CN108559981B - Preparation method of surface-enhanced infrared absorption spectrum enhanced substrate - Google Patents
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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Abstract
The invention relates to a preparation method of a surface-enhanced infrared absorption spectrum enhanced substrate and a substrate prepared by the same, in particular to a novel method for directly preparing a gold nano material on the surface of a zinc selenide prism by adopting an electroless deposition technology. The gold nano-film material is prepared by placing a chloroauric acid aqueous solution on the surface of a zinc selenide prism which is subjected to polishing treatment in advance and utilizing a chemical deposition reaction on the surface of the zinc selenide; by changing the concentration of the chloroauric acid aqueous solution and experimental conditions such as additives, reaction temperature and time, gold nano materials with different shapes and structures can be prepared on the surface of the zinc selenide prism; the gold nano-film based on the zinc selenide prism is used as an enhanced substrate for enhancing the infrared spectrum on the surface, and the lower limit of the analysis range of the infrared spectrum can be expanded to 700cm‑1To (3). The reinforced substrate has the advantages of simple structure, low cost of the preparation method, easy control, no need of special instruments and equipment, realization of large-area preparation, and easy popularization and application of the preparation technology.
Description
Technical Field
The invention relates to a preparation method of a surface-enhanced infrared absorption spectrum enhanced substrate and a substrate prepared by the same, in particular to a novel method for preparing a gold nano material on the surface of a zinc selenide prism by adopting an electroless deposition technology, belonging to the technical field of infrared spectra. The invention is used as an enhanced substrate of surface enhanced infrared absorption spectrum, and the lower limit of the analysis range of the surface enhanced infrared absorption spectrum can be expanded to 700cm-1To (3).
Background
The surface-enhanced infrared absorption spectrum is a sensitive surface-interface molecular structure characterization technology developed in the last three decades, has unique advantages in the research of the structure, conformation and orientation of interface molecules, and has shown important application prospects in the analysis and research of the interaction of biomolecules. Currently, surface-enhanced infrared absorption spectroscopy has been widely used in quantitative detection of biomolecules and in the study of specific recognition reactions and structure-activity relationships.
Due to the limitation of the light transmission range of the prism material used for surface enhanced infrared absorption spectroscopy, the cut-off wave number of the silicon prism which is most commonly used at present is 1500cm-1Many of the characteristic structures of biomolecules in the infrared fingerprint region, such as the phosphate skeleton of nucleic acid and phospholipids in cell membraneAnd the coordination structure of a protein prosthetic group and a peptide chain, etc., are generally difficult to directly observe. The spectrum analysis range of the surface enhanced infrared absorption spectrum is expanded, and the method has important significance for researching the molecular behavior of the interface.
Zinc selenide is a commonly used infrared prism material and is widely used in multiple internal reflection infrared spectroscopy. The cut-off wave number of the zinc selenide material is 650cm-1And the analysis requirements of most infrared fingerprint area structures can be met. However, there is still a lack of research on zinc selenide as a prism material in surface enhanced infrared absorption spectroscopy. The main limitation is the lack of a simple and feasible method for preparing the enhanced substrate on the surface of the zinc selenide prism. Therefore, if the reinforcing material can be directly prepared on the surface of the zinc selenide to realize infrared signal enhancement, the structure of the prism can be simplified, the signal enhancement capability is improved, and the application range of the surface-enhanced infrared absorption spectrum technology is further expanded.
The conventional method for preparing the surface enhanced substrate from zinc selenide is a vacuum evaporation or vacuum sputtering technology, and a layer of metal nano film can be deposited on the surface of the zinc selenide to be used as the enhanced substrate. The disadvantage of this method is that the enhancement factor of the metal nano-film is low. The other preparation method is a micro-nano processing technology, and the method can effectively regulate and control the shape and the size of the metal nano material, thereby improving the enhancement factor. However, this method usually requires some expensive equipment, is complicated and time-consuming to prepare, and is difficult to prepare materials in large area, thereby limiting the popularization and application of this kind of technology. Meanwhile, the acting force between the metal reinforced substrate prepared by the two technologies and zinc selenide is weaker, the metal reinforced substrate is easy to fall off, and the stability needs to be improved. In addition, the commonly used vacuum techniques use substrate materials such as copper and silver that are easily oxidized and difficult to chemically modify the surface for analytical applications.
