CN112981324B - Liquid-phase nano infrared spectrum plasmon resonance enhanced substrate and preparation method and application thereof - Google Patents
Liquid-phase nano infrared spectrum plasmon resonance enhanced substrate and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a plasmon resonance enhanced substrate used as a liquid phase nano infrared spectrum. In particular to a method for preparing a large-area highly regular and ordered metal structure array on the surface of a visible-infrared region transparent optical wafer by adopting a physical deposition technology and application thereof in liquid-phase nano infrared spectroscopy. The invention self-assembles the microspheres in the gas/liquid interface in the container, then deposits the microspheres on the surface of the optical wafer which is transparent in the visible-infrared region, prepares a metal nano film material on the surface of the optical wafer by utilizing a physical deposition technology, and can obtain a large-area highly regular and ordered metal structure array on the surface of the optical wafer which is transparent in the visible-infrared region by removing the microsphere film; the enhanced substrate prepared based on the scheme can realize the analysis of liquid phase nanoscale infrared spectrum through plasmon resonance excitation in a mid-infrared region, and the detection sensitivity can reach the monomolecular layer magnitude and is far higher than that of a common total internal reflection prism enhanced substrate, so that the enhanced substrate can be used as a novel high-performance liquid phase nanoscale infrared spectrum substrate.
Description
Technical Field
The invention relates to a plasmon resonance enhanced substrate used as a liquid phase nano infrared spectrum, a preparation method and application thereof, belonging to the field of super-resolution spectroscopy.
Background
The infrared absorption spectrum and its imaging technology are important research methods for analyzing the properties and changes of substances by spectrum and imaging based on the interaction between electronic transition, chemical bond vibration and incident light of the substances. In the infrared spectrum range, absorption spectrum acquisition and imaging analysis of nanometer level spatial resolution are realized, physical and chemical properties of substances can be researched under the sub-wavelength scale, and fine structure and functional characteristics and correlation are revealed.
However, limited by the shortcomings of the signal acquisition method, research on nanoscale infrared spectroscopy and imaging technology is limited to acquisition of infrared absorption signals of polymer films and biomacromolecules with certain thickness at the solid/gas interface. If the nano infrared technology is popularized to liquid phase, the research on material transmission, electronic exchange, energy transfer and molecular recognition is carried out on solid/liquid, gas/liquid, liquid/liquid interfaces and the like, and the nano infrared technology has an important promoting effect on the fields of life science, electrochemical energy storage and conversion, sensing, catalysis and the like based on a liquid phase system.
The liquid phase nanometer infrared spectrum collection scheme which is mainstream at present is excited by using a total internal reflection light path. According to the scheme, incident infrared laser is converged through the total internal reflection prism, so that a probe of the nano infrared detector is excited, absorption interference of a liquid phase background on infrared light can be effectively avoided, and meanwhile, nano infrared spectrum signal amplification to a certain degree is realized by means of intrinsic enhancement of an electromagnetic field on the surface of a total internal reflection light path. However, the internal reflection prism is expensive, the construction is complicated, and the optical path adjustment is difficult. Meanwhile, the internal reflection technology can only provide electromagnetic field enhancement less than ten times, and the analysis effect is poor. The current optical path design can only be used for the analysis of polymer thin films with tens of nanometers. Therefore, if a better infrared enhanced optical path design can be provided, and simple, quick and low-cost near-field signal amplification and solution background signal shielding are realized, the detection sensitivity of the nano infrared spectrum can be improved, and the application range of the nano infrared spectrum can be widened.
Among the existing electromagnetic field enhancement techniques, the use of a plasmon resonance structure is one of the most excellent and mature methods. The plasmon resonance structure is a specially designed regular and ordered nano-structure array, can gather incident light with specific wavelength, and generates a 'hot spot' with a strong electromagnetic field on the surface of the structure. Molecules located within the "hot spot" are subject to a gain photopic interaction, the infrared absorption of which can be significantly improved relative to total internal reflection prisms. However, at the present stage, no construction scheme and application of a plasmon structure capable of being applied to liquid-phase nano infrared spectrum research exist. The scheme has the advantages of low cost, easy operation, large-scale preparation and the like.
