CN112113949B - 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
- Publication number
- CN112113949B CN112113949B CN202010929107.XA CN202010929107A CN112113949B CN 112113949 B CN112113949 B CN 112113949B CN 202010929107 A CN202010929107 A CN 202010929107A CN 112113949 B CN112113949 B CN 112113949B
- Authority
- CN
- China
- Prior art keywords
- polystyrene
- polyvinyl chloride
- gold composite
- composite microsphere
- ordered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 84
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 76
- 239000004005 microsphere Substances 0.000 title claims abstract description 72
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 65
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 65
- 239000002356 single layer Substances 0.000 claims abstract description 50
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010931 gold Substances 0.000 claims abstract description 44
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001020 plasma etching Methods 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 239000000084 colloidal system Substances 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001069 Raman spectroscopy Methods 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 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
- 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
- 230000005284 excitation Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 description 16
- 238000001514 detection method Methods 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses an ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps, a preparation method and application thereof. The array is a heat-induced shrinkage polyvinyl chloride substrate and an ordered gold composite microsphere array arranged on the heat-induced shrinkage polyvinyl chloride substrate, wherein the distance between gold composite microspheres forming the microsphere array is 50-65nm, the diameter of each microsphere is 150-935nm, and the heat-induced shrinkage polyvinyl chloride substrate is formed by covering gold films on the surfaces of polystyrene spheres; the method comprises the steps of firstly placing a single-layer colloidal crystal template formed by polystyrene colloidal spheres on a thermally-induced shrinkage polyvinyl chloride substrate, then carrying out plasma etching on the single-layer colloidal crystal template carried on the thermally-induced shrinkage polyvinyl chloride substrate, and then depositing a gold film on the single-layer non-closely-spaced polystyrene sphere template carried on the thermally-induced shrinkage polyvinyl chloride substrate by using a sputtering coating method to obtain a target product. It is extremely easy to widely commercialize as a surface enhanced Raman scattering active substrate to accurately and repeatedly detect the object to be detected attached thereon in trace.
Description
Technical Field
The invention relates to a microsphere array and a preparation method and application thereof, in particular to an ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps and a preparation method and application thereof.
Background
As an ultrasensitive detection technology, the Surface Enhanced Raman Scattering (SERS) spectrum has the advantages of simplicity and rapidness in operation, fingerprint identification of 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 raman signals is mainly due to the enhancement of electromagnetic fields 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 SERS "hot spot". When the target molecules are in the hot spots, the Raman signals are amplified remarkably, and the detection sensitivity can even reach a single-molecule level. However, steric hindrance effects can seriously hinder the target molecule from entering a "hot spot", so that the detection efficiency of SERS is seriously affected, and especially when the concentration of the target molecule is very low, the problem is particularly serious due to the randomness of the distribution. To solve this problem, some beneficial attempts and efforts have been made, such as the article entitled "Manipulating'Hot Spots'from Nanometer to Angstrom:Toward Understanding Integrated Contributions of Molecule Number and Gap Size for Ultrasensitive Surface-Enhanced Raman Scattering Detection",ACS Appl.Mater.Interfaces,2019,11(42):39359-39368.(" to understand the combined contribution of molecular number and gap size to ultrasensitive surface enhanced raman scattering detection, "american society of chemistry-materials of application and interface, 2019, volume 11: 39359-39368). The SERS substrate referred to herein is a thermally shrinkable polyvinyl chloride substrate having silver nanoparticles of 65nm particle size attached thereto; during preparation, a liquid phase method is adopted to modify silver nano particles on a polyvinyl chloride substrate which can be thermally contracted by using 3-aminopropyl trimethoxysilane (APTMS); during detection, the SERS substrate is heated to shrink, and then the laser Raman spectrometer is used for measuring the pollutant attached to the SERS substrate. Although the SERS substrate can be used for detecting trace pollutants, the SERS substrate and the preparation method thereof have the defects that firstly, the morphology, the size, the gaps and the distribution of silver nano particles on a heat-shrinkable polyvinyl chloride substrate serving as the SERS substrate are uneven, so that the gaps and the arrangement period between the nano particles after the SERS substrate is heated cannot be accurately regulated and controlled, the SERS signal with strong repeatability is difficult to obtain, and the accuracy of SERS detection is affected; secondly, the preparation method cannot obtain nano particles with uniform morphology, uniform size, gaps and uniform distribution of noble metals attached to the polyvinyl chloride substrate capable of thermally shrinking.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides the ordered polystyrene@gold composite microsphere array with strong repeatability of SERS signals and accurate detection results and dynamically adjustable gaps.
