CN111017872A - Preparation method of sandwich structure composite nano array substrate - Google Patents
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Abstract
The invention discloses a preparation method of a sandwich structure composite nano array substrate, which comprises the steps of firstly, quickly forming a gold-silver alloy nano single-layer film on an oil-water interface by adopting a simple and mild metal sol self-assembly method, slowly absorbing redundant organic solvent on the upper surface of the film by virtue of an injector, and transferring the film onto a silicon wafer in a lifting mode to obtain the gold-silver alloy nano single-layer film; then transferring the graphene to the surface of the gold-silver alloy nano single-layer film by adopting a polymer protection-etching method; and finally transferring the gold-silver alloy nano single-layer film on the surface of the graphene to obtain the gold-silver alloy nano single-layer film-graphene-gold-silver alloy nano single-layer film composite nano array substrate with a sandwich structure. The preparation method has the advantages of short preparation period, simple and controllable operation, no need of any modification on gold-silver alloy nanoparticles, high repetition efficiency, and good compactness and flatness of the prepared sandwich structure composite nano array substrate.
Description
Technical Field
The invention relates to a preparation method of a composite nano array substrate with a sandwich structure, which is composed of a gold-silver alloy nano single-layer film, graphene and a gold-silver alloy nano single-layer film.
Background
With the rapid development of nanotechnology, the surface plasmon photonics of noble metal nanostructures has developed into a cross subject integrating multiple sciences such as physics, chemistry, life science, information science and the like, and has very important application prospects in the fields of new energy, material science, catalysis and the like. The surface plasmon enhancement effect of the noble metal nanostructure depends on the type, size, configuration, medium environment and the like of the material. The preparation method of the common metal nano material comprises the following steps: physical polishing method, magnetron sputtering method, ion beam etching method, metal sol self-assembly method and chemical reduction method, wherein the requirements of the metal sol self-assembly method on equipment and experimental conditions are relatively low, so that many researchers self-assemble the metal nano-structure array substrate with the micro-morphology on the oil-water interface. For example: liu et al first modified gold nanoparticles with n-butanol and ethanol, and then achieved the preparation of monolayer films of gold nanoparticles on the oil-water interface by self-assembly (d.liu, c.li, f.zhou, ethyl.capaclary-induced self-assembly of periodic Au particulate substrates a biosystem at air/water interface [ J ]. adv.mater.interface, 2017,4(10): 1600976). Lu et al synthesized gold nanocolloid by wet chemical method, modified by acrylamide, formed a film on oil-water interface by metal sol self-assembly method, then irradiated by ultraviolet laser to accelerate the volatilization of organic solvent, finally obtaining compact monolayer gold nano film (X.Lu, Y.Huang, B.Liu, et al.light-controlled shrinkage of large-area gold nanoparticle film for tunable SERS activity [ J ]. Chem.Mater,2018,30(6): 1989-1997). Although both methods can obtain noble metal nano-films, both methods require modification of the metal nanoparticles with long periods.
Disclosure of Invention
The invention aims to provide a preparation method of a sandwich structure composite nano array substrate, which does not need any modification, has the advantages of simple and controllable method, short period, high repetition efficiency and better compactness and flatness.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. preparation of gold-silver alloy nano single-layer film substrate
Adding cyclohexane into gold-silver alloy nanoparticle colloid, slowly adding absolute ethyl alcohol, and self-assembling on an oil-water interface to form a gold-silver alloy nano monolayer film; then, slowly sucking redundant cyclohexane on the surface of the film by using an injector until the surface of the film is completely covered with a layer of cyclohexane solution, and standing at normal temperature for 20-30 min to completely volatilize the cyclohexane; finally, fishing the gold-silver alloy nano single-layer film by using a clean silicon wafer in a pulling and lifting mode, and cleaning the film after the film is dried.
2. Preparation of gold-silver alloy nano single-layer film-graphene composite array substrate
Coating an anisole solution containing polymethyl methacrylate on the surface of single-layer graphene of the copper substrate, and drying at 80-100 ℃ for 0.5-2 h; soaking the dried single-layer graphene in an ammonium persulfate aqueous solution for 3-5 hours, washing residual liquid on the surface of the graphene with deionized water, transferring the graphene onto the surface of the gold-silver alloy nano single-layer film substrate prepared in the step 1, and drying the graphene at the temperature of 40-60 ℃ for 0.5-2 hours; and finally, soaking the dried substrate in acetone for 15-30 min, removing the polymethyl methacrylate on the surface of the graphene, and sequentially cleaning the substrate with absolute ethyl alcohol and deionized water to obtain the gold-silver alloy nano single-layer film-graphene composite array substrate.