Disclosure of Invention
In order to develop a novel method for simply and effectively preparing a surface-enhanced infrared absorption spectrum enhanced substrate with a wide detection range, the technical purpose of the invention is to provide a novel method which is low in cost and can prepare the surface-enhanced infrared absorption spectrum enhanced substrate in a large area, so that the enhanced substrate has the advantages of simplicity, convenience and easiness in popularization, capability of improving the enhancement effect of the surface-enhanced infrared absorption spectrum and expanding the spectrum analysis range, and label-free and high-sensitivity detection in the fields of catalysis, sensing, biological analysis and the like can be realized by utilizing the enhanced substrate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a surface-enhanced infrared absorption spectrum enhanced substrate is characterized by comprising the following steps: and (3) placing the chloroauric acid aqueous solution on the surface of the zinc selenide prism subjected to the polishing treatment in advance to perform electroless deposition reaction, and finally preparing the gold nano film material on the surface of the zinc selenide.
The preparation method comprises a pre-polishing treatment method of the zinc selenide prism, namely, the surface of the zinc selenide prism is polished by adopting alumina powder with a certain particle size and the zinc selenide prism is ultrasonically cleaned.
The shapes of the zinc selenide prisms of the invention include, but are not limited to, hemispheres.
The concentration of the chloroauric acid aqueous solution is 1 mM-24 mM, wherein additives which can be added into the aqueous solution include but are not limited to ethanol, halide and polyvinylpyrrolidone.
The conditions of the electroless deposition reaction according to the present invention are: the reaction temperature is 20-80 ℃, and the reaction time is 10 s-20 min.
The invention has the beneficial effects that:
1. the invention can directly prepare the enhanced substrate capable of enhancing the infrared signal on the surface of the zinc selenide infrared prism by a chemical deposition method, which is the most direct method for constructing the substrate.
2. According to the invention, according to the property requirements of the gold nano-film (such as obtaining the highest enhancement factor or applying the gold nano-film to an electrochemical experiment and the like), the concentration of a chloroauric acid aqueous solution and the experimental conditions of additives, reaction temperature, reaction time and the like are changed, gold nano-materials with different shapes and structures are directly prepared on the surface of a zinc selenide prism, and a substrate with a high-efficiency infrared enhancement effect is obtained;
3. the gold nano-film enhanced substrate based on the zinc selenide prism has good biocompatibility and long-term stability, and the lower limit of the spectral analysis range can be expanded to 700cm-1The method is suitable for sensitive detection and analysis of liquid samples, particularly biological samples;
4. the reinforced substrate has the advantages of simple structure, low cost of the preparation method, easy control, no need of special instruments and equipment, realization of large-area preparation, and easy popularization and application of the preparation technology.
As mentioned above, by changing the concentration of the chloroauric acid aqueous solution and the experimental conditions such as the additive, the reaction temperature and time, the gold nano-materials with different shapes and structures can be prepared on the surface of the zinc selenide prism, and the substrates with high-efficiency infrared enhancement effect can be respectively obtained:
keeping the passing condition at constant temperature of 30 ℃; adding 100 μ L of 1mM, 5mM, 10mM and 24mM chloroauric acid aqueous solution on the plane of the zinc selenide prism, reacting for 1min to obtain gold nano-materials with different sizes and shapes, and obtaining the wave number of 4000-700cm-1The infrared spectrum of (a).
By adjusting the reaction temperature at 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C and 80 deg.C, respectively adding 100 μ L of 24mM chloroauric acid aqueous solution onto the surface of zinc selenide prism, reacting for 1min to obtain gold nano materials with different sizes and shapes, and obtaining gold nano materials with wave number of 4000-700cm-1The infrared spectrum of (a).
