CN106298083B - A kind of preparation method of flexible transparent electrode - Google Patents
A kind of preparation method of flexible transparent electrode Download PDFInfo
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- CN106298083B CN106298083B CN201610967375.4A CN201610967375A CN106298083B CN 106298083 B CN106298083 B CN 106298083B CN 201610967375 A CN201610967375 A CN 201610967375A CN 106298083 B CN106298083 B CN 106298083B
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
The invention provides a kind of preparation method of flexible transparent electrode, methods described mixes polymer, organic solvent and anhydrous alcohols solvent, prepares casting solution；Obtained casting solution is placed on substrate and forms liquid film, then the substrate for being covered with liquid film is positioned in air and solidified, forms the thin polymer film with polygonal hole structure；The deposited metal film on obtained thin polymer film, obtain the thin polymer film coated with metal film；Metal film is extracted by obtained metal film and the polymer thin UF membrane, and with substrate, obtains flexible transparent electrode.Flexible transparent electrode transparency prepared by methods described is high, conducts electricity very well, and the preparation method low raw-material cost, each step operation is easy, and technological process is simple, is advantageous to carry out industrialized production.
Description
Technical field
The invention belongs to field of photoelectric technology, is related to a kind of preparation method of electrode, more particularly to a kind of flexible and transparent electricity
The preparation method of pole.
Background technology
Flexible and transparent conductive electrode is various electronic devices, including touch-screen, display, thin-film solar cells etc. are important
Part.In field of photoelectric devices, the pass of upgrading has either all been arrived in terms of industry application or basic research
The key moment.Currently commercially, transparent conductive electrode typically uses metal oxide, such as tin indium oxide (ITO) film.However,
ITO is expensive, while lacks pliability, hardly possible stretching, improper to be applied to flexible transparent electrode.Metal mesh structure electrode has
The advantages that relatively low cost, excellent mechanical flexibility, higher transmitance and electric conductivity.Therefore, these years recently, based on gold
The transparency electrode research for belonging to mesh-structured starts to obtain paying close attention to for some scholars.
The size of metal grill and the width of line are two very important parameters for flexible transparent electrode, and its is direct
Have influence on the transparency and electric conductivity of electrode.The current method for preparing flexible transparent electrode metal grill mainly has ink-jet to beat
Print, certainly nano wire coating, cracking, crystal boundary photoetching etc..But there is high, the unsuitable large area production of preparation cost in these methods
Shortcoming.Therefore consider that researchers need to seek a kind of skill of simple and efficient from the cost of manufacture and efficiency of photoelectric device
Art means prepare metal mesh structure electrode, in favor of its popularization in photoelectric device industry.
The A of CN 105280840 disclose a kind of flexible and transparent click and preparation method thereof, methods described, by carrier
Coated polymer solution on substrate, form polymer film；The nano metal ink of comb mesh pattern is prepared on the polymer film,
Metal grate electrode is formed by the high temperature anneal；The side coating with metal grate electrode is saturating on the polymer film
Bright conducting resinl simultaneously dries sintering；Under the polymer film, metal grate electrode and electrically conducting transparent glue are peeled off from carrier substrate
Come, obtain corresponding flexible transparent electrode.While electrode flexibility is ensured, the high conductance for improving nesa coating
Rate, transmitance and buckle resistance energy.It is complicated but the electrode contains multilayer film, and nanogold is needed in preparation process
Belong to ink, cost of material is high, while need to be through repeatedly sintering, and power consumption is high, complex process.
The A of CN 105895197 disclose a kind of flexible and transparent silver grid combination electrode and preparation method thereof, the electrode knot
Structure is：A/ silver grid/elastic substrates.Wherein A can be conducting polymer (PEDOT:PSS), metal-oxide semiconductor (MOS) (ZnO)
And the binary complex of these materials, substrate are elastomers, such as polyethylene terephthalate (PET), polyimides
(PI), polyvinyl alcohol (PVA), polymethyl siloxane (PDMS), urethane acrylate (PUA) and hydrogel etc..Its making side
Method be by metal grill and A materials sequentially inkjet printing in elastomer substrate.Thus obtained transparency electrode is comprehensive
Can be excellent, it is low to be embodied in sheet resistance, and light transmittance is high, flexible.But inkjet printing methods equipment is complicated, plant maintenance is stranded
Difficulty, to ingredient requirement height, it is difficult to carry out industrialized production.
Therefore, study a kind of low raw-material cost, working condition is gentle, and technique is simple, and can industrialized production side electricity
Hinder small, the method for transparency high flexibility transparency electrode is particularly important.
The content of the invention
Transparent low for the flexible transparent electrode of prior art production, cost of material is high, complex manufacturing, is not suitable for work
The problem of industry metaplasia is produced, this application provides a kind of preparation method of flexible transparent electrode, methods described low raw-material cost are raw
Mild condition is produced, technique is simple, can be with industrialized production, and the electrode resistance per square produced is low and transparency is good.
