CN106782879B - A kind of method that plasma bombardment prepares metalolic network transparent conductive electrode - Google Patents
A kind of method that plasma bombardment prepares metalolic network transparent conductive electrode Download PDFInfo
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Abstract
The invention discloses a kind of methods that plasma bombardment prepares metalolic network transparent conductive electrode, comprising the following steps: (1) substrate coating photoresist；(2) photoresist is fixed；(3) production cracking template network；(4) plasma bombardment photoresist networking；(5) nano metal network is formed；(6) photoresist is removed；(7) adhesiveness is handled.The advantages that transparent conductive electrode of this method preparation has investment low, and yield is higher, simple process, cheap, is easy to roll-to-roll industrialized production, while electrode conductivuty is preferable, transparent rate is high, alternative or part substitution ITO electro-conductive glass.
Description
Technical field
The invention belongs to membrane electrode technical fields, and in particular to a kind of plasma bombardment prepares that metalolic network is transparent to lead
The method of electrode.
Background technique
Transparent conductive electrode (Transparent conductive electrodes, TCEs), in general refers to wave
The transmissivity of visible light of the long range between 380~800nm is greater than 80%, and electrode resistance rate is lower than 10-3Ω cm's is thin
Membrane electrode.It is widely used in photoelectric device because it has excellent light transmission rate and good electric conductivity simultaneously, such as
Solar battery, touch-screen display, Organic Light Emitting Diode (OLED), Electronic Paper etc..
The type of transparent conductive electrode has very much, according to the difference of conductive material, is broadly divided into: oxide semiconductor electrode
(Transparent conductive oxide, TCO), metallic film wire electrode, conduction high polymer electrode, carbon material electricity
Extremely etc..Transparent conductive oxide electrode is occupied an leading position currently on the market, wherein tin indium oxide (Indium Tin oxide,
ITO) film and zinc oxide aluminum (Al-doped ZnO, AZO) film are extensive because it is with excellent electrical and optical performance
Using.Especially ITO was always over 50 years in the past in visible region light transmission rate with higher and lower resistivity
The hot spot of transparent conductive electrode research and application.However metal oxide is used as electrode there are limited electrical conductivity itself, matter is crisp easily
Broken, the disadvantages of being unlikely to deform, while raw material In resource is increasingly rare, and expensive, popularization has difficulties, while being difficult to full
The requirement of the growing flexible photoelectric device of new generation of foot, therefore urgent need finds one kind and can substitute ITO, photoelectric properties are excellent
And the transparent conductive film electrode with mechanical flexibility.
The research and development of various novel flexible thin-film electrode materials and structure is rapid in recent years, and one of frontier is new
Material and nanostructured films electrode.Such as high polymer conductive film, carbon nano-tube film, graphene film and nano metal
Line film.It is conductive polymer film light weight, environmentally protective, and it is natural there is the advantage being synthetically produced on a large scale, but due to processing
Property is poor, and stability is lower, and universality is poor；The special pattern of graphene film itself and have flexible well, while also having
There is good carrier mobility, but volume production technology is not yet mature；Carbon nano-tube film is needed compared with big L/D ratio, carbon pipe it is uniform
Disperse poor, the Ohmic resistance between carbon pipe is higher.In contrast, nano metal line film properties are excellent, quickly grow.It is transparent to lead
Conductive film is in addition to excellent electric conductivity, it is also necessary to excellent light transmission, the ratio between photoconductivity (σ DC/ σ opt, σ DC determining electrode
Surface resistance, σ opt determine film light transmission rate) well description transparent conductive film photoelectric properties.Research shows that: general carbon
The ratio between nanotube photoconductivity is 6-14, and graphene is~70, ITO 120-200, and nano metal line film has 215-
20000。
It can be seen that nano metal line film has outstanding electric conductivity and light transmission, and process controllability is strong, surely
Qualitative height, and then cause extensive research, and nano-silver thread is wherein outstanding figure.Silver is electric good conductor, good conductivity, thus
Nano-silver thread, which is used as electrode material, can reduce energy consumption (relative to oxide film electrode).The partial size of nano-silver thread is less than simultaneously
When visible light incident wavelength, the plasma effect of metal Nano structure enhances light transmission, and electrode is made to have good photo electric
Can, be conducive to the efficiency for improving battery device.And nano-silver thread electrode is suitble to the production such as flexible substrate.Thus nano-silver thread electricity
Pole will become the advantageous replacer of present transparent conductive electrode, by extensive concern both at home and abroad.
