CN112113949A - Ordered polystyrene @ gold composite microsphere array with dynamically-adjustable gap and preparation method and application thereof - Google Patents
Ordered polystyrene @ gold composite microsphere array with dynamically-adjustable gap and preparation method and application thereof Download PDFInfo
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- 229910052737 gold Inorganic materials 0.000 title claims abstract description 80
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 70
- 239000004005 microsphere Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 76
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 64
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 64
- 239000002356 single layer Substances 0.000 claims abstract description 45
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010931 gold Substances 0.000 claims abstract description 43
- 239000000084 colloidal system Substances 0.000 claims abstract description 41
- 239000004793 Polystyrene Substances 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 27
- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 238000001020 plasma etching Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000001069 Raman spectroscopy Methods 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 229930195730 Aflatoxin Natural products 0.000 claims description 5
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 claims description 5
- 239000005843 Thiram Substances 0.000 claims description 5
- 239000005409 aflatoxin Substances 0.000 claims description 5
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 5
- 229960002447 thiram Drugs 0.000 claims description 5
- 230000010354 integration Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 2
- 239000012491 analyte Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000001514 detection method Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 230000008602 contraction Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
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- 239000000523 sample Substances 0.000 description 2
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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
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses an ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps, and a preparation method and application thereof. The array is a thermally-induced shrinkage polyvinyl chloride substrate and an ordered gold composite microsphere array arranged on the thermally-induced shrinkage polyvinyl chloride substrate, wherein the spacing of the gold composite microspheres forming the microsphere array is 50-65nm, the sphere diameter is 150-935nm, and the gold composite microsphere array is formed by covering a gold film on the surface of a polystyrene sphere; the method comprises the steps of firstly placing a single-layer colloid crystal template formed by polystyrene colloid balls on a thermally-induced shrinkage polyvinyl chloride substrate, then carrying out plasma etching on the single-layer colloid crystal template on the thermally-induced shrinkage polyvinyl chloride substrate, and then depositing a gold film on the single-layer non-close-packed polystyrene ball template on the thermally-induced shrinkage polyvinyl chloride substrate by using a sputtering coating method to obtain a target product. It is extremely easy to be widely commercialized as a surface-enhanced Raman scattering active substrate for precisely and repeatedly detecting an analyte attached thereto in trace amounts.
Description
Technical Field
The invention relates to a microsphere array, a preparation method and application thereof, in particular to an ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps, a preparation method and application thereof.
Background
The Surface Enhanced Raman Scattering (SERS) spectrum is taken as an ultra-sensitive detection technology, has the advantages of simple and rapid operation, fingerprint identification on chemical structures and the like, and is widely applied to the fields of environmental pollutant detection, reaction monitoring, food safety detection, biosensing and the like. For noble metal substrates, the enhancement of the raman signal is mainly due to the enhancement of the electromagnetic field caused by localized surface plasmon resonance on the noble metal surface. When the gap between two noble metal nanostructures is less than 10nm, a very strong coupling electric field will be generated at the gap, commonly referred to as a SERS "hot spot". When the target molecules are in the hot spots, the Raman signals of the target molecules are remarkably amplified, and the detection sensitivity can even reach a single molecule level. However, the steric hindrance effect can seriously hinder the target molecules from entering the "hot spot", thereby seriously affecting the detection efficiency of SERS, and especially when the target molecules are at low concentration, the randomness of the distribution makes the problem more prominent. To solve this problem, some useful attempts and efforts have been made, such as an article entitled "Manipulating 'Hot Spots' from Nanometers to antibiotics: heated underlying Integrated controls of molecular Number and Gap Size for ultra sensitive Surface-Enhanced Raman Scattering Detection", ACS Appl. Mater. Interface, 2019, 11(42):39359 39368. ("Understanding the combined contribution of molecular Number and Gap Size to Ultrasensitive Surface-Enhanced Raman Scattering Detection"; American society-applied materials & interfaces, Vol. 11: 39359 39368). The SERS substrate mentioned in the article is a thermally shrinkable polyvinyl chloride substrate attached with silver nanoparticles with the particle size of 65 nm; during preparation, the silver nanoparticles are modified on a polyvinyl chloride substrate capable of thermally shrinking by using 3-aminopropyl trimethoxysilane (APTMS) by adopting a liquid phase method; during detection, the SERS substrate is heated to shrink, and then the laser Raman spectrometer is used for measuring pollutants attached to the SERS substrate. Firstly, the appearance, size, gap and distribution of silver nanoparticles on a thermally shrinkable polyvinyl chloride substrate serving as the SERS substrate are not uniform, so that the gap and arrangement period between the nanoparticles after the SERS substrate is heated cannot be accurately regulated and controlled, an SERS signal with strong repeatability is difficult to obtain, and the accuracy of SERS detection is influenced; secondly, the preparation method can not obtain the nano-particles which are attached to the polyvinyl chloride substrate and can be thermally shrunk, wherein the noble metal is neat and uniform in shape and size, and the gaps and the distribution are uniform.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides the ordered polystyrene @ gold composite microsphere array which has strong SERS signal repeatability and accurate detection result and can dynamically regulate and control the gap.
