CN105350043B - A kind of method that metal plating method prepares metalolic network transparent conductive electrode - Google Patents
A kind of method that metal plating method prepares metalolic network transparent conductive electrode Download PDFInfo
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- CN105350043B CN105350043B CN201510777346.7A CN201510777346A CN105350043B CN 105350043 B CN105350043 B CN 105350043B CN 201510777346 A CN201510777346 A CN 201510777346A CN 105350043 B CN105350043 B CN 105350043B
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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 kind of methods that metal plating method prepares high-performance metal network readezvous point conductive electrode, include the following steps：(1) cracking sacrificial layer template is prepared on substrate；(2) the depositing metal conductive seed layer in cracking sacrificial layer template；(3) removal cracking sacrificial layer template, forms metallic conduction seed layer network；(4) deposited metal is continued in metallic conduction seed layer using metal plating method, forms higher caliper and low-resistance continuous metal grid, to which high-performance metal network readezvous point conductive electrode be made.The transparent conductive electrode mainly uses metal plating method, belongs to chemical liquid phase reaction, and preparation process is simple, low in resources consumption, and large area is suitble to continuously to prepare.The transparent conductive electrode of preparation has very low sheet resistance and preferable light transmittance, while mechanical performance and environmental stability are good, are not only the advantageous replacer of INVENTIONConventional metal-oxide electrode, and is expected to be used for the industrialization of large-area transparent conductive electrode.
Description
Technical field
The invention belongs to membrane electrode technical fields, and in particular to it is saturating that a kind of metal plating method prepares high-performance metal network
The method of bright conductive electrode.
Background technology
Transparent conductive electrode is the key that the photoelectric devices such as LED (light emitting diode), solar cell, intelligent glass composition
One of part, in device carrier collection with transport and device stability and manufacturing cost suffer from important influence.
In general, transparent conductive electrode refers to that the transmissivity of the spectrum between 380nm to 780nm to lambda1-wavelength range is more than
80%, and resistivity is less than 10-3The membrane electrode of Ω cm.Nowadays, metal conductive oxide film, such as ITO (indium-doped oxygen
Change tin), FTO (tin oxide of fluorine doped) has been widely used in LED, solar cell and intelligent glass.From physical angle
It sees, the translucency and electric conductivity of material are a pair of of basic contradictions.A kind of material will have good electric conductivity, it is necessary at the same have compared with
High carrier concentration and higher carrier mobility, however the carrier of higher concentration can absorb photon and improve material pair
The absorptivity of light and reduce its transmissivity.For many years, thin from metallic film to metal conductive oxide film, conducting polymer
Film, from one-component material to multicomponent mixture material, the research of scientific research bound pair transparent conductive electrode is all around this contradiction exhibition
It opens.Metal oxide, especially ITO have higher light transmission rate and lower resistivity, past 50 years in visible region
Carry out the hot spot of always transparent conductive electrode research and application.However ITO metal oxides are used as electrode of solar battery itself
Limited electrical conductivity, and matter is crisp frangible, the defects of being unlikely to deform, while raw material resources are increasingly rare, and manufacturing price is expensive.Therefore compel
Adaptation large area low cost manufacturing high-performance conductive electrode method will be probed by being essential constantly develops to meet photoelectric device.