It mainly includes two ways that nano-silver thread, which is used as electrode, first is that being existed using the micro-nano silver conduction grid line of rule
Substrate surface obtains regular micro-nano-scale grid line, volume pair by the roll-to-roll technology such as silk-screen printing, photoetching or nano impression
Volume technology refers to that flexibility coat copper plate carries out the technology of flexible material production by coiled continuous mode.Using Roll-to-
Productivity and the degree of automation can be improved in Roll production technology.It significantly reduces manual operation, management factors, by ring
The influence of border condition (temperature, humidity cleanliness etc.) has more evenly consistent and stable dimensional discrepancy, be easy to be modified and
Compensation has higher product qualification rate, q&r.Second is that liquid phase method large area prepares random nano-silver thread film
Electrode.It is mass produced or uses expensive equipment, and investment is huge, and noble metal waste is serious, while electrical loss is larger, market
Competitiveness is extremely low；Or needing to carry out high temperature long-time heat preservation in technical process, loss is serious, and there are hidden danger for safety, economical
Property is relatively low.Therefore, for metalolic network transparent electrode, a kind of novel preparation method is needed, is meeting its performance need
On the basis of asking, accomplish to put into low, production process safety, the market competitiveness strong, to realize its large-scale production, meets society
Universality application.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that plasma bombardment prepares metalolic network transparent conductive electrode, should
Method can significantly reduce the production investment of electrode, simplify the technological process of production, has extensive adjustability, can adapt to extensively a variety of
The particular demands of device, and mechanical and environmental stability is good, is suitble to preparation of industrialization.
Above-mentioned purpose of the invention is achieved by the following technical solution: a kind of plasma bombardment prepares metal mesh
The method of network transparent conductive electrode, comprising the following steps:
(1) substrate coating photoresist: selection clean transparent substrate, coating photoresist, and control the thickness of photoresist；
(2) photoresist is fixed: to uv-exposure processing is carried out after silicon heat preservation, by photoetching adhesive curing, forming photoetching
Glue film；
(3) production cracking template: preparing the cracking liquid of collosol state, and will be cracked the photoresist film of liquid setting after hardening
Upper formation cracking liquid film, heats and controls temperature and soaking time, makes the liquid film exposure cracking formation cracking template that is cracked；
(4) plasma networking: using plasma bombardment cracking template removes the photoresist in cracking crack on floor,
The bombardment time and temperature for controlling plasma, form cracking fracture network on photoresist film, handle sample with deionized water
Product surface, the photoresist removed at cracking template and crack are remaining；
(5) nano metal network is formed: suspended nano metallic particles liquid being inserted cracking fracture network and forms nanogold
Belong to network, annealing, which is formed, stablizes linear network；
(6) it removes photoresist: substrate is placed in photoresist cleaning solution, remove photoresist, remaining nano metal network；
(7) adhesiveness is handled: being sprayed UV glue on nano metal network surface, is air-dried, adjust the smooth of nano metal network
Degree and thickness then carry out ultraviolet photoetching, form the strong metalolic network transparent conductive electrode of adhesive force.
In the method that above-mentioned plasma bombardment prepares metalolic network transparent conductive electrode:
Transparent substrates described in step (1) of the present invention include a variety of transparent materials, preferably polyethylene terephthalate
The materials such as ester PET or glass.
Using preceding needing by cleaning treatment, the process of cleaning treatment is preferably listed as follows the transparent substrates: using acetone
It rinses twice, ethyl alcohol rinses twice, and deionized water is rinsed three times, then is dried up with nitrogen.
