CN107217245A - A kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern - Google Patents
A kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern Download PDFInfo
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- CN107217245A CN107217245A CN201710363124.XA CN201710363124A CN107217245A CN 107217245 A CN107217245 A CN 107217245A CN 201710363124 A CN201710363124 A CN 201710363124A CN 107217245 A CN107217245 A CN 107217245A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1614—Process or apparatus coating on selected surface areas plating on one side
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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Abstract
A kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern, belongs to technical field of material surface treatment.The present invention can make the characteristics of light is passed through based on light transmissive material, photocatalysis electroplating method and backlight catalysis technique are organically combined, using the efficiency of light energy utilization is higher, light beam is more concentrated, intensity of illumination uniformity better way carries out light transmissive material surface metal pattern preparation, the light transmissive material inner surface for being particularly suitable for use in inner chamber prepares metal pattern.Backlight catalysis plating preparation method environmental protection, the technological process of the light transmissive material surface metal pattern of the present invention are short, production cost is low, and the metal pattern dimensional accuracy prepared is high, coating surface quality is good, high with substrate combinating strength.
Description
Technical field
The present invention relates to technical field of material surface treatment, a kind of light transmissive material surface metal pattern is in particular, provided
Backlight catalysis plating preparation method.
Technical background
With consumption electronic products such as smart mobile phone, LED illumination, tablet personal computer, transparent screen and wearable devices
Emerge in an endless stream and constantly upgrade, the light transmissive material such as glass, sapphire, lucite (PMMA) is only by feat of what is itself possessed
Special light transmitting properties and be applied widely (such as clear glass LED display, smart mobile phone display screen, sapphire LED substrate
Deng).At the same time, with the rapid advances of science and technology, the property that light transmissive material has promotes it in consumer electronics, medical treatment
The fields such as equipment, integrated circuit, modern architecture, new automobile, Aero-Space have more wide purposes.Particularly, surface
The light transmissive material for having loaded metal pattern enjoys favor because that can provide the properties such as turning circuit in related application field.
Traditional light transmissive material surface metal pattern preparation technology mainly includes magnetron sputtering method, vacuum vapor deposition method, chemistry
Plating method and sintering are by metal method.Metal pattern on light transmissive material surface is prepared using magnetron sputtering method and vacuum vapor deposition method often right
Equipment, environment etc. have more strict requirements, thus both approaches are used for laboratory research or small-scale accurate first device
The production of part.Electroless plating method because its production cost is low, be easily achieved prepare with scale be used widely, but traditional chemical is plated
Method the process such as roughened, sensitization, activation must be prepared using noble metals such as harmful substance and palladium such as chlorions on light transmissive material surface
Metal pattern.Especially, the above method uses " subtraction " preparation technology, i.e., integrally metallized to light transmissive material surface
After processing, then it is combined with technologies such as photoetching, gold is prepared on light transmissive material surface by processes such as plate-making, exposure, development, etchings
Metal patterns, have technological process length, pollute larger, coated metal and waste serious and production cost.Using burning
When knot prepares metal pattern by metal method on light transmissive material surface, combined, needed by being screen printed onto with screen printing technique more
The region coating slurry for preparing metal pattern realizes prepared by " addition ", but this method sintering temperature it is high (more 1000 DEG C with
On), energy consumption big, complex process, the metal pattern precision for preparing is low and coating uniformity and consistency are poor.