To use following technical scheme up to this purpose, the present invention：
The invention provides a kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polymer, organic solvent and anhydrous alcohols solvent are mixed, prepares casting solution；
(2) casting solution that step (1) obtains is placed on substrate and forms liquid film, then the substrate for being covered with liquid film is placed
Solidified in air, form the thin polymer film with polygonal hole structure；
(3) the deposited metal film on the thin polymer film that step (2) obtains, obtaining deposition has the polymer thin of metal film
Film；
(4) metal film for obtaining step (3) and the polymer thin UF membrane, and extract metal film with substrate, are obtained
Flexible transparent electrode.
Step (2) described polygonal hole includes the equilateral or non-etc. lateral opening of quadrangle, pentagon or hexagon etc..
The preparation method prepares line width between porosity height and hole on the surface of polymer by breathing pattern method
Polygonal hole structure, according to the line width between its Kong Yukong as model, then deposited using film deposition techniques on its surface
Layer of metal film.During this, the curved surface in hole is advantageous to surface and the separation of interior metal film in deposition, can be formed
Complete metal mesh structure.
Currently preferred technical scheme is used as below, but not as the limitation of technical scheme provided by the invention, is passed through
Following technical scheme, it can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As the technical scheme of the present invention preferably, it is fine that step (1) polymer is selected from polyimides, polycaprolactone, nitrification
Dimension element, cellulose acetate, PLA, polymethyl methacrylate, polystyrene and the block comprising one of above-mentioned polymer are total to
Any one in polymers, more preferably polymethyl methacrylate.
Preferably, step (1) described organic solvent is any in dichloromethane, chloroform, carbon disulfide or acetone
It is a kind of or at least two combination, it is described combination typical case but non-limiting examples have：The combination of dichloromethane and chloroform, two
The combination of chloromethanes and carbon disulfide, the combination of dichloromethane and acetone, combination, the chloroform of chloroform and carbon disulfide
The combination or dichloromethane of combination, carbon disulfide and acetone with acetone, the combination of chloroform and acetone etc., further preferably
For chloroform.
Preferably, step (1) the anhydrous alcohols solvent is selected from methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol or different
Any one in butanol or at least two combination, the combination is typical but non-limiting examples have：The combination of methanol and ethanol,
The combination of ethanol and normal propyl alcohol, the combination of ethanol and isopropanol, the combination of n-butanol and isobutanol, the group of ethanol and n-butanol
Conjunction, the combination or methanol of normal propyl alcohol and n-butanol, the combination of ethanol and normal propyl alcohol etc., more preferably ethanol.
As currently preferred technical scheme, the method for step (1) described mixing is organic first to dissolve the polymer in
In solvent, then anhydrous alcohols solvent is added thereto.
Preferably, the polymer is dissolved in organic solvent, make the concentration of polymer in organic solvent for 40~
120mg/mL, as 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 85mg/mL, 90mg/mL, 95mg/mL,
100mg/mL, 105mg/mL, 110mg/mL, 115mg/mL or 120mg/mL etc., it is not limited to cited numerical value, the number
Other the unrequited numerical value included in the range of value are equally applicable, more preferably 80~120mg/mL, particularly preferably
120mg/mL。
Preferably, the anhydrous alcohols solvent and organic solvent volume ratio are (5~15):1, such as 5:1、6:1、7:1、8:1、
9:1、10:1、11:1、12:1、13:1、14:1 or 15:1 etc., it is not limited to cited numerical value, the number range is interior to wrap
Other the unrequited numerical value contained are equally applicable, more preferably (8~10):1.
Preferably, the method for the dissolving is any one in concussion dissolving, stirring and dissolving, ultrasonic dissolution or heating for dissolving
Kind or at least two combination, the combination is typical but non-limiting examples have：Vibration dissolving and the combination of stirring and dissolving, stirring
Dissolving and the combination or concussion of the combination of ultrasonic dissolution, the combination of stirring and dissolving and heating for dissolving, ultrasonic dissolution and heating for dissolving
Combination of dissolving, stirring and dissolving and heating for dissolving etc., more preferably stirring and dissolving.
Preferably, the time of the dissolving is 10~60min, as 10min, 15min, 20min, 25min, 30min,
35min, 40min, 45min, 50min, 55min or 60min etc., it is not limited to cited numerical value, in the number range
Comprising other unrequited numerical value it is equally applicable, more preferably 20~40min, particularly preferably 30min.
As currently preferred technical scheme, step (2) described substrate is selected from silicon chip, glass, gold plaque, silver strip, polyester
Any one in film, Kapton, polyethylene film, polypropylene screen, silicon rubber or polytetrafluoroethylene (PTFE), further preferably
For glass.
