CN103219243B - The preparation method of pattern metal circuit - Google Patents
The preparation method of pattern metal circuit Download PDFInfo
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- CN103219243B CN103219243B CN201210376515.2A CN201210376515A CN103219243B CN 103219243 B CN103219243 B CN 103219243B CN 201210376515 A CN201210376515 A CN 201210376515A CN 103219243 B CN103219243 B CN 103219243B
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Abstract
The present invention relates to electronic manufacturing field, disclose the preparation method of a kind of pattern metal circuit.In the present invention, it is provided that a substrate；Utilize the activating solution and photoetching or printing technology prepared, preparation patterning Dopaminergics substrate surface in substrate；Wherein, activating solution there was added Dopaminergics material；The substrate that will be patterned into is placed in metal plating liquid, in the exposed local deposition layer of metal having Dopaminergics material of substrate surface；Metal plating liquid there was added reducing agent.Pattern metal circuit is patterned conductive thin film or fine-line.If patterned conductive thin film to be prepared is one side patterned conductive thin film, then in substrate in the step of preparation patterning Dopaminergics substrate surface, the one side of substrate coat cannot with the barrier layer of metal reaction after again another side in this substrate prepare patterning Dopaminergics substrate surface；Or, before the step that the substrate that will be patterned into is placed in metal plating liquid, the non-patterned one side of substrate is coated barrier layer.
Description
Technical field
The present invention relates to electronic manufacturing field, particularly to the technology of preparing of pattern metal circuit.
Background technology
Preparing metallic circuit on insulating substrate is very important production link in electronics/microelectronics industry,
In recent years, along with microelectronics and the development of semiconductor technology, the requirement of metallic circuit is improved by people day by day,
The needs of environmental protection and the pursuit of low-cost manufacturing technique are greatly excited researcher simultaneously new to exploitation
The enthusiasm of type metallic circuit technology of preparing.It is the most covered by photoresist that traditional handicraft is that photoetching after etching falls
Metal and form circuit, this " subtraction " technique causes metal waste, cost increase and environmental pollution
Etc. various problems, and along with electronic device gradually develops to miniaturization, traditional " subtraction " technique is very
Difficulty meets the requirement that circuit becomes more meticulous.
Meanwhile, transparent conductive film generally can be divided into patterning and non-patterned two kinds, and the former can pass through shape
The metallic circuit grid becoming definite shape realizes.Transparent conductive film Indium sesquioxide. currently as leading market
Stannum (ITO) thin film exist matter crisp and lack pliability, process costs is high, indium price is high and resource-constrained
Etc. problem, develop with satisfied following photoelectric device in the urgent need to the compliant conductive transparent membrane that exploitation is novel
Demand.
The common method preparing patterned transparent conductive film has inkjet printing, offset printing, roll-to-roll
Printing etc..Particle diameter usually is prepared as leading by its production method at the material such as nano silver wire etc. of nanometer scale
Electricity ink, is then printed on flexible and transparent substrate surface, leading needed for sintered rear formation by conductive ink
Electric network.Network line thickness is below the resolution of human eye, and the region without lines is transmission region.Logical
Cross the change width of lines, spacing and geometry and can control the table of nesa coating within the specific limits
Face sheet resistance and light transmittance.But using printing technology to make wire grid needs previously prepared micro-nano magnitude to lead
Electricity ink, and need to form conducting circuit by the way of sintering.And micro Nano material periphery cladding
The high temperature that stabilizer typically requires at 250 ° of C could decompose desorption, in order to obtain preferable electrical conductivity, mesh
Front ink sintering temperature is high, is not suitable for some low prices, polymer base that glass transition temperature is low
The end, and reduce the sintering temperature residual because of stabilizer by the electrical conductivity of sacrificial film.Additionally by printing
Mode be difficult to control in relatively low nanometer scale thicknesses of layers, and conductive grid is exposed in substrate
The thrust on surface, so that product surface roughness increases, and after sintering, conducting wire is glued with substrate
Attached loosely, bending time electrical conductivity drastic change easily occurs.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of pattern metal circuit so that at room temperature
The preparation of patterned conductive thin film or fine circuitry can be realized without sintering, and meeting Thin film conductive
While rate and light transmittance requirement, effective adhesion of plain conductor and different base can be realized, and effectively change
The roughness of kind film surface.
For solving above-mentioned technical problem, the invention provides the preparation method of a kind of pattern metal circuit,
Comprise the steps of
One substrate is provided；
Utilize the activating solution and photoetching or printing technology prepared, prepare patterning dopamine on the substrate
Class substrate surface；Wherein, described activating solution there was added Dopaminergics material；
The substrate of described patterning is placed in metal plating liquid, has Dopaminergics described substrate surface is exposed
The local deposition layer of metal of material；Described metal plating liquid there was added reducing agent；
Described pattern metal circuit is patterned conductive thin film or fine-line；
Wherein, if patterned conductive thin film to be prepared is one side patterned conductive thin film, then
Prepare in the step of patterning Dopaminergics substrate surface on the substrate, in the one of described substrate
In topcoating cannot with the barrier layer of metal reaction after again another side in this substrate prepare described patterning DOPA
Amine substrate surface；Or, before the step that the substrate of described patterning is placed in metal plating liquid, will
The non-patterned one side of substrate coats described barrier layer.