In order to solve problem present in above-mentioned material surface metalation preparation method, researchers are always based on new original
Manage new theory and make great efforts the new surface metalation preparation method of exploitation.Photocatalysis is grown up based on nano semiconductor material
A kind of new nanometer technology, including positive photocatalysis and backlight catalysis two ways.Positive photocatalysis refers to light source and reaction solution (such as
Plating solution) light-catalyzed reaction that is in the same side of nano semiconductor material (such as Nanometer Semiconductor Films) and carries out, backlight catalysis
Then refer to that light source and reaction solution (such as plating solution) are located at the phase heteropleural of nano semiconductor material (such as Nanometer Semiconductor Films) respectively
And the light-catalyzed reaction carried out；Positive photocatalysis is without any requirement to the light transmittance of matrix material, and backlight catalysis then requires matrix
Material is printing opacity, and light directly first can pass through light transmissive material from light transmissive material side when backlight is catalyzed, and printing opacity is then reached again
The surface of the Nanometer Semiconductor Films of another lateral load of material.By the way that positive photocatalysis mode is introduced into material surface metalized
Field, be developed it is a variety of realize material surface metallization and metal pattern photocatalysis plating preparation method.For example, being directed to
The technological process length for the preparation method presence metallized at present in the realization of the material surfaces such as glass, production cost are high, environmental pollution
Big the problems such as, applicant etc. develops photocatalysis plating preparation method and [seen：Liu Xuefeng, Xiong little Qing, thank and build a kind of tables of new
The photocatalysis chemically plating Preparation Method Chinese invention patents of face metalized synthetic material, grant number ZL200910081920.X is awarded
Weigh day 2010-08-18], its principle is to be combined Nano semiconductor photocatalysis technology with traditional chemical coating technology, wears light
Cross plating solution to be irradiated on the Nanometer Semiconductor Films of matrix surface load, so as to occur photocatalytic redox reaction, produce just
The raw coat of metal, then carries out chemical plating by activated centre of the nascent coat of metal and thickens, finally needed for matrix surface is obtained
The coat of metal of thickness.This method carries out material surface metalized, environmental protection, with low cost, technique stream using luminous energy
Journey is short and is easily achieved large-scale production, and brand-new way is provided for the low-cost high-efficiency preparation of high quality surface metallization material
Footpath.Further, the characteristics of needing photocatalytic during the bond material such as applicant surface photocatalysis plating metal, from
Control light area start with develop between Nanometer Semiconductor Films and light source place openworking template directly prepare metal pattern
Have the photocatalysis of mould control shape plate preparation method [see：Liu Xuefeng, Liu Min, Ou Yanglingxiao, wait a kind of material surface metal patterns of
Preparation method Chinese invention patents, application number 201510120018.X, applying date 2015-03-18 are plated in photocatalysis] and to swash
Light realizes that direct write prepares [seeing without mould control shape photocatalysis plating preparation method for metal pattern as light source, with reference to laser direct writing system：
A kind of preparation method Chinese invention patents of ceramic circuit board surface fine metal patterns of Liu Min, Liu Xuefeng, application number
201610855059.8, applying date 2016-09-27], improve the applicability and practicality of such method, it is to avoid traditional material
Expect first bulk metal in the preparation of surface metal pattern, " subtraction " manufacturing process of rear photoengraving removing redundance, realize
Prepared by the single process " addition " of metal pattern, simplify production procedure, saved the coated metal material such as gold, silver, copper.But,
All it is positive photocatalysis mode due to what is taken during material surface metallization is carried out using above-mentioned photocatalysis electroplating method,
It was found that there are several subject matters：1. light has to pass through plating solution and is irradiated to Nanometer Semiconductor Films surface, and plating solution is to luminous energy
The utilization ratio of luminous energy will be greatly reduced in the strong absorption being had, and easily causes decomposition of the light to plating solution；2. use is worked as
When thering is the mould control shape method to be prepared, in order to the metal pattern that improves preparation precision, it is necessary to by openworking template and matrix to be plated
It is put into simultaneously in plating solution, and the two is tried one's best is brought into close contact, to shorten light through reaching base to be plated after template transparent area
The distance in body surface face, so as to reduce influence of the light scattering to the metal pattern precision of required preparation, is particularly prepared when required
Metal pattern feature sizes it is smaller, when template transparent area hollow out gap is narrower, not only to the processing of template hollow out slot edge
Required precision is very high, but also usually in its slit surfaces can occur diffusing reflection when through template hollow out gap because of light
And cause illumination not enough and do not concentrate, produce plating leakage or the unequal defect of plating；3. when use is prepared without mould control shape method
When, then can because of laser in the scattering through during plating solution and laser beam are to plating solution metal ion and Nanometer Semiconductor Films
The impact of upper firm reducing metal simple substance Hong dissipate effect and cause that the contour accuracy of coated metal reduce, thickness evenness is poor, plated
The integrality of layer form of metal can not ensure, so as to be difficult to prepare the high metal pattern of dimensional accuracy in material surface.