Keeping the passing condition at constant temperature of 30 ℃; adding 100 μ L of 24mM chloroauric acid aqueous solution respectively containing 10% ethanol, 10mM KCl, 10mM KBr, 10mM KI and 1% polyvinylpyrrolidone into the plane of zinc selenide prism, reacting for 1min to obtain gold nanomaterials with different sizes and shapes, and obtaining the wave number of 4000-700cm-1The infrared spectrum of (a).
Keeping the passing condition at constant temperature of 30 ℃; adding 100 mu L of 24 to the plane of a zinc selenide prismRespectively reacting with mM chloroauric acid water solution for 10s, 20s, 30s, 40s, 1min, 3min and 20min to obtain gold nano materials with different sizes and shapes, wherein the wave number can be 4000-700cm-1The infrared spectrum of (a).
Due to the application of the technical scheme, the substrate with the surface enhanced infrared spectrum can be prepared, and compared with the prior art, the method has the following advantages:
the invention selects chloroauric acid to directly prepare the nano gold film on the surface of the zinc selenide prism by using an electroless deposition mode, and the reason is that the enhanced substrate is directly prepared on the surface of the prism, so that an infrared enhancing device can be simplified to the greatest extent, and the light intensity loss caused by the problem of a light path is reduced. Meanwhile, the conventional vacuum evaporation or vacuum sputtering technology adopted in the prior art has low enhancement factor, the combination of the enhanced substrate and the prism is not firm, and a high-vacuum device is required, so that the cost is high. The invention adopts the electroless deposition technology, and can directly construct the enhanced substrate on the surface of the zinc selenide prism under the conditions of normal pressure, mild reaction temperature and short reaction time. Due to the nano structure on the surface, the enhancement effect is better than that of the prior art, and the lower limit of the analysis range of the surface enhanced infrared absorption spectrum can be expanded to 700cm-1To (3). Meanwhile, the chemically deposited gold film and the surface of the prism have higher affinity, which is more beneficial to practical application. The method is a substrate method which has mild conditions, simple operation process and low cost and can be used for preparing a large amount of enhanced infrared spectra, and the enhanced substrates with different shapes can be constructed on the substrate by adjusting the experimental conditions to adapt to different experimental requirements, thereby further expanding the application range of the surface enhanced infrared spectroscopy technology.
Drawings
FIG. 1 is a scanning electron micrograph of a gold nano-film on the surface of zinc selenide in example 1 (scale: 1 μm in the figure).
Fig. 2 is an X-ray crystal diffraction pattern of the gold nano-thin film on the surface of zinc selenide in example 1.
Fig. 3 is an X-ray photoelectron spectrum of the gold nano-film on the surface of zinc selenide in example 1.
Fig. 4 is an atomic force microscope image of the gold nano-film on the surface of zinc selenide in example 1.
Fig. 5 is a graph of cyclic voltammetry scans of gold nanofilms on zinc selenide surface in example 1.
FIG. 6 is a scanning electron micrograph of the gold nano-film on the surface of zinc selenide in example 2, wherein a to c correspond to concentrations of chloroauric acid of 1mM, 5mM and 10mM, respectively (scale: 0.5 μm in the figure).
FIG. 7 is a scanning electron micrograph of the gold nano-film on the surface of zinc selenide in example 3, wherein a to e correspond to 10% ethanol, 10mM KCl, 10mM KBr, 10mM KI, and 1% polyvinylpyrrolidone, respectively (scale: 0.5 μm in the figure).
FIG. 8 is a scanning electron micrograph of the gold nano-film on the surface of zinc selenide in example 4, wherein a to f are adjusted to 20 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃ respectively corresponding to the water bath temperature in step 2 (scale: 0.5 μm in the figure).