Photoresist described in step (1) of the present invention is preferably the ultraviolet negative photoresist of BN303-60 or SU-8 negative photo
Glue can be used spin-coating method, drop-coating, knife coating etc. and carry out photoresist coating, guarantees that its thickness is uniform, surfacing, and control
Photoresist processed with a thickness of 3~20 μm.
Temperature when in step (2) of the present invention to silicon is preferably 20~150 DEG C, and the time is preferably 1~10min,
The uv-exposure time is preferably 10~100s, and the intensity of ultraviolet light is preferably 5~1000W when uv-exposure.
To be cracked preferably by the way of spin coating, drop coating or blade coating the light of liquid setting after hardening in step (3) of the present invention
Film is formed on photoresist film.
Cracking liquid described in step (3) of the present invention is preferably TiO 2 sol, egg white colloidal sol or CA600 colloidal sol, is added
Hot temperature is preferably 20~150 DEG C, and soaking time is preferably 1~40min.
Cracking liquid in the present invention has preferable mobility, adhesiveness, it is ensured that its networking that can not only be cracked, but also can protect
Substrate is protected to be readily cleaned again from plasma bombardment processing, while in subsequent process.
The gas used when using plasma bombardment template in step (4) of the present invention is preferably but not limited to argon gas, oxygen
Gas or nitrogen, bombardment time are preferably but not limited to 20~60min, and temperature is preferably but not limited to be 20~150 DEG C, power
For 100~300W, controlling sample distance bombardment source height is 5~15cm.
Bombard template surface under using plasma vacuum in step (4) of the present invention, due to be cracked template protective effect,
Only cracks photoresist is bombarded, and is constantly deepened.
Preferably suspended nano metallic particles liquid is inserted by the way of spraying or spin-on deposition in step (5) of the present invention
Cracking fracture network forms continuous nano metal network.
In suspended nano metallic particles liquid described in step (5) of the present invention nano-metal particle preparation method preferably according to
Described in patent No. CN201510034152, reaction temperature is improved preferably to 180~240 DEG C, then cooling centrifugation, obtains different grains
Diameter range nano particle；Partial size is preferably 2~100nm, and annealing temperature is preferably 40~250 DEG C, and annealing time is preferably 2~
60min。
Further, in step (5) of the present invention using spray or spin-on deposition by the way of by suspended nano metallic particles liquid
Body filling cracking fracture network forms continuous nano metal network.Then it is struck off using scraper or soft fine, soft fur round brush, is removed
Nano surface particle is removed, and is annealed by above-mentioned requirements, makes metallic particles at network, improving stability reduces resistance.
Substrate is placed in photoresist cleaning solution in step (6) of the present invention, the cleaning solution preferably includes acetone and/or different
Propyl alcohol etc..
In step (7) of the present invention preferably by the way of spraying or soaking cloth, in nano metal network surface deposition UV glue, certainly
It so air-dries, and using hot-pressing processing adjustment nano metal network flatness and thickness, it is transparent to form the strong metalolic network of adhesive force
Conductive electrode, when ultraviolet photoetching, exposure intensity is 5~1000W, and the time for exposure is 10~60s.
Detailed process are as follows: by UV glue especially 1019 and ethyl alcohol by 1:100 volume ratio proportion solution is made, sprayed or soaked
Be distributed in substrate, be adsorbed in metalolic network metal wire two sides after drying naturally, be exposed using ultraviolet lamp, light intensity 5~
1000W, time for exposure are 10~60s, fixed metalolic network improving stability with it is adhesive, it is not easily to fall off.
The principle of the present invention is: after the liquid that will be cracked is coated in that can remove on the surface of layer, certain temperature baking is cracked molten
Liquid dries out in air, shrinks and generates internal stress, generates the tiny intensive crazing cracks of lines.Then carry out plasma
Body bombardment can be cracked layer protection by plasma bombardment at crazing cracks for flawless between crackle, at any time, intensity change and
Continuous size is formed specifically to be cracked recess mesh.Nano-metal particle is then distributed at recess mesh, annealing, which is formed, to be connected
Continuous metalolic network, then cracking template is removed, coating UV glue promotes adhesive force, ultimately forms the conductive electricity of metallic transparent of function admirable
Pole.Entire production process whole can use PET, be mass produced using roll-to-roll process.
