CN106575552A - Method for forming transparent electrode and transparent electrode laminate - Google Patents
Method for forming transparent electrode and transparent electrode laminate Download PDFInfo
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- CN106575552A CN106575552A CN201580043221.XA CN201580043221A CN106575552A CN 106575552 A CN106575552 A CN 106575552A CN 201580043221 A CN201580043221 A CN 201580043221A CN 106575552 A CN106575552 A CN 106575552A
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- transparent electrode
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- protective layer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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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
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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
Abstract
The present invention relates to a method for forming a transparent electrode capable of more stably forming a transparent electrode pattern having a fine line width and a large aspect ratio, and a transparent electrode laminate formed thereby. The forming method of the transparent electrode comprises the following steps: forming a transparent electrode layer including one or more conductive substances selected from a conductive polymer, a conductive carbon-based material, a metal nanostructure, and a conductive metal oxide on a substrate; forming a protective layer including one or more polymers selected from a polysiloxane-based polymer, an acrylic-based polymer, and a urethane-based polymer on the transparent electrode layer; forming a photoresist pattern on the protective layer; and performing surface treatment on the protective layer and the transparent electrode layer in the region exposed by the photoresist pattern with an oxidizing agent to make the transparent electrode layer non-conductive.
Description
Technical field
The present invention relates to a kind of can more stably form with finer live width and aspect ratio (aspect ratio)
The forming method of the transparency electrode of larger transparent electrode pattern, and the transparency electrode layered product that thus method is formed.
Background technology
Transparency electrode is defined as to visible transparent and the thin film with electric conductivity, for Plasmia indicating panel, liquid
The numerous areas such as crystal display element, light-emitting diode, organic electroluminescent device, contact panel, solar cell.
Recently, as various elements or contact panel are by micronization and the trend of highly sensitiveization, formation is needed to have
The larger transparent electrode pattern of finer live width and aspect ratio, such as lines with thinner live width and with larger height
With the transparent electrode pattern of gap (line and space) shape.
In the past, after transparent conductivity material is formed on substrate, by using photoresistance pattern comprising exposure, development and
The photoetching process (photolithography) of etching, is etched and patterns to the transparent conductivity material, generally with
The method forms the transparent electrode pattern with lines with gap shape etc..However, during by this known method, due to by light
Resistance pattern occurs in that the top or bottom of the transparent electrode pattern with fine live width as the border etc. of the etch process of light shield
The problems such as sustaining damage, thus be difficult to form the transparent electrode pattern with outstanding electric conductivity sometimes.These problems are in transparent electricity
Pole figure case has finer live width and with more notable during more wide aspect ratio, or even there is also transparent electrode pattern and collapse
The phenomenon collapsed.
Due to problem present in these known technologies, thus constantly seek one kind can with it is more stable and well formed tool
There is the method for finer live width and the transparent electrode pattern with more wide aspect ratio.
The content of the invention
Technical problem
The present invention provides a kind of can more stably formation with the larger transparency electrode figure of fine live width and aspect ratio
The forming method of the transparency electrode of case.
The present invention also provides a kind of including the transparency electrode being formed at by the forming method of the transparency electrode on substrate
The transparency electrode layered product of pattern.
Technical scheme
For this purpose, the present invention provides a kind of forming method of transparency electrode, comprise the following steps：Will be comprising selected from conductive poly
One or more of compound, conductive carbon based material, metallic nanostructure and conductive metal oxide conductive material
Transparent electrode layer is formed on substrate；Will be comprising selected from polysiloxanes based polymer, acrylic acid series polymeric compounds and amido formate
The protective layer of one or more of based polymer polymer is formed on the transparent electrode layer；Photoresistance pattern is formed at described
On protective layer；And the protective layer and transparent electrode layer oxidant in the region exposed to the photoresistance pattern are carried out at surface
Reason, so that the transparent electrode layer non-conductive.
The present invention also provides a kind of transparency electrode layered product, and it includes protective layer, and the protective layer is comprising selected from poly- silica
One or more of methane series polymer, acrylic acid series polymeric compounds and amido formate based polymer polymer is simultaneously formed at described
On prescribed electrode layer, wherein the first area of the transparent electrode layer becomes non-conductive, remaining second area keeps electric conductivity,
And then define transparent electrode pattern.