The invention aims to provide a preparation method of the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps.
The invention further aims to provide the application of the ordered polystyrene@gold composite microsphere array with the gap capable of being dynamically regulated.
In order to solve the technical problem of the invention, the adopted technical proposal is that the ordered polystyrene@gold composite microsphere array with dynamically adjustable gap comprises a thermally-induced shrinkage polyvinyl chloride substrate and noble metal arranged on the substrate, in particular:
The noble metal is an ordered gold composite microsphere array;
the ball spacing of the gold composite microspheres forming the ordered gold composite microsphere array is 50-65nm;
the ball diameter of the gold composite microsphere with the ball spacing of 50-65nm is 150-935nm;
the gold composite microsphere with the sphere diameter of 150-935nm is formed by coating a gold film with the thickness of 25-30nm on the surface of a polystyrene sphere with the sphere diameter of 100-875 nm.
Further improvement of ordered polystyrene@gold composite microsphere array with dynamically adjustable gap:
preferably, the ordered gold composite microsphere array is a single layer loose microsphere 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 of the invention, another technical proposal is that the preparation method of the ordered polystyrene@gold composite microsphere array with dynamically adjustable gap comprises a template method, and particularly comprises the following main steps:
Step 1, placing a single-layer colloid crystal template formed by polystyrene colloid spheres with the sphere diameter of 200-1000nm on a heat-induced shrinkage polyvinyl chloride substrate to obtain the heat-induced shrinkage polyvinyl chloride substrate with the single-layer colloid crystal template thereon;
Step 2, carrying out plasma etching on a single-layer colloid crystal template on the heat-induced shrinkage polyvinyl chloride substrate to obtain the heat-induced shrinkage polyvinyl chloride substrate with a single-layer non-closely-spaced polystyrene sphere template with the spacing between two adjacent colloid spheres of 100-125 nm;
And 3, depositing a gold film with the thickness of 25-30nm on the thermally-induced shrinkage polyvinyl chloride substrate with the monolayer non-closely arranged polystyrene sphere template by using a sputtering coating method to prepare the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps.
Further improvement of the preparation method of the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps:
Preferably, the heat-shrinkable polyvinyl chloride substrate is placed in a plasma cleaner for 2 minutes, and then a single-layer colloidal crystal template is placed thereon.
Preferably, the gas atmosphere during plasma etching is argon, the power is 58W, and the time is 4-15min.
Preferably, the operating current at the time of sputter coating is 30mA.
In order to solve the technical problem of the invention, the adopted technical scheme is that the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps has the following purposes:
Sequentially placing the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps in a solution of an object to be measured for 1-2h at 105-115 ℃ for 50-70s, taking the ordered polystyrene@gold composite microsphere array as an active substrate for surface-enhanced Raman scattering, and measuring the object to be measured attached to the ordered polystyrene@gold composite microsphere array by using a laser Raman spectrometer.
Further improvement of use as an ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps:
Preferably, the wavelength of excitation light of the laser Raman spectrometer is 532nm, the power is 0.2-0.4mW, and the integration time is 6-10s.
Preferably, the test substance is rhodamine 6G, or thiram, or methyl parathion, or aflatoxin.
Compared with the prior art, the beneficial effects are that:
firstly, a scanning electron microscope is used for representing the prepared target product, and the result and the combination preparation method show that the target product consists of 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 ball spacing of the gold composite microspheres forming the ordered gold composite microsphere array is 50-65nm, the ball diameter of the gold composite microspheres with the ball spacing of 50-65nm is 150-935nm, the surface of the polystyrene spheres with the ball diameter of 100-875nm, which are the gold composite microspheres with the ball diameter of 150-935nm, is covered with a gold film with the thickness of 25-30 nm. The target product assembled by the ordered gold composite microsphere array formed by the thermal shrinkage polyvinyl chloride substrate and the gold composite microsphere array formed by the gold composite microsphere array with the set interval and the ball diameter arranged on the thermal shrinkage polyvinyl chloride substrate and the gold film coated on the surface of the polystyrene sphere is not only characterized by the thermal shrinkage polyvinyl chloride, but also is characterized by the high degree of order of the ordered gold composite microsphere array, namely the ordered gold composite microsphere array is orderly arranged in a loose shape with regular shape, size and gaps, and the shell of the gold composite microsphere is noble metal gold with SERS characteristics, and further by the organic integration of the thermal shrinkage polyvinyl chloride substrate and the ordered gold composite microsphere array arranged on the thermal shrinkage polyvinyl chloride substrate, the space steric hindrance effect in 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.