In summary, in order to solve above mentioned problem present in current light transmissive material surface metal pattern preparation, based on saturating
Luminescent material uniqueness light transmitting properties, develop a kind of efficiency of light energy utilization height, adaptability is good, high in machining efficiency, production procedure is short, green ring
Guarantor, the new method with low cost that the high metal pattern of dimensional accuracy is efficiently prepared on light transmissive material surface, with particularly significant
Meaning.
The content of the invention
The present invention can realize that plating solution and light source are located at the phase heteropleural of Nanometer Semiconductor Films respectively based on backlight catalytic way
And the characteristics of complete light-catalyzed reaction, and the efficiency of light energy utilization is high, light beam collection neutralizes the advantages of intensity of illumination uniformity is good, by it
Light transmissive material surface metal pattern preparation field is introduced, is combined with photocatalysis electroplating method and chemical plating method, exploitation one kind exists
Light transmissive material surface short route, stably, efficiently, green, the flexible new method for preparing metal pattern.It is an object of the invention to provide
The backlight catalysis plating preparation method of a kind of light transmissive material surface metal pattern so that prepared light transmissive material surface gold can be improved
The scaled fine degree of metal patterns, improves the efficiency of light energy utilization, shortens technological process, improves bath life, reduces production cost,
Mitigate environmental pollution, particularly easily can prepare metal pattern in the light transmissive material inner surface for having inner chamber, and be easily achieved
Large-scale promotion application.
The technical scheme is that：
(1) side of light transmissive material area load Nanometer Semiconductor Films is immersed in plating solution, by its unsupported nanometer half
Conductor thin film and the opposite side of plating solution is not contacted against the higher extremely short glistening light of waves of energy and short wavelength light (200~460nm) light source, also
I.e. plating solution is located at the phase heteropleural of Nanometer Semiconductor Films with light source respectively；
(2) light source is irradiated to the light transmissive material surface for being in the same side with it, and light is controlled by using openworking template
Shape of spot size have mould control shape method or using laser direct writing system control beam spot scans region shape size without mould control shape
Method obtains the light area consistent with design metal pattern geomery；
(3) light in the light area successively passes through light transmissive material and Nanometer Semiconductor Films, thin in Nano semiconductor
Film is contacted with plating solution forms the optical design consistent with original light area geomery on the surface of side, through after a while
Illumination, participates in redox reaction so that nanometer is partly led using the strong reducing property of light induced electron or the strong oxidizing property of photohole
Metal ion in body thin film surface optical pattern coverage in plating solution, which is oxidized, is reduced to metal simple-substance, generation and design gold
The nascent coat of metal of metal patterns geomery unanimously；
(4) self-catalysis chemical plating is then carried out in the plating solution using the nascent coat of metal as activated centre, realize nascent metal
The continuous growth of coating, finally light transmissive material surface short flow high efficiency prepare needed for thickness, with designed shape one
The high metal pattern of the dimensional accuracy of cause.
A kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern, its concrete technology is as follows：
1st, the side of light transmissive material area load Nanometer Semiconductor Films is immersed in plating solution, its unsupported nanometer is partly led
Body thin film and the opposite side of plating solution is not contacted against the light source that wavelength is 200~460nm；
2nd, open light source, by have mould control shape method or without mould control shape method light transmissive material against light source side surface
Light in the upper generation light area consistent with design metal pattern geomery, the light area successively passes through light transmissive material
And Nanometer Semiconductor Films, contact and formed and the illumination of light transmissive material surface on the surface of side with plating solution in Nanometer Semiconductor Films
The consistent optical design of region shape size；
Photocatalytic-oxidation occurs for the 3rd, 0.5~10min of illumination, the Nanometer Semiconductor Films surface in optical design coverage
Change reduction reaction, the metal ion in the plating solution contacted with optical design is adsorbed by photocatalytic redox into elemental metals
Nanometer Semiconductor Films surface, generates the nascent coat of metal consistent with design metal pattern geomery, is maintained during reaction
The pH value of plating solution is 7~13；
4th, continue to be in the plating solution that active centre carries out self-catalysis chemical plating using the nascent coat of metal, reaction temperature for 20~
70 DEG C, the reaction time be 0~180min, realize the nascent continuous growth of the coat of metal in the plating solution, finally loading nanometer
The high-precision metal pattern of thickness and geomery needed for the light transmissive material surface of semiconductive thin film side is prepared；
5th, by coating surface, the light transmissive material of metal pattern takes out, and dries or dries up after washing, that is, completes printing opacity material
Expect the preparation of surface metal pattern.
The light transmissive material is inorganic non-metallic light transmissive material, macromolecule light transmissive material or composite transparent material；It is described
Density is identical everywhere for luminescent material；The thickness h of the light transmissive material1For 0 ＜ h1≤ 20mm, surface roughness Ra1For 0≤Ra1≤
400nm。
The Nanometer Semiconductor Films are nano-titanium dioxide film, Nano zinc oxide film, nano silicon nitride titanium film, received
Rice vanadic acid bismuth thin film, doping vario-property nano-titanium dioxide film, doping vario-property Nano zinc oxide film, doping vario-property nano silicon nitride
At least one of titanium film, doping vario-property nanometer vanadic acid bismuth thin film；The Nanometer Semiconductor Films can be such that light source passes through and each
Locate density identical；The thickness h of the Nanometer Semiconductor Films2For 0 ＜ h2≤900nm。
The light source is at least one of linear light sorurce, non-linear light source.
It is described to there is mould control shape method to be by being placed between light source and light transmissive material by geomery and design metal figure
The template that case identical transparent area and light tight area's two parts are constituted is come the method that controls light area geomery；The template
It is made up of at least one of metal material, inorganic non-metallic material, high polymer material or composite；The template surface
Roughness Ra2For 0≤Ra2≤20μm。
Described is to control light area by laser direct writing system regulation laser facula scanning area without mould control shape method
The method of geomery；The laser direct writing system is continuous laser straight-writing system or pulse laser straight-writing system, laser scanning
Speed is less than 3000mm/s；The laser frequency of the pulse laser straight-writing system is more than 1KHz.
The formula composition (mass percent) of the plating solution is metal salt 10~40%, reducing agent 20~35%, complexing agent
25~45%, stabilizer 0~30%；Wherein, the metal salt is gold salt, silver salt, mantoquita, nickel salt, pink salt, palladium salt, aluminium salt, iron
Salt, cobalt salt, zinc salt, chromic salts, molybdenum salt, platinum salt, tungsten salt or rare-earth salts, the reducing agent are NaH2PO2·H2O、HCHO、
HOCCOOH、NaBH4Or HO (CH2CH2O)nH (n=4~450), the complexing agent is C4H4KNaO6·4H2O、
C10H14N2Na2O8·2H2O or Na3C6H5O7·2H2O, the stabilizer is C10H8N2Or K4[Fe(CN)6]。
During the metal is gold, silver, copper, nickel, tin, palladium, aluminium, iron, cobalt, zinc, chromium, molybdenum, platinum, tungsten, rare earth and its alloy
It is at least one.
Main advantages of the present invention are：
1st, this method, which is based on light transmissive material, can make the characteristics of light is passed through, and photocatalysis electroplating method is had with backlight catalysis technique
Machine is combined, using the efficiency of light energy utilization is higher, light beam is more concentrated, intensity of illumination uniformity better way carries out light transmissive material surface
Prepared by metal pattern, environmental protection, technological process are short, production cost is low, and the metal pattern dimensional accuracy prepared is high, plating
Layer surface quality is good, high with substrate combinating strength.
2nd, light does not need guiding through plating solution during being prepared using this method, it is to avoid because plating solution is to the strong of luminous energy
Absorption and the light intensity attenuation problem produced, improve the utilization ratio of luminous energy, and extend the service life of plating solution.
