CN109972128A - The method that inkjet printing combination electroless plating prepares super thin metal mesh flexible transparent electrode - Google Patents
The method that inkjet printing combination electroless plating prepares super thin metal mesh flexible transparent electrode Download PDFInfo
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- CN109972128A CN109972128A CN201910253482.4A CN201910253482A CN109972128A CN 109972128 A CN109972128 A CN 109972128A CN 201910253482 A CN201910253482 A CN 201910253482A CN 109972128 A CN109972128 A CN 109972128A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1605—Process or apparatus coating on selected surface areas by masking
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
The method that inkjet printing combination electroless plating prepares super thin metal mesh flexible transparent electrode, in the flexible substrates of cohesiveness coating, inkjet printing water-resistant polymer matrix template, electroless plating is carried out in exposed cohesiveness coating patterns, selective deposition metallic, and form ultra-thin (50nm) metal grill of super adhesion.Preparation process of the present invention be green reaction, it is simple, exempt from transfer, energy conservation and environmental protection and low cost.The square resistance of metallic transparent electrode obtained is 9 Ω/sq, it is seen that light transmission rate is evenly distributed up to 89.9%, the difference in height of metal grill and the thickness of only 50nm.By the exposure 552h under the air environment of high humility and the electrical conductance for sticking 200 test discovery super thin metal grids without significant change, there is operating reliability and stability, be expected to realize large area industrialized production.
Description
Technical field
The present invention relates to the methods that inkjet printing combination electroless plating prepares super thin metal mesh flexible transparent electrode.
Background technique
Metal grill transparent electrode is excellent due to having the characteristics that high transparency and high conductivity etc., flexible thoroughly in commercialization
It has broad application prospects in the development process of prescribed electrode and practical potentiality, but before realizing really commercialization, there are many more
Extremely important problems demand solves.Wherein most important problem is exactly to solve biggish thickness between metal grill and base material
Poor, weaker adhesion strength, the distribution of non-uniform sheet resistance and high-temperature process condition.Pass through photoetching, electrostatic spinning and patterning
The height for the metal grill transparent electrode that technology is prepared is very thick and there are node-resistances, to realize it in the opto-electronic device
Application, need to increase the techniques such as transfer, half embedding or prepare type compound transparent electrode and overcome, hence it is evident that increase electrode material
Expect the complexity of processing technology.Inkjet printing technology can overcome biggish node-resistance between grid to keep electrode surface in turn
The uniformity of resistance, but control the limitation of thickness difference between grid and base material.In addition, directly being prepared using inkjet printing
Metal grill transparent electrode generally requires higher annealing temperature, this is also runed counter to the original intention of green printing.Therefore, it realizes ultra-thin
The large area production of metal grill, which just becomes one, is worth the technical issues of studying.Electroless plating is to prepare super thin metal grid most
Ideal technical matters is realizing that low cost, large area produce and low temperature preparation has great advantages.It therefore, will be without electricity
Plating improves grid adhesion strength, it is saturating just to can solve current metal grill in conjunction with inkjet printing technology, and through appropriate interface modification
Main bugbear of prescribed electrode during practical commercial, and meet the basic demand of green printing.
Summary of the invention
The purpose of the present invention is to propose to a kind of inkjet printing combination electroless plating, to prepare super thin metal mesh flexible transparent
The method of electrode.In the flexible substrates of cohesiveness coating, the matrix template of the printable water-resistant polymer of inkjet printing,
Electroless plating, selective deposition metallic are carried out in exposed cohesiveness coating patterns, and form the super thin metal of super adhesion
Grid shows good inoxidizability and excellent transparent conductivity and uniform pattern.
The present invention is achieved by the following technical solutions.
The method that a kind of inkjet printing combination electroless plating of the present invention prepares super thin metal grid transparent electrode,
The following steps are included:
(a) weigh function of surface coated polymeric, be dissolved in deionized water, polymer quality score be 0.1~
The substrate of oxygen plasma treatment is immersed 10~30min in above-mentioned aqueous solutions of polymers by 1.0wt%, or be spun on oxygen etc. from
In the substrate of daughter processing, the substrate containing coating is put into 10~30min of baking oven and 50~80 DEG C of temperature control；
(b) configuration quality score is the printable water-resistant polymer ink of 2-16wt%.
