CN111398245B - Periodically arranged handrail type surface enhanced Raman substrate and preparation method thereof - Google Patents
Periodically arranged handrail type surface enhanced Raman substrate and preparation method thereof Download PDFInfo
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
The invention belongs to the technical field of trace detection, and particularly relates to a periodically arranged handrail-type surface enhanced Raman substrate and a preparation method thereof. The substrate comprises a substrate, wherein an 'armrest-type' nanorod array is deposited on the substrate, and an oxide layer is coated on the surface of the 'armrest-type' nanorod. The Raman substrate has excellent surface enhanced Raman effect, good storage stability and substrate microstructure uniformity. The substrate has wide application prospect in the field of trace detection of organic matters and macromolecules.
Description
Technical Field
The invention belongs to the technical field of trace detection, and particularly relates to a periodically arranged handrail-type surface enhanced Raman substrate and a preparation method thereof.
Background
The Surface Enhanced Raman Spectroscopy (SERS) technology is an advanced nondestructive detection technology, has the characteristics of ultrasensitiveness, strong fingerprint identification, short detection time and the like, and has great application prospects in the fields of analytical chemistry and biomedicine of organic matters, macromolecules, proteins or DNA genes and the like.
The SERS effect is a phenomenon in which the intensity of raman signal is significantly enhanced due to molecules approaching or adsorbing to the surface of the nanostructure. At present, scientists generally consider the electromagnetic field enhancement mechanism (surface electromagnetic field enhancement) and the charge transfer enhancement mechanism (molecular polarizability increase) to be two main enhancement mechanisms of SERS substrates. The former belongs to a physical enhancement mechanism, and the latter belongs to a chemical enhancement mechanism. The relative contribution of the chemical enhancement mechanism is always the focus of academic debate, which can explain a part of experimental phenomena, but the SERS enhancement mechanism is mainly attributed to the electromagnetic field enhancement mechanism. The more "hot spots" a SERS substrate can provide, the better the enhancement. Therefore, how to effectively increase the number of 'hot spots' is an important research direction for preparing the SERS substrate. Research literature shows that periodically arranged nanostructure substrates can provide more "hot spot" areas, thereby achieving further enhancement of the surface raman enhancement effect of the substrate. Patent application No. 201810379352.0 discloses a "surface enhanced raman scattering substrate and a method for preparing the same", which utilizes a two-electron beam codeposition method to prepare a silver-aluminum solid solution nanorod SERS substrate, the SERS substrate does not have a periodic arrangement morphology, and although the SERS substrate has a good surface enhanced raman effect, the uniformity and the repeatability of the substrate need to be further improved.
The Anodic Aluminum Oxide (AAO) template has the characteristics of simple preparation method, long-range order and the like, and can be used as a template to realize large-scale preparation of the periodic SERS substrate. Patent application No. 201520540611.5 discloses "a DNA chip based on noble metal nano-array and SERS technology", although it realizes the preparation of periodic SERS substrate, its SERS enhancement effect needs to be further improved.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a periodically arranged handrail-type surface enhanced Raman substrate and a preparation method thereof. Through design and calculation, the micro-nano structure of the substrate is adjusted, the number of 'hot spots' is increased, the surface Raman enhancement effect is realized, and the repeatability and the uniformity of the substrate test are greatly improved.
Means for solving the technical problem
Aiming at the problems, the invention provides a periodically arranged handrail-type surface enhanced Raman substrate and a preparation method thereof.
According to one embodiment of the present invention, a periodically arranged "arm-rest" surface enhanced raman substrate is provided. The substrate comprises a base, wherein an 'armrest-type' nanorod array is deposited on the base, and an oxide layer is coated on the surface of the 'armrest-type' nanorod.
In one embodiment, the substrate includes, but is not limited to, a silicon substrate, a silicon oxide substrate, a glass substrate, an organic substrate, or the like.
One embodiment is, among others, that the "walking" nanorod material includes, but is not limited to, noble metals, general metals, or nitrides, etc.
One embodiment is, among others, that the oxide layer material includes, but is not limited to, aluminum oxide, hafnium oxide, etc.; the length of the nano rod is
The preferred range is
According to a second aspect of the present invention, there is provided a method for preparing the periodically arranged "handrail-type" surface enhanced raman substrate, which uses AAO as a template, and adopts a two-step electron beam evaporation deposition method to coat an oxide layer by using an atomic layer deposition technique.
