CN114804010A - Surface-enhanced infrared absorption substrate and preparation method thereof - Google Patents

Surface-enhanced infrared absorption substrate and preparation method thereof Download PDF

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CN114804010A
CN114804010A CN202210394573.1A CN202210394573A CN114804010A CN 114804010 A CN114804010 A CN 114804010A CN 202210394573 A CN202210394573 A CN 202210394573A CN 114804010 A CN114804010 A CN 114804010A
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substrate
layer
diameter
template
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胡欢
吴少雄
田丰
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Zhejiang University ZJU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00349—Creating layers of material on a substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B1/00—Devices without movable or flexible elements, e.g. microcapillary devices
    • B81B1/006—Microdevices formed as a single homogeneous piece, i.e. wherein the mechanical function is obtained by the use of the device, e.g. cutters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/00523—Etching material
    • B81C1/00531—Dry etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light

Abstract

The invention provides a surface-enhanced infrared absorption substrate and a preparation method thereof, belonging to the technical field of functional materials. According to the invention, by using the mode of template microsphere photoetching and plasma etching, the surface enhanced infrared absorption (SEIRA) substrate can be prepared simply at low cost in a large area, the periodicity of the cylinder array in the prepared SEIRA substrate is good, the SEIRA substrate is ensured to have higher enhancement efficiency, and the problem that the SEIRA substrate in the prior art cannot give consideration to low cost and high enhancement efficiency is solved.

Description

Surface-enhanced infrared absorption substrate and preparation method thereof
Technical Field
The invention relates to the technical field of functional materials, in particular to a surface-enhanced infrared absorption substrate and a preparation method thereof.
Background
Infrared absorption spectroscopy is an important means of characterizing the chemical bond composition of a substance. Because different chemical bonds have different natural vibration frequencies, the substance can absorb light with a certain fixed frequency in the process of interacting with infrared light, and the chemical bond composition of the substance can be analyzed through the position of an absorption peak when the infrared spectrum characterization is carried out on the substance. Since the size of the molecules of a substance (nanoscale) is much smaller than the wavelength of infrared light (microscale), when the content of the substance is low, the infrared absorption spectrum is often weak or even undetectable.
The surface enhanced infrared absorption (SEIRA) spectrum technology is characterized in that a plasmon effect generated by a substrate with a nano metal structure is utilized to compress an infrared light field to a nano scale, so that the intensity of the light field can be increased, the interaction between infrared light and substance molecules is enhanced, and the detection limit of substances can be greatly improved. The enhancement factor of the SEIRA substrate is related to the composition, periodicity, etc. of the nanostructures. Generally, for the same nanostructure composition, the better the periodicity of the nanostructure, the higher the enhancement efficiency and the higher the cost required, while preparing randomly distributed nanostructures has the advantage of lower cost, but less enhancement efficiency. The existing SEIRA substrate is usually prepared by using a chemical etching method or a laser lithography method, wherein the chemical etching method has lower cost, but the enhancement efficiency of the SEIRA substrate is also lower (CN103710686A or CN 108559981A); the SEIRA substrate prepared by the Laser Lithography (Large-Area Antenna-Assisted SEIRA Substrates by Laser Interference Lithography, Shahin Bagheri, Harald Giessen, Frank Neubrech,2,11,2014, 1050-. Therefore, how to combine the high enhancement efficiency and low cost of the SEIRA substrate is a technical problem that needs to be solved at present.
Disclosure of Invention
The invention aims to provide a surface-enhanced infrared absorption substrate and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a surface-enhanced infrared absorption substrate, which comprises the following steps:
densely paving single-layer template microspheres on one side of the substrate to obtain a single-layer template microsphere layer-substrate workpiece;
performing reactive plasma etching on the single-layer template microsphere layer-substrate workpiece to reduce the diameter of the template microsphere and form a single-layer reduced-diameter template microsphere on one surface of the substrate to obtain a single-layer reduced-diameter template microsphere layer-substrate workpiece;
carrying out inductively coupled plasma etching on the single-layer reduced-diameter template microsphere layer-substrate workpiece, forming a cylinder array on one surface of the substrate, and reserving the reduced-diameter template microspheres at the top ends of the cylinders in the cylinder array to obtain a single-layer reduced-diameter template microsphere layer-cylinder array-substrate workpiece;
removing the reduced-diameter template microspheres in the single-layer reduced-diameter template microsphere layer-cylinder array-substrate workpiece to obtain a cylinder array-substrate workpiece;
and depositing a metal layer on the surface of the cylinder array-substrate workpiece with the cylinder array to obtain the surface-enhanced infrared absorption substrate.
