CN108859098A - A kind of ultra-fine, large ratio of height to width grid transparent electrode preparation method - Google Patents
A kind of ultra-fine, large ratio of height to width grid transparent electrode preparation method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/02—Moulding by agglomerating
- B29C67/04—Sintering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H—ELECTRICITY
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
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Abstract
The invention discloses a kind of ultra-fine, large ratio of height to width grid transparent electrode preparation methods, belong to increasing material manufacturing and technical field of electronic devices.Ultra-fine, large ratio of height to width grid transparent electrode preparation method of the invention sprays 3D printing and charge induction to just combining using electric field driven.Within one pulse period of AC pulse power supply, positive voltage induction generates positively charged printed material microlayer model, negative voltage induction generates negatively charged printed material microlayer model, adjacent electrification printed material microlayer model contacts after being deposited on substrate, positive and negative charge neutralizes, realize that electrification printed material microlayer model is accumulated on molded layer to positive followed by charge induction, until completing the printing of the grid of the setting number of plies.Ultra-fine, large ratio of height to width grid transparent electrode the preparation method baseplate material selectable range of the invention is wide, and can obtain the transparent electrode of high conductivity, high transparency, has good application value.
Description
Technical field
The present invention relates to increasing material manufacturings and technical field of electronic devices, specifically provide it is a kind of it is ultra-fine, large ratio of height to width grid is saturating
The preparation method of prescribed electrode.
Background technique
Transparent electrode refers to the conductive component that high transparency and low areal resistance are provided simultaneously in visible light region, transparent electricity
Pole has extremely extensively in electronic fields such as the displays such as LCD and OLED, touch screen, organic solar batteries, optoelectronic components
Application.Transparent electrode is mainly prepared using indium and tin oxide film at present, but the transparent electrode of this kind of method preparation
The problems such as destroying substrate there are frangible and preparation process high-temperature process, at the same indium itself be used as rare metal there is also resources it is withered
The hidden danger exhausted.Including graphene, carbon nanotube, metal（Gold, silver, copper）There is transparency height, sheet resistance Deng transparent electrode of new generation
Small, the advantages that cost performance is high and baseplate material selectable range is wide, show advantage outstanding and wide industrial prospect.
Currently, the method that academia and industrial circle have proposed a variety of manufacture grid transparent electrodes, such as optical lithographic methods,
A variety of manufacturing technologies such as nanoimprint, inkjet printing, aerosol printing, electrohydrodynamic jet printing.However these above-mentioned sides
Method has some limitations at present.（1）, optical lithographic methods may be implemented preparation grid transparent electrode high-resolution,
But it is mainly directed towards two-dimentional molding, it is difficult to realize large ratio of height to width, and this method manufacturing cost is high（Photoetching cost and material at
This）, large scale it is limited（Current maximum technical grade is 12 inches）；（2）, nano impression large area manufacture when, due to template
With imprinted pattern contact area excessive the problems such as will cause difficult removing, imprinted pattern deformation, faced in large scale manufacture view
Severe challenge, while preparing high-precision template and usually requiring method with electron beam lithography or focused-ion-beam lithography, it is time-consuming and
It is expensive；（3）, inkjet printing common are thermal bubble type and piezoelectric type, but all suffers from the low problem of resolution ratio at present（Line width
Greater than 20 μm）, be not able to satisfy requirement of the numerous areas such as touch screen, OLED for transparent electrode, and printed material viscosity by
Limit（Viscosity is generally limited 30cP or less）, cannot achieve the printing of heavy viscous material；（4）Although, aerosol printing beating
Print precision（Highest resolution is 5 μm at present）In terms of printed material viscosity（Lower than 2500cP）It is greatly improved, and
It can be realized large ratio of height to width structure, but existing precision is still unable to satisfy the high-resolution transparent electrode such as OLED, touch screen
Requirement（Line width is generally below 5 μm hereinafter, minimum feature is lower than 2 μm）, and the equipment cost that this method uses is very high, beats
It is limited to print material；（5）, electrohydrodynamic jet printing is in nozzle（First electrode）With substrate（Second electrode）Between apply it is high
Pressure, generates superfine jet stream from nozzle tip in a manner of " drawing " and is printed, and has printing sub-micron, nanoscale resolution
The ability of complicated micro-nano structure, and compatibility is preferably.But this method is difficult to meet the printing on the conformal substrate of curved surface, exhausted
Stability is poor when printing on edge substrate, high-resolution（It is ultra-fine）The print capacity of pattern large ratio of height to width structure is insufficient.
