CN105350043A - Method for preparing high-performance metallic network transparent conducting electrode through metal plating method - Google Patents
Method for preparing high-performance metallic network transparent conducting electrode through metal plating method Download PDFInfo
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- CN105350043A CN105350043A CN201510777346.7A CN201510777346A CN105350043A CN 105350043 A CN105350043 A CN 105350043A CN 201510777346 A CN201510777346 A CN 201510777346A CN 105350043 A CN105350043 A CN 105350043A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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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
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
Abstract
The invention discloses a method for preparing a high-performance metallic network transparent conducting electrode through a metal plating method. The method includes the following steps: (1) a fracturing sacrificial layer template is prepared on a substrate; (2) a metallic conducting seed layer is deposited on the fracturing sacrificial layer template; (3) the fracturing sacrificial layer is removed to form a metallic conducting seed layer network; and (4) metal is continuously deposited on the metallic conducting seed layer through the metal plating method, a continuous metal network with the larger thickness and the lower resistance is formed, and therefore the high-performance metallic network transparent conducting electrode is prepared. The transparent conducting electrode is mainly obtained through the metal plating method, the metal plating method belongs to a chemical liquid phase method, the preparing process is simple, resource consumption is low, and the high-performance metallic network transparent conducting electrode is suitable for large-area continuous preparation. The prepared transparent conducting electrode has the extremely-low surface resistance and the better light transmittance; meanwhile, the mechanical property and the environmental stability are good, the transparent conducting electrode is a beneficial replacer of a traditional metallic oxide electrode, and it is expected that the method is used for industrialization of the large-area transparent conducting electrode.
Description
Technical field
The invention belongs to membrane electrode technical field, be specifically related to the method for a kind of Metal plating legal system for high-performance metal network readezvous point conductive electrode.
Background technology
Transparency conductive electrode is one of key components of the photoelectric devices such as LED (photodiode), solar cell, intelligent glass, to the carrier collection in device with transport, and device stability and preparation cost have important impact.In general, transparency conductive electrode refers to and is greater than 80% to the transmissivity of the spectrum of lambda1-wavelength scope between 380nm to 780nm, and resistivity is lower than 10
-3the membrane electrode of Ω cm.Nowadays, metal conductive oxide film, such as ITO (mixing the stannic oxide of indium), FTO (mixing the stannic oxide of fluorine) have been widely used in LED, solar cell and intelligent glass.From physical angle, the light transmission of material and electroconductibility are a pair basic contradictions.Material will possess a good electroconductibility, must have higher carrier concentration and higher carrier mobility simultaneously, but the current carrier of higher concentration can absorb photons and improve material and reduce its transmissivity to the specific absorption of light.For many years, from metallic film to metal conductive oxide film, polymeric conductor films, from one-component material to multicomponent mixture material, the research of scientific research bound pair transparency conductive electrode launches around this contradiction always.Metal oxide, particularly ITO, have higher light transmission rate and lower resistivity in visible region, be the focus of transparency conductive electrode investigation and application in the past over 50 years always.But ITO metal oxide is used as the limited electrical conductivity of electrode of solar battery own, and the defect such as matter is crisp frangible, not yielding, raw material resources are day by day rare simultaneously, and manufacturing price is expensive.Therefore constantly develop to meet photoelectric device in the urgent need to probing into adaptation big area low cost manufacture high-performance transparency conductive electrode method.
