CN102391014B - Active substrate with surface enhanced Raman scattering effect - Google Patents
Active substrate with surface enhanced Raman scattering effect Download PDFInfo
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- CN102391014B CN102391014B CN 201110231298 CN201110231298A CN102391014B CN 102391014 B CN102391014 B CN 102391014B CN 201110231298 CN201110231298 CN 201110231298 CN 201110231298 A CN201110231298 A CN 201110231298A CN 102391014 B CN102391014 B CN 102391014B
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- active substrate
- reaktionsofen
- column array
- raman scattering
- scattering effect
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Abstract
The invention discloses an active substrate with a surface enhanced Raman scattering effect, and simultaneously discloses a preparation method and application of the active substrate. The preparation method of the active substrate comprises the steps of: firstly performing hydrothermal corrosion on a P-type monocrystalline silicon wafer to obtain a silicon nano-porous column array, and then performing chemical vapor deposition on the surface of the silicon nano-porous column array to grow carbon nanoparticles so as to prepare a carbon nanoparticle membrane/silicon nano-porous column array active substrate. By adopting the carbon nanoparticle membrane/silicon nano-porous column array active substrate as the active substrate with the surface enhanced Raman scattering effect, rhodamine 6G molecules with the concentration of 10<-6>mol/L can be detected, and the active substrate has the extremely strong Raman enhanced effect.
Description
Technical field
The present invention relates to have the material technology field of surface enhanced Raman scattering effect, be specifically related to a kind of active substrate with surface enhanced Raman scattering effect, also relate to simultaneously its preparation method and application.
Background technology
Raman spectrum belongs to molecular vibration spectrum, can reflect the feature structure of molecule.But because the light intensity of Raman scattering effect only is about 10 of incident intensity
-10So, when the effects on surface adsorbent carries out raman study, all to utilize certain reinforcing effect.Surface enhanced Raman scattering (Surface Enhanced Raman Scattering, SERS) is a kind of reinforcing effect with surface selectivity, the Raman signal that is adsorbed on the molecule of material surface can be amplified 10
6To 10
14Doubly, the structure and the process that deeply characterize various surfaces or interface (such as various solid-liquids, solid-gas, solid-solid interface) for people provide the information on the molecular level, are the powerfuls of research surface physics, chemical structure and character.Can important factor in order with SERS signal power occur, so the bearing basement of molecule is very crucial, thereby the research of SERS active substrate be one of the study hotspot in this field always because the molecule substrate surface form of adsorbing is the SERS effect.Wherein, gold and silver, copper three class noble metal nano systems are to study the hottest, maximum, the most obvious SERS active substrate of enhancing always.Minority basic metal such as lithium, sodium also have stronger SERS effect.Part transition metal such as iron, cobalt and nickel have also been found the SERS effect.But above-mentioned metal nano material is extremely unstable in air except gold and silver, copper, and the research of SERS research being widened gold and silver, copper material system does not in addition obtain the progress of practical significance for a long time.To Application Areas that widen SERS be had great importance if can adopt simple method to prepare the metals such as gold and silver, the copper Raman active substrate with permanent stability in addition, also may become the opportunity that the SERS theoretical investigation obtains substantial progress simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of active substrate with surface enhanced Raman scattering effect.
Simultaneously, the present invention also aims to provide a kind of preparation method with active substrate of surface enhanced Raman scattering effect.
The present invention also aims to provide a kind of application with active substrate of surface enhanced Raman scattering effect.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of active substrate with surface enhanced Raman scattering effect, and this active substrate is prepared by the method that may further comprise the steps:
(1) resistivity is inserted in the autoclave less than the p type single crystal silicon sheet of 3.0 Ω cm, filled corrosive fluid afterwards in autoclave, described p type single crystal silicon sheet in 100～200 ℃ of lower corrosion 30～60 minutes, prepares silicon nano hole column array in corrosive fluid;
(2) silicon nano hole column array is placed in the Reaktionsofen; then under the shielding gas nitrogen atmosphere in the Reaktionsofen temperature rise to 700 ℃～1200 ℃; stop afterwards in Reaktionsofen, passing into shielding gas; change in Reaktionsofen and pass into carrier gas; carrier gas is the mixed gas of nitrogen and hydrogen; carrier gas brings to carbon source dimethylbenzene in the Reaktionsofen with 0.1～0.8 ml/min; under 700 ℃～1200 ℃, carry out the chemical vapor deposition growth carbon nano-particle on the silicon nano hole column array surface; reaction times is 5～15 minutes; afterwards again under the shielding gas nitrogen atmosphere with Reaktionsofen in temperature be down to room temperature; obtain one deck carbon nano-particle in the silicon nano hole column array surface growth this moment; namely at silicon nano hole column array Surface Creation one deck carbon nano-particle rete, obtain carbon nano-particle film/silicon nano hole column array active substrate.
