CN104789950A - Photocatalytic plating preparation method for material surface metal pattern - Google Patents
Photocatalytic plating preparation method for material surface metal pattern Download PDFInfo
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Abstract
The invention relates to a photocatalytic plating preparation method for a material surface metal pattern, and belongs to the technical field of material surface treatment. The method is characterized in that the surface of a base material deposited with a nano semiconductor thin film is directly immersed in a chemical plating solution, the surface of the base material deposited with the nano semiconductor thin film faces to a light source, a mold plate is placed between the light source and the surface of the base material deposited with the nano semiconductor thin film, a light transmitting part of the mold plate is allowed to be in accurate alignment to a part, planning to prepare the metal pattern, of the surface of the base material deposited with the nano semiconductor thin film, the light source is opened for irradiation, the surface of the base material deposited with the nano semiconductor thin film is subjected to a redox reaction to generate a primary metal pattern plating layer, then chemical plating is continued to obtain a fine metal pattern plating layer, the base material having the surface plated with the metal pattern is taken out, and washing, sun-drying or blow-drying is carried out. The metal pattern plating layer of the material surface is dense, the fineness is high, the bonding strength between the material and the metal pattern is high, and the method is high in technological process, low in production cost, green and environmentally friendly, wide in applicable scope, convenient and flexible, high in yield, and easy for large-scale production.
Description
Technical field
The present invention relates to technical field of material surface treatment, the photochemical catalysis in particular, providing a kind of material surface metal pattern is coated with Preparation Method.
Technical background
Along with the fast development in the fields such as electronic information, semiconductor lighting, aerospace, automobile, decoration and defence and military, the demand of material surface being carried out to metal pattern process is growing, requires also more and more higher.
At present there are Physical, subtractive method and chemical method to the common method that material surface carries out metal pattern process.
Physical material surface being carried out to metal pattern process mainly comprises ion plating method, vacuum vapor deposition method, magnetron sputtering method etc., and this is known method.Although these Physicals can form at material surface the metal pattern that bonding strength is excellent, reliability is high and meticulous well, there is problems such as needing expensive device, productive rate is lower, production cost is high.
Subtractive method material surface being carried out to metal pattern process is a kind of method the most general at present.Being covered with layer of metal film on the whole surface of material in advance, then by being positioned at metallic membrane that redundant bit is set up by photolithographic methods, adopting traditional etch processes technology to remove, thus the metal pattern needed for obtaining at material surface.Although it is high that subtractive method has productive rate, be easy to form the advantages such as metal pattern, but need a large amount of metallic membrane to carry out etching and remove preparing in metal pattern process, therefore also exist that metallic substance waste is comparatively large, environmental pollution is serious, and be difficult to obtain the problems such as high quality fine metal patterns.
Material surface is carried out to the chemical method mainly electroless plating of metal pattern process.Electroless plating refers under not additional power source condition, has the matrix surface of catalytic activity, is utilizing the redox reaction in solution reducing metal ions to be become the metal deposition process of atoms metal.Adopt electroless plating can realize the plating comprising the various metals such as gold and silver, copper, nickel, be widely used in actual production material surface being carried out to metal pattern process.The technical process adopting traditional chemical plating to carry out the process of material surface metal pattern is alligatoring-sensitization-activation-electroless plating.Traditional electroless plating is because it is applied widely, working condition is easy to the advantages such as realization, high, the easy formation fine metal patterns of productive rate and is widely used, but there are some shortcomings: 1. technique is loaded down with trivial details, needs complicated sensitization, activation pre-treatment; 2. use the precious metals such as palladium in reactivation process, cost is high; 3. coating and basal body binding force insecure, compactness is poor; 4. the material such as chlorion is used, harmful and there is problem of environmental pollution.
As can be seen here, existing method of carrying out metal pattern process to material surface is all difficult to meet that low cost, extensive, energy-conserving and environment-protective, quality product are high, working condition is easy to realize and obtain the requirements such as fine metal patterns, therefore develop that a kind of with low cost, short route, facility investment are few, method that simple process, environmental protection, mass prepare material surface fine metal patterns, tool is of great significance.