In recent years along with the development of nanometer novel material and new texture, a frontier of transparency conductive electrode developing is two-dimensional nano novel material and structural membrane electrode, such as high polymer conductive film, carbon nano-tube film, graphene film, random nano metal line film, metal grill film.Although high polymer conductive film is more cheap and easy to get, the more weak conductive capability of superpolymer limits its widely using in the devices; Carbon nano-tube film needs comparatively big L/D ratio, and the ohmic resistance problem between the dispersed and carbon nanotube of carbon nanotube limit film face in electroconductibility; The pattern that graphene film itself is special and have good flexibility, also have good carrier mobility, but volume production technology is not yet ripe simultaneously; For random nano metal line film, regulate synthesis in enormous quantities to have the nano-silver thread of larger length-to-diameter ratio, and dispersed nano wire difficulty is very large, and the contact resistance of nano silver electrode and substrate or active layer and adhesion problem thereof are difficult to solve; Comparatively speaking, metal grill film can avoid these problems.Transparency conductive electrode, except excellent electroconductibility, also needs excellent optical transmittance, the ratio (σ of photoconductivity
dC/ σ
opt, σ
dCrefer to specific conductivity, be directly proportional to electrode surface resistance, σ
optrefer to optical conductivity, be inversely proportional to electrode light transmission rate) the good photoelectric properties describing transparency conductive electrode.Research shows: in general, and the ratio of metal grill film electrode photoelectric conductance is the highest in these two-dimensional nano novel materials, this shows that metal grill film has outstanding electroconductibility and optical transmittance.This is because tradition prepares the micro-nano metallic conduction grid line of the main service regeulations of metal grill film, namely obtain regular micro-nano-scale grid line at substrate surface by technology such as silk screen printing, photoetching or nano impressions.Thickness opposing metallic film due to conduction grid line wants thicker, the surface and interface scattering of electronics dies down, the electroconductibility of grid line is close to the electroconductibility of bulk metal, and the scattering of light effect of time wavelength dimension grid line simultaneously and coupling reduce the luminous reflectance loss that electrode part is brought.Concerning solar cell, scattering of light effect improves the sorption of active layer to light.In addition metal grill membrane electrode is applicable to the productions such as flexible substrate, and thus metal grill will become the favourable replacer of present ITO transparency conductive electrode.
But traditional metal grid electrode also exists some defects.Common metal grid electrode needs expensive preparation method's (silk screen printing, photoetching, vacuum moulding machine etc.), which increases the application cost of this electrode.In addition rely on vacuum moulding machine film forming in a large number, the big area volume production of metal grid electrode is prepared into as a difficult problem.The random metalolic network electrode that nearest solution method or template synthesis obtain, although avoid the method costly such as photoetching, but still exist need high-vacuum technology or photoelectric properties not good enough.So a kind of low cost of development and Design, the big area volume production method of preparing high-performance metal network readezvous point conductive electrode can to seem and be even more important.
Summary of the invention
The object of the present invention is to provide a kind of Metal plating legal system for the method for high-performance metal network readezvous point conductive electrode, this preparation method belongs to chemical liquid phase reaction, and technique is simple, and cost is low, is applicable to big area continuous production metalolic network transparency conductive electrode.
Above-mentioned purpose of the present invention is achieved through the following technical solutions: a kind of Metal plating legal system, for the method for high-performance metal network readezvous point conductive electrode, comprises the following steps:
(1) preparation be full of cracks sacrifice layer template on substrate;
(2) depositing metal conductive Seed Layer in be full of cracks sacrifice layer template;
(3) remove be full of cracks sacrifice layer template, form metallic conduction Seed Layer network;
(4) adopt metal electric plating method to continue metal refining in metallic conduction Seed Layer, form higher caliper and low-resistance continuous metal grid, thus obtained high-performance metal network readezvous point conductive electrode.
Metal plating legal system of the present invention is for the method for high-performance metal network readezvous point conductive electrode, the method preparation technology is simple, low in resources consumption, and applicable big area continuous production technique, the transparency conductive electrode of preparation has ultralow surface resistivity, preferably light transmission, and preferably environmental stability and mechanicalness, be not only the favourable replacer of INVENTIONConventional metal-oxide electrode, and be expected to the industrialization for large-area transparent conductive electrode.
In the method for above-mentioned Metal plating legal system for high-performance metal network readezvous point conductive electrode:
Substrate described in step of the present invention (1) can be glass, polyimide PI, polyethylene terephtalate, polydimethylsiloxane or polymetylmethacrylate.
The main raw of the be full of cracks sacrifice layer template described in step of the present invention (1) is the egg white solution of bird, acrylic polymer or metal oxide TiO
2; On substrate, the detailed process of preparation be full of cracks sacrifice layer template is: be coated on substrate by sacrifice layer dissolution homogeneity, oven drying at low temperature under natural air drying or 40 ~ 80 DEG C of conditions, forms the be full of cracks sacrifice layer template of micro-or nano size and the continuous be full of cracks network of micro-or nano size after be full of cracks.
