CN103219243A - Manufacturing method of patterning metal lines - Google Patents
Manufacturing method of patterning metal lines Download PDFInfo
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- CN103219243A CN103219243A CN2012103765152A CN201210376515A CN103219243A CN 103219243 A CN103219243 A CN 103219243A CN 2012103765152 A CN2012103765152 A CN 2012103765152A CN 201210376515 A CN201210376515 A CN 201210376515A CN 103219243 A CN103219243 A CN 103219243A
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Abstract
The invention relates to the field of electronic manufacturing, and discloses a manufacturing method of patterning metal lines. A substrate is provided. Prepared active liquid and photoetching or printing technology are utilized to manufacture the surface of a patterning dopaminergic substrate on the substrate. Dopaminergic substances are added into the active liquid. The patterning substrate is arranged inside metal plating solution, and a layer of metal is deposited at the places on which the dopaminergic substances are exposed on of the surface of the substrate. A reducing agent is added in the metal plating solution. The patterning metal lines are patterning conductive films or fine circuit lines. If the patterning conductive film to be manufactured is a single-sided patterning conductive film, then in the step of manufacturing the surface of the patterning dopaminergic substrate, a resisting layer incapable of reacting with metal is coated on one face of the substrate, and the other face of the substrate is used for manufacturing the surface of the dopaminergic substrate, or the resisting layer is coated on the face which is not patterning of the substrate before the step of arranging the patterning substrate into the metal plating solution.
Description
Technical field
The present invention relates to electronic manufacturing field, particularly the technology of preparing of pattern metal circuit.
Background technology
The preparation metallic circuit is a very important production link in electronics/microelectronics industry on insulating substrate, in recent years, along with microelectronics and development of semiconductor, people improve day by day to the requirement of metallic circuit, simultaneously the needs of environmental protection and the pursuit of low-cost manufacturing technique have greatly been excited the enthusiasm of researcher to exploitation novel metal circuit technology of preparing.Traditional handicraft forms circuit for the photoetching after etching falls the metal that is not covered by photoresist, this " subtraction " technology causes various problems such as metal waste, cost rising and environmental pollution, and along with electronic device develops to miniaturization gradually, traditional " subtraction " technology is difficult to satisfy the requirement that circuit becomes more meticulous.
Simultaneously, transparent conductive film generally can be divided into two kinds of patterning and non-patternings, and the former can realize by the metallic circuit grid that forms definite shape.At present as leading transparent conductive film tin indium oxide (ITO) film in market exist matter crisp and lack pliability, technology cost height, the indium price is high and problem such as resource-constrained, the compliant conductive transparent membrane that presses for development of new is to satisfy the demand of following photoelectric device development.
The common method for preparing the patterning transparent conductive film has inkjet printing, offset printing, roll-to-roll printing etc.Its production method is generally particle diameter is prepared into conductive ink at the material of nanometer scale such as nano silver wire etc., then conductive ink is printed on the flexible and transparent substrate surface, forms required conductive network behind sintering.The network line thickness is below the resolution of human eye, and the zone of no lines is a transmission region.Can control the resistance of surface side and the light transmittance of nesa coating within the specific limits by the width, spacing and the geometry that change lines.Micro-nano magnitude electrically conductive ink need be prepared in advance but be to use printing technology to make the lead grid, and the conducting circuit need be formed by the mode of sintering.And the peripheral stabilizer that coats of micro Nano material need could decompose desorption usually at the high temperature of 250 ° of C, in order to obtain conductivity preferably, present printing ink sintering temperature height, be not suitable for some low prices, polymeric substrates that glass transition temperature is low, and reduce the residual conductivity with sacrificial film of sintering temperature because of stabilizer.Mode by printing is difficult to thicknesses of layers is controlled at lower nanometer scale in addition, and conductive grid is the thrust that exposes at substrate surface, thereby make the product surface roughness increase, and conducting wire and substrate adhere to not firmly behind the sintering, are prone to conductivity drastic change when bending.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of pattern metal circuit, make and at room temperature need not the preparation that sintering can be realized pattern conductive film or fine circuitry, and when satisfying film conductance and light transmittance requirement, can realize effective adhesion of plain conductor and different base, and effectively improve the roughness of film surface.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of pattern metal circuit, comprise following steps:
One substrate is provided;
Utilize activating solution and the photoetching or the printing technology of preparation, preparation patterning Dopaminergics substrate surface in described substrate; Wherein, adding has the Dopaminergics material in described activating solution;
The substrate of described patterning is placed metal plating liquid, in the exposed place deposition layer of metal that the Dopaminergics material is arranged of described substrate surface; Add in the described metal plating liquid reducing agent is arranged;
Described pattern metal circuit is pattern conductive film or fine-line;
Wherein, if pattern conductive film to be prepared is a single face pattern conductive film, then
In described substrate in the step of preparation patterning Dopaminergics substrate surface, the one side of described substrate coat can't with the barrier layer of metal reaction after prepare described patterning Dopaminergics substrate surface at the another side of this substrate again; Perhaps, before the substrate with described patterning places the step of metal plating liquid, the one side of the not patterning of substrate is coated with the above barrier layer.
