CN105671525A - Method for manufacturing patterned metal film based on poly-dopamine and product thereof - Google Patents
Method for manufacturing patterned metal film based on poly-dopamine and product thereof Download PDFInfo
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- CN105671525A CN105671525A CN201610058283.4A CN201610058283A CN105671525A CN 105671525 A CN105671525 A CN 105671525A CN 201610058283 A CN201610058283 A CN 201610058283A CN 105671525 A CN105671525 A CN 105671525A
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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
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
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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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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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
The invention discloses a method for manufacturing a patterned metal film based on poly-dopamine and a product thereof. The manufacture method comprises the steps that first, a clean substrate is dipped in a dopamine solution with the pH value of 6-9 and the concentration of 0.1-10 mg/ml till a poly-dopamine film is formed on the surface of the substrate; the substrate is taken out, is washed with water and then is blow-dried with nitrogen, so that the substrate adhered with the poly-dopamine film is obtained; then a photomask is placed on the substrate adhered with the poly-dopamine, and then the substrate is radiated for 3-15 minutes in the ultraviolet light with the intensity of 10-35 mw/cm<2>, is cleaned with double distilled water, and is blow-dried with nitrogen, so that a substrate with an ultraviolet oxidized poly-dopamine is obtained; and finally metal ions are deposited on the substrate with the ultraviolet oxidized poly-dopamine. The method disclosed by the invention is applicable to any solid materials which can be both planar substrates and curved or porous surface substrates, and different pattered metal films can be manufactured; and the manufactured patterned metal films can be applied to microcircuits, microarrays and bioinstrumentation.
Description
Technical field
The invention belongs to electrical equipment field, a kind of method being specifically related to preparation pattern metal thin film based on poly-dopamine, further relate to pattern metal thin film obtained by this method.
Background technology
Patterning metallic film in various novel portable electronic devices as electrode, contact or connecting line important role. Conventional microelectronic industry generally adopt photoetching and magnetic control sputtering prepare the metallic film of patterning, this method precision is high, but costly, the cycle is tediously long, and need main equipment support, more crucially this method is only suitable for and a few inorganic hard matrix material such as silicon chip, glass, quartz etc.; Another conventional method is based on the technology of printing, but this kind of technology is also required to the surface of matrix is processed, to ensure to print adhesive strength and the stability of metal and matrix, many times also need to the matrix after printing is heated the post processings such as annealing, electronation, illumination, to improve the electric conductivity of adhesive strength and metallic film.
Therefore a kind of method being badly in need of pervasive, general preparation pattern metal thin film, it is adaptable to arbitrarily solid material surface, and different pattern metal can be prepared, such as gold, silver, copper etc.
Summary of the invention
In view of this, a kind of method that an object of the present invention is in that to provide preparation pattern metal thin film based on poly-dopamine; The two of the purpose of the present invention are in that to provide the pattern metal thin film prepared by said method.
For achieving the above object, the present invention provides following technical scheme:
1, a kind of method of preparation pattern metal thin film based on poly-dopamine, its principle schematic is as it is shown in figure 1, specifically comprise the following steps that
(1) preparation of poly-dopamine film: clean substrate is immersed in pH6～9, concentration be 0.1～10mg/mL dopamine solution in form poly-dopamine film to substrate surface, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 10～35mw/cm at ultraviolet light intensity2Irradiating 3～15 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: by metal ions in the substrate of poly-for Ultraviolet Oxidation dopamine, obtain pattern metal thin film.
In the present invention, substrate can be planar substrates, it is also possible to for curved surface or porous area substrate, material can be any material, such as microscope slide, polyester flake, silicon chip, polypropylene foil, leaves or polydimethylsiloxane. Therefore, the present invention is a kind of method of pervasive, general preparation pattern metal thin film.
Preferably, step (1) be clean substrate is immersed in pH6～9, concentration be 0.1～10mg/mL dopamine solution in 10～30 minutes, after taking out the flushing of use water, the dopamine solution that pH6～9, concentration are 0.1～10mg/mL repeats leaching several times, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film.
Preferably, step (1) be clean substrate is immersed in pH 8.5, dopamine concentration be 1～2mg/mL solution in 7 hours, rinse with water after taking-up, nitrogen dries up, and must have the substrate of poly-dopamine film. It is furthermore preferred that dopamine concentration is 2mg/mL, the trishydroxymethylaminomethane of conventional pH=8.5-hydrochloric acid buffer solution preparation.