Metal in metallic conduction Seed Layer described in step of the present invention (2) is preferably palladium, silver, gold, aluminium, copper or nickel.
Further, when adopting above-mentioned metal, in step of the present invention (2), preferably adopt magnetron sputtering method or liquid phase deposition when chapping depositing metal conductive Seed Layer in sacrifice layer template.
As one of the present invention preferred embodiment, when adopting observing and controlling sputtering method, sputtering power is preferably 50 ~ 200w, and magnetic control chamber room temp is preferably 20 ~ 25 DEG C, be full of cracks sacrifice layer template surface temperature is preferably 30 ~ 60 DEG C, and metallic conduction seed layer thickness is preferably 5 ~ 30nm.
As another preferred embodiment of the present invention, when adopting liquid phase deposition, detailed process is: metallize salts solution in be full of cracks sacrifice layer template, be heated to sacrifice layer die plate temperature and be preferably 100 ~ 300 DEG C, wherein metal salt solution decomposition obtains metallic conduction Seed Layer, after removing sacrifice layer template, preferably at 150 ~ 600 DEG C of temperature, sintering forms metallic conduction Seed Layer network.
The method removing be full of cracks sacrifice layer template in step of the present invention (3) has following several mode: when the material of the sacrifice layer template that chaps is the egg white solution of bird, washed with de-ionized water is adopted to remove sacrifice layer template, when the material of the sacrifice layer template that chaps is acrylic polymer, acetone cleaning is adopted to remove, when the material of be full of cracks sacrifice layer template is metal oxide TiO
2time, adopt mechanical friction method to remove.
The detailed process adopting metal electric plating method to continue metal refining in metallic conduction Seed Layer in step of the present invention (4) is: take tinsel as anode, with the substrate with metallic conduction Seed Layer network for negative electrode, be placed in metal electroplating solution, adjustment polar plate spacing is 0.5 ~ 3cm, connect D.C. regulated power supply, adjustment electric current is 0.005 ~ 0.05A, plating 1 ~ 60min.
Metal in tinsel of the present invention and metal electroplating solution is silver, gold, zinc, aluminium, copper or nickel.
Metal electroplating solution is the salts solution of the metal such as silver, gold, zinc, aluminium, copper and mickel or in above-mentioned metal salt solution, is added with the metal electroplating solution of other buffer reagent well known in the art and additive.
Principle of the present invention is: be coated on the thin film sacrificial layer on substrate, and volatilization of being heated during air-dry or oven drying at low temperature loses solvent, forms be full of cracks network template.Utilize this template, deposit thin metals Seed Layer, remove sacrifice layer template and can obtain seed metallization conductive layer network.Take tinsel as anode, the substrate containing metal seed layer is negative electrode, is placed in metal electroplating solution.After switching on power, anode loses electronics generation oxidizing reaction, metal becomes metallic cation and enters in solution, negative electrode generation reduction reaction simultaneously, the metallic cation be positioned near substrate Seed Layer is reduced into atoms metal owing to obtaining electronics, attachment on the seed layer, makes conductive network film thicken the effect reaching growing metal network, obtains the metalolic network transparency conductive electrode that photoelectric properties are excellent.
Tool of the present invention has the following advantages:
(1) preparation method of the present invention is easy, with low cost;
(2) the present invention can adjust the film thickness of metalolic network electrode by adjustment metal electroplating solution concentration, supply current, polar plate spacing and electroplating time, improves the ability that electrode is collected and transported current carrier;
(3) the present invention can avoid repeatedly thin film deposition processes, and replace this chemical liquid phase reaction of cheap Metal plating;
(4) metallic conduction network electrode process of the present invention is simple, and flow process is few, cheap, and productive rate is higher, is easy to industrialization.Electrode conductivuty is good simultaneously, and light transmission is excellent, and expectability improves carrier collection efficiency;
(5) the present invention is by using different types of metal electroplating solution, obtain the conductive electrode of different metal film, thus can prepare the conductive electrode of different metal as required, realize electrode and the good contact resistance of battery, thus reduction current loss, improve charge collection efficiency.