Disclosure of Invention
In order to develop a novel method for simply and effectively preparing a plasmon resonance enhanced substrate suitable for liquid phase nano infrared spectroscopy, the invention aims to provide a low-cost and large-area preparation method of a highly regular metal structure mid-infrared enhanced substrate, and the method is practically applied to liquid phase nano infrared spectroscopy analysis and imaging. The enhancement substrate is simple and easy to implement and easy to popularize, and can be used for improving the enhancement effect of the liquid-phase nano infrared spectrum and expanding the application range of nano infrared spectrum detection, so that the substrate is utilized to realize wide application in the fields of life science, electrochemical energy storage and conversion, sensing catalysis and the like.
The invention also aims to provide a preparation method of the medium infrared region plasmon resonance enhancement substrate.
The invention also aims to provide application of the medium infrared region plasmon resonance enhancement substrate in the liquid phase nano infrared field.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a mid-infrared region plasmon resonance enhanced substrate suitable for liquid-phase nano infrared spectroscopy, which consists of an optical wafer and an ordered array metal nano structure, wherein the ordered array metal nano structure is deposited on the surface of the optical wafer and is in a large-area regular and ordered metal structure array.
More specifically, the optical wafer is a polished optical wafer transparent in the visible-infrared region.
More specifically, the shapes of the optical wafer according to the present invention include, but are not limited to, a flat window and a hemispherical prism, wherein the thickness of the flat window includes, but is not limited to, 0.1mm to 2 mm.
Still further, the visible-infrared transparent optical wafers of the present invention may be made of materials including, but not limited to, zinc selenide, calcium fluoride, silicon, glass, and germanium.
More particularly, the diameter of the microsphere is 3-6 μm.
More specifically, the material of the microsphere of the present invention includes, but is not limited to, polystyrene.
The metal deposition methods described herein include, but are not limited to, electron beam evaporation, magnetron sputtering, and thermal evaporation.
The metal material of the present invention includes, but is not limited to, gold, silver, copper, and aluminum.
The method comprises the steps of self-assembling microspheres on a gas/liquid interface in a container to form a compact and ordered microsphere self-assembled monolayer, transferring the monolayer to the surface of a polished visible-infrared transparent optical wafer, preparing a metal nanostructure on the surface of the optical wafer by physical deposition, removing the microspheres, and preparing a large-area highly ordered metal structure array on the surface of the visible-infrared transparent optical wafer; by changing experimental conditions such as the type of metal subjected to physical deposition, the deposition time, the size of the microspheres and the like, large-area highly regular and ordered metal nano material arrays with different appearances and structures can be prepared on the surface of the optical wafer; the enhanced substrate prepared based on the scheme can realize liquid-phase nanoscale infrared spectrum analysis and imaging through plasmon resonance excitation of the substrate. The reinforced substrate has the advantages of simple structure, low cost of the preparation method, easy control, no need of special instruments and equipment, realization of large-area preparation, high universality and frontier performance, and easy popularization and application.
The invention also provides a preparation method of the liquid-phase nano infrared spectrum plasmon resonance enhanced substrate, which is characterized by comprising the following steps:
the method comprises the steps of self-assembling microspheres on the surface of a polished visible-infrared region transparent optical wafer, preparing a metal nano film material on the surface of the optical wafer by physical deposition, removing the microspheres, and preparing a large-area highly regular and ordered metal structure array on the surface of the visible-infrared region transparent optical wafer.
The preparation method comprises a scheme of microsphere self-assembly, and particularly adopts a polyethylene container for self-assembly.