Preferably, in step (3), the metal ion of described deposition is gold ion, silver ion or copper ion.
It is furthermore preferred that the method for deposition gold ion is that the substrate of poly-for Ultraviolet Oxidation dopamine is inserted 0.01%HAuCl4In the solution that solution mixes with 0.4mM hydroxylamine hydrochloride solution equal-volume, reacting 3～30 minutes at 18～25 DEG C, taking-up distilled water cleans, and nitrogen dries up.
Preferred, it is dropping ammonia in 10mM silver nitrate solution that deposition closes the method for silver ion, solution becomes light brown, continue dropping ammonia until solution becomes colorless, then isopyknic 3.33mM glucose solution is added to this system, the substrate of poly-for Ultraviolet Oxidation dopamine being inserted and react 2～10min in mixed solution at 18～25 DEG C, taking-up distilled water cleans, and nitrogen dries up.
It is furthermore preferred that the method for deposition copper ion is: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
2, the pattern metal thin film prepared by described method, it is preferred that described metal is gold, silver or copper.
The beneficial effects of the present invention is: a kind of method that the invention discloses preparation pattern metal thin film based on poly-dopamine, using poly-dopamine as intermediate layer in preparation process, utilize the poly-dopamine can chelating many kinds of metal ions, metal ion is made to deposit at poly-dopamine place, it is achieved that various metals is at the patterning of multiple substrate. Utilize ultraviolet luminous energy Oxidative demage to gather dopamine so that it is to lose the ability of chelated metal ions, realize the patterning of metal under the auxiliary of photomask simultaneously. Owing to poly-dopamine has very strong adsorptivity on all solids surface, such that it is able to realize the metal growth at nearly all surface of solids, this method is not limited to plane, it is also possible to carry out on curved surface and porous area, is expected in microcircuit, microarray and biological detection and is applied.
Accompanying drawing explanation
In order to make the purpose of the present invention, technical scheme and beneficial effect clearly, the present invention provides drawings described below:
Fig. 1 is the pattern metal film preparation principle schematic based on poly-dopamine.
Fig. 2 is the Raman spectrum of poly-dopamine before and after ultraviolet lighting, and wherein the disappearance of the characteristic peak of the poly-dopamine film near 1600 wave numbers demonstrates the oxidation of poly-dopamine.
Fig. 3 is the X ray diffracting spectrum after gathering dopamine and deposition copper before and after ultraviolet lighting.
Fig. 4 is the optical photograph (A: terylene (poly-(ethylene glycol terephthalate), poly (ethyleneterephthalate)) of patterned copper thin film; B: polypropylene; C: silicon chip; D: glass; E: polydimethylsiloxane (PDMS); F: ultrafilter membrane; G: leaves).
Fig. 5 be with silicon chip be substrate the different amplification electron scanning micrograph of patterned copper thin film and the copper image of X-gamma ray spectrometer (A, C, D are different amplification electron scanning micrograph; B is the copper image of X-gamma ray spectrometer).
Fig. 6 is slide be matrix patterning Ag films optical photograph.
Fig. 7 is silicon chip is that (A, C, D are different amplification electron scanning micrograph for the silver element image of the patterning different amplification electron scanning micrograph of Ag films of matrix and X-gamma ray spectrometer; B is the silver element image of X-gamma ray spectrometer).
Fig. 8 is the X ray diffracting spectrum after gathering dopamine and deposition silver before and after ultraviolet lighting.
Fig. 9 is that (A, C, D are different amplification electron scanning micrograph for the gold element image of the different amplification electron scanning micrograph of patterned gold thin film and X-gamma ray spectrometer; B is the gold element image of X-gamma ray spectrometer).
Figure 10 is the X ray diffracting spectrum after gathering dopamine and deposition gold before and after ultraviolet lighting.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail. The experimental technique of unreceipted actual conditions in embodiment, generally conventionally condition or according to manufacturer it is proposed that condition.