Accompanying drawing explanation
Fig. 1 is that in embodiment of the present invention 1-3, Metal plating legal system is for the process flow sheet of the method for high-performance metal network readezvous point conductive electrode, and wherein (1) represents preparation be full of cracks sacrifice layer template on substrate; (2) metal refining Seed Layer in sacrifice layer template is represented; (3) formation seed metallization conductive layer network is represented; (4) represent that use metal electric plating method continues metal refining on metal seed layer, prepare the metalolic network transparency conductive electrode that photoelectric properties are excellent;
Fig. 2 is the scanning electron microscope diagram sheet that the argent network obtained in the embodiment of the present invention 1 amplifies 300 times;
Fig. 3 is the scanning electron microscope diagram sheet that the argent network obtained in the embodiment of the present invention 1 amplifies 5000 times;
Fig. 4 is the scanning electron microscope diagram sheet that the metallic copper network obtained in the embodiment of the present invention 2 amplifies 300 times;
Fig. 5 is the scanning electron microscope diagram sheet that the metallic copper network obtained in the embodiment of the present invention 2 amplifies 10000 times;
Fig. 6 is the change of transmissivity with optical wavelength of the electrode sample made in the embodiment of the present invention 1 and embodiment 2.
Embodiment
Embodiment 1
The Metal plating legal system that the present embodiment provides is for the method for high-performance metal network readezvous point conductive electrode, and as shown in fig. 1, wherein (1) represents preparation be full of cracks sacrifice layer template on substrate; (2) metal refining Seed Layer in be full of cracks sacrifice layer template is represented; (3) formation seed metallization conductive layer network is represented; (4) represent that use metal electric plating method continues metal refining on seed metallization conductive network, prepare the metalolic network transparency conductive electrode that photoelectric properties are excellent.
The detailed process of each step is as follows:
(1) preparation be full of cracks sacrifice layer template on substrate
Preparation template liquid and sacrifice layer template film forming detailed process are with reference to the part preparing sacrifice layer template in patent of invention " a kind of method preparing composite transparent conductive electrode based on metal grill and metal nanometer line " (201510035791.6).Main process is that modulation obtains egg white water solution as sacrifice layer template solution, in the polyethylene terephtalate deposited on substrates template solution of cleaning, substrate being placed in temperature is that the horizontal warm table of 50 DEG C is dried, and produces the continuous be full of cracks network of micro-or nano size.
(2) metal refining Seed Layer in sacrifice layer template
Adopt the mode of magnetron sputtering metal refining gold conductive seed layer thin layer in be full of cracks sacrifice layer template substrate, sputtering power is 100W, and magnetic control chamber room temp is 20 DEG C, and be full of cracks template surface temperature is 35 DEG C, and metallic conduction seed layer thickness is 10nm.
(3) remove sacrifice layer template, form seed metallization conductive layer network
The method that sacrifice layer template adopts current to rinse is removed, the metallic gold conductive seed layer thin layer that be full of cracks sacrifice layer template deposits is put to room temperature, the method using current to rinse removes most template fragment, the non-dust cloth erasing speckling with deionized water of residue template, the substrate of conductive layer network is slowly rinsed again, until cleaning completely with deionized water.To be sure not current excessive for cleaning template, in order to avoid destroy gold seeds thin layer, finally by sample dry for standby next step.
(4) metal electric plating method is used to continue metal refining on seed metallization conductive network
The present embodiment adopts argent electrochemical plating, metal refining silver on gold seeds electrically conductive layer network, detailed process is: with the silver strip of cleaning for anode, wherein, the concrete steps of anode purge silver strip are: first use sand papering silver strip, use each ultrasonic cleaning of acetone, alcohol, deionized water 5 minutes more respectively, dry up with nitrogen.With the substrate with golden conductive seed layer thin layer of preparation in above-mentioned (three) for negative electrode, be placed in plate silver plating solution, plate silver plating solution formula is: preparation 100mL silver nitrate aqueous solution, wherein Silver Nitrate 40g/L, Sulfothiorine 225g/L, Potassium hydrogen sulfite 40g/L, pH value is 5 ~ 6, temperature 30 DEG C, polar plate spacing is 1cm, connect D.C. regulated power supply, electric current is 0.01A, and electroplating time is 5min.
