CN111115547A - Flexible columnar array structure and preparation method and application thereof - Google Patents
Flexible columnar array structure and preparation method and application thereof Download PDFInfo
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- CN111115547A CN111115547A CN201911378723.4A CN201911378723A CN111115547A CN 111115547 A CN111115547 A CN 111115547A CN 201911378723 A CN201911378723 A CN 201911378723A CN 111115547 A CN111115547 A CN 111115547A
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- 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
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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
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00214—Processes for the simultaneaous manufacturing of a network or an array of similar microstructural devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B2203/00—Basic microelectromechanical structures
- B81B2203/03—Static structures
- B81B2203/0361—Tips, pillars
Abstract
The invention relates to the technical field of surface-enhanced Raman scattering active substrates, in particular to a flexible columnar array structure and a preparation method and application thereof4‑1×106The surface of each columnar bulge is made of polytetrafluoroethylene, is resistant to corrosion of acid, alkali and various organic solvents, has strong hydrophobicity and self-cleaning property, and the surface of each columnar bulge increases the hydrophobicity of the organic substrate and the self-cleaning propertyThe flexible columnar array structure made of the Teflon plate has more and more uniform columnar bulges, so that the SERS active hot spot is greatly increased, and the surface plasma resonance coupling effect and the SERS signal of adsorbed molecules on the metal surface are improved; due to good orderliness, good signal repeatability, and good accuracy and stability during detection.
Description
Technical Field
The invention relates to the technical field of surface-enhanced Raman scattering active substrates, in particular to a flexible columnar array structure and a preparation method and application thereof.
Background
The Surface Enhanced Raman Scattering (SERS) technology overcomes the inherent weak signal of the traditional Raman spectrum, can increase the Raman intensity by several orders of magnitude, is enough to detect the Raman signal of a single molecule, can be used for trace material analysis, flow cytometry and other applications, is not enough to complete the sensitivity and the measuring speed of the traditional Raman, and has wide application and is concerned in the fields of chemical industry, catalysis, biomedicine, environment and the like.
Raman enhancement requires a metal surface with nano-scale roughness as a substrate, i.e. an activity enhancement substrate, molecules adsorbed on such a surface will produce raman enhancement, and the preparation of the activity enhancement substrate is key to obtaining good SERS effect.
At the beginning of the SERS discovery, the activity enhancing substrate was actually a rough metal surface after electrochemical corrosion. The "roughness" herein is not macroscopically rough but microscopically nano-scale rough. Because the rough microstructure of the metal surface can enable incident laser to excite local surface plasma on the metal surface, for the rough metal surface, incident photons can be coupled with extra momentum of the rough surface to realize momentum matching, the coupling of the incident photons and the surface plasma is completed, when the incident photons and the surface plasma are coupled, the intensity of an electromagnetic field of a metal surface light field is sharply increased, and the effect of surface plasma resonance is realized. Surface plasmon resonance occurs mostly near "rough" SERS hot spots with high localization.
Although SERS substrates based on rigid substrates such as silicon wafers and glass plates established at present can analyze analytes in solution state well, the detection of curved surfaces of some practical objects becomes a difficult problem in reality. At present, gold/silver nanoparticles with modified SERS activity on flexible materials such as tapes, filter papers, Polydimethylsiloxane (PDMS), etc. have been widely used and studied as SERS substrates. For example, the existing chinese patent document CN104849259 discloses a preparation method of a flexible surface-enhanced raman substrate, which includes preparation of a flexible substrate, hydrophilic treatment of the surface of the flexible substrate, silanization of the surface, and then deposition of gold nanoparticles and silver nanoparticles on the surface, and the reaction steps are many and complicated, and the uniformity of the preparation method and the active nanostructure prepared by the preparation method is difficult to control, resulting in poor detection repeatability.
Disclosure of Invention
Therefore, the invention provides a flexible columnar array structure, a preparation method and application thereof, aiming at solving the technical problems that the prior art is difficult to obtain the flexible columnar array structure with simple preparation method and enough rough and uniform columnar bulges.
