CN115125490A - Preparation method of gold nanostructure ordered array SERS substrate with clean surface - Google Patents
Preparation method of gold nanostructure ordered array SERS substrate with clean surface Download PDFInfo
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- CN115125490A CN115125490A CN202210541950.XA CN202210541950A CN115125490A CN 115125490 A CN115125490 A CN 115125490A CN 202210541950 A CN202210541950 A CN 202210541950A CN 115125490 A CN115125490 A CN 115125490A
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 44
- 239000000758 substrate Substances 0.000 title claims abstract description 33
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000010931 gold Substances 0.000 title claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 239000004793 Polystyrene Substances 0.000 claims description 60
- 229920002223 polystyrene Polymers 0.000 claims description 60
- 239000002356 single layer Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000004005 microsphere Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007738 vacuum evaporation Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001020 plasma etching Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 27
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000001771 vacuum deposition Methods 0.000 abstract description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 19
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 12
- 229940107698 malachite green Drugs 0.000 description 12
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
- C23C14/24—Vacuum evaporation
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention belongs to the technical field of nano materials, and discloses a preparation method of an SERS substrate with a gold nanostructure ordered array and a clean surface. Comprises hydrophilic treatment, film forming operation, heat treatment, etching treatment, evaporation treatment and replacement treatment. The invention combines the vacuum evaporation method and the displacement reaction to prepare a clean and efficient ordered noble metal nano structure, and has low cost, simple, convenient and easy operation and high sensitivity; in the ordered noble metal nano structure, no surfactant is introduced in the preparation process, the blank substrate is clean, and any background interference signal cannot be generated.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a gold nanostructure ordered array SERS substrate with a low-cost clean surface.
Background
Surface Enhanced Raman Spectroscopy (SERS) has become a promising technology due to its unique vibrational fingerprints and novel sensitivity. The noble metal nano structure is introduced as the SERS substrate, so that inherent weak signals of common Raman spectrum are successfully overcome, and the application of the noble metal nano structure in the aspects of chemical sensing, medical and biological detection, food safety and environmental analysis is expanded.
Sensitivity, uniformity and stability are the most critical issues for evaluating SERS substrates. In addition, the cost of substrate preparation and the cleanliness of the substrate surface are also critical to the application and popularization of SERS substrates and reliable detection of analytes. The clean SERS substrate does not generate interference signals for the detection of chemical molecules, so that more accurate and sensitive SERS signals are obtained. Direct spraying of gold films on ordered arrays is an effective method for preparing uniform, stable and clean SERS substrates. However, the method has high cost, and a large amount of gold material is consumed in the preparation process. Compared with the prior art, the method for preparing the SERS substrate by assembling the chemically synthesized gold nanoparticles on the substrate material is a low-cost SERS substrate preparation method. However, in the synthesis and assembly process of metal nanoparticles, in order to protect the growth of nanostructures and promote the ordered self-assembly of nanoparticles, surfactants such as CTAC, CTAB and PVP are generally used. However, these surfactant-coated nanocrystals can only provide a few active sites for interaction with target molecules, especially for weakly adsorbed molecules. More importantly, the SERS reaction generated by these surfactants can severely interfere with the measurement of sample molecules, especially when the target sample concentration is low. Preparing a highly sensitive, low cost, clean surface SERS substrate remains a challenging problem.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of an SERS substrate with a gold nanostructure ordered array with a clean surface.
The above purpose of the invention is realized by the following technical scheme: a preparation method of an ordered array SERS substrate with a gold nanostructure and a clean surface comprises the following steps:
1. placing a slide subjected to hydrophilic treatment in a glass vessel, placing one end of the slide on the wall of the glass vessel and the other end at the bottom of the glass vessel, adding ultrapure water to immerse 2/3 of the slide, slowly dripping a polystyrene microsphere solution at the upper end of the slide to naturally disperse the polystyrene microsphere solution in water, adding a film-forming agent to enable a single-layer polystyrene microsphere film to be more compact after a bright single-layer film is stable, slowly fishing out the single-layer polystyrene microsphere film by using a silicon wafer, and naturally drying the single-layer polystyrene microsphere film;
2. carrying out heat treatment on the polystyrene single-layer film obtained in the step 1 to ensure that the polystyrene single-layer film is firmer on a silicon wafer;
3. placing the polystyrene sphere single-layer film obtained in the step 2 in a plasma cleaning machine for etching treatment to obtain a polystyrene sphere micropore array;
4. placing the polystyrene ball micropore array obtained in the step 3 into a vacuum evaporation machine for evaporation, and evaporating a silver film on the polystyrene ball micropore array;
5. and (4) placing the structure obtained in the step (4) in a chloroauric acid solution for a displacement reaction, and cleaning with ammonia water to remove silver chloride.