The shapes of the visible-infrared region transparent optical wafer include, but are not limited to, a flat window and a hemispherical prism, wherein the thickness of the flat window includes, but is not limited to, 0.1 mm-2 mm.
The types of materials for the visible-infrared transparent optical wafer described herein include, but are not limited to, zinc selenide, calcium fluoride, silicon, glass, and germanium.
The size of the microspheres of the present invention includes, but is not limited to, 3 μm to 6 μm in diameter.
The types of materials for the microspheres described herein include, but are not limited to, polystyrene.
The metal deposition methods described herein include, but are not limited to, electron beam evaporation, magnetron sputtering, and thermal evaporation.
The metal material of the present invention includes, but is not limited to, gold, silver, copper, and aluminum.
Furthermore, the method changes the experimental parameters such as the type of metal material, the type of microsphere material, the type of optical wafer, the size of microsphere, the metal deposition thickness, the thickness of optical wafer and the like, and directly prepares the ordered nano-structure arrays of different metals with different appearances and structures on the surface of the visible-infrared region transparent optical wafer to obtain the substrate with the high-efficiency infrared enhancement effect:
specifically, under the conditions that polystyrene microspheres with the diameter of 3 mu m are used, the optical wafer is a silicon wafer with the thickness of 0.3mm, and gold with the thickness of 50nm is deposited on the surface by a vacuum evaporation method, the ion-doped optical fiber with the wave number of 4000-700cm can be obtained-1An inner infrared enhancing substrate.
Specifically, under the conditions that polystyrene microspheres with the diameter of 5 mu m are used, the optical wafer is a silicon wafer with the thickness of 0.3mm, silver and copper with the thickness of 50nm are deposited on the surface by a vacuum evaporation method, and the ion-exchange resin with the wave number of 700cm and the wave number of 4000 can be obtained-1An inner infrared enhancing substrate.
Specifically, under the conditions, polystyrene microspheres with the diameter of 3-5 mu m are used, the optical wafer is a silicon wafer with the thickness of 0.3mm, gold with the thickness of 50nm is deposited on the surface by a vacuum evaporation method, and the gold with the wave number of 4000-700 cm-doped gold can be obtained-1An inner infrared enhancing substrate.
Specifically, by using the conditions that polystyrene microspheres with a diameter of 5 μm and optical wafers of glass sheets with thicknesses of 0.1mm, 0.5mm and 1mm are used, and gold with a thickness of 50nm is deposited on the surface by a magnetron sputtering method, gold with a wave number of 4000 cm and 700cm can be obtained-1An inner infrared enhancing substrate.
Specifically, by using the conditions that polystyrene microspheres with a diameter of 5 μm are used, the optical wafer is a glass plate with a thickness of 0.5mm, gold with thicknesses of 10nm, 50nm and 100nm is deposited on the surface by a vacuum evaporation method and a magnetron sputtering method, and the wave number of 700 cm--1An inner infrared enhancing substrate.
Specifically, under the conditions, polystyrene microspheres with the diameter of 4-6 mu m are used, the optical wafer is a zinc selenide sheet with the thickness of 0.5mm, gold with the thickness of 50nm is deposited on the surface by a vacuum evaporation method, and the gold with the wave number of 4000-700cm can be obtained-1An inner infrared enhancing substrate.
The invention also provides application of the plasmon resonance enhanced substrate in liquid-phase nano infrared spectroscopy.
In particular, the present invention also provides a preferred embodiment wherein the liquid phase nano-infrared technique is light induced force microscopy and the sample is polydimethylsiloxane having a thickness of 1 nm.