Embodiment of the present invention in terms of existing technologies, activating solution by photoetching (or printing) technology and preparation forms one deck patterning Dopaminergics material nano thin-film in substrate, substrate with patterning places metal plating liquid again, utilize the adhesiveness and the reproducibility of Dopaminergics material excellence, in film surface Dopaminergics material exposed section deposition layer of metal.Thereby, distinctive adhesiveness of Dopaminergics material and reproducibility realize substrate surface metal selective deposition because making metal only generate in Dopaminergics material exposed section, and when chemical plating, need not other sensitization or generate Seed Layer, the succinct weak point consuming time of technology, environmentally friendly, metal level and substrate adhere to firmly.In addition, because the Dopaminergics material can be in as mild as a dove condition deposit in the various material surface, thus be applicable to multiple substrate, and whole process is carried out at normal temperature.And, owing to add in the metal plating liquid reducing agent is arranged, therefore when carrying out chemical plating metal, guaranteed the continuity and the conductivity of metal film.In addition,, can satisfy the demand of improving the conductive film surface roughness, also can satisfy meticulous conducting wire and must possess certain thickness requirement because metal wire thickness can be regulated and control in nanometer to micron dimension.
Need to prove, when pattern conductive film to be prepared is single face pattern conductive film, the one side of substrate coat can't with the barrier layer of metal reaction after prepare patterning Dopaminergics substrate surface at the another side of this substrate again; Perhaps, before the substrate with patterning places the step of metal plating liquid, the one side of the not patterning of substrate is coated with the above barrier layer,, has further avoided the metal waste in order to avoid another side also deposits layer of metal in follow-up chemical plating.
Preferably, reducing agent is one of following or the mixture of its combination in any: glucose, formaldehyde, tartaric acid, sodium potassium tartrate tetrahydrate, dimethyl amido borine, sodium borohydride, hydrazine dihydrochloride, hydrazine sulfate, hydrazine, sodium hypophosphite, glyoxalic acid, malic acid, inferior sodium phosphate, citric acid, natrium citricum, ascorbic acid, N, dinethylformamide, ethylene glycol, glutaraldehyde.
Preferably, metal plating liquid is the commercialization metal plating liquid, and perhaps, described metal plating liquid is composed of the following components: slaine, aqueous solvent, reducing agent, additive; Wherein, described slaine is a mantoquita, silver salt and other slaines.Make embodiment of the present invention possess application scenarios widely.
Preferably, additive is one of following or the mixture of its combination in any: ethanol, methyl alcohol, ethylenediamine tetra-acetic acid two are received, ethylenediamine, triethanolamine, thiocarbamide, bipyridine, polyethylene glycol, polyvinyl alcohol, polypyrrole alkane ketone, lauryl sodium sulfate, natrium citricum, sodium acetate, sodium pyrophosphate, potassium ferrocyanide, lead sulfate, ammonium sulfate, lactic acid, succinic acid, citric acid, propionic acid, glycolic acid, boric acid, tartrate, NaOH, potassium hydroxide, ammoniacal liquor.Make additive have characteristics such as stable plating bath, regulation and control coating character, adjustment silver plating process condition.
Preferably, photoetching technique comprises following any one photoetching technique: ultraviolet photolithographic, extreme ultraviolet photolithographic, electron beam lithography, ion beam lithography, X-ray lithography and imprint lithography; Described imprint lithography comprises hot padding, ultraviolet solidified nano impression and micro-contact printing.Because micro-contact printing can be similar to the material that the same handle of seal is coated with thereon and be printed directly in the substrate, so technology compares traditional more succinctly, and the minimum feature that obtains is more little, is particularly useful for being lower than the hundreds of nanometer, the sightless scene of circuit naked eyes.
Preferably, printing technology comprise following any one: printing, silk screen printing, inkjet printing, letterpress, intaglio printing, offset printing, heat transfer printing, xerography, roll-to-roll printing.Preferably, substrate is transparent, translucent or opaque flexibility or hard material.Make the present invention can be applicable to the preparation of metal grill transparent metal circuit, thereby be applied in solar energy, OLED, display, optics, encapsulation, IC makes, industries such as PCB manufacturing.