Summary of the invention
Technical assignment of the invention is that in view of the above problems, it is wide to provide a kind of baseplate material selectable range, and
And ultra-fine, large ratio of height to width grid transparent electrode the preparation method of high conductivity, high transparency can be obtained.
To achieve the above object, the present invention provides following technical solutions：
A kind of ultra-fine, large ratio of height to width grid transparent electrode preparation method, the preparation method spray 3D printing using electric field driven
With charge induction to just combining：Conductive nozzle is connected with AC pulse power supply, set between nozzle and insulating substrate away from
From, electric field is formed between nozzle and substrate, under electric field action nozzle tip generate cone jet stream be deposited on substrate to be formed beat
Material microlayer model is printed, wherein positive voltage induction generates positively charged printing material within one pulse period of AC pulse power supply
Expect microlayer model, negative voltage induction generates negatively charged printed material microlayer model, is deposited on adjacent electrification printed material after substrate
Microlayer model contact, positive and negative charge neutralize, and mobile substrate, the AC pulse power supply next pulse period continues to repeat positive and negative charge
Printed material microlayer model alternating deposit completes single layer mesh printing；The distance that nozzle is moved up to a thickness, molded
On the basis of layer, continues the control positive and negative voltage of AC pulse power supply and repeat the above process, by between molded layer and nozzle
Electric field action realizes that electrification printed material microlayer model is accumulated on molded layer to positive using charge induction, until completing to set
The printing of given layer number grid, grid print product and are prepared into grid transparent electrode through sintering.
Heretofore described electric field driven injection 3D printing process sprays 3D printing equipment using electric field driven to complete.Electricity
Driving injection 3D printing equipment include printing head, nozzle, AC pulse power supply, displacement platform, substrate, material feed unit and
Pressure control unit.Wherein nozzle is arranged in printing head lower end；AC pulse power supply is by signal generator and high-voltage amplifier
It collectively constitutes；Pressure control unit control compressed air is passed through into printing head；Material feed unit is connected with printing head,
Printed material is held in material feed unit.Substrate is mounted on displacement platform, according to want print pattern pre-set program control
The movement of displacement platform, displacement platform moves in real time in print procedure, and the movement of substrate is realized by the movement of displacement platform, thus
Realize print pattern on substrate.
The insulating substrate is rigidity or flexible, selection such as glass or PET in the present invention.
It is combined in the present invention using insulating substrate, conductive nozzle and AC pulse power supply.Nozzle is close in print procedure
When substrate, under AC pulse power supply effect, electrostatic induction effect occurs for nozzle and substrate, leads to substrate charge rearrangement,
Upper surface of substrate distribution is negative（Just）Charge, following table EDS maps are just（It is negative）Charge forms stable electric field, mentions between nozzle and substrate
Electric field stability during height printing.The printed material of nozzle tip is expressed into electric field force, viscous force, surface tension etc.
Stretcher strain gradually forms taylor cone under comprehensive function, as taylor cone tip charge is constantly assembled, works as electrostatic force（Electric field force）
After the surface tension of printed material, printed material drop generates superfine cone jet stream from taylor cone top jet（Jet flow direct
The diameter 1-2 order of magnitude smaller than jet size）, realize that microlayer model is deposited on substrate, in conjunction with the movement of displacement platform, realize any
It is prepared by the high-precision of complex pattern.
Electric field driven sprays 3D printing and charge induction to just combining, and the single layer mesh for completing ultra-fine line width first is beaten
Print recycles charge induction to realize the printing of ultra-fine multilayer grid to positive.
