CN103926234B - A kind of monolayer nanometer gold surface reinforced Raman active substrate and preparation method thereof - Google Patents
A kind of monolayer nanometer gold surface reinforced Raman active substrate and preparation method thereof Download PDFInfo
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- CN103926234B CN103926234B CN201410154357.5A CN201410154357A CN103926234B CN 103926234 B CN103926234 B CN 103926234B CN 201410154357 A CN201410154357 A CN 201410154357A CN 103926234 B CN103926234 B CN 103926234B
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Abstract
The invention discloses a kind of monolayer nanometer gold surface reinforced Raman active substrate and preparation method thereof, preparation method is: monocrystalline silicon surface is after concentrated sulphuric acid aoxidizes with hydrogen peroxide mixed solution, immerse in cetyl trimethylammonium bromide aqueous solution, standing 18 ~ 30 h, prepared surface-assembled has the silicon chip of bilayer；Again silicon chip is immersed in nano gold sol, stand 18 ~ 30 h, then silicon chip is dried at room temperature, obtain monolayer nanometer gold surface reinforced Raman active substrate.This preparation method is simple, it is easy to use.Through the monolayer nanometer gold surface reinforced Raman active substrate function admirable that the present invention prepares, there is the strongest signal amplifying power and reusable.
Description
Technical field
Present invention relates particularly to a kind of monolayer nanometer gold surface Raman enhancement active substrate for Raman spectrum detection and preparation method thereof.
Background technology
Raman spectrum can provide the finger print information of chemistry and biomolecular structure, is a kind of widely used Dynamic Non-Destruction Measurement.But the sensitivity of normal Raman spectrum is relatively low, once constraining the application of Raman spectrum.20 century 70s, it has been found that surface enhanced raman spectroscopy (SERS) phenomenon, i.e. due to species absorption such as molecules or very close to having the surface of certain nanostructured, the phenomenon that its Raman signal is obviously enhanced than its body phase molecule.Along with the fast development of nanotechnology, being filled with new vitality to SERS, some nanoparticle system even can make the sensitivity of Raman spectrum amplify 10,000,000,000 times.In recent years, SERS technology all achieves breakthrough in basic research and application practice field, becomes one of technology of greatest concern.
The configuration of surface adsorbed due to molecule is the key factor that whether SERS effect can occur and signal is strong and weak, and the rough surfaceization of molecule bearing basement is the most crucial, thus is the foundation stone of SERS technology about the research of SERS active-substrate.SERS substrate preparation method is a lot, as the SERS substrate of a kind of function admirable, it should easily prepared, be easy to use, and has the strongest signal amplifying power and reusable.The present invention relates to the monolayer nanometer gold surface enhanced active substrate preparation method of a kind of function admirable.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that a kind of monolayer nanometer gold surface Raman enhancement active substrate and preparation method thereof.The preparation method that the present invention provides is simple, it is easy to use, and through the monolayer nanometer gold surface reinforced Raman active substrate function admirable that preparation method of the present invention prepares, has the strongest signal amplifying power and reusable.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of preparation method of monolayer nanometer gold surface reinforced Raman active substrate, monocrystalline silicon surface is after concentrated sulphuric acid aoxidizes with hydrogen peroxide mixed solution, immersing in cetyl trimethylammonium bromide aqueous solution, stand 18 ~ 30 h, prepared surface-assembled has the silicon chip of bilayer；Again silicon chip is immersed in nano gold sol, stand 18 ~ 30 h, then silicon chip is dried at room temperature, obtain monolayer nanometer gold surface reinforced Raman active substrate.
Described concentrated sulphuric acid and hydrogen peroxide mixed solution, wherein, concentrated sulphuric acid with the volume ratio of hydrogen peroxide is: 4:1.
The oxidization time of monocrystalline silicon surface is 48 ~ 60h.
Described cetyl trimethylammonium bromide concentration of aqueous solution is 0.05 ~ 0.1 mol/L.
Described nano gold sol its preparation method is: add chlorauric acid solution in pure water, then it is heated to reflux to boiling, it is stirred vigorously down and is rapidly added sodium citrate solution and reacts, when solution colour is from after faint yellow becoming black, transferring brownish red to the most rapidly, then stopped reaction after micro-boiling (100 DEG C) 20 ~ 50min；Stirring at normal temperature is cooled to room temperature, prepares nano gold sol.
The mass fraction of chlorauric acid solution is 0.5 ~ 2 %, and the mass fraction of sodium citrate solution is 0.5 ~ 2 %.
