CN110879221A - Silicon-based silver nano surface enhanced substrate and preparation method thereof - Google Patents
Silicon-based silver nano surface enhanced substrate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silicon-based silver nano surface enhanced substrate and a preparation method thereof. The preparation method comprises the following steps: adding sodium citrate into a boiling silver nitrate solution to obtain silver sol; immersing a silicon wafer into a concentrated sulfuric acid-hydrogen peroxide mixed solution, heating, preserving heat, taking out, and immersing into a (3-aminopropyl) trimethoxy silane solution to obtain a silicon substrate; and immersing the silicon substrate into the silver sol to obtain a substrate with strong Raman enhancement capability and silver nanoparticles distributed on the substrate.
Description
Technical Field
The invention relates to the technical field of Raman detection, in particular to a silicon-based silver nano surface enhanced substrate and a preparation method thereof.
Background
The Raman spectrum belongs to the molecular rotation and vibration spectrum range and can reflect the characteristic structure of molecules. Since the 60 s of the 20 th century, the research on raman spectroscopy was driven by the rapid development of a series of technologies such as lasers, optical splitters, detectors, and computers, so that the detection environment of raman spectroscopy was greatly optimized. The raman spectroscopy technology has become an important component of modern analysis technology because of its advantages of carrying abundant material information, nondestructive testing, no need for sample preparation, etc. However, the raman scattering signal intensity is too weak, the signal-to-noise ratio is poor due to the low scattering intensity, the detection sensitivity is limited, the application is greatly limited, and the problem of high sensitivity of raman spectroscopy detection is greatly enhanced by the Surface Enhanced Raman Spectroscopy (SERS), which has a profound influence on the surface interface science and spectroscopy. The enhancement mechanism of SERS is mainly considered as an electromagnetic field enhancement mechanism and a chemical enhancement mechanism, and the advantage of high sensitivity of SERS is combined with the characteristic high selectivity of Raman spectrum, so that SERS is widely applied in various fields.
The core of the surface enhanced Raman spectrum lies in the preparation of an effective selective surface enhanced substrate, and how to prepare the SERS active substrate with strong Raman enhancement capability, uniformity and stability has important significance.
Disclosure of Invention
Based on the method, the prepared substrate has strong Raman enhancement capability, and the silver nanoparticles on the substrate are distributed.
The specific technical scheme is as follows:
a preparation method of a silicon-based silver nano surface enhanced substrate comprises the following steps:
adding sodium citrate into a boiling silver nitrate solution to obtain silver sol;
immersing a silicon wafer into a concentrated sulfuric acid-hydrogen peroxide mixed solution, heating, preserving heat, taking out, and immersing into a (3-aminopropyl) trimethoxy silane solution to obtain a silicon substrate;
immersing the silicon substrate into the silver sol.
The invention also provides a silicon-based silver nano surface enhanced substrate prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the method comprises the steps of firstly preparing silver sol by adopting a sodium citrate heating reduction method, then pretreating a silicon wafer, immersing the silicon wafer into a piranha washing solution for heating to complete hydroxylation of the silicon wafer, immersing the hydroxylated silicon wafer into a (3-aminopropyl) trimethoxy silane solution, hydrolyzing methoxyl in the (3-aminopropyl) trimethoxy silane, combining the hydrolyzed methoxyl with hydroxyl on the surface of the silicon wafer to form a Si-O-Si bond, completing silanization of the silicon wafer, and finally immersing the silanized silicon wafer into the silver sol, wherein silver nanoparticles in the silver sol are uniformly attached to the surface of a silicon substrate to form the silicon-based silver nano surface reinforced substrate. The enhanced substrate prepared by the method can greatly enhance the Raman spectrum peak of the substance, realizes the purpose of low concentration detection, has uniform distribution of silver nanoparticles on the surface of the substrate and stable substrate property, and has the advantages of low manufacturing cost, simple process, no need of sterile environment and no biological toxicity.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of the silicon-based silver nano surface enhanced substrate prepared in example 1;
FIG. 2 is a Raman spectrum of the Si-based Ag nano surface enhanced substrate prepared in example 1;
FIG. 3 is a Raman spectrum of the substrate prepared in example 1 after adsorbing the R6G solution;
fig. 4 is a raman spectrum of the substrate prepared in example 2 after adsorbing the R6G solution.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A preparation method of a silicon-based silver nano surface enhanced substrate comprises the following steps:
adding sodium citrate into a boiling silver nitrate solution to obtain silver sol;
immersing a silicon wafer into a concentrated sulfuric acid-hydrogen peroxide mixed solution, heating, preserving heat, taking out, and immersing into a (3-aminopropyl) trimethoxy silane solution to obtain a silicon substrate;
immersing the silicon substrate into the silver sol.
The method firstly adopts a sodium citrate heating reduction method to prepare the silver sol. The specific method comprises the following steps: dropwise adding the sodium citrate aqueous solution into the boiling silver nitrate aqueous solution, continuously heating for 1-2 h, and naturally cooling to room temperature after heating to obtain the silver sol.
It will be appreciated that the cooled silver sol can also be centrifuged and purified and then stored at 4 ℃.