Stable electric field is formed under the action of AC pulse power supply, between nozzle and substrate, is improved in print procedure
Electric field stability, to guarantee grid high-resolution（It is ultra-fine）The stability of printing, and accumulated in fact by charge induction to positive
The accurate accumulation of microlayer model in existing multilayer print procedure, to realize the preparation of ultra-fine large ratio of height to width grid transparent electrode.
Preferably, the preparation method of the transparent electrode specifically includes following steps
S1：Printing initialization
Printed material is packed into material feed unit, AC pulse power supply is connected with nozzle, nozzle is moved to initial print position
It sets, sets the distance between nozzle and substrate；
S2：Print first layer grid
The running parameter of AC pulse power supply is set, starts AC pulse power supply, forms electric field between nozzle and substrate, by
The printed material that material feed unit is expressed into nozzle tip forms taylor cone, in pulse period of AC pulse power supply
Just（It is negative）Band is being formed just under voltage effect（It is negative）The printed material microlayer model of charge is deposited at cone jet stream to substrate from taylor cone
On, in bearing for same pulse period（Just）The lower band that formed of voltage effect is born（Just）The printed material microlayer model of charge is from taylor cone
It deposits at cone jet stream to substrate, the printed material microlayer model of adjacent belts xenogenesis charge neutralizes, and makes printable layer electroneutral, mobile
Substrate continues to repeat just in the next pulse period（It is negative）, it is negative（Just）Printed material charge microlayer model alternating deposit is complete to substrate
It is printed at first layer grid；
S3：Print second layer grid
On the basis of the first layer grid of printing, nozzle is moved up to the distance of a thickness, while substrate counter motion,
The parameter of AC pulse power supply is adjusted, the control positive and negative voltage of AC pulse power supply continues to repeat the process of step S2, utilizes charge
Induction realizes that electrification printed material microlayer model is precisely accumulated on molded layer to positive, completes the printing of second layer grid；
S4：Print multi-layer net
The process of step S3 is repeated, realizes the printing of setting number of plies grid；
S5：Printing terminates, and removes the grid printing product of the printed setting number of plies, and sintering is prepared into grid transparent electrode.
Preferably, being deposited on substrate after electrification printed material microlayer model is deposited on substrate using light source irradiation
Printed material microlayer model is irradiated by light source and realizes printed material rapid curing.
Preferably, irradiating the printed material microlayer model being deposited on substrate using UV light source, the UV light source is irradiated
Cheng Caiyong area source radiation modality, irradiated area 100cm*100cm, intensity of illumination 1.0-1.3W/cm2, peak wavelength is
385-405nm, light application time are 45-60 seconds.
It is radiated at the printed material microlayer model being deposited on substrate using UV light source, passes through UV light source and printed material
Effect generates heat and realizes the rapid curing of printed material microlayer model on substrate, to mitigate in multilayer print procedure, prints
After material jet deposition to substrate, in substrate or the lower booth phenomenon of printable layer, preferably guarantee that the line width of printing and height are wide
Than.
Preferably, the main component of the printed material is graphene, carbon nanotube, nano-Ag particles, Nanometer Copper
One or more particles mixing of grain, nanogold particle.
Wherein, when the main component of printed material is that a variety of particles mix, the ratio of each substance is divided into following scenario described：
1）When graphene is mixed with carbon nanotube, two kinds of substances are mixed with arbitrary proportion；
2）Nano-Ag particles, nano copper particle, nanogold particle the mixing of any two or three of particle when, it is mixed with arbitrary proportion
It closes；
3）When printed material be graphene and nano-Ag particles, nano copper particle, nanogold particle it is one or more mix when,
The content of graphene is no more than 10wt%, other substances are mixed with arbitrary proportion；
4）When printed material mixes for carbon nanotube with nano-Ag particles, nano copper particle, the one or more of nanogold particle
When, the content of carbon nanotube is no more than 15wt%, other substances are mixed with arbitrary proportion；
5）When printed material is graphene, carbon nanotube and nano-Ag particles, nano copper particle, one kind of nanogold particle or more
When kind mixing, the content of graphene is no more than 10wt%, and the content of carbon nanotube is no more than 15wt%, other substances are with arbitrary proportion
Mixing.