Preferably, the diameter of the template microsphere is 150 nm-2.8 μm.
Preferably, the diameter of the template microspheres with reduced diameters is 10-200 nm smaller than that of the template microspheres.
Preferably, the time of the reactive plasma etching is 10-120 s.
Preferably, the height of the column is 0.1-1 μm, and the diameter is 140 nm-3 μm; the distance between adjacent pillars is the decrease in diameter of the template microspheres.
Preferably, the time for the inductively coupled plasma etching is 20 s-3 min.
Preferably, the removing means of the template microspheres with reduced diameter comprises a mechanical stripping method or a chemical etching method.
Preferably, the metal layer comprises an adhesion layer and a functional layer which are stacked, and the adhesion layer is arranged between the pillar array-substrate product and the functional layer; the material of the adhesion layer comprises titanium or chromium, and the material of the functional layer comprises gold, aluminum, silver, platinum or copper.
Preferably, the thickness of the adhesion layer is 1-5 nm, and the thickness of the functional layer is 15-200 nm.
The invention provides a surface-enhanced infrared absorption substrate prepared by the preparation method in the technical scheme, which comprises a substrate, a cylinder array and a metal layer, wherein the cylinder array is arranged on one surface of the substrate, the cylinder array is formed by a plurality of cylinders which are periodically distributed, and the metal layer is arranged on the upper surfaces of the cylinders and the surface of the substrate exposed between the cylinders.
The invention provides a preparation method of a surface-enhanced infrared absorption substrate, which comprises the following steps: densely paving single-layer template microspheres on one side of the substrate to obtain a single-layer template microsphere layer-substrate workpiece; performing reactive plasma etching on the single-layer template microsphere layer-substrate workpiece to reduce the diameter of the template microsphere and form a single-layer reduced-diameter template microsphere on one surface of the substrate to obtain a single-layer reduced-diameter template microsphere layer-substrate workpiece; performing inductively coupled plasma etching on the substrate in the single-layer diameter-reduced template microsphere layer-substrate workpiece, forming a cylinder array on one surface of the substrate, and reserving the diameter-reduced template microspheres at the top ends of the cylinders in the cylinder array to obtain the single-layer diameter-reduced template microsphere layer-cylinder array-substrate workpiece; removing the reduced-diameter template microspheres in the single-layer reduced-diameter template microsphere layer-cylinder array-substrate workpiece to obtain a cylinder array-substrate workpiece; and depositing a metal layer on the surface of the cylinder array-substrate workpiece with the cylinder array to obtain the surface-enhanced infrared absorption substrate. According to the invention, by using the mode of template microsphere photoetching and plasma etching, the SEIRA substrate can be prepared simply at low cost in a large area, the periodicity of the cylinder array in the prepared SEIRA substrate is good, the SEIRA substrate is ensured to have higher enhancement efficiency, and the problem that the SEIRA substrate in the prior art cannot give consideration to both low cost and high enhancement efficiency is solved.
Furthermore, the invention can adjust the period of the column array structure (including the diameter of the columns and the spacing distance between adjacent columns) by adjusting the size of the template microsphere, thereby adjusting the wavelength of infrared enhancement, for example, when the diameter of the template microsphere is 150 nm-3 μm, the corresponding wavelength of enhancement is 1050 nm-21 μm.
Drawings
FIG. 1 is a schematic view of the present invention for preparing a surface enhanced infrared absorbing substrate;
FIG. 2 is an electron micrograph (reference length 200nm) of a surface-enhanced infrared absorbing substrate according to the present invention;
FIG. 3 is a pictorial view of an SEIRA substrate prepared in example 1;
fig. 4 is a graph of the ir enhancement effect of the SEIRA substrate prepared in example 1;
fig. 5 is a graph of the effect of different diameter polystyrene microspheres on the infrared enhancement wavelength of a SEIRA substrate.