Meanwhile, the method also carries out pretreatment on the silicon wafer. The method specifically comprises the following steps: immersing the silicon wafer into a washing solution of piranha for heating to complete hydroxylation of the silicon wafer, immersing the hydroxylated silicon wafer into a (3-aminopropyl) trimethoxy silane solution, hydrolyzing methoxyl in the (3-aminopropyl) trimethoxy silane, and combining the hydrolyzed silicon wafer with hydroxyl on the surface of the silicon wafer to form a Si-O-Si bond to complete silanization of the silicon wafer.
Specifically, the washing liquid of the piranha is a mixed solution prepared from 98% concentrated sulfuric acid and 30% hydrogen peroxide in a volume ratio of 7: 3.
Hydroxylating the silicon wafer, namely immersing the silicon wafer into a washing liquid of 'piranha', preferably heating to 70-90 ℃, and keeping the temperature for 10-30 min, more preferably heating to 80 ℃, and keeping the temperature for 20 min.
The hydroxylated silicon wafer is then subjected to a silylation process by immersing the hydroxylated silicon wafer in a solution of (3-aminopropyl) trimethoxysilane, preferably in a solution of (3-aminopropyl) trimethoxysilane, in ethanol. The mass fraction of (3-aminopropyl) trimethoxysilane is 3 to 10%, and more preferably the mass fraction of (3-aminopropyl) trimethoxysilane is 5%.
The immersion time in the (3-aminopropyl) trimethoxysilane solution is preferably 4h to 6h, more preferably 5 h. At this time, methoxy groups in (3-aminopropyl) trimethoxysilane are hydrolyzed and then combined with hydroxyl groups on the surface of the silicon wafer to form Si-O-Si bonds, thereby completing silanization treatment.
It will be appreciated that the wafer may be cleaned and decontaminated prior to being subjected to the hydroxylation process. Specifically, the silicon wafer is respectively placed in deionized water and absolute ethyl alcohol, ultrasonic treatment is carried out for 2min-5min, impurities on the surface of the silicon wafer are removed, and then nitrogen is used for drying.
Similarly, after the silicon wafer is silanized, the method also comprises the step of cleaning the silicon substrate. Specifically, the surface of the silicon substrate is cleaned by deionized water, and then the silicon substrate is placed in a thermostat with the temperature of 120 ℃ for heat preservation for 30 min.
And (3) immersing the silicon substrate subjected to silanization treatment into the prepared silver sol, standing for 10-14 h, and taking out, wherein the silver nanoparticles are uniformly attached to the silicon surface to form the silicon-based silver nano surface enhanced substrate.
It is understood that the surface may be sequentially washed with absolute ethanol and deionized water to remove the non-attached silver nanoparticles, and the substrate is stored in deionized water at normal temperature.
The following is a further description with reference to specific examples.
Example 1
The embodiment provides a silicon-based silver nano surface enhanced substrate and a preparation method thereof, and the method comprises the following steps:
1. dropwise adding the sodium citrate aqueous solution into the boiling silver nitrate aqueous solution, continuously heating for 1h, and then naturally cooling. And centrifuging and purifying the cooled silver sol solution, and storing the silver sol solution in an environment at 4 ℃.
2. Cutting the silicon wafer to aboutThe silicon wafer is placed in deionized water and absolute ethyl alcohol with the size of 1cm multiplied by 1cm for ultrasonic treatment for 3min to remove impurities on the silicon surface, and then is dried by nitrogen. Placing the impurity-removed silicon wafer in washing solution of "piranha" (H)2SO4):V(30％H2O2)＝7:3]Heating to 80 ℃, and keeping the temperature for 20min, wherein a layer of hydroxyl is attached to the surface of the silicon wafer in the process. Immersing the hydroxylated silicon slice into APTMS [ (3-aminopropyl) trimethoxy silane ] with the mass fraction of 5%]And (3) placing the silicon wafer in an ethanol solution for 5 hours to ensure that methoxy in APTMS molecules is hydrolyzed and then is combined with hydroxyl on the surface of the silicon wafer to form a Si-O-Si bond, thereby completing the silanization of the silicon wafer. And cleaning the reacted silicon wafer by using deionized water, and then placing the silicon wafer in a constant temperature cabinet with the temperature of 120 ℃ for 30min to obtain the silicon substrate.
3. And (3) placing the silicon chip subjected to silanization treatment into the silver sol, standing for 12h, and taking out the silicon chip to enable the silver nanoparticles to be uniformly attached to the surface of the silicon substrate to form the silicon-based silver nano surface enhanced substrate. And sequentially washing the surface with absolute ethyl alcohol and deionized water to remove the unattached silver nanoparticles, and storing in the deionized water at normal temperature.
Fig. 1 is a scanning electron microscope image of the surface of the silicon-based silver nano surface enhanced substrate prepared in this example, and it can be seen from the image that silver nano particles are uniformly deposited on the silicon surface.
The enhancement effect of the silicon-based silver nano-substrate prepared in the embodiment is detected by using R6G as a probe molecule. FIG. 2 shows the Raman spectrum of the Si-based Ag nano surface enhanced substrate itself, and FIG. 3 shows 1X 10-6mol/L R6G Raman spectra of the substrate of this example after enhancement. Comparing fig. 2 and fig. 3, a plurality of characteristic peaks of R6G molecules appear in fig. 3, which indicates that the silicon-based silver nano surface enhanced substrate prepared in this embodiment has a significant enhancing effect.
Example 2
The embodiment provides a silicon-based silver nano surface enhanced substrate and a preparation method thereof, and the method comprises the following steps:
1. adding the sodium citrate aqueous solution into the boiling silver nitrate aqueous solution dropwise, continuously heating for 30min, and then naturally cooling. And centrifuging and purifying the cooled silver sol solution, and storing the silver sol solution in an environment at 4 ℃.
2. The silicon wafer is cut to about 1cm × 1cm in size, placed in deionized water and absolute ethyl alcohol respectively for 3min of ultrasound to remove impurities on the surface of the silicon, and then dried by nitrogen. Placing the impurity-removed silicon wafer in washing solution of "piranha" (H)2SO4):V(30％H2O2)＝7:3]Heating to 80 deg.C, cooling at normal temperature, and attaching a layer of hydroxyl on the surface of the silicon wafer. Immersing the hydroxylated silicon slice into APTMS [ (3-aminopropyl) trimethoxy silane ] with the mass fraction of 5%]And (3) placing the silicon wafer in an ethanol solution for 2h to ensure that methoxy in APTMS molecules is hydrolyzed and then is combined with hydroxyl on the surface of the silicon wafer to form a Si-O-Si bond, thereby completing silanization of the silicon wafer. And cleaning the reacted silicon wafer by using deionized water, and then placing the silicon wafer in a constant temperature cabinet with the temperature of 120 ℃ for 30min to obtain the silicon substrate.
3. And (3) placing the silicon chip subjected to silanization treatment into the silver sol, standing for 12h, and taking out the silicon chip to enable the silver nanoparticles to be uniformly attached to the surface of the silicon substrate to form the silicon-based silver nano surface enhanced substrate. And sequentially washing the surface with absolute ethyl alcohol and deionized water to remove the unattached silver nanoparticles, and storing in the deionized water at normal temperature.
The enhancement effect of the silicon-based silver nano-substrate prepared in the embodiment is detected by using R6G as a probe molecule. FIG. 4 is 1X 10-6mol/L R6G Raman spectra of the substrate of this example after enhancement. Comparing fig. 3 and fig. 4, the characteristic peak enhancement effect of R6G in fig. 3 is obvious, which indicates that the enhancement effect of the silicon-based silver nano surface enhancement substrate prepared in this example is weaker than that of example 1.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a silicon-based silver nano surface enhanced substrate is characterized by comprising the following steps:
adding sodium citrate into a boiling silver nitrate solution to obtain silver sol;
immersing a silicon wafer into a concentrated sulfuric acid-hydrogen peroxide mixed solution, heating, preserving heat, taking out, and immersing into a (3-aminopropyl) trimethoxy silane solution to obtain a silicon substrate;
immersing the silicon substrate into the silver sol.
2. The method for preparing the silicon-based silver nano surface enhanced substrate according to claim 1, wherein the mass fraction of the (3-aminopropyl) trimethoxysilane in the (3-aminopropyl) trimethoxysilane solution is 3-10%.
3. The method for preparing the silicon-based silver nano surface enhanced substrate according to claim 2, wherein the solvent in the (3-aminopropyl) trimethoxysilane solution is ethanol.
4. The method for preparing the silicon-based silver nano surface enhanced substrate according to claim 3, wherein the immersion time in the (3-aminopropyl) trimethoxysilane solution is 4-6 h.
5. The method for preparing the silicon-based silver nano surface enhanced substrate according to claim 1, wherein the heating is specifically: heating to 70-90 deg.C.
6. The method for preparing the silicon-based silver nano surface enhanced substrate according to claim 1, wherein the heat preservation time is 10min to 30 min.
7. The method for preparing the silicon-based silver nano surface enhanced substrate according to any one of claims 1 to 6, wherein the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 7:3, the concentrated sulfuric acid is sulfuric acid with a mass fraction of 98%, and the hydrogen peroxide is hydrogen peroxide with a mass fraction of 30%.
8. The method for preparing the silicon-based silver nano surface enhanced substrate according to any one of claims 1 to 6, wherein sodium citrate is added into a boiling silver nitrate solution and heated for 1h to 2h to obtain silver sol.
9. The method for preparing the silicon-based silver nano surface enhanced substrate according to any one of claims 1 to 6, wherein the silicon substrate is immersed in the silver sol, and is taken out after standing for 10h to 14 h.
10. A silicon-based silver nano surface enhanced substrate prepared by the preparation method of any one of claims 1 to 9.
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| CN113203726A (en) * | 2021-05-11 | 2021-08-03 | 江苏大学 | Preparation method of surface-enhanced Raman substrate for rapidly detecting fluorene in haze particles |
| CN115753729A (en) * | 2022-11-10 | 2023-03-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method and application of silver-based glass sheet |
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