CN111337471A - Preparation method of SERS substrate based on nanoimprint and electrochemical deposition technology - Google Patents
Preparation method of SERS substrate based on nanoimprint and electrochemical deposition technology Download PDFInfo
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Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
Abstract
The invention discloses a preparation method of an SERS substrate based on nanoimprint and electrochemical deposition technologies, which comprises the following steps: (1) preparing a porous nano-imprinting template through electron beam exposure; (2) transferring the porous nano-imprinting template graph to imprinting glue through nano-imprinting, and curing and demolding; (3) removing residual glue and etching to transfer the pattern of the porous nano-imprint template; (4) removing the imprinting glue to obtain a uniform nano structure on the substrate; (5) preparing a molybdenum film and a gold film on the obtained nanostructure through magnetron sputtering, and increasing the conductivity of the sample; (6) gold nanoparticles were prepared on the resulting substrate by electrochemical deposition. The SERS substrate prepared by the method can be prepared in a large area, and has the advantages of good repeatability, high enhancement factor, uniform and controllable structure and low cost.
Description
Technical Field
The invention relates to the field of optical devices, in particular to a preparation method of an SERS substrate based on nanoimprint and electrochemical deposition technologies.
Background
The analysis and detection of trace substances in a complex system is an important component in applied chemistry, the Surface Enhanced Raman Spectroscopy (SERS) has various advantages in this respect, and the Surface Plasmon Resonance (SPR) can enhance the Raman signal of molecules in a local optical electric field, so that the method has the advantages of high sensitivity, strong specificity, wide application range, simple operation and the like, is widely applied to key scientific fields of life, medicine, chemistry, environment, food safety and the like, and is a high-efficiency analysis and detection technology with great application prospect.
For SERS, it is most important to develop an effective enhancing substrate based on metal nanostructures. At present, silver (Ag) and gold (Au) nanostructure ordered arrays and colloidal particle solutions thereof are widely used, and a sol substrate is easy to oxidize and agglomerate, so that Raman signals are uneven and poor in repeatability. A number of studies have explored the preparation of solid substrates with high sensitivity, good uniformity, and good reproducibility. Patent 201910620837.9 discloses inducing self-assembly of nano-metal particles on a stretchable polymeric film to form nano-metal chains as a SERS substrate, which is low in cost but poor in reproducibility. Patent 201910718767.0 discloses a highly sensitive SERS substrate, which is prepared by preparing a nanopillar array by wet etching and combining with MOF for surface modification, but the prepared nanopillar array has poor orderliness and the repeatability of the SERS substrate is not high. Patent 201610929950.1 fills the AAO template with noble metal nanoparticle clusters, transfers the nanoparticles to PMMA after being inverted on the PMMA, and dries to obtain the SERS substrate with regular distribution, but the method has complex transfer and cleaning operations, is difficult to realize large-area preparation, and has high cost. Patent 201210543908.8 discloses a method for preparing a large-area SERS substrate, which uses an advanced femtosecond laser to prepare a hard microstructure master, and uses sputtering and other methods to prepare a gold film, but the effect of enhancing signals is still to be verified compared with gold nanoparticles.
Therefore, the SERS substrate with high sensitivity, good uniformity, good repeatability and low cost has important significance.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide the preparation method of the SERS substrate based on the nanoimprint and electrochemical deposition technology, which has the advantages of large-area preparation, good repeatability, high enhancement factor, uniform and controllable structure and low cost.