Detailed Description
The invention provides a preparation method of a surface-enhanced infrared absorption substrate, which comprises the following steps:
densely paving single-layer template microspheres on one side of the substrate to obtain a single-layer template microsphere layer-substrate workpiece;
performing reactive plasma etching on the single-layer template microsphere layer-substrate workpiece to reduce the diameter of the template microsphere and form a single-layer reduced-diameter template microsphere on one surface of the substrate to obtain a single-layer reduced-diameter template microsphere layer-substrate workpiece;
performing inductively coupled plasma etching on the substrate in the single-layer diameter-reduced template microsphere layer-substrate workpiece, forming a cylinder array on one surface of the substrate, and reserving the diameter-reduced template microspheres at the top ends of the cylinders in the cylinder array to obtain the single-layer diameter-reduced template microsphere layer-cylinder array-substrate workpiece;
removing the reduced-diameter template microspheres in the single-layer reduced-diameter template microsphere layer-cylinder array-substrate workpiece to obtain a cylinder array-substrate workpiece;
and depositing a metal layer on the surface of the cylinder array-substrate workpiece with the cylinder array to obtain the surface-enhanced infrared absorption substrate.
In the present invention, unless otherwise specified, the starting materials for the preparation are all commercially available products well known to those skilled in the art.
The invention densely lays single-layer template microspheres on a single surface of a substrate to obtain a single-layer template microsphere layer-substrate workpiece. In the present invention, the template microspheres preferably include polystyrene microspheres or silica microspheres, in the present invention, the substrate preferably includes a semiconductor substrate or a polymer substrate, the material of the semiconductor substrate preferably includes silicon, silica, gallium nitride or silicon carbide, and the material of the polymer substrate preferably includes Polyimide (PI) or Polydimethylsiloxane (PDMS). In the invention, the diameter of the template microsphere is preferably 150 nm-2.8 μm, and the corresponding enhancement wavelength is preferably 1050 nm-21 μm; the diameter of the template microsphere is more preferably 300 nm-2 μm.
In the present invention, the method for densely paving a single-layer template microsphere on a single surface of a substrate preferably comprises the following steps:
carrying out hydrophilic treatment on the substrate to obtain a hydrophilic substrate;
dropwise adding water on one side of the hydrophilic substrate to form a water layer on part of the surface of the hydrophilic substrate;
and dripping the emulsion of the template microspheres in a region without the water layer on the surface of the hydrophilic substrate to contact the emulsion of the template microspheres with the water layer, then densely paving the template microspheres on the surface of the water layer in a single-layer manner, removing the water layer, and densely paving the template microspheres on one side of the hydrophilic substrate in a single-layer manner.
The substrate is subjected to hydrophilic treatment to obtain the hydrophilic substrate. In the present invention, the substrate is preferably cleaned before use, and the cleaning method is not particularly limited in the present invention, and the substrate can be cleaned. Taking a substrate as an example, the method specifically comprises the steps of placing a silicon wafer in a piranha solution, carrying out ultrasonic treatment for 4-6 min, then washing the silicon wafer with water, and drying the silicon wafer by a nitrogen gun for later use; the piranha solution is preferably prepared from concentrated sulfuric acid and hydrogen peroxide according to a volume ratio of 7:3, the mass fraction of the concentrated sulfuric acid is preferably 70-98%, and the mass fraction of the hydrogen peroxide is preferably 28-30%. According to the invention, the substrate is preferably placed in oxygen plasma for hydrophilic treatment, and the time of hydrophilic treatment is preferably 4-6 min, and more preferably 5 min.
After the hydrophilic substrate is obtained, water is dripped on one side of the hydrophilic substrate, and a water layer is formed on part of the surface of the hydrophilic substrate. In the present invention, the water is preferably deionized water.