3. Preparation of sandwich structure composite nano array substrate
Preparing a gold-silver alloy nano single-layer film according to the method in the step 1, transferring the gold-silver alloy nano single-layer film to the gold-silver alloy nano single-layer film-graphene composite array substrate prepared in the step 2, and washing the gold-silver alloy nano single-layer film with absolute ethyl alcohol and deionized water respectively after the surface of the gold-silver alloy nano single-layer film is dried to obtain the gold-silver alloy nano single-layer film-graphene-gold-silver alloy nano single-layer film composite nano array substrate with a sandwich structure.
In the step 1, the volume ratio of the gold-silver alloy nanoparticle colloid to the cyclohexane and the absolute ethyl alcohol is preferably 1 (0.3-0.6) to 0.6-0.7.
In the step 2, the polymethyl methacrylate solution preferably contains 6 to 10% by mass of polymethyl methacrylate.
In the step 2, the concentration of ammonium persulfate in the ammonium persulfate aqueous solution is preferably 0.2-0.5 mol/L.
The invention has the following beneficial effects:
under the condition of no modifier, firstly, a metal sol self-assembly method is adopted, after the gold-silver alloy nano single-layer film is formed by self-assembly on an oil-water interface, the redundant organic solvent on the surface of the film is slowly absorbed by virtue of an injector, the volatilization time of the organic solvent is shortened, the formation of the compact gold-silver alloy nano single-layer film is accelerated, and the assembly of the gold-silver alloy nano single-layer film array is realized. And then transferring single-layer graphene on the surface of the gold-silver alloy nano single-layer film array by adopting a polymer protection-etching method to obtain the gold-silver alloy nano single-layer film-graphene composite array substrate. And finally, transferring the gold-silver alloy nano single-layer film to graphene of the composite substrate to obtain the gold-silver alloy nano single-layer film-graphene-gold-silver alloy nano single-layer film composite nano array substrate with a sandwich structure. The preparation method is simple and controllable, the preparation period is short, the repetition efficiency is high, and the prepared sandwich structure composite nano array substrate has better compactness and flatness.
Drawings
FIG. 1 is a diagram of a gold-silver alloy nano monolayer film.
FIG. 2 is an SEM image of a gold-silver alloy nano monolayer film array substrate.
Fig. 3 is an SEM image of the gold-silver alloy nano monolayer film-graphene composite array substrate.
Fig. 4 is an SEM image of a composite nano array substrate of a sandwich structure composed of a gold-silver alloy nano monolayer film-graphene-gold-silver alloy nano monolayer film.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. Preparation of gold-silver alloy nano single-layer film substrate
8mL of the prepared gold-silver alloy nanoparticle colloid (prepared according to the literature "Q.Han, C.Zhang, W.Gao, et. Ag-Au alloy nanoparticles: synthesis and in situ monitoring SERS of platinum catalysts [ J ]. Sensors and Actuators B,2016,231: 609-. In order to shorten the self-assembly preparation period and promote the formation of a compact nano single-layer film, the excessive cyclohexane on the surface of the film is slowly absorbed by using an injector until the surface of the film is just completely covered with a layer of cyclohexane solution, and the film is placed at normal temperature for 30min to completely volatilize the cyclohexane. Ultrasonically cleaning a silicon wafer with a polished single surface by using acetone, absolute ethyl alcohol and deionized water respectively, taking out the silicon wafer and drying the silicon wafer by using nitrogen, fishing the formed gold-silver alloy nano single-layer film by using the cleaned silicon wafer in a pulling mode, and washing the formed gold-silver alloy nano single-layer film by using the absolute ethyl alcohol and the deionized water in sequence after the formed gold-silver alloy nano single-layer film is dried to obtain a single-layer compact gold-silver alloy nano single-layer film substrate.
2. Preparation of gold-silver alloy nano single-layer film-graphene composite array substrate
An anisole solution containing 6 wt% polymethyl methacrylate (PMMA) was coated on the surface of single-layer graphene of a copper substrate by means of a spin coater, and then dried in an oven at 80 ℃ for 1 h. And placing the dried single-layer graphene in 50mL0.2mol/L ammonium persulfate aqueous solution, soaking for 4 hours, taking out, washing residual liquid on the surface of the graphene with deionized water, transferring the residual liquid to the surface of the gold-silver alloy nano single-layer film substrate, and placing the substrate in an oven at 60 ℃ for drying for 1.5 hours. And finally, soaking the dried substrate in acetone for 30min, removing PMMA on the surface of the graphene, taking out, and then respectively cleaning with absolute ethyl alcohol and deionized water to obtain the gold-silver alloy nano single-layer film-graphene composite array substrate.