The technical scheme of the invention is as follows:
a preparation method of the SERS substrate based on the nano-imprinting and electrochemical deposition technology is characterized by comprising the following steps:
(1) preparing a porous nano-imprinting template through electron beam exposure;
(2) uniformly spin-coating the imprinting glue on a substrate, transferring the porous nano-imprinting template pattern onto the imprinting glue through nano-imprinting, and curing and demolding;
(3) removing residual glue and etching to transfer the porous nano-imprint template pattern to obtain a nano structure;
(4) removing the imprinting glue to obtain a uniform nano structure on the substrate;
(5) preparing a molybdenum film and a gold film on the obtained nanostructure by magnetron sputtering equipment, introducing argon gas and using a direct current power supply or a radio frequency power supply, and increasing the conductivity of the sample;
(6) preparing the nano gold particles on the obtained substrate through electrochemical deposition to obtain the SERS substrate.
The method according to the above, wherein the material of the porous nano-imprint template in step (1) is quartz, nickel plate or PDMS.
According to the method, before nano imprinting, the substrate is cleaned by ethanol and acetone in the step (2), wherein the substrate is made of a silicon wafer or glass; spin-coating the nano-imprint glue on the surface of the substrate by using a spin coating instrument, then obtaining a porous nano-imprint template graph by adopting a nano-imprint technology, placing the porous nano-imprint template graph in an exposure device, curing the porous nano-imprint template graph, and then demolding; the demolding method is mechanical demolding.
The method according to the above, characterized in that the etching in step (3) is made by wet etching or dry etching; the dry etching conditions were: the etching gas is Cl2And HBr, Cl2HBr gas flow rate is 60 sccm-120 sccm and 10 sccm-60 sccm respectively, pressure is 200 mTorr-400 mTorr, power is 250W-500W, and etching time is 10 s-180 s; the wet etching conditions are as follows: preparing hydrofluoric acid base corrosive liquid with a volume ratio of 1: 2-2: 1 by using hydrofluoric acid and nitrate solution, wherein the concentration of the hydrofluoric acid is 2 mmol-5 mmol, the etching time is 10 min-5 h, and stirring to keep the concentration consistent.
The method according to the above, characterized in that the conditions of magnetron sputtering in step (5) are: the sputtering pressure is 1Pa to 2Pa, the sputtering power is 40W to 80W, the argon gas flow is 10sccm to 30sccm, the sputtering rate is 0.3nm/s to 0.5nm/s, the bias voltage is 80V to 100V, and molybdenum with the thickness of 5nm to 10nm and gold with the thickness of 20nm to 30nm are subjected to magnetron sputtering; the molybdenum film is an adhesion layer, and the gold film is a seed layer.
The method is characterized in that in the step (6), the substrate to be deposited is placed in an electrolyte, and the electrolyte is 10mmol to 50mmol of chloroauric acid prepared by using concentrated sulfuric acid or PBS buffer solution as a solvent; the gold nanoparticles were deposited using cyclic voltammetry under the following conditions: the SERS substrate is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the potential is-0.2V-0.6V, the pulse is 50 mV/s-100 mV/s, the number of scanning cycles is 15-30, and nano gold particles are formed on the nano structure through a cyclic voltammetry, wherein the distance between the nano gold particles is 10 nm-50 nm, and the size is 10 nm-30 nm.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) after mechanical stripping by adopting the method, the nano-imprint template can be repeatedly used, so that the substrate has uniform and controllable structure, good repeatability and low cost, and is suitable for large-scale production.
(2) The introduction of the electrodeposition technology can prepare the nano metal particles with different intervals and sizes by process regulation, so that the substrate sensitivity is improved, the signal enhancement is controllable, and the repeatability is improved.
Drawings
FIG. 1 is a schematic view of a porous nano-imprinting stamp according to the present invention;
FIG. 2 is a schematic view of a nanoimprint process of the present invention, wherein (a) is a schematic view before imprinting, (b) is a schematic view before imprinting, (c) is a schematic view after demolding, and (d) is a schematic view of removing residual glue;
FIG. 3 is a schematic diagram of the use of etching to form nanostructures in accordance with the present invention;
FIG. 4 is a schematic diagram of the present invention illustrating the preparation of gold nanoparticles by electrodeposition on nanostructures;
FIG. 5 is an SEM image of the preparation of gold nanoparticles using electrodeposition on a Si wafer sputtered with 20nm Au according to example 1.