Embodiment 1, a kind of preparation pattern metal thin film based on poly-dopamine method
A kind of method of preparation pattern metal thin film based on poly-dopamine, comprises the steps:
(1) preparation of poly-dopamine film: clean substrate is immersed in the pH8.5 of new preparation, concentration be 2mg/mL dopamine solution in form poly-dopamine film to substrate surface, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 20mw/cm at ultraviolet light intensity2Irradiating 10 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: by metal ions in the substrate of poly-for Ultraviolet Oxidation dopamine, obtain pattern metal thin film.
For proving the oxidable poly-dopamine of ultraviolet lighting, the Raman spectrum before and after the substrate ultraviolet lighting of the poly-dopamine film of detection, result is as shown in Figure 2. Result shows, the disappearance of the characteristic peak of poly-dopamine film near 1600 wave numbers after ultra-vioket radiation, it was shown that poly-dopamine is by oxidized after ultraviolet lighting.
Embodiment 2, a kind of preparation patterned copper thin film based on poly-dopamine method
With terylene, (poly-(ethylene glycol terephthalate) prepares patterned copper thin film for substrate, specifically comprises the following steps that
(1) preparation of poly-dopamine film: clean terylene is immersed in the pH6 of brand-new, concentration be 0.1mg/mL dopamine solution in 10 minutes, after taking out the flushing of use water, the dopamine solution that pH6, concentration are 0.1mg/mL repeats submergence 20 times, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 10mw/cm at ultraviolet light intensity2Irradiating 15 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
Prepare patterned copper thin film with polypropylene for substrate, specifically comprise the following steps that
(1) preparation of poly-dopamine film: clean polypropylene is immersed in the pH7 of new preparation, concentration be 1mg/mL dopamine solution in 12 minutes, after taking out the flushing of use water, the dopamine solution that pH7, concentration are 1mg/mL repeats submergence 18 times, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 15mw/cm at ultraviolet light intensity2Irradiating 12 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
Prepare patterned copper thin film with silicon chip for substrate, specifically comprise the following steps that
(1) preparation of poly-dopamine film: clean silicon chip is immersed in the pH8.5 of new preparation, concentration be 2mg/mL dopamine solution in 20 minutes, after taking out the flushing of use water, the dopamine solution that pH8.5, concentration are 2mg/mL repeats submergence 10 times, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 35mw/cm at ultraviolet light intensity2Irradiating 3 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
Prepare patterned copper thin film with glass for substrate, specifically comprise the following steps that
(1) preparation of poly-dopamine film: clean glass is immersed in the pH9 of new preparation, concentration be 10mg/mL dopamine solution in 30 minutes, after taking out the flushing of use water, the dopamine solution that pH9, concentration are 10mg/mL repeats submergence 5 times, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 20mw/cm at ultraviolet light intensity2Irradiating 8 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
Prepare patterned copper thin film with polydimethylsiloxane (PDMS) for substrate, specifically comprise the following steps that
(1) preparation of poly-dopamine film: clean polydimethylsiloxane is immersed in the pH8 of new preparation, concentration be 5mg/mL dopamine solution in 25 minutes, after taking out the flushing of use water, the dopamine solution that pH8, concentration are 5mg/mL repeats submergence 8 times, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 30mw/cm at ultraviolet light intensity2Irradiating 5 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
Prepare patterned copper thin film with ultrafilter membrane for substrate, specifically comprise the following steps that
(1) preparation of poly-dopamine film: clean ultrafilter membrane is immersed in the pH6.5 of new preparation, concentration be 1.5mg/mL dopamine solution in 30 minutes, after taking out the flushing of use water, the dopamine solution that pH6.5, concentration are 1.5mg/mL repeats submergence 12 times, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 25mw/cm at ultraviolet light intensity2Irradiating 8 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
Prepare patterned copper thin film with leaves for substrate, specifically comprise the following steps that
(1) preparation of poly-dopamine film: clean leaves is immersed in the pH8.5 of new preparation, concentration be 2mg/mL dopamine solution in 7 hours, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 15mw/cm at ultraviolet light intensity2Irradiating 15 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
X ray detection being utilized with leaves with the poly-substrate of dopamine film, the poly-dopamine of Ultraviolet Oxidation and metal pattern for patterned copper thin film prepared by substrate, result is as shown in Figure 3. Result shows, before and after Ultraviolet Oxidation and copper deposition front and back X ray collection of illustrative plates there are differences, it was shown that ultraviolet light can aoxidize poly-dopamine film, can form patterned copper thin film in the substrate that the poly-dopamine of Ultraviolet Oxidation processes.