3rd, using when thering is the mould control shape backlight catalysis plating preparation method to prepare metal pattern on light transmissive material surface, it is to avoid light
Line scatters the influence to the metal pattern precision of required preparation in the solution, while it is narrower in template to solve light in plating solution
Diffusing reflection occurs in hollow out gap to be made the illumination of Nanometer Semiconductor Films surface not enough or does not concentrate the plating leakage caused or plating uneven
The problems such as.
When the 4th, using metal pattern is prepared on light transmissive material surface without mould control shape backlight catalysis plating preparation method, laser is not required to
Through plating solution, it is to avoid because the impact of metal ion and nascent metal in laser scattering in the plating solution and to plating solution Hong dissipate make
Into coated metal contour accuracy reduction, thickness evenness is poor the problems such as, substantially increase the preparation precision of metal pattern.
5th, metal pattern can be prepared in the light transmissive material inner surface for having inner chamber using this method, breaches traditional photocatalysis
Electroplating method is difficult to the limitation in material inner surface metal lining, and realizes that technique is easy, with low cost.
6th, material to be plated is not required to be completely immersed in plating solution in this method preparation process, is easy to follow-up cleaning and plating solution is lost
It is few, it is advantageously implemented low cost, large-scale production.
Embodiment
The present invention is specifically described with reference to embodiments, it is necessary to it is pointed out here that be that the present embodiment is served only for pair
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, and the those of skill in the art in the field can
To make some nonessential modifications and adaptations according to the content of the invention described above.
Embodiment 1：
It is 0.5mm, surface roughness Ra in thickness1For 1nm, the printing opacity Al of even density2O3Substrate surface prepares a thickness
The nano-titanium dioxide film for 120nm and uniform-light transmission is spent, by Al2O3Substrate, which is placed on, fills formula composition (mass fraction)
For 20%CuSO4·5H2O, 25%HOCCOOH, 35% complexing agent (C4H4KNaO6·4H2O), 20% mixed stabilizer
(C10H8N2、K4[Fe(CN)6]) plating solution container on, make Al2O3The side leaching of substrate surface load nano-titanium dioxide film
Enter in plating solution, then both are positioned on the workbench of pulse laser straight-writing system together, and make Al2O3Substrate surface is not
Load nano-titanium dioxide film and the side of plating solution is not contacted against the LASER Light Source that wavelength is 355nm；In laser direct-writing system
The shape data of the weight of input five concentric circles in the control computer of system, and set the manner of execution of workbench to rotate,
Laser frequency is that 50KHz, sweep speed are 300mm/s；Light source is opened, laser facula is existed according to the scanning pattern of setting
Al2O3Substrate is inswept against the surface of light source side, the light area of the weight concentric circles of generation five；Light in light area
Successively pass through Al2O3Substrate and nano-titanium dioxide film, shape on the surface of side is contacted with plating solution in nano-titanium dioxide film
Into the optical design of five weight concentric circles of size constancy；Laser facula persistently scans illumination 1min, in optical design covering
In the range of nano-titanium dioxide film surface occur photocatalytic redox reaction, make in the plating solution that is contacted with optical design
Copper ion is adsorbed on nano-titanium dioxide film surface by photocatalytic redox into copper simple substance, is generated consistent with design size
The nascent copper coating of five weight concentric circles, the pH value that plating solution is maintained during reaction is 12.5；Continue in the plating solution to surface system
For the Al of nascent copper coating2O3Substrate carries out self-catalysis chemical plating, and reaction temperature is 45 DEG C, the reaction time is 60min, realizes
The continuous growth of nascent copper coating in the plating solution, is finally loading the Al of nano-titanium dioxide film side2O3Substrate surface system
The standby copper coating for obtaining required thickness, high dimensional accuracy five weights concentric circles；Five heavy concentric circle diagrams by coating surface
The Al of case copper coating2O3Substrate takes out, and dries or dries up after washing, that is, completes Al2O3The heavy concentric circles copper of substrate surface five
The preparation of coating.