Further, the size of the polystyrene spheres in the step 1 is 200 nm-1000 nm, the solvent of the polystyrene sphere solution is a mixed solution of water and ethanol, and the volume ratio of the water to the ethanol is 1: 1.
Furthermore, the dosage of the polystyrene microsphere solution in the step 1 is 10-40 muL.
Further, the film forming agent added in step 1 is sodium dodecyl sulfate solution with the concentration of 100mM and the dosage of 10 μ L.
Further, the temperature of the heat treatment in step 2 was 110 ℃ for 4 minutes.
Further, the time of the plasma etching treatment in step 3 is 9 minutes.
Further, the vacuum degree of the vacuum evaporation silver film in the step 4 is 9.5 × 10 -5 Pa, current 120mA, and deposition time 30 minutes.
Further, the thickness of the silver film in the step 4 is 50 nm-200 nm.
Further, the concentration of the chloroauric acid solution in the step 5 is 0.2mmol/L, and the reaction time is 0-40 minutes.
Further, the reaction temperature in step 5 was 25 ℃.
Compared with the prior art, the invention has the beneficial effects that: the invention combines the vacuum evaporation method and the displacement reaction to prepare a clean and efficient ordered noble metal nano structure, and has low cost, simple, convenient and easy operation and high sensitivity; in the ordered noble metal nano structure, no surfactant is introduced in the preparation process, the blank substrate is clean, and any background interference signal cannot be generated.
Drawings
The invention will be further explained with reference to the drawings and the detailed description
FIG. 1 is a schematic diagram of a process for simply and conveniently preparing ordered noble metal nanostructures according to the present invention;
FIG. 2 is a scanning electron microscope (A) of the ordered noble metal nanostructure obtained from example 1 soaking in chloroauric acid for 10 minutes and a SERS spectrum (B) of malachite green molecules using the ordered noble metal nanostructure as a substrate;
FIG. 3 is a scanning electron microscope (A) of the ordered noble metal nanostructure obtained from example 2 by soaking in chloroauric acid for 20 minutes and a SERS spectrum (B) of malachite green molecules using the ordered noble metal nanostructure as a substrate;
fig. 4 is a scanning electron microscope (a) of the ordered noble metal nanostructure obtained from example 3 by soaking in chloroauric acid for 30 minutes and a SERS spectrum (B) of malachite green molecules based on the ordered noble metal nanostructure.
Fig. 5 is a scanning electron microscope (a) of the ordered noble metal nanostructure obtained from example 3 by soaking in chloroauric acid for 40 minutes and a SERS spectrum (B) of malachite green molecules based on the ordered noble metal nanostructure.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
S1.1, placing the slide subjected to hydrophilic treatment in a glass dish, placing one end of the slide on the wall of the glass dish and the other end of the slide at the bottom of the glass dish, and adding ultrapure water to immerse 2/3 of the slide. Slowly drop 20. mu.L of polystyrene microsphere solution onto the top of the slide, allowing it to disperse naturally in water. After the bright single-layer film is stable, 10 mu L of 100mM film-forming agent sodium dodecyl sulfate solution is added to ensure that the single-layer film of the polystyrene spheres is more compact, and the single-layer film of the polystyrene spheres is slowly fished out by using a silicon wafer and is naturally dried.
S1.2 the polystyrene single-layer film obtained in the step S1.1 is subjected to heat treatment for 4min at 110 ℃ so that the polystyrene single-layer film is firmer on a silicon wafer.
S1.3, placing the polystyrene sphere single-layer film obtained in the step S1.2 in a plasma cleaning machine, and carrying out etching treatment for 9min to obtain the polystyrene sphere micropore array.
S1.4 placing the polystyrene ball micropore array obtained in the step S1.3 in a vacuum evaporation machine, and keeping the vacuum degree at 9.5 multiplied by 10 -5 And (3) evaporating for 30min under Pa and current of 120mA, and evaporating a silver film on the polystyrene ball micropore array.
S1.5, the structure obtained in the step S1.4 is placed in a chloroauric acid solution with the concentration of 0.2mmol/L, a displacement reaction is carried out for 10min at the temperature of 25 ℃, and then ammonia water is used for cleaning to remove silver chloride.
In this example, a scanning electron micrograph of the ordered noble metal nanostructure is shown in fig. 2 (a). It can be seen that the noble metal nanostructuring obtained in this example still has large voids. Taking malachite green as a probe, and collecting an SERS spectrum of the malachite green based on the noble metal nanostructure prepared in the step S1.5, as shown in fig. 2 (B).