Description of drawings
Fig. 1 is the preparation method's flow chart according to the pattern metal circuit of first embodiment of the invention;
Fig. 2 is according to the process schematic representation that utilizes conventional lithography process pattern metal circuit in the first embodiment of the invention;
Fig. 3 prepares the process schematic representation of metallic circuit figure according to the template stamping technique that utilizes in the first embodiment of the invention;
Fig. 4 is the optical microscope photograph according to the metal grill of the transparent conductive film for preparing in the first embodiment of the invention;
Fig. 5 is the SEM figure according to the metal grill part of the transparent conductive film for preparing in the first embodiment of the invention;
Fig. 6 is the optical microscope photograph according to the fine-line for preparing in the first embodiment of the invention;
Fig. 7 is according to the local SEM figure of the fine-line for preparing in the first embodiment of the invention;
Fig. 8 is the preparation method's flow chart according to the pattern metal circuit of second embodiment of the invention.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, the embodiments of the present invention are explained in detail below in conjunction with accompanying drawing.Yet, persons of ordinary skill in the art may appreciate that in each execution mode of the present invention, in order to make the reader understand the application better many ins and outs have been proposed.But,, also can realize each claim of the application technical scheme required for protection even without these ins and outs with based on the many variations and the modification of following each execution mode.
First execution mode of the present invention relates to a kind of preparation method of pattern metal circuit, as preparation transparent conductive film or fine-line.Idiographic flow as shown in Figure 1.
In step 101, provide a substrate.This substrate can be for transparent, translucent or opaque flexibility or hard material.In addition, need carry out pre-treatment, clean up and drying substrate.In the present embodiment, the substrate form includes but not limited to sheet etc., is applicable to metal, inorganic non-metallic, polymer, composite material etc. simultaneously.
Then, in step 102, utilize the activating solution of photoetching technique and preparation, preparation patterning Dopaminergics substrate surface in substrate; Wherein, adding has the Dopaminergics material in activating solution.
Specifically, at first, need the configuration activating solution, with the Dopaminergics substance dissolves wherein, can add oxidant as required.In the present embodiment, the pH buffer substance in this activating solution is any one in sodium dihydrogen phosphate-citrate buffer solution, sodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, barbital sodium hydrochloride buffer, Tris-hydrochloride buffer, the sodium carbonate-sodium bicarbonate buffer liquid.The pH value of this activating solution is 2-11, is preferably 7-9, and solvent is a water, when pending substrate is incompatible with water, and the alternative organic solvent that adds, as alcohols, ethers, ketone amide-type etc.
The Dopaminergics material that adds in the activating solution is the Dopaminergics material of following arbitrary structural formula, perhaps is condensate, ligand, acid salt or the basic salt of the Dopaminergics material of following arbitrary structural formula:
Wherein, the R group is the alkyl of alkyl or replacement; R
1, R
2Group is the alkyl of H, alkyl or replacement.For example: 3, the 4-dihydroxyphenylalanine (DOPA/DOPA), 3,4-dihydroxy benzenes ethamine (dopamine/DA), tyrosine (Tyrosine), DOPA quinone (Dopaquinone), dopamine quinone (Dopaminequinone), cyclodopa (Cyclodopa/Leucodopachrome), cyclodopa amine (Leucodopaminechrome), dopachrome (Dopachrome), dopamine pigment (Dopaminechrome), cysteinyl dopa (Cysteinyldopa), 5, the 6-dihydroxy indole, eumelanin (Eumelanin), pheomelanin (Pheomelanin), adrenaline (Epinephrine), one or more mixtures in the norepinephrine (Norepinephrine).
Then, substrate is placed the activating solution of configuration, leave standstill a period of time, the time of immersing activating solution is 1 second-100 hours, and reaction temperature is no more than 100 ° of C.Wherein, activating solution is exposed in the air or aerating oxygen or the following oxidizing substance of adding, comprises ammonium persulfate, sodium metaperiodate, sodium perchlorate, copper sulphate 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 (this moment, the substrate surface load had the Dopaminergics material), photoetching is carried out in the one side substrate of need patterning, obtain patterning Dopaminergics substrate surface.It will be appreciated by those skilled in the art that, can be at the activating solution that utilizes photoetching technique and preparation, before preparation patterning Dopaminergics substrate surface in the substrate, requirement design according to light transmittance and conductivity obtains the pattern that needs form in substrate, as the requirement design live width line-spacing according to light transmittance and conductivity, the pattern of design is made up of intersection or Uncrossed straight line, curve or broken line.The material (material that promptly is used for photoetching or printing) that is used to form pattern comprises photoresist, impression glue, ink and various not with the material of metal reaction etc.
In the present embodiment, photoetching technique comprises following any one photoetching technique:
Ultraviolet photolithographic, extreme ultraviolet photolithographic, electron beam lithography, ion beam lithography, X-ray lithography and imprint lithography; Wherein, imprint lithography comprises hot padding, ultraviolet solidified nano impression and micro-contact printing.When using micro-contact printing, also can will treat that patterning materials directly impresses in area load and has in the substrate of Dopaminergics material, obtains having the substrate of patterning Dopaminergics substrate surface by using the patterned polymer die.