Summary of the invention
Nano semiconductor photocatalysis technology combines with traditional chemical coating technology by the present invention, the body material of the surface deposition Nanometer Semiconductor Films of metal pattern process is carried out for object with plan, the substrate material surface of depositing nano semiconductor film is directly immersed in chemical plating fluid, and by the substrate material surface of depositing nano semiconductor film facing to light source, between light source and the substrate material surface of depositing nano semiconductor film, placing template, (this template is made up of light transmission part and lightproof part, wherein the shape of light transmission part is the shape of standby metal pattern of drawing up, for hollow out or transparent, and rest part is lighttight), open light source, light beam is made to be irradiated to the substrate material surface of depositing nano semiconductor film by light transmission part straight line in template, the image spots of required preparation is irradiated at the substrate material surface of depositing nano semiconductor film, by the illumination of for some time, the strong reducing property of light induced electron or the strong oxidizing property of photohole is utilized to participate in redox reaction, the metal ion in chemical plating fluid is made to be reduced to metal simple-substance the substrate material surface of depositing nano semiconductor film is oxidized, produce nascent metal level, afterwards using nascent metal as active centre, in chemical plating fluid reductive agent effect under, nascent metal level carries out electroless plating reaction, realize the continuation reduction deposition of metal ion on nascent metal level, the fine metal patterns coating of desired thickness is formed at the substrate material surface of depositing nano semiconductor film, develop a kind of short route, green, the material surface metal pattern photochemical catalysis of low cost is coated with Preparation Method, solve the required equipment costliness that current material surface metal pattern preparation method exists, environmental requirement is tight, not easily realize mass-producing preparation, environmental pollution is larger, technical process is long, production cost is high, quality product is difficult to meet the problems such as service requirements.
The photochemical catalysis of material surface metal pattern is coated with a Preparation Method, and its concrete technology is as follows:
1, directly immersed in chemical plating fluid by the substrate material surface of depositing nano semiconductor film, the substrate material surface of depositing nano semiconductor film is facing to light source;
2, between light source and the substrate material surface of depositing nano semiconductor film, place template, the substrate material surface of the light transmission part in template and depositing nano semiconductor film is drawn up for the position exactitude position of metal pattern;
3, open light source, make wavelength be the light beam of 200 ~ 400nm is irradiated to depositing nano semiconductor film substrate material surface by the light transmission part straight line in template;
4, illumination 1 ~ 10min, makes the metal ion in chemical plating fluid be reduced to metal simple-substance the substrate material surface of depositing nano semiconductor film is oxidized, and produce nascent metal pattern coating, maintaining bath pH value between the reaction period is 7 ~ 13;
5, continue to carry out electroless plating to the substrate material surface of the depositing nano semiconductor film completing redox reaction, temperature of reaction 30 ~ 50 DEG C, reaction times 60 ~ 240min, realize the continuous reduction deposition of metal ion on nascent metal pattern coating, obtain certain thickness fine metal patterns coating at the substrate material surface of depositing nano semiconductor film;
6, by coating surface, the body material of metal pattern takes out, washing, airing or dry up, and namely to complete the metal pattern preparation of substrate material surface.
Described Nanometer Semiconductor Films is nano-titanium dioxide film, Nano zinc oxide film, Nanometer Semiconductor Films through doping vario-property.
Described body material is metallic substance, ceramic, macromolecular material or matrix material.
Formula composition (mass percent) of described chemical plating fluid is metal-salt 20 ~ 40%, reductive agent 20 ~ 35%, complexing agent 25 ~ 30%, stablizer 0 ~ 30%; Wherein, described metal-salt is mantoquita, nickel salt, golden salt, silver salt, aluminium salt, molysite, cobalt salt, pink salt, zinc salt, chromic salts, molybdenum salt, palladium salt, platinum salt, tungsten salt or rare-earth salts, and described reductive agent is HOCCOOH, HCHO, NaH
2pO
2h
2o or HO (CH
2cH
2o)
nh (n=4 ~ 450), described complexing agent is KNaC
4h
4o
64H
2o, EDTA-2Na or C
6h
5na
3o
72H
2o, described stablizer is C
10h
8n
2or K
4fe (CN)
6h
2o.
Described template is made up of light transmission part and lightproof part, and wherein the shape of light transmission part is the shape of standby metal pattern of drawing up, and be hollow out or transparent, and rest part is lighttight; Described template is made up of at least one in metallic substance, ceramic, macromolecular material or matrix material.