(c) water-resistant polymer ink is packed into ink-jet printer, and is compiled in mapping software or directly by printer
Then the matrix pattern of journey software design difference line width and line spacing carries out inkjet printing in the substrate obtained by step (a), waits ink
Matrix mask plate is obtained after water rapid draing, it is spare.
(d) metal complex solution and reducing agent solvent are configured, is uniformly mixed, then the substrate containing matrix mask plate is quick
It is put into mixed solution and carries out electroless plating reaction 5-30min, the selective deposition metallic on exposed cohesiveness coating, and
Form metal grill pattern.
(e) sample for obtaining step (d) with n,N-Dimethylformamide (DMF) dissolve mask plate, dissolution time be 3~
60s.Then, several times then successively are cleaned with ethyl alcohol and deionized water, N2Drying, it is final to realize that height is prepared without transfer printing in low temperature
The super thin metal grid transparent electrode of adhesion.
The substrate of oxygen plasma treatment described in step (a), including polyethylene terephthalate (PET) film,
Polyvinyl alcohol (PVA) film, polyimides (PI) film, polyethylene naphthalate (PEN) film, preferably poly- terephthaldehyde
Sour glycol ester (PET).
The preferred poly-dopamine of function of surface coated polymeric (PDA), poly-L-Lysine (PLL) described in step (a) are gathered
One of aziridine (PEI) or polypropylene amine (PAA) are a variety of.
When function of surface coated polymeric described in step (a) is poly-L-Lysine, polyethyleneimine or polypropylene amine,
It is preferred that being dissolved separately in deionized water by 0.1~0.5wt%；When the function of surface coated polymeric is poly-dopamine, lead to
It crosses dopamine and is dissolved in buffer solution autoxidation formation poly-dopamine, the buffer solution is to add in every 200mL deionized water
0.09g trihydroxymethylaminomethane hydrochloride and 0.17g trishydroxymethylaminomethane.
The printable preferred polystyrene of water-resistant polymer (PS), polymethyl methacrylate described in step (b)
(PMMA), polyacrylonitrile (PAN) or polyethylene (PE) etc..
When printable water-resistant polymer described in step (b) is polystyrene (PS), preferably dissolved by 14-16wt%
In N,N-dimethylformamide (DMF)；The printable water-resistant polymer is polymethyl methacrylate (PMMA), gathers
Whens acrylonitrile (PAN) or polyethylene (PE) etc., n,N-Dimethylformamide (DMF) preferably is dissolved separately in by 2-5wt%；It is described
Polymer solution temperature be 50-80 DEG C.
Metal complex solution described in step (d) is silver ammino solution or potassium tartrate copper solution, and reducing agent is glucose
With the mixed solution or formalin of methanol.
Further, the metal complex solution described in the step (d) chooses silver ammino solution, and reducing agent chooses glucose and first
When the mixed solution of alcohol, configuration process is as follows:
1) silver ammino solution configures: configuring 0.23~0.24mol/L silver nitrate solution, 0.25~0.26mol/ with deionized water
L potassium hydroxide solution is dripped potassium hydroxide solution in nitric acid silver Rong Ye ﹕ potassium hydroxide solution=40~44 μ L of 20mL ﹕ ratio
It is added in silver nitrate solution, the ammonium hydroxide that concentration is 28~32% is added dropwise after solution is muddy becomes to clarify again to solution, spare；
2) mixed solution of glucose and methanol configures: 1.85~1.9mol/L glucose solution is configured with ionized water, it will
Absolute methanol solution is added drop-wise to glucose solution, and dripping quantity is that 0.5~0.8mL anhydrous methanol is added in every 1mL grape solution, obtains
Mixed solution it is spare；
3) by step 1) and 2) in acquired solution mix after stir and pour into surface plate, and by the function of the plate containing matrix mask
Coated substrate is put into, and is reacted 5~10min, is obtained conductive grid film；
Further, the metal complex solution described in the step (d) is chosen for potassium tartrate copper solution, and reducing agent chooses first
When aldehyde solution, configuration process is as follows:
1) with ionized water configure 0.0056~0.0057mol/L palladium chloride, after dissolution by palladium chloride Rong Ye ﹕ concentrated hydrochloric acid=
The ratio of 0.17~0.18mL of 20mL ﹕, concentrated hydrochloric acid is added in palladium chloride solution, spare after mixing；
2) potassium tartrate copper solution configures: configuring 0.038~0.042mol/L cupric sulfate pentahydrate solution, dissolution with ionized water
Afterwards, it adds 0.05~0.052mol/L sodium potassium tartrate tetrahydrate to be dissolved, is eventually adding 0.043~0.044mol/L hydroxide
Sodium obtains potassium tartrate copper complex solution after dissolution completely, by potassium tartrate copper complex solution: reducing agent formalin=
Formalin is added to potassium tartrate copper complex solution by the ratio of 1~2mL of 20mL ﹕, spare after mixing.