Example 2
S2.1, placing the slide subjected to hydrophilic treatment in a glass dish, placing one end of the slide on the wall of the glass dish and the other end of the slide at the bottom of the glass dish, and adding ultrapure water to immerse 2/3 of the slide. Slowly drop 20. mu.L of polystyrene microsphere solution onto the top of the slide, allowing it to disperse naturally in water. After the bright single-layer film is stable, 10 mu L of 100mM film-forming agent sodium dodecyl sulfate solution is added to ensure that the single-layer film of the polystyrene spheres is more compact, and the single-layer film of the polystyrene spheres is slowly fished out by using a silicon wafer and is naturally dried.
S2.2, the polystyrene single-layer film obtained in the step S2.1 is subjected to heat treatment for 4min at the temperature of 110 ℃, so that the polystyrene single-layer film is firmer on a silicon wafer.
And S2.3, placing the polystyrene sphere single-layer film obtained in the step S2.2 in a plasma cleaning machine, and carrying out etching treatment for 9min to obtain the polystyrene sphere micropore array.
S2.4 placing the polystyrene ball micropore array obtained in the step S2.3 into a vacuum evaporation machine, and keeping the vacuum degree at 9.5 multiplied by 10 -5 And (4) evaporating for 30min under Pa and 120mA of current, and evaporating a silver film on the polystyrene ball micropore array.
S2.5, placing the structure obtained in the step S2.4 in a chloroauric acid solution with the concentration of 0.2mmol/L, performing a displacement reaction at the temperature of 25 ℃ for 20min, and then cleaning with ammonia water to remove silver chloride.
In this example, a scanning electron micrograph of the ordered noble metal nanostructure was obtained as shown in fig. 3 (a). It can be seen that the noble metal nanostructures obtained in this example have significantly reduced voids. Taking malachite green as a probe, and collecting an SERS spectrum of the malachite green based on the noble metal nanostructure prepared in the step S2.5, as shown in fig. 3 (B). The improvement in SERS performance can be seen due to the significant enhancement of the electromagnetic field due to nanoparticle aggregation.
Example 3
S3.1, placing the slide subjected to hydrophilic treatment in a glass dish, placing one end of the slide on the wall of the glass dish and the other end of the slide at the bottom of the glass dish, and adding ultrapure water to immerse 2/3 of the slide. Slowly drop 20. mu.L of polystyrene microsphere solution onto the top of the slide, allowing it to disperse naturally in water. After the bright single-layer film is stable, 10 mu L of 100mM film-forming agent sodium dodecyl sulfate solution is added to ensure that the single-layer film of the polystyrene spheres is more compact, and the single-layer film of the polystyrene spheres is slowly fished out by using a silicon wafer and is naturally dried.
S3.2, the polystyrene single-layer film obtained in the step S3.1 is subjected to heat treatment for 4min at the temperature of 110 ℃, so that the polystyrene single-layer film is firmer on a silicon wafer.
And S3.3, placing the polystyrene sphere single-layer film obtained in the step S3.2 in a plasma cleaning machine, and carrying out etching treatment for 9min to obtain the polystyrene sphere micropore array.
S3.4 placing the polystyrene ball micropore array obtained in the step S3.3 in a vacuum evaporation machine, and keeping the vacuum degree at 9.5 multiplied by 10 -5 And (3) evaporating for 30min under Pa and current of 120mA, and evaporating a silver film on the polystyrene ball micropore array.
S3.5, placing the structure obtained in the step S3.4 in a chloroauric acid solution with the concentration of 0.2mmol/L, performing a displacement reaction at the temperature of 25 ℃ for 30min, and then cleaning with ammonia water to remove silver chloride.
In this example, a scanning electron micrograph of the ordered noble metal nanostructures is shown in FIG. 4. The resulting noble metal nanostructure voids in this example can be seen to be further reduced. Taking malachite green as a probe, and collecting an SERS spectrum of the malachite green based on the noble metal nanostructure prepared in the step S3.5, as shown in fig. 4 (B). Further improvement in SERS performance can be seen.
Example 4
S4.1, placing the slide subjected to hydrophilic treatment in a glass dish, placing one end of the slide on the wall of the glass dish and the other end of the slide at the bottom of the glass dish, and adding ultrapure water to immerse 2/3 of the slide. Slowly drop 20. mu.L of polystyrene microsphere solution onto the top of the slide, allowing it to disperse naturally in water. After the bright single-layer film is stable, 10 mu L of 100mM film-forming agent sodium dodecyl sulfate solution is added to ensure that the single-layer film of the polystyrene spheres is more compact, and the single-layer film of the polystyrene spheres is slowly fished out by using a silicon wafer and is naturally dried.