Described metal is at least one in copper, nickel, gold and silver, aluminium, iron, cobalt, tin, zinc, chromium, molybdenum, palladium, platinum, tungsten, rare earth and alloy thereof.
Major advantage of the present invention is:
1, the present invention take Nanometer Semiconductor Films as transition layer, realize the plating of metal pattern at substrate material surface, the original metal pattern thickness of coating on Nanometer Semiconductor Films top layer can reach nano level, and particle is tiny, even compact, be conducive to the densification of subsequent chemistry metallic design coating, and bonding strength between body material and metal pattern coating is high, the high-performance service requirements of effects on surface metal pattern formed material can be met completely.
2, the present invention utilizes nano semiconductor material under light illumination can the characteristic of metal ion in redox chemistry plating solution, eliminate the etching in the preparation of conventional metals patterning or the operation such as sensitization, activation in chemically plating Preparation Method, simplify the preparation technology of material surface metal pattern, shorten Production Flow Chart.
3, the present invention is without the need to using the precious metal element such as palladium, tin, without objectionable impuritiess such as chlorions in plating solution, has the advantages such as production cost is low, environmental protection.
4, present invention can be implemented in different matrix material surface and prepare meticulous metal pattern, have applied widely, convenient, flexible, can the feature such as further genralrlization application.
5, the present invention can combine with other process for treating surface follow-up, not only can enhance productivity further, controls the thickness of substrate material surface metal pattern coating, and can also prepare stratiform composite pattern coating at substrate material surface.
6, the present invention has that facility investment is few, environmental requirement is not high, simple process, cost are low, is easy to realize the features such as extensive preparation.
Embodiment
Below in conjunction with embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the those of skill in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1:
It is 25%CuSO that formula composition (massfraction) is directly immersed in the aluminium alloy plate of depositing nano zinc-oxide film surface
45H
2o 15gL
-1, 30%HOCCOOH 7.4gL
-1, 25% mixed twine mixture (KNaC
4h
4o
64H
2o 25gL
-1, EDTA-2Na 25gL
-1), 20% mixed stabilizer (C
10h
8n
210mgL
-1, K
4fe (CN)
6h
2o 30mgL
-1) chemical plating fluid in, the aluminium alloy plate of depositing nano zinc-oxide film surface is facing to light source; Plastic mould is placed between light source and the aluminium alloy plate surface of depositing nano zinc-oxide film, plastic mould is made up of light transmission part and lightproof part, wherein the shape of light transmission part is circular, draws up for the position exactitude position of circular copper pattern by the aluminium alloy plate surface of the light transmission part on plastic mould and depositing nano zinc-oxide film; Open light source, make wavelength be 254nm light beam by the light transmission part straight line on plastic mould be irradiated to depositing nano zinc-oxide film aluminium alloy plate surface; Illumination 5min carries out redox reaction, makes to produce circular nascent copper pattern coating on the aluminium alloy plate surface of depositing nano zinc-oxide film, and maintaining bath pH value between the reaction period is 12.5; Electroless plating is carried out to the aluminium alloy plate surface of the depositing nano zinc-oxide film completing redox reaction, temperature of reaction 40 DEG C, reaction times 120min, realize the continuation reduction deposition of cupric ion on the nascent copper pattern coating of circle, obtain certain thickness meticulous circular copper pattern coating on the aluminium alloy plate surface of depositing nano zinc-oxide film; By coating surface, the aluminium alloy plate of circular copper pattern takes out, and washing, dries up, and namely completes the circular copper pattern preparation on aluminium alloy plate surface.