The invention discloses a flexible columnar array structure, which comprises,
the Teflon substrate and the columnar projections are uniformly arranged on the Teflon substrate, the maximum transverse size of the tops of the columnar projections is 200nm-850nm, the height of the columnar projections is 250nm-1.6 mu m, and the minimum distance between the edges of the adjacent columnar projections is 80nm-200 nm.
Optionally, each square millimeter of the teflon substrate comprises 8 × 104-1×106The columnar projections.
The invention also provides a preparation method of the flexible columnar array structure, which comprises the following steps:
s1, cleaning the Teflon substrate;
s2, preparing a hexagonal close-packed monolayer ordered polystyrene microsphere array on the surface of the Teflon substrate obtained in the step S1 by using polystyrene microspheres with the particle size of 300nm-1 mu m;
s3, performing reactive ion etching on the hexagonal close-packed single-layer ordered polystyrene microsphere array obtained in the step S2 to obtain a flexible columnar array structure.
Optionally, in step S1, the teflon plate is sequentially placed into deionized water, absolute ethyl alcohol, acetone, concentrated sulfuric acid, hydrogen peroxide, and deionized water to be ultrasonically cleaned for 15-30min, and then dried at 120 ℃.
Optionally, in step S2, mixing a polystyrene microsphere suspension with a content of 2.5 wt% and a diameter of 300nm to 1 μm with absolute ethyl alcohol in equal volume, performing ultrasonic dispersion for 15 to 30min to obtain a polystyrene microsphere diluent, and then preparing a hexagonal close-packed monolayer ordered polystyrene microsphere array on the teflon plate by using the polystyrene microsphere diluent; wherein, the ultrasonic frequency is 20-40KHz, and the power is 300-1000W.
Optionally, in step S2, the teflon plate is fixed on a movable plastic flat plate, the prepared polystyrene microspheres are self-assembled on the teflon plate, and after the assembly is completed, the continuous heating and drying at 30-40 ℃ are performed, so as to obtain the hexagonal close-packed single-layer ordered polystyrene microsphere array.
Optionally, in step S3, the reactive ion etching uses sulfur hexafluoride as a working gas, the etching current is 3A, the gas flow rate is 20-50scc/min, the gas pressure is 1-4Pa, the etching power is 150-.
The invention also provides a surface-enhanced Raman scattering substrate, which comprises the flexible columnar array of claim 1 or 2 or the flexible columnar array structure prepared by the preparation method of the flexible columnar array structure of any one of claims 3 to 7, wherein a gold film is arranged on one surface provided with the columnar protrusions, and the thickness of the gold film is 20-40 nm.
The invention also provides a preparation method of the surface-enhanced Raman scattering substrate, which is characterized in that a gold film is deposited on the surface of the flexible columnar array structure by adopting a magnetron sputtering deposition method, the processing current of the magnetron sputtering deposition is 20mA, and the protective gas is N2The degree of vacuum was controlled to 8X 10-4Pa, sputtering rate 0.3 nm/s.
The technical scheme of the invention has the following advantages:
1. the invention discloses a flexible columnar array structure, which comprises a Teflon substrate and columnar bulges uniformly arranged on the Teflon substrate, wherein the maximum transverse size of the top of each columnar bulge is 200-850 nm, the height of each columnar bulge is 250-1.6 mu m, the minimum distance between the edges of the adjacent columnar bulges is 80-200 nm, the columnar bulges have larger depth-width ratio, the wax on the surfaces of the columnar bulges is specifically composed of fluoropolymer, acid and alkali resistance and various organic solvents, impurities are not easy to introduce during detection, the flexible columnar array structure has stable property and small surface tension, has stronger hydrophobicity and certain self-cleaning property, the columnar bulges are constructed on the surfaces of the columnar bulges, the hydrophobicity and the self-cleaning property of an organic substrate are more obviously increased, pollutants cannot appear before and after film coating, SERS detection can be directly carried out on the coated film, and the flexible columnar array structure prepared from the polymer has denser and more uniform columnar bulges, the depth-to-width ratio of the columnar protrusions is larger, so that SERS active hot spots on the whole silicon column array are greatly increased, the surface plasma resonance coupling effect is greatly improved, and SERS signals of adsorbed molecules on the metal surface are greatly improved; and the orderliness is good, the signal repeatability is good, the accuracy and the stability during detection are good, and the Raman performance is excellent.