Detailed Description
Referring to fig. 1 to 4, a method for preparing a SERS substrate based on nanoimprint and electrochemical deposition technology according to the present invention includes the following steps: (1) preparing a porous nano-imprinting template through electron beam exposure; the porous nano-imprint template is made of quartz, a nickel plate or PDMS. (2) Uniformly spin-coating the imprinting glue on a substrate, transferring the porous nano-imprinting template pattern onto the imprinting glue through nano-imprinting, and curing and demolding; before nano imprinting, cleaning a substrate by using ethanol and acetone, wherein the substrate is made of a silicon wafer or glass material; spin-coating the nano-imprint glue on the surface of the substrate by using a spin coating instrument, then obtaining a porous nano-imprint template graph by adopting a nano-imprint technology, placing the porous nano-imprint template graph in an exposure device, curing the porous nano-imprint template graph, and then demolding; the demolding method is mechanical demolding. (3) Removing residual glue and etching to transfer the porous nano-imprint template pattern to obtain a nano structure; the etching is made by wet etching or dry etching; the dry etching conditions were: the etching gas is Cl2And HBr, Cl2HBr gas flow rate of 60 sccm-120 sccm and 10 sccm-60 sccm, respectively, and pressure of 200mTorr @400mTorr, 250-500W power and 10-180 s etching time; the wet etching conditions are as follows: preparing hydrofluoric acid base corrosive liquid with a volume ratio of 1: 2-2: 1 by using hydrofluoric acid and nitrate solution, wherein the concentration of the hydrofluoric acid is 2 mmol-5 mmol, the etching time is 10 min-5 h, and stirring to keep the concentration consistent. (4) And removing the imprinting glue to obtain a uniform nano structure on the substrate. (5) Preparing a molybdenum film and a gold film on the obtained nanostructure by magnetron sputtering equipment, introducing argon gas and using a direct current power supply or a radio frequency power supply, and increasing the conductivity of the sample; the magnetron sputtering conditions are as follows: the sputtering pressure is 1Pa to 2Pa, the sputtering power is 40W to 80W, the argon gas flow is 10sccm to 30sccm, the sputtering rate is 0.3nm/s to 0.5nm/s, the bias voltage is 80V to 100V, and molybdenum with the thickness of 5nm to 10nm and gold with the thickness of 20nm to 30nm are subjected to magnetron sputtering; the molybdenum film is an adhesion layer, and the gold film is a seed layer. (6) Preparing the nano gold particles on the obtained substrate through electrochemical deposition to obtain the SERS substrate. Placing a substrate to be deposited in electrolyte, wherein the electrolyte is 10-50 mmol of chloroauric acid prepared by using concentrated sulfuric acid or PBS buffer solution as a solvent; the gold nanoparticles were deposited using cyclic voltammetry under the following conditions: the SERS substrate is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the potential is-0.2V-0.6V, the pulse is 50 mV/s-100 mV/s, the number of scanning cycles is 15-30, and nano gold particles are formed on the nano structure through a cyclic voltammetry, wherein the distance between the nano gold particles is 10 nm-50 nm, and the size is 10 nm-30 nm.
The present invention will be described in detail with reference to the following examples, which are merely preferred embodiments of the present invention. Based on the embodiments of the present invention, the technical solutions obtained by those skilled in the art without creative efforts will fall within the protection scope of the present invention.
Example 1
(1) And preparing a porous nano imprinting template through electron beam exposure, wherein the template is made of quartz. The aperture of the nano-imprint template is 200nm, and the hole spacing is 200 nm.
