CN101614668A - Silicon nanowire sensor and application thereof based on surface enhanced Raman scattering effect - Google Patents
Silicon nanowire sensor and application thereof based on surface enhanced Raman scattering effect Download PDFInfo
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- CN101614668A CN101614668A CN200910089511A CN200910089511A CN101614668A CN 101614668 A CN101614668 A CN 101614668A CN 200910089511 A CN200910089511 A CN 200910089511A CN 200910089511 A CN200910089511 A CN 200910089511A CN 101614668 A CN101614668 A CN 101614668A
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Abstract
The present invention relates to silicon nanowire sensor and application thereof based on surface enhanced Raman scattering effect.This silicon nanowire sensor is that a kind of surface of coupling has at the bottom of enhancing Raman scattering effect and the stable high active group and Raman spectrometer together is built into.At the bottom of the described active group, be by being distributed in the silicon nanowire array that monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and be netted Nano silver grain film and constitute at the stand pattern on the silicon nanowire array top of arranging of vertical orientation.Further do not contain SiO at the bottom of the described active group
2And Ag
2O, feasible very clean as the Raman collection of illustrative plates at the bottom of the active group of Raman detection substrate, thus greatly reduced of the interference of the assorted peak of active group copy for the record or for reproduction body to the detection of organism target molecule.At the bottom of the coupling active group of the present invention and the silicon nanowire sensor together constructed of Raman spectrometer can make detection by quantitative to the organism target molecule solution of unknown concentration.
Description
Technical field
The present invention relates to nano structure device based on surface enhanced Raman scattering effect, be particularly related to a kind of coupling surface and have and strengthen at the bottom of the high active group of Raman scattering effect and stability and silicon nanowire sensor that Raman spectrometer is together constructed, and carry out detection by quantitative the organism target molecule solution of unknown concentration with this silicon nanowire sensor.
Background technology
Surface enhanced raman spectroscopy (SERS) as a kind of detection of biological solution, medical solutions, chemical solution in the detection means of super low concentration target molecule, since being found, be subjected to paying close attention to widely always.Significantly Raman spectrum strengthens effect, and the detection that point-device feature peak position makes this technology be applied to super low concentration target molecule in the solution becomes possible (Ala M.Alak and Tuan Vo-Dinh.Anal.Chem.1987.59.2149-2153; Jyotirmoy Sarkar, Joydeep Chowdhury, and G.B.Talapatra.J Phys.Chem.C.2007,10049-10061).
The hypothesis of explaining Surface enhanced raman spectroscopy mechanism has a lot, wherein strengthen and take as the leading factor with physics, promptly, metal (as: gold, silver) interaction of nano particle under light field caused collective's resonance (surface plasma body resonant vibration) of conduction electron in the nano particle, strengthens the remarkable enhancing that has caused Raman signal thereby produce the local electromagnetic field at the metal nanoparticle gap location.And the suitable dimension of metal nanoparticle is the necessary condition (Steven R.Emory, William E.Haskins, and Shuming Nie.J.Am.Chem.Soc.1998) that the local electromagnetic field strengthens.
Surface enhanced raman spectroscopy is because it detects advantages such as rapid and sensitivity height, become a kind of emerging detection means rapidly, therefore construct that people have also made a lot of trials (Chanda Ranjit Yonzon aspect the sensor using SERS, Christy L.Haynes, Xiaoyu Zhang, Joseph T.Walsh, andRichard P.Van Duyne Anal Chem, 2004,76; Luca Guerrini, Jos V.Garcia-Ramos, Concepin Domingo, and Santiago Sanchez-Cortes, Langmuir, 2006,22; XianliangZheng, Dang Guo, Yunliang Shao, Shaojie Jia, Shuping Xu, Bing Zhao, WeiqingXu, Charlie Corredor and Joph R.Lombardi, Langmuir, 2008,24; SaratchandraShanmukh, Les Jones, Jeremy Driskell, Yiping Zhao, Richard Dluhy, and Ralph A.Tripp.Nano Lett, 2006,6), construct difficult point aspect the sensor and also just be detection by quantitative to target molecule, i.e. controlled preparation aspect at the bottom of the active group using SERS.