2. According to the preparation method of the flexible columnar array structure, the polystyrene microspheres with different diameters are used as masks to perform reactive ion etching, the preparation method is simple, and the prepared flexible columnar bulge is regular in shape and good in repeatability.
3. The surface-enhanced Raman scattering substrate comprises the flexible columnar array, wherein a gold film is arranged on one surface of the flexible columnar array, which is provided with the columnar protrusions, the thickness of the gold film is 20-40nm, the preparation method is deposition through magnetron sputtering, and the preparation method is simple and good in practicability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1a is an electron microscope image of a hexagonal close-packed monolayer of ordered polystyrene microspheres on the surface of a Teflon plate in example 1;
FIG. 1b is an electron microscope image of the flexible columnar array structure in example 1;
FIG. 2a is an electron micrograph of a hexagonal close-packed monolayer of ordered polystyrene microspheres on the surface of a Teflon plate in example 2;
FIG. 2b is an electron micrograph of the flexible columnar array structure of example 2;
FIG. 3a is an electron micrograph of a hexagonal close-packed monolayer of ordered polystyrene microspheres from the surface of the Teflon sheet in example 3;
FIG. 3b is an electron micrograph of the flexible columnar array structure of example 3;
FIG. 4a is an electron microscope image of a hexagonal close-packed monolayer ordered polystyrene microsphere on the surface of a silicon sheet in comparative example 1;
FIG. 4b is an electron micrograph of the silicon pillar array structure of comparative example 1;
FIG. 5a is an electron microscope image of a hexagonal close-packed monolayer ordered polystyrene microsphere on the surface of a silicon sheet in comparative example 2;
FIG. 5b is an electron micrograph of the silicon pillar array structure in comparative example 2;
FIG. 6a is an electron microscope image of a hexagonal close-packed monolayer ordered polystyrene microsphere on the surface of a silicon sheet in comparative example 3;
FIG. 6b is an electron micrograph of the silicon pillar array structure in comparative example 3
FIGS. 7a and 7b are schematic diagrams of a flexible columnar array structure obtained by removing polystyrene microspheres from the structure of FIG. 3b in example 3;
FIGS. 7c and 7d are the structure of the silicon pillar array obtained by removing the polystyrene microspheres from the structure of FIG. 6b in comparative example 3;
FIG. 8 is a flow chart of the flexible columnar array fabrication process according to the present invention;
FIG. 9 is a diagram showing the Raman detection result obtained in test example 2;
fig. 10 is a schematic diagram of raman detection results obtained in test example 3.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The preparation process of the flexible surface-enhanced Raman scattering substrate provided by the invention is shown in FIG. 8, wherein FIG. 1 shows a single-layer ordered polystyrene microsphere array structure constructed on a Teflon plate; FIG. 2 shows the result of reactive ion etching of the structure of FIG. 1; and (3) a flexible organic columnar array structure obtained by removing residual polystyrene microspheres from the structure in the step (2) by using a cleaning solvent.