Secondly, the prepared target product is used as an SERS active substrate, and rhodamine 6G, thiram, methyl parathion, aflatoxin and the like which are to be detected are tested for multiple times and multiple batches under different concentrations respectively, so that the consistency and repeatability of detection are very good at multiple points and any point on the target product.
Thirdly, the preparation method is simple, scientific and effective. The ordered polystyrene@gold composite microsphere array with strong repeatability of SERS signals and accurate detection results, namely a gap which can be dynamically regulated, is prepared, and has the advantages of simple process and high reliability during preparation, and has the characteristic of low manufacturing cost; and further, the target product is very easy to be widely commercialized and used as a surface enhanced Raman scattering active substrate to accurately and repeatedly detect trace amounts of rhodamine 6G or thiram or methyl parathion or aflatoxin and the like which are the objects to be detected attached to the surface enhanced Raman scattering active substrate.
Drawings
FIG. 1 shows one of results of characterization of an intermediate product and a target product obtained by the preparation method by using a Scanning Electron Microscope (SEM). 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-densely arranged polystyrene sphere template on a thermally-shrinkable polyvinyl chloride substrate of one of the intermediate products after plasma etching, fig. 1c is an SEM image of a target product, and fig. 1d is an SEM image of a target product after pre-adsorption-thermal shrinkage.
FIG. 2 is one of the results of characterizing the distance between two adjacent microspheres during heat-induced shrinkage of the resulting target product at 110℃with a scanning electron microscope over time. Wherein, FIG. 2a is an SEM image of the target product at 0s heat shrinkage, FIG. 2b is an SEM image of the target product at 25s heat shrinkage, and FIG. 2c is an SEM image of the target product at 60s heat shrinkage.
Fig. 3 shows one of the results of characterization of SERS performance of the target product prepared under different conditions before and after heat-induced shrinkage using a laser raman spectrometer using rhodamine 6G as a probe molecule.
Fig. 4 shows one of the results of characterizing SERS performance of the target product obtained by using rhodamine 6G as a probe molecule under two different conditions, i.e., pre-adsorption-thermal shrinkage-pre-heat shrinkage-adsorption, by using a laser raman spectrometer.
Detailed Description
The preferred mode of the present invention will be described in further detail with reference to the accompanying drawings.
First, from commercial sources or by itself:
a heat-shrinkable 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:
And step 1, firstly placing the heat-induced shrinkage polyvinyl chloride substrate in a plasma cleaner for cleaning for 2min. And then placing a single-layer colloid crystal template formed by polystyrene colloid spheres with the sphere diameter of 200nm on the thermally-induced shrinkage polyvinyl chloride substrate to obtain the thermally-induced shrinkage polyvinyl chloride substrate with the single-layer colloid crystal template.
Step 2, carrying out plasma etching on a single-layer colloid crystal template carried on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere is argon, the power is 58W, and the time is 4min, and the thermal shrinkage polyvinyl chloride substrate with a single-layer non-close-packed polystyrene sphere template with the interval between two adjacent colloid spheres of 100nm is obtained.
Step 3, a sputtering coating method is used for a single-layer non-closely arranged polystyrene sphere template on the thermally-induced shrinkage polyvinyl chloride substrate, and a gold film with the thickness of 25nm is deposited on the single-layer non-closely arranged polystyrene sphere template; wherein, the working current during sputtering coating is 30mA. An ordered polystyrene @ gold composite microsphere array with gaps that are similar to those shown in fig. 1c and that can be dynamically adjusted as shown in the curves in fig. 3 and 4 was prepared.
