CN103389297A - Quick preparation method of SERS (surface-enhanced Raman scattering) active substrate with inverted cone - Google Patents
Quick preparation method of SERS (surface-enhanced Raman scattering) active substrate with inverted cone Download PDFInfo
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- CN103389297A CN103389297A CN2013103418664A CN201310341866A CN103389297A CN 103389297 A CN103389297 A CN 103389297A CN 2013103418664 A CN2013103418664 A CN 2013103418664A CN 201310341866 A CN201310341866 A CN 201310341866A CN 103389297 A CN103389297 A CN 103389297A
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Abstract
The invention belongs to the technical field of laser Raman spectrum and trace narcotic detection and in particular relates to a high-sensitivity SERS (surface-enhanced Raman scattering) sensor active substrate used for detecting narcotics and a preparation method thereof. The invention provides an SERS active substrate with an inverted cone. The SERS active substrate is of a precious metal inverted cone nano array structure coated on a substrate, wherein the precious metal materials are silver, copper and gold. The high-sensitivity SERS sensor active substrate has SER activity and high repetitive rate, and can be used for detecting trace compounds such as narcotics, explosives and the like.
Description
Technical field
The invention belongs to laser Raman spectroscopy and trace illicit drugs inspection technical field, be specifically related to a kind of sensor of high sensitivity SERS for detection of drugs active substrate and preparation method thereof; More particularly, the present invention relates to a kind of surface reinforced Raman active that has, repetition rate is high, can be used for high sensitivity SERS sensor active substrate of the detections such as trace compound such as drugs, explosive and preparation method thereof.
Background technology
As the common method of analyzing molecules vibrational spectrum, the laser raman technology be widely used in differentiating material molecular structure, analyze the field such as Surface bonding state.Yet the Ramam effect signal often very a little less than, when the concentration of tested molecule is less, or the effects on surface adsorbent is while surveying, conventional laser Raman method just seems unable to do what one wishes.Surface enhanced raman spectroscopy (SERS) effect can make the Raman scattering of molecule signal that is adsorbed on the textured metal substrate surface greatly be strengthened, therefore be used as a kind of highly sensitive surface analysis Detection Techniques, in fields such as trace analysis and qualitative detection, Surface Science, bio-science, obtained broad research.
It is simple that desirable SERS active substrate should have the preparation method, even surface roughness, the characteristics such as effective, good reproducibility that strengthen.The method for preparing the SERS substrate commonly used: the one, utilize chemistry or electrochemical method to make the surface of metal electrode roughening, obtain having the rough surface of high-specific surface area; Another kind method is the metal-sol that preparation has nanoscale, load is had the substrate of metal-sol particle as strengthening substrate.The maximum enhancing substrate of application at present is silver or golden sol particle, have stronger SERS effect, but signal reproducibility and poor stability is not easy to store.Given this, develop a kind ofly possess simultaneously simple, even surface roughness, enhancing is effective, and having the active SERS substrate of enough stability and repeatability necessary, this has great importance widening the application of SERS at aspects such as trace minute qualitative detection and unimolecule system spectrum.
Based on the explosive drugs detection instrument that laser Raman spectroscopy is sent out, its core is development and the exploitation of SERS sensor; And the gordian technique of SERS sensor is the performance of high sensitivity SERS active substrate on detecting head.The quality of this active substrate, can cause other difference of detecting concentration level even more than 10000 times, will affect greatly detection sensitivity and the performance of drugs detection system.The active substrate SERS enhancer of report is basically all 10 now
6Rank, be used for super quick detection trace drugs and also have certain difficulty.Such as national 11th Five-Year science and technology supporting project just requires will reach 100ng/ml to drugs such as the lowest detectable limit such as ketamine, KET in body fluid or urine, roughly in the 100ppb rank.This high sensor active substrate will have very big meaning to improving the sensitivity of explosive drugs SERS detection instrument.
Summary of the invention
The purpose of this invention is to provide a kind of high sensitivity SERS sensor active substrate, thereby the solution the above-mentioned problems in the prior art, this high sensitivity SERS active substrate of the present invention should have high SERS enhancing and sensitivity, tack is good, volume is little, good portability.
For achieving the above object, the present invention adopts following operation steps:
(1) monocrystalline silicon surface is used successively ethanol, acetone, deionized water rinsing clean.
(2) silicon chip is positioned over wool making solution for monocrystalline silicon pieces, carries out surface etch, obtain the back taper array.
(3) substrate is taken out, rinse well with deionized water, and with nitrogen, dry up.
(4), at etch silicon substrate surface evaporation or sputter gold, silver or copper, make the active substrate of SERS.
In the present invention, described precious metal film layer adopts magnetron sputtering or metal evaporation to be formed on substrate.The thickness of metallic film, to 500nm, preferably is about 200nm at 50nm.
In the present invention, etching liquid is NaOH 0.1%-3%, isopropyl alcohol 2%-10%, and all the other are water.
In the present invention, during the substrate etching, solution temperature is 70-80 ℃.
In the present invention, the substrate etching time is 10-20 minute.
The SERS active substrate preparation method that the present invention proposes, simple to operate, favorable reproducibility, reduced the consumption of reagent and sample, reduced the time of sample preparation and detection, have portable, economical, fast, efficiently, characteristics accurately, have a good application prospect at aspects such as trace analysis, qualitative detection.