As currently preferred technical scheme, the thickness of step (2) described liquid film is 0.1~0.3mm, as 0.1mm,
0.11mm, 0.12mm, 0.15mm, 0.18mm, 0.2mm, 0.22mm, 0.25mm, 0.28mm, 0.29mm or 0.3mm etc., but not
Cited numerical value is only limitted to, other the unrequited numerical value included in the number range are equally applicable.
Preferably, the humidity of step (2) described air be 60~90%, such as 60%, 61%, 62%, 65%, 68%,
70%th, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 89% or 90% etc., it is not limited to cited number
It is worth, other the unrequited numerical value included in the number range are equally applicable, and more preferably 70~80%.
Air humidity has a great impact to the porosity and line width of polymer film, if air humidity is less than 60% meeting
During causing organic solvent volatilization, hydrone adhesion amount is reduced, and causes increasing for polymer film line width；And humidity is more than
90% can cause to merge seriously between water droplet, form irregular pore structure or even cannot get loose structure.Due to polymer film
Line width and porosity cross the transparency for the metal film that big city's influence is subsequently generated, therefore should strictly control the humidity of air.
Preferably, the hardening time of step (2) described solidification is 0.5~2h, as 0.5h, 0.6h, 0.7h, 0.8h, 0.9h,
1h, 1.2h, 1.5h, 1.8h, 1.9h or 2h etc., it is not limited to cited numerical value, included in the number range other
Unrequited numerical value is equally applicable, more preferably 1~1.5h.
Preferably, the porosity for the polymer film that step (2) obtains be 54~81.7%, such as 54%, 56%,
58%th, 60%, 65%, 70%, 75%, 76%, 78%, 80% or 81.7% etc., it is not limited to cited numerical value, should
Other the unrequited numerical value included in number range are equally applicable.
Preferably, the main distribution of line width for the polymer film that step (2) obtains is 150~350nm, such as
150nm, 160nm, 180nm, 200nm, 220nm, 250nm, 280nm, 300nm, 320nm, 340nm or 350nm etc., but simultaneously not only
It is limited to cited numerical value, other the unrequited numerical value included in the number range are equally applicable.
Can the porosity of polymer film surface and the width of line be the passes for the flexible transparent electrode that prepare excellent performance
Key.The polymer film porosity that step (2) obtains may be up to 81.7%, at the same the main distribution of line width be 150~
350nm, this structure are advantageous to the transmission of light, so that the transparency of electrode significantly increases, while electrode is had well
Electric conductivity.
As currently preferred technical scheme, step (3) described metal is appointed in gold, silver, copper or aluminium and its alloy
Anticipate a kind of or at least two combinations, the combination typical case but non-limiting examples have：The combination of gold and silver, Jin Hetong group
Close, silver and the combination of copper, the combining of copper and aluminium, the combining of silver and aluminium, gold and the combination of aluminium or the combination of gold, silver and copper etc..
Preferably, step (3) described painting method is selected from vapour deposition process, liquid phase method of formation, oxidizing process, diffusion method, electricity
Plating method, vacuum thermal evaporation, DC sputtering, magnetron sputtering method, radio frequency sputtering method, pulsed laser deposition or molecular beam epitaxy
Any one in growth method, more preferably vacuum thermal evaporation.
As the present invention preferably technical scheme, the metal film that step (3) is obtained and the polymer thin UF membrane
Method is：The thin polymer film that the deposition that step (3) is obtained has metal film is placed in the second organic solvent, makes the polymer
Film is completely dissolved.
Preferably, second organic solvent in dichloromethane, chloroform, carbon disulfide or acetone any one
Or at least two combination, it is described combination typical case but non-limiting examples have：The combination of dichloromethane and chloroform, dichloromethane
The combination of alkane and carbon disulfide, the combination of dichloromethane and acetone, combination, the chloroform and third of chloroform and carbon disulfide
The combination of ketone, the combination or dichloromethane of carbon disulfide and acetone, the combination of chloroform and acetone etc..
As currently preferred technical scheme, step (4) described substrate is for dimethyl silicone polymer and/or to polyphenyl two
Formic acid glycol ester.
Preferably, extracting method is described in step (4)：Metal film is carried from solvent from air side with the substrate
Go out, the surface of metallic film adhesion substrate.
Preferably, the metal film for being adhered to substrate surface is dried after step (4) the extraction metal film.
Preferably, the drying means selected from vacuum drying, heat drying, forced air drying or spontaneously dry in one kind or
At least two combination, the combination is typical but non-limiting examples have：Vacuum drying and the combination of heat drying, heat drying
Combination of combination or forced air drying and natural drying with forced air drying etc., is more preferably spontaneously dried.