The present invention has the advantage that
(1) early period of the invention prepares high-performance conductive electrode using natural cracking template, but due to using
Extensive vacuum equipment, investment is big, and production cost is higher, or uses chemical method, and controllability is poor, and the present invention uses plasma
Body bombards method, and production cost is low, and high production efficiency, simple process, controllability is strong, is suitable for a variety of demands；
(2) the method for the present invention preparation combines roll-to-roll process, can continuously be mass produced, technical maturity, without extensive
Change, production capacity limitation are small；
(3) the method for the present invention can be selected by bombardment intensity, time combination except layer choosing, can adjust metal nanometer line on a large scale
Line footpath realizes the diversification of electrode performance, meets different demands；
(4) substrate of the present invention is selectively big, can be widely applied to various flexible, hard materials, is widely used in various set
It is standby；
(5) the method for the present invention can be coated with by UV glue and the adjustment of rolling pressure size, the metal for regulating and controlling transparent electrode are received
Rice noodles height and surface roughness meet special laboratory and industrial requirement.
Detailed description of the invention
Fig. 1 is the deposition that layer material can be removed in the method for 1-3 of the embodiment of the present invention, wherein 1, baking oven；2, Meyer stick；3, light
Photoresist；11, ultraviolet lamp；
Fig. 2 is the deposition and dry and chap of the skin of cracking liquid in the method for 1-3 of the embodiment of the present invention, wherein 1, baking oven；2, Meyer
Stick；4, be cracked liquid；
Fig. 3 is the recessed grain of plasma bombardment networking network in the method for 1-3 of the embodiment of the present invention, and removes cracking template, wherein
5, plasma processor；6, deionized water；
Fig. 4 is that nano-metal particle sprays in the method for 1-3 of the embodiment of the present invention, and removes and can form metal mesh except layer
Network, wherein 1, baking oven；7, nano particle spray gun；8, removal tool；9, cleaning solution；10, oscillator device；13, cylinder；
Fig. 5 is the spraying of UV glue, drying in the method for 1-3 of the embodiment of the present invention, is compacted promote adhesive force, formation is stablized high saturating
Bright conductive electrode, wherein 1, baking oven；11, ultraviolet lamp；12, UV glue；13, cylinder；
Fig. 6 is to amplify 20 times under optical microscopy in the method for 1-3 of the embodiment of the present invention, and substrate coating is cracked after liquid, from
So cracking Prototype drawing that cracking is formed；
Fig. 7 is to amplify 100 times under optical microscopy, nano-metal particle fills out cloth tortoise in the method for 1-3 of the embodiment of the present invention
Recess mesh figure is split, mark unit is μm；
Fig. 8 is the transmission of egg cracking template, CA600 cracking template and ito glass in 1-3 method of the embodiment of the present invention
Rate comparison diagram.
Specific embodiment
Embodiment 1
As shown in Figs. 1-5, a kind of plasma bombardment provided in this embodiment prepares metalolic network transparent conductive electrode
Method.It includes five key steps: first is that substrate with can except the selection of layer is fixed, second is that the deposition of cracking liquid, and be cracked at
Template, third is that plasma bombardment method forms metalolic network groove, fourth is that the coating of nano-metal particle and it is annealed into network,
Fifth is that ultraviolet glue compaction, controls surface topography, transparent conductive electrode is obtained.