One embodiment is, among others, the following: 1) placing the substrate coated with the AAO template on a substrate table, and vertically depositing a nanorod array by adopting electron beam evaporation; subsequently, removing the AAO template by using a physical method; 2) on the nanorod array substrate prepared in the step 1), utilizing electron beam evaporation deposition to obliquely grow a nanorod array, and preparing a surface enhanced Raman substrate with a periodic 'handrail-type' nanostructure; 3) and (3) depositing an oxide layer to coat the armrest-type nanorod structure prepared in the step 2) by utilizing an atomic layer deposition technology. One embodiment is that, the AAO template features include, but are not limited to, cylindrical through holes, V-shaped through holes, and irregular cross-section through holes; the structure of the prepared nanorod array is consistent with that of the template.
In one embodiment, in step 1), the substrate stage rotation rate during deposition is 5-80rpm, preferably 10-50 rpm.
One embodiment is that, wherein, the deposition angle of the periodic 'handrail type' surface enhanced raman substrate is 85 to 89 degrees. The angle is calculated by taking the vertical direction of the substrate or the vertical deposition nano rod in the step 1) as the angle calculation reference.
The invention has the advantages of
Compared with the prior art, the invention has the following advantages: (1) the SERS substrates realize periodic arrangement, and the enhancement effect is greatly improved; (2) the manufacturing method is simple, and does not cause harm to the environment; (3) the preparation of substrates of different materials can be realized according to actual requirements; (4) the detection repeatability and the substrate uniformity are greatly improved.
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Drawings
Fig. 1 is a scanning electron microscope image of a periodic "handrail-type" surface enhanced raman substrate prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the AAO template used in the preparation of example 1 and the vertically deposited silver nanorod array
Fig. 3 shows the change of the enhancement effect of the periodic "arm-rest" surface-enhanced raman substrate prepared in example 2 of the present invention on glucose molecules.
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto.
The preparation method adopted by the invention comprises the following steps: 1) and (3) placing the substrate coated with the AAO template on a substrate table, and vertically depositing the nanorod array by adopting electron beam evaporation. Removing the AAO template by a physical method; 2) and placing the nanorod array substrate prepared by vertical deposition on a sample table, and further carrying out electron beam evaporation deposition to obliquely grow a nanorod array to prepare the periodic handrail-type surface enhanced Raman substrate. 3) The prepared periodic handrail-type surface enhanced Raman substrate is coated with an oxide layer by utilizing an atomic layer deposition technology, so that the storage property and the stability of the substrate are improved. The oxide layer mainly coats the nano-rods, so that the nano-rods are protected from being oxidized or polluted; since the cladding is done using ALD methods, there must also be a few monolayers of or double layers of oxide between the rods.
In the step 1), the preparation method of the nanorod array by electron beam evaporation and vertical deposition comprises the following steps: fixing the substrate on a substrate table of an electron beam evaporation coating machine at the temperature of 298K; the target metal is adopted as an evaporation target material, and a reaction chamber of an electron beam evaporation coating machine is pumped to 1 multiplied by 10-5～9×10-5High vacuum of Pa; the incident angle of the substrate table to the evaporation beam current was adjusted to 0 degree and the substrate table was rotated at a rate of 10-50 rpm. According to AAO template sizeAnd depositing and growing a nanorod array with a corresponding length on the substrate of the substrate table.
In the step 1), the AAO template has a shape including, but not limited to, a cylindrical through hole, a V-shaped through hole, a through hole with a different cross section (such as a polygonal shape), and the like; the structure of the prepared nanorod array is consistent with that of the template.
In step 1) of the method, the rotation speed of the sample stage is 5-80rpm, and the preferred rotation speed is 10-50rpm during the deposition process. After the deposition is finished, the method also comprises a step of removing the AAO template by using a physical method.
In the step 2), the preparation method of the periodic "handrail-type" surface-enhanced raman substrate by electron beam evaporation deposition inclined growth comprises the following steps: fixing the substrate deposited with the periodic nanorod array on a substrate table of an electron beam evaporation coating machine at the temperature of 298K; the target metal is adopted as an evaporation target material, and a reaction chamber of an electron beam evaporation coating machine is pumped to 1 multiplied by 10-5～9×10-5High vacuum of Pa; adjusting the incident angle of the substrate table and the evaporation beam to be 85-89 degrees, and then obliquely depositing and growing a periodic 'handrail-shaped' surface enhanced Raman substrate on the substrate.
In step 1) and step 2) of the above method, the substrate includes, but is not limited to, a silicon substrate, a silicon oxide substrate, a glass substrate, or an organic substrate.
In step 1) and step 2) of the above method, the deposition material includes, but is not limited to, noble metals (e.g., gold, silver), general metals (e.g., copper), nitrides (e.g., titanium nitride, hafnium nitride), and the like.