As the present invention preferably technical scheme, the described method comprises the following steps：
(1) polymer being mixed with organic solvent, 10~60min of stirring and dissolving, polymer concentration is 40~120mg/mL,
Anhydrous alcohols solvent is added, prepares casting solution；
(2) casting solution that step (1) obtains is placed on substrate, forms 0.1~0.3mm liquid film, then be covered with described
The substrate of liquid film, which is positioned in the air that humidity is 60~90%, to be solidified, and prepares the polymer thin with polygonal hole structure
Film；
(3) the deposited metal film on the thin polymer film that step (2) obtains, obtaining deposition has the polymer thin of metal film
Film；
(4) metal film for obtaining step (3) and the polymer thin UF membrane, and extract metal film with substrate, are obtained
Flexible transparent electrode.
Compared with prior art, the present invention at least has the advantages that：
(1) the invention provides a kind of preparation method of flexible transparent electrode, methods described first to be prepared using breathing group method
Polymer film, the porosity of obtained polymer film may be up to 81.7%, and the main distribution of line width is 150~350nm,
Therefore the metal film that metal deposit is prepared on the polymer film, equally with corresponding porosity and line width, institute
The electrode transparency obtained with film preparation is up to 95%, while resistance per square is less than 12 Ω/, has good electric conductivity.
(2) the invention provides a kind of preparation method of flexible transparent electrode, using cheap polymer as raw material, drop
The low cost of raw material, while each step operation of the preparation method is easy, technological process is simple, is advantageous to carry out industrial metaplasia
Production.
Brief description of the drawings
Fig. 1：A kind of flow chart that flexible transparent electrode is prepared using breathing pattern method；
Fig. 2 a：The SEM figures for the porous polylactic acid film that embodiment 1 is prepared；
Fig. 2 b：The line width distribution map for the porous polylactic acid film that embodiment 1 is prepared；
Fig. 3 a：The SEM figures for the polystyrene porous membrane that embodiment 2 is prepared；
Fig. 3 b：The line width distribution map for the polystyrene porous membrane that embodiment 2 is prepared；
Fig. 4 a：The SEM figures for the polystyrene porous membrane that embodiment 3 is prepared；
Fig. 4 b：The line width distribution map for the polystyrene porous membrane that embodiment 3 is prepared；
Fig. 5 a：The SEM figures for the polymethyl methacrylate perforated membrane that embodiment 4 is prepared；
Fig. 5 b：The line width distribution map for the polymethyl methacrylate perforated membrane that embodiment 4 is prepared；
Fig. 6 a：The SEM figures for the polymethyl methacrylate perforated membrane that embodiment 5 is prepared；
Fig. 6 b：The line width distribution map for the polymethyl methacrylate perforated membrane that embodiment 5 is prepared；
Fig. 7 a：The SEM figures for the polymethyl methacrylate perforated membrane that embodiment 6 is prepared；
Fig. 7 b：The line width distribution map for the polymethyl methacrylate perforated membrane that embodiment 6 is prepared；
In Fig. 1, a- polymer solution knifing steps, b- breathings pattern method prepares perforated membrane step, c- film deposition techniques
Deposited metal film step, d- are immersed in solution, thin polymer film dissolving step, and e- flexible and transparents substrate is extracted molten from air side
Metal grill step in liquid, dry to obtain flexible transparent electrode step under f- normal temperature.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are defined by claims.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting
Embodiment is as follows：
Specific embodiment of the invention part provides one kind, and the preparation method of flexible transparent electrode as shown in Figure 1 is described
Method comprises the following steps：
(1) polymer, organic solvent and anhydrous alcohols solvent are mixed, prepares casting solution；
(2) casting solution that step (1) obtains is placed on substrate and forms liquid film, then the substrate for being covered with liquid film is placed
Solidified in air, form the thin polymer film with polygonal hole structure；
(3) the deposited metal film on the thin polymer film that step (2) obtains, obtaining deposition has the polymer thin of metal film
Film；
(4) metal film for obtaining step (3) and the polymer thin UF membrane, and extract metal film with substrate, are obtained
Flexible transparent electrode.
In Fig. 1, a- polymer solution knifing steps, b- breathings pattern method prepares perforated membrane step, c- film deposition techniques
Deposited metal film step, d- are immersed in solution, thin polymer film dissolving step, and e- flexible and transparents substrate is extracted molten from air side
Metal grill step in liquid, dry to obtain flexible transparent electrode step under f- normal temperature.
Embodiment 1
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) PLA is mixed with chloroform, stirring and dissolving 30min, polymer concentration 80mg/mL, adds nothing
The ratio of alcoholic solvent, absolute ethyl alcohol and chloroform is 10:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on glass plate, forms 0.2mm liquid film, then liquid film is covered with by described
Substrate be positioned over humidity be 75% air in solidified, prepare with polygonal hole structure thin polymer film；
(3) using vacuum thermal evaporation deposition copper film on the thin polymer film that step (2) obtains, obtaining deposition has copper film
Thin polymer film；
(4) copper film that step (3) obtains is put into chloroform with the thin polymer film and separated, thing template to be polymerized
After dissolving, copper film is extracted from air side with to polyethylene terephthalate (PET) substrate, copper mold is adhered to pet sheet face, will
The copper film for being adhered to substrate surface is spontaneously dried, and obtains flexible transparent electrode.
The thin polymer film that step (2) is prepared carries out SEM and line width distribution characterizes, as a result as shown in Figure 2.
The transparency that flexible transparent electrode is prepared is 75.6%, resistance per square is 36 Ω/.
Embodiment 2
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polystyrene is mixed with chloroform, stirring and dissolving 30min, polymer concentration 80mg/mL, added
The ratio of anhydrous ethanol solvent, absolute ethyl alcohol and chloroform is 5:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on glass plate, forms 0.2mm liquid film, then liquid film is covered with by described
Substrate be positioned over humidity be 85% air in solidified, prepare with polygonal hole structure thin polymer film；
(3) vacuum thermal evaporation deposited gold film is used on the thin polymer film that step (2) obtains, obtaining deposition has golden film
Thin polymer film；
(4) golden film that step (3) obtains is put into chloroform with the thin polymer film and separated, thing template to be polymerized
After dissolving, golden film is extracted from air side with dimethyl silicone polymer (PDMS) substrate, golden film is adhered to PDMS surfaces, will adhered to
Spontaneously dried in the golden film of substrate surface, obtain flexible transparent electrode.
The thin polymer film that step (2) is prepared carries out SEM and line width distribution characterizes, as a result as shown in the figure.
The transparency that flexible transparent electrode is prepared is 93%, resistance per square is 8.6 Ω/.
Embodiment 3
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polystyrene is mixed with chloroform, stirring and dissolving 30min, polymer concentration 120mg/mL, added
The ratio of anhydrous ethanol solvent, absolute ethyl alcohol and chloroform is 5:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on glass plate, forms 0.2mm liquid film, then liquid film is covered with by described
Substrate be positioned over humidity be 85% air in solidified, prepare with polygonal hole structure thin polymer film；
(3) vacuum thermal evaporation deposited gold film is used on the thin polymer film that step (2) obtains, obtaining deposition has golden film
Thin polymer film；
(4) golden film that step (3) obtains is put into chloroform with the thin polymer film and separated, thing template to be polymerized
After dissolving, golden film is extracted from air side with dimethyl silicone polymer (PDMS) substrate, golden film is adhered to PDMS surfaces, will adhered to
Spontaneously dried in the golden film of substrate surface, obtain flexible transparent electrode.
The thin polymer film that step (2) is prepared carries out SEM and line width distribution characterizes, as a result as shown in Figure 4.
The transparency that flexible transparent electrode is prepared is 76.4%, resistance per square is 34.6 Ω/.
Embodiment 4
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polymethyl methacrylate is mixed with chloroform, stirring and dissolving 30min, polymer concentration 80mg/
ML, adds anhydrous ethanol solvent, and the ratio of absolute ethyl alcohol and chloroform is 10:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on glass plate, forms 0.2mm liquid film, then liquid film is covered with by described
Substrate be positioned over humidity be 80% air in solidified, prepare with polygonal hole structure thin polymer film；
(3) obtain being coated with silverskin using vacuum thermal evaporation deposition silverskin on the thin polymer film that step (2) obtains
Thin polymer film；
(4) silverskin that step (3) obtains is put into chloroform with the thin polymer film and separated, thing template to be polymerized
After dissolving, silverskin is extracted from air side with dimethyl silicone polymer (PDMS) substrate, silverskin is adhered to PDMS surfaces, will adhered to
Spontaneously dried in the silver of substrate surface, obtain flexible transparent electrode.
The thin polymer film that step (2) is prepared carries out SEM and line width distribution characterizes, as a result as shown in Figure 5.
The transparency that flexible transparent electrode is prepared is 95%, resistance per square is 12 Ω/.
Embodiment 5
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polymethyl methacrylate is mixed with chloroform, stirring and dissolving 30min, polymer concentration 120mg/
ML, adds anhydrous ethanol solvent, and the ratio of absolute ethyl alcohol and chloroform is 15:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on glass plate, forms 0.2mm liquid film, then liquid film is covered with by described
Substrate be positioned over humidity be 80% air in solidified, prepare with polygonal hole structure thin polymer film；
(3) using vacuum thermal evaporation deposition silverskin on the thin polymer film that step (2) obtains, obtaining deposition has silverskin
Thin polymer film；
(4) silverskin that step (3) obtains is put into chloroform with the thin polymer film and separated, thing template to be polymerized
After dissolving, silverskin is extracted from air side with dimethyl silicone polymer (PDMS) substrate, silverskin is adhered to PDMS surfaces, will adhered to
Spontaneously dried in the silverskin of substrate surface, obtain flexible transparent electrode.
The thin polymer film that step (2) is prepared carries out SEM and line width distribution characterizes, as a result as shown in Figure 6.
The transparency that flexible transparent electrode is prepared is 89.3%, resistance per square is 18 Ω/.
Embodiment 6
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polymethyl methacrylate is mixed with chloroform, stirring and dissolving 30min, polymer concentration 120mg/
ML, adds anhydrous ethanol solvent, and the ratio of absolute ethyl alcohol and chloroform is 10:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on glass plate, forms 0.2mm liquid film, then liquid film is covered with by described
Substrate be positioned over humidity be 80% air in solidified, prepare with polygonal hole structure thin polymer film；
(3) using vacuum thermal evaporation deposition silverskin on the thin polymer film that step (2) obtains, obtaining deposition has silverskin
Thin polymer film；
(4) silverskin that step (3) obtains is put into chloroform with the thin polymer film and separated, thing template to be polymerized
After dissolving, silverskin is extracted from air side with dimethyl silicone polymer (PDMS) substrate, silverskin is adhered to PDMS surfaces, will adhered to
Spontaneously dried in the silverskin of substrate surface, obtain flexible transparent electrode.
The thin polymer film that step (2) is prepared carries out SEM and line width distribution characterizes, as a result as shown in Figure 7.
The transparency that flexible transparent electrode is prepared is 91.8%, resistance per square is 14 Ω/.
Embodiment 7
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polycaprolactone is mixed with dichloromethane, stirring and dissolving 60min, polymer concentration 90mg/mL, added
The ratio of absolute methanol solvent, absolute methanol and chloroform is 10:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on silicon plate, forms 0.1mm liquid film, then by the liquid film that is covered with
Substrate, which is positioned in the air that humidity is 60%, to be solidified, and prepares the thin polymer film with polygonal hole structure；
(3) vacuum thermal evaporation deposition of aluminum film is used on the thin polymer film that step (2) obtains, obtaining deposition has aluminium film
Thin polymer film；
(4) aluminium film that step (3) obtains is put into dichloromethane with the thin polymer film and separated, thing template to be polymerized
After dissolving, aluminium film is extracted from air side with dimethyl silicone polymer (PDMS) substrate, aluminium film is adhered to PDMS surfaces, will adhered to
Spontaneously dried in the aluminium film of substrate surface, obtain flexible transparent electrode.
The transparency that flexible transparent electrode is prepared is 81.4%, resistance per square is 23.4 Ω/.
Embodiment 8
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polyimides is mixed with carbon disulfide, stirring and dissolving 10min, polymer concentration 100mg/mL, added
Anhydrous normal propyl alcohol solvent, the ratio of anhydrous normal propyl alcohol and chloroform is 8:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on polyester film, forms 0.3mm liquid film, then liquid is covered with by described
The substrate of film, which is positioned in the air that humidity is 90%, to be solidified, and prepares the thin polymer film with polygonal hole structure；
(3) using DC sputtering deposition silverskin on the thin polymer film that step (2) obtains, obtaining deposition has silverskin
Thin polymer film；
(4) silverskin that step (3) obtains is put into carbon disulfide with the thin polymer film and separated, thing template to be polymerized
After dissolving, silverskin is extracted from air side with polyethylene terephthalate (PET) substrate, silverskin is adhered to pet sheet face, will
The silverskin for being adhered to substrate surface is spontaneously dried, and obtains flexible transparent electrode.
The transparency that flexible transparent electrode is prepared is 80.5%, resistance per square is 31.4 Ω/.
Embodiment 9
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) polycaprolactone is dissolved in chloroform, stirring and dissolving 40min, polymer concentration 110mg/mL, added different
The ratio of propanol solvent, isopropanol and chloroform is 12:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on polyester film, forms 0.25mm liquid film, then be covered with described
The substrate of liquid film, which is positioned in the air that humidity is 75%, to be solidified, and prepares the thin polymer film with polygonal hole structure；
(3) obtained on the thin polymer film that step (2) obtains using DC sputtering coating silverskin coated with silverskin
Thin polymer film；
(4) silverskin that step (3) obtains is put into chloroform with the thin polymer film and separated, thing template to be polymerized
After dissolving, silverskin is extracted from air side with polyethylene terephthalate (PET) substrate, silverskin is adhered to pet sheet face, will
The silverskin for being adhered to substrate surface is spontaneously dried, and obtains flexible transparent electrode.