The detailed process of each step is as follows:
(1) substrate be fixed with the selection that can remove layer
(1) substrate material selected is PET, and 5cm × 5cm is cleaned using spray gun, including twice of acetone spray, and ethyl alcohol is clear
It washes twice, deionized water sprays three times, and subsequent use is dried with nitrogen, and keeps clean；
(2) layer that removes selected is photoresist 3, BN303-60 negative photoresist, by its even application in substrate, using straight
Diameter 10mm, the at the uniform velocity stable rolling of 20 μm of wet-film thickness of Meyer stick 2, after film forming, it is 110 DEG C that temperature is adjusted in baking oven 1, and is protected
Warm 3min, and 11 power 100w of ultraviolet lamp is set, at sample 15cm vertical height, 60s is exposed, photoresist film is obtained,
Middle photoresist with a thickness of 3~20 μm.
(2) liquid that is cracked is deposited on dry and chap of the skin
(1) the cracking liquid 4 chosen, egg white colloidal sol is at low cost, is easy to remove, nontoxic to be easy to get, and is added into clean beaker
The deionized water of 12.0mL adds 4.0mL egg white, and supersonic cleaning machine ultrasonic vibration 20min, 1000rpm are centrifuged 5min,
Take supernatant liquor to get egg white colloidal sol；
(2) being sprayed at egg white colloidal sol can be except layer, and using diameter 10mm, 20 μm of wet-film thickness of Meyer stick 2 is at the uniform velocity rolled
Pressure, film forming, it is 40 DEG C that temperature is adjusted in baking oven 1, and keeps the temperature 20min, and exposure cracking Cheng Mo obtains cracking template, and be cracked template
Shape is as shown in Figure 6 under 20 times of optical microscopies.
(3) plasma bombardment is at network groove
(1) cracking template is placed in plasma processor 5, regulation power 300W, gas is Ar gas, bombards plate distance
The template that is cracked is at upper vertical 7cm height, and for temperature at 80 DEG C ± 5 DEG C, using plasma bombards 30min, and it is recessed to form network
Slot.
(2) it is rinsed using deionized water 6, washes away template surface remnants template, obtain cracking fracture network.
(4) coating of nano-metal particle and it is annealed into network
(1) take ladder be distributed < 10nm, 30~50nm, 90~100nm nano metal Argent grain, according to the ratio of 5:3:2
Being made into mass concentration is 20% solution, and solvent is ethyl alcohol, is sprayed at tortoise with substrate at 30 ° of oblique angles using nano particle spray gun 7
Split on fracture network, then using oscillator device 10 vibrate after, scratched on film with such as the blade of removal tool 8, removal it is more
Remaining particle, it is as shown in Figure 7 that nano-metal particle fills out cloth cracking recess mesh.
(2) by template by baking oven 1, setting temperature is 180 DEG C, and keeps the temperature 30min, is annealed, particle fusion networking
Network is deposited on groove；
(3) template for melting into network is cleaned, immerses such as acetone of cleaning solution 9, impregnates 1min, in the process stirrer
100rpm stirring, takes out, and is at the uniform velocity rolled 10 times with cylinder 13 such as stainless steel metal column, and compacting forms nano metal network.
(5) ultraviolet glue compacting solidification
(1) with the volume ratio of 1:100 configuration UV glue especially 1019: ethanol solution is sprayed at substrate using UV glue 12
30 DEG C of temperature dry 5min are arranged in baking oven 1 in nano metal network surface；
(2) cylinder 13 is used, such as stainless steel metal column, gently rolls 10 times, controls nanometer line network height, improve coarse
Degree.
(3) at 15cm height, 30s then is exposed above the samples vertical using the ultraviolet lamp 11 of 100W power, solidification is purple
Outer glue.
Same method repeats to prepare electrode, obtains transparent conductive electrode sample 1,2,3,4.Its sheet resistance and light transmittance are respectively about
For (18 Ω/sq, 81%), (22 Ω/sq, 85%), (25 Ω/sq, 83%), (19 Ω/sq, 86%).
The average transmittance of four samples with the relationship of wavelength and compared with embodiment 2-3 it is as shown in Figure 8.