In step 2) of the above method, the length of the nanorods of the "arm rest" part of the periodic "arm rest" surface enhanced Raman substrate is generally equal to
The preferred range is
In the step 2) of the method, the periodic handrail-type surface enhanced Raman substrate can be used for preparing nanorod arrays with different handrail-type structures by adjusting the deposition angle (85-89 degrees).
In step 3), the material of the coated oxide layer includes, but is not limited to, aluminum oxide, hafnium oxide, and the like.
The invention takes AAO as a template, adopts a two-step electron beam evaporation deposition method to prepare the periodically arranged handrail-type surface enhanced Raman substrate, has simple and easy-to-realize operation, and can prepare SERS enhanced substrates with different hot point contents by controlling the deposition time and the deposition angle.
Examples
The present invention is described in more detail by way of examples, but the present invention is not limited to the following examples.
Example 1
The periodic "" arm-rest "" surface enhanced Raman substrate of this example was prepared by two-step electron-beam evaporation using AAO as a template (see FIG. 1). The method comprises the following steps:
(1) sequentially ultrasonically cleaning a monocrystalline silicon wafer substrate by using acetone, alcohol and deionized water and airing for later use;
(2) transferring the AAO template to a pretreated substrate, and fixing the AAO template on a substrate table of an electron beam evaporation coating machine;
(3) at the temperature of 298K, silver particles are taken as a target material, a reaction chamber of an electron beam evaporation coating machine is pumped to 2 multiplied by 10-5High vacuum of Pa; the substrate table was rotated at a rate of 10 rpm;
(4) vertically depositing nano silver by adopting electron beam evaporation to obtain a silver nanorod array (shown in figure 2);
(5) after the AAO template is removed by a physical method, the silver nanorod array monocrystalline silicon substrate obtained by deposition is fixed on a substrate table of an electron beam evaporation coating machine.
(6) At the temperature of 298K, silver particles are taken as a target material, a reaction chamber of an electron beam evaporation coating machine is pumped to 2 multiplied by 10-5High vacuum of Pa; adjusting the substrate table to make the angle between the evaporation beam current and the normal of the substrate table reach 86 degrees, making the substrate table stationary, utilizing electron beam evaporation deposition to obliquely grow the nanorod array,preparation of
A periodic "handrail-type" surface enhanced raman substrate of length.
(7) The prepared periodic handrail-type surface enhanced Raman substrate is coated with 2 cycles of alumina oxide layers by utilizing an atomic layer deposition technology, so that the storage property and the stability of the substrate are improved.
(8) Configuration 1 × 10-6A Methylene Blue (MB) solution in mol/L;
(9) putting the periodic handrail-type surface enhanced Raman substrate prepared in the step 1-7 into the solution to be tested prepared in the step 8, and soaking for 30 minutes;
(10) putting the periodic handrail-type surface enhanced Raman substrate attached with the trace Methylene Blue (MB) in the step 9 into a Raman spectrometer, selecting a light source with the wavelength of 785nm, and measuring the Raman spectrum;
example 2
The periodic "" arm-rest "" surface enhanced Raman substrate of this embodiment is prepared by two-step electron beam evaporation deposition using AAO as a template. The method comprises the following steps:
(1) sequentially ultrasonically cleaning a monocrystalline silicon wafer substrate by using acetone, alcohol and deionized water and airing for later use;
(2) transferring the AAO template to a pretreated substrate, and fixing the AAO template on a substrate table of an electron beam evaporation coating machine;
(3) at the temperature of 298K, silver particles are taken as a target material, a reaction chamber of an electron beam evaporation coating machine is pumped to 2 multiplied by 10-5High vacuum of Pa; the substrate table was rotated at a rate of 30 rpm;
(4) vertically depositing nano silver by adopting electron beam evaporation to obtain a silver nanorod array;
(5) after the AAO template is removed by a physical method, the silver nanorod array monocrystalline silicon substrate obtained by deposition is fixed on a substrate table of an electron beam evaporation coating machine.
(6) At the temperature of 298K, silver particles are used as a target material, and a reaction chamber of an electron beam evaporation coating machine is pumpedTo 2X 10-5High vacuum of Pa; adjusting the substrate table to make the angle between the evaporation beam and the normal of the substrate table be 86 degrees, making the substrate table still, and utilizing electron beam evaporation deposition to obliquely grow the nanorod array to prepare the nano-rod array
A periodic "handrail-type" surface enhanced raman substrate of length.
(7) The prepared periodic handrail-type surface enhanced Raman substrate is coated with 1 cycle of alumina oxide layer by utilizing the atomic layer deposition technology, so that the storage property and the stability of the substrate are improved.