The transparency that flexible transparent electrode is prepared is 85.4%, resistance per square is 28.6 Ω/.
Embodiment 10
A kind of preparation method of flexible transparent electrode, the described method comprises the following steps：
(1) cellulose acetate acetone is mixed, stirring and dissolving 50min, polymer concentration 100mg/mL, added anhydrous
The ratio of n-butanol solvent, absolute ethyl alcohol and chloroform is 12:1, prepare casting solution；
(2) casting solution that step (1) obtains is placed on polyester film, forms 0.15mm liquid film, then be covered with described
The substrate of liquid film, which is positioned in the air that humidity is 90%, to be solidified, and prepares the thin polymer film with polygonal hole structure；
(3) using vacuum thermal evaporation deposition silverskin on the thin polymer film that step (2) obtains, obtaining deposition has silverskin
Thin polymer film；
(4) silverskin that step (3) obtains is put into acetone with the thin polymer film and separated, thing template dissolving to be polymerized
Afterwards, silverskin is extracted from air side with polyethylene terephthalate (PET) substrate, silverskin is adhered to pet sheet face, will adhered to
Spontaneously dried in the silverskin of substrate surface, obtain flexible transparent electrode.
The transparency that flexible transparent electrode is prepared is 83.4%, resistance per square is 39 Ω/.
Comparative example 1：
A kind of preparation method of flexible transparent electrode, methods described except air in step (2) humidity be 40% in addition to, its
His step is same as Example 1.
The transparency that flexible transparent electrode is prepared is 27%, resistance per square is 53 Ω/.
Comparative example 2：
A kind of preparation method of flexible transparent electrode, methods described except air in step (2) humidity be 95% in addition to, its
His step is same as Example 1.
The transparency that flexible transparent electrode is prepared is 35%, resistance per square is 78 Ω/.
Using a kind of flexible transparent electrode provided by the invention it can be seen from embodiment 1-10 and comparative example 1 and 2
Preparation method, the thin polymer film that porosity is high and line width is small is prepared by using breathing group case method, and made based on it
For metal film, the metal film combines to form flexible transparent electrode with flexible substrates, and the electrode transparency of preparation is high, resistance per square
It is small, there is good pliability and electric conductivity.Meanwhile air humidity has a great influence to flexible transparent electrode, air humidity
The transparency degradation of electrode can be caused less than 60% or more than 90%.
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implemented.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of part selected by the present invention
And the increase of accessory, selection of concrete mode etc., all fall within protection scope of the present invention and it is open within the scope of.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, 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 equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of preparation method of flexible transparent electrode, it is characterised in that the described method comprises the following steps：
(1) polymer, organic solvent and anhydrous alcohols solvent are mixed, prepares casting solution；
(2) casting solution that step (1) obtains is placed on substrate and forms liquid film, then the substrate for being covered with liquid film is positioned over sky
Solidified in gas, form the thin polymer film with polygonal hole structure；
(3) the deposited metal film on the thin polymer film that step (2) obtains, obtaining deposition has the thin polymer film of metal film；
(4) metal film for obtaining step (3) and the polymer thin UF membrane, and extract metal film with substrate, obtain flexibility
Transparency electrode；
The thickness of step (2) described liquid film is 0.1~0.3mm；
The humidity of step (2) described air is 60~90%；
The hardening time of step (2) described solidification is 0.5~2h；
The porosity for the thin polymer film that step (2) obtains is 54~81.7%；
The main distribution of line width for the thin polymer film that step (2) obtains is 150~350nm.
2. preparation method according to claim 1, it is characterised in that step (1) described polymer is selected from polyimides, gathers oneself
Lactone, nitrocellulose, cellulose acetate, PLA, polymethyl methacrylate, polystyrene and comprising above-mentioned polymer it
Any one in one block copolymer；
Step (1) described organic solvent in dichloromethane, chloroform, carbon disulfide or acetone any one or at least two
The combination of kind；
Step (1) the anhydrous alcohols solvent is any one in methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol or isobutanol
Kind or at least two combination.
3. preparation method according to claim 1 or claim 2, it is characterised in that the method for step (1) described mixing is first by polymerization
Thing is dissolved in organic solvent, then adds anhydrous alcohols solvent thereto；
The polymer is dissolved in organic solvent, and it is 40~120mg/mL to make the concentration of polymer in organic solvent；
The anhydrous alcohols solvent and organic solvent volume ratio are (5~15):1；
The method of the dissolving is any one in concussion dissolving, stirring and dissolving, ultrasonic dissolution or heating for dissolving or at least two
The combination of kind；
The time of the dissolving is 10~60min.
4. preparation method according to claim 1 or claim 2, it is characterised in that step (2) described substrate is selected from silicon chip, glass, gold
It is any one in piece, silver strip, polyester film, Kapton, polyethylene film, polypropylene screen, silicon rubber or polytetrafluoroethylene (PTFE)
Kind.