Therefore, all the time preparation strengthen effect obviously, research aspect the good stability, repeatable high Raman scattering active substrate emerge in an endless stream (El-Sayed, M.A.Acc.Chem.Res.2001,34,257-264; Baohua Zhang, Haishui Wang, Lehui Lu, Kelong Ai, Guo Zhang, andXiaoli Cheng, Adv.Funct.Mater.2008,18,2348-2355; ); Wherein, mainly be divided into two kinds of dry method and wet methods in preparing the method that detects substrate, dry method is as (Li-LiBao, Shannon M.Mahurin such as sputter, evaporations, Chen-Du Liang and Sheng Dai, Journal of RamanSpectroscopy.2003); Wet method as: gel-sol method (Steven E, J.Bell and Narayana M, S.Sirimuthu, JACS.2006).Dry method is because at the technical elements comparative maturity, so aspect such as control pattern and size all has superiority under microscale, but its shortcoming is that experimentation is too complicated, cost is too high, thereby is difficult to realize aspect practical application.Wet method is introduced the sensitivity that impurity influences detection easily because advantages such as its simple low cost are subjected to extensive concern gradually during still owing to preparation.Before this, we have prepared (CN200910079487.6) at the bottom of the active group based on silicon nanowires with wet method, yet, be restricted in the controlled preparation of size and the aspects such as homogeneity of particle always, and because the assorted peak of substrate itself, when other species that detect except that the hyperfluorescence species, be subjected to the restriction of sensitivity aspect always.This has also just had a strong impact on uses the application of wet method aspect fabricate devices.
Summary of the invention
The purpose of this invention is to provide a kind of coupling surface has and strengthens at the bottom of the high active group of Raman scattering effect and stability and the silicon nanowire sensor based on surface enhanced Raman scattering effect that Raman spectrometer is together constructed.
Another object of the present invention provides a kind of surface of removing to be had and strengthens the method for disturbing assorted peak at the bottom of Raman scattering effect and the active group that stability is high.
Another purpose of the present invention provides the application based on the silicon nanowire sensor of surface enhanced Raman scattering effect.
Silicon nanowire sensor based on surface enhanced Raman scattering effect of the present invention, it is when with Raman spectrometer the organism target molecule being done to detect, with (carrier that is equivalent to the organism target molecule at the bottom of the active group) at the bottom of the active group as the Raman detection substrate, can to the organism target molecule (as, rhodamine 6G, sevin etc.) make detection by quantitative, thereby realize the formation of sensor.Silicon nanowire sensor of the present invention is at the bottom of the described active group of coupling and Raman spectrometer together is built into.That is, rely on high sensitivity at the bottom of this active group and stable repeatability, with its as the Raman detection substrate when the organism target molecule is made Raman detection, can detection by quantitative go out the content of organism target molecule, thereby realize constructing of sensor.So-called sensor, first to detect be any species exactly, second can detect its content.
Be that the surface has at the bottom of enhancing Raman scattering effect and the stable high active group at the bottom of the described active group, it is by being distributed in the silicon nanowire array that monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and is netted Nano silver grain film and constitutes at the stand pattern on the silicon nanowire array top of arranging of vertical orientation.
SiO is not further contained at the bottom of having the high active group enhancing Raman scattering effect and stable in described surface
2And Ag
2O.
It is that size by grain size comparison homogeneous is that the Nano silver grain of 150nm～1 μ m constitutes that described pattern is netted Nano silver grain film; Described pattern is the Nano silver grain in the netted Nano silver grain film, can prepare the Nano silver grain of different size by the concentration that changes silver nitrate in the silver plating solution, particle size range is between 100nm～1 μ m, and can improve the homogeneity of grain size greatly, thereby improved stability at the bottom of the active group and repeatable greatly by controlling the silver-plated time.
Silicon nanowires in the described silicon nanowire array and the spacing between the silicon nanowires are 150nm～8 μ m.
The length of described silicon nanowires is about about 5～35 μ m, and diameter is about 150～250nm.
The thickness that described pattern is netted Nano silver grain film is 100nm～1.2 μ m.