3) substrate of gained matrix mask plate pattern is first put into static 2min in the solution of step 1), be then quickly put into
30min is reacted in the solution of step 2).
The method of the present invention selects environmental protection, low cost, the ink easily removed, meets the basic demand of green printing.And ink-jet
Printing technique can design different mask patterns while avoiding metal grill node-resistance problem to prepare different demands
Grid electrode pattern, and die plate pattern have high-resolution.Exempt to turn it is worth noting that, electroless plating techniques of the invention belong to
Print technique, have many advantages, such as it is simple, easy, can cryogenic conditions large area solution processing.The present invention selects the soft of cohesiveness coating
Property substrate, cohesiveness polymer coating has many amino, hydroxyl, catechol functional group etc., (soft in modification different base
Property, rigidity) when can form superpower gluing layer, while adjusting metal nucleation and non-uniform topographical, and then it is equal to solve metal grill
The adhesion problem of even pattern and metal grill and substrate.The printable water-resistant polymer of inkjet printing in above-mentioned substrate
Matrix template, the water-resistant polymer template of selection can prevent metallic from penetrating polymer template and pollution meshed raceway,
The clean and tidy metal grill of edge clear is prepared in realization.Finally, it is only applied in exposed cohesiveness by low-temperature electricity-free plated deposition
Selective deposition metallic on layer pattern, and then the ultra-thin silver-colored grid of super adhesion is formed, therefore, metal grid electrode shows
Good inoxidizability out, excellent transparent conductivity and non-uniform topographical.Compared with photoetching technique, in addition to avoiding exposure, showing
Shadow and high-temperature process and etc., there is whole preparation process of the invention low temperature to exempt from transfer, low cost, environmental protection and simple process stream
The advantages of journey is final for realizing that preparation flexible extensible photoelectric device and the printing of roll-to-roll large area are of great significance
The commercial applications of the super thin metal grid transparent electrode of mechanical firmness lay the foundation.Meanwhile we are it is also believed that electroless plating is auxiliary
It helps inkjet printing that can improve simple and efficient method for the following actual production flexible metal electrode, is wearable electronic product
Business application provides prospect.
Beneficial effects of the present invention are as follows:
The entire preparation process of metallic transparent electrode of the invention is no more than 80 DEG C, preparation process be green reaction, it is simple,
Exempt from transfer, energy conservation and environmental protection and low cost.High cohesiveness of the invention and ultra-thin metal grill flexible transparent electrode are on surface
The printable water-resistant polymer template of inkjet printing in the polymer-modified substrate of functional coating, then coheres in exposed height
The metallic film of electroless deposition non-uniform topographical is made on property coating.The square resistance of metallic transparent electrode obtained be 9 Ω/
Sq, it is seen that light transmission rate is evenly distributed up to 89.9%, the difference in height of metal grill and the thickness of only 50nm.In existing research very
Rare report is able to achieve ultra-thin metal grill flexible transparent electrode by exempting from the electroless plating techniques of transfer, realizes business with current
The thickness (705nm) of the silver-colored grid electrode of change is advantageously.With commercialization indium tin oxide transparent electrode and commercialized silver-colored net
Lattice electrode is compared, and after 552h is exposed under the air environment of high humility and sticks 200 times, prepared super thin metal grid is saturating
The electrical conductance of prescribed electrode test is without significant change.
In addition, prepared super thin metal grid transparent electrode has excellent inoxidizability and superpower adhesion, tool
There are operating reliability and practicability, roll-to-roll large area printing technology can be directly realized by.Under cryogenic, inkjet printing and nothing
Electroplating technology is all the process flow that can amplify preparation.Therefore, metallic film is prepared without high-temperature calcination technique to improve
Electric conductivity, simplification of flowsheet and energy conservation and environmental protection are expected to realize large area industrialized production.
Detailed description of the invention
Fig. 1 is the silver-colored mesh flexible transparent electrode (Ag mesh@PDA/PET) of inkjet printing combination electroless plating techniques preparation
Pictorial diagram.Wherein, silver-colored grid edge clear.
