CN112775434A - Preparation method and application of nano star-chain-shaped nano structure array - Google Patents
Preparation method and application of nano star-chain-shaped nano structure array Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
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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
Abstract
The invention relates to a preparation method and application of a nano star chain-shaped nano structure array, which comprises the following steps: (1) obtaining a photoresist layer with a micro-nano structure array pattern on the surface of a substrate material by wet etching, wherein the micro-nano structure array pattern is composed of a plurality of two-dimensional strip-shaped hollow unit structures; (2) and dripping nano star particle sol on the surface of the substrate material with the photoresist layer for multiple times, naturally drying, depositing gold nano particles in the hollow unit structure, and removing the photoresist to finally obtain a plurality of nano star chain-shaped nano structure arrays on the surface of the substrate material. The invention can construct the discrete nano materials in the prior art into nano chains with nano scale, so that the distance between nano particles reaches the nano scale, the distance between nano chains also has the nano scale, the invention can be applied to a surface enhanced Raman scattering substrate, the local field enhancement effect is improved, and the gold nanostar chain-shaped nano structure array has better photoelectric effect.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a preparation method and application of a nano star chain-shaped nano structure array.
Background
In recent years, precious metal nano materials have attracted wide interest in the field of nanotechnology due to unique characteristics of optical, electrical, mechanical and catalytic effects, biocompatibility and the like, and particularly have great application prospects in photovoltaic synergy or Raman inspection technologies.
The surface plasmon effect of the metal nanoparticles is that the surface electron cloud of the nanoparticles is excited by the electric field in the incident electromagnetic wave (or incident light), so that the interaction is generated, and the surface plasmon is formed. Such surface plasmons can generate electric fields with higher amplitudes than the incident electromagnetic wave 103-107Multiple local electric field strength. In the field of nanotechnology, it is called a hotspot. The field local effect can be utilized in the photovoltaic field to enhance the absorption of the nearby photovoltaic material to the incident light, and the hot spot can be utilized in the Raman field to improve the Raman signal in the Raman detection process.
In the prior art, for example, a processing method of nano and micro holes is disclosed in a Chinese patent 201711349542.X, and a micro-nano composite structure metal particle dot array can be prepared; for example, chinese patent 201710637648.3 discloses a method for preparing a surface-enhanced raman scattering substrate, which is also a dot array having a discrete structure. While the discrete dot array can improve the local field enhancement effect to a certain extent, the improvement degree is limited.
Disclosure of Invention
In order to further improve the technical problem of the local field enhancement effect of the micro-nano structure, a preparation method and application of a nano star chain-shaped nano structure array are provided. The method comprises the steps of preparing a two-dimensional photoresist film with a hollowed-out strip-shaped structure on a flat substrate such as glass, conductive glass and a silicon wafer by utilizing a photoetching technology, wherein a hollowed-out area is called as a template for depositing gold nano-star particles, preparing the gold nano-star particles by a chemical method, and then depositing the gold nano-star in the hollowed-out area of the photoresist film by a multi-drop coating method; and finally, stripping off the photoresist to obtain the gold nano star chain-shaped nano structure array. The basic unit of the gold nano star chain-shaped nano structure array is the gold nano star, and the gold nano star has a sharp pointed angle structure relative to other morphological materials, so that a more obvious surface plasmon effect can be obtained. In addition, the gold nanostar particles are in chain distribution through the template constraint of the hollow area, the distance between the nanostars is within the nanometer size range, the optical coupling effect can be generated, the local field enhancement effect is further improved, and the gold nanostar chain nanostructure array has a better photoelectric effect.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a nano star chain-shaped nano structure array comprises the following steps:
(1) obtaining a photoresist layer with a micro-nano structure array pattern on the surface of a clean and flat substrate material by wet etching, wherein the micro-nano structure array pattern is composed of a plurality of two-dimensional strip-shaped hollow unit structures;
(2) and dripping nano star particle sol on the surface of the substrate material with the photoresist layer for multiple times, naturally drying, depositing gold nano particles in the hollow unit structure, and removing the photoresist to finally obtain a plurality of nano star chain-shaped nano structure arrays on the surface of the substrate material.
Further, the wet etching method comprises the following steps: spin-coating a layer of photoresist on the surface of the substrate material, drying to obtain a photoresist film, exposing the photoresist film by adopting a mask with a two-dimensional strip-shaped micro-nano structure array pattern, and post-drying and developing after exposure, thereby obtaining the photoresist layer with the micro-nano structure array pattern on the surface of the substrate material.
