CN115011932B - Porous cone array with broadband and omnibearing surface-enhanced Raman scattering and preparation method thereof - Google Patents
Porous cone array with broadband and omnibearing surface-enhanced Raman scattering and preparation method thereof Download PDFInfo
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- 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
Abstract
A porous cone array with broadband and omnibearing surface-enhanced Raman scattering and a preparation method thereof belong to the technical field of surface-enhanced Raman spectroscopy materials. The porous cone array prepared by the invention has the performance of broadband and omnibearing light absorption, provides a multiple hot spot and limited-field enhanced electromagnetic field, and has sensitive quantitative and trace detection performance. The method still has good detection capability under different excitation wavelengths or different incidence angles, namely the detection capability of broadband and omnibearing surface enhanced Raman scattering. The broadband performance means that the broadband Raman spectrometer has universality under different Raman excitation wavelengths, and a complex process of designing and preparing different nano-micro structures to match the Raman excitation wavelengths is avoided; the omnibearing performance means that the device has universality under different incidence angles, and errors caused by experimental operation can be reduced. The invention provides an effective and convenient preparation method for preparing a broadband and omnibearing surface-enhanced Raman scattering substrate, and has important significance for the practical application of Raman detection.
Description
Technical Field
The invention belongs to the technical field of surface-enhanced Raman spectroscopy materials, and particularly relates to a porous cone array with broadband and omnibearing surface-enhanced Raman scattering and a preparation method thereof.
Background
Surface-Enhanced Raman Scattering (SERS), which is a vibration spectroscopy technique capable of amplifying Raman Scattering signals of analytes and providing abundant molecular structure information [1] Because of its ultrasensitive detection ability, it has wide application in biosensing, environmental monitoring and drug detection [2-4] 。
The enhanced electromagnetic field of the metal nano-micro structure brought by the Localized Surface Plasmon Resonance (LSPR) is beneficial to improving the Surface enhanced Raman scattering, and has been widely concerned in the last decade, and various different nano-micro structuresIs designed and prepared [5-7] . The general strategy for preparing the nano-micro structures is to design a specific structure size, so that the LSPR peak position of the nano-micro structures is matched with the SERS excitation wavelength to amplify the Raman scattering signal of the object to be detected, so that the nano-micro structures with different sizes are required to be prepared to match the Raman excitation wavelength, and the design is complex, and consumes much time and labor. Therefore, the design of the surface enhanced Raman scattering substrate which is universal under various excitation wavelengths has very important significance. In addition, the general SERS substrate shows good signal response only when light vertically enters, so that the prepared SERS substrate with good detection performance when light enters from different inclined angles, namely the omnibearing SERS substrate is beneficial to reducing errors caused by experimental operation and has very important significance. In conclusion, the method for preparing the substrate with the broadband and omnibearing surface enhanced Raman scattering by the aid of the method is simple and low in cost, and has important significance.
[1]Langer,J.；Jimenez de Aberasturi,D.；Aizpurua,J.；Alvarez-Puebla,R.A.；Auguie,B.；Baumberg,J.Liz-Marzan,L.M.et al.,ACS Nano 2020,14,28-117.
[2]Liu,Y.；Kim,M.；Cho,S.H.；Jung,Y.S.,Nano Today 2021,37,101063.
[3]Xu,K.；Zhou,R.；Takei,K.；Hong,M.,Adv.Sci.2019,6,1900925.
[4]Chen,J.；Huang,Y.；Kannan,P.；Zhang,L.；Lin,Z.；Zhang,J.；Chen,T.；Guo,L.,Anal.Chem.2016,88,2149-2155.
[5]Ma,J.；Liu,W.；Ma,Z.；Song,P.；Zhao,Y.；Yang,F.；Wang,X.,Nanoscale 2019,11,20194-20198.
[6]Lee,N.；Kim,R.；Kim,J.Y.；Ko,J.B.；Park,S.-H.K.；Kim,S.O.；Brongersma,M.L.；Shin,J.,ACS Photonics 2021,8,1616-1622.
[7]Huang,F.M.；Wilding,D.；Speed,J.D.；Russell,A.E.；Bartlett,P.N.；Baumberg,J.J.,Nano Lett 2011,11,1221-1226.
Disclosure of Invention
The invention aims to provide a simple and low-cost porous cone array with broadband and omnibearing surface-enhanced Raman scattering and a preparation method thereof.