Example 1
This example provides an embodiment of a method for preparing a flexible surface-enhanced raman scattering substrate, the preparation process is shown in fig. 8 and described as follows:
s1 cutting a Teflon plate with the thickness of 1mm into a size of 2cm multiplied by 2cm, then sequentially putting the Teflon plate into deionized water, absolute ethyl alcohol, acetone, 1.84g/ml concentrated sulfuric acid, 1.1g/ml hydrogen peroxide water and deionized water for ultrasonic cleaning, wherein the ultrasonic frequency is 30KHz, the power is 200W, ultrasonic cleaning is carried out in each liquid for 20min, and the Teflon plate is put into an oven for drying at 120 ℃ after cleaning;
s2, mixing 30 mu L of polystyrene microsphere suspension with the content of 2.5 wt% and the diameter of 300nm with absolute ethyl alcohol in equal volume, and then carrying out ultrasonic oscillation for 20min with the ultrasonic frequency of 30KHz and the power of 500W to prepare uniformly dispersed polystyrene microsphere ethanol diluent; fixing the dried Teflon plate on a movable plastic flat plate by using a double-sided adhesive, self-assembling the prepared 300nm polystyrene microsphere ethanol diluent on the Teflon plate by using surface tension, preparing a 300nm hexagonal close-packed monolayer ordered polystyrene microsphere array on the Teflon plate, as shown in figure 1a, after the assembly is finished, transferring the plastic plate to an oven, continuously heating at 30 ℃ until water on the Teflon plate is naturally air-dried, and constructing a regular hexagonal close-packed monolayer ordered polystyrene microsphere array on the Teflon surface as shown in figure 1 a;
s3, performing reactive ion etching on the Teflon board with the 300nm hexagonal close-packed single-layer ordered polystyrene microsphere array obtained in the step S2, using sulfur hexafluoride as working gas, controlling the etching current to be 3A, controlling the gas flow to be 35scc/min, maintaining the gas pressure to be 1-4Pa, controlling the etching power to be 200W, and etching time to be 120S, and obtaining the structure shown in figure 1b after etching; then using CH2Cl2Washing away the polystyrene microspheres to obtain a flexible columnar array structure;
the transverse maximum size of the top of the columnar bulge of the flexible columnar array is 200nm-240nm, the height is 250nm-320nm, and the minimum distance between the adjacent edges of the columnar bulge is 80nm-100 m;
the number of the columnar projections on the Teflon substrate per square millimeter is 9 multiplied by 106-1×107A plurality of;
s4, using the flexible columnar array structure prepared in the step S3 as a template, adopting a magnetron sputtering deposition method and taking N as protective gas2The degree of vacuum was controlled to 8X 10-4Pa, sputtering rate of 0.3nm/s, processing current of magnetron sputtering deposition of 20mA, and depositing a layer of gold film with thickness of 30nm on the surface of the template for Raman detection.
Example 2
This example provides an embodiment of preparing a surface-enhanced raman scattering substrate, which is described as follows:
s1 cutting a Teflon plate with the thickness of 1mm into a size of 2cm multiplied by 2cm, then sequentially putting the Teflon plate into deionized water, absolute ethyl alcohol, acetone, 1.84g/ml concentrated sulfuric acid, 1.1g/m hydrogen peroxide water and deionized water for ultrasonic cleaning, wherein the ultrasonic frequency is 20KHz, the power is 300W, ultrasonic cleaning is carried out in each liquid for 15min, and the Teflon plate is put into an oven for drying at 100 ℃ after cleaning;
s2, mixing 30 mu L of polystyrene microsphere suspension with the content of 2.5 wt% and the diameter of 500nm with absolute ethyl alcohol in equal volume, and then carrying out ultrasonic oscillation for 15min at the ultrasonic frequency of 20KHz and the power of 300W to prepare uniformly dispersed polystyrene microsphere ethanol diluent; fixing the dried Teflon plate on a movable plastic flat plate by using a double-sided adhesive tape, self-assembling the prepared 500nm polystyrene microsphere ethanol diluent on the Teflon plate by using surface tension, preparing a 500nm hexagonal close-packed monolayer ordered polystyrene microsphere array on the Teflon plate, and transferring the plastic plate to an oven for continuous heating at 30 ℃ until water on the Teflon plate is naturally air-dried after the assembly is finished, so that a regular hexagonal close-packed monolayer ordered polystyrene microsphere array can be constructed on the Teflon surface, as shown in figure 2 a;
s3, performing reactive ion etching on the Teflon board with the 500nm hexagonal close-packed single-layer ordered polystyrene microsphere array obtained in the step S2, using sulfur hexafluoride as working gas, controlling the etching current to be 3A, controlling the gas flow to be 20scc/min, maintaining the gas pressure to be 1-4Pa, controlling the etching power to be 150W, and etching time to be 240S, and obtaining the structure shown in figure 2b after etching; then using CH2Cl2Washing away the polystyrene microspheres to obtain a flexible columnar array structure;
the transverse maximum size of the top of the columnar bulge of the flexible columnar array is 380nm-400nm, the height of the columnar bulge is 480nm-500nm, and the minimum distance between the edges of the adjacent columnar bulges is 80nm-120 nm;
the number of the columnar projections on the Teflon substrate per square millimeter is 3 multiplied by 106-4×106A plurality of;
s4, using the flexible columnar array structure prepared in the step S3 as a template, adopting a magnetron sputtering deposition method and taking N as protective gas2The degree of vacuum was controlled to 8X 10-4Pa, sputtering rate of 0.3nm/s, magnetron sputtering deposition processing current of 20mA, and depositing a gold film with thickness of 20nm on the surface of the template for Raman detection.