Embodiment 2
As shown in Figs. 1-5, the method that plasma bombardment provided in this embodiment prepares metalolic network transparent conductive electrode, packet
Include following steps:
The detailed process of each step is as follows:
(1) substrate be fixed with the selection that can remove layer
(1) substrate material selected is PET, and 5cm × 5cm is cleaned using spray gun, including acetone cleans twice, and ethyl alcohol is clear
It washes twice, deionized water is cleaned three times, and subsequent use is dried with nitrogen, and keeps clean；
(2) layer that removes selected is photoresist 3, and SU-8 negative photoresist uses diameter by its even application in substrate
10mm, the at the uniform velocity stable rolling film forming of 15 μm of wet-film thickness of Meyer stick 2.In baking oven 1,150 DEG C of heat preservation 6min.Ultraviolet lamp is set
11 power are 1000W, at sample upper vertical 10cm height, expose 10s, obtain photoresist, wherein photoresist with a thickness of 3~20
μm。
(2) liquid that is cracked is deposited on dry and chap of the skin
(1) the cracking liquid 4 chosen is CA600 colloidal sol, is used as nail enamel composition more, has been mass produced, at low cost, nontoxic
It is easy to get；
(2) by colloidal sol along 3 drop of glass sheet edges proportional spacing drop, using Meyer stick 2, diameter 10mm, 15 μm of wet-film thickness
It at the uniform velocity rolls, forms a film；30min, exposure cracking Cheng Mo are kept the temperature at 1,25 DEG C of baking oven, obtains cracking template, cracking shape of template exists
Under 20 times of optical microscopies as shown in Figure 6.
(3) plasma bombardment is at network groove
(1) cracking template is placed in plasma processor 5, setting power is 300W, and gas is Ar gas, bombards plate distance
Sample is to control temperature at upper vertical 5cm height at 100 DEG C ± 5 DEG C, bombard 20min, form network groove；
(2) it is at the uniform velocity rinsed using deionized water 6, washes away template surface remnants template, obtain cracking fracture network.
(4) coating of nano-metal particle and it is annealed into network
(1) take ladder be distributed < 10nm, 30~50nm, 90~100nm nano metal Argent grain, according to the ratio of 4:4:2
It is made into the solution of mass fraction 20%, solvent is ethyl alcohol.Cracking fracture network is sprayed at using 7,30 ° of oblique angles of nano particle spray gun
On, then using the oscillation of oscillator device 10, after spontaneously drying, using removal tool 8, such as soft fine, soft fur round brush is medium on glass
Dynamics wiping, removes excess particles；It is as shown in Figure 7 that nano-metal particle fills out cloth cracking recess mesh；
(2) template is annealed, particle fusion is deposited on groove at network by 1,200 DEG C of heat preservation 20min of baking oven；
(3) template for melting into network is cleaned, immerses 9 acetone of cleaning solution, impregnate 2min, taken out, and with cylinder 13,
It such as stainless steel metal column, at the uniform velocity rolls 10 times, compacting forms nano metal network.
(5) ultraviolet glue compacting solidification
(1) with the proportional arrangement UV glue of 1:100 especially 1019: the solution of ethyl alcohol is sprayed to form nanometer using UV glue 12
Metalolic network surface, in baking oven 1,25 DEG C of heat preservation 5min；
(2) cylinder 13 is used, such as stainless steel metal column, gently at the uniform velocity rolls 10 times, controls nanometer line network height, improve
Roughness；
(3) ultraviolet lamp 11 is used, power 10W is set, above the samples vertical at 15cm height, 60s is exposed, solidifies ultraviolet
Glue obtains electrode.
Same method repeats to prepare electrode, obtains transparent conductive electrode sample 1,2,3,4.Its sheet resistance and light transmittance are respectively about
For (21 Ω/sq, 87%), (17 Ω/sq, 88%), (15 Ω/sq, 83%), (17 Ω/sq, 84%).
The average transmittance of four samples with the relationship of wavelength and compared with embodiment 1 and embodiment 3 such as Fig. 8 institute
Show.