Illustrate in detail further below the transparency electrode of a specific embodiment of the invention forming method and
Thus the transparency electrode layered product that method is formed.
An a kind of specific embodiment of the invention, there is provided forming method of transparency electrode, comprises the following steps：
By comprising in electric conductive polymer, conductive carbon based material, metallic nanostructure and conductive metal oxide
The transparent electrode layer for planting above conductive material is formed on substrate；Will be comprising selected from polysiloxanes based polymer, acrylic acid seriess
The protective layer of one or more of polymer and amido formate based polymer polymer is formed on the transparent electrode layer；Will
Photoresistance pattern is formed on the protective layer；And the protective layer and transparent electrode layer in the region that the photoresistance pattern is exposed
It is surface-treated with oxidant, so that the transparent electrode layer non-conductive.
For the forming method of this specific embodiment, the predetermined transparency electrode comprising conductive material is initially formed
Layer, after re-forming predetermined protective layer, by photoetching process the photoresistance for defining transparent electrode pattern is formed on the protective layer
Pattern.Then, not the photoresistance pattern removed into the transparent electrode layer in the region exposed etc. as light shield, but to being revealed
The protective layer and transparent electrode layer in the region for going out is surface-treated with oxidant.
In this surface treatment process, the oxidant can optionally make leading for transparent electrode layer by protective layer
Conductive substances are aoxidized, and its result can make transparent electrode layer non-conductive (so-calledization in the region that the photoresistance pattern exposes
The property learned ON/OFF techniques).The result of this technique is carried out, between the transparent electrode layer in non-conductive region, can be formed still
The transparent electrode layer of the remaining area of old holding electric conductivity, the transparent electrode layer of the holding electric conductivity can form on the whole transparent
Electrode pattern.
According to the method for this specific embodiment, also still leave in the non-conductive region between transparent electrode pattern
Transparent electrode layer and protective layer, therefore etching causes the risk that transparent electrode pattern is damaged or electrical characteristics are reduced to reduce to minimum,
Even if formed that there is finer live width and the transparent electrode pattern compared with wide aspect ratio, transparent electrode pattern is actually there will not be
The risk caved in.Therefore, it can be formed well with finer live width and the transparency electrode figure with outstanding electrical characteristics
Case, can be highly suitable for contact panel, various display elements or solar cell etc. by the transparent electrode pattern.
With reference to the accompanying drawings according to one specific embodiment of each description of the process transparency electrode forming method.Fig. 1 is
Order according to each technique schematically shows the flow chart of the forming method of the transparency electrode of a specific embodiment.
First figure of Fig. 1 is referred to, in the method for a specific embodiment, first will be comprising selected from conductive poly
One or more of compound, conductive carbon based material, metallic nanostructure and conductive metal oxide conductive material
Transparent electrode layer is formed on substrate.
Now, it is contemplated that be suitable for the species of the element of the forming method of this case transparency electrode etc., conventional base plate can conduct
The substrate, is not particularly limited to this, for example visible ray is shown light transmission and the transparency any glass substrate or
Person's resin substrate etc. can be used as the substrate.
In addition, the transparent electrode layer can be formed by the following method：According to the conventional electricity comprising the conductive material
Pole forming method, forms comprising described more than one conductive materials and the organic solvent either solution of water-based solvent or dispersion
After liquid, coat and be dried on transparency carrier.Now, it is described molten as needed according to the species of the conductive material
Liquid or dispersion liquid can also be comprising appropriate dispersants or adhesive etc..
And, the transparent electrode layer can be using the known any conductive material (example that can form transparency electrode
Such as, electric conductive polymer, conductive carbon based material, metallic nanostructure or conductive metal oxide etc.) formed, to this
It is not particularly limited.These conductive materials can specifically enumerate polyphenylamine series of polymers (polyaniline), polypyrrole system and gather
The electric conductive polymer such as compound (polypyrrole) or polythiophene based polymer (polythiophene)；CNT or graphite
The conductive carbon based material such as alkene；The metallic nanostructure such as nano-silver thread (AgNw) or copper nano-particle；Tin indium oxide (Indium
Tin Oxide) or the conductive metal oxide such as antimony tin (Antimony Tin oxide), in addition can also use
Various conductive materials are forming the transparency electrode.