Has the advantages that:
1. the invention selects the microsphere self-assembly film to prepare and obtain a large-area highly regular and ordered metal structure array on the surface of a visible-infrared region transparent optical wafer by utilizing physical deposition, and further the metal structure array is used for liquid phase nano infrared spectrum analysis. Meanwhile, the microsphere self-assembly film used in the scheme is combined with a physical deposition method, a large-area highly regular and ordered metal structure array can be realized on a wafer scale, the cost is far lower than technologies such as electron beam etching, and the operation is easier. In addition, by changing the experimental conditions of the metal types and the deposition time of physical deposition, the size of the microspheres and the like, large-area highly regular and ordered metal nano structure arrays with different appearances and structures can be prepared on the surface of the optical wafer to adapt to different experimental requirements, and the application range of the liquid phase nano infrared technology is further expanded.
2. The invention can construct a microsphere array on the surface of any visible-infrared region transparent optical wafer through a mask construction technology, and further prepares a large-area highly regular and ordered metal structure array on the surface of the optical wafer by using the microsphere array as a mask through a physical deposition scheme, so that the metal structure array is used for detection and imaging of liquid-phase nano infrared spectroscopy. Compared with the total internal reflection prism, the method has higher electromagnetic field convergence effect, and can realize higher-sensitivity nano infrared spectrum and imaging analysis. Meanwhile, the optical path is simple, and the construction method is convenient, so that the method is more economical.
3. The method can change the experimental conditions such as the type of metal materials, the type of microspheres, the type of optical wafers, the size of microspheres, the metal deposition time, the thickness of the optical wafers and the like according to the requirements for enhancing the properties of the substrate (such as obtaining the highest enhancement factor or applying the highest enhancement factor to an electrochemical experiment and the like), and directly prepare regular and ordered nano material arrays of different metals with different morphologies and structures on the surface of the optical wafers which are transparent in a visible-infrared region to obtain the substrate with the efficient infrared enhancement effect;
4. the substrate based on the visible-infrared region transparent optical wafer and the large-area plasmon resonance structure can realize nano infrared spectrum detection with the thickness of 1-2nm in the vertical direction and the thickness of better than 10nm in the horizontal direction in a liquid phase, and is suitable for sensitive detection and analysis imaging of liquid samples, particularly biological samples;
5. the reinforced substrate has the advantages of simple structure, low cost of the preparation method, easy control, no need of special instruments and equipment, realization of large-area preparation, and easy popularization and application of the preparation technology.
Drawings
FIG. 1 is a scanning electron micrograph of a polystyrene template on the surface of a silicon wafer in example 1.
FIG. 2 is a scanning electron microscope image of the regular and ordered gold nanostructure array on the surface of the silicon wafer in example 1.
FIG. 3 is an infrared spectrum of the gold nanostructure array with regular and ordered surface of the silicon wafer in example 1.
Fig. 4 is a scanning electron microscope image of the regular and ordered silver and copper nanostructure array on the surface of the silicon wafer in example 2, wherein a and b correspond to the metal species silver and copper, respectively.
FIG. 5 is a scanning electron microscope image of the regular and ordered Au nanostructure array on the surface of the silicon chip in example 3, wherein a and b correspond to polystyrene microspheres with diameters of 4 μm and 5 μm, respectively.
FIG. 6 is a scanning electron microscope image of the gold nanostructure array with regular and ordered surface of the glass sheet in example 4, and the thicknesses of the glasses a-c are 0.1mm, 0.5mm and 1.0mm, respectively.
FIG. 7 is a scanning electron microscope image of the regular and ordered gold nanostructure array on the surface of the glass sheet in example 5, wherein a-c correspond to the gold thicknesses of 10nm, 50nm and 100nm, respectively.
Fig. 8 is an atomic force microscope image of the gold nanostructure array with regular and ordered zinc selenide surface in example 6.
FIG. 9 is a single-beam reflection intensity diagram of a regular and ordered gold nanostructure array on the surface of zinc selenide, and the spectrum transparency range of the single-beam reflection intensity diagram can be expanded to 700cm-1。
FIG. 10 is a liquid phase nano infrared absorption spectrum of 1nm polydimethylsiloxane on the surface of a nano infrared probe on a gold nanostructure (microsphere size is 4 μm) on the surface of zinc selenide, and the spectrum detection range can be effectively expanded to 770cm-1。
FIG. 11 is a liquid phase nano infrared imaging of 1nm polydimethylsiloxane on the surface of a nano infrared probe on a gold nanostructure (microsphere size 4 μm) on the surface of zinc selenide.