Embodiment of the present invention in terms of existing technologies, by photoetching (or printing) technology and preparation
Activating solution in substrate, form a pattern layers Dopaminergics material nano thin-film, then the base that will be patterned into
The end, is placed in metal plating liquid, utilizes adhesiveness and the reproducibility of Dopaminergics material excellence, at film surface
Layer of metal is deposited at Dopaminergics packaged material.Due to the distinctive adhesiveness of Dopaminergics material and reduction
Property metal is only generated at Dopaminergics packaged material thus realize substrate surface metal selective and sink
Long-pending, and when chemical plating without other sensitization or generation Seed Layer, concise in technology is the shortest, to environment friend
Good, metal level adheres to firmly with substrate.Further, since Dopaminergics material can be in condition as mild as a dove
Under be deposited on various material surface, so being applicable to multiple substrate, and whole process is carried out at room temperature.And
And, owing to metal plating liquid there was added reducing agent, therefore when carrying out chemical plating metal, it is ensured that metal
The seriality of film and electric conductivity.Further, since metal thickness can regulate and control in nanometer to micron dimension, both
The demand improving conductive film surface roughness can be met, also can meet fine conductive circuit and must possess necessarily
The requirement of thickness.
It should be noted that when patterned conductive thin film to be prepared is one side patterned conductive thin film,
The one side of substrate coat cannot with the barrier layer of metal reaction after again another side in this substrate prepare pattern
Change Dopaminergics substrate surface；Or, before the step that the substrate that will be patterned into is placed in metal plating liquid,
The non-patterned one side of substrate is coated described barrier layer, in order to avoid another side is also in follow-up chemical plating
Deposition layer of metal, further avoid metal waste.
Preferably, reducing agent is the mixture of one below or its combination in any: glucose, formaldehyde, wine
Stone acid, sodium potassium tartrate tetrahydrate, dimethyl amido borine, sodium borohydride, hydrazine dihydrochloride, Hydrazinium sulfate, hydrazine,
Sodium hypophosphite, glyoxalic acid, malic acid, sodium hypophosphite, citric acid, sodium citrate, ascorbic acid,
N,N-dimethylformamide, ethylene glycol, glutaraldehyde.
Preferably, metal plating liquid is commercialization metal plating liquid, or, described metal plating liquid is by following components
Composition: slaine, aqueous solvent, reducing agent, additive；Wherein, described slaine is mantoquita, silver salt
And other slaines.Embodiment of the present invention is possessed and is widely applied scene.
Preferably, additive is the mixture of one below or its combination in any: ethanol, methanol, second two
Amine tetraacethyl two is received, ethylenediamine, triethanolamine, thiourea, bipyridyl, Polyethylene Glycol, polyvinyl alcohol,
Polypyrrole alkanone, sodium lauryl sulphate, sodium citrate, sodium acetate, sodium pyrophosphate, potassium ferrocyanide,
Lead sulfate, ammonium sulfate, lactic acid, succinic acid, citric acid, propanoic acid, hydroxyacetic acid, boric acid, tartaric acid
Salt, sodium hydroxide, potassium hydroxide, ammonia.Make additive have stable plating solution, regulation and control coating character,
Adjust the characteristics such as silver plating process condition.
Preferably, photoetching technique comprises any one photoetching technique following: ultraviolet photolithographic, extreme ultraviolet photolithographic,
Beamwriter lithography, ion beam lithography, X-ray lithography and imprint lithography；Described imprint lithography includes hot pressing
Print, ultraviolet solidified nano impressing and micro-contact printing.Due to micro-contact printing, can be similar to seal the same
Being printed directly in substrate being applied to material thereon, therefore technique is compared traditional more succinct, obtains
Little live width is the least, is particularly suited for less than hundreds of nanometer, the sightless scene of circuit naked eyes.
Preferably, printing technology comprise following any one: printing, silk screen printing, inkjet printing, convex
Version printing, intaglio printing, offset printing, heat transfer printing, xerography, roll-to-roll printing.Preferably
Ground, substrate is transparent, translucent or opaque flexibility or hard material.Make present invention can apply to
The preparation of metal grill transparent metal circuit, thus apply at solar energy, OLED, display, optics
Device, encapsulation, the industries such as IC manufactures, PCB manufacture.