After a water layer is formed on part of the surface of the hydrophilic substrate, the method comprises the steps of dripping an emulsion of template microspheres in a region without the water layer on the surface of the hydrophilic substrate to enable the emulsion of the template microspheres to be in contact with the water layer, then, densely paving the template microspheres on the surface of the water layer in a single-layer manner, removing the water layer, and densely paving the template microspheres on one side of the hydrophilic substrate in the single-layer manner. In the invention, the mass fraction of the template microspheres in the emulsion of the template microspheres is preferably 5-10%, and the solvent is preferably water. In the present invention, the emulsion of the template microspheres is preferably mixed with propylene glycol for use, and the volume ratio of the emulsion of the template microspheres to the propylene glycol is preferably 1: (1-3), more preferably 1: 2. In the invention, in the presence of propylene glycol, when water is contacted with the emulsion of the template microspheres, the template microspheres in the emulsion can be densely paved on the surface of the water in a single layer due to the Marangoni effect, the water layer is removed after standing, and the template microspheres are densely paved on one surface of the hydrophilic substrate in a single layer form to obtain a single-layer template microsphere layer-substrate workpiece. In the invention, the standing time is preferably 10-20 min, and the standing is used for completely discharging water on the substrate. In the present invention, the water layer is preferably removed by sucking water out with a dropper.
After the monolayer template microsphere layer-substrate workpiece is obtained, the monolayer template microsphere layer-substrate workpiece is subjected to reactive plasma etching to reduce the diameter of the template microsphere and form a monolayer diameter-reduced template microsphere on one surface of the substrate, so that the monolayer diameter-reduced template microsphere layer-substrate workpiece is obtained. In the invention, the time of the reactive plasma etching (RIE) is preferably 10-120 s, and more preferably 60 s; in the reactive plasma etching process, the oxygen plasma is used for reacting with the template microsphere, so that the diameter of the template microsphere is uniformly reduced. In the invention, the diameter of the template microsphere with reduced diameter is preferably 10-200 nm smaller than that of the template microsphere, and more preferably 60 nm.
After a single-layer diameter-reduced template microsphere layer-substrate part is obtained, the substrate in the single-layer diameter-reduced template microsphere layer-substrate part is subjected to inductive coupling plasma etching, a cylinder array is formed on one surface of the substrate, and the diameter-reduced template microspheres are reserved at the top ends of the cylinders in the cylinder array, so that the single-layer diameter-reduced template microsphere layer-cylinder array-substrate part is obtained. In the present invention, the etching gas used for the inductively coupled plasma etching (ICP) is preferably determined according to the material of the substrate, and particularly, when the material of the substrate is silicon dioxide, the etching gas is preferably CHF 3 And Ar, the CHF 3 And Ar are preferably in a volume ratio of 1: (1-5), more preferably 1: 4; when the substrate is made of gallium nitride, the etching gas is preferably Cl 2 And BCl 3 Said Cl 2 And BCl 3 The volume ratio of (1-5): 1, more preferably 3: 1; when the substrate is made of silicon carbide, the etching gas is preferably SF 6 And C 4 F 8 Said SF 6 And C 4 F 8 The volume ratio of (1-12): 4, more preferably 9: 4. In the invention, the time for the inductively coupled plasma etching is preferably 20s to 3min, and more preferably 1.5 min. In the invention, in the process of the inductively coupled plasma etching, due to the mask effect of the template microspheres, periodically arranged columns, namely a column array, can be obtained on one surface of the substrate; the height of the column is preferably 0.1-1 μm, and more preferably 400 nm; the diameter of the column is preferably 140 nm-3 μm, and more preferably 440 nm; the distance between adjacent pillars is preferably a reduction in the diameter of the template microspheres.
After a single-layer diameter-reduced template microsphere layer-cylinder array-substrate workpiece is obtained, the diameter-reduced template microspheres in the single-layer diameter-reduced template microsphere layer-cylinder array-substrate workpiece are removed, and a cylinder array-substrate workpiece is obtained. The method for removing the template microspheres with reduced diameters is not particularly limited, and the method known by the person skilled in the art can be adopted, and specifically, a mechanical stripping method or a chemical etching method can be adopted. In the present invention, the mechanical peeling method preferably peels the reduced-diameter template microspheres from the tips of the pillars using an adhesive material, which preferably comprises tape or Polydimethylsiloxane (PDMS); the chemical etching method preferably adopts oxygen plasma to react with the template microspheres with the reduced diameters so as to remove the template microspheres by etching, and the reaction time is preferably 3-20 min, more preferably 10 min.