The method relates to a colloid microsphere interface assembly method, a mask etching method and a physical vapor deposition method. The whole process is simple to operate, high in controllability, efficient and low in cost. By combining a mask etching method and a physical vapor deposition technology, a porous cone array with broadband and omnibearing surface enhanced Raman scattering can be prepared in a large area, the optical properties of broadband and omnibearing light capture are favorable for capturing incident light, a limited-area enhanced electromagnetic field is further formed, multiple hot spots are provided, and trace and quantitative detection of an analyte is realized. Further, the porous cone array also has good Raman detection performance under different Raman excitation wavelengths or different incidence angles. The porous cone array can realize broadband and omnibearing surface enhanced scattering detection and has important significance on the practical application of Raman detection. The broadband performance means that the broadband Raman spectrometer has universality under different Raman excitation wavelengths, and a complex process of designing and preparing different nano-micro structures to match the Raman excitation wavelengths is avoided; the omnibearing performance means that the device has universality under different incidence angles, and errors caused by experimental operation can be reduced.
The invention relates to a porous cone array with broadband and omnibearing surface enhanced Raman scattering and a preparation method thereof, comprising the following steps:
1) After the substrate is subjected to hydrophilic treatment, spin-coating a layer of polystyrene toluene solution (100-300 mg/mL) at the rotating speed of 1000-3000 rpm, and placing for 10-60 minutes at the temperature of 80-100 ℃ so as to obtain a polystyrene film with the cured thickness of 2-10 mu m on the substrate;
2) Dropwise adding deionized water ethanol dispersion liquid of polystyrene microspheres (the diameter is 1-4 mu m) onto the surface of deionized water, then dropwise adding an anionic surfactant, obtaining a polystyrene microsphere monomolecular layer in hexagonal close arrangement by a gas-liquid interface method, and then transferring the polystyrene microsphere monomolecular layer onto the substrate obtained in the step 1) and cured with a polystyrene film; after natural drying, placing the substrate in a reactive plasma etcher for mask etching, etching the lower polystyrene film simultaneously under the mask action of the upper polystyrene microspheres, and forming a micro-cone array by the lower polystyrene film when the upper polystyrene microspheres are just etched and disappear, so as to obtain the polystyrene micro-cone array on the substrate (the thickness of the polystyrene film is larger than the diameter of the polystyrene microspheres, and the flat film part between the polystyrene micro-cone and the micro-cone is still polystyrene, so that the whole micro-cone is continuous; the height of the micro-cone is slightly less than the diameter of the polystyrene microspheres, for example, the diameter of the polystyrene microspheres is 3 mu m, and the height of the finally obtained micro-cone is about 2.5 mu m);
3) Dropwise adding deionized water ethanol dispersion liquid of polystyrene microspheres (the diameter is 180-700 nm) onto the surface of deionized water, then dropwise adding an anionic surfactant, obtaining a polystyrene microsphere monomolecular layer in hexagonal close arrangement by a gas-liquid interface method, then transferring the polystyrene microsphere monomolecular layer onto a hydrophilic substrate, naturally drying, and then placing the polystyrene microsphere monomolecular layer into a reactive plasma etching machine for etching to reduce the diameter of the polystyrene microspheres to 120-600 nm; a layer of gold film with the thickness of 60-150 nm is deposited by thermal evaporation perpendicular to the surface of the substrate, the gold film covers the upper surface of the etched polystyrene microspheres and the hydrophilic substrate between the polystyrene microspheres, then the substrate is immersed in a toluene solution, and the polystyrene microspheres and the gold film on the upper surface of the polystyrene microspheres are removed by ultrasonic treatment for 1-5 minutes, so that a gold nanopore array film (the pore diameter is equal to the diameter of the etched polystyrene microspheres, namely 120-600 nm) is obtained on the substrate;