Embodiment 2:
It is 30%CuSO that formula composition (massfraction) is directly immersed in the alumina ceramic plate of depositing nano titanium deoxid film surface
45H
2o 15gL
-1, 30%HOCCOOH 7.4gL
-1, 30% mixed twine mixture (KNaC
4h
4o
64H
2o 25gL
-1, EDTA-2Na 25gL
-1), 10% mixed stabilizer (C
10h
8n
210mgL
-1, K
4fe (CN)
6h
2o 30mgL
-1) chemical plating fluid in, the alumina ceramic plate of depositing nano titanium deoxid film surface is facing to light source; Metal titanium template is placed between light source and the alumina ceramic plate surface of depositing nano titanium deoxid film, metal titanium template is made up of light transmission part and lightproof part, the shape that wherein light transmission part is formed is cartoon smiling face, draws up for the position exactitude position of cartoon smiling face copper pattern by the alumina ceramic plate surface of the light transmission part in metal titanium template and depositing nano titanium deoxid film; Open light source, make wavelength be 360nm light beam by the light transmission part straight line in metal titanium template be irradiated to depositing nano titanium deoxid film alumina ceramic plate surface; Illumination 10min carries out redox reaction, and make the nascent copper pattern coating producing cartoon smiling face on the alumina ceramic plate surface of depositing nano titanium deoxid film, maintaining bath pH value between the reaction period is 12; Electroless plating is carried out to the alumina ceramic plate surface of the depositing nano titanium deoxid film completing redox reaction, temperature of reaction 35 DEG C, reaction times 180min, realize the continuation reduction deposition of cupric ion on the nascent copper pattern coating of cartoon smiling face, obtain certain thickness meticulous cartoon smiling face copper pattern coating on the alumina ceramic plate surface of depositing nano titanium deoxid film; By coating surface, the alumina ceramic plate of cartoon smiling face copper pattern takes out, washing, airing, namely completes the cartoon smiling face copper pattern preparation on alumina ceramic plate surface.
Embodiment 3:
It is 35%NiSO that formula composition (massfraction) is directly immersed in the AlN ceramic sheet of depositing nano zinc-oxide film surface
46H
2o 30gL
-1, 35%NaH
2pO
2h
2o 30gL
-1, 30%C
6h
5na
3o
72H
2o20gL
-1chemical plating fluid in, the AlN ceramic sheet of depositing nano zinc-oxide film surface is facing to light source; Copper Foil template is placed between light source and the AlN ceramic sheet surface of depositing nano zinc-oxide film, Copper Foil template is made up of light transmission part and lightproof part, the shape that wherein light transmission part is formed is fan ring, draws up for the position exactitude position fanning ring nickel pattern by the AlN ceramic sheet surface of the light transmission part in Copper Foil template and depositing nano zinc-oxide film; Open light source, make wavelength be 365nm light beam by the light transmission part straight line in Copper Foil template be irradiated to depositing nano zinc-oxide film AlN ceramic sheet surface; Illumination 6min carries out redox reaction, and make the nascent nickel pattern coating producing fan ring on the AlN ceramic sheet surface of depositing nano zinc-oxide film, maintaining bath pH value between the reaction period is 9.5; Electroless plating is carried out to the AlN ceramic sheet surface of the depositing nano zinc-oxide film completing redox reaction, temperature of reaction 45 DEG C, reaction times 120min, realize the continuation reduction deposition of nickel ion on the nascent nickel pattern coating of fan ring, obtain certain thickness meticulous fan ring nickel pattern coating on the AlN ceramic sheet surface of depositing nano zinc-oxide film; By coating surface, the AlN ceramic sheet of fan ring nickel pattern takes out, washing, and namely airing completes the fan ring nickel pattern preparation on AlN ceramic sheet surface.
Embodiment 4:
It is 40%NiSO that formula composition (massfraction) is directly immersed in the polyimide resin film surface that deposited nitrogen-doped nanometer titanium dioxide film
46H
2o 30gL
-1, 30%NaH
2pO
2h
2o 30gL
-1, 30%C
6h
5na
3o
72H
2o 20gL
-1chemical plating fluid in, deposited the polyimide resin film surface of nitrogen-doped nanometer titanium dioxide film facing to light source; Photosensory membrane template is placed between light source and the polyimide resin film surface that deposited nitrogen-doped nanometer titanium dioxide film, photosensory membrane template is made up of light transmission part and lightproof part, the shape that wherein light transmission part is formed is Olympic Five Ring, the position exactitude position of standby Olympic Five Ring nickel pattern of being drawn up in the light transmission part in photosensory membrane template and the polyimide resin film surface that deposited nitrogen-doped nanometer titanium dioxide film; Open light source, make wavelength be 254nm light beam by the light transmission part straight line in photosensory membrane template be irradiated to deposited nitrogen-doped nanometer titanium dioxide film polyimide resin film surface; Illumination 10min carries out redox reaction, and make the nascent nickel pattern coating producing Olympic Five Ring on the polyimide resin film surface that deposited nitrogen-doped nanometer titanium dioxide film, maintaining bath pH value between the reaction period is 9; Electroless plating is carried out to the polyimide resin film surface that deposited nitrogen-doped nanometer titanium dioxide film completing redox reaction, temperature of reaction 50 DEG C, reaction times 90min, realize the continuation reduction deposition of nickel ion on the nascent nickel pattern coating of Olympic Five Ring, obtain certain thickness meticulous Olympic Five Ring nickel pattern coating on the polyimide resin film surface that deposited nitrogen-doped nanometer titanium dioxide film; By coating surface, the polyimide resin film of Olympic Five Ring nickel pattern takes out, and washing, dries up, and namely completes the Olympic Five Ring nickel pattern preparation on polyimide resin film surface.