The invention also aims to provide a preparation method of the ordered polystyrene @ gold composite microsphere array, wherein the gap of the ordered polystyrene @ gold composite microsphere array can be dynamically regulated and controlled.
The invention also aims to solve the technical problem of providing the application of the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps.
In order to solve the technical problem, the technical scheme adopted by the invention is that the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps comprises a thermally-induced shrinkage polyvinyl chloride substrate and noble metals arranged on the thermally-induced shrinkage polyvinyl chloride substrate, and particularly comprises the following components in percentage by weight:
the noble metal is an ordered gold composite microsphere array;
the ball pitch of the gold composite microspheres forming the ordered gold composite microsphere array is 50-65 nm;
the sphere diameter of the gold composite microspheres with the sphere spacing of 50-65nm is 150-935 nm;
the gold composite microsphere with the sphere diameter of 150-935nm is a polystyrene sphere with the sphere diameter of 100-875nm, and the surface of the polystyrene sphere is coated with a gold film with the thickness of 25-30 nm.
The ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps is further improved:
preferably, the ordered gold composite microsphere array is a single-layer loose sphere array in an ordered hexagonal arrangement.
Preferably, the gold film consists of gold particles having a particle size of 5-20 nm.
In order to solve another technical problem, another technical scheme adopted by the invention is that the preparation method of the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps comprises a template method, and particularly comprises the following main steps:
step 2, carrying out plasma etching on the single-layer colloid crystal template on the thermally-induced shrinkage polyvinyl chloride substrate to obtain the thermally-induced shrinkage polyvinyl chloride substrate of the single-layer non-close-packed polystyrene ball template with the distance between two adjacent colloid balls being 100-125 nm;
and 3, depositing a 25-30nm gold film on the thermally-induced shrinkage polyvinyl chloride substrate with the single-layer non-close-packed polystyrene sphere template by using a sputtering coating method to prepare the ordered polystyrene @ gold composite microsphere array with dynamically-adjustable gaps.
The preparation method of the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps is further improved as follows:
preferably, the thermally-induced shrinkage polyvinyl chloride substrate is placed in a plasma cleaning machine to be cleaned for 2min, and then the single-layer colloid crystal template is placed on the thermally-induced shrinkage polyvinyl chloride substrate.
Preferably, the gas atmosphere during plasma etching is argon, the power is 58W, and the time is 4-15 min.
Preferably, the operating current during sputter coating is 30 mA.
In order to solve another technical problem, another technical scheme adopted by the invention is that the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps has the following applications:
the ordered polystyrene @ gold composite microsphere array with the dynamically adjustable gap is sequentially placed in a solution of an object to be measured for 1-2h at 105-115 ℃ for 50-70s, then the array is used as an active substrate for surface enhanced Raman scattering, and a laser Raman spectrometer is used for measuring the object to be measured attached to the array.
The application of the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps is further improved:
preferably, the excitation light of the laser Raman spectrometer has the wavelength of 532nm, the power of 0.2-0.4mW and the integration time of 6-10 s.
Preferably, the substance to be detected is rhodamine 6G, or thiram, or methyl parathion, or aflatoxin.