Additionally, the transparent electrode layer can have about 0.03 μm to 0.5 μm or about 0.05 μm to 0.3 μm of thickness.If
The thickness of the transparent electrode layer is excessively thin, then active surface resistance is greatly reduced, and sheet resistance can be caused uneven, if described
The thickness of transparent electrode layer is blocked up, then transparency or optical characteristics may be reduced.
And, the transparent electrode layer can have about 80 Ω/sq to 400 Ω/sq or about 150 Ω/sq to 280 Ω/sq
Sheet resistance.
In addition, after the transparent electrode layer is formed, can gather including selected from polysiloxanes based polymer, acrylic acid seriess
The protective layer of one or more of compound and amido formate based polymer polymer is formed on the transparent electrode layer.It is this
Surface treatment of the protective layer in following use oxidants and the non-conductive chemical industry of the transparent electrode layer based on the surface treatment
Can protect transparent electrode layer in skill, and the phenomenon that transparent electrode layer removed by the oxidant can be suppressed.That is, by being formed
This protective layer, the transparent electrode layer of certain area will not be removed, simply oxidant after protective layer with transparent electrode layer
Reaction, such that it is able to only carry out the selective oxidation and non-conductive of the transparent electrode layer.As a result, a tool can be reached
The effect that the suppression transparent electrode pattern that the method for body embodiment to be reached caves in.
In view of the effect of this protective layer, the protective layer can with polysiloxanes based polymer, acrylic acid series polymeric compounds or
Being formed, wherein polysiloxanes based polymer is more suitable for person's amido formate based polymer.This polysiloxanes based polymer exists
With more outstanding surface characteristic can be shown during the oxidizer treatment, when forming protective layer with polysiloxanes based polymer,
While can the insulation effect related to electric conductivity be minimized, original purpose, i.e. resistance to water and chemical-resistant are also outstanding,
Higher coating and tack are also showed that to photoresistance pattern thereon.
This polysiloxanes based polymer and the protective layer comprising the polysiloxanes based polymer can be comprising selected from alcoxyls
Base silane system monomer (alkyloxy silane monomer), amino containing silane system monomer (amino silane monomer), second
Alkenyl silanes system monomer (vinyl silane monomer), epoxy silane system monomer (epoxy silane monomer), first
Base acryloxy silane system monomer (methacryloxy silane monomer), isocyanatosilanes system monomer
A kind of polymerization in (isocyanate silane monomer) and silicon fluoride system monomer (fluoro silane monomer)
Thing or two or more copolymers.
Specifically, the polysiloxanes based polymer and protective layer can be comprising selected from tetraethoxysilanes
(tetraethoxysilane), VTES (vinyltriethoxysilane), vinyl trimethoxy silicon
Alkane (vinyltrimethoxysilane), vinyl three ('beta '-methoxy ethyoxyl) silane (vinyltris (β-
Methoxyethoxy) silane), γ-methacryloxypropyl trimethoxy silane (γ-
Methacryloxypropyltrimethoxysilane), β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane (β-(3,
4-epoxycyclohexyl) ethyltrimethoxysilane), γ-glycydoxy trimethoxy silane
(γ-glycidoxypropyltrimethoxysilane), γ-mercaptopropyl trimethoxysilane (γ-
Mercaptopropyltrimethoxysilane), γ-amine propyl-triethoxysilicane (γ-
Aminopropyltriethoxysilane), N- β-(amine ethyl)-γ-amine propyl trimethoxy silicane (N- β-
(aminoethyl)-γ-aminopropyltritrimethoxysilane), γ-urea propyl-triethoxysilicane (γ-
Ureidopropyltriethoxysilane), phenyl triethoxysilane (phenyltriethoxysilane), the second of methyl three
TMOS (methyltriethoxysilane), MTMS (methyltrimethoxysilane), polyoxy
Change ethylene modified silane monomer (polyethylene oxide modified silane monomer), poly- methyl ethoxy silicon
One kind in oxygen alkane (polymethylethoxysiloxane) and hexamethyldisiloxane (hexamethyldisilazine)
Polymer or two or more copolymers.