Cut off the electricity supply after having electroplated, sample is taken out with tweezers, sample to be soaked in deionized water after 10min, taking-up dries up, obtain silver-colored network readezvous point conductive electrode, as shown in Fig. 2,3, two figure represent that argent network that metal electric plating method obtains amplifies the scanning electron microscope diagram sheet of 300 times and 5000 times respectively, as can be seen from Fig. 2,3, the homogeneity of sample and the density of silver all better.
The metalolic network transparency conductive electrode that the present embodiment prepares based on Metal plating method has good photoelectric properties, test obtains result as shown in solid line in Fig. 6, the transmissivity of sample is 79.7%, and when transmissivity keeps higher, surface resistivity can be low to moderate 0.079 Ω/sq; What the present embodiment used simultaneously is flexible substrate, thus can be applicable in flexible device.
Embodiment 2
The Metal plating legal system that the present embodiment provides is for the method for high-performance metal network readezvous point conductive electrode, and as shown in fig. 1, wherein (1) represents preparation be full of cracks sacrifice layer template on substrate; (2) metal refining Seed Layer in be full of cracks sacrifice layer template is represented; (3) formation seed metallization conductive layer network is represented; (4) represent that use metal electric plating method continues metal refining on seed metallization conductive network, prepare the metalolic network transparency conductive electrode that photoelectric properties are excellent.
The detailed process of each step is as follows:
(1) preparation be full of cracks sacrifice layer template on substrate
Preparation template liquid and sacrifice layer template film forming detailed process are with reference to the part preparing sacrifice layer template in patent of invention " a kind of method preparing composite transparent conductive electrode based on metal grill and metal nanometer line " (201510035791.6).Main process is that modulation obtains egg white water solution as sacrifice layer template solution, and in the polyimide PI deposited on substrates template solution of cleaning, substrate being placed in temperature is that the horizontal warm table of 60 DEG C is dried, and produces the continuous be full of cracks network of micro-or nano size.
(2) metal refining Seed Layer in sacrifice layer template
Adopt the mode of magnetron sputtering metal refining Ag films conductive layer in be full of cracks sacrifice layer template substrate, sputtering power is 200W, and magnetic control chamber room temp is 25 DEG C, and be full of cracks template surface temperature is 45 DEG C, and metallic conduction layer thickness is 20nm.
(3) remove sacrifice layer template, form seed metallization conductive layer network
The method that sacrifice layer template adopts current to rinse is removed, the argent film conductive layer that sacrifice layer template deposits is put to room temperature, the method using current to rinse removes most template fragment, the non-dust cloth erasing speckling with deionized water of residue template, the substrate of conductive layer network is slowly rinsed again, until cleaning completely with deionized water.Be sure not current during cleaning excessive, in order to avoid destroy silver-colored conductive mesh winding thread, finally by sample dry for standby next step.
(4) metal electric plating method is used to continue metal refining on seed metallization conductive network
The present embodiment adopts metallic copper electrochemical plating, silver-colored Seed Layer network grows copper, detailed process is: with the copper sheet of cleaning for anode, wherein, the concrete steps of anode purge copper sheet are: first remove oxide on surface with sand papering copper sheet, use each ultrasonic cleaning of acetone, alcohol, deionized water 5 minutes more respectively, dry up with nitrogen.With the substrate containing silver conductive layer for negative electrode, be placed in plating solution for copper-plating used, plating solution for copper-plating used formula is: the aqueous solution of preparation 100mL copper sulfate and other additive, wherein copper sulfate 40g/L, trisodium phosphate 150g/L, disodium-hydrogen 25g/L, ammonium nitrate 12g/L, pH value is 8.5, temperature 25 DEG C.Polar plate spacing is 1.5cm, and connect D.C. regulated power supply, electric current is 0.005A, and electroplating time is 15min.Cut off the electricity supply after having electroplated, sample is taken out with tweezers, sample to be soaked in deionized water after 20min, taking-up dries up, obtain copper networks transparency conductive electrode, as shown in Fig. 4,5, two figure represent that metallic copper network that chemical liquid phase reaction obtains amplifies the scanning electron microscope diagram sheet of 300 times and 10000 times respectively, as can be seen from Fig. 4,5, the homogeneity of sample and the density of copper all better.