Then, in step 103, the substrate of patterning is placed metal plating liquid, in the exposed place deposition layer of metal that the Dopaminergics material is arranged of substrate surface, wherein, adding in the metal plating liquid has reducing agent.This reducing agent is one of following or the mixture of its combination in any:
Glucose, formaldehyde, tartaric acid, sodium potassium tartrate tetrahydrate, dimethyl amido borine, sodium borohydride, hydrazine dihydrochloride, hydrazine sulfate, hydrazine, sodium hypophosphite, glyoxalic acid, malic acid, inferior sodium phosphate, citric acid, natrium citricum, ascorbic acid, N, dinethylformamide, ethylene glycol, glutaraldehyde.
Specifically, metal plating liquid is the commercialization metal plating liquid, and perhaps, described metal plating liquid is composed of the following components: slaine, aqueous solvent, reducing agent, additive; Wherein, described slaine is mantoquita or silver salt.Silver salt can be the mixture of one of following or its combination in any: silver nitrate, silver perchlorate, silver-colored Cymag, silver-colored potassium cyanide, silver tetrafluoroborate, silver acetate, silver sulfate, silver bromide, silver chlorate, silver oxide, silver carbonate, silver orthophosphate.Mantoquita can be the mixture of one of following or its combination in any: copper sulphate, copper chloride, copper nitrate, Schweinfurt green, copper carbonate and hydrate thereof, Kocide SD, cuprous oxide, cupric oxide.Additive can be the mixture of one of following or its combination in any: ethanol, methyl alcohol, ethylenediamine tetra-acetic acid two is received, ethylenediamine, triethanolamine, ethylenediamine tetra-acetic acid, thiocarbamide, bipyridine, polyethylene glycol, polyvinyl alcohol, polypyrrole alkane ketone, lauryl sodium sulfate, natrium citricum, sodium acetate, sodium pyrophosphate, potassium ferrocyanide, lead sulfate, ammonium sulfate, nickelous sulfate, lactic acid, succinic acid, citric acid, propionic acid, glycolic acid, boric acid, tartrate, NaOH, potassium hydroxide, ammoniacal liquor.The concentration of silver salt in plating bath is 0.001-2mol/L, and reducing agent content is 0.001-10mol/L, additive level 0-20mol/L.
Because the Dopaminergics material can adhere at various organic or inorganic matrix surfaces, and adhesive property excellence, the Dopaminergics material is owing to contain a large amount of amino and hydroxyl simultaneously, effective adsorbing metal ions, and the effect by reducing agent, it is reduced into metal, therefore can deposit layer of metal, and process is simple in film surface Dopaminergics material exposed section.
Such as preparing circuit with chemical silvering is example, in this step, prepares certain density silver salt solution, will be placed in one a period of time through the substrate that obtains after the step 102, adds reducing agent again, for improving coating quality, can add suitable additive; Take out substrate after a period of time, clean.
Then, in step 104, remove the material that is used for photoetching or printing in the photoetching process in step 102, as photoresist, impression glue, printing ink, not with the material of metal reaction etc.
What deserves to be mentioned is, if substrate two-sided all needed to form pattern, then will treat that by photoetching patterning materials forms pattern on the substrate two sides, through after the step 104, what obtain is the conductive film that the substrate two sides all forms pattern.
If need form pattern to the single face of substrate, then in step 102, before substrate is placed the activating solution of configuration, earlier the one side of substrate coat can't with the barrier layer of metal reaction, make that the one side scribble the barrier layer can't load Dopaminergics material, the another side of this substrate is the one side that needs patterning.Perhaps, in step 102, the one side of optional substrate is as the one side of need patterning, after finishing photoetching and obtaining patterning Dopaminergics substrate surface, the one side of the not patterning of this substrate coated the barrier layer.
The one side of described substrate coat can't with the barrier layer of metal reaction after prepare described patterning Dopaminergics substrate surface at the another side of this substrate again; Perhaps, before the substrate with described patterning places the step of metal plating liquid, the one side of the not patterning of substrate is coated the barrier layer.The barrier layer comprise photoresist, impression glue, ink etc. various not with the material of metal reaction.In order to avoid another side also deposits layer of metal in follow-up chemical plating, further avoided the metal waste.
That is to say, the substrate after cleaning simultaneously can be coated the barrier layer, place activating solution, take out after a period of time; Substrate after maybe will cleaning places activated solution, and a period of time is simultaneously coated the barrier layer at it after taking out.Utilize photoetching technique not to be coated with the barrier layer and simultaneously form required pattern in substrate.
Owing in the conductive film process of preparation single face pattern, on the one side of substrate, scribble the barrier layer, therefore, in step 104, when removing patterning materials, also need remove the barrier layer, as Fig. 2, shown in Figure 3.Description of symbols among Fig. 2 is as follows: 210 are substrate; 220 is the Dopaminergics material; 230 is the barrier layer; 240 is photoresist; 250 is the metal of chemical plating.
Be that the transparent conductive film of elementary cell, meticulous silver-colored circuit, the latticed copper lines transparent conductive film of preparation for preparing on the flexible substrates are that example is specifically described with the square net with preparation below.