Described surface is prepared by following method at the bottom of having enhancing Raman scattering effect and stable high active group:
1) prepares the silicon nanowire array that vertical orientation is stood and arranged with the method for chemical etching
I) will place the mixed solution of liquor argenti nitratis ophthalmicus and hydrofluorite to soak 1～3 minute with the monocrystalline silicon substrate (purpose is to remove the oxide film on monocrystalline silicon substrate surface) that hydrofluoric acid dips is crossed, wherein the concentration of silver nitrate is 5mmol/L～10mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L;
Ii) will soak the silver-colored etching liquid that places hydrogen peroxide to mix with the monocrystalline silicon substrate of hydrofluorite mixed solution of pernitric acid with hydrofluorite, at etching temperature is to carry out etching under 40～50 ℃ 15～35 minutes, at the monocrystalline silicon substrate surface deposition silver ion place is arranged, Si can be etched down, and do not deposit the silver ion place, Si can be retained, thereby go out the silicon nanowire array that vertical orientation is stood and arranged in the monocrystalline silicon substrate surface etch, the silicon nanowires length that etches is about about 5～35 μ m, diameter is about 150～250nm, and silicon nanowires in the silicon nanowire array and the spacing between the silicon nanowires are 150nm～8 μ m; Wherein the concentration of the hydrogen peroxide in the etching liquid is 2mmol/L～4mmol/L, and the concentration of hydrofluorite is 4.8～5.5mol/L;
2) be netted Nano silver grain film in the vertical orientation silicon nanowire array top deposition morphology of arranging of standing
The monocrystalline silicon substrate of the silicon nanowire array that the surface etch that step 1) is obtained has vertical orientation to stand to arrange successively through chloroazotic acid soak, after the hydrofluoric acid dips, be statically placed in and soaked in the liquor argenti nitratis ophthalmicus that concentration is 1mmol/L～50mmol/L silver-plated 1～15 minute, on the stand top of the silicon nanowire array arranged of vertical orientation, go out pattern by the in-situ reducing reactive deposition between silver ion and Si-H and be netted Nano silver grain film, obtain described surface and have at the bottom of enhancing Raman scattering effect and the stable high active group.
Described monocrystalline silicon substrate is P type (100) monocrystalline silicon substrate preferably.
Test findings shows: deposit in the process of netted Nano silver grain film on the silicon nanowire array top, concentration by silver nitrate in the control silver plating solution, can prepare the silver particles of different-grain diameter size (particle diameter of Nano silver grain can be controlled between 150nm～1 μ m) and (see Fig. 1, Fig. 2, Fig. 3, Fig. 4 Fig. 5), thereby has realized the controlled preparation of Nano silver grain size.Improved the homogeneity of particle size greatly by controlling the silver-plated time, thereby improved as the stability at the bottom of the active group of Raman detection substrate and repeatable.
The described surface that obtains can be used as the detection substrate use that detects fluorescence molecule (as rhodamine 6G) at the bottom of having the high active group enhancing Raman scattering effect and stable; In order to make this active group scope of application wider, the surface can be had strengthen Raman scattering effect and active group that stability is high at the bottom of further place HF to soak, at the bottom of removing this active group, disturb assorted peak, make very clean as the Raman collection of illustrative plates at the bottom of the active group of Raman detection substrate, thereby the assorted peak that has greatly reduced active group copy for the record or for reproduction body has improved sensitivity to the interference that the organism target molecule detects.Its method is: the surface that will obtain has and strengthens that to place mass concentration at the bottom of Raman scattering effect and the active group that stability is high be that 1～5% HF soaks (being generally about 20 minutes), with the SiO that contains in removing at the bottom of this active group fully
2And Ag
2O, thereby SiO in removing at the bottom of the active group
2And Ag
2The assorted peak of O is to the influence of Raman detection, as Figure 10 and shown in Figure 11.