Compared with the prior art, the beneficial effects are that:
firstly, the prepared target product is characterized by using a scanning electron microscope, and the result is combined with the preparation method to obtain the target product which consists of a thermally-shrinkable polyvinyl chloride substrate and an ordered gold composite microsphere array arranged on the thermally-shrinkable polyvinyl chloride substrate; the gold composite microspheres for forming the ordered gold composite microsphere array have the sphere spacing of 50-65nm, the diameter of the gold composite microspheres with the sphere spacing of 50-65nm is 150-935nm, and the surface of the polystyrene spheres with the diameter of 100-875nm is coated with a gold film with the thickness of 25-30 nm. The target product assembled by the ordered gold composite microsphere array consisting of the thermally shrinkable polyvinyl chloride substrate and the gold composite microspheres with set spacing, sphere diameter and gold film covered on the surfaces of the polystyrene spheres is characterized by the thermally shrinkable polyvinyl chloride and also has the ordered hexagonal arrangement of orderly shape, size and gap of the gold composite microspheres forming the array due to the high orderliness of the ordered gold composite microsphere array, and the space steric effect in the actual SERS detection is greatly overcome and the SERS detection efficiency, sensitivity and signal repeatability of the target product to the object to be detected are greatly improved due to the organic integration of the thermally shrinkable polyvinyl chloride substrate and the ordered gold composite microsphere array arranged thereon because the shell of the gold composite microspheres is noble metal gold with SERS characteristics.
Secondly, the prepared target product is used as an SERS active substrate, multiple times of multiple batches of tests are respectively carried out on rhodamine 6G, thiram, methyl parathion, aflatoxin and the like to be tested under different concentrations, and the consistency and repeatability of the tests are very good at multiple points and any point on the target product.
Thirdly, the preparation method is simple, scientific and effective. The method not only prepares the target product with strong SERS signal repeatability and accurate detection result, namely the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps, but also has the advantages of simple process and high reliability during preparation and has the characteristic of low manufacturing cost; further, the target product is easy to be widely commercialized as a surface enhanced Raman scattering active substrate for accurately and repeatedly detecting trace amounts of the substance to be detected attached to the surface enhanced Raman scattering active substrate, namely rhodamine 6G, thiram, methyl parathion, aflatoxin and the like.
Drawings
Fig. 1 is one of results of characterization using a Scanning Electron Microscope (SEM) for each of an intermediate product and a target product obtained by the preparation method. Wherein, fig. 1a is an SEM image of a single-layer colloidal crystal template composed of polystyrene colloidal spheres on a thermally-shrinkable polyvinyl chloride substrate of one of the intermediate products, fig. 1b is an SEM image of a single-layer non-close-packed polystyrene spherical template on a thermally-shrinkable polyvinyl chloride substrate after plasma etching of one of the intermediate products, fig. 1c is an SEM image of a target product, and fig. 1d is an SEM image of the target product after pre-adsorption-thermal shrinkage.
FIG. 2 is one of the results of the characterization of the distance between two adjacent microspheres during the thermal shrinkage at 110 ℃ of the prepared target product with heating time by using a scanning electron microscope. Wherein, fig. 2a is an SEM image of the target product at 0s thermal shrinkage, fig. 2b is an SEM image of the target product at 25s thermal shrinkage, and fig. 2c is an SEM image of the target product at 60s thermal shrinkage.
FIG. 3 shows one of the results of a laser Raman spectrometer characterization of the SERS performance of the prepared target product under different conditions before and after thermal contraction with rhodamine 6G as a probe molecule.
FIG. 4 shows one of the results of SERS performance characterization of the target product under two different conditions of pre-adsorption-thermal contraction and pre-heating contraction-adsorption by using a laser Raman spectrometer with rhodamine 6G as a probe molecule.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
First commercially available or manufactured on its own:
thermally shrinking a polyvinyl chloride substrate;
a single-layer colloid crystal template formed by polystyrene colloid spheres with the sphere diameter of 200-1000 nm;
a plasma etcher;
a sputter coating machine;
a plasma cleaning machine.
Then:
example 1
The preparation method comprises the following specific steps:
Step 2, carrying out plasma etching on a single-layer colloid crystal template on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere during etching is argon, the power is 58W, and the time is 4min, so as to obtain the heat-shrinkable polyvinyl chloride substrate with the single-layer non-close-packed polystyrene ball template with the distance between two adjacent colloid balls being 100 nm.