Embodiment 3
As shown in Figs. 1-5, the method that plasma bombardment provided in this embodiment prepares metalolic network transparent conductive electrode, packet
Include following steps:
The detailed process of each step is as follows:
(1) substrate be fixed with the selection that can remove layer
(1) substrate material selected is glass, and 5cm × 5cm is cleaned using spray gun, including acetone cleans twice, and ethyl alcohol is clear
It washes twice, deionized water is cleaned three times, and subsequent use is dried with nitrogen, and keeps clean；
(2) layer that removes selected is photoresist 3, BN303-60 negative photoresist, by its even application in substrate, using straight
Diameter 10mm, the at the uniform velocity stable rolling film forming of 6 μm of wet-film thickness of Meyer stick 2, in baking oven 1, ultraviolet lamp is arranged in 20 DEG C of heat preservation 4min
11, power 100W at sample upper vertical 10cm height, expose 30s；It repeats above step 5 times, obtains photoresist, wherein photoetching
Glue with a thickness of 3~20 μm.
(2) liquid that is cracked is deposited on dry and chap of the skin
(1) the cracking liquid 4 chosen is TiO 2 sol, and performance is stablized, has been mass produced, has been easily obtained.It is configured
It is as follows, clean beaker is taken, dehydrated alcohol 12mL is added, butyl titanate 4mL is then added, stirs evenly and obtains a；Take clean burning
Dehydrated alcohol 12mL is added in cup, and glacial acetic acid 32.2mL, deionized water 1mL is added, and stirs evenly and obtains b；A, b is uniformly mixed, room
The lower 800rpm/min of temperature stirs 480min, obtains c；10mL dehydrated alcohol is added in c, is exposed in air and stirs 2160min, obtain
Obtain TiO 2 sol.
(2) by colloidal sol along 2 drop of glass sheet edges proportional spacing drop, using Meyer stick 2, diameter 10mm, 6 μm of wet-film thickness even
Speed rolling, film forming；In baking oven 1,120 DEG C of heat preservation 10min, cracking obtains cracking template at mould, and the shape of template that is cracked is in 20 times of optics
Under microscope as shown in Figure 6.
(3) plasma bombardment is at network groove
(1) cracking template is placed in plasma processor 5, setting power is 300W, gas N2Gas bombards plate distance
Sample is to control temperature at upper vertical 10cm height at 120 DEG C ± 5 DEG C, bombard 15min, form network groove；
(2) it is at the uniform velocity rinsed using deionized water 6, washes away template surface remnants template, obtain cracking fracture network.
(4) coating of nano-metal particle and it is annealed into network
(1) take ladder be distributed < 10nm, 30~50nm, 90~100nm nano metal Argent grain, according to the ratio of 3:5:2
It is made into the solution of mass concentration 20%, solvent is ethyl alcohol.Cracking fracture network is sprayed at using 7,30 ° of oblique angles of nano particle spray gun
On, then using the oscillation of oscillator device 10, after spontaneously drying, using removal tool 8, as flexible nonwoven rolling cloth is medium on glass
Dynamics wiping, removes excess particles；Obtain substrate.It is as shown in Figure 7 that nano-metal particle fills out cloth cracking recess mesh.
(2) template is annealed, particle fusion is deposited on groove at network by 1,210 DEG C of heat preservation 15min of baking oven；
(3) template for melting into network is cleaned, immerses 9 isopropanol of cleaning solution, impregnate 2min, taken out, and use cylinder
13, it such as stainless steel metal column, at the uniform velocity rolls 10 times, compacting forms nano metal network.
(5) ultraviolet glue compacting solidification
(1) with the proportional arrangement UV glue of 1:100 especially 1019: the solution of ethyl alcohol is sprayed at nano metal using UV glue 12
Network surface, in baking oven 1,35 DEG C of heat preservation 10min；
(2) cylinder 13 is used, such as stainless steel metal column, gently at the uniform velocity rolls 10 times, controls nanometer line network height, improve
Roughness；
(3) ultraviolet lamp 11 is used, power 1000W is set, above the samples vertical at 15cm height, exposes 10s, solidification is purple
Outer glue；
Same method repeats to prepare electrode, obtains transparent conductive electrode sample 1,2,3,4.Its sheet resistance and light transmittance are respectively about
For (22 Ω/sq, 87%), (25 Ω/sq, 88%), (27 Ω/sq, 81%), (28 Ω/sq, 84%).