Embodiment 5:
The glass pane surface of depositing nano titanium deoxid film directly being immersed formula composition (massfraction) is 25%CuSO
45H
2o 15gL
-1, 25%HOCCOOH 7.4gL
-1, 25% mixed twine mixture (KNaC
4h
4o
64H
2o 25gL
-1, EDTA-2Na 25gL
-1), 25% mixed stabilizer (C
10h
8n
210mgL
-1, K
4fe (CN)
6h
2o 30mgL
-1) chemical plating fluid in, the glass pane surface of depositing nano titanium deoxid film is facing to light source; Photosensory membrane template is placed between light source and the glass pane surface of depositing nano titanium deoxid film, photosensory membrane template is made up of light transmission part and lightproof part, the shape that wherein light transmission part is formed is matts, draws up for the position exactitude position of matts copper pattern by the glass pane surface of the light transmission part in photosensory membrane template and depositing nano titanium deoxid film; Open light source, make wavelength be the light beam of 365nm is irradiated to depositing nano titanium deoxid film glass pane surface by the light transmission part straight line in photosensory membrane template; Illumination 5min carries out redox reaction, and make the nascent copper pattern coating producing matts in the glass pane surface of depositing nano titanium deoxid film, maintaining bath pH value between the reaction period is 12.7; Electroless plating is carried out to the glass pane surface of the depositing nano titanium deoxid film completing redox reaction, temperature of reaction 45 DEG C, reaction times 120min, realize the continuation reduction deposition of cupric ion on the nascent copper pattern coating of matts, obtain certain thickness meticulous matts copper pattern coating in the glass pane surface of depositing nano titanium deoxid film; By coating surface, the sheet glass of matts copper pattern takes out, washing, airing, namely completes the matts copper pattern preparation of glass pane surface.
Claims (6)
1. the photochemical catalysis of material surface metal pattern is coated with a Preparation Method, it is characterized in that, is directly immersed in chemical plating fluid by the substrate material surface of depositing nano semiconductor film, and the substrate material surface of depositing nano semiconductor film is facing to light source; Between light source and the substrate material surface of depositing nano semiconductor film, place template, the substrate material surface of the light transmission part in template and depositing nano semiconductor film is drawn up for the position exactitude position of metal pattern; Open light source, make wavelength be the light beam of 200 ~ 400nm is irradiated to depositing nano semiconductor film substrate material surface by the light transmission part straight line in template; Illumination 1 ~ 10min, makes the metal ion in chemical plating fluid be reduced to metal simple-substance the substrate material surface of depositing nano semiconductor film is oxidized, and produce nascent metal pattern coating, maintaining bath pH value between the reaction period is 7 ~ 13; Continue to carry out electroless plating to the substrate material surface of the depositing nano semiconductor film completing redox reaction, temperature of reaction 30 ~ 50 DEG C, reaction times 60 ~ 240min, realize the continuous reduction deposition of metal ion on nascent metal pattern coating, obtain certain thickness fine metal patterns coating at the substrate material surface of depositing nano semiconductor film; By coating surface, the body material of metal pattern takes out, washing, airing or dry up, and namely to complete the metal pattern preparation of substrate material surface.
2. a kind of photochemical catalysis of material surface metal pattern is coated with Preparation Method as claimed in claim 1, it is characterized in that, described Nanometer Semiconductor Films is nano-titanium dioxide film, Nano zinc oxide film, Nanometer Semiconductor Films through doping vario-property.