Preferably, graphene, carbon nanotube, nano-Ag particles, nano copper particle, one or more of nanogold particle
Grain Dispersed precipitate is in printed material, and furthermore printed material further includes organic solvent, thickener, surfactant.Organic solvent
It is preferential to select terpinol, tributyl citrate or isopropanol.Thickener preferentially selects ethyl cellulose.Surfactant preferentially selects
With Tween 80 or polyvinylpyrrolidone PVP-K30.Wherein the dielectric constant of printed material, surface tension and viscosity are in the invention
Grid transparent electrode preparation method in play decisive role, the viscosity of printed material is 10000cP-20000cP.Using
The printed material that graphene, carbon nanotube, nano-Ag particles, nano copper particle, nanogold particle etc. are prepared as main component
Dielectric constant, surface tension be able to satisfy the demand of the preparation method.
Preferably, the running parameter of the AC pulse power supply includes voltage, frequency and duty ratio, wherein voltage is
500-1500V, frequency 1-2000Hz, duty ratio 1%-80%.
Preferably, the nozzle is metallic nozzle or inner wall coats conductive material, the internal diameter of nozzle is 0.1-500 μm.
Preferably, the distance between the nozzle and substrate are 0.1mm-0.5mm.
Preferably, the movement speed of the substrate is 100mm/s-300mm/s.
Preferably, grid printing product is sintered in sintering furnace, sintering furnace is heated to 120-150 DEG C, by net
Lattice printing product keeps the temperature 5-10min in sintering furnace.
Compared with prior art, ultra-fine, large ratio of height to width grid transparent electrode preparation method of the invention has following prominent
Beneficial effect out：
（One）In the preparation method of the grid transparent electrode, it is based on electric field driven jet deposition 3D printing technique, using exchange
The pulse power generates positive and negative voltage, mutually neutralizes after positive and negative electrification printed material microlayer model is deposited on substrate to realize,
Interference of the residual charge to electric field is reduced, guarantees the stability and reliability of print procedure, more preferably print quality is obtained, is more
Charge induction provides guarantee to positive stability certainly during layer heap product；
（Two）Realize that microlayer model precisely deposits in multilayer print procedure, guarantees layer-layer essence to positive accumulation by charge induction
Standard realizes printed material rapid curing to just, and using the irradiation of UV light source, to realize on the basis of not increasing line width big
The preparation of depth-width ratio grid is prepared into ultra-fine, large ratio of height to width grid, the grid transparent electrode of preparation is made to have both excellent light transmission
Rate and conductivity；
（Three）It is printed using the superfine taylor cone jet stream that forceful electric power field force is formed, minute yardstick even sub-micron scale line may be implemented
The printing of structure makes the grid transparent electrode of preparation have ultrahigh resolution（5 μm or less）, can satisfy OLED, touch screen etc.
Requirement of the field to high-resolution transparent electrode, expands application field；
（Four）The limitation that the method for the invention overcomes traditional electric Printing techniques to require substrate conduction, is suitable for isolation material
Substrate is applicable to the substrate printing of any thickness, reduces printing and require；
（Five）In conjunction with the unrestricted advantage of substrate material, this method can print on arbitrary height solid object surface, be suitable for
The printing of non-smooth surface, curved surface, more particularly to realize the printing of conformal substrate；
（Six）Fine liquid drop spray is driven using powerful electric field force in this method, high viscosity even very high viscosity may be implemented
Printed material stablizes printing, keeps printed material range of viscosities unrestricted；
（Seven）The equipment that the method utilizes is simple, and operating cost is low, and the printing model of spray printing can be effective as required
Avoid the waste of expensive printed material, save the cost.