Example 3
This example provides an embodiment of preparing a surface-enhanced raman scattering substrate, which is described as follows:
s1 cutting a Teflon plate with the thickness of 1mm into a size of 2cm multiplied by 2cm, then sequentially putting the Teflon plate into deionized water, absolute ethyl alcohol, acetone, 1.84g/ml concentrated sulfuric acid, 1.1g/m hydrogen peroxide water and deionized water for ultrasonic cleaning, wherein the ultrasonic frequency is 40KHz, the power is 300-1000W, ultrasonic cleaning is carried out in each liquid for 15-30min, and the Teflon plate is dried in an oven at the temperature of 100-120 ℃ after cleaning;
s2, mixing 30 mu L of polystyrene microsphere suspension with the content of 2.5 wt% and the diameter of 1 mu m with absolute ethyl alcohol in equal volume, and then carrying out ultrasonic oscillation for 30min with the ultrasonic frequency of 40KHz and the power of 1000W to prepare uniformly dispersed polystyrene microsphere ethanol diluent; fixing the dried Teflon plate on a movable plastic flat plate by using a double-sided adhesive tape, self-assembling the prepared 1-micron polystyrene microsphere ethanol diluent on the Teflon plate by using surface tension, preparing a 1-micron hexagonal close-packed monolayer ordered polystyrene microsphere array on the Teflon plate, and transferring the plastic plate to an oven for continuous heating at 40 ℃ until water on the Teflon plate is naturally air-dried after the assembly is finished, so that a regular hexagonal close-packed monolayer ordered polystyrene microsphere array can be constructed on the Teflon surface, as shown in fig. 3 a;
s3, performing reactive ion etching on the Teflon board with the 1-micron hexagonal close-packed single-layer ordered polystyrene microsphere array obtained in the step S2, using sulfur hexafluoride as working gas, controlling the etching current to be 3A, controlling the gas flow to be 50scc/min, maintaining the gas pressure to be 1-4Pa, controlling the etching power to be 250W, and etching time to be 360S, and obtaining the structure shown in figure 3b after etching; then using CH2Cl2Washing away the polystyrene microspheres to obtain a flexible columnar array structure, as shown in fig. 7a and 7 b;
the surface roughness of the columnar array structure as seen in fig. 7a and 7b is not related to the step of removing the polystyrene microspheres, mainly because the object photographed by using the field emission scanning electron microscope needs to have conductivity, but neither PS spheres nor teflon plates have conductivity, and the scanning SEM image may result in bending of the area, or because the teflon plates are macroscopically flat, but the substrate itself has some local roughness;
the transverse maximum size of the top of the columnar bulge of the flexible columnar array is 800nm-850nm, the height of the columnar bulge is 1500nm-1600nm, and the minimum distance between the edges of the adjacent columnar bulges is 150nm-200 nm;
the number of the columnar projections on the Teflon substrate per square millimeter is 9 multiplied by 105-1×106A plurality of;
s4, using the flexible columnar array structure prepared in the step S3 as a template, adopting a magnetron sputtering deposition method and taking N as protective gas2The degree of vacuum was controlled to 8X 10-4Pa, sputtering rate of 0.3nm/s, processing current of magnetron sputtering deposition of 20mA, and depositing a layer of gold film with thickness of 40nm on the surface of the template for Raman detection.