FIG. 12 is a liquid phase nano infrared absorption spectrum of 1nm polydimethylsiloxane on the surface of a nano infrared probe on a gold nanostructure (microsphere size is 5 μm) on the surface of zinc selenide, and the spectrum detection range can be effectively expanded to 770cm-1。
FIG. 13 is a liquid phase nano infrared imaging of 1nm polydimethylsiloxane on the surface of a nano infrared probe on a gold nanostructure (microsphere size 5 μm) on the surface of zinc selenide.
FIG. 14 shows gold nano-junctions formed on the surface of zinc selenide by 1nm polydimethylsiloxane on the surface of a nano infrared probeThe spectrum detection range of the structured (microsphere size of 6 mu m) liquid phase nano infrared absorption spectrum can be effectively expanded to 770cm-1。
FIG. 15 is a liquid phase nano infrared imaging of 1nm polydimethylsiloxane on the surface of a nano infrared probe on a gold nanostructure (microsphere size 6 μm) on the surface of zinc selenide.
FIG. 16 is an atomic force microscope image and a super-high spatial resolution liquid phase nano infrared imaging of 1nm polydimethylsiloxane on the surface of a nano infrared probe on a gold nanostructure (microsphere size is 6 μm) on the surface of zinc selenide, wherein, a is the atomic force microscope image, and b is the super-high spatial resolution liquid phase nano infrared imaging image.
Detailed Description
Example 1
1) Self-assembly of polystyrene microspheres: and ultrasonically cleaning the silicon wafer substrate by using ethanol, and reserving for later use after cleaning. And cleaning the polyethylene container by using deionized water and ethanol in sequence, and drying for later use. Deionized water was injected into the vessel. A visible-infrared transparent silicon wafer (thickness: 0.3mm) was placed just below the liquid surface to be raised. When the water surface is stable, dripping a solution of polystyrene microspheres (diameter: 3 μm) at the center of the container to perform self-assembly on a gas-liquid interface, when the polystyrene microspheres are paved on the whole liquid surface and large-area uniform reflection bright spots appear, indicating that the preparation of the polystyrene microsphere single layer which is orderly and closely arranged is finished, stopping dripping the solution of the polystyrene microspheres, and standing for 5 min. And transferring the self-assembled monolayer of the polystyrene microspheres to a visible-infrared region transparent silicon wafer right below, moving to a flat position, and naturally evaporating the solvent to obtain the visible-infrared region transparent silicon wafer with the self-assembled monolayer of the polystyrene microspheres deposited, wherein the appearance of the visible-infrared region transparent silicon wafer is shown in the attached figure 1.
2) The method for preparing the regular and ordered metal nano structure array on the surface of the optical wafer comprises the following steps: the surface of the silicon chip with the self-assembled monolayer of polystyrene microspheres deposited on the surface faces the direction of a gold target material for vacuum evaporation, and a gold film with the thickness of 50nm is evaporated on the surface of the silicon chip by controlling the parameters of an instrument. And after the evaporation is finished, removing the polystyrene microsphere layer on the surface, washing the whole substrate by using ultrapure water, and finally drying the silicon wafer by using nitrogen, namely depositing the large-area regular and ordered gold nanostructure array on the surface of the silicon wafer, wherein the morphology of the array is shown in the attached figure 2. Fig. 3 is an infrared spectrogram of a gold nanostructure array with regular and ordered silicon wafer surface, from which it can be seen that the gold nanostructure array has an obvious mid-infrared plasmon resonance absorption signal, and can be used for enhancing an infrared signal.