4) Slowly and obliquely immersing the gold nanopore array membrane substrate obtained in the step 3) into hydrofluoric acid aqueous solution (5-10 wt%), so that the gold nanopore array membrane is peeled off from the substrate and floats on a gas-liquid interface; then another hydrophilic substrate is immersed into the hydrofluoric acid aqueous solution, the floating gold nanopore array is slowly fished up and then released on the surface of the deionized water; then, the floating gold nanopore array membrane is slowly fished up by using the polystyrene microcone array substrate obtained in the step 2), the polystyrene microcone array membrane is placed in a reactive plasma etching machine after natural drying, etching is carried out by using the gold nanopore array membrane as a mask, a porous structure is formed on the polystyrene flat membrane between the polystyrene microcone array and the microcones, the aperture is 150-630 nm (the aperture of the finally formed porous structure is 150-630 nm due to anisotropic etching and is slightly larger than the aperture of 120-600 nm of the gold nanopore array membrane), and the pore depth is 400-900 nm; removing the gold nano-pore array film by using a gold etching agent, washing by using deionized water, and after natural drying, performing thermal evaporation and deposition on a silver film with the thickness of 30-80 nm vertical to the surface of the substrate to obtain the silver porous cone array with the broadband and omnibearing surface-enhanced Raman scattering;
5) Placing the silver porous cone array obtained in the step 4) on a sample table of an optical fiber spectrometer to test the reflection spectrum of the silver porous cone array, and then changing the angle of an incident light source to test the reflection spectrum of the silver porous cone array under different incident angles;
6) Soaking the silver porous cone array obtained in the step 4) in a solution with the concentration of 10 -7 ～10 -17 M p-mercaptoaniline analyte ethanol solution is taken out for 5-15 hours, slowly dried by blowing with nitrogen, and then tested with a Raman spectrometer for surface enhanced Raman scattering spectrum;
7) Soaking the silver porous cone array obtained in the step 4) in a solution with the concentration of 10 -7 And (3) adding M into the p-mercaptoaniline ethanol solution for 5-15 hours, taking out, slowly drying by using nitrogen, changing the light incidence angle and the excitation wavelength by using a Raman spectrometer, and testing the broadband and omnibearing surface enhanced Raman scattering spectrum.
Further, the air conditioner is provided with a fan,
the substrate in the step 1) is a glass sheet or a quartz sheet.
In the step 2), the deionized water ethanol dispersion liquid of the polystyrene microspheres (the diameter is 1-4 mu m) is prepared by adding 1-6 mL of deionized water into 1-15 wt% of deionized water dispersion liquid of 1-5 mL of polystyrene microspheres, performing ultrasonic treatment for 10-35 minutes, and then centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; removing supernatant, adding 1-6 mL of deionized water into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; repeating the steps of adding deionized water, ultrasonic treatment and centrifugation for 5-12 times to the centrifuged lower polystyrene microsphere precipitate; removing supernatant, adding 1-6 mL of mixed solution of ethanol and deionized water (the volume ratio is 1:1) into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; repeating the steps of adding the mixed solution of ethanol and deionized water into the lower polystyrene microsphere precipitate obtained after centrifugation, and performing ultrasonic treatment and centrifugation for 5-12 times; adding 1-5 mL of mixed solution of ethanol and deionized water (the volume ratio is 1:1) into the polystyrene microsphere precipitate obtained by the last centrifugation, and performing ultrasonic treatment for 40-100 minutes to obtain the deionized water ethanol dispersion of the polystyrene microspheres (the diameter is 1-4 mu m).
The etching conditions in the step 2) are as follows: the pressure is 5-15 mTorr, the oxygen flow is 20-60 sccm, the etching power is 100-200W, and the etching time is 8-15 minutes.
The deionized water ethanol dispersion liquid of the polystyrene microspheres (the diameter is 180-700 nm) in the step 3) is prepared by adding 1-6 mL of deionized water into 1-15 wt% and 1-5 mL of deionized water dispersion liquid of the polystyrene microspheres, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; removing supernatant, adding 1-6 mL of deionized water into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; repeating the steps of adding deionized water, ultrasonic treatment and centrifugation for 5-12 times to the centrifuged lower polystyrene microsphere precipitate; removing supernatant, adding 1-6 mL of mixed solution of ethanol and deionized water (the volume ratio is 1:1) into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; adding the mixed solution of ethanol and deionized water into the centrifuged lower-layer polystyrene microsphere precipitate, and performing ultrasonic treatment and centrifugation for 5-12 times; adding 1-5 mL of mixed solution of ethanol and deionized water (the volume ratio is 1:1) into the polystyrene microsphere precipitate obtained by the last centrifugation, and performing ultrasonic treatment for 40-100 minutes to obtain deionized water ethanol dispersion of polystyrene microspheres (the diameter is 180-700 nm).
The etching conditions in the step 3) are as follows: the pressure is 5-15 mTorr, the oxygen flow is 20-60 sccm, the etching power is 50-200W, and the etching time is 2-6 minutes. The degree of vacuum of thermal deposition is 5X 10 -4 ～2×10 -4 Pa, deposition rate of
The etching conditions in the step 4) are as follows: the pressure is 5-15 mTorr, the oxygen flow is 20-60 sccm, the etching power is 50-200W, and the etching time is 2-8 minutes. The degree of vacuum of thermal deposition is 5X 10 -4 ～2×10 -4 Pa, deposition rate of
The spectrum range in the step 5) is 400-1000 nm.
And 6) the laser wavelength of the Raman spectrometer is 633nm, the laser transmittance is 2.5-15%, and the accumulation time is 5-10 seconds.
And 7) the laser wavelength incidence angle of the Raman spectrometer is 0-60 degrees, the excitation wavelengths are 532nm, 633nm and 785nm, the laser transmittance is 2.5-15 percent, and the accumulation time is 5-15 seconds.
The steps of the invention are simple to operate, and the prepared porous cone array has optical performance of broadband and omnibearing light capture, thereby further limiting the field to enhance the electromagnetic field, providing multiple hot spots and having the performance of sensitively detecting the analyte quantitatively and in a trace way. The method has good detection capability under different Raman excitation wavelengths or when light enters from different inclined angles, provides a simple, convenient and low-cost preparation method for preparing a broadband and omnibearing surface-enhanced Raman scattering substrate, and has important significance for practical application of Raman detection.
Drawings
FIG. 1 is a schematic flow chart of the preparation of a porous cone array; the nano-porous silver film comprises a hydrophilic substrate 1, a polystyrene film 2, polystyrene microspheres 3 (the diameter is 1-4 mu m), a polystyrene micro-cone array 4, a gold nano-porous array film template 5 (the aperture is 120-600 nm), a polystyrene porous cone array 6 and a silver film 7.D represents the depth (400-900 nm) of the etched hole on the porous cone.
FIG. 2 is a Scanning Electron Microscope (SEM) picture of an array of porous cones. The oblique view is shown in (A) and the cross-sectional view is shown in (B). From SEM, it can be seen that, by etching with a gold nanopore array membrane (aperture 220 nm) as a template, porous structures are formed on polystyrene micro-cone arrays and the polystyrene flat membrane part between the micro-cones, and sharp edges are formed at the same time, so as to provide multiple hot spots and improve surface enhanced Raman scattering.
FIG. 3 shows (A) the concentration of analyte p-mercaptoaniline on a multi-well cone array of 10 -7 ～10 -17 Surface enhanced raman scattering spectrum at M. At analyte concentrations as low as 10 -17 And a characteristic Raman peak can be still observed when M is adopted, so that the porous cone array has sensitive trace detection capability. (B) Is 1140cm -1 The Raman intensity is in a relation graph with the change of the analyte concentration, and a good linear relation proves that the porous cone array has sensitive quantitative detection capability.
FIG. 4 is a graph (A) showing the reflectance spectrum of a porous cone at different incident angles (0-60 deg.) with slightly increasing reflectance (but not absolutely, e.g., with respect to the incident angles of 30 deg. and 45 deg., 45 deg. within 400-650 nm is slightly less reflectance and 30 deg. within 650-1000 nm is less reflectance, and with the exception of this, the reflectance at other angles is increased with increasing angle, but less than 10% at different incident angles within the range of 400-900 nm, demonstrating the omnidirectional, broadband light trapping performance of the porous cone array; therefore, the optical performance of broadband and omnibearing light capture of the porous cone array is beneficial to improving the surface enhanced Raman scattering. (B) For Raman spectra of analytes at different angles of incidence, 1140cm can be seen -1 And 1438cm -1 The Raman intensity of the porous cone array is hardly reduced along with the increase of the incident angle of light, and the fact that the porous cone array has the performance of omnibearing surface enhanced Raman scattering is proved. (C) The Raman spectrum under the excitation wavelengths of 532nm, 633nm and 785nm, the Raman characteristic peaks of the analytes under different excitation wavelengths are clear and distinguishable, and the fact that the porous cone array has the performance of broadband surface enhanced Raman scattering is proved.
Detailed Description
Example 1: preparation of hydrophilic glass sheets
Cutting the glass sheet into a size with the width of 2cm and the length of 2.5cm by a glass cutter, placing the cut glass sheet into a mixed solution of concentrated sulfuric acid (the mass fraction is 98%) and hydrogen peroxide (the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 7:3), heating for 3 hours in a water bath kettle at 80 ℃, washing for about 6 times by deionized water, and drying by nitrogen to obtain the hydrophilic glass sheet.
Example 2: preparation of polystyrene film
A toluene solution of polystyrene (concentration of 200 mg/mL) was spin-coated on a hydrophilic glass plate at 3000rmp using a bench-top spin coater, and was then placed in an oven at 100 ℃ for 10 minutes, and then removed to be naturally cooled to room temperature, to obtain a polystyrene thin film having a cured thickness of 5 μm based on a glass substrate.
Example 3: preparation of polystyrene microsphere ethanol and deionized water dispersion
At room temperature, 1mL of 10wt% polystyrene microsphere aqueous dispersion with the diameter of 3 μm is taken, 6mL of deionized water is dripped into the aqueous dispersion, ultrasonic treatment is carried out for 20 minutes at 100% power, and then centrifugation is carried out for 20 minutes at the rotating speed of 8600 rpm; removing the supernatant, adding 6mL of deionized water into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 20 minutes, and centrifuging at the rotating speed of 8600rpm for 20 minutes; repeating the steps of adding deionized water into the polystyrene microsphere sediment at the lower layer, performing ultrasonic treatment and centrifuging for 6 times; removing the supernatant, adding 3mL of mixed solution of ethanol and deionized water (the volume ratio is 1:1) into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 20 minutes, and then centrifuging at 8600rpm for 20 minutes; adding the mixed solution of absolute ethyl alcohol and deionized water into the lower polystyrene microsphere precipitate, and performing ultrasonic treatment and centrifugal treatment for 6 times; and adding 3mL of mixed solution of ethanol and deionized water (the volume ratio is 1:1) into the polystyrene microsphere precipitate obtained at the last time, and performing ultrasonic treatment for 50 minutes to obtain the deionized water ethanol dispersion of the polystyrene microsphere with the diameter of 3 mu m.
At room temperature, 1mL of 10wt% polystyrene microsphere aqueous dispersion with the diameter of 300nm is taken, 6mL of deionized water is dripped into the aqueous dispersion, and after ultrasonic treatment is carried out for 20 minutes at 100% power, the aqueous dispersion is centrifuged at 8900rpm for 20 minutes; removing the supernatant, adding 6mL of deionized water into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 20 minutes, and centrifuging at 8900rpm for 20 minutes; repeating the steps of adding deionized water into the polystyrene microsphere sediment at the lower layer, performing ultrasonic treatment and centrifuging for 6 times; removing the supernatant, adding 3mL of mixed solution of ethanol and deionized water (the volume ratio is 1:1) into the lower polystyrene microsphere precipitate, carrying out ultrasonic treatment for 20 minutes, and then centrifuging at 8900rpm for 20 minutes; adding the mixed solution of absolute ethyl alcohol and deionized water into the lower polystyrene microsphere precipitate, and performing ultrasonic treatment and centrifugal treatment for 6 times; and adding 3mL of mixed solution of ethanol and deionized water (the volume ratio is 1:1) into the polystyrene microsphere precipitate obtained at the last time, and performing ultrasonic treatment for 50 minutes to obtain the polystyrene microsphere deionized water ethanol dispersion liquid with the diameter of 300 nm.
Example 4: preparation of hexagonal close-packed monolayer polystyrene colloidal crystal
0.5mL of the polystyrene microsphere deionized water ethanol dispersion solution with the diameter of 3 micrometers prepared in example 3 was sucked by a disposable medical syringe (the model specification is 1 mL), slowly injected into a deionized water-air interface in a culture dish, and then 2 drops of sodium dodecyl sulfate aqueous solution with the concentration of 8wt% were added dropwise so that the polystyrene microspheres were arranged in a hexagonal close-packing manner, thereby obtaining a polystyrene microsphere monolayer structure with the diameter of 3 micrometers. The glass substrate of the polystyrene film solidified with the thickness of 5 μm in the example 2 is obliquely extended below the liquid level, the monolayer microspheres are slowly fished up and placed on the inclined plane for natural drying, and the monolayer closely-arranged polystyrene colloidal crystals (the diameter is 3 μm) based on the polystyrene film are obtained.
0.5mL of the 300nm diameter polystyrene microsphere deionized water ethanol dispersion prepared in example 3 was slowly injected into a culture dish at the deionized water-air interface row by a disposable medical syringe (model specification of 1 mL), and then 2 drops of an 8wt% aqueous solution of sodium dodecyl sulfate were added dropwise, and the polystyrene microspheres were arranged in a hexagonal close-packed manner to form a monolayer structure. The other hydrophilic glass substrate prepared in example 1 was tilted to a position below the liquid level, and the monolayer microspheres were slowly scooped up and placed on a slope for natural drying to obtain a monolayer tightly-arranged polystyrene colloidal crystal (diameter 300 nm) based on a glass substrate.
Example 5: preparation of gold nanopore array membrane
The polystyrene microsphere substrate with the diameter of 300nm prepared in the example 4 is placed in a reactive plasma etching machine, and the etching temperature is 20 ℃, the etching power is 100W, the etching pressure is 10mTorr, and oxygen is addedThe polystyrene microsphere is reduced to 220nm in diameter by etching for 180 seconds under the condition of the gas flow rate of 60 sccm. The sample was then placed in a vacuum evaporation coating apparatus at 5X 10 -4 Under Pa vacuum degree, gold film with thickness of 80nm is deposited by thermal evaporation perpendicular to the surface of the substrate at deposition speed
The gold film covers the upper surface of the etched polystyrene microspheres and the glass substrate between the polystyrene microspheres; and immersing the substrate in a toluene solution for ultrasonic treatment for 1 minute, and removing the etched polystyrene microspheres and the gold film on the surface of the polystyrene microspheres to obtain the gold nanopore array membrane template (with the aperture of 220 nm) based on the glass substrate.
Example 6: preparation of polystyrene microcone array
The polystyrene microsphere substrate with a diameter of 3 μm based on the polystyrene thin film prepared in example 4 was placed in a reactive plasma etcher and etched for 10 minutes under the conditions of an etching temperature of 20 ℃, an etching power of 200W, an etching pressure of 10mTorr, and an oxygen flow rate of 60 sccm. The lower polystyrene film is etched simultaneously under the action of the mask of the upper polystyrene microspheres, and when the upper polystyrene microspheres are just etched and disappear, the lower polystyrene film forms a microcone array, so that a polystyrene microcone array is obtained on the substrate (the thickness (5 mu m) of the polystyrene film is larger than the diameter (3 mu m) of the polystyrene microspheres, the flat film part between the polystyrene microcones and the microcones is still polystyrene, so that the whole microcones are continuous, and the height of the microcones is about 2.5 mu m and is slightly smaller than the diameter of the polystyrene microspheres).
Example 7: preparation of polystyrene porous cone array
The gold nanopore array membrane substrate prepared in example 5 was obliquely immersed in a hydrofluoric acid aqueous solution (10 wt%), so that the gold nanopore array membrane was peeled off from the substrate and floated at a gas-liquid interface; immersing another hydrophilic glass substrate into the hydrofluoric acid aqueous solution to slowly pick up the floating gold nanopore array, and then releasing the gold nanopore array on the surface of deionized water; immersing the polystyrene micro-cone array substrate prepared in the embodiment 6 into deionized water and slowly fishing up to attach the gold nanopore array membrane on the surface of the polystyrene micro-cone array substrate, and naturally drying at room temperature; placing the sample in a reactive plasma etcher, and forming a porous structure on a polystyrene flat film between a polystyrene micro-cone array and a micro-cone under the action of a mask of an upper layer gold nano-pore array film under the conditions that the etching temperature is 20 ℃, the etching power is 200W, the etching pressure is 10mTorr and the oxygen flow rate is 50sccm, wherein the pore diameter is 250nm (the pore diameter of the finally formed porous structure is slightly larger than the pore diameter (220 nm) of the gold nano-pore array film due to anisotropic etching); and removing the upper layer of gold nanopore array film by using a gold etching agent to obtain the polystyrene porous cone array.
Example 8: vapor deposition method of metal layer
The polystyrene porous cone array substrate treated in example 7 was placed on a sample stage of a vacuum evaporation coating apparatus in a direction perpendicular to the substrate at 5X 10 -4 Depositing silver by thermal evaporation under the vacuum degree of Pa, and the deposition speed
And depositing the silver porous cone array to a thickness of 50nm to obtain the silver porous cone array.
Example 9: method for testing trace detection capability of porous cone array
The sample obtained in example 8 was immersed in a solution having a concentration of 10 -7 ～10 -17 And (3) the p-mercaptoaniline analyte of M is put in an ethanol solution for 12 hours, taken out and dried by nitrogen, and the sample is placed on a detection table of a Raman spectrometer for Raman spectrum measurement.