Recently as the development of nanometer new material and new construction, a frontier of transparent conductive electrode developing is two dimension
Nanometer new 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 weaker conductive capability of high polymer limits
Its being widely used in the devices；Carbon nano-tube film is needed compared with big L/D ratio, and the evenly dispersed and carbon nanometer of carbon nanotube
Ohmic resistance problem between pipe limits electric conductivity in the face of film；The special pattern of graphene film itself and with fine
Flexibility, while also there is good carrier mobility, but volume production technology is not yet ripe；It is thin for random nano metal line
Film, adjusting high-volume synthesis has the nano-silver thread of larger draw ratio and evenly dispersed nano wire difficult, and nanometer
The contact resistance and its adhesion problem of silver electrode and substrate or active layer are difficult to solve；In contrast, metal grill film
It can be to avoid these problems.Transparent conductive electrode is in addition to excellent electric conductivity, it is also necessary to excellent light transmission, photoconductivity it
Than (σDC/σopt, σDCRefer to conductivity, σ directly proportional to electrode surface resistanceoptRefer to optical conductivity, be inversely proportional with electrode light transmission rate) very
The photoelectric properties of good description transparent conductive electrode.Research shows that：In general, the ratio between metal grill film electrode photoelectric conductance
It is highest in these two-dimensional nano new materials, it can be seen that metal grill film has outstanding electric conductivity and light transmission
Rate.This is because tradition prepares the main micro-nano metallic conduction grid line using rule of metal grill film, i.e., in substrate table
Face obtains regular micro-nano-scale grid line by technologies such as silk-screen printing, photoetching or nano impressions.Due to the thickness of conductive grid line
Degree opposing metallic film wants thick, and the surface and interface scattering of electronics dies down, and the electric conductivity of grid line is close to bulk metal
Electric conductivity, while the light scattering effect and coupling of secondary wavelength dimension grid line reduce the light reflection damage that electrode section is brought
It loses.For solar cell, light scattering effect improves absorption of the active layer to light.In addition metal grill membrane electrode
It is suitble to the productions such as flexible substrate, thus metal grill will be as the advantageous replacer of present transparent conductive electrode.
However, there is some defects for traditional metal grid electrode.Common metal grid electrode needs expensive preparation
Method (silk-screen printing, photoetching, vacuum deposition etc.), this improves the application cost of the electrode.In addition vacuum deposition is largely relied on
Film forming so that the large area volume production of metal grid electrode is prepared into as problem.What nearest solwution method or template were prepared
Random metalolic network electrode, although avoid the method costly such as photoetching, but still exist need high-vacuum technology or
Photoelectric properties are not good enough.So a kind of low cost of exploitation design, can large area volume production prepare the conductive electricity of high-performance metal network readezvous point
The method of pole, which seems, to be even more important.
Invention content
The purpose of the present invention is to provide the sides that a kind of metal plating method prepares high-performance metal network readezvous point conductive electrode
Method, the preparation method belong to chemical liquid phase reaction, and simple process and low cost, being suitble to large area continuously to prepare, metalolic network is transparent to lead
Electrode.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：A kind of metal plating method preparation high-performance gold
The method for belonging to network readezvous point conductive electrode, includes the following steps：
(1) cracking sacrificial layer template is prepared on substrate；
(2) the depositing metal conductive seed layer in cracking sacrificial layer template；
(3) removal cracking sacrificial layer template, forms metallic conduction seed layer network；
(4) deposited metal is continued in metallic conduction seed layer using metal plating method, forms higher caliper and low resistance
Continuous metal grid, to which high-performance metal network readezvous point conductive electrode be made.
The method that metal plating method of the present invention prepares high-performance metal network readezvous point conductive electrode, this method preparation process letter
It is single, it is low in resources consumption, and it is suitble to the continuous preparation process of large area, the transparent conductive electrode of preparation has ultralow surface electricity
Resistance, preferable translucency, and preferable environmental stability and mechanicalness are not only the advantageous of INVENTIONConventional metal-oxide electrode and replace
Dai Zhe, and it is expected to be used for the industrialization of large-area transparent conductive electrode.
In above-mentioned metal plating method prepares the method for high-performance metal network readezvous point conductive electrode：
Substrate described in step (1) of the present invention can be glass, polyimides PI, polyethylene terephthalate
PET, polydimethylsiloxane or polymetylmethacrylate.
The main material of cracking sacrificial layer template described in step (1) of the present invention is the egg white solution of birds, acrylic acid tree
Lipopolymer or metal oxide TiO2；Prepare on substrate cracking sacrificial layer template detailed process be：By sacrificial layer solution
On substrate, low temperature drying under the conditions of natural air drying or 40~80 DEG C forms the cracking of micro-or nano size to even application after cracking
The continuous cracking network of sacrificial layer template, that is, micro-or nano size.