Example 2
The preparation method comprises the following specific steps:
And step 1, firstly placing the heat-induced shrinkage polyvinyl chloride substrate in a plasma cleaner for cleaning for 2min. And then placing a single-layer colloid crystal template formed by polystyrene colloid spheres with the sphere diameter of 400nm on the thermally-induced shrinkage polyvinyl chloride substrate to obtain the thermally-induced shrinkage polyvinyl chloride substrate with the single-layer colloid crystal template.
Step 2, carrying out plasma etching on a single-layer colloid crystal template carried on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere is argon, the power is 58W, the time is 6.7min, and the thermal shrinkage polyvinyl chloride substrate with the single-layer non-closely arranged polystyrene sphere template with the spacing between two adjacent colloid spheres of 106nm is obtained.
Step 3, a sputtering coating method is used for a monolayer non-closely arranged polystyrene sphere template on the thermally-induced shrinkage polyvinyl chloride substrate, and a gold film with the thickness of 26.3nm is deposited on the monolayer non-closely arranged polystyrene sphere template; wherein, the working current during sputtering coating is 30mA. An ordered polystyrene @ gold composite microsphere array with gaps that are similar to those shown in fig. 1c and that can be dynamically adjusted as shown in the curves in fig. 3 and 4 was prepared.
Example 3
The preparation method comprises the following specific steps:
And step 1, firstly placing the heat-induced shrinkage polyvinyl chloride substrate in a plasma cleaner for cleaning for 2min. And then placing a single-layer colloid crystal template formed by polystyrene colloid spheres with the sphere diameter of 600nm on the thermally-induced shrinkage polyvinyl chloride substrate to obtain the thermally-induced shrinkage polyvinyl chloride substrate with the single-layer colloid crystal template.
Step 2, carrying out plasma etching on a single-layer colloid crystal template carried on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere is argon, the power is 58W, the time is 9.5min, and the thermal shrinkage polyvinyl chloride substrate with the single-layer non-closely arranged polystyrene sphere template with the interval between two adjacent colloid spheres of 113nm is obtained.
Step 3, a sputtering coating method is used for a monolayer non-closely arranged polystyrene sphere template on the thermally-induced shrinkage polyvinyl chloride substrate, and a gold film with the thickness of 27.5nm is deposited on the monolayer non-closely arranged polystyrene sphere template; wherein, the working current during sputtering coating is 30mA. An ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps as shown in fig. 1c and as shown in curves in fig. 3 and 4 is prepared.
Example 4
The preparation method comprises the following specific steps:
And step 1, firstly placing the heat-induced shrinkage polyvinyl chloride substrate in a plasma cleaner for cleaning for 2min. And then placing a single-layer colloid crystal template formed by polystyrene colloid spheres with the sphere diameter of 800nm on the thermally-induced shrinkage polyvinyl chloride substrate to obtain the thermally-induced shrinkage polyvinyl chloride substrate with the single-layer colloid crystal template.
Step 2, carrying out plasma etching on a single-layer colloid crystal template carried on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere is argon, the power is 58W, and the time is 12.5min, and the thermal shrinkage polyvinyl chloride substrate with the single-layer non-closely arranged polystyrene sphere template with the spacing of 119nm between two adjacent colloid spheres is obtained.
Step 3, a sputtering coating method is used for a monolayer non-closely arranged polystyrene sphere template on the thermally-induced shrinkage polyvinyl chloride substrate, and a gold film with the thickness of 28.8nm is deposited on the monolayer non-closely arranged polystyrene sphere template; wherein, the working current during sputtering coating is 30mA. An ordered polystyrene @ gold composite microsphere array with gaps that are similar to those shown in fig. 1c and that can be dynamically adjusted as shown in the curves in fig. 3 and 4 was prepared.
Example 5
The preparation method comprises the following specific steps:
and step 1, firstly placing the heat-induced shrinkage polyvinyl chloride substrate in a plasma cleaner for cleaning for 2min. And then placing a single-layer colloid crystal template formed by polystyrene colloid spheres with the sphere diameter of 1000nm on the thermally-induced shrinkage polyvinyl chloride substrate to obtain the thermally-induced shrinkage polyvinyl chloride substrate with the single-layer colloid crystal template.