Accompanying drawing explanation
Fig. 1 is the preparation method flow chart of the pattern metal circuit according to first embodiment of the invention；
Fig. 2 is according to utilizing conventional lithography process pattern metal circuit in first embodiment of the invention
Process schematic representation；
Fig. 3 is to prepare metallic circuit figure according to the template stamping technique that utilizes in first embodiment of the invention
The process schematic representation of shape；
Fig. 4 is according to the light of the metal grill of the transparent conductive film of preparation in first embodiment of the invention
Learn microphotograph；
Fig. 5 is according to the metal grill local of the transparent conductive film of preparation in first embodiment of the invention
SEM figure；
Fig. 6 is according to the optical microscope photograph of the fine-line of preparation in first embodiment of the invention；
Fig. 7 is the fine-line local SEM figure according to preparation in first embodiment of the invention；
Fig. 8 is the preparation method flow chart of the pattern metal circuit according to second embodiment of the invention.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to this
Bright each embodiment is explained in detail.But, it will be understood by those skilled in the art that
In each embodiment of the present invention, propose many technology to make reader be more fully understood that the application thin
Joint.But, even if there is no these ins and outs and many variations based on following embodiment and amendment,
The application each claim technical scheme required for protection can also be realized.
First embodiment of the present invention relates to the preparation method of a kind of pattern metal circuit, such as preparation thoroughly
Bright conductive film or fine-line.Idiographic flow is as shown in Figure 1.
In a step 101, it is provided that a substrate.This substrate can be transparent, translucent or opaque soft
Property or hard material.It addition, need substrate to carry out pre-treatment, clean up and be dried.In this enforcement
In mode, substrate topography includes but not limited to lamellar etc., is simultaneously suitable for metal, inorganic non-metallic, gathers
Compound, composite etc..
Then, in a step 102, the activating solution of photoetching technique and preparation is utilized, preparation figure in substrate
Case Dopaminergics substrate surface；Wherein, activating solution there was added Dopaminergics material.
Specifically, firstly, it is necessary to configuration activating solution, Dopaminergics material is dissolved wherein, according to need
Want to add oxidant.In present embodiment, the pH buffer substance in this activating solution is biphosphate
Sodium-citrate buffer solution, disodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, barbital sodium hydrochloride buffer,
Any one in Tris-hydrochloride buffer, sodium carbonate-bicarbonate buffer.The pH value of this activating solution
For 2-11, it is therefore preferable to 7-9, solvent is water, when pending substrate is incompatible with water, optional
Property add organic solvent, such as alcohols, ethers, ketone amide-type etc..
The Dopaminergics material that Dopaminergics material is following any structure formula added in activating solution, or
The polymer of Dopaminergics material, ligand, acid salt or basic salt for following any structure formula:
Wherein, R group is alkyl or substituted alkyl；R1, R2Group is H, alkyl or substituted alkane
Base.Such as: 3,4-dihydroxyphenyl-L-alanine (DOPA/DOPA), 3,4-dihydroxy benzenes ethamine is (many
Bar amine/DA), tyrosine (Tyrosine), DOPA quinone (Dopaquinone), dopamine quinone
(Dopaminequinone), cyclodopa (Cyclodopa/Leucodopachrome), cyclodopa amine
(Leucodopaminechrome), dopachrome (Dopachrome), dopamine pigment
(Dopaminechrome), cysteinyl dopa (Cysteinyldopa), 5,6-dihydroxy indole,
Eumelanin (Eumelanin), pheomelanin (Pheomelanin), epinephrine (Epinephrine),
One or more mixture in norepinephrine (Norepinephrine).
Then, substrate is placed in the activating solution of configuration, stands a period of time, immerse the time of activating solution
Being 1 second-100 hours, reaction temperature is less than 100 ° of C.Wherein, activating solution exposes in atmosphere or logical
Enter oxygen or add following oxidizing substance, including Ammonium persulfate., sodium metaperiodate, sodium perchlorate, sulphuric acid
Copper etc.；Described Dopaminergics material is modified substrate and is carried out in water or in other inorganic and organic solvents.
Then, from activating solution, take out substrate (now substrate surface is loaded with Dopaminergics material), will
The one side substrate that need to pattern carries out photoetching, obtains patterning Dopaminergics substrate surface.Art technology
Personnel are appreciated that and can utilize the activating solution of photoetching technique and preparation, preparation patterning in substrate
Before Dopaminergics substrate surface, design according to the requirement of light transmittance and electrical conductivity and obtain needing in substrate
The pattern formed, as the requirement according to light transmittance and electrical conductivity designs live width line-spacing, the pattern of design is by handing over
Fork or Uncrossed straight line, curve or broken line composition.For formed pattern material (i.e. for photoetching or
The material of printing) include photoresist, impressing glue, ink and various not with the material etc. of metal reaction.
In the present embodiment, photoetching technique comprises any one photoetching technique following:
Ultraviolet photolithographic, extreme ultraviolet photolithographic, beamwriter lithography, ion beam lithography, X-ray lithography and impressing
Photoetching；Wherein, imprint lithography includes hot padding, ultraviolet solidified nano impressing and micro-contact printing.When making
With during micro-contact printing also can by use patterned polymer die material to be patterned directly imprinted in
Area load has in the substrate of Dopaminergics material, obtains the base with patterning Dopaminergics substrate surface
The end.