Comparative example 1
The present comparative example provides an embodiment of preparing a surface-enhanced raman scattering substrate, which is described in detail as follows:
s1, cutting a silicon wafer with the thickness of 1mm into a size of 2cm multiplied by 2cm, then sequentially putting the silicon wafer into deionized water, absolute ethyl alcohol, acetone, 1.84g/ml concentrated sulfuric acid, 1.1g/m hydrogen peroxide water and deionized water for ultrasonic cleaning, wherein the ultrasonic frequency is 30KHz, the power is 200W, ultrasonic cleaning is carried out in each liquid for 20min, and the silicon wafer is put into an oven for drying at 120 ℃ after cleaning;
s2, mixing 30 mu L of polystyrene microsphere suspension with the content of 2.5 wt% and the diameter of 300nm with absolute ethyl alcohol in equal volume, and then carrying out ultrasonic oscillation for 20min with the ultrasonic frequency of 30KHz and the power of 500W to prepare uniformly dispersed polystyrene microsphere ethanol diluent; fixing the dried silicon wafer on a movable plastic flat plate by using a double-sided adhesive, self-assembling the prepared 300nm polystyrene microsphere ethanol diluent on the silicon wafer by using surface tension, then preparing a 300nm hexagonal close-packed monolayer ordered polystyrene microsphere array on the silicon wafer by adopting a gas-liquid interface self-assembling method, as shown in figure 4a, after the assembly is finished, transferring the plastic plate to an oven, continuously heating at 30 ℃ until the water on the silicon wafer is naturally dried, and thus constructing a regular hexagonal close-packed monolayer ordered polystyrene microsphere array on the surface of Teflon as shown in figure 4 a;
s3, performing reactive ion etching on the Teflon board with the 300nm hexagonal close-packed single-layer ordered polystyrene microsphere array obtained in the step S2, using sulfur hexafluoride as working gas, controlling the etching current to be 3A, controlling the gas flow to be 35scc/min, maintaining the gas pressure to be 1-4Pa, controlling the etching power to be 200W, and etching time to be 120S, and obtaining the structure shown in figure 4b after etching; then using CH2Cl2Washing away the polystyrene microspheres to obtain a columnar array structure;
the transverse maximum size of the top of each columnar bulge of the columnar array is 200nm-220nm, the height of each columnar bulge is 200nm-220nm, and the minimum distance between the adjacent edges of the columnar bulges is 100nm-120 m;
the number of columnar projections on each square millimeter substrate is 9 multiplied by 106-1×107And (4) respectively.
S4, using the flexible columnar array structure prepared in the step S3 as a template, adopting a magnetron sputtering deposition method and taking N as protective gas2The degree of vacuum was controlled to 8X 10-4Pa, sputtering rate of 0.3nm/s, processing current of magnetron sputtering deposition of 20mA, and depositing a layer of gold film with thickness of 30nm on the surface of the template for Raman detection.
Comparative example 2
The present comparative example provides an embodiment of preparing a surface-enhanced raman scattering substrate, which is described in detail as follows:
s1, cutting a silicon wafer with the thickness of 1mm into a size of 2cm multiplied by 2cm, then sequentially putting the silicon wafer into deionized water, absolute ethyl alcohol, acetone, 1.84g/ml concentrated sulfuric acid, 1.1g/m hydrogen peroxide water and deionized water for ultrasonic cleaning, wherein the ultrasonic frequency is 20KHz, the power is 300W, ultrasonic cleaning is carried out in each liquid for 15min, and the silicon wafer is put into an oven for drying at 100 ℃ after cleaning;
s2, mixing 30 mu L of polystyrene microsphere suspension with the content of 2.5 wt% and the diameter of 500nm with absolute ethyl alcohol in equal volume, and then carrying out ultrasonic oscillation for 15min at the ultrasonic frequency of 20KHz and the power of 300W to prepare uniformly dispersed polystyrene microsphere ethanol diluent; fixing the dried silicon wafer on a movable plastic flat plate by using a double-sided adhesive tape, self-assembling the prepared 500nm polystyrene microsphere ethanol diluent on the silicon wafer by using surface tension, then preparing a 500nm hexagonal close-packed monolayer ordered polystyrene microsphere array on the silicon wafer by using a gas-liquid interface self-assembly method, as shown in figure 5a, after the assembly is finished, transferring the plastic plate to an oven, continuously heating at 30 ℃ until the water on the silicon wafer is naturally dried, and thus constructing a regular hexagonal close-packed monolayer ordered polystyrene microsphere array on the surface of Teflon as shown in figure 5 a;
s3, performing reactive ion etching on the Teflon board with the 500nm hexagonal close-packed single-layer ordered polystyrene microsphere array obtained in the step S2, using sulfur hexafluoride as working gas, controlling the etching current to be 3A, controlling the gas flow to be 20scc/min, maintaining the gas pressure to be 1-4Pa, controlling the etching power to be 150W, and controlling the etching time to be 100S, so that the structure shown in FIG. 5b can be obtained after etching; then using CH2Cl2Washing away the polystyrene microspheres to obtain a columnar array structure;
the transverse maximum size of the top of each columnar bulge of the columnar array is 350nm-400nm, the height of each columnar bulge is 350nm-400nm, and the minimum distance between the adjacent edges of the columnar bulges is 150nm-180 m;
the number of columnar projections on each square millimeter substrate is 3 multiplied by 106-4×106And (4) respectively.