1. preparation is the transparent conductive film of elementary cell with the square net:
(1) according to the width and the spacing of light transmittance and resistivity requirement planning grid metallic circuit, this example is live width 25 μ m, line-spacing 100 μ m;
(2) be that the clear PET film (being substrate) of 50 μ m places acetone ultrasonic with thickness, use washed with de-ionized water again, dry;
(3) activating solution of preparation Tris-hydrochloric acid, pH=8.5 adds Dopamine hydrochloride, Tris concentration 1.2mg/mL, Dopamine hydrochloride concentration 2mg/mL puts into the PET after the cleaning, 15 ° of C of reaction temperature, reaction time 0.5h takes out PET, deionized water rinsing, oven dry;
(4) photoetching, positive glue spin coating, turn-over, gluing once more, preceding baking, exposure is developed, the back baking;
(5) preparing metal plating bath, AgNO
3Concentration is 0.2%, and ammoniacal liquor adds to solution and just clarifies, and adds small amount of ethanol, and the glucose consumption is the twice of silver nitrate molal quantity;
(6) PET with patterning immerses in the metal plating liquid, stirs, and takes out deionized water rinsing, alcohol flushing after 2-4 minute;
(7) stripper cleans with photoresist, deionized water rinsing, and alcohol flushing dries, and obtains regular dargyrome lattice, and its silver-colored line edge is smooth, and as shown in Figure 4, square resistance is 9 Ω/sq.The SEM(scanning electron microscopy of prepared metal grill part) figure as shown in Figure 5.
2. the meticulous silver-colored circuit on the preparation flexible substrates:
(1) is that the translucent PET film of 50 μ m places acetone ultrasonic with thickness, uses washed with de-ionized water again, dry;
(2) activating solution of preparation Tris-hydrochloric acid, pH=8.5 adds Dopamine hydrochloride, Tris concentration 1.2mg/mL, Dopamine hydrochloride concentration 2mg/mL puts into the PET after the cleaning, 15 ° of C of reaction temperature, reaction time 0.5h takes out PET, deionized water rinsing, oven dry;
(3) photoetching, positive glue spin coating, turn-over, gluing once more, preceding baking, exposure is developed, the back baking;
(4) preparing metal plating bath, AgNO
3Concentration is 0.2%, and ammoniacal liquor adds to solution and just clarifies, and adds small amount of ethanol, and glucose is pressed silver nitrate molal quantity twice and added;
(5) PET with patterning enters in the metal plating liquid, stirs, and takes out deionized water rinsing, alcohol flushing behind the 2-4min;
(6) stripper cleans with photoresist, and washed with de-ionized water is used alcohol flushing again, dries.Can obtain the micron order fine-line by the method, its circuit edge smooth (shown in Figure 6), silver-colored line does not come off under the ultrasonication, silver-colored line square resistance 1 Ω/sq.The local SEM figure of prepared fine-line as shown in Figure 7.
3. prepare latticed copper lines transparent conductive film
(1) according to the width and the spacing of light transmittance and resistivity requirement planning grid metallic circuit, makes dimethyl silicone polymer (PDMS) patterning template, make the width of template recess identical with metallic circuit with spacing according to the width and the spacing of metallic circuit;
(2) be that the clear PET film of 50 μ m places acetone ultrasonic with thickness, use washed with de-ionized water, drying again;
(3) activating solution of preparation Tris-hydrochloric acid, pH=8.5 adds Dopamine hydrochloride, Tris concentration 1.2mg/mL, Dopamine hydrochloride concentration 2mg/mL puts into the PET after the cleaning, 15 ° of C of reaction temperature, reaction time 0.5h takes out PET, deionized water rinsing, oven dry;
(4) drying is touched in PDMS patterning template and impression splicing;
(5) PDMS patterning template is placed on the PET film of step 3) processing, apply 4kg pressure, 60 ° of C of temperature remove template, stay the impression glue pattern on the PET film;
(6) preparing metal plating bath, copper chloride (CuCl
2) concentration is 0.2%, adds ethylenediamine tetra-acetic acid (EDTA), boric acid (H
3BO
3), NaOH (NaOH), adjusting pH is 8-9, extraordinarily goes into dimethyamine borane (DMAB) by copper chloride molal quantity 3 again;
(7) PET with patterning immerses in the metal plating liquid, stirs, and takes out deionized water rinsing behind the 20min;
(8) acetone cleans and removes impression glue.
Thereby, distinctive adhesiveness of Dopaminergics material and reproducibility realize substrate surface metal selective deposition because making metal only generate in Dopaminergics material exposed section, and when chemical plating, need not other sensitization or generate Seed Layer, the succinct weak point consuming time of technology, environmentally friendly, metal level and substrate adhere to firmly.In addition, because the Dopaminergics material can be in as mild as a dove condition deposit in the various material surface, thus be applicable to multiple substrate, and whole process is carried out at normal temperature.And, owing to add in the metal plating liquid reducing agent is arranged, therefore when carrying out chemical plating metal, guaranteed the continuity and the conductivity of metal film.In addition,, can satisfy the demand of improving the conductive film surface roughness, also can satisfy meticulous conducting wire and must possess certain thickness requirement because metal wire thickness can be regulated and control in nanometer to micron dimension.