Then, in step 103, the substrate that will be patterned into is placed in metal plating liquid, naked at substrate surface
Dew has the local deposition layer of metal of Dopaminergics material, wherein, there was added reducing agent in metal plating liquid.
This reducing agent is the mixture of one below or its combination in any:
Glucose, formaldehyde, tartaric acid, sodium potassium tartrate tetrahydrate, dimethyl amido borine, sodium borohydride, two
Hydrazine hydrochloride, Hydrazinium sulfate, hydrazine, sodium hypophosphite, glyoxalic acid, malic acid, sodium hypophosphite, citric acid,
Sodium citrate, ascorbic acid, N,N-dimethylformamide, ethylene glycol, glutaraldehyde.
Specifically, metal plating liquid is commercialization metal plating liquid, or, described metal plating liquid is by following group
It is grouped into: slaine, aqueous solvent, reducing agent, additive；Wherein, described slaine is mantoquita or silver
Salt.Silver salt can be the mixture of one below or its combination in any: silver nitrate, silver perchlorate, silver cyanogen
Change sodium, silver potassium cyanide, silver tetrafluoroborate, silver acetate, silver sulfate, Silver monobromide, silver chloride, silver oxide,
Disilver carbonate, silver phosphate.Mantoquita can be the mixture of one below or its combination in any: copper sulfate, chlorine
Change copper, copper nitrate, Schweinfurt green, curpic carbonate and hydrate thereof, Copper hydrate, Red copper oxide, copper oxide.
Additive can be the mixture of one below or its combination in any: ethanol, methanol, ethylenediaminetetraacetic acid
Two receive, ethylenediamine, triethanolamine, ethylenediaminetetraacetic acid, thiourea, bipyridyl, Polyethylene Glycol, poly-second
Enol, polypyrrole alkanone, sodium lauryl sulphate, sodium citrate, sodium acetate, sodium pyrophosphate, ferrous iron
Potassium cyanide, lead sulfate, ammonium sulfate, nickel sulfate, lactic acid, succinic acid, citric acid, propanoic acid, hydroxyl second
Acid, boric acid, tartrate, sodium hydroxide, potassium hydroxide, ammonia.Silver salt concentration in the plating solution is
0.001-2mol/L, reducing agent content is 0.001-10mol/L, additive level 0-20mol/L.
Owing to Dopaminergics material can adhere at various organic or inorganic matrix surfaces, and caking property
Can be excellent, Dopaminergics material is due to containing a large amount of amino and hydroxyl simultaneously, can active adsorption metal ion,
And by the effect of reducing agent, it is reduced into metal, therefore can be naked at film surface Dopaminergics material
Deposit layer of metal at dew, and process is simple.
Such as, prepare as a example by circuit by chemical silvering, in this step, prepare certain density silver salt
Solution, is placed in one the substrate obtained after step 102 a period of time, adds reducing agent, for
Improve coating quality, suitable additive can be added；Take out substrate after a period of time, clean.
Then, at step 104, remove in photoetching process in a step 102 for photoetching or printing
Material, as photoresist, impressing glue, ink, not with the material etc. of metal reaction.
It is noted that if the two-sided of substrate is required for being formed pattern, then will be treated by photoetching
Patterning materials forms pattern on substrate two sides, and after step 104, obtain is that substrate two sides is equal
Form the conductive film of pattern.
If needing to form pattern to the one side of substrate, the most in a step 102, join substrate is placed in
Before the activating solution put, the first one side in substrate is coated cannot be with the barrier layer of metal reaction so that scribble
The one side on barrier layer cannot load Dopaminergics material, and the another side of this substrate is the one side that need to pattern.
Or, in a step 102, the one side of optional substrate, as the one side that need to pattern, obtains completing photoetching
After patterning Dopaminergics substrate surface, the non-patterned one side of this substrate is coated barrier layer.
The one side of described substrate coat cannot with the barrier layer of metal reaction after again at another of this substrate
Described patterning Dopaminergics substrate surface is prepared in face；Or, the substrate of described patterning is being placed in gold
Before belonging to the step in plating solution, the non-patterned one side of substrate is coated barrier layer.Barrier layer includes photoetching
Glue, impressing glue, ink etc. various not with the material of metal reaction.In order to avoid in follow-up chemical plating another
Face also deposits layer of metal, further avoid metal waste.
It is to say, the substrate one side after cleaning can be coated barrier layer, it is placed in activating solution, one section
Take out after time；Substrate after maybe cleaning is placed in activated solution, after a period of time takes out, at one
Barrier layer in topcoating.Utilize photoetching technique to be not coated with barrier layer one side in substrate and form desirable pattern.
Owing to, during the conductive film preparing one side pattern, the one side of substrate scribbling barrier layer,
Therefore, at step 104, removing while patterning materials, also needing to remove barrier layer, as Fig. 2,
Shown in Fig. 3.Description of symbols in Fig. 2 is as follows: 210 is substrate；220 is Dopaminergics material；230
For barrier layer；240 is photoresist；250 is the metal of chemical plating.