Silicon nanowire sensor based on surface enhanced Raman scattering effect of the present invention is when the detection by quantitative that is used for the organism target molecule solution of unknown concentration, the raman signatures peak intensity of detected organism target molecule strengthens along with the increase of organism target molecule solution concentration, all take the logarithm back linear in concentration and intensity, the calibration curve of the raman signatures peak intensity by drawing organism target molecule solution concentration and detected organism target molecule, can determine the concentration of organism target molecule detected in the solution by the intensity of the detected feature Raman peaks of silicon nanowire sensor of the present invention, thereby realize detection by quantitative the organism target molecule solution of unknown concentration.As, detected rhodamine 6G and (seen Fig. 6, Fig. 7) with a kind of common organic nitrogen pesticide-sevin (seeing Fig. 8,9).
Description of drawings
Fig. 1. the positive SEM picture of the netted Nano silver grain film on the silicon nanowire array top of the embodiment of the invention 1, its top Nano silver grain film is reticulate texture, and the neat homogeneous of pattern, silver particles particle diameter are 100～200nm.
Fig. 2. the positive SEM picture of the netted Nano silver grain film on the silicon nanowire array top of the embodiment of the invention 2, its top Nano silver grain film is reticulate texture, and the neat homogeneous of pattern, silver particles particle diameter are 250～400nm.
Fig. 3. the side SEM picture of the netted Nano silver grain film on the silicon nanowire array top of the embodiment of the invention 2, the netted Nano silver grain film thickness in top is 300～600nm.
Fig. 4. the positive SEM picture of the netted Nano silver grain film on the silicon nanowire array top of the embodiment of the invention 3, its top Nano silver grain film is reticulate texture, and the neat homogeneous of pattern, silver particles particle diameter are 500～700nm.
Fig. 5. the positive SEM picture of the netted Nano silver grain film on the silicon nanowire array top of the embodiment of the invention 6, its top Nano silver grain film is reticulate texture, and the neat homogeneous of pattern, silver particles particle diameter are about 1 μ m
Fig. 6. as detecting substrate, be 10 at the bottom of the active group of the embodiment of the invention 2 to concentration
-8～10
-17The Raman collection of illustrative plates that the rhodamine 6G of mol/L (R6G) solution detects.
Fig. 7. the present invention executes at the bottom of the active group of example 2 as detecting substrate, and having detected concentration is 10
-8～10
-17Behind the rhodamine 6G of mol/L (R6G) solution, at R6G at 1362cm
-1The characteristic peak at place is according to concentration and the intensity calibration curve that the back draws of all taking the logarithm.
Fig. 8. as detecting substrate, be 10 at the bottom of the active group of the embodiment of the invention 3 to concentration
-2～10
-7Western little Raman collection of illustrative plates that detects because of solution of mol/L.
Fig. 9. the present invention executes at the bottom of the active group of example 3 as detecting substrate, and having detected concentration is 10
-2～10
-7Mol/L's is western little because of behind the solution, at 1378cm
-1The characteristic peak at place is according to concentration and the intensity calibration curve that the back draws of all taking the logarithm.
Figure 10. the present invention executes at the bottom of the active group of example 4 as detecting substrate, directly does the Raman test, the Raman collection of illustrative plates of the detection substrate that obtains before handling without step 3).
Figure 11. the present invention executes at the bottom of the active group of example 4 as detecting substrate, directly does the Raman test, the Raman collection of illustrative plates of the detection substrate that obtains after handling through step 3).
1E-18 among the figure represents 10
-18, 1E-17 represents 10
-17, 1E-16 represents 10
-16... by that analogy.
Embodiment
Embodiment 1
1) will place the mixed solution of liquor argenti nitratis ophthalmicus and hydrofluorite to soak taking-up after 2.5 minutes with P type (100) monocrystalline silicon substrate that hydrofluoric acid dips was cleaned, wherein the concentration of silver nitrate is 5mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; To soak pernitric acid silver and P type (100) monocrystalline silicon substrate of hydrofluorite mixed solution then places the container that fills the etching liquid that hydrogen peroxide mixes with hydrofluorite to carry out etching 35 minutes, the container that wherein fills the etching liquid that hydrogen peroxide mixes with hydrofluorite is to be placed in the water-bath, the temperature of water-bath is 50 ℃, the concentration of the hydrogen peroxide in the etching liquid is 4mmol/L, and the concentration of hydrofluorite is 5.5mol/L; At P type (100) monocrystalline silicon substrate surface deposition the silver ion place is arranged, Si can be etched down, and depositing silver ion place not, Si can be retained, thereby go out the silicon nanowire array that vertical orientation is stood and arranged in surface etch, silicon nanowires in the silicon nanowire array that etches and the spacing between the silicon nanowires are 150nm～8 μ m, and silicon nanowires is about 33 μ m, and diameter is 150～250nm.