Step 2, carrying out plasma etching on a single-layer colloid crystal template carried on the thermally-induced shrinkage polyvinyl chloride substrate; wherein, the gas atmosphere is argon, the power is 58W, the time is 15min, and the thermal shrinkage polyvinyl chloride substrate with the single-layer non-closely arranged polystyrene sphere template with the interval between two adjacent colloid spheres being 125nm is obtained.
Step 3, a sputtering coating method is used for a monolayer non-closely arranged polystyrene sphere template on the thermally-induced shrinkage polyvinyl chloride substrate, and a gold film with the thickness of 30nm is deposited on the monolayer non-closely arranged polystyrene sphere template; wherein, the working current during sputtering coating is 30mA. An ordered polystyrene @ gold composite microsphere array with gaps that are similar to those shown in fig. 1c and that can be dynamically adjusted as shown in the curves in fig. 3 and 4 was prepared.
The application of the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps is as follows:
Sequentially placing an ordered polystyrene@gold composite microsphere array with a dynamically adjustable gap into an object to be measured solution for 1-2h at 105-115 ℃ for 50-70s, taking the ordered polystyrene@gold composite microsphere array as an active substrate for surface-enhanced Raman scattering, and measuring an object to be measured attached to the active substrate by using a laser Raman spectrometer to obtain a result shown in or similar to a graph shown in FIG. 3 or a graph 4; wherein the wavelength of excitation 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 modifications and variations to the ordered polystyrene @ gold composite microsphere array with dynamically adjustable gaps of the present invention and the preparation method and use thereof without departing from the spirit and scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. The preparation method of 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 is characterized in that:
The noble metal is an ordered gold composite microsphere array;
the ball spacing of the gold composite microspheres forming the ordered gold composite microsphere array is 50-65nm;
the ball diameter of the gold composite microsphere with the ball spacing of 50-65nm is 150-935nm;
The gold composite microsphere with the sphere diameter of 150-935nm is formed by coating a gold film with the thickness of 25-30nm on the surface of a polystyrene sphere with the sphere diameter of 100-875 nm;
Sequentially placing an ordered polystyrene@gold composite microsphere array with a dynamically adjustable gap in a solution of an object to be measured for 1-2h at 105-115 ℃ for 50-70s, taking the ordered polystyrene@gold composite microsphere array as an active substrate for surface-enhanced Raman scattering, and measuring the object to be measured attached to the ordered polystyrene@gold composite microsphere array by using a laser Raman spectrometer;
The preparation method of the ordered polystyrene@gold composite microsphere array comprises the following steps:
Step 1, placing a single-layer colloid crystal template formed by polystyrene colloid spheres with the sphere diameter of 200-1000nm on a heat-induced shrinkage polyvinyl chloride substrate to obtain the heat-induced shrinkage polyvinyl chloride substrate with the single-layer colloid crystal template thereon;
Step 2, carrying out plasma etching on a single-layer colloid crystal template on the heat-induced shrinkage polyvinyl chloride substrate to obtain the heat-induced shrinkage polyvinyl chloride substrate with a single-layer non-closely-spaced polystyrene sphere template with the spacing between two adjacent colloid spheres of 100-125 nm;
And 3, depositing a gold film with the thickness of 25-30nm on the thermally-induced shrinkage polyvinyl chloride substrate with the monolayer non-closely arranged polystyrene sphere template by using a sputtering coating method to prepare the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps.
2. The method for preparing the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps according to claim 1, wherein the ordered gold composite microsphere array is a single-layer loose microsphere array which is arranged in an ordered hexagonal manner.
3. The method for preparing the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps according to claim 1, wherein the gold film consists of gold particles with the particle size of 5-20 nm.
4. The method for preparing the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps according to claim 1, wherein a single-layer colloidal crystal template is placed on a thermally-induced shrinkage polyvinyl chloride substrate and is cleaned in a plasma cleaner for 2min.
5. The method for preparing the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps according to claim 1, which is characterized in that the gas atmosphere during plasma etching is argon, the power is 58W and the time is 4-15min.
6. The method for preparing the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps according to claim 1, which is characterized in that the working current during sputtering coating is 30mA.
7. The method for preparing the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps according to claim 1, which is characterized in that the excitation light of a laser Raman spectrometer has a wavelength of 532nm, a power of 0.2-0.4mW and an integration time of 6-10s.