Fig. 4 is the optical photograph that different base prepares patterned copper thin film, wherein A with terylene (poly-(ethylene glycol terephthalate), poly (ethyleneterephthalate)) for substrate; B is with polypropylene for substrate; C is with silicon chip for substrate; D is with glass for substrate; E is with polydimethylsiloxane (PDMS) for substrate; F is with ultrafilter membrane for substrate; G is with leaves for substrate.
By be substrate with silicon chip patterned copper thin film be scanned electron microscopic observation, result is as shown in Figure 5. Result shows, metallic copper deposits at poly-dopamine film place, and has no deposition at the poly-dopamine place through Ultraviolet Oxidation, it was shown that the method for the present invention can prepare patterned copper thin film.
Embodiment 3
A kind of method of preparation patterning Ag films based on poly-dopamine, comprises the steps:
(1) preparation of poly-dopamine film: clean microscope slide is immersed in the pH of new preparation 8.5, dopamine concentration be 2mg/mL solution in 7 hours, rinse with distilled water after taking-up, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: placing a photomask by having in the substrate of poly-dopamine film, ultraviolet light intensity is 35mw/cm2Irradiating 15 minutes under condition, then clean with distilled water, nitrogen dries up;
(3) metal pattern: drip ammonia in 10mM silver nitrate solution, solution becomes light brown, continue dropping ammonia until solution becomes colorless, then isopyknic 3.33mM glucose solution is added to this system, the substrate of Ultraviolet Oxidation is inserted mixed solution reacts under room temperature (18～25 DEG C) 2～10min, cleaning with distilled water after taking-up, nitrogen dries up.
The patterning Ag films optical photograph that the present embodiment prepares is as shown in Figure 6. Result shows, adopts the method for the present embodiment to be successfully obtained patterning Ag films.
According to above-mentioned identical method with silicon chip for substrate preparation patterning Ag films, then will be patterned into Ag films sem observation, electron scanning micrograph is as shown in Figure 7. Result display argent deposits at poly-dopamine film place, and has no deposition of silver at the poly-dopamine place through Ultraviolet Oxidation, it was shown that the method for the present invention can prepare patterning Ag films.
Fig. 8 is that patterning Ag films utilizes X ray detection with the poly-substrate of dopamine film, the poly-dopamine of Ultraviolet Oxidation and silver patterned film, and result is as shown in Figure 8. As shown in Figure 8, X ray collection of illustrative plates there are differences before and after Ultraviolet Oxidation and before and after deposition of silver, it was shown that ultraviolet light can aoxidize poly-dopamine film, and the substrate processed through the poly-dopamine of Ultraviolet Oxidation can form patterning Ag films.
Embodiment 4
A kind of method of preparation patterned gold thin film based on poly-dopamine, comprises the steps:
(1) preparation of poly-dopamine film: clean microscope slide is immersed in the pH of new preparation 8.5, dopamine concentration be 2mg/mL solution in 7 hours, rinse with distilled water after taking-up, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: placing a photomask by having in the substrate of poly-dopamine film, ultraviolet light intensity is 35mw/cm2Irradiating 15 minutes under condition, then clean with distilled water, nitrogen dries up;
(3) metal pattern: by 0.01%HAuCl4Solution mixes with 0.4mM hydroxylamine hydrochloride solution equal-volume, the substrate of Ultraviolet Oxidation is inserted in mixed solution, reacts 3～30 minutes under room temperature (18～25 DEG C), cleans with distilled water after taking-up, and nitrogen dries up.
Then will be patterned into gold thin film sem observation, electron scanning micrograph is as shown in Figure 9. Result display Aurum metallicum deposits at poly-dopamine film place, and has no gold deposition at the poly-dopamine place through Ultraviolet Oxidation, it was shown that the method for the present invention can prepare patterned gold thin film.
Figure 10 is that patterning Ag films utilizes X ray detection with the poly-substrate of dopamine film, the poly-dopamine of Ultraviolet Oxidation and gold patterned film, and result is as shown in Figure 10. As shown in Figure 10, X ray collection of illustrative plates there are differences before and after Ultraviolet Oxidation and before and after deposition of silver, it was shown that ultraviolet light can aoxidize poly-dopamine film, and the substrate surface processed through the poly-dopamine of Ultraviolet Oxidation can form patterned gold thin film.