Pure water, chlorauric acid solution, the volume ratio of sodium citrate solution be: 100:0.5 ~ 2:0.5 ~ 2.
Obtained nano gold sol can show use, or preparation is placed in 4 DEG C of refrigerators stand-by, the storage life of keeping in Dark Place and is at least 4 months.
The application of the monolayer nanometer gold surface reinforced Raman active substrate that a kind of preparation method as above prepares, detects for Raman spectrum.
The beneficial effects of the present invention is:
The preparation method that the present invention provides is simple, it is easy to use, and through the monolayer nanometer gold surface reinforced Raman active substrate function admirable that preparation method of the present invention prepares, has the strongest signal amplifying power and reusable.
Accompanying drawing explanation
Fig. 1 is the purple light visible ray spectrogram of the nano gold sol that embodiment 1 prepares；
Fig. 2 is the field scanning electromicroscopic photograph that the monolayer nanometer gold surface reinforced Raman active substrate that embodiment 1 prepares amplifies 100,000 times；
Fig. 3 is the field scanning electromicroscopic photograph that the monolayer nanometer gold surface reinforced Raman active substrate that embodiment 1 prepares amplifies 30,000 times；
Fig. 4 be the monolayer nanometer gold surface reinforced Raman active substrate for preparing of embodiment 1 when Raman spectrum detects, at the Raman spectrogram of variable concentrations basic orange II；
Fig. 5 is the monolayer nanometer gold surface reinforced Raman active substrate photo under the microscope of the attachment variable concentrations basic orange II solution that embodiment 1 prepares.
Detailed description of the invention
Present invention the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.
Following embodiment instrument and reagent are as follows: the confocal Raman of Invia laser capture microdissection (Lei Shaoni company of Britain)；Nova NanoSEM 230 field emission scanning electron microscope (FEI Co. of the U.S.)；TU-1950 ultraviolet-uisible spectrophotometer (Beijing Puxi General Instrument Co., Ltd)；
Basic orange II standard substance are purchased from Dr.Ehrenstorfer company, gold chloride is purchased from Aladdin reagent company limited, cetyl trimethylammonium bromide (CTAB), trisodium citrate, hydrochloric acid, nitric acid, concentrated sulphuric acid and hydrogen peroxide are purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and monocrystalline silicon piece (0.5 × 0.5 cm) is purchased from Foochow Gao Te Electro-optical Technology, INC. (US) 62 Martin Road, Concord, Massachusetts 017.
Embodiment
1
All glass drying ovens soak with chloroazotic acid before using, wash, are dried.
The synthesis of nano gold sol: add chlorauric acid solution 1 mL of 1 % in 100 mL pure water, solution is heated to reflux to boiling, it is stirred vigorously down sodium citrate solution 1 mL being rapidly added 1 %, after reacting 1 min, it is seen that solution colour is become black from faint yellow, transfer the most rapidly brownish red to, stopped reaction after the most micro-boiling 30 min, taking out stirring at normal temperature and be cooled to room temperature, can obtain nano gold sol, this nano gold sol is placed in 4 DEG C of refrigerator lucifuges and at least can preserve 4 months.
The preparation of monolayer nanometer gold surface reinforced Raman active substrate: carry out aoxidizing 48h to monocrystalline silicon surface with hydrogen peroxide mixed solution (concentrated sulphuric acid: hydrogen peroxide=4:1, V/V) with concentrated sulphuric acid, make silicone hydroxyl fine and close on silicon chip surface band.Then the silicon chip processed is immersed in the aqueous solution containing 0.05 mol/L CTAB, stand 24 h so that CTAB is self-assembled into bilayer at substrate surface.The silicon chip that surface-assembled has CTAB bilayer again immerses in the nano gold sol that surface is electronegative and stands 24 h, make golden nanometer particle self-assemble to be adsorbed with the solid substrate surface of CTAB bilayer by Electrostatic Absorption method, form uniform nano particle single layer structure.Finally the solid phase substrate being adsorbed with monolayer nanometer gold is dried at room temperature, obtain homogeneous monolayer nanometer gold surface reinforced Raman active substrate.