Fig. 2 is silver-colored mesh flexible transparent electrode (Ag mesh@PDA/PET) prepared by the embodiment of the present invention 1 and commercialization silver
The difference in height comparison diagram of grid (Commercial Ag grids).
Fig. 3 is silver-colored mesh flexible transparent electrode (Ag mesh@PDA/PET) prepared by the embodiment of the present invention 1 and commercialization indium
Tin-oxide flexible electrode (ITO/PET) and the difference for being commercialized silver-colored mesh flexible electrode (Commercial Ag grids)
The uv-vis spectra (UV-vis) of square resistance and corresponding light transmittance.
Fig. 4 is silver-colored mesh flexible transparent electrode (Ag mesh@PDA/PET) prepared by the embodiment of the present invention 1 and commercialization indium
Tin-oxide flexible electrode (ITO/PET), the silver-colored mesh flexible electrode (Commercial Ag grids) of commercialization are opposite 85%
The square resistance trend chart tested after exposure 552h in the air of humidity.
Fig. 5 is silver-colored mesh flexible transparent electrode (Ag mesh@PDA/PET) prepared by the embodiment of the present invention 1 and commercialization indium
Tin-oxide flexible electrode (ITO/PET) is commercialized silver-colored mesh flexible electrode (Commercial Ag grids) progress 200 times
Stick the square resistance trend chart of test.
Specific embodiment
The present invention will be described further by following embodiment.
Embodiment 1.
A) weigh 0.09g trihydroxymethylaminomethane hydrochloride and 0.17g trishydroxymethylaminomethane be dissolved in 200mL go from
In sub- water, poly-dopamine (PDA) solution is formed after 0.4g dopamine (DA) dissolution is added；
B) substrate of oxygen plasma treatment (polyethylene terephthalate, PET) is immersed into buffer solution a) immediately
In and react 20min, the substrate of the coating containing PDA is put into 15min in 60 DEG C of baking oven；
C) polystyrene (PS) of 2.5015g is weighed, stirring and dissolving is in the N of 15mL, N- dimethyl under the conditions of 60 DEG C of oil baths
In formamide, it is configured to the PS ink of 15wt%；
D) PS ink is packed into ink-jet printer, and designs 300 μm of line widths and 2mm line spacing in printer programming software
Then matrix pattern carries out inkjet printing in the substrate with PDA coating, obtain matrix mask plate after waiting inks rapid draing
Pattern；
E) 0.815g silver nitrate is added in 20mL deionized water, stirring is dissolved, and 40 μ L 0.25mol/L hydrogen are added dropwise
Potassium oxide solution, 28% ammonium hydroxide (about 950 μ L) is added dropwise after solution is muddy becomes to clarify again to solution；
F) 6.84g glucose is added in 20mL deionized water, stirring is dissolved, and it is molten to be added to 10mL anhydrous methanol
Reducing agent is used as in liquid.
G) by step e) and f) in acquired solution quickly stir after pour into surface plate, and will be by square obtained in step d)
The substrate of battle array mask pattern is put into reaction 5min.
H) step g) is obtained into the dissolution that sample is put into the progress 3-5s time in n,N-Dimethylformamide, successively uses ethyl alcohol
Several times are cleaned with deionized water, N2It is saturating that high close-burning super thin metal grid is prepared eventually by no transfer process in drying
Prescribed electrode.
Embodiment 2.
A) weigh 0.09g trihydroxymethylaminomethane hydrochloride and 0.17g trishydroxymethylaminomethane be dissolved in 200mL go from
In sub- water, poly-dopamine (PDA) solution is formed after 0.4g dopamine (DA) dissolution is added；
B) substrate of oxygen plasma treatment (polyethylene terephthalate, PET) is immersed into buffer solution a) immediately
In and react 20min, the substrate of the coating containing PDA is put into 15min in 60 DEG C of baking oven；
C) polymethyl methacrylate (PMMA) of 0.0427g is weighed, stirring and dissolving is in 15mL's under the conditions of 60 DEG C of oil baths
In n,N-Dimethylformamide, it is configured to the PMMA ink of 0.3wt%；
D) PMMA ink is packed into ink-jet printer, and designs 300 μm of line widths and 2mm line spacing in printer programming software
Matrix pattern, inkjet printing is then carried out in the substrate with PDA coating, obtains matrix mask after waiting inks rapid draing
Plate pattern；
E) 0.02g palladium chloride is added in 20mL deionized water and is dissolved, 0.1715mL concentrated hydrochloric acid is added, after dissolution completely
It is spare；
F) 0.2g cupric sulfate pentahydrate is added in 20mL deionized water, stirring is dissolved, and 0.4516g winestone is then added to
Sour potassium sodium is dissolved, and 0.35g sodium hydroxide is eventually adding, and adds 1mL formaldehyde after dissolving completely.