Detailed description of the invention
Fig. 1 is that electric field driven injection 3D is beaten in ultra-fine, large ratio of height to width grid transparent electrode preparation method of the present invention
Printing apparatus schematic diagram；
Fig. 2 is that AC pulse power supply negative voltage is made in ultra-fine, large ratio of height to width grid transparent electrode preparation method of the present invention
Printed material stress diagram under；
Fig. 3 is that AC pulse power supply positive voltage is made in ultra-fine, large ratio of height to width grid transparent electrode preparation method of the present invention
Printed material stress diagram under；
Fig. 4 is that the principle of ultra-fine, large ratio of height to width grid transparent electrode preparation method printing first layer grid of the present invention is shown
It is intended to；
Fig. 5 is the principle signal of ultra-fine, large ratio of height to width grid transparent electrode preparation method printing multi-layer net of the present invention
Figure；
Fig. 6 is the grid printing system after ultra-fine, large ratio of height to width grid transparent electrode preparation method multilayer printing of the present invention
Part schematic diagram；
Fig. 7 is 30 layers of net of ultra-fine, large ratio of height to width grid transparent electrode preparation method preparation described in the embodiment of the present invention one
Lattice print product schematic diagram；
Fig. 8 is the printing sintered transversal cross-section schematic illustration of tissue of product of grid shown in Fig. 7；
Fig. 9 is 20 layers of net of ultra-fine, large ratio of height to width grid transparent electrode preparation method preparation described in the embodiment of the present invention two
Lattice print product schematic diagram；
Figure 10 is the three dimensional structure diagram after the printing product printing first layer of grid shown in Fig. 9；
Figure 11 is that the printing product of grid shown in Fig. 9 prints the three dimensional structure diagram after the 20th layer.
Specific embodiment
Below in conjunction with drawings and examples, to ultra-fine, large ratio of height to width grid transparent electrode preparation method of the invention
It is described in further detail.
Ultra-fine, large ratio of height to width grid transparent electrode preparation method of the invention utilizes electric field driven injection 3D printing and electricity
Lotus induction is to just combining.
Electric field driven is sprayed 3D printing process and is completed by electric field driven injection 3D printing equipment.As shown in Figure 1, electric field driven
Injection 3D printing equipment includes printing head, nozzle, signal generator, high-voltage amplifier, displacement platform, substrate, material supply list
Member and pressure control unit.Nozzle is mounted on printing head lower end.Material feed unit is connected with printing head, and material supply is single
Nanometer silver paste is held in member.Pressure control unit control compressed air is passed through into printing head.Signal generator and height press
Big device collectively constitutes AC pulse power supply.AC pulse power supply is connected with nozzle.Substrate is mounted on displacement platform, is beaten as needed
It is patterned the movement routine of pre-set program control bit moving stage.Displacement platform moves in real time in print procedure, passes through displacement platform
Movement realize the movement of substrate, to realize print pattern on substrate.
The preparation method of High Performance Grid transparent electrode of the invention starts material if good the distance between nozzle and substrate
Expect feed unit, pressure control unit, signal generator, high-voltage amplifier and displacement platform, forms electricity between nozzle and substrate
?.Nanometer silver paste is expressed into nozzle tip by material feed unit, and nanometer silver paste is comprehensive in electric field force, viscous force, surface tension etc.
Cooperation forms taylor cone with lower stretcher strain, under the negative voltage effect in one pulse period of AC pulse power supply, such as Fig. 2 institute
Show, negative voltage induction generates negatively charged nanometer silver paste microlayer model, when electric field force is more than the surface of nanometer silver paste microlayer model
After power, negatively charged nanometer silver paste drop generates superfine cone jet stream from taylor cone top jet, is deposited on substrate.It is handing over
It flows under the positive voltage effect in one pulse period of the pulse power, as shown in figure 3, positive voltage induction generates positively charged nanometer
Silver paste microlayer model, after electric field force is more than the surface tension of nanometer silver paste microlayer model, positively charged nanometer silver paste drop is from Thailand
It strangles cone top part injection and generates superfine cone jet stream, be deposited on substrate, while being received using what the irradiation of UV light source was deposited on substrate
Rice silver paste microlayer model.The nanometer silver paste microlayer model for being deposited on substrate rear adjacent belts xenogenesis charge is in contact, and positive and negative charge neutralizes.
Continue to repeat positive and negative charge nanometer silver paste microlayer model alternating deposit on substrate in the AC pulse power supply next pulse period,
Single layer mesh printing is completed, as shown in Figure 4.The distance that nozzle is moved up to a thickness, on the basis of molded layer, after
The continuous control positive and negative voltage repetitive process of AC pulse power supply utilizes charge by the electric field action between molded layer and nozzle
Induction realizes that charged nanosize silver paste microlayer model is accumulated on molded layer to positive, as shown in figure 5, until completing the setting number of plies
The printing of grid, as shown in Figure 6.