Example 2
The preparation method of this example is the same as example 1, wherein the diameter of the polystyrene microspheres in step 1 is adjusted to 5 μm, the metal species in step 2 is adjusted to silver and copper, and under the condition that other conditions are not changed, a large-area highly ordered metal nanostructure array is obtained on the surface of the optical wafer, and the morphologies of the metal nanostructure array are respectively shown in fig. 4.
Example 3
The preparation method of this embodiment is the same as that of embodiment 1, wherein the diameters of the polystyrene microspheres in step 1 are adjusted to 4 μm and 5 μm, and under the condition that other conditions are not changed, a large-area highly-ordered gold nanostructure array is obtained on the surface of the optical wafer, and the morphologies of the gold nanostructure array are respectively shown in fig. 5.
Example 4
The preparation method of this embodiment is the same as that of embodiment 1, wherein the diameter of the polystyrene microsphere in step 1 is adjusted to 5 μm, the metal deposition method in step 2 is adjusted to magnetron sputtering, the optical substrate is adjusted to glass, the thicknesses of the optical substrate are respectively 0.1mm, 0.5mm and 1.0mm, and under the condition that other conditions are not changed, a large-area highly ordered gold nanostructure array is obtained on the surface of the optical wafer, and the morphologies of the gold nanostructure array are respectively shown in fig. 6.
Example 5
The preparation method of this embodiment is the same as that of embodiment 1, wherein the diameter of the polystyrene microsphere in step 1 is adjusted to 5 μm, the metal deposition method in step 2 is adjusted to magnetron sputtering, the sputtering thicknesses are respectively 10nm, 50nm and 100nm, the optical substrate is adjusted to glass with a thickness of 0.1mm, and under the condition that other conditions are not changed, a large-area highly-ordered gold nanostructure array is obtained on the surface of the optical wafer, and the morphologies of the gold nanostructure array are respectively shown in fig. 7.
Example 6
The preparation method of the substrate of this embodiment is the same as that of embodiment 1, wherein the optical wafer is adjusted to be zinc selenide with a thickness of 0.5mm, the size of the microsphere is 4 μm, under the condition that other conditions are not changed, a large-area highly ordered gold nanostructure array is obtained on the surface of the optical wafer, and the morphology of the array is shown in fig. 8. Fig. 9 is a graph showing the infrared absorption spectrum of the prepared enhanced substrate in water, and it can be seen that the enhanced substrate structure has an obvious mid-infrared plasmon resonance absorption signal, which can be used for enhancing an infrared signal. And then, assembling the enhanced substrate on a light induction force microscope, adjusting a light path, and converging an infrared light beam from the bottom of the substrate to focus the infrared light beam on a needle point of the light induction force microscope. A quantity of deionized water is added to the substrate surface to allow it to pass over the tip. Subsequently, infrared spectrum measurement is carried out on polydimethylsiloxane with the thickness of 1nm modified on the surface of the light-induced force needle point at the tip of the metal structure in a liquid phase environment by using a tapping mode and a side band mode of a probe, and the result is shown in figure 10. Subsequently, imaging scanning is carried out by utilizing the infrared characteristic peak of the polydimethoxysiloxane, as shown in figure 11, and super-resolution infrared imaging can be realized in a liquid phase environment.
Example 8
The substrate of this example was prepared in the same manner as in example 7, wherein the size of the microspheres was adjusted to 5 μm. Subsequently, infrared spectrum measurement is carried out on polydimethylsiloxane with the thickness of 1nm modified on the surface of the light induction force needle point at the tip of the metal structure by using a light induction force microscope in a liquid phase environment in a tapping and probe sideband mode, and the result is shown in figure 12. Subsequently, imaging scanning is carried out by utilizing the infrared characteristic peak of the polydimethoxysiloxane, as shown in figure 13, and super-resolution infrared imaging can be realized in a liquid phase environment.