(8) Configuration 3 × 10-4A glucose solution of mol/L;
(9) putting the periodic handrail-type surface enhanced Raman substrate prepared in the step 1-7 into the solution to be tested prepared in the step 8, and soaking for 30 minutes;
(10) and (3) putting the periodic 'handrail type' surface enhanced Raman substrate attached with the trace glucose in the step (9) into a Raman spectrometer, and selecting a light source with the wavelength of 785nm to perform Raman spectrum measurement (see figure 3).
Comparative examples
Prepared by a double electron beam evaporation deposition method. The method comprises the following steps:
(1) ultrasonically cleaning a silicon substrate with a polished single surface one by using acetone, absolute ethyl alcohol and deionized water, and airing;
(2) fixing the pretreated substrate on a sample table of a dual-electron-beam evaporation coating machine;
(3) at room temperature, using silver and aluminum as target materials, separating two crucibles by 4cm, pumping the chamber of the double electron beam evaporation coating machine to a vacuum degree of 9 × 10-5Pa；
(4) Adjusting the incident angle of the two electron beams to 85 degrees, making the sample stage stationary, and controlling the coating rate of silver to be
Controlling the coating rate of aluminum to
Co-depositing a surface enhanced Raman substrate consisting of silver-aluminum solid solution nanorod arrays with the length of about 300nm on a substrate of a sample table;
(5) taking out the surface enhanced Raman substrate prepared in the step (4), and soaking the surface enhanced Raman substrate in the prepared 10-5Soaking in a methylene blue solution of mol/L for 30min, and then testing the Raman spectrum;
(6) the limit of testing of the test substrates by two-electron fabrication was found to be (10)-9mol/L) less than the substrate (10) prepared according to the invention-12mol/L)。
Industrial applicability
The substrate reinforcing effect is greatly improved, the manufacturing method is simple, no harm is caused to the environment, the detection repeatability and the substrate uniformity are greatly improved, and the substrate reinforcing method has high practicability.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. The periodically arranged handrail-type surface enhanced Raman substrate is characterized in that the substrate comprises a substrate, an handrail-type nanorod array is deposited on the substrate, an oxide layer is coated on the surface of the handrail-type nanorod, the handrail-type nanorod comprises a vertical part and an inclined part, the vertical part is perpendicular to the substrate, and the included angle between the inclined part and the extension line of the vertical part is 85-89 degrees.
2. The raman substrate of claim 1, wherein the substrate comprises but is not limited to a silicon substrate, a silicon oxide substrate, a glass substrate or an organic substrate.
3. The raman substrate of claim 1, wherein "walk-behind" nanorod materials include, but are not limited to, noble metals and nitrides.
4. The raman substrate of claim 1, wherein the oxide layer material includes, but is not limited to, aluminum oxide, hafnium oxide; the length of the nanorod is 0.1 k A-20 k A.
5. The method for preparing a periodically arranged 'handrail-type' surface enhanced Raman substrate according to any one of claims 1-4, wherein the substrate is prepared by a two-step electron beam evaporation deposition method using AAO as a template, and the oxide layer is coated by using an atomic layer deposition technique.
6. The method of preparing a raman substrate according to claim 5, comprising the steps of: 1) placing the substrate coated with the AAO template on a substrate table, and vertically depositing a nanorod array by adopting electron beam evaporation; subsequently, removing the AAO template by using a physical method;
2) on the nanorod array substrate prepared in the step 1), utilizing electron beam evaporation deposition to obliquely grow a nanorod array, and preparing a surface enhanced Raman substrate with a periodic 'handrail-type' nanostructure;
3) and (3) depositing an oxide layer to coat the armrest-type nanorod structure prepared in the step 2) by utilizing an atomic layer deposition technology.
7. The method for preparing a Raman substrate according to claim 5, wherein the AAO template features include, but are not limited to, cylindrical through holes, V-shaped through holes and irregular cross-section through holes; the structure of the prepared nanorod array is consistent with that of the template.
8. The method for preparing a raman substrate according to claim 5 wherein in step 1), the substrate stage rotation rate during deposition is 5 to 80 rpm.
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| US8206631B1 (en) * | 2008-09-18 | 2012-06-26 | Carnegie Mellon University | Methods of making dry adhesives |
| CN102879379A (en) * | 2012-09-18 | 2013-01-16 | 清华大学 | Method for preparing broken-line type inclined silver nanorod array surface enhanced Raman substrate |
| CN107399716B (en) * | 2017-07-31 | 2018-03-16 | 广东工业大学 | The preparation method and its linear array of the variable metal break nano-wire array of diameter |
| CN108893715B (en) * | 2018-07-27 | 2020-05-19 | 中国科学院合肥物质科学研究院 | Method for preparing nanocone array SERS substrate by changing oxidation potential in stepped mode |
| CN109136860B (en) * | 2018-09-18 | 2020-07-31 | 北京科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
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