That is to say that present embodiment possesses following advantage:
1) high selectivity: metal is only having Dopaminergics material existence place deposition;
2) extensive adaptability: the Dopaminergics material not only can deposit adhesion on hard inorganic substrates such as metal, glass, can also load in substrates such as semiconductor, polymer;
3) have the Dopaminergics material of one deck adhesion property excellence in the middle of coating and the substrate, adhesion is good than conventional method, and the coat of metal does not come off under condition such as ultrasonic;
4) all processes all can be carried out at normal temperature, weak point consuming time;
5) thickness of coating can be regulated and control in nanometer to micron dimension, and square resistance is little;
6) after the film bending, film resiativity changes little;
7) can realize making on the substrate two sides simultaneously circuit;
8) reproducibility and the adhesiveness that have of Dopaminergics material itself makes its surface need not the plating that reactivation can realize metal level, and the metal level densification, the thickness homogeneous;
9) diversity of patterning mode and flexibility: can adopt multiple modes such as photoetching and printing to realize patterning;
10) whole process need not large-scale instrument and equipment.
And, because the substrate in the present embodiment can be for transparent, translucent or opaque flexibility or hard material.Therefore can be applicable to the preparation of metal grill transparent conductive film and fine-line, thereby be applied in solar energy, OLED, display, optics, encapsulation, IC makes, industries such as PCB manufacturing.
Second execution mode of the present invention relates to a kind of preparation method of pattern metal circuit.Second execution mode and first execution mode are roughly the same, main distinction part is: in the first embodiment, at first in substrate, modify one deck Dopaminergics material, realize the substrate surface patterning by technology such as photoetching again, substrate with patterning places metal plating liquid then, add reducing agent etc., make, at last photoresist etc. is removed in the exposed local selective deposition layer of metal of Dopaminergics material.And in second embodiment of the invention, in substrate, form pattern by technology such as photoetching, deposit one deck Dopaminergics material again, then photoresist etc. is removed, stay the figure of Dopaminergics material, immerse equally subsequently in the metal plating liquid, add reducing agent, deposit layer of metal where at the Dopaminergics material.
Specifically, as shown in Figure 8, step 801 is similar with step 101, does not repeat them here.
In step 802, photoetching activates after forming pattern in the substrate, promptly prepares patterning Dopaminergics substrate surface in the following manner in substrate:
At first, the one side of the need patterning of substrate is carried out photoetching, form required pattern.Such as, form double-side pattern as need, then will treat that by photoetching patterning materials forms pattern on the substrate two sides, place activated solution to take out after a period of time.Similar with first execution mode, photoetching technique comprises following any one photoetching technique: ultraviolet photolithographic, extreme ultraviolet photolithographic, electron beam lithography, ion beam lithography, X-ray lithography and imprint lithography; Wherein, imprint lithography comprises hot padding, ultraviolet solidified nano impression and micro-contact printing.It will be understood by those skilled in the art that micro-contact printing can be similar to the material that the same handle of seal is coated with thereon and be printed directly in the substrate, more succinct than traditional, the minimum feature that obtains is more little, is particularly useful for being lower than the hundreds of nanometer, the sightless scene of naked eyes.
Then, substrate is placed activating solution, this activating solution and first execution mode are similar, do not repeat them here.
Then, from activating solution, after the taking-up substrate, remove the photoresist that forms in the photoetching process, obtain patterning Dopaminergics substrate surface.
Certainly, if pattern conductive film to be prepared is a single face pattern conductive film, equally can the one side of substrate coat can't with the barrier layer of metal reaction after prepare described patterning Dopaminergics substrate surface at the another side of this substrate again, as simultaneously coating the barrier layer in substrate, to treat that at another side patterning materials forms pattern, places activated solution to take out after a period of time by photoetching; Perhaps, before the substrate with patterning places the step of metal plating liquid, the one side of the not patterning of substrate is coated the barrier layer.
In step 803, the substrate of patterning is placed metal plating liquid, in the exposed place deposition layer of metal that the Dopaminergics material is arranged of substrate surface.This step is similar with step 103, does not repeat them here.
The 3rd execution mode of the present invention relates to a kind of preparation method of pattern metal circuit.The 3rd execution mode and first or second execution mode are roughly the same, and main distinction part is: at first or second execution mode, be by photoetching technique, and preparation patterning Dopaminergics substrate surface in substrate; And in the present embodiment, be by printing technology, preparation patterning Dopaminergics substrate surface in substrate.