S4.2, the polystyrene single-layer film obtained in the step S4.1 is subjected to heat treatment for 4min at 110 ℃ so that the polystyrene single-layer film is firmer on a silicon wafer.
And S4.3, placing the polystyrene sphere single-layer film obtained in the step S4.2 in a plasma cleaning machine, and carrying out etching treatment for 9min to obtain the polystyrene sphere micropore array.
S4.4 placing the polystyrene ball micropore array obtained in the step S4.3 into a vacuum evaporation machine, and keeping the vacuum degree at 9.5 multiplied by 10 -5 And (3) evaporating for 30min under Pa and current of 120mA, and evaporating a silver film on the polystyrene ball micropore array.
S4.5, placing the structure obtained in the step S4.4 in a chloroauric acid solution with the concentration of 0.2mmol/L, performing a displacement reaction at the temperature of 25 ℃ for 40min, and then cleaning with ammonia water to remove silver chloride.
In this example, a scanning electron micrograph of the ordered noble metal nanostructures is shown in FIG. 5. It can be seen that the noble metal nano-structure obtained in this example has high density and obvious stacking. Taking malachite green as a probe, and collecting an SERS spectrum of the malachite green based on the noble metal nanostructure prepared in the step S4.5, as shown in fig. 5 (B). The SERS performance is seen to be reduced because the narrow nanogap is not conducive to the entry of sample molecules into the hot spot region.
The preparation method is simple to operate, low in cost and high in sensitivity. Meanwhile, a surfactant is not used in the preparation process, so that the cleanliness of the substrate is greatly improved, and a new way for preparing the efficient and clean SERS substrate is provided.
The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (10)
1. A preparation method of an ordered array SERS substrate with a gold nanostructure and a clean surface is characterized by comprising the following steps:
s1, placing a slide subjected to hydrophilic treatment in a glass vessel, placing one end of the slide on the wall of the glass vessel and one end of the slide at the bottom of the glass vessel, adding ultrapure water to immerse 2/3 of the slide, slowly dripping a polystyrene microsphere solution at the upper end of the slide to naturally disperse the polystyrene microsphere solution in water, adding a film-forming agent after a bright single-layer film is stable, slowly fishing out the film-forming agent by using a silicon wafer, and naturally drying;
s2, carrying out heat treatment on the polystyrene single-layer film obtained in the step S1;
s3, placing the polystyrene sphere single-layer film obtained in the step S2 in a plasma cleaning machine, and performing etching treatment under fixed power to obtain a polystyrene sphere micropore array;
s4, placing the polystyrene ball micropore array obtained in the step S3 in a vacuum evaporation machine for evaporation, and evaporating a silver film on the polystyrene ball micropore array;
s5, placing the structure obtained in the step S4 in a chloroauric acid solution for a displacement reaction, and cleaning with ammonia water to remove silver chloride.
2. The method for preparing the gold nanostructure ordered array SERS substrate with the clean surface as claimed in claim 1, wherein the size of the polystyrene sphere in step S1 is 200nm to 1000nm, the solvent of the polystyrene sphere solution is a mixed solution of water and ethanol, and the volume ratio of the water to the ethanol is 1: 1.
3. The method for preparing the SERS substrate with the gold nanostructure ordered array having the clean surface according to claim 1, wherein an amount of the polystyrene microsphere solution used in the step S1 is 10 μ L to 40 μ L.
4. The method for preparing the gold nanostructure ordered array SERS substrate with the clean surface as claimed in claim 1, wherein the film forming agent added in step S1 is sodium dodecyl sulfate solution with concentration of 100mM and dosage of 10 μ L.
5. The method for preparing the gold nanostructure ordered array SERS substrate having a clean surface according to claim 1, wherein the temperature of the heat treatment in step S2 is 110 ℃ and the time is 4 minutes.
6. The method for preparing the SERS substrate according to claim 1, wherein the plasma etching in step S3 is performed for 9 minutes.
7. The method for preparing the gold nanostructure ordered array SERS substrate with the clean surface as claimed in claim 1, wherein the vacuum degree of vacuum evaporation of the silver film in the step S4 is 9.5 x 10 -5 Pa, current 120mA, and deposition time 30 minutes.
8. The method for preparing the gold nanostructure ordered array SERS substrate with the clean surface as claimed in claim 1, wherein the silver film in step S4 has a thickness of 50nm to 200 nm.
9. The method for preparing the SERS substrate with the gold nanostructure ordered array having the clean surface as claimed in claim 1, wherein the concentration of the chloroauric acid solution in the step S5 is 0.2mmol/L, and the reaction time is 0-40 minutes.
10. The method for preparing the gold nanostructure ordered array SERS substrate having a clean surface according to claim 1, wherein the reaction temperature in step S5 is 25 ℃.
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