G) substrate of gained matrix mask plate pattern in step d) is first put into static 2min in the solution of step e), then
It is quickly put into the solution of step f) and reacts 30min.
H) step g) is obtained into the dissolution that sample is put into the progress 30-60s time in n,N-Dimethylformamide, successively uses second
Pure and mild deionized water cleans several times, N2High close-burning super thin metal grid is prepared eventually by no transfer process in drying
Transparent electrode.
Embodiment 3.
A) weigh 0.09g trihydroxymethylaminomethane hydrochloride and 0.17g trishydroxymethylaminomethane be dissolved in 200mL go from
In sub- water, poly-dopamine (PDA) solution is formed after 0.4g dopamine (DA) dissolution is added；
B) substrate of oxygen plasma treatment (polyethylene terephthalate, PET) is immersed into buffer solution a) immediately
In and react 20min, the substrate of the coating containing PDA is put into 15min in 60 DEG C of baking oven；
C) polyacrylonitrile (PAN) of 0.0712g is weighed, stirring and dissolving is in the N of 15mL, N- dimethyl under the conditions of 60 DEG C of oil baths
In formamide, it is configured to the PAN ink of 0.5wt%；
D) PS ink is packed into ink-jet printer, and designs 300 μm of line widths and 2mm line spacing in printer programming software
Then matrix pattern carries out inkjet printing in the substrate with PDA coating, obtain matrix mask plate after waiting inks rapid draing
Pattern；
E) 0.815g silver nitrate is added in 20mL deionized water, stirring is dissolved, and 40 μ L 0.25mol/L hydrogen are added dropwise
Potassium oxide solution, 28% ammonium hydroxide (about 950 μ L) is added dropwise after solution is muddy becomes to clarify again to solution；
F) 6.84g glucose is added in 20mL deionized water, stirring is dissolved, and it is molten to be added to 10mL anhydrous methanol
Reducing agent is used as in liquid.
G) by step e) and f) in acquired solution quickly stir after pour into surface plate, and will be by square obtained in step d)
The substrate of battle array mask pattern is put into reaction 5min.
H) step g) is obtained into the dissolution that sample is put into the progress 30-60s time in n,N-Dimethylformamide, successively uses second
Pure and mild deionized water cleans several times, N2High close-burning super thin metal grid is prepared eventually by no transfer process in drying
Transparent electrode.
Embodiment 4.
A) weigh 0.09g trihydroxymethylaminomethane hydrochloride and 0.17g trishydroxymethylaminomethane be dissolved in 200mL go from
In sub- water, poly-dopamine (PDA) solution is formed after 0.4g dopamine (DA) dissolution is added；
B) substrate of oxygen plasma treatment (polyethylene terephthalate, PET) is immersed into buffer solution a) immediately
In and react 20min, the substrate of the coating containing PDA is put into 15min in 60 DEG C of baking oven；
C) weigh 0.0427g polyethylene (PE), under the conditions of 80 DEG C of oil baths stirring and dissolving in n,N-Dimethylformamide,
It is configured to the PE ink of 0.3wt%；
D) PS ink is packed into ink-jet printer, and designs 300 μm of line widths and 2mm line spacing in printer programming software
Then matrix pattern carries out inkjet printing in the substrate with PDA coating, obtain matrix mask plate after waiting inks rapid draing
Pattern；
E) 0.815g silver nitrate is added in 20mL deionized water, stirring is dissolved, and 40 μ L 0.25mol/L hydrogen are added dropwise
Potassium oxide solution, 28% ammonium hydroxide (about 950 μ L) is added dropwise after solution is muddy becomes to clarify again to solution；
F) 6.84g glucose is added in 20mL deionized water, stirring is dissolved, and it is molten to be added to 10mL anhydrous methanol
Reducing agent is used as in liquid.