Step 3, depositing a 25 nm-thick gold film on the single-layer non-close-packed polystyrene ball template on the thermally-shrinkable polyvinyl chloride substrate by using a sputtering coating method; wherein the working current during sputtering coating is 30 mA. An array of dynamically gap-controllable ordered polystyrene @ gold composite microspheres similar to that shown in FIG. 1c, and as shown by the curves in FIGS. 3 and 4, was prepared.
Example 2
The preparation method comprises the following specific steps:
Step 2, carrying out plasma etching on a single-layer colloid crystal template on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere during etching is argon, the power is 58W, and the time is 6.7min, so as to obtain the thermotropic contraction polyvinyl chloride substrate with a monolayer non-close-packed polystyrene ball template with the distance between two adjacent colloid balls being 106 nm.
Step 3, depositing a gold film with the thickness of 26.3nm on the single-layer non-close-packed polystyrene ball template on the thermally-induced shrinkage polyvinyl chloride substrate by using a sputtering coating method; wherein the working current during sputtering coating is 30 mA. An array of dynamically gap-controllable ordered polystyrene @ gold composite microspheres similar to that shown in FIG. 1c, and as shown by the curves in FIGS. 3 and 4, was prepared.
Example 3
The preparation method comprises the following specific steps:
Step 2, carrying out plasma etching on a single-layer colloid crystal template on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere during etching is argon, the power is 58W, and the time is 9.5min, so as to obtain the thermotropic contraction polyvinyl chloride substrate with the single-layer non-close-spaced polystyrene ball template with the distance between two adjacent colloid balls being 113 nm.
Step 3, depositing a gold film with the thickness of 27.5nm on the single-layer non-close-packed polystyrene ball template on the thermal shrinkage polyvinyl chloride substrate by using a sputtering coating method; wherein the working current during sputtering coating is 30 mA. The ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps as shown in FIG. 1c and as shown by the curves in FIG. 3 and FIG. 4 was prepared.
Example 4
The preparation method comprises the following specific steps:
Step 2, carrying out plasma etching on a single-layer colloid crystal template on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere during etching is argon, the power is 58W, and the time is 12.5min, so as to obtain the thermotropic contraction polyvinyl chloride substrate with the single-layer non-close-spaced polystyrene ball template with the distance between two adjacent colloid balls of 119 nm.
Step 3, depositing a gold film with the thickness of 28.8nm on the single-layer non-close-packed polystyrene ball template on the thermally-induced shrinkage polyvinyl chloride substrate by using a sputtering coating method; wherein the working current during sputtering coating is 30 mA. An array of dynamically gap-controllable ordered polystyrene @ gold composite microspheres similar to that shown in FIG. 1c, and as shown by the curves in FIGS. 3 and 4, was prepared.
Example 5
The preparation method comprises the following specific steps:
Step 2, carrying out plasma etching on a single-layer colloid crystal template on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere during etching is argon, the power is 58W, and the time is 15min, so as to obtain the heat-shrinkable polyvinyl chloride substrate with the single-layer non-close-packed polystyrene ball template with the distance between two adjacent colloid balls being 125 nm.
Step 3, depositing a gold film with the thickness of 30nm on the single-layer non-close-packed polystyrene ball template on the thermally-shrinkable polyvinyl chloride substrate by using a sputtering coating method; wherein the working current during sputtering coating is 30 mA. An array of dynamically gap-controllable ordered polystyrene @ gold composite microspheres similar to that shown in FIG. 1c, and as shown by the curves in FIGS. 3 and 4, was prepared.
The ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps has the following applications:
sequentially placing the ordered polystyrene @ gold composite microsphere array with the dynamically adjustable gap in a solution of an object to be measured for 1-2h at 105-115 ℃ for 50-70s, taking the array as an active substrate for surface enhanced Raman scattering, and measuring the object to be measured attached to the array by using a laser Raman spectrometer to obtain a result which is as shown in or similar to that shown in figure 3 or figure 4; wherein the wavelength of exciting light of the laser Raman spectrometer is 532nm, the power is 0.2-0.4mW, the integration time is 6-10s, and the object to be detected is rhodamine 6G, or thiram, or methyl parathion, or aflatoxin.