Further, if the photoresist is a positive photoresist, the micro-nano structure array pattern of the corresponding mask is a light-transmitting part, and the rest of the mask is a non-light-transmitting part; if the photoresist is a negative photoresist, the micro-nano structure array pattern of the corresponding mask is a non-light-transmitting part, and the rest of the mask is a light-transmitting part.
Further, the thickness of the photoresist layer is more than 200 nm; the space between the strip-shaped hollow unit structures is 200 nm-1000 nm, and the width of the strip-shaped hollow unit structures is 80 nm-150 nm.
Further, the preparation process of the nano star particle sol comprises the following steps:
uniformly mixing a 0.01M chloroauric acid solution and a 0.1M CTAB solution, adding a 0.01mM sodium borohydride solution, uniformly mixing to obtain a gold seed solution, and storing the gold seed solution in a dark place for 2 hours for later use; the volume ratio of the chloroauric acid solution to the CTAB solution to the sodium borohydride solution is 1:30: 2.4;
uniformly mixing 0.01M chloroauric acid solution and 0.1M CTAB solution, and then sequentially adding 0.01M silver nitrate solution and 0.1M ascorbic acid solution to obtain growth solution for later use; the volume ratio of the chloroauric acid solution to the CTAB solution to the silver nitrate solution to the ascorbic acid solution is 2:47.5:0.3: 0.32;
thirdly, adding the gold seed solution into the growth solution according to the volume ratio of the gold seed solution to the growth solution of 1:1000, uniformly mixing, standing for more than 3 hours at room temperature, then aging for 12 hours, and centrifuging for many times to remove redundant reactants to obtain gold nano-star particle sol, wherein the size range of gold nano-star particles in the sol is 40-80 nm.
Still further, the microstructure of the gold nano-star is a star-like structure having at least three corners.
Further, the photoresist is removed by placing the photoresist in a stripping solution, and then the remaining photoresist layer is removed.
Further, the substrate material is one of glass, conductive glass, and a highly doped silicon wafer, but is not limited thereto.
On the other hand, the invention provides a nano star chain-shaped nano structure array obtained on the surface of the substrate by the preparation method, which is applied to the surface enhanced Raman scattering substrate.
The beneficial technical effects are as follows:
according to the nanostar chain-like nanostructure array, a photoetching development technology (wet etching) is adopted to obtain a photoresist layer with a two-dimensional strip-like micro-nano structure array pattern of a mask on a substrate, the micro-nano structure array pattern is composed of a plurality of two-dimensional strip-like hollowed-out units, gold nanostar sol prepared by a seed crystal growth method is dripped into the photoresist layer, namely the plurality of hollowed-out units, and after natural drying, the photoresist layer is removed, so that the nanostar chain-like nanostructure with gold nanostars on the surface of the substrate or the chain-like nanostructure with gold nanostars can be obtained. The invention can construct the discrete nano materials in the prior art into nano chains with nano scale, so that the distance between nano particles reaches the nano scale, the distance between nano chains also has the nano scale, the optical coupling effect can be generated, the local field enhancement effect is further improved, and the gold nanostar chain-shaped nano structure array has better photoelectric effect.
The mask plate adopted by photoetching development can obtain a hollow strip-shaped two-dimensional micro-nano structure array on the substrate correspondingly, so that the distance between nano chains formed by nano stars deposited in the hollow unit area can be controlled, and the mask plate has the function of regulating and controlling the distribution distance between the nano chain arrays so as to further achieve the function of controlling the appearance of the nano chains; in addition, the size of the particles of the gold nano-star elements is regulated and controlled by preparing gold nano-star sol, and the deposition density of the nano-particles in the nano-chain is regulated and controlled by the times of dripping the sol; the method can effectively and conveniently control the length and the micro appearance of the gold nano chain and realize the optimization of the photoelectric property of the nano chain structure.
According to the gold nano star chain-shaped nano structure array prepared by the invention, from the electric field enhancement effect, the elements in the chain-shaped nano structure are gold nano stars, on one hand, the gold nano star has a more obvious local field enhancement effect compared with nano particles with other shapes, on the other hand, the gold nano star particle elements form the chain-shaped nano structure, the distance between the gold nano star chains and the chains is in a nano scale, the coupling effect can be further generated, the electric field intensity of a nano material coupling area is further improved, and the local field enhancement effect is further improved.
The invention combines the photoetching technology and the dripping coating mode, and has no limit on the preparation area, so that the material can be prepared in a large area, and the application and the industrialization prospect are enlarged.
Drawings
Fig. 1 is a schematic diagram of a chain-like nanostructure array of nanostars according to the present invention, wherein the gold nanostars are pentagons and are not used for defining the micro-morphology of the gold nanostars, but only illustrated by the shape of the pentagons.