Further, the protective layer comprising the polysiloxanes based polymer is higher in order to have to other adjacent layer
Adhesion or adhesion and guarantee relatively low sheet resistance, the polysiloxanes based polymer and protective layer can include about 60 weights
The tetraethoxysilane and about 10 weight % to 40 weight % of amount weight % of % to 90 is selected from VTES, second
Thiazolinyl trimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silicon
Alkane, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, γ-glycydoxy trimethoxy silane, γ-mercapto
Propyl trimethoxy silicane, γ-amine propyl-triethoxysilicane, N- β-(amine ethyl)-γ-amine propyl trimethoxy silicane, γ-
Urea propyl-triethoxysilicane, phenyl triethoxysilane, MTES, MTMS, polyoxygenated
The copolymerization of one or more of ethylene modified silane monomer, poly- methylethoxy radical siloxane and hexamethyldisiloxane compound
Thing.
If in the monomer for synthesizing the copolymer, the content of tetraethoxysilane to be less than 60 weight %, then the guarantor
The sheet resistance of sheath may be greatly increased.If in addition, in the monomer for synthesizing the copolymer, tetraethoxysilane
Content exceeds 90 weight %, then the density of the protective layer may be too high or the phenomenon that surface is split occurs, and water-fast
Property may be substantially reduced.
Additionally, in addition to this polysiloxanes based polymer, can be using acrylic acid series polymeric compounds or amido formate
Based polymer is not particularly limited forming the protective layer to this specific example, can be used as conductive layer protective layer or
Any known acrylic acid series polymeric compounds of coating etc. or amido formate based polymer can be used, to this without especially limit
System.
In addition, the protective layer can have about 0.05 μm to 0.4 μm or about 0.12 μm to 0.35 μm of thickness.And,
As described above, the transparent electrode layer with this protective layer can have about 80 Ω/sq to 400 Ω/sq or about 150 Ω/sq extremely
The sheet resistance of 280 Ω/sq.Thus, it is non-in the surface treatment of following use oxidants and the transparent electrode layer of certain area
In conducting technique, can suitably protect the transparent electrode layer of bottom and optionally carry out non-conductive, such that it is able to make
The transparent electrode pattern and layered product for ultimately forming shows outstanding electrical characteristics.
In addition, after the transparent electrode layer and protective layer described in being formed in order, as shown in figure 1, on the protective layer
The photoresistance pattern in the region for defining transparent electrode pattern to be formed can be formed.
This photoresistance pattern can be by using the exposure of commonly known photosensitive resin composition or Photoresisting agent composition
And developing process is forming.For the condition and method of this exposed and developed technique, the species by each Photoresisting agent composition is
Those of ordinary skill in the art are it is well known that therefore description is omitted.
And, can use the eurymeric comprising alkali soluble resins as the Photoresisting agent composition for being used to be formed the photoresistance pattern
Photoresisting agent composition can either use the monomer comprising more than one reactive functional group or comprising polymer and light initiator
Negative light resistance agent composition, but be more suitable for use eurymeric Photoresisting agent composition.
Additionally, the photoresistance pattern can be formed by the following method：Formed and there are about 1 μm to 5 μm or about 2 μm to 4 μm
Thickness Photoresisting agent composition layer after, carry out rotine exposure and developing process.If the thickness of Photoresisting agent composition layer is excessively thin,
Then spot or outward appearance can be produced on the Photoresisting agent composition layer (pattern) and/or protective layer etc. during exposed and developed
Damage, and then it is possible that nebulousurine phenomenon.If the thickness of the Photoresisting agent composition layer is blocked up, cannot because being difficult exposure
Fully develop or live width can be caused inconsistent.
In addition, being formed after described photoresistance pattern, as shown in figure 1, the guarantor in the region exposed to the photoresistance pattern
Sheath and transparent electrode layer are surface-treated with oxidant, so that the transparent electrode layer non-conductive.When carrying out this mistake
Cheng Shi, the oxidant makes the transparent electrode layer of protective layer bottom optionally aoxidize and non-conductive by protective layer.Finally,
Expose and the oxidized region for processing in photoresistance pattern, transparent electrode layer is remained with the state of non-conductive, and remaining
Region, transparent electrode layer keeps the state of conducting, such that it is able to form transparent electrode pattern.