The metal in metallic conduction seed layer described in step (2) of the present invention is preferably palladium, silver, gold, aluminium, copper or nickel.
When further, using above-mentioned metal, in the depositing metal conductive in sacrificial layer template that is cracked in step (2) of the present invention
Magnetron sputtering method or liquid phase deposition are preferably used when seed layer.
When as a preferred embodiment of the present invention, using observing and controlling sputtering method, sputtering power is preferably 50~
200w, temperature is preferably 20~25 DEG C in magnetron chamber, and cracking sacrificial layer template surface temperature is preferably 30~60 DEG C, and metal is led
Electric seed layer thickness is preferably 5~30nm.
As another preferred embodiment of the present invention, when using liquid phase deposition, detailed process is：It is sacrificial being cracked
Spray metal salting liquid in domestic animal layer template, it is preferably 100~300 DEG C, wherein metal salt solution to be heated to sacrificial layer die plate temperature
Decomposition obtains metallic conduction seed layer, and after removing sacrificial layer template, preferably sintering forms metal and leads at a temperature of 150~600 DEG C
Electric seed layer network.
The method of removal cracking sacrificial layer template has following methods in step (3) of the present invention：When cracking sacrificial layer mould
When the material of plate is the egg white solution of birds, removal sacrificial layer template is cleaned using deionized water, when the material of cracking sacrificial layer template
It when material is acrylic polymer, is cleaned and is removed using acetone, when the material of cracking sacrificial layer template is metal oxide
TiO2When, it is removed using mechanical friction method.
Continue the detailed process of deposited metal in step (4) of the present invention in metallic conduction seed layer using metal plating method
It is：It using sheet metal as anode, using the substrate with metallic conduction seed layer network as cathode, is placed in metal electroplating solution, adjusts
Pole plate spacing is 0.5~3cm, connects D.C. regulated power supply, and adjusting electric current is 0.005~0.05A, and 1~60min is electroplated.
Metal in sheet metal and metal electroplating solution of the present invention is silver, gold, zinc, aluminium, copper or nickel.
Metal electroplating solution is the salting liquid of metals such as silver, gold, zinc, aluminium, copper and mickel or is added in above-mentioned metal salt solution
There is the metal electroplating solution of other buffers and additive well known to this field.
The principle of the present invention is：Coated on the thin film sacrificial layer on substrate, air-dries or the heated volatilization of when low temperature drying is lost
Solvent is removed, cracking network template is formed.Using this template, deposit thin metals seed layer, metal can be obtained in removal sacrificial layer template
Kind conducting layer network.Using sheet metal as anode, the substrate containing metal seed layer is cathode, is placed in metal electroplating solution.It connects
Behind energization source, anode loses electronics and oxidation reaction occurs, and metal becomes metal cation and enters in solution, while cathode occurs also
Original reaction, the metal cation near substrate seed layer are reduced into metallic atom due to obtaining electronics, are attached to seed
On layer, so that conductive network film is thickened and achieve the effect that grow metalolic network, obtain that the excellent metalolic network of photoelectric properties is transparent to lead
Electrode.
The invention has the advantages that：
(1) preparation method of the present invention is easy, of low cost；
(2) present invention can adjust by adjusting metal electroplating solution concentration, source current, pole plate spacing and electroplating time
The film thickness of metalolic network electrode improves the ability that electrode is collected and transports carrier；
(3) present invention can avoid multiple 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 is few, cheap, and yield is higher, is easy to industry
Change.Electrode conductivuty is good simultaneously, and translucency is excellent, and expectability improves carrier collection efficiency；
(5) present invention can obtain the conductive electrode of different metal film by using different types of metal electroplating solution, because
And the conductive electrode of different metal can be prepared as needed, electrode and the good contact resistance of battery are realized, to reduce electricity
Stream loss, improves charge collection efficiency.