Embodiment 2：
It is 0.8mm, surface roughness Ra in wall thickness1One is prepared for 6nm, the even density quartzy vial inner surface of printing opacity
Thickness degree is the nitrogen-doped nanometer titanium dioxide film of 200nm and uniform-light transmission, is 20% by formula composition (mass fraction)
NiSO4·6H2O, 30%NaH2PO2·H2O, 25% complexing agent Na3C6H5O7·2H2O, 25% stabilizer C10H8N2Plating solution injection
In quartz glass bottle, in the inner surface immersion plating solution for making quartz glass bottle load nitrogen-doped nanometer titanium dioxide film, and make it
The outer surface of unsupported nitrogen-doped nanometer titanium dioxide film against wavelength be 365nm high-pressure sodium lamp light source；By rough surface
Spend Ra2The outer surface of quartz glass bottle is wrapped in for the polyimides template that 200nm, transparent area are parallel lines candy strip,
And by the transparent area in template with needing the part for preparing metal pattern to be aligned on quartz glass bottle；Light source is opened, makes light
Line is irradiated to quartz glass bottle outer surface by the transparent area in template, generates the light area of parallel lines candy strip；Light
Quartz glass bottle wall and nitrogen-doped nanometer titanium dioxide film are successively passed through according to the light in region, in nitrogen-doped nanometer titanium dioxide
Titanium film contacts the optical design for the parallel lines candy strip that size constancy is formed on the surface of side with plating solution；Illumination
Photocatalytic redox reaction occurs for 5min, the nitrogen-doped nanometer titanium dioxide film surface in optical design coverage,
The nickel ion in the plating solution contacted with optical design is set to be adsorbed by photocatalytic redox into nickel simple substance in nitrogen-doped nanometer dioxy
Change titanium film surface, generate the nascent nickel coating of the parallel lines candy strip consistent with design size, plating is maintained during reaction
The pH value of liquid is 13；Continue the quartz glass bottle progress self-catalysis chemistry that inner surface in the plating solution is prepared for nascent nickel coating
Plating, reaction temperature is 35 DEG C, the reaction time is 90min, the nascent continuous growth of nickel coating in the plating solution is realized, finally in quartz
The nickel coating of thickness, high dimensional accuracy parallel lines candy strip needed for vial inner surface is prepared；By quartzy glass
Plating solution in glass bottle is poured out, and is dried or is dried up after washing, that is, completes quartz glass bottle inner surface parallel lines candy strip nickel
The preparation of coating.
Embodiment 3：
It is 1.0mm, surface roughness Ra in thickness1Prepared for the arch printing opacity MgO substrate surfaces of 370nm, even density
A layer thickness is the Nano zinc oxide film of 260nm and uniform-light transmission, and MgO substrates are placed on and fill formula composition (quality point
Number) it is 35%AgNO3, 30%HCHO, 35%NH4On the container of OH plating solution, make MgO substrate surface supported nano zinc oxides thin
In the side immersion plating solution of film, and make the unsupported Nano zinc oxide film in its surface and do not contact the side of plating solution be against wavelength
254nm ultraviolet lamp light source；By surface roughness Ra2Placed for the arch copper mold plate that 350nm, transparent area are Chinese knot pattern
On the surface of the unsupported Nano zinc oxide film side of MgO substrates, and system will be needed on the transparent area in template and MgO substrates
The part of standby metal pattern is aligned；Light source is opened, light is irradiated to MgO substrates against light by the transparent area in template
On the surface of source side, the light area of Chinese knot pattern is generated；Light in light area successively passes through MgO substrates and nanometer
Zinc-oxide film, the light for the Chinese knot pattern that size constancy is formed on the surface of side is contacted with plating solution in Nano zinc oxide film
Learn pattern；Illumination 10min, it is anti-that photocatalytic redox occurs for the Nano zinc oxide film surface in optical design coverage
Should, the silver ion in the plating solution contacted with optical design is adsorbed thin in nano zine oxide into silver-colored simple substance by photocatalytic redox
Film surface, generates the nascent silvering of the Chinese knot pattern consistent with design size, and the pH value that plating solution is maintained during reaction is 12；
The MgO substrates for continuing in the plating solution to be prepared for surface nascent silvering carry out self-catalysis chemical plating, and reaction temperature is 40 DEG C, instead
It is 100min between seasonable, realizes the nascent continuous growth of silvering in the plating solution, finally loading Nano zinc oxide film one
The silvering of thickness, high dimensional accuracy Chinese knot pattern needed for the MgO substrate surfaces of side are prepared；By coating surface
The MgO substrates of Chinese knot pattern silvering take out, and dry or dry up after washing, that is, complete MgO substrate surface Chinese knot patterns
The preparation of silvering.