The metalolic network transparency conductive electrode that the present embodiment prepares based on Metal plating method has good photoelectric properties, test obtains result as shown in phantom in Figure 6, the transmissivity of sample is 80.1%, and when transmissivity keeps higher, surface resistivity can be low to moderate 0.25 Ω/sq.What the present embodiment used simultaneously is flexible substrate, thus can be applicable in flexible device.
Embodiment 3
The Metal plating legal system that the present embodiment provides is for the method for high-performance metal network readezvous point conductive electrode, and as shown in fig. 1, wherein (1) represents preparation be full of cracks sacrifice layer template on substrate; (2) metal refining Seed Layer in be full of cracks sacrifice layer template is represented; (3) formation seed metallization conductive layer network is represented; (4) represent use metal electric plating method continued growth metal on seed metallization conductive network, prepare the metalolic network transparency conductive electrode that photoelectric properties are excellent.
The detailed process of each step is as follows:
(1) preparation be full of cracks sacrifice layer template on substrate
Preparation template liquid and sacrifice layer template film forming detailed process are with reference to the part preparing be full of cracks template in patent of invention " a kind of method based on be full of cracks template synthesis porous metal film transparency conductive electrode " (ZL201310122824.1).Main process be modulation obtain titanium dioxide ethanolic soln as sacrifice layer template solution, the glass substrate of cleaning deposits template solution, level table substrate being placed in room temperature is dried, produces the continuous be full of cracks network of micro-or nano size.
(2) metal refining Seed Layer in sacrifice layer template
The present embodiment selects liquid phase method to deposit, and is having TiO
2the glass substrate of sacrifice layer sprays PdCl
2solution (mass concentration is 85%) 0.5mL, heated substrate to 150 DEG C, PdCl
2decompose and obtain Pd metal, after removing sacrifice layer template, then under sample being positioned over 400 DEG C of temperature, sintering makes Pd combination finer and close, forms the Pd seed thin layer that thickness is about 20nm.
(3) remove sacrifice layer template, form seed metallization conductive layer network
After temperature-stable, the sample of metal refining Pd film is taken out, with mechanical attrition method, the be full of cracks template on substrate is removed, and dip in the cleaning of a little raw spirit effects on surface with non-dust cloth, rinse the substrate having Seed Layer network again with slow-flowing stream with deionized water, be sure not current excessive, in order to avoid destroy Pd seed thin layer.After forming metal Pd kind conducting layer network, by sample dry for standby next step.
(4) metal electric plating method is used to continue metal refining on seed metallization conductive network
The present embodiment adopts metallic copper electrochemical plating, palladium kind conducting layer network grows copper, detailed process is: with the copper sheet of cleaning for anode, wherein, the concrete steps of anode purge copper sheet are: first remove oxide on surface with sand papering copper sheet, use each ultrasonic cleaning of acetone, alcohol, deionized water 5 minutes more respectively, dry up with nitrogen.With the substrate containing palladium metal Seed Layer for negative electrode, be placed in plating solution for copper-plating used, plating solution for copper-plating used formula is: the aqueous solution of preparation 100mL copper sulfate and other additive, wherein Silver Nitrate 40g/L, Sulfothiorine 225g/L, Potassium hydrogen sulfite 40g/L, pH value is 8.5, temperature 25 DEG C.Polar plate spacing is 2cm, and connect D.C. regulated power supply, electric current is 0.02A, and electroplating time is 10min.Cut off the electricity supply after having electroplated, take out sample with tweezers, be soaked in by sample in deionized water after 30min, taking-up dries up, and obtains copper networks transparency conductive electrode.