G) by step e) and f) in acquired solution quickly stir after pour into surface plate, and will be by square obtained in step d)
The substrate of battle array mask pattern is put into reaction 5min.
H) it step g) is obtained sample is put into carry out the dissolution of 30-60s time in 60 DEG C of n,N-Dimethylformamide, according to
It is secondary to clean several times with ethyl alcohol and deionized water, N2High close-burning ultra-thin gold is prepared eventually by no transfer process in drying
Belong to grid transparent electrode.
Obtained sample is characterized through instrument detection in above-described embodiment 1, and result is as follows:
(1) as shown in Figure 1, silver-colored mesh flexible transparent electrode (the Ag mesh@of inkjet printing combination electroless plating techniques preparation
PDA/PET) pictorial diagram shows silver-colored grid edge clear.
(2) as shown in Figure 2, with the silver-colored grid height that is commercialized silver-colored mesh flexible electrode (Commercial Ag grids)
(750nm) is compared, and prepared metallic film transparent electrode (Ag mesh@PDA/PET) shows have in wide area
Ultra-thin (50nm) grid of good uniform thickness.Ultra-thin grid is highly advantageous for the application of photovoltaic device.
(3) from the figure 3, it may be seen that with commercialization indium tin oxide flexible electrode (ITO/PET), the silver-colored mesh flexible electrode of commercialization
(Commercial Ag grids) is compared, and prepared metallic film transparent electrode (Ag mesh@PDA/PET) has excellent
Translucency and electric conductivity.
(4) as shown in Figure 4, with commercialization indium-tin oxide electrode (ITO/PET), be commercialized silver-colored mesh flexible electrode
(Commercial Ag grids) is compared, and in the air of 85% relative humidity after exposure 552h, prepared metallic film is saturating
The square resistance of prescribed electrode (Ag mesh@PDA/PET) remains unchanged, and shows that its silver-colored grid electrode has excellent stability,
With operating reliability and practicability.
(5) as shown in Figure 5, with commercialization indium-tin oxide electrode (ITO/PET), be commercialized silver-colored mesh flexible electrode
(Commercial Ag grids) is compared, after 200 cohesivenesses are tested, prepared metallic film transparent electrode (Ag
Mesh@PDA/PET) square resistance remain unchanged, show that adhesive force is strong between silver-colored grid and substrate.
Claims (9)
1. a kind of method that inkjet printing combination electroless plating prepares super thin metal grid transparent electrode, it is characterized in that include with
Lower step:
(a) function of surface coated polymeric is weighed, is dissolved in deionized water, polymer quality score is 0.1~1.0wt%, will
The substrate of oxygen plasma treatment immerses 10~30min in above-mentioned aqueous solutions of polymers, or is spun on oxygen plasma treatment
In substrate, the substrate containing coating is put into 10~30min of baking oven and 50~80 DEG C of temperature control；
(b) configuration quality score is the printable water-resistant polymer ink of 2-16wt%；
(c) water-resistant polymer ink is packed into ink-jet printer, and in mapping software or is directly programmed by printer soft
Part designs the matrix pattern of different line widths and line spacing, then carries out inkjet printing in the substrate obtained by step (a), waits inks fast
Matrix mask plate is obtained after rapid-curing cutback is dry, it is spare；
(d) metal complex solution and reducing agent solvent are configured, is uniformly mixed, then the substrate containing matrix mask plate is quickly put into
Electroless plating is carried out in mixed solution and reacts 5-30min, the selective deposition metallic on exposed cohesiveness coating, and is formed
Metal grill pattern；
(e) sample for obtaining step (d) n,N-Dimethylformamide dissolves mask plate, and dissolution time is 3~60s；Then,
Several times successively are cleaned with ethyl alcohol and deionized water again, N2Drying, it is final to realize that high-adhesiveness is prepared without transfer printing in low temperature
Super thin metal grid transparent electrode.
2. a kind of inkjet printing combination electroless plating according to claim 1 prepares super thin metal grid transparent electrode
Method, it is characterized in that the substrate of oxygen plasma treatment described in step (a) is pet film, poly- second
Enol film, Kapton, polyethylene naphthalate film.
3. a kind of inkjet printing combination electroless plating according to claim 1 prepares super thin metal grid transparent electrode
Method, it is characterized in that function of surface coated polymeric described in step (a) is poly-dopamine, poly-L-Lysine, polyethyleneimine
Or one of polypropylene amine or a variety of.
