherein the static contact angle of the pretreating substrates is 55-65 °.
3. transparent conductive film according to claim 1 or 2, wherein the preparation method of the pretreating substrates includes：Optionally
Ground contacts the first base material with silane coupling agent, then carries out plasma treatment or ultraviolet lighting processing, wherein described first
Base material is selected from least one of quartz plate, sheet glass, PMMA film, PET film and PDMS films.
4. transparent conductive film according to claim 1, wherein the conductive material includes nano particle, nano wire and gathers
Close at least one of object.
5. transparent conductive film according to claim 4, wherein the nano particle and nano wire are each independently selected from
At least one of platinum, gold, silver, copper, palladium, cobalt and nickel.
6. transparent conductive film according to claim 4, wherein the polymer be selected from polythiophene, Polyglycolic acid fibre,
At least one of polyaniline and polyphenylacetylene.
7. transparent conductive film according to claim 1, wherein the irregular grid pattern be selected from irregular quadrilateral and
At least one of irregular hexagon.
8. transparent conductive film according to claim 7, wherein the line width of the irregular quadrilateral and irregular hexagon
It is 0.5-10 μm.
9. a kind of preparation method of transparent conductive film, which is characterized in that this method comprises the following steps：
1) preparing surface, there is the default template of convex array, the convex array to divide in the way of forming irregular pattern
Cloth；
2) bubble formation with interlayer using the default template and pretreating substrates as lower substrate and upper substrate composition
System；
3) the conductive material assembles concentration containing micro-bubble, and melting by micro-bubble are filled in the bubble formation system
It closes, forms patterning array of bubbles；
4) solvent in the conductive material assembles concentration is removed, conductive material patterns array of bubbles on pretreating substrates and is
Template assemblies, tightly packed formation irregular grid pattern；
5) default template is detached with pretreating substrates；
Wherein, the static contact angle of the pretreating substrates is 10-70 °.
10. preparation method according to claim 9, wherein gas in the conductive material assembles concentration containing micro-bubble
The volume fraction of bubble be 40-90%, a diameter of 0.1-150 μm of the micro-bubble；The conduction material containing micro-bubble
Expect that assembles concentration is generated by physical method or chemical method.
11. preparation method according to claim 10, wherein the physical method is fluid focus method or supercritical ultrasonics technology.
12. preparation method according to claim 10, wherein the chemical method is that can generate the chemical reaction of gas
Method.
13. preparation method according to claim 12, wherein the chemical method is selected from hydrogen peroxide, hydrogen peroxide
The catalytic decomposition of urea, the hydrolysis of boron hydride, the acidolysis reaction of carbonate and bicarbonate acidolysis reaction one kind or
It is a variety of.
14. preparation method according to claim 9, wherein the conductive material assembles concentration include conductive material, solvent and
Surfactant.
15. preparation method according to claim 14, wherein the conductive material includes nano particle, nano wire and gathers
Close at least one of object；The solvent is selected from water, methanol, ethyl alcohol, acetone, ethylene glycol, isopropanol, diethylene glycol (DEG), ethylene glycol first
Ether, ethylene glycol ethyl ether, butyl glycol ether, ethylene glycol phenyl ether, ethylene glycol benzyl oxide, furfuryl alcohol, diethylene glycol methyl ether, diethylene glycol ether, two
Glycol butyl ether, triethylene glycol methyl ether, diacetone alcohol, tridecanol, tetradecyl alchohol, dioctyl phthalate, ethyl acetate, acetic acid fourth
In ester, cyclohexanone, dimethylbenzene, bicyclohexyl, hexamethylene, n-butanol, butanone, repefral and D-sorbite
It is at least one；The surfactant is selected from anion surfactant, cationic surfactant, amphoteric ion surface-active
At least one of agent and nonionic surfactant.
16. preparation method according to claim 15, wherein the nano particle and nano wire are each independently selected from
At least one of platinum, gold, silver, copper, palladium, cobalt and nickel, the polymer are selected from polythiophene, Polyglycolic acid fibre, polyaniline
At least one of with polyphenylacetylene.
17. according to the preparation method described in any one of claim 14-16, wherein in the conductive material assembles concentration
The content of conductive material is 0.1-60 weight %.
18. preparation method according to claim 9, wherein
The default template is obtained by being etched on the second base material, second base material be selected from silicon chip, aluminium flake, copper sheet,
At least one of PDMS films, PET film, PMMA film and PVMS films；
The static contact angle of the pretreating substrates is 55-65 °.
19. preparation method according to claim 9, wherein the preparation method of the pretreating substrates includes：Optionally,
The first base material is contacted with silane coupling agent, then carries out plasma treatment or ultraviolet lighting processing, wherein the first base material
Selected from least one of quartz plate, sheet glass, PMMA film, PET film and PDMS films.
20. preparation method according to claim 19, wherein
The silane coupling agent is selected from perfluor siloxanes, dichloro siloxanes, vinylsiloxane, aminopropyl siloxane and poly- diformazan
At least one of radical siloxane；
The condition of the plasma treatment includes：Time is 5-60s, power 40-100W；
The condition of ultraviolet lighting processing includes：Light application time is 12-20h, power 300-500W.
21. preparation method according to claim 9, wherein the convex array is columnar arrays.
22. preparation method according to claim 21, wherein the convex array is formed at intervals not by columnar arrays
Regular quadrilateral and/or the mode of irregular hexagon are distributed.
23. the preparation method according to claim 21 or 22, wherein the columnar arrays are selected from cylindrical-array, cylindroid
At least one of array and polyhedron pillar array structure.
24. the method according to claim 21 or 22, wherein the height of the column in the columnar arrays is 5-50 μm.
25. the method according to claim 21 or 22, wherein the spacing of the column in the columnar arrays is 5-60 μm.
26. the method according to claim 21 or 22, wherein the radius of the column in the columnar arrays is 1-20 μm.
27. the transparent conductive film that the method according to any one of claim 9-26 is prepared.
28. the transparent conductive film described in any one of claim 1-8 and claim 27 is in touch screen and display
Using.
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| CN102723126A (en) * | 2012-05-09 | 2012-10-10 | 崔铮 | Random-grid-based graphical transparent conductive thin film |
| KR101632346B1 (en) * | 2014-03-28 | 2016-06-21 | 금호전기주식회사 | Mesh type conductive film and method of fabricating the same |
| CN106079677A (en) * | 2016-06-14 | 2016-11-09 | 中国科学院化学研究所 | A kind of patterning Two-Dimensional Bubble array and its preparation method and application |
| CN106082118A (en) * | 2016-06-14 | 2016-11-09 | 中国科学院化学研究所 | A kind of method based on gas masterplate assemble nanometer material and goods thereof and application |
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| CN102723126A (en) * | 2012-05-09 | 2012-10-10 | 崔铮 | Random-grid-based graphical transparent conductive thin film |
| KR101632346B1 (en) * | 2014-03-28 | 2016-06-21 | 금호전기주식회사 | Mesh type conductive film and method of fabricating the same |
| CN106079677A (en) * | 2016-06-14 | 2016-11-09 | 中国科学院化学研究所 | A kind of patterning Two-Dimensional Bubble array and its preparation method and application |
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