As for this surface treatment oxidant, can using will not actually remove or damage the protective layer and
Transparent electrode layer (for example, the forward and backward protective layer thickness change of the surface treatment is for about below 200nm) and by the protection
Layer the transparent electrode layer can be made optionally to aoxidize and non-conductive arbitrary substance.This oxidant more specifically can be with example
Lift and be selected from hypochlorous acid or its salt (such as hypochlorite or the hypochlorous acid with the sour state for mixing such as acetic acid), dichromic acid or its salt
(alkali metal salt such as such as potassium salt), cross the tool such as mangaic acid or its salt (alkali metal salt such as such as potassium salt), hydrogen peroxide, nitric acid or hydrochloric acid
A kind of material in oxidizing strong acid and copper chloride and the mixture of acid (such as hydrochloric acid etc.) or in these materials
Two or more materials mixture, other various oxidants can also be used.
Wherein, it is more suitable for using hypochlorous acid or its salt, because have and transparent electrode layer can be made optionally to aoxidize and non-led
Electrification and will not produce the characteristic of the defects such as spot or nebulousurine (defect) in protective layer and transparency electrode layer surface.And, more
It is adapted to the hypoclorous acid form (referring to following embodiments 2) to mix the weak acid such as hypochlorite and acetic acid using the oxidant.By
This, more will not on the protection layer produce defect, transparency electrode is aoxidized and non-conductive.
And, using the process of surface treatment of the oxidant, can adopt and be diluted to this oxidizer composition with liquid
The method in surface is coated with or sprayed after debita spissitudo.
In addition, after described oxidant surface treatment step, the step of removing the photoresistance pattern can also be carried out, this
Kind of photoresistance pattern removes technique and can carry out according to conventional photoresistance pattern stripping technology etc..
Through the technique of a described specific embodiment, it is possible to form transparency electrode layered product, it includes：Base
Plate；Transparent electrode layer, the transparent electrode layer is comprising selected from electric conductive polymer, conductive carbon based material, metal Nano structure
One or more of thing and conductive metal oxide conductive material, and be formed on substrate；And protective layer, it is described
Protective layer is comprising selected from one or more of polysiloxanes based polymer, acrylic acid series polymeric compounds and amido formate based polymer
Polymer, and be formed on the transparent electrode layer, wherein the first area of the transparent electrode layer becomes non-conductive,
Remaining second area keeps electric conductivity, and then defines transparent electrode pattern.
In this transparency electrode layered product, the transparent electrode layer of the first area can with 150 Ω/sq extremely
The state of the non-conductive of the sheet resistance of 280 Ω/sq is remained on substrate, and the transparent electrode layer of remaining second area can
The outstanding electric conductivity for keeping conductive material intrinsic.Therefore, it can be formed fine transparent electrode pattern, and non-conductive
The transparent electrode layer and protective layer of first area is still remained, therefore can better form finer transparency electrode figure
Case, will not occur caving in for transparent electrode pattern.
By the forming method of the transparency electrode of one specific embodiment, variously-shaped transparent electricity can be formed
Pole figure case, typically can be suitably formed the first area of the non-conductive transparent electrode layer and remaining second area it is saturating
The lines of the pattern form that prescribed electrode layer is alternately arranged with plural lines and the transparent electrode pattern of gap form.Thus, may be used
Particularly well to form the transparent electrode pattern of the lines with very fine live width and compared with wide aspect ratio and gap form,
The risk of pattern collapse is not had.
Invention effect
According to the present invention can provide a kind of transparency electrode forming method and thus method formed transparency electrode layered product,
During known lithography processes are carried out, transparent electrode pattern is damaged or electrical characteristics the forming method of the transparency electrode
The risk of reduction reduces to minimum, even if formed having finer live width and the transparent electrode pattern compared with wide aspect ratio, actually
There will not be the risk that transparent electrode pattern caves in.
Therefore, it is suitable for the present invention and can be formed well and there is finer live width and with the transparent of outstanding electrical characteristics
Electrode pattern, can be highly suitable for contact panel, various display elements or solar cell by the transparent electrode pattern
Deng.