(2) And uniformly spin-coating the imprinting glue on the substrate, transferring the template graph to the imprinting glue through nano imprinting, and curing and demolding. Before nano-imprinting, the substrate is cleaned by ethanol and acetone, and is a silicon wafer. The thickness of the imprinting glue is 50nm, the nano imprinting glue is coated on the surface of the substrate in a spin coating mode through a spin coating instrument, then a pattern is obtained through an ultraviolet imprinting technology, a sample is placed in an exposure device to be solidified, and then mechanical demolding is conducted.
(3) And removing the line glue through a plasma glue removing machine, and etching the residual layer by controlling the gas flow and the radio frequency voltage etched by the plasma to obtain the nano structure. The etching gas is Cl2And HBr, Cl2And HBr gas flow at 100sccm and 50sccm, respectively, at a pressure of 200mTorr, at a power of 300W, and for an etch time of 100 s.
(4) And removing the residual imprinting glue to obtain a uniform nano structure on the substrate.
(5) And preparing a molybdenum film and a gold film on the obtained nano structure by magnetron sputtering equipment, introducing argon and using a direct current power supply. The sputtering conditions of the molybdenum film are as follows: sputtering 5nm of molybdenum under the sputtering condition of the molybdenum film under the sputtering pressure of 1Pa, the power of 80W, the flow rate of argon gas of 20sccm, the sputtering rate of 25nm/min and the bias of 80V. The sputtering conditions of the gold thin film were: sputtering under the sputtering condition of the gold thin film, gold of 20nm was sputtered under the sputtering pressure of 1Pa, the power of 60W, Ar, the gas flow rate of 30sccm, the sputtering rate of 20nm/min, and the bias of 100V.
(6) Gold nanoparticles were prepared on the resulting substrate by electrochemical deposition. Placing a substrate to be deposited in electrolyte, wherein the electrolyte is 10mmol of chloroauric acid prepared by using concentrated sulfuric acid as a solvent; and depositing the nano-gold particles by using a cyclic voltammetry through an electrochemical workstation, wherein the SERS substrate is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, the potential is-0.2V-0.6V, the pulse is 50mV/s, the number of scanning cycles is 15, and the nano-gold particles are formed on the nano-structure by using the cyclic voltammetry.
Fig. 5 shows an SEM image of the gold nanoparticles prepared using electrodeposition on a sputtered Si sheet of 20nm thickness Au.
Example 2
(1) And preparing a porous nano imprinting template through electron beam exposure, wherein the template is made of quartz. The aperture of the nano-imprint template is 200nm, and the hole spacing is 200 nm.
(2) And uniformly spin-coating the imprinting glue on the substrate, transferring the template graph to the imprinting glue through nano imprinting, and curing and demolding. Before nano-imprinting, the substrate is cleaned by ethanol and acetone, and the substrate is glass. The thickness of the imprinting glue is 150nm, the nano imprinting glue is coated on the surface of the substrate in a spin coating mode through a spin coating instrument, then a pattern is obtained through an ultraviolet imprinting technology, a sample is placed in an exposure device to be solidified, and then mechanical demolding is conducted.
(3) And removing the residual layer by using a plasma photoresist remover and etching by using an HF wet method to obtain the nano structure.
(4) And removing the residual imprinting glue to obtain a uniform nano structure on the substrate.
(5) And preparing a molybdenum film and a gold film on the obtained nano structure by magnetron sputtering equipment, introducing argon and using a direct current power supply. The sputtering conditions of the molybdenum film are as follows: the sputtering pressure was 1Pa, the power was 80W, Ar, the gas flow rate was 20sccm, the sputtering rate was 25nm/min, and the bias was 80V, and 5nm of molybdenum was sputtered under the sputtering conditions for the molybdenum thin film described above. The sputtering conditions of the gold thin film were: sputtering under the sputtering condition of the gold thin film, under a sputtering pressure of 1Pa, a power of 60W, an argon gas flow of 30sccm, a sputtering rate of 20nm/min, and a bias of 100V, 20nm of gold was sputtered.