S4, using the flexible columnar array structure prepared in the step S3 as a template, adopting a magnetron sputtering deposition method and taking N as protective gas2The degree of vacuum was controlled to 8X 10-4Pa, sputtering rate of 0.3nm/s, magnetron sputtering deposition processing current of 20mA, and depositing a layer of gold film with the thickness of 20nm on the surface of the template for Raman short.
Comparative example 3
The present comparative example provides an embodiment of preparing a surface-enhanced raman scattering substrate, which is described in detail as follows:
s1, cutting a silicon wafer with the thickness of 1mm into a size of 2cm multiplied by 2cm, then sequentially putting the silicon wafer into deionized water, absolute ethyl alcohol, acetone, 1.84g/ml concentrated sulfuric acid, 1.1g/m hydrogen peroxide water and deionized water for ultrasonic cleaning, wherein the ultrasonic frequency is 40KHz, the power is 300-1000W, ultrasonic cleaning is carried out in each liquid for 15-30min, and the silicon wafer is put into an oven for drying at the temperature of 100-120 ℃ after cleaning;
s2, mixing 30 mu L of polystyrene microsphere suspension with the content of 2.5 wt% and the diameter of 1 mu m with absolute ethyl alcohol in equal volume, and then carrying out ultrasonic oscillation for 30min with the ultrasonic frequency of 40KHz and the power of 1000W to prepare uniformly dispersed polystyrene microsphere ethanol diluent; fixing the dried silicon wafer on a movable plastic flat plate by using a double-sided adhesive tape, self-assembling the prepared 1-micron polystyrene microsphere ethanol diluent on the silicon wafer by using surface tension, then preparing a 1-micron hexagonal close-packed monolayer ordered polystyrene microsphere array on the silicon wafer by adopting a gas-liquid interface self-assembling method, as shown in figure 6a, after the assembly is completed, transferring the plastic plate to an oven, continuously heating at 40 ℃ until the water on the silicon wafer is naturally air-dried, and constructing a regular hexagonal close-packed monolayer ordered polystyrene microsphere array on the surface of Teflon as shown in figure 6 a;
s3, performing reactive ion etching on the Teflon board with the 1-micron hexagonal close-packed single-layer ordered polystyrene microsphere array obtained in the step S2, using sulfur hexafluoride as working gas, controlling the etching current to be 3A, controlling the gas flow to be 50scc/min, maintaining the gas pressure to be 1-4Pa, controlling the etching power to be 250W, and controlling the etching time to be 140S, and obtaining the structure shown in FIG. 6b after etching; then using CH2Cl2Washing away the polystyrene microspheres to obtain a columnar array structure, as shown in FIGS. 7c and 7 d;
the lateral maximum size of the top of each columnar protrusion of the columnar array is 650nm-700nm, the height of each columnar protrusion is 1000m-1200nm, and the minimum distance between the edges of the adjacent columnar protrusions is 350nm-400 m;
the number of columnar projections on each square millimeter substrate is 9 multiplied by 105-1×106And (4) respectively.
S4, using the flexible columnar array structure prepared in the step S3 as a template, adopting a magnetron sputtering deposition method and taking N as protective gas2The degree of vacuum was controlled to 8X 10-4Pa, the sputtering rate is 0.3nm/s, the processing current of magnetron sputtering deposition is 20mA, and a layer of gold film with the thickness of 40nm is deposited on the surface of the template, so that the template is obtained.