After the cylinder array-substrate part is obtained, the metal layer is deposited on the surface of the cylinder array-substrate part with the cylinder array, and the surface-enhanced infrared absorption substrate is obtained. In the present invention, the pillar array-substrate part has a pillar array surface, specifically including the upper surfaces of pillars and the exposed substrate surface between the pillars. In the present invention, the metal layer preferably includes an adhesion layer and a functional layer, which are stacked, and the adhesion layer is disposed between the pillar array-substrate article and the functional layer; the material of the adhesion layer preferably comprises titanium or chromium, and the thickness of the adhesion layer is preferably 1-5 nm, more preferably 3 nm; the material of the functional layer preferably comprises gold, aluminum, silver, platinum or copper, and the thickness of the functional layer is preferably 15-200 nm, and more preferably 30 nm. In the present invention, the method of depositing the metal layer preferably includes a magnetron sputtering method, an electron beam evaporation method, or a thermal evaporation method; the deposition rates of the adhesion layer and the functional layer are preferably selected
Figure BDA0003596883810000071
More preferably
Figure BDA0003596883810000072
The invention provides a surface-enhanced infrared absorption substrate prepared by the preparation method in the technical scheme, which comprises a substrate, a cylinder array and a metal layer, wherein the cylinder array is arranged on one surface of the substrate, the cylinder array is formed by a plurality of cylinders which are periodically distributed, and the metal layer is arranged on the upper surfaces of the cylinders and the surface of the substrate exposed between the cylinders.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Taking a four-inch silicon wafer as a substrate, placing the silicon wafer in a piranha solution (prepared by concentrated sulfuric acid and hydrogen peroxide according to the volume ratio of 7:3, wherein the mass fraction of the concentrated sulfuric acid is 98 percent, and the mass fraction of the hydrogen peroxide is 30 percent) for 5min by ultrasonic treatment, then washing the silicon wafer with deionized water, and finally drying the silicon wafer with a nitrogen gun; placing the cleaned silicon wafer in oxygen plasma, and carrying out hydrophilic treatment for 5min to make the surface of the silicon wafer hydrophilic;
dripping deionized water on the hydrophilic surface of the silicon wafer by using a rubber head dropper, and forming a deionized water layer on the partial surface of the silicon wafer; mixing an emulsion of polystyrene microspheres (the mass fraction of the polystyrene microspheres in the emulsion of the polystyrene microspheres is 5%, the solvent is water, and the diameter of the polystyrene microspheres is 500nm) with propylene glycol according to a volume ratio of 1:2, then dropwise adding a drop of the obtained mixture to a region without a water layer on the surface of a silicon wafer, and when the two liquid surfaces meet each other, the polystyrene microspheres in the emulsion can be densely paved on the surface of deionized water in a single layer due to the Marangoni effect; standing for 10min, and sucking out deionized water with a suction pipe to obtain silicon wafer with single-layer polystyrene microsphere of 500nm diameter and corresponding enhancement wavelength of 3.5 μm (corresponding infrared wave number of 2857 cm) -1 )；
Placing the silicon wafer paved with the single-layer polystyrene microspheres into reactive plasma etching (RIE) equipment, etching the polystyrene microspheres by using oxygen plasma for 60s, and uniformly reducing the diameter of the polystyrene microspheres by 60nm to obtain the silicon wafer paved with the polystyrene microspheres with the reduced diameter;