The nano gold sol, the monolayer nanometer gold surface reinforced Raman active substrate that embodiment 1 are prepared characterize.It is respectively adopted ultraviolet-uisible spectrophotometer with field emission scanning electron microscope, prepared nano gold sol and monolayer nanometer gold SERS active-substrate to be studied.Fig. 1 is the UV-Vis scans spectrum of synthesized nano gold sol, and the maximized surface plasma resonance peak of this nano gold sol is positioned at 546 nm, and peak type is narrower and symmetrical, shows that this nanostructured size is relatively uniform.Fig. 2, Fig. 3 are the field scanning electromicroscopic photograph of active substrate, are respectively and amplify 100,000 times, 30,000 times.It can be seen that nano gold sol shape is homogeneous, spherical in class being arranged in equably on silicon chip, particle diameter is about 55 nm；Illustrate that nano Au particle self-assembles to be adsorbed with the solid substrate surface of CTAB bilayer by Electrostatic Absorption method, the nano Au particle single layer structure having been formed uniform.
Embodiment
2
All glass drying ovens soak with chloroazotic acid before using, wash, are dried.
The synthesis of nano gold sol: add the chlorauric acid solution 2mL of 0.5wt % in 100 mL pure water, solution is heated to reflux to boiling, it is stirred vigorously down sodium citrate solution 0.5 mL being rapidly added 2wt%, visible solution colour is become black from faint yellow, transfer the most rapidly brownish red, stopped reaction after the most micro-boiling 50min to, take out stirring at normal temperature and be cooled to room temperature, can obtain nano gold sol, this nano gold sol is placed in 4 DEG C of refrigerator lucifuges and at least can preserve 4 months.
The preparation of monolayer nanometer gold surface reinforced Raman active substrate: monocrystalline silicon surface is aoxidized 60 h with concentrated sulphuric acid and hydrogen peroxide mixed solution (concentrated sulphuric acid: hydrogen peroxide=4:1, V/V), makes silicone hydroxyl fine and close on silicon chip surface band.Then the silicon chip processed is immersed in the aqueous solution containing 0.1mol/L CTAB, stand 30 h so that CTAB is self-assembled into bilayer at substrate surface.The silicon chip that surface-assembled has CTAB bilayer again immerses and stands 18h in the nano gold sol that surface is electronegative, make golden nanometer particle self-assemble to be adsorbed with the solid substrate surface of CTAB bilayer by Electrostatic Absorption method, form uniform nano particle single layer structure.Finally the solid phase substrate being adsorbed with monolayer nanometer gold is dried at room temperature, obtain homogeneous monolayer nanometer gold surface reinforced Raman active substrate.
Application Example
1
Weigh appropriate basic orange II standard substance, with pure water be configured to concentration be respectively 0.001,0.005,0.01,0.05,0.1, the solution of 0.5mmol/L, the monolayer nanometer gold surface reinforced Raman active substrate 6 embodiment 1 made is respectively placed in wherein soaks 2 h, takes out and carries out Raman spectrum detection the most after drying.With the solid alkaline orange II being attached on monocrystalline silicon piece, Raman spectrum being carried out peak position calibration, set Raman spectrum optical maser wavelength as 633 nm, LASER Light Source energy is 5 %, and time of exposure is 10 s.
Fig. 4 be monolayer nanometer gold surface reinforced Raman active substrate when Raman spectrum detects, at the Raman spectrogram of variable concentrations basic orange II；In figure, a is the Raman spectrogram (scattering (SERS) effect without Raman spectrum) of solid alkaline orange II standard substance being attached on monocrystalline silicon piece, in figure, b-g is the Raman enhanced spectrum of the basic orange II solution of the variable concentrations of the surface reinforced Raman active substrate being attached to synthesis, and wherein the concentration of b-g basic orange II is respectively as follows: 0.5,0.1,0.05,0.01,0.005 and 0.001 mmol/L.From fig. 4, it can be seen that during without SERS effect, the Raman signal of basic orange II is more weak, and ambient interferences is stronger.And when, after monolayer nanometer gold absorption basic orange II molecule, significantly enhancing the Raman signal of basic orange II molecule, and the intensity at peak and concentration positive correlation.From fig. 4, it can be seen that the principal character peak of basic orange II has: 803 cm-1、917 cm-1、999 cm-1、1150 cm-1、1181 cm-1、1272 cm-1、1290 cm-1、1378 cm-1、1594 cm-1With 1619 cm-1.This with document (Xie Y, et al.Talanta,
2012,100:32-37) report is consistent, and by feature spectral peak, basic orange II can be carried out qualitative analysis.
Fig. 5 is the substrate photo under the microscope of attachment variable concentrations basic orange II solution, and research shows, when basic orange II solution concentration is more than 0.5 mmol/L, the nanometer gold on monocrystal silicon produces reunites, and makes Raman signal produce bigger error.When the concentration of basic orange II is gradually reduced, the degree that nanometer gold is reunited is gradually reduced, but when the concentration of basic orange II is less than 0.001mmol/L, the more difficult identification of Raman signal.The basic orange II concentration optimum range measured under the conditions of Ben is: 0.001mmol/L-0.5mmol/L.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.