Description of the drawings
Fig. 1 is the method that metal plating method prepares high-performance metal network readezvous point conductive electrode in 1-3 of the embodiment of the present invention
Process flow chart, wherein (1) indicate prepare on substrate cracking sacrificial layer template；(2) it indicates to deposit in sacrificial layer template
Metal seed layer；(3) it indicates to form seed metallization conduction layer network；(4) it indicates using metal plating method on metal seed layer
Continue deposited metal, the excellent metalolic network transparent conductive electrode of photoelectric properties is prepared；
Fig. 2 is that the metallic silver network obtained in the embodiment of the present invention 1 amplifies 300 times of scanning electron microscope diagram piece；
Fig. 3 is that the metallic silver network obtained in the embodiment of the present invention 1 amplifies 5000 times of scanning electron microscope diagram piece；
Fig. 4 is that the metal copper networks obtained in the embodiment of the present invention 2 amplify 300 times of scanning electron microscope diagram piece；
Fig. 5 is that the metal copper networks obtained in the embodiment of the present invention 2 amplify 10000 times of scanning electron microscope diagram piece；
Fig. 6 is the transmissivity of manufactured electrode sample in Example 1 and Example 2 of the present invention with the variation of optical wavelength.
Specific implementation mode
Embodiment 1
The method that metal plating method provided in this embodiment prepares high-performance metal network readezvous point conductive electrode, in Fig. 1
It is shown, wherein (1) indicates to prepare cracking sacrificial layer template on substrate；(2) deposited metal in cracking sacrificial layer template is indicated
Seed layer；(3) it indicates to form seed metallization conduction layer network；(4) it indicates using metal plating method in seed metallization conductive network
The excellent metalolic network transparent conductive electrode of photoelectric properties is prepared in upper continuation deposited metal.
The detailed process of each step is as follows：
(1) cracking sacrificial layer template is prepared on substrate
Patent of invention is referred to pallet liquid and sacrificial layer template film forming detailed process《One kind being based on metal grill and metal
The method that nano wire prepares composite transparent conductive electrode》(201510035791.6) part of sacrificial layer template is prepared in.Mainly
Process is that modulation obtains egg white water solution as sacrificial layer template solution, is served as a contrast in clean polyethylene terephtalate
Template solution is deposited on bottom, and substrate is placed on the horizontal warm table that temperature is 50 DEG C and is dried, the continuous of micro-or nano size is generated
Be cracked network.
(2) the deposited metal seed layer in sacrificial layer template
Deposited metal gold conductive seed layer thin layer, sputtering in cracking sacrificial layer template substrate by the way of magnetron sputtering
Power is 100W, and temperature is 20 DEG C in magnetron chamber, and cracking template surface temperature is 35 DEG C, and metallic conduction seed layer thickness is
10nm。
(3) sacrificial layer template is removed, seed metallization conduction layer network is formed
The method removal that sacrificial layer template is rinsed using flow, the metallic gold deposited in cracking sacrificial layer template is conductive
Seed layer thin layer is put to room temperature, and most template fragments are removed using the method that flow is rinsed, and remaining template is with speckling with deionized water
Non-dust cloth erasing, then slowly rinses the substrate for having conductive layer network with deionized water, until cleaning is completely.Cleaning template is sure not
Flow is excessive, in order to avoid destroying gold seeds thin layer, is finally dried for standby sample in next step.
(4) continue deposited metal on seed metallization conductive network using metal plating method
The present embodiment uses metallic silver galvanoplastic, and deposited metal silver, detailed process are on gold seeds electrically conductive layer network：
Using clean silver strip as anode, wherein cleaning anode silver strip the specific steps are：It is first polished silver strip with sand paper, then respectively with third
Ketone, alcohol, deionized water are respectively cleaned by ultrasonic 5 minutes, are dried up with nitrogen.Prepared in above-mentioned (three) with golden conductive seed layer
The substrate of thin layer is cathode, is placed in plate silver plating solution, plate silver plating solution formula is：100mL silver nitrate aqueous solutions are prepared, wherein
Silver nitrate 40g/L, sodium thiosulfate 225g/L, potassium bisulfite 40g/L, pH value are 5~6,30 DEG C of temperature, and pole plate spacing is
1cm connects D.C. regulated power supply, electric current 0.01A, electroplating time 5min.