Such as, after modifying one deck Dopaminergics material in the substrate, realize the substrate surface patterning by printing technology again, substrate with patterning places metal plating liquid then, add reducing agent etc., make that the material that will be used to print is removed at last in the exposed local selective deposition layer of metal of Dopaminergics material.Perhaps, in substrate, form pattern, deposit one deck Dopaminergics material again by printing technology, the material that will be used to print is removed then, stays the figure of Dopaminergics material, immerses in the metal plating liquid equally subsequently, add reducing agent, deposit layer of metal where at the Dopaminergics material.
In the present embodiment, the mode of printing comprises printing, silk screen printing, inkjet printing, letterpress, intaglio printing, offset printing, heat transfer printing, xerography, roll-to-roll printing etc., and the material that can be used for printing is various printing ink, photoresist, impression glue, polymer solution such as polyesters, polyacrylic, polyamide-based etc.
Be that example is specifically described to adopt mode of printing to prepare latticed copper lines transparent conductive film below:
(1) is that the clear PET film of 50 μ m places acetone ultrasonic with thickness, uses washed with de-ionized water, drying again;
(2) activating solution of preparation Tris-hydrochloric acid, pH=8.5 adds Dopamine hydrochloride, Tris concentration 1.2mg/mL, Dopamine hydrochloride concentration 2mg/mL puts into the PET after the cleaning, 15 ° of C of reaction temperature, reaction time 0.5h takes out PET, deionized water rinsing, oven dry;
(3) mode by ink jet printing is printed on the acetone soln of linear phenolic resin on the pet substrate that step (2) is handled, and its printed pattern requires design according to film light transmittance and conductivity;
(4) preparing metal plating bath, copper chloride (CuCl
2) concentration is 0.2%, adds ethylenediamine tetra-acetic acid (EDTA), boric acid (H
3BO
3), NaOH (NaOH), adjusting pH is 8-9, extraordinarily goes into dimethyamine borane (DMAB) by copper chloride molal quantity 3 again;
(5) PET with patterning immerses in the metal plating liquid, stirs, and takes out deionized water rinsing behind the 20min;
(6) acetone cleans and removes phenolic resins.
Be not difficult to find that present embodiment can realize the technique effect of first or second execution mode equally, as need not other sensitization or generate Seed Layer when the chemical plating, the succinct weak point consuming time of technology, environmentally friendly, metal level and substrate adhere to firmly, metal layer thickness is all first-class, does not repeat them here.
The step of top the whole bag of tricks is divided, and is just clear in order to describe, and can merge into a step during realization or some step is split, and is decomposed into a plurality of steps, as long as comprise identical logical relation, all in the protection range of this patent; To adding inessential modification in the algorithm or in the flow process or introduce inessential design, but the core design that does not change its algorithm and flow process is all in the protection range of this patent.
Persons of ordinary skill in the art may appreciate that the respective embodiments described above are to realize specific embodiments of the invention, and in actual applications, can do various changes to it in the form and details, and without departing from the spirit and scope of the present invention.
Claims (17)
1. the preparation method of a pattern metal circuit is characterized in that, comprises following steps:
One substrate is provided;
Utilize activating solution and the photoetching or the printing technology of preparation, preparation patterning Dopaminergics substrate surface in described substrate; Wherein, adding has the Dopaminergics material in described activating solution;
The substrate of described patterning is placed metal plating liquid, in the exposed place deposition layer of metal that the Dopaminergics material is arranged of described substrate surface; Add in the described metal plating liquid reducing agent is arranged;
Described pattern metal circuit is pattern conductive film or fine-line;
Wherein, if pattern conductive film to be prepared is a single face pattern conductive film, then in described substrate in the step of preparation patterning Dopaminergics substrate surface, the one side of described substrate coat can't with the barrier layer of metal reaction after prepare described patterning Dopaminergics substrate surface at the another side of this substrate again; Perhaps, before the substrate with described patterning places the step of metal plating liquid, the one side of the not patterning of substrate is coated with the above barrier layer.
2. the preparation method of pattern metal circuit according to claim 1 is characterized in that, described reducing agent is one of following or the mixture of its combination in any:
Glucose, formaldehyde, tartaric acid, sodium potassium tartrate tetrahydrate, dimethyl amido borine, sodium borohydride, hydrazine dihydrochloride, hydrazine sulfate, hydrazine, sodium hypophosphite, glyoxalic acid, malic acid, inferior sodium phosphate, citric acid, natrium citricum, ascorbic acid, N, dinethylformamide, ethylene glycol, glutaraldehyde.
3. the preparation method of pattern metal circuit according to claim 1 is characterized in that, activating solution and the photoetching or the printing technology of described utilization preparation in the step of preparation patterning Dopaminergics substrate surface, comprise following substep in described substrate:
Described substrate is placed described activating solution;
After from described activating solution, taking out described substrate, photoetching or printing are carried out in the one side substrate of need patterning, obtained described patterning Dopaminergics substrate surface;
After the substrate with described patterning places the step of metal plating liquid, also carry out following steps:
Remove the material that is used for photoetching or printing in described photoetching or the printing process.