Further, described corrosive fluid is that the hydrofluoric acid of 8.00～15.00 mol/l and iron nitrate aqueous solution that concentration is 0.02～0.08 mol/l form by concentration.The volume compactedness of described corrosive fluid in autoclave is 60～90%.
Described Reaktionsofen is the horizontal pipe stove.
The application of the above-mentioned active substrate with surface enhanced Raman scattering effect, described active substrate rhodamine 6G in for detection of solution divides the period of the day from 11 p.m. to 1 a.m, can detect that concentration is 10 in the solution
-6The rhodamine 6G molecule of mol/L.
The detection method that adopts described active substrate to detect rhodamine 6G molecule in the solution is: described active substrate is inserted 10
-6Soak 30 min in the rhodamine 6G aqueous solution of mol/L, take out, under air conditions, dry, do afterwards the Raman spectrum test.The test condition of Raman spectrum test is: the employing wavelength is that the green glow of 532nm is made light source, 20 seconds time shutter, scan 2 times, and the wave number sweep limit is 400cm
-1～1800cm
-1
Adopting carbon nano-particle film provided by the invention/silicon nano hole column array active substrate to detect respectively concentration as the active substrate with surface enhanced Raman scattering effect is 10
-4Mol/L～10
-6The rhodamine 6G molecule of mol/L, the result shows, and this active substrate has demonstrated extremely strong Raman reinforcing effect, and concentration is 10
-6The raman characteristic peak of the rhodamine 6G molecule of mol/L is high-visible.The surface enhanced Raman scattering effect ability of carbon nano-particle film provided by the invention/silicon nano hole column array active substrate can with gold, the comparing favourably of copper nano material, even be better than the surface enhanced Raman scattering ability of gold and copper nano material.
Carbon nano-particle film provided by the invention/silicon nano hole column array active substrate does not use any metal that comprises gold and silver, copper coin kind metal in the preparation, cost is low, and nontoxic, stable performance, can be in air natural storage long period and the not change of generation performance.In addition, also have the advantages such as preparation technology is simple, repetition rate is high, applied range.Carbon nano-particle film/silicon nano hole column array active substrate will be developed the technical fields such as Single Molecule Detection, chemistry and industry, biomolecules, archaeology and is all had potential application prospect in future.
Description of drawings
Fig. 1 (a) is the stereoscan photograph of the silicon nano hole column array substrate that makes in the embodiment of the invention 1;
Fig. 1 (b) is the stereoscan photograph of carbon nano-particle film/silicon nano hole column array of making in the embodiment of the invention 1;
Fig. 2 is the transmission electron microscope photo of the carbon nano-particle on the carbon nano-particle film/silicon nano hole column array that makes in the embodiment of the invention 1;
Fig. 3 is the Raman spectrogram of carbon nano-particle film/silicon nano hole column array of making in the embodiment of the invention 1;
Fig. 4 is in the test example, with carbon nano-particle film/silicon nano hole column array of making in the embodiment of the invention 1 as Raman active substrate, to different concns (10
-4Mol/L, 10
-5Mol/L, 10
-6Mol/L) the rhodamine 6G molecule in the rhodamine 6G aqueous solution detects the Raman spectrogram that obtains.
Embodiment
Embodiment 1
Preparation carbon nano-particle film/silicon nano hole column array active substrate, step is as follows:
(1) resistivity is inserted in the autoclave less than the p type single crystal silicon sheet of 3.0 Ω cm, in autoclave, fill corrosive fluid afterwards, corrosive fluid is the corrosive fluid that the hydrofluoric acid of 8.00mol/l and iron nitrate aqueous solution that concentration is 0.08 mol/l form by concentration, liquor capacity compactedness in the autoclave is 90%, 100 ℃ of lower corrosion 60 minutes, prepare the substrate material silicon nano hole column array, its stereoscan photograph is seen shown in Fig. 1 (a);
(2) silicon nano hole column array that step (1) is made places in the horizontal pipe stove; then under nitrogen atmosphere in the Reaktionsofen temperature rise to 700 ℃; stop afterwards in the horizontal pipe stove, passing into nitrogen; change in the horizontal pipe stove and pass into carrier gas; carrier gas is the mixed gas of nitrogen and hydrogen; the volume ratio of nitrogen and hydrogen is nitrogen: hydrogen=7:3; carrier gas brings to carbon source dimethylbenzene in the Reaktionsofen with 0.8 ml/min; under 700 ℃, carry out the chemical vapor deposition growth carbon nano-particle on the silicon nano hole column array surface; reaction times is 15 minutes; afterwards again under the shielding gas nitrogen atmosphere with Reaktionsofen in temperature be down to room temperature; obtain one deck carbon nano-particle in the silicon nano hole column array surface growth this moment; namely at silicon nano hole column array Surface Creation one deck carbon nano-particle rete; make carbon nano-particle film/silicon nano hole column array active substrate; the stereoscan photograph of carbon nano-particle film/silicon nano hole column array active substrate is seen shown in Fig. 1 (b); the transmission electron microscope photo of the carbon nano-particle on carbon nano-particle film/silicon nano hole column array active substrate as shown in Figure 2, the Raman spectrogram of carbon nano-particle film/silicon nano hole column array active substrate is as shown in Figure 3.
Embodiment 2
Preparation carbon nano-particle film/silicon nano hole column array active substrate, step is as follows:
(1) resistivity is inserted in the autoclave less than the p type single crystal silicon sheet of 3.0 Ω cm, in autoclave, fill corrosive fluid afterwards, corrosive fluid is the corrosive fluid that the hydrofluoric acid of 15.00mol/l and iron nitrate aqueous solution that concentration is 0.02 mol/l form by concentration, liquor capacity compactedness in the autoclave is 80%, 180 ℃ of lower corrosion 30 minutes, prepare the substrate material silicon nano hole column array;
(2) silicon nano hole column array that step (1) is made places in the horizontal pipe stove; then under nitrogen atmosphere in the Reaktionsofen temperature rise to 1100 ℃; stop afterwards in the horizontal pipe stove, passing into nitrogen; change in the horizontal pipe stove and pass into carrier gas; carrier gas is the mixed gas of nitrogen and hydrogen; the volume ratio of nitrogen and hydrogen is nitrogen: hydrogen=1:1; carrier gas brings to carbon source dimethylbenzene in the Reaktionsofen with 0.5 ml/min; under 1100 ℃, carry out the chemical vapor deposition growth carbon nano-particle on the silicon nano hole column array surface; reaction times is 10 minutes; afterwards again under the shielding gas nitrogen atmosphere with Reaktionsofen in temperature be down to room temperature; obtain one deck carbon nano-particle in the silicon nano hole column array surface growth this moment; namely at silicon nano hole column array Surface Creation one deck carbon nano-particle rete, make carbon nano-particle film/silicon nano hole column array active substrate.
The surface enhanced Raman scattering effect of the carbon nano-particle film that test example embodiment 1 makes/silicon nano hole column array active substrate detects
The carbon nano-particle film that makes take embodiment 1/silicon nano hole column array active substrate is 10 to concentration respectively as the surface enhanced Raman scattering effect active substrate
-4Mol/L, 10
-5Mol/L, 10
-6Rhodamine 6G molecule in the rhodamine 6G aqueous solution of mol/L detects.Pre-treatment carbon nano-particle film/silicon nano hole column array active substrate before detecting, at first carbon nano-particle film/silicon nano hole column array active substrate is placed in the dehydrated alcohol and infiltrates 2 minutes, deionized water rinsing is 3 times afterwards, then carbon nano-particle film/silicon nano hole column array active substrate is put in the potassium chloride solution of 0.1mol/L and soaks half hour, stain to remove possible ion, then deionized water rinsing is 4 times, and pre-treatment is complete.It is 10 that pretreated carbon nano-particle film/silicon nano hole column array active substrate is placed into respectively concentration
-4Mol/L, 10
-5Mol/L, 10
-6In the rhodamine 6G aqueous solution of mol/L, soaked 30 minutes, then from solution, take out and be put on the filter paper, naturally dry in the air, do subsequently the Raman spectrum test, test condition: the employing wavelength is that the green glow of 532nm is made light source, 20 seconds time shutter, scan 2 times, the wave number sweep limit is 400cm
-1～1800cm
-1The Raman spectrum of rhodamine 6G molecule as shown in Figure 4 in each the concentration rhodamine 6G aqueous solution that obtains.As can be seen from Figure 4, detect with carbon nano-particle film/silicon nano hole column array active substrate, concentration is 10
-6The raman characteristic peak of rhodamine 6G molecule is high-visible in the rhodamine 6G aqueous solution of mol/L.
Claims (10)
1. the active substrate with surface enhanced Raman scattering effect is characterized in that, described active substrate is prepared by the method that may further comprise the steps:
(1) resistivity is inserted in the autoclave less than the p type single crystal silicon sheet of 3.0 Ω, filled corrosive fluid afterwards in autoclave, described p type single crystal silicon sheet in 100～200 ℃ of lower corrosion 30～60 minutes, prepares silicon nano hole column array in corrosive fluid;
(2) silicon nano hole column array is placed in the Reaktionsofen; then under the shielding gas nitrogen atmosphere in the Reaktionsofen temperature rise to 700 ℃～1200 ℃; stop afterwards in Reaktionsofen, passing into shielding gas; change in Reaktionsofen and pass into carrier gas; carrier gas is the mixed gas of nitrogen and hydrogen; carrier gas brings to carbon source dimethylbenzene in the Reaktionsofen with 0.1～0.8mL/min; under 700 ℃～1200 ℃, carry out the chemical vapor deposition growth carbon nano-particle on the silicon nano hole column array surface; reaction times is 5～15 minutes; afterwards again under the shielding gas nitrogen atmosphere with Reaktionsofen in temperature be down to room temperature, obtain carbon nano-particle film/silicon nano hole column array active substrate.