3. a kind of photochemical catalysis of material surface metal pattern is coated with Preparation Method as claimed in claim 1, it is characterized in that, described body material is metallic substance, ceramic, macromolecular material or matrix material.
4. a kind of photochemical catalysis of material surface metal pattern is coated with Preparation Method as claimed in claim 1, it is characterized in that, the prescription quality percentage ratio of described chemical plating fluid consists of metal-salt 20 ~ 40%, reductive agent 20 ~ 35%, complexing agent 25 ~ 30%, stablizer 0 ~ 30%; Wherein, described metal-salt is mantoquita, nickel salt, golden salt, silver salt, aluminium salt, molysite, cobalt salt, pink salt, zinc salt, chromic salts, molybdenum salt, palladium salt, platinum salt, tungsten salt or rare-earth salts, and described reductive agent is HOCCOOH, HCHO, NaH
2pO
2h
2o or HO (CH
2cH
2o)
nh (n=4 ~ 450), described complexing agent is KNaC
4h
4o
64H
2o, EDTA-2Na or C
6h
5na
3o
72H
2o, described stablizer is C
10h
8n
2or K
4fe (CN)
6h
2o.
5. a kind of photochemical catalysis of material surface metal pattern is coated with Preparation Method as claimed in claim 1, it is characterized in that, described template is made up of light transmission part and lightproof part, wherein the shape of light transmission part is the shape of standby metal pattern of drawing up, be hollow out or transparent, and rest part is lighttight; Described template is made up of at least one in metallic substance, ceramic, macromolecular material or matrix material.
6. a kind of photochemical catalysis of material surface metal pattern is coated with Preparation Method as claimed in claim 1, it is characterized in that, described metal is at least one in copper, nickel, gold and silver, aluminium, iron, cobalt, tin, zinc, chromium, molybdenum, palladium, platinum, tungsten, rare earth and alloy thereof.
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| CN201510120018.XA CN104789950A (en) | 2015-03-18 | 2015-03-18 | Photocatalytic plating preparation method for material surface metal pattern |
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| CN201510120018.XA CN104789950A (en) | 2015-03-18 | 2015-03-18 | Photocatalytic plating preparation method for material surface metal pattern |
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|---|---|---|---|---|
| CN107217245A (en) * | 2017-05-22 | 2017-09-29 | 北京科技大学 | A kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern |
| CN108441843A (en) * | 2018-03-13 | 2018-08-24 | 北京科技大学 | Preparation method is plated in the laser direct-writing preform photocatalysis of material surface metal pattern |
| CN111203371A (en) * | 2020-01-16 | 2020-05-29 | 浙江大学 | Preparation method of surface metal pattern |
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| CN101550546A (en) * | 2009-04-08 | 2009-10-07 | 北京科技大学 | A preparation method of surface metallized composite material through chemical plating under photocatalysis |
| CN103646835A (en) * | 2013-12-02 | 2014-03-19 | 北京科技大学 | A ceramic electric vacuum tube with a metalized end face and a method for producing same |
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| JP2006077322A (en) * | 2004-09-06 | 2006-03-23 | Samsung Electro Mech Co Ltd | Electroless plating method of printed circuit board using photocatalyst |
| CN1896311A (en) * | 2005-12-08 | 2007-01-17 | 郑州大学 | Direct composite method for coating magnesium-alloy surface with nano-titanium dioxide |
| CN101457353A (en) * | 2009-01-05 | 2009-06-17 | 合肥工业大学 | Chemical depositing Ni-P-nano titanic oxide photocatalysis composite coating plating solution and plating method thereof |
| CN101550546A (en) * | 2009-04-08 | 2009-10-07 | 北京科技大学 | A preparation method of surface metallized composite material through chemical plating under photocatalysis |
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| CN107217245A (en) * | 2017-05-22 | 2017-09-29 | 北京科技大学 | A kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern |
| CN108441843A (en) * | 2018-03-13 | 2018-08-24 | 北京科技大学 | Preparation method is plated in the laser direct-writing preform photocatalysis of material surface metal pattern |
| CN108441843B (en) * | 2018-03-13 | 2020-02-18 | 北京科技大学 | Laser direct-writing preformed photocatalytic plating preparation method for metal patterns on surface of material |
| CN111203371A (en) * | 2020-01-16 | 2020-05-29 | 浙江大学 | Preparation method of surface metal pattern |
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