Embodiment 4：
It is 3.0mm, surface roughness Ra in wall thickness1For 50nm, the even density saturating ultraviolet light black glass of hollow ellipsoid shape
It is 170nm and the nanometer vanadic acid bismuth thin film of uniform-light transmission that glass component inner surface, which prepares a layer thickness, by formula composition (quality point
Number) it is 25%CuSO4·5H2O, 25%HO (CH2CH2O)nH (n=4~450), 30% complexing agent (C4H4KNaO6·4H2O)、
20% mixed stabilizer (C10H8N2、K4[Fe(CN)6]) plating solution injection black glass member lumens in, make component load nanometer
In the inner surface immersion plating solution of vanadic acid bismuth thin film, the work that black glass part then is positioned over into continuous laser straight-writing system is put down
On platform, and make the outer surface of its unsupported nanometer vanadic acid bismuth thin film against the LASER Light Source that wavelength is 310nm；It is straight in continuous laser
The shape data that hexagonal snowflake pattern is inputted in the control computer of system is write, and the manner of execution of workbench is set for space
Three-axis moving, sweep speed are 500mm/s；Light source is opened, makes laser facula according to the scanning pattern of setting in black glass portion
Part outer surface is inswept, generates the light area of hexagonal snowflake pattern；Light in light area successively passes through parts walls and nanometer
Vanadic acid bismuth thin film, the hexagonal snowflake pattern of formation size constancy on the surface of side is contacted with plating solution in nanometer vanadic acid bismuth thin film
Optical design；Laser facula persistently scans illumination 2min, the nanometer vanadic acid bismuth thin film surface hair in optical design coverage
Third contact of a total solar or lunar eclipse catalytic oxidation-reduction reacts, and makes copper ion in the plating solution that is contacted with optical design by photocatalytic redox into copper simple substance
Absorption generates the nascent copper coating of the hexagonal snowflake pattern consistent with design size on nanometer vanadic acid bismuth thin film surface, reacts the phase
Between maintain plating solution pH value be 12.6；Continue the black glass part progress that inner surface in the plating solution is prepared for nascent copper coating
Self-catalysis chemical plating, reaction temperature is 48 DEG C, the reaction time is 100min, realizes the nascent continuous life of copper coating in the plating solution
Long, finally the copper of thickness, high dimensional accuracy hexagonal snowflake pattern needed for black glass component inner surface is prepared is plated
Layer；Plating solution in black glass part is poured out, dries or dries up after washing, that is, complete hollow ellipsoid shape black glass part
The preparation of inner surface hexagonal snowflake pattern copper coating.