4. the preparation method of pattern metal circuit according to claim 3 is characterized in that, the described material that is used for photoetching or printing comprises:
Photoresist, impression glue, printing ink, not with the material of metal reaction.
5. the preparation method of pattern metal circuit according to claim 1 is characterized in that, activating solution and the photoetching or the printing technology of described utilization preparation in the step of preparation patterning Dopaminergics substrate surface, comprise following substep in described substrate:
One side to the need patterning of described substrate is carried out photoetching or printing, forms required pattern;
Described substrate is placed described activating solution;
After from described activating solution, taking out described substrate, remove the material that is used for photoetching or printing in described photoetching or the printing process, obtain described patterning Dopaminergics substrate surface.
6. according to the preparation method of each described pattern metal circuit in the claim 3 to 5, it is characterized in that,
When described substrate was placed described activating solution, described activating solution was exposed in the air, perhaps, oxygen was passed in the described activating solution, perhaps, added oxidizing substance in described activating solution.
7. according to the preparation method of each described pattern metal circuit in the claim 3 to 5, it is characterized in that,
It is 1 second to 100 hours that described substrate places the duration in the described activating solution;
Reaction temperature when described substrate places in the described activating solution is less than 100 ° of C.
8. the preparation method of pattern metal circuit according to claim 1, it is characterized in that the pH buffer substance is any one in sodium dihydrogen phosphate-citrate buffer solution, sodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, barbital sodium hydrochloride buffer, Tris-hydrochloride buffer, the sodium carbonate-sodium bicarbonate buffer liquid in the described activating solution.
9. the preparation method of pattern metal circuit according to claim 1 is characterized in that,
The pH value scope of described activating solution is 2 to 11.
10. the preparation method of pattern metal circuit according to claim 1, it is characterized in that, the Dopaminergics material that described Dopaminergics material is following arbitrary structural formula perhaps is condensate, ligand, acid salt or the basic salt of the Dopaminergics material of following arbitrary structural formula:
Wherein, R is alkyl or substituted alkyl, R
1Be H, alkyl or substituted alkyl, R
2Be H, alkyl or substituted alkyl.
11. the preparation method of pattern metal circuit according to claim 1 is characterized in that, described metal plating liquid is the commercialization metal plating liquid, and perhaps, described metal plating liquid is composed of the following components:
Slaine, aqueous solvent, reducing agent, additive;
Wherein, described slaine is mantoquita or silver salt.
12. the preparation method of pattern metal circuit according to claim 11 is characterized in that,
Described silver salt is one of following or the mixture of its combination in any:
Silver nitrate, silver perchlorate, silver-colored Cymag, silver-colored potassium cyanide, silver tetrafluoroborate, silver acetate, silver sulfate, silver bromide, silver chlorate, silver oxide, silver carbonate, silver orthophosphate;
Described mantoquita is one of following or the mixture of its combination in any:
Copper sulphate, copper chloride, copper nitrate, Schweinfurt green, copper carbonate and hydrate thereof, Kocide SD, cuprous oxide, cupric oxide.
13. the preparation method of pattern metal circuit according to claim 11 is characterized in that,
Described additive is one of following or the mixture of its combination in any:
Ethanol, methyl alcohol, ethylenediamine tetra-acetic acid two are received, ethylenediamine, triethanolamine, ethylenediamine tetra-acetic acid, thiocarbamide, bipyridine, polyethylene glycol, polyvinyl alcohol, polypyrrole alkane ketone, lauryl sodium sulfate, natrium citricum, sodium acetate, sodium pyrophosphate, potassium ferrocyanide, lead sulfate, ammonium sulfate, nickelous sulfate, lactic acid, succinic acid, citric acid, propionic acid, glycolic acid, boric acid, tartrate, NaOH, potassium hydroxide, ammoniacal liquor.
14. the preparation method of pattern metal circuit according to claim 1 is characterized in that, described photoetching technique comprises following any one photoetching technique:
Ultraviolet photolithographic, extreme ultraviolet photolithographic, electron beam lithography, ion beam lithography, X-ray lithography and imprint lithography;
Described imprint lithography comprises hot padding, ultraviolet solidified nano impression and micro-contact printing;
Described printing technology comprises:
Printing, silk screen printing, inkjet printing, letterpress, intaglio printing, offset printing, heat transfer printing, xerography, roll-to-roll printing.
15. the preparation method of pattern metal circuit according to claim 1 is characterized in that, also comprises following steps:
In activating solution and the photoetching or the printing technology of described utilization preparation, before preparation patterning Dopaminergics substrate surface in the described substrate,
Requirement according to light transmittance and conductivity is provided with the pattern that need form in described substrate.
16. the preparation method of pattern metal circuit according to claim 15 is characterized in that,
The pattern that described need form in substrate is made up of intersection or Uncrossed straight line, curve or broken line.
17. the preparation method of pattern metal circuit according to claim 1 is characterized in that,
Described substrate is transparent, translucent or opaque flexibility or hard material.
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