The method of the present invention is except pattern metal thin film in above-mentioned substrate, it is also possible to showing growth at other solids, substrate can be planar structure, it is also possible to for curved surface or porous area. The pattern metal thin film prepared is expected in microcircuit, microarray and biological detection to be applied.
What finally illustrate is, preferred embodiment above is only in order to illustrate technical scheme and unrestricted, although the present invention being described in detail by above preferred embodiment, but skilled artisan would appreciate that, in the form and details it can be made various change, without departing from claims of the present invention limited range.
Claims (10)
1. the method based on the preparation pattern metal thin film of poly-dopamine, it is characterised in that comprise the steps:
(1) preparation of poly-dopamine film: clean substrate is immersed in pH6～9, concentration be 0.1～10mg/mL dopamine solution in form poly-dopamine film to substrate surface, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film;
(2) the poly-dopamine of Ultraviolet Oxidation: will place photomask in the substrate with poly-dopamine film of step (1) gained, is then 10～35mw/cm at ultraviolet light intensity2Irradiating 3～15 minutes under condition, then clean with distilled water, nitrogen dries up, and obtains the substrate of the poly-dopamine of Ultraviolet Oxidation;
(3) metal pattern: by metal ions in the substrate of poly-for Ultraviolet Oxidation dopamine, obtain pattern metal thin film.
2. the method for a kind of preparation pattern metal thin film based on poly-dopamine according to claim 1, it is characterised in that: in step (1), described substrate is microscope slide, polyester flake, silicon chip, polypropylene foil, leaves or polydimethylsiloxane.
3. the method for a kind of preparation pattern metal thin film based on poly-dopamine according to claim 1, it is characterized in that: step (1) be clean substrate is immersed in pH6～9, concentration be 0.1～10mg/mL dopamine solution in 10～30 minutes, after taking out the flushing of use water, the dopamine solution that pH6～9, concentration are 0.1～10mg/mL repeats submergence several times, after taking-up water rinses, nitrogen dries up, and must have the substrate of poly-dopamine film.
4. the method for a kind of preparation pattern metal thin film based on poly-dopamine according to claim 1, it is characterized in that: step (1) be clean substrate is immersed in pH 8.5, dopamine concentration be 1～2mg/mL solution in 7 hours, rinse with water after taking-up, nitrogen dries up, and must have the substrate of poly-dopamine film.
5. the method for a kind of preparation pattern metal thin film based on poly-dopamine according to claim 1, it is characterised in that: in step (3), the metal ion of described deposition is gold ion, silver ion or copper ion.
6. the method for a kind of preparation pattern metal thin film based on poly-dopamine according to claim 5, it is characterised in that: the method for deposition gold ion is that the substrate of poly-for Ultraviolet Oxidation dopamine is inserted 0.01%HAuCl4In the solution that solution mixes with 0.4mM hydroxylamine hydrochloride solution equal-volume, reacting 3～30 minutes at 18～25 DEG C, taking-up distilled water cleans, and nitrogen dries up.
7. the method for a kind of preparation pattern metal thin film based on poly-dopamine according to claim 5, it is characterized in that: the method for deposition silver ion for dripping ammonia in 10mM silver nitrate solution, solution becomes light brown, continue dropping ammonia until solution becomes colorless, then isopyknic 3.33mM glucose solution is added to this system, the substrate of poly-for Ultraviolet Oxidation dopamine being inserted and react 2～10min in mixed solution at 18～25 DEG C, taking-up distilled water cleans, and nitrogen dries up.
8. the method for a kind of preparation pattern metal thin film based on poly-dopamine according to claim 5, it is characterised in that: the method for deposition copper ion is: preparation is containing 50mMEDTA, 50mMCuCl2And 0.1MH3BO3Solution, regulate pH be 7, the dimethyamine borane solution that concentration is 0.1M adding volume obtains mixed solution, the substrate of Ultraviolet Oxidation being inserted in mixed solution, 40 DEG C of logical nitrogen react 2 hours, clean with distilled water after taking-up, nitrogen dries up, and obtains copper patterning thin film.
9. the pattern metal thin film that method described in any one of claim 1～8 prepares.
10. the pattern metal thin film described in claim 9, it is characterised in that: described metal is gold, silver or copper.
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