FIG. 2 is a schematic flow chart of the preparation of the nanostar chain-like nanostructure array according to embodiments 1 to 4.
In the figure, 1-substrate material, 2-gold nano star chain-shaped nano structure, 21-gold nano star particles, 31-photoresist film and 3-photoresist layer with two-dimensional strip-shaped hollow units.
FIG. 3 is a SERS test chart of different substrates, wherein Sample A represents and Sample B represents the product of example 4 as a substrate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
Example 1
The wet etching is adopted to prepare the photoresist layer with the two-dimensional strip-shaped hollow unit structure, and the process is as shown in figure 2:
firstly, a substrate 1 such as glass or conductive glass or a silicon wafer is thoroughly cleaned through the processes of detergents such as acetone, isopropanol and the like to remove impurity ions (as shown in figure 2-I);
and then, a positive photoresist film 31 (shown in a figure 2-II) is spin-coated on the substrate 1, the thickness of the photoresist layer is more than 200nm, after drying, a mask with a two-dimensional strip-shaped micro-nano structure array pattern is used for exposure, after exposure, post-drying and developing are carried out, so that the photoresist layer 3 (shown in a figure 2-III) of the micro-nano structure array pattern is obtained on the surface of the substrate 1, the micro-nano structure array pattern is formed by a plurality of two-dimensional strip-shaped hollow unit structures, and the pattern in the mask is copied into the photoresist film 31 in the exposure and developing process.
If the spin-coated photoresist is a positive photoresist in the above process, the micro-nano structure array pattern of the corresponding mask is a light-transmitting part, and the rest of the mask is a non-light-transmitting part; if the spin-coated photoresist is a negative photoresist, the micro-nano structure array pattern of the corresponding mask is a non-light-transmitting part, and the rest of the mask is a light-transmitting part.
The spacing between the strip-shaped hollow unit structures of the photoresist layer 3 obtained in this embodiment was measured to be 1000nm, and the width of the hollow unit structure was measured to be 100 nm.
Example 2
Preparing gold nano-star particle sol:
uniformly mixing 0.250mL of chloroauric acid solution (0.01M) and 7.5mL of CTAB solution (0.1M), adding 0.6mL of sodium borohydride solution (0.01M), slightly shaking to form dark brown gold seed solution, and storing the dark brown gold seed solution for 2 hours in a dark place for later use;
secondly, taking another 10mL small bottle, adding 4.75mL of the CTAB solution and 0.2mL of the chloroauric acid solution into the small bottle, slightly shaking the small bottle to uniformly mix the CTAB solution and the chloroauric acid solution, then sequentially adding 0.03mL of silver nitrate solution (0.01M) and 0.032mL of ascorbic acid solution (0.1M) in sequence, and mixing to obtain a colorless growth solution for later use;
and thirdly, adding 20 mu l of gold seed solution into 20mL of growth solution, uniformly shaking and mixing, standing at room temperature for more than 3h to obtain dark blue gold nano-star particle sol, aging for 12h, centrifuging twice, and removing redundant reactants to obtain pure gold nano-star particle sol.
The particle size distribution of the gold nano-star in the gold nano-star particle sol of the present example was measured to be about 40nm to 80 nm.
Example 3
Depositing gold nano-star particles:
the gold nano-star particle sol prepared in example 2 (see fig. 2-iv) was applied by drop coating onto the surface of the photoresist layer 3 having a strip-like hollow unit structure, and naturally dried, and the distribution density of the gold nano-star was monitored by a scanning electron microscope to ensure that a chain-like nano-structure of nano-star was formed in the hollow unit structure. According to the actual situation, the gold nano-star particle sol can be dripped for many times, and the gold nano-star particles are ensured to be in a continuous chain distribution state in the strip-shaped hollow unit structure of the photoresist layer (as shown by a mark 2 in figure 1).
Example 4
Removing the photoresist layer to obtain a nano star-chain nano structure array:
by a standard stripping process, according to the properties of the photoresist, selecting a corresponding stripping solution, immersing the entire material in embodiment 3 in the corresponding stripping solution, so as to remove the photoresist layer 3 and the excess gold nanostar particles (as shown in fig. 2-v) attached to the surface layer of the photoresist layer 3, and finally obtaining a plurality of gold nanostar chain-like nanostructure arrays (as shown in fig. 1) on the substrate 1.
Example 5
In order to verify that the nanostar chain-like nanostructure array obtained on the surface of the substrate can be used for a surface-enhanced Raman scattering substrate, the nanostar chain-like nanostructure array is detected and compared with a substrate with nanostars randomly dripped.