putting the silicon chip paved with the polystyrene microspheres with the reduced diameter into an inductively coupled plasma etching (ICP) device, and introducing SF 6 Gas and C4F 8 Gas, said SF 6 Gas and C 4 F 8 The volume ratio of the gas is 9:4, and the silicon wafer is etched for the etching time ofForming a silicon column array which is periodically arranged on the surface of a silicon wafer after etching for 90s due to the mask effect of the polystyrene microspheres with the reduced diameter, wherein the polystyrene microspheres with the reduced diameter are reserved at the top ends of the silicon columns, the height of the silicon columns is 400nm, the diameter of the silicon columns is 440nm, and the distance between every two adjacent columns is the reduced amount of the diameter of the polystyrene microspheres;
removing the reduced-diameter polystyrene microspheres at the top ends of the silicon columns by adopting a mechanical stripping method, specifically, adhering PDMS (polydimethylsiloxane) on the reduced-diameter polystyrene microspheres at the top ends of the silicon columns on the surface of the silicon wafer, and then tearing off the PDMS to obtain the silicon wafer with the silicon column array;
depositing 3nm titanium as an adhesion layer on the surface of a silicon wafer with a silicon column array (including the upper surface of the silicon columns and the surface of the silicon wafer exposed between the silicon columns) by adopting an electron beam evaporation method, wherein the deposition rate is
Figure BDA0003596883810000081
Then depositing 30nm gold as a functional layer on the surface of the adhesive layer at a deposition rate of
Figure BDA0003596883810000082
A surface enhanced infrared absorbing substrate is obtained.
Fig. 1 is a schematic view of the preparation of a surface-enhanced infrared absorption substrate, and fig. 2 is an electron micrograph (reference length of 200nm) of the preparation of a surface-enhanced infrared absorption substrate.
Fig. 3 is a physical diagram of the SEIRA substrate prepared in example 1, and it can be seen from fig. 3 that the surface enhanced infrared substrate prepared by the method of the present invention has an area up to four inches of silicon.
Example 2
A surface-enhanced infrared absorption substrate was prepared as in example 1 except that the diameter of the polystyrene microspheres was 300nm and the time for etching the polystyrene microspheres with oxygen plasma was 30 seconds.
Example 3
A surface-enhanced infrared absorption substrate was prepared as in example 1, except that the diameter of the polystyrene microspheres was 400nm and the time for etching the polystyrene microspheres with oxygen plasma was 40 seconds.
Example 4
A surface-enhanced infrared absorption substrate was prepared as in example 1, except that the diameter of the polystyrene microspheres was 600nm and the time for etching the polystyrene microspheres with oxygen plasma was 60 seconds.
Example 5
A surface-enhanced infrared absorption substrate was prepared as in example 1, except that the diameter of the polystyrene microspheres was 1000nm and the time for etching the polystyrene microspheres with oxygen plasma was 100 seconds.
Application example 1
Preparing an ethanol solution of octadecanethiol with the concentration of 0.01mol/L, placing the SEIRA substrate prepared in the embodiment 1 in the ethanol solution of octadecanethiol for standing for 12 hours, then taking out the SEIRA substrate and washing the SEIRA substrate with ethanol, forming a layer of octadecanethiol molecular film on the gold surface of the SEIRA substrate, drying the SEIRA substrate with the octadecanethiol molecular film attached by a nitrogen gun, and placing the SEIRA substrate with the octadecanethiol molecular film attached in an infrared absorption test instrument to obtain the infrared absorption spectrum of the octadecanethiol. Fig. 4 is a graph showing the infrared enhancement effect of the SEIRA substrate, wherein ODT-SEIRA represents the infrared spectrum of octadecanethiol measured on the SEIRA substrate, and ODT-Au represents the infrared spectrum of octadecanethiol measured on the gold surface of the pillar-free array structure, and it can be seen that the vibration absorption peak of the C-H bond is significantly enhanced after the SEIRA substrate is used. On the gold surface without the pillar array structure, the infrared absorption rate of a carbon-hydrogen bond in octadecanethiol is about 0.01 percent; while the infrared absorption of the carbon-hydrogen bond in octadecanethiol at the surface of the SEIRA substrate was about 1%, the efficiency of the enhancement was approximately 100 times.