3. Preparation of sandwich structure composite nano array substrate
Preparing a gold-silver alloy nano single-layer film according to the method in the step 1, transferring the gold-silver alloy nano single-layer film to the gold-silver alloy nano single-layer film-graphene composite array substrate prepared in the step 2, and washing the gold-silver alloy nano single-layer film with absolute ethyl alcohol and deionized water respectively after the surface of the gold-silver alloy nano single-layer film is dried to obtain the gold-silver alloy nano single-layer film-graphene-gold-silver alloy nano single-layer film composite nano array substrate with the sandwich structure.
As can be seen from fig. 1, a uniform gold-silver alloy nano monolayer film with a large area is formed on the oil-water interface by adopting a metal sol self-assembly method. By means of HITACHI S-4800 field emission scanning electron microscope characterization produced by Hitachi, Japan, it can be seen from SEM photograph of gold-silver alloy nano monolayer film array substrate (see FIG. 2) that gold-silver alloy nano particles with uniform size are self-assembled to form a compact monolayer film, and the area of the nano monolayer film is larger. According to the SEM photograph (shown in figure 3) of the gold-silver alloy nano single-layer film-graphene composite array substrate, the substrate is a double-layer film composite array structure consisting of a gold-silver alloy nano single-layer film and single-layer graphene, and the single-layer graphene on the surface of the substrate is flatly paved on the compact gold-silver alloy nano single-layer film. On the basis, the composite nano array substrate with the sandwich structure, which is composed of the gold-silver alloy nano single-layer film-graphene-gold-silver alloy nano single-layer film, is obtained, and is shown in figure 4.
Claims (4)
1. A preparation method of a sandwich structure composite nano array substrate is characterized by comprising the following steps:
(1) preparation of gold-silver alloy nano single-layer film substrate
Adding cyclohexane into gold-silver alloy nanoparticle colloid, slowly adding absolute ethyl alcohol, and self-assembling on an oil-water interface to form a gold-silver alloy nano monolayer film; then, slowly sucking redundant cyclohexane on the surface of the film by using an injector until the surface of the film is completely covered with a layer of cyclohexane solution, and standing at normal temperature for 20-30 min to completely volatilize the cyclohexane; finally, fishing the gold-silver alloy nano single-layer film by using a clean silicon wafer in a lifting mode, and cleaning the film after the film is dried;
(2) preparation of gold-silver alloy nano single-layer film-graphene composite array substrate
Coating an anisole solution containing polymethyl methacrylate on the surface of single-layer graphene of the copper substrate, and drying at 80-100 ℃ for 0.5-2 h; soaking the dried single-layer graphene in an ammonium persulfate aqueous solution for 3-5 hours, washing residual liquid on the surface of the graphene with deionized water, transferring the graphene onto the surface of the gold-silver alloy nano single-layer film substrate prepared in the step (1), and drying the graphene at 40-60 ℃ for 0.5-2 hours; finally, soaking the dried substrate in acetone for 15-30 min, removing polymethyl methacrylate on the surface of the graphene, and sequentially cleaning the substrate with absolute ethyl alcohol and deionized water to obtain a gold-silver alloy nano single-layer film-graphene composite array substrate;
(3) preparation of sandwich structure composite nano array substrate
Preparing a gold-silver alloy nano single-layer film according to the method in the step (1), transferring the gold-silver alloy nano single-layer film to the gold-silver alloy nano single-layer film-graphene composite array substrate prepared in the step (2), and washing the surface of the gold-silver alloy nano single-layer film with absolute ethyl alcohol and deionized water respectively after the surface of the gold-silver alloy nano single-layer film is dried to obtain the composite nano array substrate with a sandwich structure consisting of the gold-silver alloy nano single-layer film-graphene-gold-silver alloy nano single-layer film.
2. The method for preparing the sandwich structure composite nano array substrate according to claim 1, wherein the method comprises the following steps: in the step (1), the volume ratio of the gold-silver alloy nanoparticle colloid to cyclohexane and absolute ethyl alcohol is 1 (0.3-0.6) to (0.6-0.7).
3. The method for preparing the sandwich structure composite nano array substrate according to claim 1, wherein the method comprises the following steps: in the step (2), the mass content of the polymethyl methacrylate in the polymethyl methacrylate-containing anisole solution is 6-10%.
4. The method for preparing the sandwich structure composite nano array substrate according to claim 1, wherein the method comprises the following steps: in the step (2), the concentration of ammonium persulfate in the ammonium persulfate aqueous solution is 0.2-0.5 mol/L.
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| CN114203326A (en) * | 2021-12-13 | 2022-03-18 | 中国核动力研究设计院 | Graphene-packaged ultrathin nickel-63 radiation source film and preparation method and application thereof |
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| CN114203326A (en) * | 2021-12-13 | 2022-03-18 | 中国核动力研究设计院 | Graphene-packaged ultrathin nickel-63 radiation source film and preparation method and application thereof |
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