5. preparation method according to claim 1 or claim 2, it is characterised in that step (3) described metal is selected from gold, silver, copper or aluminium
And its any one in alloy or at least two combination；
Step (3) described deposition process is selected from vapour deposition process, liquid phase method of formation, oxidizing process, diffusion method, galvanoplastic, Vacuum Heat
Appoint in vapour deposition method, DC sputtering, magnetron sputtering method, radio frequency sputtering method, pulsed laser deposition or molecular beam epitaxial growth method
Meaning is a kind of.
6. preparation method according to claim 1 or claim 2, it is characterised in that polymerize the metal film that step (3) obtains with described
The method of thing thin film separation is：The thin polymer film that the deposition that step (3) is obtained has metal film is placed in the second organic solvent,
It is completely dissolved the thin polymer film；
Second organic solvent in dichloromethane, chloroform, carbon disulfide or acetone any one or at least two
Combination.
7. preparation method according to claim 1 or claim 2, it is characterised in that step (4) described substrate is dimethyl silicone polymer
And/or to polyethylene terephthalate；
Extracting method is described in step (4)：Metal film is proposed from solvent from air side with the substrate, metal film glues
The surface of attached substrate；
The metal film for being adhered to substrate surface is dried after step (4) the extraction metal film；
The one kind or at least two of the drying means in vacuum drying, heat drying, forced air drying or natural drying
Combination.
8. preparation method according to claim 1, it is characterised in that the described method comprises the following steps：
(1) polymer is mixed with organic solvent, 10~60min of stirring and dissolving, polymer concentration is 80~120mg/mL, then is added
Enter anhydrous alcohols solvent, prepare casting solution；
(2) casting solution that step (1) obtains is formed into 0.1~0.3mm liquid film as on substrate, then liquid film is covered with by described
Substrate be positioned over humidity be 60~90% air in solidified, prepare with polygonal hole structure thin polymer film；
(3) the deposited metal film on the thin polymer film that step (2) obtains, obtaining deposition has the thin polymer film of metal film；
(4) metal film for obtaining step (3) and the polymer thin UF membrane, and extract metal film with substrate, obtain flexibility
Transparency electrode.
9. preparation method according to claim 2, it is characterised in that step (1) described polymer is poly-methyl methacrylate
Ester；
Step (1) described organic solvent is chloroform；
Step (1) the anhydrous alcohols solvent is ethanol.
10. preparation method according to claim 3, it is characterised in that the polymer is dissolved in organic solvent, makes polymerization
The concentration of thing in organic solvent is 80~120mg/mL；
The anhydrous alcohols solvent and organic solvent volume ratio are (8~10):1；
The method of the dissolving is stirring and dissolving；
The time of the dissolving is 20~40min.
11. preparation method according to claim 10, it is characterised in that the polymer is dissolved in organic solvent, makes to gather
The concentration of compound in organic solvent is 120mg/ml；
The anhydrous alcohols solvent is 10 with organic solvent volume ratio:1；
The time of the dissolving is 30min.
12. preparation method according to claim 4, it is characterised in that step (2) described substrate is glass.
13. preparation method according to claim 1, it is characterised in that the humidity of step (2) described air be 70%~
80%；
1~the 1.5h of hardening time of step (2) described solidification.
14. preparation method according to claim 5, it is characterised in that step (3) described deposition process is vacuum thermal evaporation
Method.
15. preparation method according to claim 7, it is characterised in that step (4) described drying means is natural drying.
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| CN107761401B (en) * | 2017-11-30 | 2020-09-08 | 南方科技大学 | Heat-preservation waterproof antibacterial multifunctional cloth and preparation method and application thereof |
| CN108511133B (en) * | 2018-03-19 | 2019-12-20 | 南昌大学 | Preparation method of transfer-free high-cohesiveness metal grid transparent electrode |
| CN109330590B (en) * | 2018-12-07 | 2022-05-27 | 南方科技大学 | Epidermal electrode for epidermal signal acquisition and application thereof |
| CN110487450B (en) * | 2019-08-23 | 2021-09-07 | 南方科技大学 | Flexible touch sensor and preparation method and application thereof |
| CN110742597B (en) * | 2019-10-23 | 2022-04-22 | 哈尔滨工业大学 | Method for preparing TPU/PDMS three-dimensional porous nerve electrode |
| CN113061285B (en) * | 2021-02-26 | 2021-10-22 | 中国科学院深圳先进技术研究院 | Preparation method of ultrathin porous stretchable film electrode |
| CN113834859A (en) * | 2021-09-23 | 2021-12-24 | 广州天极电子科技股份有限公司 | Preparation method and test method of micron-sized electrode for grain boundary performance of grain boundary layer |
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