Claims (6)
1. the preparation method of a monolayer nanometer gold surface reinforced Raman active substrate, it is characterized in that: monocrystalline silicon surface is after concentrated sulphuric acid aoxidizes with hydrogen peroxide mixed solution, immersing in cetyl trimethylammonium bromide aqueous solution, stand 18 ~ 30 h, prepared surface-assembled has the silicon chip of bilayer；Again silicon chip is immersed in nano gold sol, stand 18 ~ 30 h, then silicon chip is dried at room temperature, obtain monolayer nanometer gold surface reinforced Raman active substrate；The oxidization time of monocrystalline silicon surface is 48 ~ 60h；
Described concentrated sulphuric acid and hydrogen peroxide mixed solution, wherein, concentrated sulphuric acid with the volume ratio of hydrogen peroxide is: 4:1；
Described cetyl trimethylammonium bromide concentration of aqueous solution is 0.05 ~ 0.1 mol/L.
The preparation method of a kind of monolayer nanometer gold surface reinforced Raman active substrate the most according to claim 1, it is characterized in that: described nano gold sol its preparation method is: in pure water, add chlorauric acid solution, then it is heated to reflux to boiling, it is stirred vigorously down and is rapidly added sodium citrate solution and reacts, when solution colour is from after faint yellow becoming black, transferring brownish red to the most rapidly, then stopped reaction after micro-boiling 20 ~ 50min；Stirring at normal temperature is cooled to room temperature, prepares nano gold sol.
The preparation method of a kind of monolayer nanometer gold surface reinforced Raman active substrate the most according to claim 2, it is characterised in that: the mass fraction of chlorauric acid solution is 0.5 ~ 2 %, and the mass fraction of sodium citrate solution is 0.5 ~ 2%.
The preparation method of a kind of monolayer nanometer gold surface reinforced Raman active substrate the most according to claim 2, it is characterised in that: pure water, chlorauric acid solution, the volume ratio of sodium citrate solution be: 100:0.5 ~ 2:0.5 ~ 2.
The preparation method of a kind of monolayer nanometer gold surface reinforced Raman active substrate the most according to claim 2, it is characterised in that: obtained nano gold sol can show use, or preparation is placed in 4 DEG C of refrigerators stand-by, the storage life of keeping in Dark Place and is at least 4 months.
6. the application of the monolayer nanometer gold surface reinforced Raman active substrate that a preparation method as claimed in claim 1 prepares, it is characterised in that: for the Raman spectrum detection of basic orange II that concentration range is 0.001mmol/L-0.5mmol/L.
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| CN104198460A (en) * | 2014-09-05 | 2014-12-10 | 福州大学 | Method for detecting caffeine in foods by virtue of enhanced Raman spectrum |
| CN104445985A (en) * | 2014-12-12 | 2015-03-25 | 南京理工大学 | Method for preparing surface enhanced Raman substrate for rapid field detection of explosives and powders |
| CN104535554A (en) * | 2014-12-31 | 2015-04-22 | 贵州省流通环节食品安全检验中心 | Method for measuring basic orange II in chili product through surface-enhanced Raman spectrometry |
| CN104697979A (en) * | 2015-03-31 | 2015-06-10 | 中华人民共和国龙岩出入境检验检疫局 | Method for detecting aspartame in food through raman enhancement spectrum |
| CN105954255A (en) * | 2016-04-26 | 2016-09-21 | 中国科学院生态环境研究中心 | Antimony detection method |
| CN107447206A (en) * | 2017-08-31 | 2017-12-08 | 浙江工业大学 | A kind of nanogold self assembly Si sheet materials and its application |
| CN110579461A (en) * | 2019-05-15 | 2019-12-17 | 上海交通大学 | Preparation method and application of SERS performance detection biosensor |
| CN110726709A (en) * | 2019-10-28 | 2020-01-24 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of secondary deep graphene oxide loaded nanogold composite SERS enhanced substrate |
| CN110927140A (en) * | 2019-11-27 | 2020-03-27 | 浙江工业大学 | Method for rapidly preparing nano Ag film surface enhanced Raman substrate through liquid-liquid interface |
| CN111060645A (en) * | 2019-12-25 | 2020-04-24 | 安徽中科赛飞尔科技有限公司 | SERS detection method for adulterated drugs |
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