2. the active substrate with surface enhanced Raman scattering effect according to claim 1 is characterized in that, described corrosive fluid is that the hydrofluoric acid of 8.00～15.00mol/L and iron nitrate aqueous solution that concentration is 0.02～0.08mol/L form by concentration.
3. the active substrate with surface enhanced Raman scattering effect according to claim 1 is characterized in that, the volume compactedness of described corrosive fluid in autoclave is 60～90%.
4. the active substrate with surface enhanced Raman scattering effect according to claim 1 is characterized in that, described Reaktionsofen is the horizontal pipe stove.
5. the preparation method with active substrate of surface enhanced Raman scattering effect claimed in claim 1 is characterized in that, may further comprise the steps:
(1) resistivity is inserted in the autoclave less than the p type single crystal silicon sheet of 3.0 Ω, filled corrosive fluid afterwards in autoclave, described p type single crystal silicon sheet in 100～200 ℃ of lower corrosion 30～60 minutes, prepares silicon nano hole column array in corrosive fluid;
(2) silicon nano hole column array is placed in the Reaktionsofen; then under the shielding gas nitrogen atmosphere in the Reaktionsofen temperature rise to 700 ℃～1200 ℃; stop afterwards in Reaktionsofen, passing into shielding gas; change in Reaktionsofen and pass into carrier gas; carrier gas is the mixed gas of nitrogen and hydrogen; carrier gas brings to carbon source dimethylbenzene in the Reaktionsofen with 0.1～0.8mL/min; under 700 ℃～1200 ℃, carry out the chemical vapor deposition growth carbon nano-particle on the silicon nano hole column array surface; reaction times is 5～15 minutes; afterwards again under the shielding gas nitrogen atmosphere with Reaktionsofen in temperature be down to room temperature, obtain carbon nano-particle film/silicon nano hole column array active substrate.
6. the preparation method with active substrate of surface enhanced Raman scattering effect according to claim 5, it is characterized in that, described corrosive fluid is that the hydrofluoric acid of 8.00～15.00mol/L and iron nitrate aqueous solution that concentration is 0.02～0.08 mol/L form by concentration.
7. the preparation method with active substrate of surface enhanced Raman scattering effect according to claim 5 is characterized in that, the volume compactedness of described corrosive fluid in autoclave is 60～90%.
8. the preparation method with active substrate of surface enhanced Raman scattering effect according to claim 5 is characterized in that, described Reaktionsofen is the horizontal pipe stove.
9. the application with active substrate of surface enhanced Raman scattering effect claimed in claim 1 is characterized in that, described active substrate rhodamine 6G in for detection of solution divides the period of the day from 11 p.m. to 1 a.m, can detect that concentration is 10 in the solution
-6The rhodamine 6G molecule of mol/L.
10. the application with active substrate of surface enhanced Raman scattering effect according to claim 9 is characterized in that, the detection method that adopts described active substrate to detect rhodamine 6G molecule in the solution is: described active substrate is inserted 10
-6Soaked 30 minutes in the rhodamine 6G aqueous solution of mol/L, take out, dry under the air conditions, do afterwards the Raman spectrum test, the test condition of Raman spectrum test is: the employing wavelength is that the green glow of 532nm is made light source, 20 seconds time shutter, scan 2 times, the wave number sweep limit is 400cm
-1～1800cm
-1
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| CN104132921B (en) * | 2014-07-07 | 2016-06-22 | 华南师范大学 | A kind of method that surface Raman enhancement active substrate is prepared in chemically based vapour deposition |
| CN106556587B (en) * | 2016-11-15 | 2019-02-19 | 山东师范大学 | Surface enhanced Raman substrate and preparation method based on two-dimentional stannic selenide nanometer sheet |
| CN107188184B (en) * | 2017-04-28 | 2020-04-24 | 杭州芬得检测技术有限公司 | Hydrothermal preparation method of porous silicon material and preparation method of gas fluorescence sensor |
| CN113624742B (en) * | 2021-08-31 | 2022-05-20 | 重庆大学 | Hydrogen enhanced Raman spectroscopy detection method for sulfhydryl gas in plasmon MOF |
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| CN101672786B (en) * | 2009-03-12 | 2011-04-06 | 中国科学院理化技术研究所 | Active substrate with surface provided with enhanced raman scattering effect and production method and application thereof |
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