8. The method for preparing the ordered polystyrene@gold composite microsphere array with dynamically adjustable gaps according to claim 1, wherein the object to be detected is rhodamine 6G, or thiram, or methyl parathion, or aflatoxin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010929107.XA CN112113949B (en) | 2020-09-07 | 2020-09-07 | Ordered polystyrene@gold composite microsphere array with dynamically adjustable gap and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010929107.XA CN112113949B (en) | 2020-09-07 | 2020-09-07 | Ordered polystyrene@gold composite microsphere array with dynamically adjustable gap and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112113949A CN112113949A (en) | 2020-12-22 |
| CN112113949B true CN112113949B (en) | 2024-05-14 |
Family
ID=73803286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010929107.XA Active CN112113949B (en) | 2020-09-07 | 2020-09-07 | Ordered polystyrene@gold composite microsphere array with dynamically adjustable gap and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112113949B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114354568A (en) * | 2021-12-06 | 2022-04-15 | 西北大学 | Surface-enhanced Raman spectrum substrate, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2020
- 2020-09-07 CN CN202010929107.XA patent/CN112113949B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Manipulating "hot spots" from nanometer to Angstrom: Toward understanding integrated contributions of molecule number and gap size for ultrasensitive surface-enhanced raman scattering detection;Hui Lu et al.;《Applied materials &interfaces》;第39359-39368页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112113949A (en) | 2020-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Highly ordered arrays of hat-shaped hierarchical nanostructures with different curvatures for sensitive SERS and plasmon-driven catalysis | |
| Asiala et al. | Characterization of hotspots in a highly enhancing SERS substrate | |
| Addison et al. | Nanoparticle-containing structures as a substrate for surface-enhanced Raman scattering | |
| Cara et al. | Influence of the long-range ordering of gold-coated Si nanowires on SERS | |
| Xia | A Review on Applications of Two‐Dimensional Materials in Surface‐Enhanced Raman Spectroscopy | |
| Zhang et al. | Tapered fiber probe modified by Ag nanoparticles for SERS detection | |
| Cao et al. | A highly reproducible and sensitive fiber SERS probe fabricated by direct synthesis of closely packed AgNPs on the silanized fiber taper | |
| Dong et al. | Flexible and transparent Au nanoparticle/graphene/Au nanoparticle ‘sandwich’substrate for surface-enhanced Raman scattering | |
| Liu et al. | The SERS response of semiordered Ag nanorod arrays fabricated by template oblique angle deposition | |
| Liu et al. | Fabrication, characterization, and high temperature surface enhanced Raman spectroscopic performance of SiO 2 coated silver particles | |
| Zheng et al. | Surface‐Enhanced Raman Scattering (SERS) Substrate based on large‐area well‐defined gold nanoparticle arrays with high SERS uniformity and stability | |
| Elsayed et al. | Silicon-based SERS substrates fabricated by Electroless etching | |
| Yang et al. | 3D hotspots platform for plasmon enhanced Raman and second harmonic generation spectroscopies and quantitative analysis | |
| Prasad et al. | Ripple mediated surface enhanced Raman spectroscopy on graphene | |
| CN112113949B (en) | Ordered polystyrene@gold composite microsphere array with dynamically adjustable gap and preparation method and application thereof | |
| Oates et al. | Combinatorial surface-enhanced Raman spectroscopy and spectroscopic ellipsometry of silver island films | |
| CN104975279B (en) | A kind of colloidal sol and method for preparing surface enhanced Raman substrate | |
| Wu et al. | Ultrawideband surface enhanced Raman scattering in hybrid graphene fragmented‐gold substrates via cold‐etching | |
| CN110146485B (en) | Gold triangular pit array material and preparation method and application thereof | |
| Yin et al. | Highly sensitive and stable SERS substrate fabricated by co-sputtering and atomic layer deposition | |
| Hu et al. | Preparation and SERS performance of gold nanoparticles-decorated patterned silicon substrate | |
| RU2543691C2 (en) | Renewable carrier for surface-enhanced raman scattering detection | |
| JP7247493B2 (en) | Substrate for surface-enhanced Raman analysis | |
| Ermina et al. | Silver particles embedded in silicon: The fabrication process and their application in surface enhanced Raman scattering (SERS) | |
| Nowak et al. | Preparation and characterization of long-term stable SERS active materials as potential supports for medical diagnostic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |