CN114354568A - Surface-enhanced Raman spectrum substrate, preparation method and application - Google Patents
Surface-enhanced Raman spectrum substrate, preparation method and application Download PDFInfo
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- CN114354568A CN114354568A CN202111478970.9A CN202111478970A CN114354568A CN 114354568 A CN114354568 A CN 114354568A CN 202111478970 A CN202111478970 A CN 202111478970A CN 114354568 A CN114354568 A CN 114354568A
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- G01—MEASURING; TESTING
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- 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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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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Abstract
The invention provides a surface-enhanced Raman spectrum substrate, a preparation method and application; firstly, carrying out fine etching on a microsphere self-assembled monolayer film substrate or a microsphere self-assembled monolayer film glass slide to prepare a fine etching substrate; and then performing primary coating and secondary coating on the fine etching substrate to prepare a surface enhanced Raman spectrum substrate, wherein the gap between adjacent microspheres on the surface enhanced Raman spectrum substrate is 5-10 nm. According to the preparation method, the atomic layer deposition technology is used for preparing the surface-enhanced Raman spectrum substrate, and an inductive coupling plasma etching method and an electron beam evaporation method are combined, so that the signal enhancement effect of the surface-enhanced Raman spectrum substrate can be remarkably improved. The surface-enhanced Raman spectrum substrate can be applied to trace explosive detection.
Description
Technical Field
The invention belongs to the technical field of Raman spectroscopy, relates to a surface-enhanced Raman spectroscopy substrate, and particularly relates to a surface-enhanced Raman spectroscopy substrate, a preparation method and application thereof.
Background
With the development of science and technology and the promotion of globalization process, terrorist attack events frequently occur, which causes great panic and uneasiness to society, seriously threatens the personal and property safety of the social public, and brings extremely serious negative effects to economic development. The rapid and effective detection of the explosives is an important way for maintaining the national security and the social stability. The existing detection method mainly carries out proximity type, close distance, intrusive type and contact type sampling through police dogs or manual handheld equipment, and brings great threat to the personal safety of detection personnel; in an actual detection scene, all explosives appear in trace dose, so that a detection technology for rapidly and accurately detecting and accurately identifying trace explosives in a non-invasive, non-contact and remote and on-site manner is urgently needed to be developed.
The Raman spectrum technology has the advantages of strong anti-interference capability, simple sample preparation, wide measurable spectrum range, easiness in detecting trace samples and the like, and is an important research direction for detecting and identifying trace explosives in recent years. However, the conventional Raman scattering signal is weak (the scattering cross section is 10)-29～10-32cm2Range, compared to about 10 of the fluorescence scattering cross section-16cm2Much weaker, about 1014Double), the detection sensitivity is low, and the application is greatly limited. From 197In 7 years, after Van Duyne et al disclosed the mechanism of the Surface Enhanced Raman scattering phenomenon, Surface Enhanced Raman Spectroscopy (SERS) technology, which takes localized Surface plasmon resonance, chemical adsorption, and charge transfer between particles as basic principles, is becoming a means for detecting trace explosives in recent years due to its superior performance.
Patent No. CN108760713B discloses a method for preparing a uniform surface-enhanced Raman spectrum substrate based on gold nanoparticles, which is characterized in that gold nanoparticles which are densely and uniformly distributed are controllably generated on a silicon wafer through a process of step-by-step generation of gold atoms-gold seed crystals-gold nanoparticles. However, the process is easily affected by the dropping speed of the reagent, and the finally obtained gold nanoparticles are compact in distribution but different in particle size, so that the signal enhancement effect is unsatisfactory.
The patent with the publication number of CN209542455U discloses a PMMA (polymethyl methacrylate) spaced gold nanocube and gold film composite structure low-concentration detection surface-enhanced Raman spectrum substrate, strong resonance coupling is generated through interaction of local surface plasmas around the gold nanocube and transmission surface plasmas at the interface of a PMMA film and a gold film, so that the composite structure has higher electric field enhancement and generates strong surface-enhanced Raman spectrum signals.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a surface-enhanced Raman spectrum substrate, a preparation method and application, and solves the technical problem that the signal enhancement effect of the surface-enhanced Raman spectrum substrate is difficult to improve by adopting a relatively simple process in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a surface-enhanced Raman spectrum substrate comprises a fine etching substrate, wherein the fine etching substrate is a microsphere self-assembled single-layer film substrate or a microsphere self-assembled single-layer film glass slide and is prepared by fine etching, and a plurality of microspheres are arranged on the microsphere self-assembled single-layer film substrate and the microsphere self-assembled single-layer film glass slide;
the microspheres are sequentially provided with a first plating layer and a second plating layer from the inner layer to the outer layer;
gaps between the adjacent microspheres after the coating of the first coating and the second coating and the fine etching are 5-10 nm.
The invention also has the following technical characteristics:
specifically, the average grain diameter of the microspheres is 2-8 μm; the thickness of the first plating layer is 5 nm; the thickness of the second coating is 90-93 nm.
Specifically, the microspheres are polystyrene microspheres; the first coating is Al2O3Film plating; the second plating layer is an Ag film plating layer or an Au film plating layer.
Preferably, the second plating layer is an Au film plating layer.
The invention also discloses a preparation method of the surface-enhanced Raman spectrum substrate, which comprises the following steps:
step one, preparing a microsphere self-assembly monolayer film substrate; or preparing a microsphere self-assembled monolayer film glass slide;
step two, preparing a fine etching substrate;
performing fine etching on the surface of the microsphere self-assembled single-layer film substrate or the microsphere self-assembled single-layer film glass slide prepared in the step one to prepare a fine etching substrate;
step three, preparing a first coating fine etching substrate;
performing first film coating on the fine etching substrate prepared in the step two to prepare a first coating fine etching substrate; the coating temperature of the first coating is 80-92 ℃, and the first coating comprises 200-300 cycles; the film layer plated by the first film plating is a first plating layer;
preparing a surface enhanced Raman spectrum substrate;
performing secondary film coating on the first coating fine etching substrate prepared in the step three to prepare a surface enhanced Raman spectrum substrate; the film layer plated by the second plating is a second plating layer.
Specifically, in the second step, the conditions of the fine etching are as follows: the etching pressure is 7-10 mTorr, the etching voltage is 95-110W, and the etching gas is O2The gas flow rate is 50-60 sccm, and the etching time is 70-80 s.
Specifically, in the third step, each cycle of the first film coating comprises four times of gapless pulses, the first pulse adopts trimethylaluminum, and the pulse duration of the first pulse is 5 s; the second pulse being N2The pulse duration of the second pulse is 1 s; third pulse with H2O (gaseous), the pulse duration of the third pulse being 5 s; the fourth pulse is N2The pulse duration of the fourth pulse is 1 s.
Specifically, in the fourth step, the second coating condition is that the pressure of the reaction chamber is lower than 10-5Pa, deposition rate of
The first coating fine etch substrate is not heated during the second coating process.
Specifically, in the first step, the method for preparing the microsphere self-assembled monolayer film substrate comprises the following steps:
step 1.1.1, preparing microsphere suspension;
dissolving polystyrene microspheres in water to prepare a suspension A, and centrifuging the suspension to obtain a precipitate B; resuspending the precipitate B with absolute ethyl alcohol to obtain a suspension B, and centrifuging the suspension B to obtain a precipitate C; resuspending the precipitate C with n-butanol to obtain microsphere suspension;
step 1.1.2, preparing a precursor solution;
carrying out ultrasonic treatment on the microsphere suspension prepared in the step 1.1.1 for 15 minutes to prepare a precursor solution;
step 1.1.3, preparing a microsphere self-assembled monolayer film;
dropwise adding the precursor solution prepared in the step 1.1.2 into deionized water to prepare a self-assembly mixed solution, and standing the self-assembly mixed solution at room temperature until self-assembly is completed to prepare a microsphere self-assembly single-layer film; after the self-assembly is finished, the self-assembly mixed solution is divided into an upper layer and a lower layer, wherein the upper layer is a water layer, and the lower layer is an organic layer, wherein the water layer contains a microsphere self-assembly single-layer film;
step 1.1.4, attaching a microsphere self-assembly single-layer film;
inclining the pretreated glass slide, slowly inserting the inclined pretreated glass slide into the water layer in the step 1.3, slowly pulling the glass slide out of the water layer, and naturally drying the pretreated glass slide completely pulled out of the water layer so as to attach the microsphere self-assembly single-layer film in the water layer to the glass slide to prepare the microsphere self-assembly single-layer film glass slide;
step 1.1.5, fixing the microsphere self-assembly single-layer film;
inclining the microsphere self-assembly single-layer film glass slide prepared in the step 1.1.4, inserting the inclined microsphere self-assembly single-layer film glass slide into deionized water, fishing out the microsphere self-assembly single-layer film by adopting a pretreated micro-nano pore substrate after the microsphere self-assembly single-layer film floats on the water surface, so that the microsphere self-assembly single-layer film is attached to the pretreated micro-nano pore substrate, heating the pretreated micro-nano pore substrate attached with the microsphere self-assembly single-layer film at 110 ℃ to fix the microsphere self-assembly single-layer film on the micro-nano pore substrate, and preparing a microsphere self-assembly single-layer film substrate;
in the first step, the method for preparing the microsphere self-assembly monolayer film glass slide comprises the following steps:
step 1.2.1, the same as step 1.1.1;
step 1.2.2, the same as step 1.1.2;
step 1.2.3, attaching and fixing the microsphere self-assembly single-layer film;
and (3) dropwise adding the precursor prepared in the step (1.2.2) onto the pretreated glass slide, standing until the self-assembly is completed, and then naturally drying to prepare the microsphere self-assembled monolayer glass slide.
The invention also protects the application of the surface-enhanced Raman spectrum substrate in trace explosive detection.
The invention also protects the application of the surface-enhanced Raman spectrum substrate prepared by the preparation method of the surface-enhanced Raman spectrum substrate in trace explosive detection.
Compared with the prior art, the invention has the following beneficial technical effects:
on the surface-enhanced Raman spectrum substrate, the gap between adjacent microspheres is 5-10 nm; the area capable of generating the enhancement effect on the surface enhanced Raman spectrum substrate is distributed on the rough second coating in the micro-nano pores and the microsphere gaps; the surface-enhanced Raman spectrum substrate can effectively enhance signals of Raman scattering light.
According to the preparation method of the surface-enhanced Raman spectrum substrate, the atomic layer deposition technology is used for preparing the surface-enhanced Raman spectrum substrate, and an inductive coupling plasma etching method and an electron beam evaporation method are combined, so that the preparation method can obviously improve the signal enhancement effect of the surface-enhanced Raman spectrum substrate.
In the invention, the fine etching is carried out by adopting an inductively coupled plasma etching method, so that the particle size of the microspheres can be reduced, and gaps are generated among the microspheres which are closely arranged, thereby forming a non-closely arranged microsphere structure; the first coating is carried out by adopting an atomic layer deposition technology, so that the precise regulation and control of the microsphere gap can be realized; and the electron beam evaporation method is adopted for secondary film coating, so that the precise regulation and control of the microsphere gap can be further realized. The preparation method is relatively simple in process, and the prepared surface enhanced Raman spectrum substrate is good in signal enhancement effect.
(III) the surface enhanced Raman spectrum substrate can be applied to detection of trace explosives, and has very important practical significance for maintaining national safety and social stability.
Drawings
FIG. 1 is a schematic cross-sectional view of a microsphere self-assembled monolayer film substrate of example 1.
FIG. 2 is a schematic cross-sectional view of a finely etched substrate in example 1.
FIG. 3 is a schematic cross-sectional view of the structure of the substrate for surface enhanced Raman spectroscopy in example 1.
Fig. 4 shows the raman spectrum curve measured by the remote raman spectrometer in example 1, where a is the raman spectrum curve spectrum of the microsphere self-assembled monolayer film substrate, and b is the raman spectrum curve spectrum of the surface enhanced raman spectrum substrate.
FIG. 5 is a schematic cross-sectional view of a microsphere self-assembled monolayer slide in example 2.
FIG. 6 is a schematic cross-sectional view of the structure of the substrate for surface enhanced Raman spectroscopy in example 2.
Fig. 7 is a raman spectrum curve spectrum obtained by the remote raman spectrometer test in example 2, in which a is a raman spectrum curve spectrum of the microsphere self-assembled monolayer film glass slide, and b is a raman spectrum curve spectrum of the surface enhanced raman spectrum substrate.
FIG. 8 is a scanning electron micrograph of a microsphere self-assembled monolayer attached to a microsphere self-assembled monolayer slide in example 2.
FIG. 9 is a scanning electron micrograph of non-closely packed microspheres after microetching in example 2.
The meaning of each reference number in the figures is: 1-microsphere, 2-pretreatment of a micro-nano pore substrate, 3-first coating, 4-second coating and 5-pretreatment of a glass slide.
The technical solution of the present invention is further illustrated by the following examples.
Detailed Description
The analysis of the comprehensive background technology shows that the research on the preparation method which has relatively simple process and good signal enhancement effect of the prepared surface-enhanced Raman spectrum substrate has important significance for the surface-enhanced Raman spectrum substrate.
Atomic Layer Deposition (ALD) was originally called atomic layer epitaxy, a method of chemical vapor deposition, and was originally proposed by Tuomo, Finnish scientists in 1977 and used for polycrystalline phosphor materials ZnS: Mn and amorphous Al2O3A technique developed for insulating films, these materials being used for flat panel displays. The principle is that substances are plated on the surface of a substrate layer by layer in the form of a monoatomic film through continuous surface reaction, and a precursor is adsorbed and reacts with the surface of the substrate through alternate pulsed gas phase reactionTo achieve thin film growth. The atomic layer deposition technology has the greatest characteristic that the thickness of the film can be accurately controlled within Hermitian
On the order of magnitude, on the surface of a complex structure, such as a porous material with ultrahigh depth-width ratio grooves and complex curves, 100% complete coverage and defect-free film growth are carried out, and the shape-keeping property and uniformity are good.
The invention relates to a preparation method of a surface-enhanced Raman spectrum substrate, which comprises the steps of firstly carrying out fine etching on a microsphere self-assembled monolayer film substrate or a microsphere self-assembled monolayer film glass slide to prepare a fine etching substrate; and then carrying out primary coating and secondary coating on the fine etching substrate to prepare the surface-enhanced Raman spectrum substrate.
The gap between adjacent microspheres on the surface-enhanced Raman spectrum substrate is 5-10 nm; the area capable of generating the enhancement effect on the surface enhanced Raman spectrum substrate is distributed on the rough second coating in the micro-nano pores and the microsphere gaps; the surface-enhanced Raman spectrum substrate can effectively enhance signals of Raman scattering light. According to the preparation method of the surface-enhanced Raman spectrum substrate, the atomic layer deposition technology is used for preparing the surface-enhanced Raman spectrum substrate, and the inductive coupling plasma etching method and the electron beam evaporation method are combined, so that the signal enhancement effect of the surface-enhanced Raman spectrum substrate can be remarkably improved. The surface-enhanced Raman spectrum substrate can be applied to trace explosive detection.
In the invention:
the inductively coupled plasma etcher used for the fine etch is one known in the art.
The high temperature atomic layer/chemical vapor deposition system used for the first coating was developed by the institute of chemistry in the recent generation of western ann, model MCRI FH ALD FH-2-HT.
The electron beam evaporator used for the second coating was purchased from Fulin scientific engineering GmbH, and the model was Fulin FU-16 PEB-ITO.
The microspheres are polystyrene microspheres with the average particle size of 2-8 mu m.
The remote Raman spectrometer used for obtaining the Raman curve is developed by the Siann optical precision mechanical research institute of Chinese academy of sciences, and has the model number of RS-L3-532.
It should be noted that all instruments and consumables of the present invention are those known in the art, unless otherwise specified.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
the embodiment discloses a preparation method of a surface-enhanced Raman spectrum substrate, which specifically comprises the following steps:
step one, preparing a microsphere self-assembly monolayer film substrate;
step 1.1.1, preparing microsphere suspension;
dissolving 8 mu m polystyrene microspheres in water to prepare a suspension A, and centrifuging the suspension to obtain a precipitate B; resuspending the precipitate B with absolute ethyl alcohol to obtain a suspension B, and centrifuging the suspension B to obtain a precipitate C; resuspending the precipitate C with n-butanol to obtain microsphere suspension;
in the embodiment, the two centrifugation speeds are both 5000rpm, and the centrifugation time is 15 min;
step 1.1.2, preparing a precursor solution;
and (3) carrying out ultrasonic treatment on the microsphere suspension prepared in the step 1.1.1 for 15 minutes to prepare a precursor solution.
Step 1.1.3, preparing a microsphere self-assembled monolayer film;
and (2) slowly dripping 300 mu L of the precursor solution prepared in the step 1.1.2 into a beaker filled with deionized water along the inner wall of the clean beaker to prepare a self-assembly mixed solution, standing the self-assembly mixed solution for a moment at room temperature until the self-assembly is finished, wherein the self-assembly mixed solution is divided into an upper layer and a lower layer after the self-assembly is finished, the upper layer is a water layer, and the lower layer is an organic layer, wherein the water layer contains the microsphere self-assembly monolayer film.
Step 1.1.4, attaching a microsphere self-assembly single-layer film;
slowly inclining the pretreated glass slide to ensure that the glass slide keeps an angle of 45 degrees with the horizontal direction, inserting the inclined glass slide into the water layer in the step 1.1.3, slowly lifting and pulling the glass slide out of the water layer, and keeping the angle of 45 degrees between the glass slide and the horizontal direction when the glass slide is lifted and pulled out; then, the glass slide is naturally dried by keeping an inclination angle of 10-30 degrees, so that the microsphere self-assembly single-layer film in the water layer is attached to the glass slide to prepare the microsphere self-assembly single-layer film glass slide;
in this example, the pretreatment slide glass was hydrophilically treated to have a size of 1.8 o 2.5cm2The slide glass of (1).
Step 1.1.5, fixing the microsphere self-assembly single-layer film;
slowly inclining the microsphere self-assembly single-layer film glass slide prepared in the step 1.1.4, keeping an angle of 45 degrees between the microsphere self-assembly single-layer film glass slide and the horizontal direction, inserting the inclined microsphere self-assembly single-layer film glass slide into a container filled with deionized water, fishing out the microsphere self-assembly single-layer film by adopting a pretreated micro-nano pore substrate after the microsphere self-assembly single-layer film floats on the water surface, attaching the microsphere self-assembly single-layer film on the micro-nano pore substrate, heating the micro-nano pore substrate attached with the microsphere self-assembly single-layer film in a drying oven at 110 ℃ for a certain time, and fixing the microsphere self-assembly single-layer film on the micro-nano pore substrate to prepare a microsphere self-assembly single-layer film substrate, wherein the substrate is shown in figure 1;
in this embodiment, the micro-nano pore substrate is pretreated as follows: sequentially carrying out ultrasonic cleaning twice by using acetone and absolute ethyl alcohol, wherein the ultrasonic cleaning time is 15min each time; the micro-nano pore substrate is a micro-channel plate with the diameter of 2.5cm, the pore diameter of 6 mu m and the thickness of 0.451 mm.
Step two, preparing a fine etching substrate;
performing fine etching on the surface of the microsphere self-assembled single-layer film substrate prepared in the step 1.5 by using an inductively coupled plasma etching machine to prepare a fine etched substrate, as shown in fig. 2; the conditions for the fine etching were: etching pressureThe intensity is 7-10 mTorr, the etching voltage is 95-110W, the etching gas is O2The gas flow rate is 50-60 sccm, the etching time is 70-80 s, the fine etching can enable gaps to be generated between adjacent microspheres, and the gaps after the fine etching are smaller than or equal to 200 nm;
in the embodiment, the fine etching can reduce the average particle size of the microspheres, so that gaps are generated among the microspheres which are closely arranged to form a non-closely arranged microsphere structure, and the size of the gap among the microspheres can be regulated and controlled by parameters such as etching power, reaction time, airflow rate and the like; the fine etching is realized by an inductively coupled plasma etching machine; the etch voltage refers to the spiral coil coupling voltage.
Step three, preparing a first coating fine etching substrate;
performing first coating on the fine etching substrate prepared in the second step by adopting a high-temperature atomic layer/chemical vapor deposition system, wherein the coating temperature is 80-92 ℃, and preparing a first coating fine etching substrate after about 250 cycles; the film layer coated on the fine etching substrate by the second coating is a first coating, and the first coating is Al with the thickness of 5nm2O3Film plating;
each cycle of the first film coating comprises four times of gapless pulses, wherein the first pulse adopts trimethylaluminum, and the pulse duration of the first pulse is 5 s; the second pulse being N2The pulse duration of the second pulse is 1 s; third pulse with H2O (gaseous), the pulse duration of the third pulse being 5 s; the fourth pulse is N2The pulse duration of the fourth pulse is 1 s;
in this embodiment, the atomic layer deposition technique is used to plate a certain thickness of Al on the substrate2O3The film can realize the precise regulation and control of the pore size and the gap size of the microspheres.
Preparing a surface enhanced Raman spectrum substrate;
performing secondary film coating on the first coating fine etching substrate prepared in the third step by using an electron beam evaporation plating machine to prepare a surface enhanced Raman spectrum substrate, as shown in FIG. 3; the film layer coated by the second coating isThe second plating layer is an Au film plating layer with the thickness of 90-93 nm; the second coating is carried out under the condition that the pressure of the reaction chamber is lower than 10-5Pa, deposition rate of
The first coating fine etching substrate is not heated in the second coating process; and the gap between adjacent microspheres on the finally prepared surface-enhanced Raman spectrum substrate is 5-10 nm, and the gap is calculated according to the gap after the fine etching and the thicknesses of the first coating and the second coating.
Verification of the effects of example 1:
the preparation concentration is 10-7And respectively taking 20 mu L of M rhodamine 6G solution, respectively dropwise adding the M rhodamine 6G solution on the surface-enhanced Raman spectrum substrate finally prepared in the embodiment and the microsphere self-assembled monolayer film substrate prepared in the step 1.1.4 in the embodiment, and testing at a position of 2M by using a remote Raman spectrometer to obtain a Raman curve, wherein the Raman curve is shown in figure 4.
As can be seen from fig. 4, in the present embodiment, compared to the microsphere self-assembled monolayer film substrate, the surface of the surface-enhanced raman spectroscopy substrate has an obvious enhancement effect, and the enhancement factor EF value of the surface-enhanced raman spectroscopy substrate obtained by calculation is 5 × 107。
Example 2:
the embodiment discloses a preparation method of a surface-enhanced Raman spectrum substrate, which specifically comprises the following steps:
step one, preparing a microsphere self-assembly single-layer film glass slide;
in this example, step 1.2.1 is essentially the same as step 1.1.1 of example 1, except that the microspheres in the microsphere suspension have an average particle size of 2 μm.
In this example, step 1.2.2 is the same as step 1.1.2 of example 1.
Step 1.2.3, attaching and fixing the microsphere self-assembly single-layer film;
and (3) slowly dripping 30 mu L of the precursor solution prepared in the step (1.2.2) onto the pretreated glass slide, standing for a moment until the self-assembly process is finished, and naturally drying to prepare the microsphere self-assembly single-layer film glass slide, wherein a microsphere self-assembly single-layer film attached to the microsphere self-assembly single-layer film glass slide is shown in a figure 5, and a microsphere self-assembly single-layer film attached to the microsphere self-assembly single-layer film glass slide is shown in a figure 8.
In this example, the second step is substantially the same as the second step of example 1, except that the surface of the microsphere self-assembled monolayer film slide prepared in step 1.2.3 is subjected to fine etching, and the prepared fine etching substrate is shown in fig. 9.
In this example, step three is the same as step three in example 1.
In this embodiment, the fourth step is the same as the fourth step in embodiment 1, and the prepared surface-enhanced raman spectroscopy substrate is shown in fig. 6.
Effect verification of example 2:
the preparation concentration is 10-720 μ L of M rhodamine 6G (R6G) solution was taken, and was respectively dropped on the surface enhanced raman spectroscopy substrate finally prepared in this example and the microsphere self-assembled monolayer film slide glass prepared in step 1.2.3 in this example, and a raman curve was obtained by testing at 2M with a remote raman spectrometer, as shown in fig. 7.
As shown in fig. 7, in the present embodiment, compared to the microsphere self-assembled monolayer glass slide, the surface of the surface-enhanced raman spectroscopy substrate has a significant enhancement effect, and the enhancement factor EF value calculated is 4.8 × 106。
Claims (10)
1. A surface-enhanced Raman spectrum substrate is characterized by comprising a fine etching substrate, wherein the fine etching substrate is a microsphere self-assembled single-layer film substrate or a microsphere self-assembled single-layer film glass slide prepared by fine etching, and a plurality of microspheres are arranged on the microsphere self-assembled single-layer film substrate and the microsphere self-assembled single-layer film glass slide;
the microspheres are sequentially provided with a first plating layer and a second plating layer from the inner layer to the outer layer;
gaps between the adjacent microspheres after the coating of the first coating and the second coating and the fine etching are 5-10 nm.
2. The surface-enhanced raman spectroscopy substrate of claim 1, wherein the microspheres have an average particle size of 2 μ ι η to 8 μ ι η; the thickness of the first plating layer is 5 nm; the thickness of the second coating is 90-93 nm.
3. The surface-enhanced raman spectroscopy substrate of claim 1, wherein the microspheres are polystyrene microspheres; the first coating is Al2O3Film plating; the second plating layer is an Ag film plating layer or an Au film plating layer.
4. A method for preparing a surface-enhanced raman spectroscopy substrate according to any one of claims 1 to 3, comprising the steps of:
step one, preparing a microsphere self-assembly monolayer film substrate; or preparing a microsphere self-assembled monolayer film glass slide;
step two, preparing a fine etching substrate;
performing fine etching on the surface of the microsphere self-assembled single-layer film substrate or the microsphere self-assembled single-layer film glass slide prepared in the step one to prepare a fine etching substrate;
step three, preparing a first coating fine etching substrate;
performing first film coating on the fine etching substrate prepared in the step two to prepare a first coating fine etching substrate; the coating temperature of the first coating is 80-92 ℃, and the first coating comprises 200-300 cycles; the film layer plated by the first film plating is a first plating layer;
preparing a surface enhanced Raman spectrum substrate;
performing secondary film coating on the first coating fine etching substrate prepared in the step three to prepare a surface enhanced Raman spectrum substrate; the film layer plated by the second plating is a second plating layer.
5. The method for preparing the surface-enhanced Raman spectroscopy substrate according to claim 4, wherein in the second step, the conditions of the fine etching are as follows: etching ofThe pressure is 7-10 mTorr, the etching voltage is 95-110W, the etching gas is O2The gas flow rate is 50-60 sccm, and the etching time is 70-80 s.
6. The method for preparing the surface-enhanced Raman spectroscopy substrate according to claim 4, wherein in the third step, each cycle of the first coating comprises four pulses without intervals, the first pulse is made of trimethylaluminum, and the pulse duration of the first pulse is 5 s; the second pulse being N2The pulse duration of the second pulse is 1 s; third pulse with H2O (gaseous), the pulse duration of the third pulse being 5 s; the fourth pulse is N2The pulse duration of the fourth pulse is 1 s.
7. The method for preparing the surface-enhanced Raman spectroscopy substrate of claim 4, wherein in the fourth step, the second coating is performed under a condition that a pressure in the reaction chamber is lower than 10-5Pa, deposition rate of
The first coating fine etch substrate is not heated during the second coating process.
8. The method for preparing the surface-enhanced Raman spectroscopy substrate according to claim 4, wherein in the first step, the method for preparing the microsphere self-assembled monolayer film substrate comprises the following steps:
step 1.1.1, preparing microsphere suspension;
dissolving polystyrene microspheres in water to prepare a suspension A, and centrifuging the suspension to obtain a precipitate B; resuspending the precipitate B with absolute ethyl alcohol to obtain a suspension B, and centrifuging the suspension B to obtain a precipitate C; resuspending the precipitate C with n-butanol to obtain microsphere suspension;
step 1.1.2, preparing a precursor solution;
carrying out ultrasonic treatment on the microsphere suspension prepared in the step 1.1.1 for 15 minutes to prepare a precursor solution;
step 1.1.3, preparing a microsphere self-assembled monolayer film;
dropwise adding the precursor solution prepared in the step 1.1.2 into deionized water to prepare a self-assembly mixed solution, and standing the self-assembly mixed solution at room temperature until self-assembly is completed to prepare a microsphere self-assembly single-layer film; after the self-assembly is finished, the self-assembly mixed solution is divided into an upper layer and a lower layer, wherein the upper layer is a water layer, and the lower layer is an organic layer, wherein the water layer contains a microsphere self-assembly single-layer film;
step 1.1.4, attaching a microsphere self-assembly single-layer film;
inclining the pretreated glass slide, slowly inserting the inclined pretreated glass slide into the water layer in the step 1.3, slowly pulling the glass slide out of the water layer, and naturally drying the pretreated glass slide completely pulled out of the water layer so as to attach the microsphere self-assembly single-layer film in the water layer to the glass slide to prepare the microsphere self-assembly single-layer film glass slide;
step 1.1.5, fixing the microsphere self-assembly single-layer film;
inclining the microsphere self-assembly single-layer film glass slide prepared in the step 1.1.4, inserting the inclined microsphere self-assembly single-layer film glass slide into deionized water, fishing out the microsphere self-assembly single-layer film by adopting a pretreated micro-nano pore substrate after the microsphere self-assembly single-layer film floats on the water surface, so that the microsphere self-assembly single-layer film is attached to the pretreated micro-nano pore substrate, heating the pretreated micro-nano pore substrate attached with the microsphere self-assembly single-layer film at 110 ℃ to fix the microsphere self-assembly single-layer film on the micro-nano pore substrate, and preparing a microsphere self-assembly single-layer film substrate;
in the first step, the method for preparing the microsphere self-assembly monolayer film glass slide comprises the following steps:
step 1.2.1, the same as step 1.1.1;
step 1.2.2, the same as step 1.1.2;
step 1.2.3, attaching and fixing the microsphere self-assembly single-layer film;
and (3) dropwise adding the precursor prepared in the step (1.2.2) onto the pretreated glass slide, standing until the self-assembly is completed, and then naturally drying to prepare the microsphere self-assembled monolayer glass slide.
9. Use of a surface enhanced raman spectroscopy substrate according to any one of claims 1 to 3 for trace explosives detection.
10. The use of the surface-enhanced Raman spectroscopy substrate prepared by the method for preparing a surface-enhanced Raman spectroscopy substrate according to any one of claims 4 to 8 for trace explosive detection.
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