Embodiment one
Using nano-Ag particles as the main component of printed material in the present embodiment.Printed material is by organic solvent, thickener, table
The nano-Ag particles of face activating agent and Dispersed precipitate composition.
Detailed process is as follows for the embodiment
S1：Printing initialization
Nanometer silver paste is packed into material feed unit, wherein nanometer silver paste uses tetra- kinds of sizes of 20nm, 60nm, 80nm and 100nm
Nano-Ag particles are formed according to mass fraction 20wt.%, 30wt.%, 30wt.%, 20wt.% respectively, and the viscosity of nanometer silver paste is
13000 cP, silver content 65wt.%, surface tension 44dyne/cm, volume resistivity are 5.5 × 10-6Ω·cm.Exchange arteries and veins
It rushes power supply to be connected with nozzle, nozzle uses stainless steel syringe needle, and internal diameter is 60 μm.Nozzle is moved to initial printing position, is set
Good the distance between nozzle and substrate are 0.3mm, and the mobile speed of displacement platform is set as 200 mm/s.Substrate is using non-treated
Pet substrate, the conductivity of substrate are 10-21/ Sm, with a thickness of 0.3mm.
S2：Print first layer silver grid
The operating voltage that AC pulse power supply is arranged is 1200V, frequency 1000Hz, duty ratio 55%.Start alternating-current pulse electricity
Source forms taylor cone by the nanometer silver paste that material feed unit is expressed into nozzle.In a pulse period of AC pulse power supply
Negative voltage effect under form negatively charged nanometer silver paste microlayer model, superfine cone jet stream is generated from taylor cone top jet,
It is deposited on substrate.The nanometer silver paste microlayer model being deposited on substrate is irradiated using UV light source simultaneously, using area source mode, is shone
Penetrating area is 100cm*100cm, and irradiation luminous intensity is 1.0W/cm2, peak wavelength 405nm, light application time is 45 seconds, is being beaten
UV light source is always maintained at irradiation during print.Band is formed under the positive voltage effect of the same pulse period of AC pulse power supply
The nanometer silver paste microlayer model of positive charge generates superfine cone jet stream from taylor cone top jet, is deposited on substrate.Adjacent belts are different
The nanometer silver paste microlayer model of kind charge neutralizes, and makes printable layer electroneutral.Continue in the AC pulse power supply next pulse period
Positive and negative nanometer silver paste microlayer model alternating deposit is repeated in substrate, completes the printing of first layer silver grid.
S3：Print second layer silver grid
On the basis of the first layer silver grid of printing, nozzle is moved up to the distance of a thickness, continues control exchange arteries and veins
The process that the positive and negative voltage of power supply repeats step S2 is rushed, realizes charged nanosize to positive using charge induction under the action of electric field
Silver paste microlayer model is precisely accumulated on molded layer, as the mobile completion second layer silver grid of displacement platform prints.
S4：Print multilayer silver grid
The process for repeating step S3, realizes the printing of 30 layers of silver-colored grid, and the structure of silver-colored grid printing product is as shown in Figure 7.Silver-colored net
The line width that lattice print product is 7 μm, and depth-width ratio 0.35, the period is 200 μm.
S5：Printing terminates, and sintering furnace is heated to 120 DEG C, and silver-colored grid printing product is then put into sintering furnace inside holding
5min takes out and silver-colored grid transparent electrode is made.It is illustrated in figure 8 the transversal cross-section tissue of silver-colored grid transparent electrode.It is silver-colored after tested
The light transmittance of grid transparent electrode is 91.6%, and sheet resistance is 8.1 Ω/sq.
Embodiment two
Using the mixture of nano-Ag particles and graphene as the main component of printed material in the present embodiment.Printed material is by having
Solvent, thickener, surfactant and Dispersed precipitate nano-Ag particles nano-Ag particles and graphene composition.