Example 10: method for detecting broadband and omnibearing light capture property of porous cone array
The sample obtained in example 8 was placed on a sample stage of a fiber spectrometer, and the reflectance spectrum was measured in a wavelength range of 400 to 1000nm, and the reflectance properties thereof were measured at different incident angles.
Example 11: method for detecting broadband and omnibearing surface Raman enhanced scattering of porous cone array
The sample obtained in example 8 was soaked at a concentration of 10 -7 M p-mercaptoaniline ethanol solution for 12 hours, and takingAnd drying the discharged nitrogen, and testing the broadband and omnibearing surface enhanced Raman scattering spectrum by using a Raman spectrometer under different incident angles and different excitation wavelengths.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the method scheme of the present invention in any way. Any simple modifications, equivalent changes and modifications of the above embodiments according to the method substance of the present invention fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a porous cone array with broadband and omnibearing surface enhanced Raman scattering comprises the following steps:
1) After the substrate is subjected to hydrophilic treatment, spin-coating a layer of polystyrene toluene solution with the concentration of 100-300 mg/mL at the rotating speed of 1000-3000 rpm, and placing for 10-60 minutes at the temperature of 80-100 ℃ so as to obtain a polystyrene film with the cured thickness of 2-10 mu m on the substrate;
2) Dropwise adding deionized water ethanol dispersion liquid of polystyrene microspheres with the diameter of 1-4 mu m onto the surface of deionized water, then dropwise adding an anionic surfactant, obtaining a polystyrene microsphere monomolecular layer in hexagonal close arrangement by a gas-liquid interface method, and then transferring the polystyrene microsphere monomolecular layer to the substrate with the cured polystyrene film obtained in the step 1); after natural drying, placing the substrate in a reactive plasma etcher for mask etching, etching the lower polystyrene film simultaneously under the mask action of the upper polystyrene microspheres, and forming a micro-cone array on the lower polystyrene film when the upper polystyrene microspheres are etched and disappear, thereby obtaining the polystyrene micro-cone array on the substrate;
3) Dropwise adding deionized water ethanol dispersion liquid of polystyrene microspheres with the diameter of 180-700 nm to the surface of deionized water, then dropwise adding an anionic surfactant, obtaining a polystyrene microsphere monomolecular layer in hexagonal close arrangement by a gas-liquid interface method, then transferring the polystyrene microsphere monomolecular layer to a hydrophilic substrate, naturally drying, and then placing the polystyrene microsphere monomolecular layer in a reactive plasma etching machine for etching to reduce the diameter of the polystyrene microspheres to 120-600 nm; then a layer of gold film with the thickness of 60-150 nm is deposited in a way of thermal evaporation and is vertical to the surface of the substrate, the gold film covers the upper surface of the etched polystyrene microspheres and the hydrophilic substrate among the polystyrene microspheres, then the substrate is immersed in a toluene solution, and the polystyrene microspheres are removed by ultrasonic treatment for 1-5 minutes, so that the gold nanopore array membrane is obtained on the substrate;
4) Slowly and obliquely immersing the substrate of the gold nanopore array membrane obtained in the step 3) into a hydrofluoric acid aqueous solution with the concentration of 5-10 wt% to peel off the gold nanopore array membrane from the substrate and float on a gas-liquid interface; then another hydrophilic substrate is immersed into the hydrofluoric acid aqueous solution, the floating gold nanopore array is slowly fished up and then released on the surface of the deionized water; then, slowly taking the floating gold nanopore array membrane out by using the polystyrene microcone array substrate obtained in the step 2), naturally drying the gold nanopore array membrane, placing the gold nanopore array membrane in a reactive plasma etching machine, etching by using the gold nanopore array membrane as a mask, and forming a porous structure on the polystyrene flat membrane between the polystyrene microcone array and the microcones, wherein the pore diameter is 150-630 nm, and the pore depth is 400-900 nm; and then removing the gold nano-pore array film by using a gold etching agent, washing by using deionized water, and after natural drying, performing thermal evaporation and deposition on a silver film with the thickness of 30-80 nm vertical to the surface of the substrate, thereby obtaining the silver porous cone array with the broadband and omnibearing surface-enhanced Raman scattering.
2. The method of claim 1, wherein the array of porous cones with broadband, omnidirectional surface-enhanced raman scattering comprises: the substrate in the step 1) is a glass sheet or a quartz sheet.