Description of the drawings
Fig. 1 is the forming method of the transparency electrode that a specific embodiment is schematically shown according to each technique order
Flow chart.
Fig. 2 illustrates the electricity before being surface-treated in example 2 and after surface treatment (after photoresistance pattern is removed)
Sub- microphotograph.
Specific embodiment
The present invention is further described in the examples below that.But, the following example is only intended to illustrate the present invention, this
The content of invention is not limited to the following example.
[formation of electrode layer]
By electric conductive polymer PEDOT:PSS (poly- (3,4- Ethylenedioxy Thiophenes) polystyrolsulfon acid (Poly (3,4-
Ethylenedioxythiophene) Polystyrene sulfonate), solid 1wt%) dispersion liquid and nanometer silver
Mixing of the dispersion liquid of line (solid 1wt%) respectively using IPA (isopropanol), MeOH (methanol) and DMSO (dimethyl sulfoxide) is molten
Agent is prepared.By the conductive polymer dispersion and nano-silver thread dispersion liquid with 1：1 weight ratio is mixed, and is mixed
It is (poly- to stupid dioctyl phthalate second that compound coats the PET that thickness is 100 μm using rod coater with 6.86 μm of coating fluid thickness
Ester) on base material.Then, hot air drying is carried out under conditions of 120 DEG C/1min, to form transparent electrode layer.It is confirmed, it is this
The sheet resistance of transparent electrode layer is 80 Ω/sq.
[embodiment 1]
In order to form protective layer coating solution on electrode layer, first by the weight portions of TEOS (tetraethoxysilane) 16.08,
The weight portions of PTMS (phenyltrimethoxysila,e) 4.02, the weight portion of water 23.55, the weight portions of IPA (isopropanol) 54.95, acetic acid 1.4
After weight portion mixing, sol gel reaction is carried out at 70 DEG C, the response time is 3 hours, to form polysiloxane series polymerization
Thing.Thus sol gel reaction liquid 100g is obtained.Now, solid is 7.8wt%.Diluent isopropanol is utilized with 1 to this：4
Weight ratio be diluted, to prepare protective layer coating solution 500g.Solid now is 1.56wt%.
This protective layer coating solution is coated on the base for being formed with electrode layer using rod coater with 11.43 μm of thickness
On material, hot air drying is then carried out under conditions of 120 DEG C/10min.Thus, the protective layer that thickness is 0.178um, Jing are formed
Confirmation sheet resistance is 90 Ω/sq.
Then, U.S. willing photoresist (eurymeric, Positive Type) the product type SJ-631 of generation is entered in east using stick coating method
(10cP, solid 23wt%) is coated on formed protective layer, and is dried 1 minute at a temperature of 120 DEG C, to form thickness
Degree is for about 2.5 μm of photoresist layer, then is carried out after 50mJ exposures, using east with model SUSS Microtec MA-6 exposure sources
Enter the U.S. willing developer solution DPD-200 (product type) of generation to be developed at normal temperatures, the time is 25 seconds, to form photoresistance figure
Case.
Then, by hypochlorite, (Hypochroite Salt, 12%) are diluted in distilled water, and it is 3% to prepare concentration
After aqueous hypochlorite solution, the protective layer and transparent electrode layer in the region exposed to the photoresistance pattern are carried out at surface
Reason.
[embodiment 2]
By hypochlorite (Hypochroite Salt, 12%) with acetic acid with 1:1 content mixing, with prepare 6% it is mixed
Compound.Confirmed, now the chemical property of the mixture is acidity, and with hypoclorous acid form presence.Using the mixture
The protective layer and transparent electrode layer in the region exposed to the photoresistance pattern is surface-treated.In addition, by with reality
Apply the identical method of example 1 and form transparency electrode layered product and pattern.
[embodiment 3]
The product PED-2102 (solid 30wt%) that water dispersible amido formate based polymer, i.e. love are respected into chemistry is sharp
With diluent isopropanol with 1：9 weight ratio is diluted, to prepare protective layer coating solution 500g.Solid now is
3wt%.