S1：Printing initialization
Nanometer silver paste and graphene are packed into material feed unit, wherein nanometer silver paste uses 20nm, 60nm, 80nm and 100nm
Four kinds of sized nanostructures Argent grains are formed according to mass fraction 20wt.%, 30wt.%, 30wt.%, 20wt.% respectively, nanometer silver paste
Viscosity is 18000cP, silver content 70wt.%, surface tension 50dyne/cm, and volume resistivity is 5.0 × 10-6Ω·cm。
The mass fraction of graphene is 10%.AC pulse power supply is connected with nozzle, and nozzle inner walls coat conductive material, and internal diameter is 30 μm.
Nozzle is moved to initial printing position, setting the distance between nozzle and substrate is 0.3mm, and the mobile speed of displacement platform is set
It is set to 240 mm/s.Substrate uses non-treated sheet glass, conductivity 10-11/ Sm, with a thickness of 1mm.
S2：Print first layer grid
The operating voltage that AC pulse power supply is arranged is 1500V, frequency 1200Hz, duty ratio 60%.Start alternating-current pulse electricity
The mixture in source, the nanometer silver paste and graphene that are expressed into nozzle by material feed unit forms taylor cone.In alternating-current pulse electricity
Negatively charged nanometer silver paste and graphene microlayer model are formed under the negative voltage effect of one pulse period in source, from Taylor's vertex of a cone
Portion's injection generates superfine cone jet stream, is deposited on substrate.The nanometer silver paste being deposited on substrate is irradiated using UV light source simultaneously
With graphene microlayer model, using area source mode, irradiated area 100cm*100cm, irradiation luminous intensity is 1.3W/cm2, peak value
Wavelength is 385nm, and light application time is 60 seconds, and UV light source is always maintained at irradiation in print procedure.In the same of AC pulse power supply
Positively charged nanometer silver paste and graphene microlayer model are formed under the positive voltage effect of one pulse period, is sprayed from taylor cone top
It penetrates and generates superfine cone jet stream, be deposited on substrate.The nanometer silver paste and graphene microlayer model of adjacent belts xenogenesis charge neutralize, and make
Printable layer electroneutral.Continue to repeat positive and negative nanometer silver paste and the micro- liquid of graphene in the AC pulse power supply next pulse period
Alternating deposit is dripped in substrate, completes the printing of first layer grid.
S3：Print second layer grid
On the basis of the first layer grid of printing, nozzle is moved up to the distance of a thickness, continues to control alternating-current pulse
The positive and negative voltage of power supply repeats the process of step S2, realizes charged nanosize silver to positive using charge induction under the action of electric field
Slurry and graphene microlayer model are precisely accumulated on molded layer, as the mobile completion second layer grid of displacement platform prints.
S4：Print multi-layer net
The process for repeating step S3, realizes the printing of 20 layers of grid, and the structure of final grid printing product is as shown in Figure 9.Net
The line width that lattice print product is 3 μm, and depth-width ratio 0.3, the period is 150 μm.
S5：Printing terminates, and sintering furnace is heated to 150 DEG C, and grid printing product is then put into sintering furnace inside holding
10min takes out and grid transparent electrode is made.The three-dimensional structure of the first layer of product, Tu11Suo are printed for grid as shown in Figure 10
It is shown as the 20th layer of three-dimensional structure of grid printing product.The light transmittance of grid transparent electrode is 89.2% after tested, and sheet resistance is
5.3 Ω/sq。
Embodiment described above, the only present invention more preferably specific embodiment, those skilled in the art is at this
The usual variations and alternatives carried out within the scope of inventive technique scheme should be all included within the scope of the present invention.