FIG. 9 is a scanning electron micrograph of the gold nano-film on the surface of zinc selenide in example 5, wherein a to f are adjusted to 10s, 20s, 30s, 40s, 3min and 20min (scale: 1 μm in the figure) respectively corresponding to the reaction time in step 2.
FIG. 10 is a graph of single-beam total internal reflection intensity of gold nano-film on the surface of zinc selenide, and the spectral transparency range of the single-beam total internal reflection intensity can be expanded to 700cm-1。
FIG. 11 is the infrared absorption spectrum of the oligonucleotides of gold nano-film adsorbed on the surface of zinc selenide, and the spectrum detection range can be effectively expanded to 700cm-1。
Detailed Description
Example 1
1) The pre-polishing treatment method of the zinc selenide prism comprises the following steps: polishing the plane of a hemispherical zinc selenide prism with the diameter of 20mm on a chamois by using alumina powder with the diameter of 1.0 mu m for 2min, cleaning the polished surface by using ultrapure water, sequentially performing ultrasonic treatment on the polished surface in absolute ethyl alcohol and the ultrapure water for 10min, and drying the polished surface by using nitrogen for later use.
2) The method for depositing the gold nano film on the surface of the zinc selenide prism comprises the following steps: the plane of the hemispherical zinc selenide prism faces upwards and is horizontally placed in a polytetrafluoroethylene beaker, and the temperature is kept at 30 ℃ by adopting water bath heating; adding 100 mu L of 24mM chloroauric acid aqueous solution on the plane of the zinc selenide prism, reacting for 1min, washing the surface of the zinc selenide prism with a large amount of ultrapure water, immediately taking out the zinc selenide prism, washing the whole prism with ultrapure water, and finally blowing the prism with nitrogen to dry, namely depositing the gold thin film on the surface of the zinc selenide prism, wherein the appearance of the gold thin film is shown in figure 1. Fig. 2 and 3 show an X-ray crystal diffraction spectrum and an X-ray photoelectron energy spectrum of a zinc selenide prism and a gold-plated zinc selenide prism, respectively, and it can be seen that the prism surface has an obvious signal peak of gold after gold plating, so that the nano structure on the prism surface is mainly composed of gold, and a small amount of gold selenide exists at the same time, and these chemicals can increase the binding force between the gold nano structure and the surface, so that the enhanced substrate has good stability in an aqueous solution. Fig. 4 is an atomic force microscope image of the prepared gold nanostructure, and it can be seen that the height of the gold nanostructure is about 30 nm. Fig. 5 is a cyclic voltammetry scan graph of a gold nano-film on the surface of zinc selenide, which can reveal the chemical mechanism of obtaining gold nano-structure by the reaction and deposition of zinc selenide and chloroauric acid.
Example 2
The preparation method of this example is the same as example 1, wherein the concentrations of the chloroauric acid aqueous solution in step 2 are adjusted to 1mM, 5mM and 10mM under the condition that other conditions are not changed, a gold thin film is obtained on the surface of the zinc selenide prism, and the appearance is shown in FIG. 6.
Example 3
The preparation method of this example is the same as example 1, wherein 10% ethanol, 10mM KCl, 10mM KBr, 10mM KI, and 1% polyvinylpyrrolidone are added to the chloroauric acid aqueous solution in step 2, respectively, and under the same conditions, a gold thin film is obtained on the surface of the zinc selenide prism, and the morphology of the gold thin film is shown in fig. 7.
Example 4
The preparation method of this embodiment is the same as that of embodiment 1, wherein the water bath temperature in step 2 is adjusted to 20 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃, and under the condition that other conditions are not changed, a gold thin film is obtained on the surface of the zinc selenide prism, and the shapes of the gold thin film are respectively shown in fig. 8.
Example 5
The preparation method of this example is the same as example 1, wherein the reaction time in step 2 is adjusted to 10s, 20s, 30s, 40s, 3min and 20min, and under the condition that other conditions are not changed, a gold thin film is obtained on the surface of the zinc selenide prism, and the appearance of the gold thin film is shown in fig. 9.