It cuts off the power after the completion of plating, takes out sample with tweezers, sample is soaked in deionized water after 10min, take out
Drying is to get silver-colored network readezvous point conductive electrode, and as shown in Fig. 2,3, two figures indicate the metallic silver that metal plating method obtains respectively
Network amplifies 300 times and 5000 times of scanning electron microscope diagram piece, can be seen that from Fig. 2,3 sample uniformity and
The consistency of silver is all preferable.
The present embodiment has good photo electric based on the metalolic network transparent conductive electrode that metal plating method is prepared
Can, test obtains shown in solid in result such as Fig. 6, and the transmissivity of sample is 79.7%, keeps higher in transmissivity,
Sheet resistance can be down to 0.079 Ω/sq；It is flexible substrate that the present embodiment, which uses, simultaneously, thus be can be applied in flexible device.
Embodiment 2
The method that metal plating method provided in this embodiment prepares high-performance metal network readezvous point conductive electrode, in Fig. 1
It is shown, wherein (1) indicates to prepare cracking sacrificial layer template on substrate；(2) deposited metal in cracking sacrificial layer template is indicated
Seed layer；(3) it indicates to form seed metallization conduction layer network；(4) it indicates using metal plating method in seed metallization conductive network
The excellent metalolic network transparent conductive electrode of photoelectric properties is prepared in upper continuation deposited metal.
The detailed process of each step is as follows：
(1) cracking sacrificial layer template is prepared on substrate
Patent of invention is referred to pallet liquid and sacrificial layer template film forming detailed process《One kind being based on metal grill and metal
The method that nano wire prepares composite transparent conductive electrode》(201510035791.6) part of sacrificial layer template is prepared in.Mainly
Process is that modulation obtains egg white water solution as sacrificial layer template solution, and deposition template is molten on clean polyimides PI substrates
Substrate is placed on the horizontal warm table that temperature is 60 DEG C and dries, generates the continuous cracking network of micro-or nano size by liquid.
(2) the deposited metal seed layer in sacrificial layer template
In the deposited metal Ag films conductive layer in sacrificial layer template substrate that is cracked, sputtering power by the way of magnetron sputtering
For 200W, temperature is 25 DEG C in magnetron chamber, and cracking template surface temperature is 45 DEG C, and metallic conduction layer thickness is 20nm.
(3) sacrificial layer template is removed, seed metallization conduction layer network is formed
The method removal that sacrificial layer template is rinsed using flow, the metallic silver Thin film conductive that will be deposited in sacrificial layer template
Layer is put to room temperature, and most template fragments, the remaining template non-dust cloth for speckling with deionized water are removed using the method that flow is rinsed
Erasing, then the substrate for having conductive layer network is slowly rinsed with deionized water, until cleaning is complete.It is excessive to be sure not flow when cleaning,
In order to avoid destroying silver-colored conductive mesh winding thread, finally sample is dried for standby in next step.
(4) continue deposited metal on seed metallization conductive network using metal plating method
The present embodiment uses metallic copper galvanoplastic, grows copper on silver-colored seed layer network, detailed process is：With clean copper
Piece is anode, wherein cleaning anode copper sheet the specific steps are：Oxide on surface first is removed with sand paper polishing copper sheet, then is distinguished
Respectively it is cleaned by ultrasonic 5 minutes with acetone, alcohol, deionized water, is dried up with nitrogen.Using the substrate containing silver conductive layer as cathode, set
In plating solution for copper-plating used, plating solution for copper-plating used formula is：Prepare the aqueous solution of 100mL copper sulphate and other additives, wherein sulfuric acid
Copper 40g/L, sodium pyrophosphate 150g/L, disodium-hydrogen 25g/L, ammonium nitrate 12g/L, pH value 8.5,25 DEG C of temperature.Between pole plate
Away from for 1.5cm, D.C. regulated power supply, electric current 0.005A, electroplating time 15min are connected.It cuts off the power, uses after the completion of plating
Tweezers take out sample, and sample is soaked in deionized water after 20min, take out drying to get copper networks transparent conductive electrode, such as
Fig. 4, shown in 5, two figures indicate respectively the metal copper networks that chemical liquid phase reaction obtains amplify 300 times and 10000 times scanning it is electric
Sub- microscope photograph, as can be seen that the uniformity of sample and the consistency of copper are all preferable from Fig. 4,5.