This protective layer coating solution is coated on the base for being formed with electrode layer using rod coater with 11.43 μm of thickness
On material, hot air drying is then carried out under conditions of 120 DEG C/10min.Thus, it is 0.34um protective layers to form thickness, confirmed
Sheet resistance is 110 Ω/sq.Subsequent technique is same as Example 2, after forming photoresistance pattern, with aqueous hypochlorite solution to light
The protective layer and transparent electrode layer in the region that resistance pattern exposes is surface-treated.
[embodiment 4]
By water-dispersible acrylic's ester based polymer, Ji Gao terebinths limited company (Takamatsh oil＆fat
Co., LTD) product PESRESIN A-645GH (solid 30wt%) using diluent isopropanol with 1：9 weight ratios carry out dilute
Release, to prepare protective layer coating solution 500g.Solid now is 3wt%.
This protective layer coating solution is coated on the base for being formed with electrode layer using rod coater with 11.43 μm of thickness
On material, hot air drying is then carried out under conditions of 120 DEG C/10min.Thus, the protective layer that thickness is 0.33um is formed, Jing is true
Sheet resistance is recognized for 110 Ω/sq.Subsequent technique is same as Example 2, after forming photoresistance pattern, with aqueous hypochlorite solution pair
The protective layer and transparent electrode layer in the region that photoresistance pattern exposes is surface-treated.
First, by (photoresistance pattern is moved before being surface-treated with hypochlorous acid in the embodiment 2 and after surface treatment
Except rear) electron micrograph be shown in Fig. 2.
In addition, the transparent electrode pattern characteristic to embodiment 1,2,3 and 4, is estimated according to following standard, by assessment knot
Fruit is shown in table 1 below.
(1) surface characteristic assessment：According to following standard, to whether being surface-treated forward and backward protective layer and transparent electrode layer
Produce chemical change to be estimated.
○：The forward and backward variable quantity determined by colour difference meter is Δ Eab<3, Haze<0.5
△：The forward and backward variable quantity determined by colour difference meter only meets one and (that is, only meets Δ Eab relative to "○"<3 or
Haze<One in 0.5)
X：The forward and backward variable quantity determined by colour difference meter is Δ Eab>3, Haze>0.5
(2) defect estimation on transparency electrode surface：According to following standard, to protective layer and transparency electrode after surface treatment
The surface of layer produces the degree of defect and is estimated.
○：The defects such as the no foreign body of transparent electrode pattern observation sum 100% to lines and gap (line＆Space)；
△：The transparent electrode pattern observation sum more than 80% in lines and gap (line＆Space) is lacked without foreign body etc.
Fall into；
X：The transparent electrode pattern observation sum more than 60% in lines and gap (line＆Space) is lacked without foreign body etc.
Fall into.
(3) it is whether breaking to assess：According to following standard, to after surface treatment between surface treatment region and untreated areas
Transparent electrode layer whether breaking be estimated
○：Sum 100% is determined to lines and the transparent electrode pattern of gap (line＆Space) breaking；
△：It is breaking to the transparent electrode pattern measure sum more than 80% in lines and gap (line＆Space)；
X：It is breaking to the transparent electrode pattern measure sum more than 60% in lines and gap (line＆Space).
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Surface characteristic is assessed | △ | ○ | ○ | ○ |
| Defect estimation | ○ | ○ | ○ | ○ |
| It is whether breaking to assess | ○ | ○ | ○ | ○ |
Refer to Fig. 2 and upper table 1, confirmed by embodiment 1 and 2 define surface treatment region and untreated areas it
Between be open circuit good clear electrode pattern.In addition, embodiment 3 and 4 is referred to, with amido formate based polymer or propylene
When sour based polymer forms protective layer, it is also possible to form the good clear electrode pattern equivalent to embodiment 1 and 2.
Additionally, it is that transparent electrode layer is oxidized (chemical change) in surface treatment region to form this transparent electrode pattern
Caused by the phenomenon of non-conductive.And, do not have in the surface treatment region, the protective layer and transparent electrode layer yet
By physical damnification, original thickness is actually still kept, defect is not almost produced in overall up-protective layer and transparent electrode layer,
So as to keep good surface characteristic etc..