The metalolic network transparency conductive electrode that the present embodiment prepares based on Metal plating method has good photoelectric properties, and the transmissivity of test sample is 75 ~ 85%, and when transmissivity keeps higher, surface resistivity can be low to moderate 0.5 Ω/below sq.What the present embodiment used simultaneously is whole soln method, and whole preparation process does not use any high-vacuum apparatus, and the electrode thus can prepared by the restriction of instrument space volume, can not can be built production product line for the different low costs that needs, realize big area and produce.
Above-described embodiment is the present invention's preferably embodiment, but embodiments of the present invention are not restricted to the described embodiments, such as, in metal electric plating method growing metal network layer, metal is except silver, outside copper, other metals can also be adopted as zinc, aluminium or nickel etc., and the method for stringer metal conducting layer at least can adopt magnetron sputtering method and metal-salt thermal decomposition method, the change done under other any does not deviate from spirit of the present invention and principle, modify, substitute, combination, simplify, all should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (10)
1. Metal plating legal system, for a method for high-performance metal network readezvous point conductive electrode, is characterized in that comprising the following steps:
(1) preparation be full of cracks sacrifice layer template on substrate;
(2) depositing metal conductive Seed Layer in be full of cracks sacrifice layer template;
(3) remove be full of cracks sacrifice layer template, form metallic conduction Seed Layer network;
(4) adopt metal electric plating method to continue metal refining in metallic conduction Seed Layer, form higher caliper and low-resistance continuous metal grid, thus obtained high-performance metal network readezvous point conductive electrode.
2. Metal plating legal system according to claim 1 is for the method for high-performance metal network readezvous point conductive electrode, it is characterized in that: the substrate described in step (1) is glass, polyimide PI, polyethylene terephtalate, polydimethylsiloxane or polymetylmethacrylate.
3. Metal plating legal system according to claim 1 is for the method for high-performance metal network readezvous point conductive electrode, it is characterized in that: the main raw of the be full of cracks sacrifice layer template described in step (1) is the egg white solution of bird, acrylic polymer or metal oxide TiO
2; On substrate, the detailed process of preparation be full of cracks sacrifice layer template is: be coated on substrate by sacrifice layer dissolution homogeneity, and oven drying at low temperature under natural air drying or 40 ~ 80 DEG C of conditions, forms the be full of cracks sacrifice layer template of micro-or nano size after be full of cracks.
4. Metal plating legal system according to claim 1 is for the method for high-performance metal network readezvous point conductive electrode, it is characterized in that: the metal in the metallic conduction Seed Layer described in step (2) is palladium, silver, gold, aluminium, copper or nickel.
5. Metal plating legal system according to claim 4 is for the method for high-performance metal network readezvous point conductive electrode, it is characterized in that: adopt magnetron sputtering method or liquid phase deposition when chapping depositing metal conductive Seed Layer in sacrifice layer template in step (2).
6. Metal plating legal system according to claim 5 is for the method for high-performance metal network readezvous point conductive electrode, it is characterized in that: when adopting observing and controlling sputtering method, sputtering power is 50 ~ 200w, magnetic control chamber room temp is 20 ~ 25 DEG C, be full of cracks sacrifice layer template surface temperature is 30 ~ 60 DEG C, and metallic conduction seed layer thickness is 5 ~ 30nm.
7. Metal plating legal system according to claim 5 is for the method for high-performance metal network readezvous point conductive electrode, when it is characterized in that adopting liquid phase deposition, detailed process is: metallize salts solution in be full of cracks sacrifice layer template, being heated to sacrifice layer die plate temperature is 100 ~ 300 DEG C, wherein metal salt solution decomposition obtains metallic conduction Seed Layer, after removing sacrifice layer template, at 150 ~ 600 DEG C of temperature, sintering forms metallic conduction Seed Layer network.