Below with in the preparation transparent conductive film with square net as elementary cell, preparation flexible substrates
Fine silver circuit, prepare grid-shaped metal copper cash transparent conductive film as a example by be specifically described.
1. the preparation transparent conductive film with square net as elementary cell:
(1) width and spacing, this reality of planning grid metallic circuit is required according to light transmittance and resistivity
Example is live width 25 μm, line-spacing 100 μm；
(2) clear PET film (i.e. substrate) that thickness is 50 μm is placed in acetone ultrasonic, then
Clean with deionized water, dry；
(3) prepare the activating solution of Tris-hydrochloric acid, pH=8.5, add dopamine hydrochloride, Tris concentration 1.2
Mg/mL, dopamine hydrochloride concentration 2mg/mL, put into the PET after cleaning, 15 ° of C of reaction temperature,
Response time 0.5h, takes out PET, deionized water rinsing, dries；
(4) photoetching, positive glue spin coating, turn-over, again gluing, front baking, exposure, development, after bake；
(5) preparing metal plating solution, AgNO3Concentration is 0.2%, and ammonia adds to solution and just clarifies, and adds
Entering a small amount of ethanol, glucose consumption is the twice of silver nitrate molal quantity；
(6) PET that will be patterned into immerses in metal plating liquid, and stirring was taken out after 2-4 minute, go from
Sub-water rinses, alcohol flushing；
(7) stripper cleans with photoresist, deionized water rinsing, and alcohol flushing dries, advised
Whole silver wire grid, its silver wire flush edge, as shown in Figure 4, square resistance is 9 Ω/sq.Prepared
The SEM(scanning electron microscope of metal grill local) figure is as shown in Figure 5.
2. the fine silver circuit in preparation flexible substrates:
(1) the translucent PET film that thickness is 50 μm is placed in acetone ultrasonic, then uses deionization
Water cleans, and dries；
(2) prepare the activating solution of Tris-hydrochloric acid, pH=8.5, add dopamine hydrochloride, Tris concentration 1.2
Mg/mL, dopamine hydrochloride concentration 2mg/mL, put into the PET after cleaning, 15 ° of C of reaction temperature, instead
0.5h between Ying Shi, takes out PET, deionized water rinsing, dries；
(3) photoetching, positive glue spin coating, turn-over, again gluing, front baking, exposure, development, after bake；
(4) preparing metal plating solution, AgNO3Concentration is 0.2%, and ammonia adds to solution and just clarifies, and adds
Entering a small amount of ethanol, glucose is pressed silver nitrate molal quantity twice and is added；
(5) PET that will be patterned into enters in metal plating liquid, and stirring is taken out after 2-4min, deionization
Water rinses, alcohol flushing；
(6) stripper cleans with photoresist, and deionized water cleans, then with alcohol flushing, dries.Logical
Cross the method and can obtain micron order fine-line, its line edges smooth (shown in Fig. 6), ultrasonication
Lower silver wire does not falls off, silver wire square resistance 1 Ω/sq.Prepared fine-line local SEM schemes such as Fig. 7
Shown in.
3. prepare grid-shaped metal copper cash transparent conductive film
(1) width and the spacing of planning grid metallic circuit is required according to light transmittance and resistivity, according to
The width of metallic circuit and spacing make polydimethylsiloxane (PDMS) patterned template, make template
The width of recess is identical with metallic circuit with spacing；
(2) clear PET film that thickness is 50 μm is placed in acetone ultrasonic, then uses deionized water
Clean, be dried；
(3) prepare the activating solution of Tris-hydrochloric acid, pH=8.5, add dopamine hydrochloride, Tris concentration 1.2
Mg/mL, dopamine hydrochloride concentration 2mg/mL, put into the PET after cleaning, 15 ° of C of reaction temperature, instead
0.5h between Ying Shi, takes out PET, deionized water rinsing, dries；
(4) PDMS patterned template and impressing are gluedd joint tactile, be dried；
(5) PDMS patterned template is placed on the PET film that step 3) processes, applies 4kg pressure
Power, 60 ° of C of temperature, remove template, leave impressing glue pattern on a pet film；
(6) preparing metal plating solution, copper chloride (CuCl2) concentration is 0.2%, adds ethylenediamine tetrem
Acid (EDTA), boric acid (H3BO3), sodium hydroxide (NaOH), regulation pH is 8-9, then presses
Copper chloride molal quantity 3 times adds dimethyamine borane (DMAB)；
(7) PET that will be patterned into immerses in metal plating liquid, and stirring is taken out after 20min, deionization
Water rinses；
(8) acetone cleans and removes impressing glue.