The present embodiment has good photo electric based on the metalolic network transparent conductive electrode that metal plating method is prepared
Can, test obtains that result is as shown in phantom in Figure 6, and the transmissivity of sample is 80.1%, keeps higher in transmissivity,
Sheet resistance can be down to 0.25 Ω/sq.It is flexible substrate that the present embodiment, which uses, simultaneously, thus be can be applied in flexible device.
Embodiment 3
The method that metal plating method provided in this embodiment prepares high-performance metal network readezvous point conductive electrode, in Fig. 1
It is shown, wherein (1) indicates to prepare cracking sacrificial layer template on substrate；(2) deposited metal in cracking sacrificial layer template is indicated
Seed layer；(3) it indicates to form seed metallization conduction layer network；(4) it indicates using metal plating method in seed metallization conductive network
The excellent metalolic network transparent conductive electrode of photoelectric properties is prepared in upper continued growth metal.
The detailed process of each step is as follows：
(1) cracking sacrificial layer template is prepared on substrate
Patent of invention is referred to pallet liquid and sacrificial layer template film forming detailed process《One kind is prepared based on cracking template
The method of porous metal film transparent conductive electrode》The part of cracking template is prepared in (ZL 2,013 1 0122824.1).Mainly
Process is to modulate the ethanol solution for obtaining titanium dioxide as sacrificial layer template solution, and template is deposited in clean glass substrate
Substrate is placed on the level table of room temperature and dries by solution, generates the continuous cracking network of micro-or nano size.
(2) the deposited metal seed layer in sacrificial layer template
The present embodiment selects liquid phase method deposition, is there is TiO2PdCl is sprayed in the glass substrate of sacrificial layer2(quality is dense for solution
Degree is 85%) 0.5mL, and heating substrate is to 150 DEG C, PdCl2Decomposition obtains Pd metals, after removing sacrificial layer template, then by sample
Sintering keeps Pd combinations finer and close at a temperature of being positioned over 400 DEG C, forms the Pd seed thin layers of thickness about 20nm.
(3) sacrificial layer template is removed, seed metallization conduction layer network is formed
Temperature takes out the samples of deposited metal Pd films after stablizing, with mechanical attrition method by the cracking template on substrate
Removal, is used in combination non-dust cloth to dip in a little absolute alcohol to removing surface, then has seed layer net with deionized water with slow-flowing stream flushing
The substrate of network, it is excessive to be sure not flow, in order to avoid destroy Pd seed thin layers.After forming metal Pd kind conducting layer network, sample is dried
Do spare next step.
(4) continue deposited metal on seed metallization conductive network using metal plating method
The present embodiment uses metallic copper galvanoplastic, grows copper on palladium kind conducting layer network, detailed process is：With cleaning
Copper sheet be anode, wherein cleaning anode copper sheet the specific steps are：Oxide on surface first is removed with sand paper polishing copper sheet, then
Respectively it is cleaned by ultrasonic 5 minutes with acetone, alcohol, deionized water respectively, is dried up with nitrogen.It is with the substrate containing Metal Palladium seed layer
Cathode is placed in plating solution for copper-plating used, and plating solution for copper-plating used formula is：The aqueous solution of 100mL copper sulphate and other additives is prepared,
Middle silver nitrate 40g/L, sodium thiosulfate 225g/L, potassium bisulfite 40g/L, pH value 8.5,25 DEG C of temperature.Pole plate spacing is
2cm connects D.C. regulated power supply, electric current 0.02A, electroplating time 10min.It cuts off the power after the completion of plating, is taken with tweezers
Go out sample, sample is soaked in deionized water after 30min, takes out drying to get copper networks transparent conductive electrode.