Claims (10)
1. a kind of ultra-fine, large ratio of height to width grid transparent electrode preparation method, it is characterised in that：The preparation method is driven using electric field
Dynamic injection 3D printing and charge induction are to just combining：Conductive nozzle is connected with AC pulse power supply, setting nozzle and insulation
The distance between substrate forms electric field between nozzle and substrate, and nozzle tip generates cone jet stream and is deposited under electric field action
Printed material microlayer model is formed on substrate, wherein positive voltage induction is generating band just within one pulse period of AC pulse power supply
The printed material microlayer model of charge, negative voltage induction generate negatively charged printed material microlayer model, are deposited on adjacent after substrate
The contact of printed material microlayer model is charged, positive and negative charge neutralizes, and mobile substrate, the AC pulse power supply next pulse period continues weight
Multiple positive and negative charge printed material microlayer model alternating deposit completes single layer mesh printing；By nozzle move up a thickness away from
From, on the basis of molded layer, continue control the positive and negative voltage of AC pulse power supply repeat the above process, pass through molded layer
Electric field action between nozzle realizes electrification printed material microlayer model heap on molded layer to positive using charge induction
Product, until completing the printing of setting number of plies grid, grid prints product and is prepared into grid transparent electrode through sintering.
2. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 1, it is characterised in that：Specifically
Include the following steps
S1：Printing initialization
Printed material is packed into material feed unit, AC pulse power supply is connected with nozzle, nozzle is moved to initial print position
It sets, sets the distance between nozzle and substrate；
S2：Print first layer grid
The running parameter of AC pulse power supply is set, starts AC pulse power supply, forms electric field between nozzle and substrate, by
The printed material that material feed unit is expressed into nozzle tip forms taylor cone, in pulse period of AC pulse power supply
Just（It is negative）Band is being formed just under voltage effect（It is negative）The printed material microlayer model of charge is deposited at cone jet stream to substrate from taylor cone
On, in bearing for same pulse period（Just）The lower band that formed of voltage effect is born（Just）The printed material microlayer model of charge is from taylor cone
It deposits at cone jet stream to substrate, the printed material microlayer model of adjacent belts xenogenesis charge neutralizes, and makes printable layer electroneutral, mobile
Substrate continues to repeat just in the next pulse period（It is negative）, it is negative（Just）Printed material charge microlayer model alternating deposit is complete to substrate
It is printed at first layer grid；
S3：Print second layer grid
On the basis of the first layer grid of printing, nozzle is moved up to the distance of a thickness, while substrate counter motion,
The parameter of AC pulse power supply is adjusted, the control positive and negative voltage of AC pulse power supply continues to repeat the process of step S2, utilizes charge
Induction realizes that electrification printed material microlayer model is precisely accumulated on molded layer to positive, completes the printing of second layer grid；
S4：Print multi-layer net
The process of step S3 is repeated, realizes the printing of setting number of plies grid；
S5：Printing terminates, and removes the grid printing product of the printed setting number of plies, and sintering is prepared into grid transparent electrode.
3. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 1 or 2, it is characterised in that：Band
After electric printed material microlayer model is deposited on substrate, the printed material microlayer model being deposited on substrate is irradiated using light source.
4. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 3, it is characterised in that：Using
UV light source irradiates the printed material microlayer model being deposited on substrate, and the UV light source irradiation process uses area source radiation modality,
Irradiated area is 100cm*100cm, intensity of illumination 1.0-1.3W/cm2, peak wavelength 385-405nm, light application time is
45-60 seconds.
5. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 4, it is characterised in that：It is described
The main component of printed material be graphene, carbon nanotube, nano-Ag particles, nano copper particle, nanogold particle one kind or
A variety of particle mixing.
6. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 5, it is characterised in that：It is described
The running parameter of AC pulse power supply includes voltage, frequency and duty ratio, and wherein voltage is 500-1500V, frequency 1-
2000Hz, duty ratio 1%-80%.
7. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 6, it is characterised in that：It is described
Nozzle is metallic nozzle or inner wall coats conductive material, and the internal diameter of nozzle is 0.1-500 μm.
8. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 7, it is characterised in that：It is described
The distance between nozzle and substrate are 0.1mm-0.5mm.
9. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 8, it is characterised in that：It is described
The movement speed of substrate is 100mm/s-300mm/s.
10. ultra-fine, large ratio of height to width grid transparent electrode preparation method according to claim 9, it is characterised in that：Grid
Printing product is sintered in sintering furnace, and sintering furnace is heated to 120-150 DEG C, and grid printing product is protected in sintering furnace
Warm 5-10min.
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