Description of drawings
Fig. 1. be SERS active substrate high-amplification-factor scanning electron microscope of the present invention (SEM) pattern photo.
Fig. 2. be the present invention take the 10nM isonicotinic acid as probe molecule, relatively (A) is adsorbed on the SERS active substrate, (B) Raman spectrum of silicon base.Exciting light is 532nm, and firing time is 5s.
Specific embodiments
Embodiment 1
(100) crystal orientation monocrystalline silicon is positioned in etching liquid, and etching liquid concentration is NaOH 3%, isopropyl alcohol 10%, and all the other are water, and solution temperature is 70 ℃, and etching time is 10 minutes.After etching is complete, substrate is taken out, deionized water rinsing and nitrogen dry up., in the hot evaporation 100nm of substrate surface thickness gold thin film, make the SERS active substrate.
Embodiment 2
(100) crystal orientation monocrystalline silicon is positioned in etching liquid, and etching liquid concentration is NaOH 1%, isopropyl alcohol 5%, and all the other are water, and solution temperature is 80 ℃, and etching time is 15 minutes.After etching is complete, substrate is taken out, deionized water rinsing and nitrogen dry up., in the hot evaporation 200nm of substrate surface thickness gold thin film, make the SERS active substrate.
Claims (8)
1. fast preparation method with the active substrate of back taper SERS, described SERS active substrate is to be coated in on-chip noble metal back taper nano array structure, described precious metal material be silver-colored, copper and/or gold.
2., by the active substrate of SERS claimed in claim 1, it is characterized in that, its making step is as follows:
(1) monocrystalline silicon surface is used successively ethanol, acetone, deionized water rinsing clean;
(2) silicon chip is positioned over wool making solution for monocrystalline silicon pieces, carries out surface etch, obtain the back taper array;
(3) substrate is taken out, rinse well with deionized water, and with nitrogen, dry up;
(4), at etch silicon substrate surface evaporation or sputter gold, silver or copper, make the active substrate of SERS.
3., by the fast preparation method of the active substrate of the described SERS of claim 1 or 2, it is characterized in that, in described noble metal back taper nano array structure, nanometer cone diameter is 800-100nm, and the nanocone body length is 300-600nm.
4., by the fast preparation method of the active substrate of the described SERS of claim 1 or 2, it is characterized in that, the thickness of described precious metal film layer is that 100nm is to 300nm.
5., by the fast preparation method of the active substrate of the described SERS of claim 1 or 2, it is characterized in that, described precious metal film layer adopts magnetron sputtering or metal evaporation to be formed on substrate.
6., by the fast preparation method of the active substrate of the described SERS of claim 1 or 2, it is characterized in that, during the substrate etching, solution temperature is 70-80 ℃.
7., by the fast preparation method of the active substrate of the described SERS of claim 1 or 2, it is characterized in that, the substrate etching time is 10-20 minute.
8., by the fast preparation method of the active substrate of the described SERS of claim 1 or 2, it is characterized in that, etching liquid is NaOH 0.1%-3%, isopropyl alcohol 2%-10%, and all the other are water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111413313A (en) * | 2020-03-31 | 2020-07-14 | 江苏海尔森检测技术服务有限公司 | Detection method of phthalate compound |
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| WO2006048660A1 (en) * | 2004-11-04 | 2006-05-11 | Mesophotonics Limited | Metal nano-void photonic crystal for enhanced raman spectroscopy |
| CN1811389A (en) * | 2006-02-10 | 2006-08-02 | 厦门大学 | Micro-fluid control chip with surface enhanced Raman spectral active substrate and producing method thereof |
| US7321422B2 (en) * | 2004-09-16 | 2008-01-22 | Hewlett-Packard Development Company, L.P. | SERS-active structures having nanoscale dimensions |
| CN102483379A (en) * | 2009-07-30 | 2012-05-30 | 惠普开发有限公司 | Nanowire light concentrators for performing raman spectroscopy |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7321422B2 (en) * | 2004-09-16 | 2008-01-22 | Hewlett-Packard Development Company, L.P. | SERS-active structures having nanoscale dimensions |
| WO2006048660A1 (en) * | 2004-11-04 | 2006-05-11 | Mesophotonics Limited | Metal nano-void photonic crystal for enhanced raman spectroscopy |
| CN1811389A (en) * | 2006-02-10 | 2006-08-02 | 厦门大学 | Micro-fluid control chip with surface enhanced Raman spectral active substrate and producing method thereof |
| CN102483379A (en) * | 2009-07-30 | 2012-05-30 | 惠普开发有限公司 | Nanowire light concentrators for performing raman spectroscopy |
Non-Patent Citations (2)
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| N.M.B.PERNEY等: "Tuning localized Plasmon cavities for optimized surface-enhanced Raman scattering", 《PHYSICAL REVIEW B》, vol. 76, 20 July 2007 (2007-07-20) * |
| 王丽娟等: "异丙醇溶液对单晶硅太阳能电池表面织构化的影响", 《内蒙古师范大学学报（自然科学汉文版）》, vol. 40, no. 1, 15 January 2011 (2011-01-15) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111413313A (en) * | 2020-03-31 | 2020-07-14 | 江苏海尔森检测技术服务有限公司 | Detection method of phthalate compound |
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