Owing to the distinctive adhesiveness of Dopaminergics material and reproducibility make metal only at Dopaminergics material
Exposed section generates thus realizes substrate surface metal selective deposition, and when chemical plating without other sensitization
Or generation Seed Layer, concise in technology is the shortest, environmentally friendly, and metal level adheres to firmly with substrate.Separately
Outward, owing to Dopaminergics material can be deposited on various material surface under conditions of as mild as a dove, thus suitable
For multiple substrate, and whole process is carried out at room temperature.It is additionally, since in metal plating liquid and there was added reduction
Agent, therefore when carrying out chemical plating metal, it is ensured that the seriality of metal film and electric conductivity.It addition, by
Can regulate and control in nanometer to micron dimension in metal thickness, can meet and improve conductive film surface roughness
Demand, also can meet fine conductive circuit and must possess certain thickness requirement.
It is to say, present embodiment possesses following advantage:
1) high selectivity: metal is only depositing with the presence of at Dopaminergics material；
2) extensive adaptability: Dopaminergics material is possible not only in the inorganic substrate such as metal, glass
Upper deposit adhesion, it is also possible to load in the substrate such as quasiconductor, polymer；
3) there is, in the middle of coating and substrate, the Dopaminergics material that one layer of adhesion property is excellent, adhesion is relatively
Conventional method is good, and the coat of metal does not falls off under the conditions of ultrasonic grade；
4) all processes all can be carried out at room temperature, the shortest；
5) thickness of coating can regulate and control in nanometer to micron dimension, and square resistance is little；
6), after thin film bending, film resiativity change is little；
7) can realize making circuit on substrate two sides simultaneously；
8) Dopaminergics material itself has reproducibility and adhesiveness so that its surface is without reactivation
Can realize the plating of metal level, and metal level is fine and close, thickness is homogeneous；
9) multiformity of patterned manner and motility: the various ways such as photoetching and printing can be used to realize
Patterning；
10) whole process is without large-scale instrument and equipment.
The substrate being additionally, since in present embodiment can be transparent, translucent or opaque flexibility or
Hard material.Therefore can be applicable to the preparation of metal grill transparent conductive film and fine-line, thus should
It is used in solar energy, OLED, display, optics, encapsulation, the industries such as IC manufactures, PCB manufacture.
Second embodiment of the present invention relates to the preparation method of a kind of pattern metal circuit.Second implements
Mode is roughly the same with the first embodiment, is in place of the main distinction: in the first embodiment, first
In substrate, first modify one layer of Dopaminergics material, then realize substrate surface patterning by technology such as photoetching,
Then the substrate that will be patterned into is placed in metal plating liquid, adds reducing agent etc. so that at Dopaminergics material
Exposed local selectivity deposition layer of metal, finally removes photoresist etc..And it is real in the present invention second
Execute in mode, in substrate, form pattern by technology such as photoetching, redeposited one layer of Dopaminergics material,
Then photoresist etc. is removed, leaves the figure of Dopaminergics material, immerse the most equally in metal plating liquid,
Add reducing agent, deposit layer of metal where at Dopaminergics material.
Specifically, as shown in Figure 8, step 801 is similar with step 101, does not repeats them here.
In step 802, substrate is lithographically formed pattern postactivated, the most in the following manner in substrate
Preparation patterning Dopaminergics substrate surface:
First, the one side of the need patterning of substrate is carried out photoetching, the pattern needed for formation.Such as,
As double-side pattern need to be formed, then by photoetching, material to be patterned is formed pattern on substrate two sides, be placed in
Activated solution took out after a period of time.Similar with the first embodiment, photoetching technique comprise following arbitrarily
A kind of photoetching technique: ultraviolet photolithographic, extreme ultraviolet photolithographic, beamwriter lithography, ion beam lithography, X-ray
Photoetching and imprint lithography；Wherein, imprint lithography includes that hot padding, ultraviolet solidified nano impressing contact with micro-
Printing.It will be understood by those skilled in the art that micro-contact printing can be similar to the same of seal and be applied to it
On material be printed directly in substrate, more succinct than traditional, the minimum feature obtained is the least, the suitableeest
For less than hundreds of nanometer, the sightless scene of naked eyes.
Then, substrate being placed in activating solution, this activating solution and the first embodiment are similar to, at this no longer
Repeat.
Then, after taking out substrate from activating solution, remove the photoresist formed in photoetching process, obtain figure
Case Dopaminergics substrate surface.
Certainly, if patterned conductive thin film to be prepared is one side patterned conductive thin film, equally
The one side of substrate coat cannot with the barrier layer of metal reaction after again another side in this substrate prepare described
Patterning Dopaminergics substrate surface, as coated barrier layer in substrate one side, being engraved in another side by light will
Material to be patterned forms pattern, is placed in activated solution and takes out after a period of time；Or, by pattern
Before the step that the substrate changed is placed in metal plating liquid, the non-patterned one side of substrate is coated barrier layer.
In step 803, the substrate that will be patterned into is placed in metal plating liquid, substrate surface exposed have many
The local deposition layer of metal of bar amine substance.This step is similar with step 103, does not repeats them here.