4. a kind of inkjet printing combination electroless plating according to claim 1 prepares super thin metal grid transparent electrode
Method, it is characterized in that function of surface coated polymeric described in step (a) is poly-L-Lysine, polyethyleneimine or polypropylene
When amine, deionized water is dissolved separately in by 0.1~0.5wt%；When the function of surface coated polymeric is poly-dopamine, lead to
It crosses dopamine and is dissolved in buffer solution autoxidation formation poly-dopamine, the buffer solution is to add in every 200mL deionized water
0.09g trihydroxymethylaminomethane hydrochloride and 0.17g trishydroxymethylaminomethane.
5. a kind of inkjet printing combination electroless plating according to claim 1 prepares super thin metal grid transparent electrode
Method, it is characterized in that printable water-resistant polymer described in step (b) is polystyrene, polymethyl methacrylate, gathers
Acrylonitrile or polyethylene.
6. a kind of inkjet printing combination electroless plating according to claim 1 prepares super thin metal grid transparent electrode
Method, it is characterized in that being dissolved in when printable water-resistant polymer described in step (b) is polystyrene by 14-16wt%
N,N-dimethylformamide；The printable water-resistant polymer is polymethyl methacrylate, polyacrylonitrile or poly- second
When alkene, n,N-Dimethylformamide is dissolved separately in by 2-5wt%；The polymer solution temperature is 50-80 DEG C.
7. a kind of inkjet printing combination electroless plating according to claim 1 prepares super thin metal grid transparent electrode
Method, it is characterized in that metal complex solution described in step (d) is silver ammino solution or potassium tartrate copper solution, reducing agent is Portugal
The mixed solution or formalin of grape sugar and methanol.
8. a kind of inkjet printing combination electroless plating according to claim 1 or claim 7 prepares the transparent electricity of super thin metal grid
The method of pole, it is characterized in that working as metal complex solution described in step (d) chooses silver ammino solution, reducing agent chooses glucose and first
When the mixed solution of alcohol, configuration process is as follows:
1) silver ammino solution configures: configuring 0.23~0.24mol/L silver nitrate solution, 0.25~0.26mol/L hydrogen with deionized water
Potassium hydroxide solution is added dropwise in nitric acid silver Rong Ye ﹕ potassium hydroxide solution=40~44 μ L of 20mL ﹕ ratio for potassium oxide solution
Into silver nitrate solution, the ammonium hydroxide that concentration is 28~32% is added dropwise after solution is muddy becomes to clarify again to solution, spare；
2) mixed solution of glucose and methanol configures: 1.85~1.9mol/L glucose solution is configured with ionized water, it will be anhydrous
Methanol solution is added drop-wise to glucose solution, and dripping quantity is that 0.5~0.8mL anhydrous methanol is added in every 1mL grape solution, and what is obtained is mixed
Close solution for standby；
3) by step 1) and 2) in acquired solution mix after stir and pour into surface plate, and by the functional coating of the plate containing matrix mask
Substrate is put into, and is reacted 5~10min, is obtained conductive grid film.
9. a kind of inkjet printing combination electroless plating according to claim 1 or claim 7 prepares the transparent electricity of super thin metal grid
The method of pole, it is characterized in that working as metal complex solution described in step (d) is chosen for potassium tartrate copper solution, reducing agent chooses first
When aldehyde solution, configuration process is as follows:
1) 0.0056~0.0057mol/L palladium chloride is configured with ionized water, palladium chloride Rong Ye ﹕ concentrated hydrochloric acid=20mL ﹕ is pressed after dissolution
The ratio of 0.17~0.18mL, concentrated hydrochloric acid is added in palladium chloride solution, spare after mixing；
2) potassium tartrate copper solution configures: 0.038~0.042mol/L cupric sulfate pentahydrate solution is configured with ionized water, after dissolution,
It adds 0.05~0.052mol/L sodium potassium tartrate tetrahydrate to be dissolved, is eventually adding 0.043~0.044mol/L sodium hydroxide, it is molten
Potassium tartrate copper complex solution is obtained after solution is complete, by potassium tartrate copper complex solution: reducing agent formalin=20mL ﹕ 1~
Formalin is added to potassium tartrate copper complex solution by the ratio of 2mL, spare after mixing；
3) substrate of gained matrix mask plate pattern is first put into static 2min in the solution of step 1), is then quickly put into step
2) 30min is reacted in solution.
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