Example 9
The substrate of this example was prepared in the same manner as in example 7, wherein the size of the microspheres was adjusted to 6 μm. Subsequently, infrared spectrum measurement is carried out on polydimethylsiloxane with the thickness of 1nm modified on the surface of the light induction force needle point at the tip of the metal structure by using a light induction force microscope in a liquid phase environment in a tapping and probe sideband mode, and the result is shown in figure 14. Subsequently, imaging scanning is carried out by utilizing the infrared characteristic peak of the polydimethoxysiloxane, as shown in figure 15, and super-resolution infrared imaging can be realized in a liquid phase environment.
Example 10
The substrate of this example was prepared in the same manner as in example 7, wherein the size of the microspheres was adjusted to 6 μm. Subsequently, using a light-induced force microscope, in a liquid phase environment, using tap and probe sideband modes, an ultra-small range imaging scan was performed using the infrared signature of the polydimethoxysiloxane, as shown in figure 16, and it was found that the prepared substrate was capable of supporting super-resolution infrared imaging with spatial resolution better than 10nm in a liquid phase environment.
The method of the invention prepares the plasmon resonance enhancement substrate of liquid phase nanometer infrared spectrum on the surface of the optical wafer which is transparent in the visible-infrared region, and is not limited to the embodiment; the characterization and application of the liquid-phase nano infrared spectrum plasmon resonance enhanced substrate prepared by the method are shown in attached figures 1-16.
The method for preparing a liquid-phase nano infrared spectrum plasmon resonance enhanced substrate and the substrate prepared thereby provided by the present invention are introduced in detail above, and the specific examples herein illustrate the principles and embodiments of the present invention, and the above examples are only helpful for understanding the method and the core concept thereof. It should be noted that it will be apparent to those skilled in the art that several modifications and improvements can be made to the present invention without departing from the principle of the invention, and these are also within the scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of a liquid-phase nano infrared spectrum plasmon resonance enhanced substrate is characterized by comprising the following steps:
self-assembly of microspheres: self-assembling the microspheres on a gas/liquid interface in a container to form a close-packed self-assembled microsphere monolayer, and then transferring the monolayer to the surface of a visible-infrared transparent optical wafer subjected to polishing treatment in advance;
preparing a metal nano structure: preparing a nano metal structure on the surface of a visible-infrared region transparent optical wafer with the surface covered with the microsphere monolayer by utilizing physical deposition;
removing the microspheres; removing the microsphere monolayer, cleaning with water, drying, preparing a large-area highly regular metal structure array on the surface of the optical wafer transparent in a visible-infrared region, wherein the nano metal structure array is a large-area regular metal structure array,
the optical wafer comprises zinc selenide, calcium fluoride, silicon, glass and germanium;
the material types of the metal nano structure comprise gold, silver, copper and aluminum;
the diameter of the microsphere is 3-6 μm.
2. The preparation method according to claim 1, wherein the self-assembly of the microspheres is carried out by injecting deionized water into a container, and placing a visible-infrared transparent optical wafer below the liquid level; and (3) dropwise adding a microsphere solution into the container when the water surface is stable, and carrying out self-assembly on a gas-liquid interface to prepare a microsphere monolayer.
3. The method of claim 1, wherein the shape of the optical wafer comprises a flat window and a hemispherical prism, and wherein the thickness of the flat window is 0.1mm to 2 mm.
4. The method of claim 1, wherein the nano-metal is deposited by electron beam evaporation, magnetron sputtering, or thermal evaporation.
5. The liquid phase nano infrared spectrum plasmon resonance enhanced substrate prepared by the preparation method of any one of claims 1 to 4.
6. Use of the plasmonic resonance-enhanced substrate of claim 5 in liquid phase nano infrared spectroscopy.
7. Use according to claim 6, characterized in that: the application of the liquid phase nano infrared spectrum comprises a light induction force microscope, a scanning near-field optical microscope, a photothermal resonance microscope and a peak force nano infrared microscope.
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