The average transmittance of four samples with the relationship of wavelength and compared with embodiment 1-2 it is as shown in Figure 8.
The above is only non-limiting embodiment of the invention, for those of ordinary skill in the art, not
Under the premise of being detached from the invention design and not making creative work, various modifications and improvements can be made, these are all
It belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of method that plasma bombardment prepares metalolic network transparent conductive electrode, it is characterized in that the following steps are included:
(1) substrate coating photoresist: selection clean transparent substrate, coating photoresist, and control the thickness of photoresist；
(2) photoresist is fixed: to uv-exposure processing is carried out after silicon heat preservation, by photoetching adhesive curing, it is thin to form photoresist
Film；
(3) production cracking template: preparing the cracking liquid of collosol state, shape on the photoresist film of liquid setting after hardening that will be cracked
At cracking liquid film, temperature and soaking time are heated and controlled, makes the liquid film exposure cracking formation cracking template that is cracked；
(4) plasma networking: using plasma bombardment cracking template removes the photoresist in cracking crack on floor, control
The bombardment time and temperature of plasma, form cracking fracture network on photoresist film, handle sample table with deionized water
Face, the photoresist removed at cracking template and crack are remaining；
(5) nano metal network is formed: suspended nano metallic particles liquid being inserted cracking fracture network and forms nano metal net
Network, annealing, which is formed, stablizes linear network；
(6) it removes photoresist: substrate is placed in photoresist cleaning solution, remove photoresist, remaining nano metal network；
(7) adhesiveness handle: nano metal network surface spray UV glue, air-dry, adjust nano metal network flatness and
Thickness then carries out ultraviolet photoetching, forms the strong metalolic network transparent conductive electrode of adhesive force.
2. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that:
Transparent substrates described in step (1) are polyethylene terephtalate or glass.
3. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that:
Photoresist described in step (1) is the ultraviolet negative photoresist of BN303-60 or SU-8 negative photoresist, and controls the thickness of photoresist
Degree is 3~20 μm.
4. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that:
Temperature when in step (2) to silicon is 20~150 DEG C, and the time is 1~10min, and the uv-exposure time is 10~100s,
The intensity of ultraviolet light is 5~1000W when uv-exposure.
5. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that:
The liquid that will be cracked by the way of spin coating, drop coating or blade coating in step (3), which is arranged to be formed on photoresist film after hardening, to be cracked
Liquid film.
6. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that:
Cracking liquid described in step (3) is TiO 2 sol, egg white colloidal sol or CA600 colloidal sol, and heating temperature is 20~150 DEG C,
Soaking time is 1~40min.
7. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that:
The gas that uses is argon gas, oxygen or nitrogen when using plasma bombards template in step (4), bombardment time is 20~
60min, temperature are 20~150 DEG C, and power is 100~300W, and control sample distance bombardment source height is 5~15cm.
8. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that:
Suspended nano metallic particles liquid is inserted cracking fracture network and formed by the way of spraying or spin-on deposition in step (5) and is connected
Continuous nano metal network.
9. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, it is characterized in that:
The partial size of nano-metal particle is 2~100nm, annealing temperature 40 in suspended nano metallic particles liquid described in step (5)
~250 DEG C, annealing time is 2~60min.
10. the method that plasma bombardment according to claim 1 prepares metalolic network transparent conductive electrode, feature
It is: in step (7) by the way of spraying or soaking cloth, in nano metal network surface deposition UV glue, natural air drying, and uses heat
Pressure processing adjustment nano metal network flatness and thickness form the strong metalolic network transparent conductive electrode of adhesive force, ultraviolet light
When exposure, exposure intensity is 5~1000W, and the time for exposure is 10~60s.
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