It is apparent that those skilled in the art can make various changes and modifications to the gap-dynamically adjustable ordered polystyrene @ gold composite microsphere array of the present invention, and the preparation method and use thereof, without departing from the spirit and scope of the present invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (10)
1. The ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps comprises a thermally-shrinkable polyvinyl chloride substrate and a noble metal arranged on the thermally-shrinkable polyvinyl chloride substrate, and is characterized in that:
the noble metal is an ordered gold composite microsphere array;
the ball pitch of the gold composite microspheres forming the ordered gold composite microsphere array is 50-65 nm;
the sphere diameter of the gold composite microspheres with the sphere spacing of 50-65nm is 150-935 nm;
the gold composite microsphere with the sphere diameter of 150-935nm is a polystyrene sphere with the sphere diameter of 100-875nm, and the surface of the polystyrene sphere is coated with a gold film with the thickness of 25-30 nm.
2. The ordered polystyrene @ gold composite microsphere array of claim 1, wherein the ordered gold composite microsphere array is a single-layer loose sphere array with an ordered hexagonal arrangement.
3. The ordered polystyrene @ gold composite microsphere array according to claim 1, wherein the gold film is composed of gold particles with a particle size of 5-20 nm.
4. The preparation method of the ordered polystyrene @ gold composite microsphere array with the dynamically adjustable gap as claimed in claim 1, which comprises a template method and is characterized by mainly comprising the following steps:
step 1, placing a single-layer colloid crystal template consisting of polystyrene colloid spheres with the sphere diameter of 200-1000nm on a thermally-induced shrinkage polyvinyl chloride substrate to obtain the thermally-induced shrinkage polyvinyl chloride substrate with the single-layer colloid crystal template thereon;
step 2, carrying out plasma etching on the single-layer colloid crystal template on the thermally-induced shrinkage polyvinyl chloride substrate to obtain the thermally-induced shrinkage polyvinyl chloride substrate of the single-layer non-close-packed polystyrene ball template with the distance between two adjacent colloid balls being 100-125 nm;
and 3, depositing a 25-30nm gold film on the thermally-induced shrinkage polyvinyl chloride substrate with the single-layer non-close-packed polystyrene sphere template by using a sputtering coating method to prepare the ordered polystyrene @ gold composite microsphere array with dynamically-adjustable gaps.
5. The method for preparing the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gap as claimed in claim 4, wherein the single-layer colloidal crystal template is cleaned in a plasma cleaning machine for 2min before being placed on the thermally-induced shrinkage polyvinyl chloride substrate.
6. The method for preparing the ordered polystyrene @ gold composite microsphere array with the dynamically adjustable gap as claimed in claim 4, wherein the gas atmosphere during plasma etching is argon, the power is 58W, and the time is 4-15 min.
7. The method for preparing the ordered polystyrene @ gold composite microsphere array with the dynamically adjustable gap as claimed in claim 4, wherein the working current during sputtering coating is 30 mA.
8. The use of the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps as claimed in claim 1, wherein:
the ordered polystyrene @ gold composite microsphere array with the dynamically adjustable gap is sequentially placed in a solution of an object to be measured for 1-2h at 105-115 ℃ for 50-70s, then the array is used as an active substrate for surface enhanced Raman scattering, and a laser Raman spectrometer is used for measuring the object to be measured attached to the array.
9. The use of the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gap as claimed in claim 8, wherein the excitation light of the laser raman spectrometer has a wavelength of 532nm, a power of 0.2-0.4mW and an integration time of 6-10 s.
10. The use of the ordered polystyrene @ gold composite microsphere array with the dynamically adjustable gap as claimed in claim 8, wherein the substance to be detected is rhodamine 6G, or thiram, or methyl parathion, or aflatoxin.
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| CN102747320A (en) * | 2012-07-31 | 2012-10-24 | 武汉大学 | Preparation method of noble metal nano-particle array |
| CN106048537A (en) * | 2016-06-22 | 2016-10-26 | 天津大学 | Method for preparing SERS substrate by combining colloidal sphere self-assembly with ion-sputtering coating |
| CN110514638A (en) * | 2019-07-12 | 2019-11-29 | 东南大学 | A kind of hot spot intensity surface enhanced Raman scattering substrate and preparation method |
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| CN114354568A (en) * | 2021-12-06 | 2022-04-15 | 西北大学 | Surface-enhanced Raman spectrum substrate, preparation method and application |
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