Third embodiment of the present invention relates to the preparation method of a kind of pattern metal circuit.3rd implements
Mode is roughly the same with the first or second embodiment, is in place of the main distinction: real first or second
Execute mode, be by photoetching technique, preparation patterning Dopaminergics substrate surface in substrate；And at this
In embodiment, it is by printing technology, preparation patterning Dopaminergics substrate surface in substrate.
Such as, after one layer of Dopaminergics material is modified in substrate, then realize substrate by printing technology
Patterned surface, the substrate that then will be patterned into is placed in metal plating liquid, adds reducing agent etc. so that
The local selectivity deposition layer of metal of Dopaminergics packaged material, finally removes the material being used for printing.
Or, in substrate, form pattern, redeposited one layer of Dopaminergics material by printing technology, then will
Material for printing removes, and leaves the figure of Dopaminergics material, immerses the most equally in metal plating liquid,
Add reducing agent, deposit layer of metal where at Dopaminergics material.
In present embodiment, the mode of printing include printing, silk screen printing, inkjet printing, letterpress,
Intaglio printing, offset printing, heat transfer printing, xerography, roll-to-roll printing etc., can be used for printing
Material be various ink, photoresist, impressing glue, polymer solution such as polyesters, polyacrylic,
Polyamide-based etc..
Concrete to use mode of printing to carry out as a example by preparing grid-shaped metal copper cash transparent conductive film below
Illustrate:
(1) clear PET film that thickness is 50 μm is placed in acetone ultrasonic, then uses deionized water
Clean, be dried；
(2) prepare the activating solution of Tris-hydrochloric acid, pH=8.5, add dopamine hydrochloride, Tris concentration 1.2
Mg/mL, dopamine hydrochloride concentration 2mg/mL, put into the PET after cleaning, 15 ° of C of reaction temperature,
Response time 0.5h, takes out PET, deionized water rinsing, dries；
(3) by the way of ink jet printing, the acetone soln of linear phenolic resin is printed on through step (2)
On the pet substrate processed, its printed pattern designs according to thin film light transmittance and conduction needs；
(4) preparing metal plating solution, copper chloride (CuCl2) concentration is 0.2%, adds ethylenediamine tetrem
Acid (EDTA), boric acid (H3BO3), sodium hydroxide (NaOH), regulation pH is 8-9, then presses
Copper chloride molal quantity 3 times adds dimethyamine borane (DMAB)；
(5) PET that will be patterned into immerses in metal plating liquid, and stirring is taken out after 20min, deionization
Water rinses；
(6) acetone cleans and removes phenolic resin.
It is seen that, present embodiment equally realizes the technique effect of the first or second embodiment,
As when chemical plating without other sensitization or generate Seed Layer, concise in technology is the shortest, environmentally friendly,
Metal level adheres to firmly with substrate, and metal layer thickness is the most first-class, does not repeats them here.
The step of the most various methods divides, and is intended merely to describe clear, it is achieved time can merge into one
Step or split some step, is decomposed into multiple step, as long as comprising identical logical relation,
All in the protection domain of this patent；To adding inessential amendment in algorithm or in flow process or drawing
Enter inessential design, but do not change the core design of its algorithm and flow process all at the protection model of this patent
In enclosing.
It will be understood by those skilled in the art that the respective embodiments described above are realize the present invention concrete
Embodiment, and in actual applications, can to it, various changes can be made in the form and details, and the most inclined
From the spirit and scope of the present invention.
Claims (15)
1. the preparation method of a pattern metal circuit, it is characterised in that comprise the steps of
One substrate is provided；
Utilize the activating solution and photoetching or printing technology prepared, prepare patterning dopamine on the substrate
Class substrate surface；Wherein, described activating solution there was added Dopaminergics material；
The described substrate that will be patterned into is placed in metal plating liquid, has Dopaminergics described substrate surface is exposed
The local deposition layer of metal of material；Described metal plating liquid there was added reducing agent；
Described pattern metal circuit is patterned conductive thin film or fine-line；
Wherein, if patterned conductive thin film to be prepared is one side patterned conductive thin film, then described
In substrate in the step of preparation patterning Dopaminergics substrate surface, the one side in described substrate is coated cannot
With behind the barrier layer of metal reaction again another side in this substrate prepare described patterning Dopaminergics substrate
Surface；Or, before the step that the described substrate that will be patterned into is placed in metal plating liquid, by substrate not
The one side of patterning coats described barrier layer；
Wherein, the described activating solution utilizing preparation and photoetching or printing technology, prepare figure on the substrate
In the step of case Dopaminergics substrate surface, comprise following sub-step: described substrate is placed in described work
Change in liquid；After taking out described substrate from described activating solution, the one side substrate that need to pattern is carried out photoetching
Or printing, obtain described patterning Dopaminergics substrate surface；
After the step that the described substrate that will be patterned into is placed in metal plating liquid, also perform following steps:
Remove the material for photoetching or printing in described photoetching or printing process.