The present embodiment has good photo electric based on the metalolic network transparent conductive electrode that metal plating method is prepared
Can, the transmissivity of test sample is 75~85%, keeps higher in transmissivity, sheet resistance can be down to 0.5 Ω/sq
Below.It is whole soln method that the present embodiment, which uses, simultaneously, and any high-vacuum apparatus is not used in whole preparation process, thus can prepare
Electrode can not be limited by instrument space volume, can build production producing line for different needs low costs, realize big
Area produces.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Metal is in addition to silver, other than copper in limitation, such as metal plating method growth metal mesh network layers, can also use other metals such as zinc,
Aluminium or nickel etc., and magnetron sputtering method and metal salt thermal decomposition method at least may be used in the method for stringer metal conducting layer,
He it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications, should be
The substitute mode of effect, is included in protection scope of the present invention.
Claims (4)
1. a kind of method that metal plating method prepares metalolic network transparent conductive electrode, it is characterized in that including the following steps：
(1) cracking sacrificial layer template is prepared on substrate；
(2) the depositing metal conductive seed layer in cracking sacrificial layer template；
(3) removal cracking sacrificial layer template, forms metallic conduction seed layer network；
(4) deposited metal is continued in metallic conduction seed layer using metal plating method, forms higher caliper and low-resistance company
Continuous metal grill, to which metalolic network transparent conductive electrode be made；
Substrate described in step (1) is glass, polyimides PI, polyethylene terephtalate, polydimethylsiloxanes
Alkane PDMS or polymetylmethacrylate；The main material of cracking sacrificial layer template described in step (1) is birds
Egg white solution, acrylic polymer or metal oxide TiO2；The detailed process of cracking sacrificial layer template is prepared on substrate
For：On substrate by sacrificial layer solution even application, low temperature drying under the conditions of natural air drying or 40~80 DEG C, forms micro- after cracking
The cracking sacrificial layer template of nano-scale；
The metal in metallic conduction seed layer described in step (2) is gold, silver or palladium；In cracking sacrificial layer mould in step (2)
Magnetron sputtering method or liquid phase deposition are used on plate when depositing metal conductive seed layer；
The method of removal cracking sacrificial layer template is in step (3)：When the egg white solution that the material of cracking sacrificial layer template is birds
When, removal sacrificial layer template is cleaned using deionized water, when the material for the sacrificial layer template that is cracked is acrylic polymer,
It is cleaned and is removed using acetone, when the material of cracking sacrificial layer template is metal oxide TiO2When, it is removed using mechanical friction method；
Continuing the detailed process of deposited metal in step (4) in metallic conduction seed layer using metal plating method is：With metal
Piece is anode, using the substrate with metallic conduction seed layer network as cathode, is placed in metal electroplating solution, adjusts pole plate spacing and is
0.5~3cm connects D.C. regulated power supply, and adjusting electric current is 0.005~0.05A, and 1~60min is electroplated.
2. the method that metal plating method according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that：It adopts
When with observing and controlling sputtering method, sputtering power is 50~200w, and temperature is 20~25 DEG C in magnetron chamber, and be cracked sacrificial layer template surface
Temperature is 30~60 DEG C, and metallic conduction seed layer thickness is 5~30nm.
3. the method that metal plating method according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that adopting
When with liquid phase deposition, detailed process is：The spray metal salting liquid in cracking sacrificial layer template, is heated to sacrificial layer template temperature
Degree is 100~300 DEG C, and wherein metal salt solution decomposes to obtain metallic conduction seed layer, after removing sacrificial layer template, 150~
Sintering forms metallic conduction seed layer network at a temperature of 600 DEG C.
4. the method that metal plating method according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that：Institute
Metal in the sheet metal and metal electroplating solution stated is silver or copper.
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