Firstly, preparing a solution of rhodamine 6G, wherein the concentration of the rhodamine 6G is 1 multiplied by 10-6mol/L。
Dripping 200 microliter of nano star particle sol on the surface of glass randomly and drying to obtain a Sample A; taking the product obtained in the embodiment 4 of the invention as Sample B, dripping 10 microliters of rhodamine 6G solution on the surfaces of the Sample A and the Sample B respectively, airing, and then placing under a Raman instrument respectively to measure the SERS spectrum.
The SERS spectrum is shown in FIG. 3, the characteristic peak of Sample A of the nano star randomly coated on the glass surface is not obvious and can not be clearly identified; but the Sample B forming the nanostar chain-shaped nanostructure array has obviously high sensitivity in characteristic peak. The nano star chain-shaped nano structure array is beneficial to detection of Raman signals, and the high-sensitivity surface-enhanced Raman scattering substrate can be obtained by using the method.
The photoresist, stripping solution, in the above examples are well known to those skilled in the art. The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A preparation method of a nano star chain-shaped nano structure array is characterized by comprising the following steps:
(1) obtaining a photoresist layer with a micro-nano structure array pattern on the surface of a clean and flat substrate material by wet etching, wherein the micro-nano structure array pattern is composed of a plurality of two-dimensional strip-shaped hollow unit structures;
(2) and dripping nano star particle sol on the surface of the substrate material with the photoresist layer for multiple times, naturally drying, depositing gold nano particles in the hollow unit structure, and removing the photoresist to finally obtain a plurality of nano star chain-shaped nano structure arrays on the surface of the substrate material.
2. The method for preparing the nano star chain-shaped nano structure array according to claim 1, wherein the wet etching method comprises the following steps: spin-coating a layer of photoresist on the surface of the substrate material, drying to obtain a photoresist film, exposing the photoresist film by adopting a mask with a two-dimensional strip-shaped micro-nano structure array pattern, and post-drying and developing after exposure, thereby obtaining the photoresist layer with the micro-nano structure array pattern on the surface of the substrate material.
3. The method for preparing a nano star chain-like nanostructure array according to claim 2, wherein if the photoresist is a positive photoresist, the corresponding micro-nano structure array pattern of the mask is a light-transmitting part, and the rest of the mask is a non-light-transmitting part; if the photoresist is a negative photoresist, the micro-nano structure array pattern of the corresponding mask is a non-light-transmitting part, and the rest of the mask is a light-transmitting part.
4. The method for preparing a nanostar chain nanostructure array of claim 1, wherein the photoresist layer has a thickness of 200nm or more; the space between the strip-shaped hollow unit structures is 200 nm-1000 nm, and the width of the strip-shaped hollow unit structures is 80 nm-150 nm.
5. The method for preparing a nanostar chain-like nanostructure array of claim 1, wherein the nanostar particle sol is prepared by:
uniformly mixing a 0.01M chloroauric acid solution and a 0.1M CTAB solution, adding a 0.01mM sodium borohydride solution, uniformly mixing to obtain a gold seed solution, and storing the gold seed solution in a dark place for 2 hours for later use; the volume ratio of the chloroauric acid solution to the CTAB solution to the sodium borohydride solution is 1:30: 2.4;
uniformly mixing 0.01M chloroauric acid solution and 0.1M CTAB solution, and then sequentially adding 0.01M silver nitrate solution and 0.1M ascorbic acid solution to obtain growth solution for later use; the volume ratio of the chloroauric acid solution to the CTAB solution to the silver nitrate solution to the ascorbic acid solution is 2:47.5:0.3: 0.32;
thirdly, adding the gold seed solution into the growth solution according to the volume ratio of the gold seed solution to the growth solution of 1:1000, uniformly mixing, standing for more than 3 hours at room temperature, then aging for 12 hours, and centrifuging for many times to remove redundant reactants to obtain gold nano-star particle sol, wherein the size range of gold nano-star particles in the sol is 40-80 nm.
6. The method as claimed in claim 5, wherein the gold nanostar microstructure is a star structure having at least three corners.
7. The method as claimed in claim 1, wherein the photoresist is removed by placing the substrate in a stripping solution, and then removing the remaining photoresist layer.
8. The method as claimed in claim 1, wherein the substrate material is one of glass, conductive glass, and highly doped silicon wafer.
9. The nanostar chain-like nanostructure array prepared by the preparation method according to any one of claims 1 to 8 is applied to a surface-enhanced Raman scattering substrate.
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