The preparation method of pattern metal circuit the most according to claim 1, it is characterised in that
Described reducing agent is the mixture of one below or its combination in any:
Glucose, formaldehyde, tartaric acid, sodium potassium tartrate tetrahydrate, dimethyl amido borine, sodium borohydride, two
Hydrazine hydrochloride, Hydrazinium sulfate, hydrazine, sodium hypophosphite, glyoxalic acid, malic acid, sodium hypophosphite, citric acid,
Sodium citrate, ascorbic acid, N,N-dimethylformamide, ethylene glycol, glutaraldehyde.
The preparation method of pattern metal circuit the most according to claim 1, it is characterised in that
The described material for photoetching or printing comprises:
Photoresist, impressing glue, ink.
4. according to the preparation method of the pattern metal circuit according to any one of claim 1,3, its
It is characterised by,
When described substrate being placed in described activating solution, described activating solution exposes in atmosphere, or,
Oxygen is passed in described activating solution, or, described activating solution adds oxidizing substance.
5. according to the preparation method of the pattern metal circuit according to any one of claim 1,3, its
It is characterised by,
Described substrate be placed in described activating solution time a length of 1 second to 100 hours；
Reaction temperature when described substrate is placed in described activating solution is less than 100 DEG C.
The preparation method of pattern metal circuit the most according to claim 1, it is characterised in that
In described activating solution, pH buffer substance is sodium dihydrogen phosphate-citrate buffer solution, disodium hydrogen phosphate-phosphoric acid
Sodium dihydrogen buffer, barbital sodium hydrochloride buffer, Tris-hydrochloride buffer, sodium carbonate-bicarbonate
Any one in buffer.
The preparation method of pattern metal circuit the most according to claim 1, it is characterised in that
The pH value range of described activating solution is 2 to 11.
The preparation method of pattern metal circuit the most according to claim 1, it is characterised in that
Described Dopaminergics material is the Dopaminergics material of following any structure formula, or is following any structure
The polymer of Dopaminergics material, ligand, acid salt or the basic salt of formula:
Wherein, R is alkyl or replaces alkyl, R1For H, alkyl or replacement alkyl, R2For H, alkane
Base or replacement alkyl.
The preparation method of pattern metal circuit the most according to claim 1, it is characterised in that
Described metal plating liquid is commercialization metal plating liquid, or, described metal plating liquid is composed of the following components:
Slaine, aqueous solvent, reducing agent, additive；
Wherein, described slaine is mantoquita or silver salt.
The preparation method of pattern metal circuit the most according to claim 9, it is characterised in that
Described silver salt is the mixture of one below or its combination in any:
Silver nitrate, silver perchlorate, silver Cyanogran., silver potassium cyanide, silver tetrafluoroborate, silver acetate, sulphuric acid
Silver, Silver monobromide, silver chloride, silver oxide, Disilver carbonate, silver phosphate；
Described mantoquita is the mixture of one below or its combination in any:
Copper sulfate, copper chloride, copper nitrate, Schweinfurt green, curpic carbonate and hydrate thereof, Copper hydrate, oxygen
Change cuprous, copper oxide.
The preparation method of 11. pattern metal circuits according to claim 9, it is characterised in that
Described additive is the mixture of one below or its combination in any:
Ethanol, methanol, ethylenediaminetetraacetic acid two are received, ethylenediamine, triethanolamine, ethylenediaminetetraacetic acid,
Thiourea, bipyridyl, Polyethylene Glycol, polyvinyl alcohol, polypyrrole alkanone, sodium lauryl sulphate, Fructus Citri Limoniae
Acid sodium, sodium acetate, sodium pyrophosphate, potassium ferrocyanide, lead sulfate, ammonium sulfate, nickel sulfate, lactic acid,
Succinic acid, citric acid, propanoic acid, hydroxyacetic acid, boric acid, tartrate, sodium hydroxide, potassium hydroxide,
Ammonia.
The preparation method of 12. pattern metal circuits according to claim 1, it is characterised in that
Described photoetching technique comprises any one photoetching technique following:
Ultraviolet photolithographic, extreme ultraviolet photolithographic, beamwriter lithography, ion beam lithography, X-ray lithography and impressing
Photoetching；
Described imprint lithography includes hot padding, ultraviolet solidified nano impressing and micro-contact printing；
Described printing technology comprises:
Printing, silk screen printing, letterpress, intaglio printing, offset printing, heat transfer printing, electrostatic
Duplicating, roll-to-roll printing.
The preparation method of 13. pattern metal circuits according to claim 1, it is characterised in that
Also comprise the steps of
At the described activating solution and photoetching or printing technology utilizing and preparing, prepare patterning on the substrate
Before Dopaminergics substrate surface,
Requirement according to light transmittance and electrical conductivity arranges the pattern that need to be formed on the substrate.
The preparation method of 14. pattern metal circuits according to claim 13, it is characterised in that
The described pattern that need to be formed in substrate is by intersecting or Uncrossed straight line, curve or broken line form.
The preparation method of 15. pattern metal circuits according to claim 1, it is characterised in that
Described substrate is transparent, translucent or opaque flexibility or hard material.
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