Claims (11)
1. a kind of forming method of transparency electrode, comprises the following steps：
Will be comprising in electric conductive polymer, conductive carbon based material, metallic nanostructure and conductive metal oxide
The transparent electrode layer of more than one conductive materials be formed on substrate；
Will be comprising selected from one or more of polysiloxanes based polymer, acrylic acid series polymeric compounds and amido formate based polymer
The protective layer of polymer is formed on the transparent electrode layer；
Photoresistance pattern is formed on the protective layer；And
The protective layer and transparent electrode layer in the region exposed to the photoresistance pattern is surface-treated with oxidant, so that institute
State transparent electrode layer non-conductive.
2. the forming method of transparency electrode according to claim 1, wherein,
The conductive material is selected from polyphenylamine series of polymers, polypyrrole based polymer, polythiophene based polymer, carbon nanometer
One or more of pipe, Graphene, nano-silver thread, copper nano-particle, tin indium oxide and antimony tin material.
3. the forming method of transparency electrode according to claim 1, wherein,
Tetraethoxysilane of the polysiloxanes based polymer comprising 60 weight % to 90 weight % and 10 weight % are to 40 weights
Amount % selected from VTES, vinyltrimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane,
γ-methacryloxypropyl trimethoxy silane, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, γ-shrink
Glycerin ether epoxide propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, γ-amine propyl-triethoxysilicane, N- β-
(amine ethyl)-γ-amine propyl trimethoxy silicane, γ-urea propyl-triethoxysilicane, phenyl triethoxysilane, methyl three
Ethoxysilane, MTMS, polyethylene oxide modified silane monomer, poly- methylethoxy radical siloxane and hexamethyl
The copolymer of one or more of disilazane compound.
4. the forming method of transparency electrode according to claim 1, wherein,
The transparent electrode layer has 0.03 μm to 0.5 μm of thickness and the sheet resistance of 80 Ω/sq to 400 Ω/sq.
5. the forming method of transparency electrode according to claim 1, wherein,
The protective layer has 0.05 μm to 0.40 μm of thickness.
6. the forming method of transparency electrode according to claim 1, wherein,
The oxidant comprising hypochlorous acid or its salt, dichromic acid or its salt, cross mangaic acid or its salt, hydrogen peroxide, nitric acid, hydrochloric acid and
One or more of copper chloride and the mixture of acid.
7. the forming method of transparency electrode according to claim 1, wherein,
There are plural lines to be alternately arranged for the transparent electrode layer in the non-conductive region and the transparent electrode layer in remaining region
Pattern form.
8. the forming method of transparency electrode according to claim 1, further comprising the steps of：
After the oxidant surface treatment, the photoresistance pattern is removed.
9. a kind of transparency electrode layered product, including：
Substrate；
Transparent electrode layer, the transparent electrode layer is comprising selected from electric conductive polymer, conductive carbon based material, metal Nano structure
One or more of thing and conductive metal oxide conductive material, and be formed on substrate；And
Protective layer, the protective layer includes poly- selected from polysiloxanes based polymer, acrylic acid series polymeric compounds and amido formate system
One or more of compound polymer, and be formed on the transparent electrode layer,
Wherein, the first area of the transparent electrode layer becomes non-conductive, and remaining second area keeps electric conductivity, Jin Erjie
Determine transparent electrode pattern.
10. transparency electrode layered product according to claim 1, wherein,
The transparent electrode layer of the non-conductive of the first area has the sheet resistance of 150 Ω/sq to 280 Ω/sq.
11. transparency electrode layered products according to claim 1, wherein,
The transparent electrode layer of the first area and second area has the pattern form that plural lines are alternately arranged.
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| PCT/KR2015/008059 WO2016024743A1 (en) | 2014-08-13 | 2015-07-31 | Method for forming transparent electrode and transparent electrode laminate |
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| CN108962504A (en) * | 2018-08-06 | 2018-12-07 | 深圳市希诺威光电科技有限公司 | A kind of preparation method and patterned transparent electrode of patterned transparent electrode |
| CN114127548A (en) * | 2019-07-12 | 2022-03-01 | 株式会社恩西提 | Harmful chemical substance detection device |
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| WO2016024743A1 (en) | 2016-02-18 |
| KR102243747B1 (en) | 2021-04-23 |
| KR20160020230A (en) | 2016-02-23 |
| TWI683039B (en) | 2020-01-21 |
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