Test example 1
Surface-enhanced Raman scattering substrate pair 10 obtained in example 3 and comparative example 3 was used-7Performing Raman performance detection on 4-ATP with Mol/L concentration, wherein the Raman spectrum detection has the excitation wavelength of 785nm, the excitation power of 2mW and the integration time of 1 s; the results are shown in fig. 9, which illustrates that the flexible substrate provided in example 3 of the present application can significantly improve the signal intensity and increase the sensitivity and accuracy of detection.
Test example 2
The surface-enhanced Raman scattering substrate pair 10 obtained in example 3 was used-5Performing Raman performance uniformity detection on 4-ATP with Mol/L concentration, and performing Raman performance detection on 10 points randomly selected on a Teflon plate, wherein the Raman spectrum detection has the excitation wavelength of 785nm, the excitation power of 2mW and the integration time of 10 s; the results are shown in FIG. 10, which shows better reproducibility of detection.
It is to be understood that the above examples are illustrative only for the purpose of clarity of description and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (9)
1. A flexible columnar array structure is characterized by comprising,
the Teflon substrate and the columnar projections are uniformly arranged on the Teflon substrate, the maximum transverse size of the tops of the columnar projections is 200nm-850nm, the height of the columnar projections is 250nm-1.6 mu m, and the minimum distance between the edges of the adjacent columnar projections is 80nm-200 nm.
2. The flexible columnar array structure of claim 1, comprising 8 x 10 per square millimeter of the teflon substrate4-1×106The columnar projections.
3. A method for preparing a flexible columnar array structure according to claim 1 or 2, comprising the steps of:
s1, cleaning the Teflon substrate;
s2, preparing a hexagonal close-packed monolayer ordered polystyrene microsphere array on the surface of the Teflon substrate obtained in the step S1 by using polystyrene microspheres with the particle size of 300nm-1 mu m;
s3, performing reactive ion etching on the hexagonal close-packed single-layer ordered polystyrene microsphere array obtained in the step S2 to obtain a flexible columnar array structure.
4. The method for preparing a flexible columnar array structure according to claim 4, wherein in step S1, the Teflon plate is sequentially placed into deionized water, absolute ethyl alcohol, acetone, concentrated sulfuric acid, hydrogen peroxide and deionized water for ultrasonic cleaning for 15-30min respectively, and then dried at 120 ℃.
5. The method for preparing a flexible columnar array structure according to claim 3 or 4, wherein in step S2, a polystyrene microsphere suspension with a diameter of 300nm to 1 μm and a content of 2.5 wt% is taken and mixed with absolute ethyl alcohol in equal volume, and then ultrasonic dispersion is carried out for 15 to 30min to obtain a polystyrene microsphere diluent, and then a hexagonal close-packed monolayer ordered polystyrene microsphere array is prepared on the Teflon plate by using the polystyrene microsphere diluent; wherein, the ultrasonic frequency is 20-40KHz, and the power is 300-1000W.
6. The method for preparing a flexible columnar array structure according to any one of claims 3 to 5, wherein in step S2, the Teflon plate is fixed on a movable plastic flat plate, the prepared polystyrene microspheres are self-assembled on the Teflon plate, and after the assembly, the continuous heating and drying at 30-40 ℃ are carried out, so as to obtain the hexagonal close-packed single-layer ordered polystyrene microsphere array.
7. The method for preparing the flexible column array structure according to any one of claims 3 to 6, wherein in the step S3, sulfur hexafluoride is used as a working gas for reactive ion etching, the etching current is 3A, the gas flow rate is 20 to 50scc/min, the gas pressure is 1 to 4Pa, the etching power is 150-.
8. A surface-enhanced Raman scattering substrate, which comprises the flexible columnar array according to claim 1 or 2, or the flexible columnar array structure prepared by the preparation method of the flexible columnar array structure according to any one of claims 3 to 7, wherein a gold film is arranged on the side provided with the columnar protrusions, and the thickness of the gold film is 20-40 nm.
9. The method for preparing the surface-enhanced Raman scattering substrate according to claim 8, wherein a magnetron sputtering deposition method is adopted to deposit a gold film on the surface of the flexible columnar array structure, the processing current of the magnetron sputtering deposition is 20mA, and the protective gas is N2The degree of vacuum was controlled to 8X 10-4Pa, sputtering rate 0.3 nm/s.
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