(6) Gold nanoparticles were prepared on the resulting substrate by electrochemical deposition. Placing a substrate to be deposited in electrolyte, wherein the electrolyte is 10mmol of chloroauric acid prepared by using concentrated sulfuric acid as a solvent; and depositing the nano-gold particles by using a cyclic voltammetry through an electrochemical workstation, wherein the SERS substrate is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, the potential is-0.2V-0.6V, the pulse is 50mV/s, and the number of scanning turns is 30, and the nano-gold particles are formed on the nano-structure by using the cyclic voltammetry.
Claims (6)
1. A preparation method of the SERS substrate based on the nano-imprinting and electrochemical deposition technology is characterized by comprising the following steps:
(1) preparing a porous nano-imprinting template through electron beam exposure;
(2) uniformly spin-coating the imprinting glue on a substrate, transferring the porous nano-imprinting template pattern onto the imprinting glue through nano-imprinting, and curing and demolding;
(3) removing residual glue and etching to transfer the porous nano-imprint template pattern to obtain a nano structure;
(4) removing the imprinting glue to obtain a uniform nano structure on the substrate;
(5) preparing a molybdenum film and a gold film on the obtained nanostructure by magnetron sputtering equipment, introducing argon gas and using a direct current power supply or a radio frequency power supply, and increasing the conductivity of the sample;
(6) preparing the nano gold particles on the obtained substrate through electrochemical deposition to obtain the SERS substrate.
2. The method according to claim 1, wherein the material of the porous nano-imprinting stamp of step (1) is quartz, nickel plate or PDMS.
3. The method according to claim 1, wherein in the step (2), before nanoimprinting, the substrate is cleaned by using ethanol and acetone, and is made of silicon wafers or glass; spin-coating the nano-imprint glue on the surface of the substrate by using a spin coating instrument, then obtaining a porous nano-imprint template graph by adopting a nano-imprint technology, placing the porous nano-imprint template graph in an exposure device, curing the porous nano-imprint template graph, and then demolding; the demolding method is mechanical demolding.
4. The method according to claim 1, wherein the etching in step (3) is made by wet etching or dry etching; the dry etching conditions were: the etching gas is Cl2And HBr, Cl2HBr gas flow rate is 60 sccm-120 sccm and 10 sccm-60 sccm respectively, pressure is 200 mTorr-400 mTorr, power is 250W-500W, and etching time is 10 s-180 s; the wet etching conditions are as follows: preparing hydrofluoric acid base corrosive liquid with a volume ratio of 1: 2-2: 1 by using hydrofluoric acid and nitrate solution, wherein the concentration of hydrofluoric acid is2 mmol-5 mmol, etching time is 10 min-5 h, and stirring is carried out to keep the concentration consistent.
5. The method according to claim 1, wherein the conditions of magnetron sputtering in step (5) are: the sputtering pressure is 1Pa to 2Pa, the sputtering power is 40W to 80W, the argon gas flow is 10sccm to 30sccm, the sputtering rate is 0.3nm/s to 0.5nm/s, the bias voltage is 80V to 100V, and molybdenum with the thickness of 5nm to 10nm and gold with the thickness of 20nm to 30nm are subjected to magnetron sputtering; the molybdenum film is an adhesion layer, and the gold film is a seed layer.
6. The method according to claim 1, wherein the substrate to be deposited is placed in an electrolyte in step (6), wherein the electrolyte is 10mmol to 50mmol of chloroauric acid prepared by using concentrated sulfuric acid or PBS buffer solution as a solvent; the gold nanoparticles were deposited using cyclic voltammetry under the following conditions: the SERS substrate is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the potential is-0.2V-0.6V, the pulse is 50 mV/s-100 mV/s, the number of scanning cycles is 15-30, and nano gold particles are formed on the nano structure through a cyclic voltammetry, wherein the distance between the nano gold particles is 10 nm-50 nm, and the size is 10 nm-30 nm.
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