3. The method of claim 1, wherein the array of porous cones with broadband, omnidirectional surface-enhanced raman scattering comprises: in the step 2), the deionized water ethanol dispersion solution of polystyrene microspheres with the diameter of 1-4 microns is prepared by adding 1-6 mL of deionized water into the deionized water dispersion solution of polystyrene microspheres with the concentration of 1-15 wt%, 1-5 mL and the diameter of 1-4 microns, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; removing supernatant, adding 1-6 mL of deionized water into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; repeating the steps of adding deionized water into the lower polystyrene microsphere precipitate obtained after centrifugation, performing ultrasonic treatment and centrifuging for 5 to 12 times; removing supernatant, and adding 1-6 mL of polystyrene microsphere precipitate with the volume ratio of 1:1, carrying out ultrasonic treatment for 10-35 minutes on the mixed solution of the absolute ethyl alcohol and the deionized water, and centrifuging for 10-35 minutes at the rotating speed of 5000-9000 rpm; adding the mixed solution of ethanol and deionized water into the centrifuged lower-layer polystyrene microsphere precipitate, and performing ultrasonic treatment and centrifugation for 5-12 times; adding 1-5 mL of polystyrene microsphere precipitate obtained by the last centrifugation, wherein the volume ratio of the polystyrene microsphere precipitate is 1:1, and performing ultrasonic treatment for 40-100 minutes to obtain the deionized water ethanol dispersion liquid of the polystyrene microspheres with the diameter of 1-4 mu m.
4. The method of claim 1, wherein the array of porous cones with broadband, omnidirectional surface-enhanced raman scattering comprises: the reactive plasma etching conditions in the step 2) are 5-15 mTorr of pressure, 20-60 sccm of oxygen flow, 100-200W of etching power and 8-15 minutes of etching time.
5. The method of claim 1, wherein the array of porous cones with broadband, omnidirectional surface-enhanced raman scattering comprises: in the step 3), the deionized water ethanol dispersion liquid of polystyrene microspheres with the diameter of 180-700 nm is prepared by adding 1-6 mL of deionized water into the deionized water dispersion liquid of polystyrene microspheres with the concentration of 1-15 wt%, 1-5 mL and the diameter of 180-700 nm, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; removing supernatant, adding 1-6 mL of deionized water into the lower polystyrene microsphere precipitate, performing ultrasonic treatment for 10-35 minutes, and centrifuging at the rotating speed of 5000-9000 rpm for 10-35 minutes; repeating the steps of adding deionized water into the lower polystyrene microsphere precipitate obtained after centrifugation, performing ultrasonic treatment and centrifuging for 5 to 12 times; removing the supernatant, and adding 1-6 mL of polystyrene microsphere precipitate with the volume ratio of 1:1, performing ultrasonic treatment on the mixed solution of the ethanol and the deionized water for 10 to 35 minutes, and centrifuging the mixed solution for 10 to 35 minutes at the rotating speed of 5000 to 9000 rpm; adding the mixed solution of ethanol and deionized water into the centrifuged lower-layer polystyrene microsphere precipitate, and performing ultrasonic treatment and centrifugation for 5-12 times; adding 1-5 mL of polystyrene microsphere precipitate obtained by the last centrifugation, wherein the volume ratio of the polystyrene microsphere precipitate is 1:1, and performing ultrasonic treatment for 40-100 minutes to obtain the deionized water ethanol dispersion of the polystyrene microspheres with the diameter of 180-700 nm.
6. The method of claim 1, wherein the array of porous cones with broadband, omnidirectional surface-enhanced raman scattering comprises: in the step 3), the reactive plasma etching conditions comprise pressure of 5-15 mTorr, oxygen flow of 20-60 sccm, etching power of 50-200W and etching time of 2-6 minutes; the degree of vacuum of thermal deposition is 5X 10 -4 ～2×10 -4 Pa, deposition rate of
7. The method of claim 1, wherein the array of porous cones with broadband, omnidirectional surface-enhanced raman scattering comprises: in the step 4), the reactive plasma etching conditions comprise pressure of 5-15 mTorr, oxygen flow of 20-60 sccm, etching power of 50-200W and etching time of 2-8 minutes; the degree of vacuum of thermal deposition is 5X 10 -4 ～2×10 -4 Pa, deposition rate of
8. A porous cone array with broadband, omni-directional surface enhanced raman scattering, comprising: is prepared by the process of any one of claims 1 to 7.
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