8. Metal plating legal system according to claim 1 is for the method for high-performance metal network readezvous point conductive electrode, it is characterized in that the method removing be full of cracks sacrifice layer template in step (3) is: when the material of the sacrifice layer template that chaps is the egg white solution of bird, washed with de-ionized water is adopted to remove sacrifice layer template, when the material of the sacrifice layer template that chaps is acrylic polymer, acetone cleaning is adopted to remove, when the material of be full of cracks sacrifice layer template is metal oxide TiO
2time, adopt mechanical friction method to remove.
9. Metal plating legal system according to claim 1 is for the method for high-performance metal network readezvous point conductive electrode, it is characterized in that the detailed process adopting metal electric plating method to continue metal refining in metallic conduction Seed Layer in step (4) is: take tinsel as anode, with the substrate with metallic conduction Seed Layer network for negative electrode, be placed in metal electroplating solution, adjustment polar plate spacing is 0.5 ~ 3cm, connect D.C. regulated power supply, adjustment electric current is 0.005 ~ 0.05A, plating 1 ~ 60min.
10. Metal plating legal system according to claim 9 is for the method for high-performance metal network readezvous point conductive electrode, it is characterized in that: the metal in described tinsel and metal electroplating solution is silver, gold, zinc, aluminium, copper or nickel.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510777346.7A CN105350043B (en) | 2015-11-13 | 2015-11-13 | A kind of method that metal plating method prepares metalolic network transparent conductive electrode |
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| CN105762305A (en) * | 2016-04-28 | 2016-07-13 | Tcl集团股份有限公司 | Composite anode, QLED device, and preparation methods thereof |
| CN106328260A (en) * | 2016-08-24 | 2017-01-11 | 华南师范大学 | Full-liquid phase preparation method of metal mesh transparent conductive electrode |
| CN106782879A (en) * | 2016-11-30 | 2017-05-31 | 华南师范大学 | A kind of method that low cost plasma body bombardment prepares metalolic network transparency conductive electrode |
| CN107034503A (en) * | 2017-04-28 | 2017-08-11 | 哈尔滨工业大学 | It is a kind of to electroplate the method that enhancing nano wire Mesh connection prepares Conducting Films with High Performance |
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| CN110098063A (en) * | 2019-03-29 | 2019-08-06 | 华东师范大学 | A kind of flexibility gold electrode and preparation method |
| CN109862631A (en) * | 2019-04-04 | 2019-06-07 | 浙江大学 | A kind of preparation method of NEW TYPE OF COMPOSITE plate Electric radiant Heating Film |
| CN110747439A (en) * | 2019-09-11 | 2020-02-04 | 南京柔导科技有限公司 | Preparation method of micron-sized ultrathin metal sheet for conductive adhesive filler |
| CN110747439B (en) * | 2019-09-11 | 2022-04-19 | 南京柔导科技有限公司 | Preparation method of micron-sized ultrathin metal sheet for conductive adhesive filler |
| CN111180110A (en) * | 2019-12-27 | 2020-05-19 | 华南师范大学 | Preparation method of composite metal network transparent conductive electrode |
| CN111180110B (en) * | 2019-12-27 | 2021-11-30 | 华南师范大学 | Preparation method of composite metal network transparent conductive electrode |
| CN112768116A (en) * | 2020-12-09 | 2021-05-07 | 华南师范大学 | Preparation method of flexible transparent conductive electrode with low surface roughness |
| CN113201718A (en) * | 2021-04-01 | 2021-08-03 | 深圳仕上电子科技有限公司 | Plating chamber inner wall component with sacrificial layer, preparation method and cleaning method thereof |
| EP4194589A4 (en) * | 2021-10-26 | 2023-06-14 | Contemporary Amperex Technology Co., Limited | Copper plating solution and negative electrode composite current collector prepared therefrom |
| US11932959B2 (en) | 2021-10-26 | 2024-03-19 | Contemporary Amperex Technology Co., Limited | Copper plating solution and negative electrode composite current collector prepared using same |
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| CN114566329A (en) * | 2022-02-14 | 2022-05-31 | 苏州大学 | Piezoelectric cable and preparation method thereof |
| CN114566329B (en) * | 2022-02-14 | 2022-11-18 | 苏州大学 | Piezoelectric cable and preparation method thereof |
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