Example 6
In the same manner as in example 1, a single beam pattern was collected in the attenuated total reflection mode. Then 200 mul of aqueous solution containing 1M NaCl was added to the surface of the zinc selenide hemispherical prism deposited with the gold nano-film, and an infrared background spectrum was collected, as shown in FIG. 10, it can be seen that up to 700cm-1The single beam intensity is still not attenuated. Then 100 muL of 1 muM oligonucleotide (5 '-SH-AAA AA-3') with thiol-modified terminal is added, and the infrared spectrum of the sample is collected to obtain clear signals of single-layer oligonucleotide molecules, as shown in figure 11, which shows that the prepared enhanced substrate has good signal enhancement effect, and the lower detection limit can be expanded to 700cm-1Nearby.
The method of the invention prepares the surface enhanced infrared absorption spectrum enhanced substrate on the surface of the zinc selenide prism, and is not limited to the embodiment; the characterization of the gold nano-film on the surface of the zinc selenide prism prepared by the method and the characterization are shown in figures 1-9.
While the above detailed description of the method for preparing a surface enhanced infrared absorption spectrum enhancement substrate and the substrate prepared thereby provided by the present invention has been provided, the specific examples herein illustrate the principles and implementations of the invention, and the examples above are only provided to assist in understanding the method and the core concept of the invention, it should be noted that a person skilled in the art could make several optimizations and modifications without departing from the principles of the invention, and such are within the scope of the claims of the present invention.
Claims (8)
1. A preparation method of a surface-enhanced infrared absorption spectrum enhanced substrate is characterized in that chloroauric acid aqueous solution is placed on the surface of a zinc selenide prism subjected to polishing treatment in advance to perform chemical deposition reaction, and finally a gold nano-film material is prepared on the surface of the zinc selenide, wherein the chemical deposition reaction is performed under the condition that the reaction time is 10 s-20 min; the concentration of the chloroauric acid in the chloroauric acid aqueous solution is 1 mM-24 mM.
2. The method of claim 1, further comprising pre-polishing the zinc selenide prisms.
3. The method for preparing the surface-enhanced infrared absorption spectrum enhanced substrate according to claim 2, wherein the pre-polishing treatment method comprises the steps of polishing the surface of the zinc selenide prism by using alumina powder with a certain particle size and carrying out ultrasonic cleaning.
4. The method of claim 1, wherein the prism of zinc selenide is hemispherical in shape.
5. The method for preparing a substrate with enhanced surface-enhanced infrared absorption spectrum according to claim 1, wherein the additive added to the aqueous chloroauric acid solution is ethanol, halide or polyvinylpyrrolidone.
6. A method of preparing a surface enhanced infrared absorption spectroscopy enhanced substrate according to claim 1 wherein the conditions of the chemical deposition reaction are: the reaction temperature is 20-80 ℃.
7. A method of preparing a surface enhanced infrared absorption spectroscopy enhanced substrate according to claim 1 wherein the conditions of the chemical deposition reaction are: the concentration of the chloroauric acid solution is 24mM, the reaction temperature is 30 ℃, and the reaction time is 1 min.
8. A surface-enhanced infrared absorption spectrum enhancing substrate produced by the production method according to any one of claims 1 to 7.
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| CN201034936Y (en) * | 2007-03-29 | 2008-03-12 | 复旦大学 | Surface reinforced infra red spectrum optical apparatus |
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| CN201034936Y (en) * | 2007-03-29 | 2008-03-12 | 复旦大学 | Surface reinforced infra red spectrum optical apparatus |
| CN101539519A (en) * | 2009-04-21 | 2009-09-23 | 山东大学 | Method and device for generating electriferous excitors in quantum well by undoped photo excitation |
| US9244268B2 (en) * | 2013-02-14 | 2016-01-26 | The United States Of America, As Represented By The Secretary Of The Navy | Actively tunable polar-dielectric optical devices |
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