Application example 2
According to the method of application example 1, an octadecanethiol molecular film is prepared on the surface of the SEIRA substrate prepared in the embodiment 2-5, and then infrared spectrum test is carried out to obtain the infrared reflection spectrum of each substrate. FIG. 5 is a graph showing the effect of different diameter polystyrene microspheres on the IR enhancement wavelength of a SEIRA substrate, where the curves in FIG. 5 representing different diameter polystyrene microspheres correspond to SEIRA substrates having different pillar array structure periodsThe depressed peak value of the infrared reflection spectrum is the infrared wavelength which can be enhanced. Specifically, the infrared wave number of the SEIRA substrate prepared when the diameter of the polystyrene microsphere is 300nm is 4762cm -1 (wavelength 2100 nm); the infrared wave number of the SEIRA substrate prepared when the diameter of the polystyrene microsphere is 400nm is 3570cm -1 (wavelength 2800 nm); the infrared wave number of the SEIRA substrate prepared when the diameter of the polystyrene microsphere is 600nm is 2380cm -1 (wavelength 4200 nm); the infrared wave number of the SEIRA substrate prepared when the diameter of the polystyrene microsphere is 1000nm is 1410cm -1 (wavelength 7090 nm). Therefore, the invention can adjust the period of the column array structure by adjusting the size of the polystyrene microsphere, thereby adjusting the infrared enhanced wavelength.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for preparing a surface-enhanced infrared absorption substrate comprises the following steps:
densely paving single-layer template microspheres on one side of the substrate to obtain a single-layer template microsphere layer-substrate workpiece;
performing reactive plasma etching on the single-layer template microsphere layer-substrate workpiece to reduce the diameter of the template microsphere and form a single-layer reduced-diameter template microsphere on one surface of the substrate to obtain a single-layer reduced-diameter template microsphere layer-substrate workpiece;
performing inductively coupled plasma etching on the substrate in the single-layer diameter-reduced template microsphere layer-substrate workpiece, forming a cylinder array on one surface of the substrate, and reserving the diameter-reduced template microspheres at the top ends of the cylinders in the cylinder array to obtain the single-layer diameter-reduced template microsphere layer-cylinder array-substrate workpiece;
removing the reduced-diameter template microspheres in the single-layer reduced-diameter template microsphere layer-cylinder array-substrate workpiece to obtain a cylinder array-substrate workpiece;
and depositing a metal layer on the surface of the cylinder array-substrate workpiece with the cylinder array to obtain the surface-enhanced infrared absorption substrate.
2. The method according to claim 1, wherein the diameter of the template microsphere is 150nm to 3 μm.
3. The method according to claim 1 or 2, wherein the diameter of the template microspheres with reduced diameters is 10 to 200nm smaller than the diameter of the template microspheres.
4. The preparation method according to claim 3, wherein the reactive plasma etching time is 10-120 s.
5. The method according to claim 3, wherein the pillars have a height of 0.1 to 1 μm and a diameter of 140nm to 2.8 μm; the distance between adjacent columns is the reduction of the diameter of the template microsphere.
6. The method according to claim 5, wherein the time for the inductively coupled plasma etching is 20s to 3 min.
7. The method of claim 1, wherein the reducing diameter template microsphere is removed by mechanical stripping or chemical etching.
8. The method of claim 1, wherein the metal layer comprises an adhesion layer and a functional layer in a stacked arrangement, the adhesion layer being disposed between the pillar array-substrate article and the functional layer; the material of the adhesion layer comprises titanium or chromium, and the material of the functional layer comprises gold, aluminum, silver, platinum or copper.
9. The method according to claim 8, wherein the adhesive layer has a thickness of 1 to 5nm, and the functional layer has a thickness of 15 to 200 nm.
10. The surface-enhanced infrared absorption substrate prepared by the preparation method of any one of claims 1 to 9, which comprises a substrate, a pillar array and a metal layer, wherein the pillar array is arranged on one side of the substrate, the pillar array is formed by a plurality of pillars which are periodically distributed, and the metal layer is arranged on the upper surfaces of the pillars and the surface of the substrate exposed between the pillars.
CN202210394573.1A 2022-04-14 2022-04-14 Surface-enhanced infrared absorption substrate and preparation method thereof Pending CN114804010A (en)

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