Claims (8)
1. the backlight catalysis plating preparation method of a kind of light transmissive material surface metal pattern, it is characterised in that preparation technology is：
(1) side of light transmissive material area load Nanometer Semiconductor Films is immersed in plating solution, by its unsupported Nano semiconductor
Film and the opposite side of plating solution is not contacted against the light source that wavelength is 200~460nm；
(2) open light source, by have mould control shape method or without mould control shape method in light transmissive material against on the surface of light source side
Light in generation and the consistent light area of design metal pattern geomery, the light area successively through light transmissive material with
Nanometer Semiconductor Films, contact with plating solution in Nanometer Semiconductor Films and are formed and light transmissive material surface area of illumination on the surface of side
The consistent optical design of domain geomery；
(3) photochemical catalytic oxidation occurs for 0.5~10min of illumination, the Nanometer Semiconductor Films surface in optical design coverage
Reduction reaction, makes the metal ion in the plating solution contacted with optical design received by photocatalytic redox into elemental metals absorption
Rice semiconductive thin film surface, generates the nascent coat of metal consistent with design metal pattern geomery, plating is maintained during reaction
The pH value of liquid is 7~13；
(4) continue to carry out self-catalysis chemical plating by active centre of the nascent coat of metal in the plating solution, reaction temperature is 20~70
DEG C, the reaction time be 0~180min, realize the nascent continuous growth of the coat of metal in the plating solution, finally loading nanometer half
The high-precision metal pattern of thickness and geomery needed for the light transmissive material surface of conductor thin film side is prepared；
(5) by coating surface, the light transmissive material of metal pattern takes out, and dries or dries up after washing, that is, completes light transmissive material table
The preparation of face metal pattern.
2. a kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern as claimed in claim 1, its feature exists
In the light transmissive material is inorganic non-metallic light transmissive material, macromolecule light transmissive material or composite transparent material；The light transmissive material
Density is identical everywhere；The thickness h of the light transmissive material1For 0 ＜ h1≤ 20mm, surface roughness Ra 1 are 0≤Ra1≤400nm.
3. a kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern as claimed in claim 1, its feature exists
In the Nanometer Semiconductor Films are nano-titanium dioxide film, Nano zinc oxide film, nano silicon nitride titanium film, nano V
Sour bismuth thin film, doping vario-property nano-titanium dioxide film, doping vario-property Nano zinc oxide film, doping vario-property Nano titanium nitride are thin
At least one of film, doping vario-property nanometer vanadic acid bismuth thin film；The Nanometer Semiconductor Films can be such that light source passes through and close everywhere
Degree is identical；The thickness h of the Nanometer Semiconductor Films2For 0 ＜ h2≤900nm。
4. a kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern as claimed in claim 1, its feature exists
In the light source is at least one of linear light sorurce, non-linear light source.
5. a kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern as claimed in claim 1, its feature exists
In described to there is mould control shape method to be identical with design metal pattern by geomery by being placed between light source and light transmissive material
Transparent area and the template that constitutes of light tight area's two parts come the method that controls light area geomery；The template is by gold
At least one of category material, inorganic non-metallic material, high polymer material or composite are made；The template surface roughness
Ra2For 0≤Ra2≤20μm。
6. a kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern as claimed in claim 1, its feature exists
In described is to control light area shape chi by laser direct writing system regulation laser facula scanning area without mould control shape method
Very little method；The laser direct writing system is continuous laser straight-writing system or pulse laser straight-writing system, and laser scanning speed is small
In 3000mm/s；The laser frequency of the pulse laser straight-writing system is more than 1KHz.
7. a kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern as claimed in claim 1, its feature exists
In the formula composition (mass percent) of, the plating solution be metal salt 10~40%, reducing agent 20~35%, complexing agent 25~
45%th, stabilizer 0~30%；Wherein, the metal salt be gold salt, silver salt, mantoquita, nickel salt, pink salt, palladium salt, aluminium salt, molysite,
Cobalt salt, zinc salt, chromic salts, molybdenum salt, platinum salt, tungsten salt or rare-earth salts, the reducing agent are NaH2PO2·H2O、HCHO、HOCCOOH、
NaBH4Or HO (CH2CH2O)nH (n=4~450), the complexing agent is C4H4KNaO6·4H2O、C10H14N2Na2O8·2H2O or
Na3C6H5O7·2H2O, the stabilizer is C10H8N2Or K4[Fe(CN)6]。
8. a kind of backlight catalysis plating preparation method of light transmissive material surface metal pattern as claimed in claim 1, its feature exists
In the metal is at least one in gold, silver, copper, nickel, tin, palladium, aluminium, iron, cobalt, zinc, chromium, molybdenum, platinum, tungsten, rare earth and its alloy
Kind.
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