2) P type (100) monocrystalline silicon substrate of the surface etch that step 1) the is obtained silicon nanowire array that has vertical orientation to stand to arrange soaks through chloroazotic acid successively, mass concentration is after 5% the hydrofluoric acid dips, taking-up be statically placed in soak in the liquor argenti nitratis ophthalmicus that concentration is 1mmol/L 15 minutes silver-plated, standing at vertical orientation, to deposit thickness be that the pattern of 150～300nm is netted Nano silver grain film for the top of the silicon nanowire array arranged, obtain by being distributed in the silicon nanowire array that P type (100) monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and stand at the bottom of the pattern on the silicon nanowire array top of arranging is surface that netted Nano silver grain film constitutes and has the active group that strengthens Raman scattering effect at vertical orientation, it is that diameter by size comparison homogeneous is that the Nano silver grain of 100～200nm constitutes (see figure 1) that described pattern is netted Nano silver grain film.
3) will be by step 2) to place mass concentration at the bottom of the active group that obtains be that 1% HF soaked 20 minutes, the SiO that contains in can removing at the bottom of this active group fully
2And Ag
2O, thereby SiO in having removed at the bottom of the active group
2And Ag
2The assorted peak of O has at the bottom of enhancing Raman scattering effect and the stable high active group thereby obtain the surface the influence of Raman detection.
At the bottom of the active group that step 3) is obtained and the Raman spectrometer coupling be built into silicon nanowire sensor, rhodamine 6G is done the Raman test.(solution concentration is selected from 10 as the rhodamine 6G solution of solvent preparation variable concentrations with absolute ethyl alcohol
-8Mol/L～10
-17Among the mol/L scope), with micro syringe the rhodamine 6G drips of solution of 5 microlitre variable concentrations is added at the bottom of the active group that step 3) obtains in (detection substrate), treat solvent evaporates after, do the Raman test.Detected the rhodamine 6G solution of variable concentrations, the raman signatures peak intensity of finding rhodamine 6G strengthens along with the increase of rhodamine 6G solution concentration, linear in concentration and the intensity back of all taking the logarithm, thus the linear scaled curve after having drawn solution concentration and rhodamine 6G raman signatures peak intensity and all taking the logarithm.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and sevin is done the Raman test.(solution concentration is selected from 10 because of solution as solvent preparation variable concentrations western little with absolute ethyl alcohol
-2Mol/L～10
-7Among the mol/L scope), with micro syringe western little with 5 microlitre variable concentrations because of drips of solution is added at the bottom of the active group that step 3) obtains in (detection substrate), treat solvent evaporates after, do the Raman test.Detected the western little of variable concentrations because of solution, find western little because of the raman signatures peak intensity along with the little increase because of solution concentration in west strengthens, linear in concentration and the intensity back of all taking the logarithm, thus it is little because of the linear scaled curve of raman signatures peak intensity after all taking the logarithm to have drawn solution concentration and west.
Embodiment 2
1) will place the mixed solution of liquor argenti nitratis ophthalmicus and hydrofluorite to soak taking-up after 1.5 minutes with P type (100) monocrystalline silicon substrate that hydrofluoric acid dips was cleaned, wherein the concentration of silver nitrate is 8mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; To soak pernitric acid silver and P type (100) monocrystalline silicon substrate of hydrofluorite mixed solution then places the container that fills the etching liquid that hydrogen peroxide mixes with hydrofluorite to carry out etching 15 minutes, the container that wherein fills the etching liquid that hydrogen peroxide mixes with hydrofluorite is to be placed in the water-bath, the temperature of water-bath is 40 ℃, the concentration of the hydrogen peroxide in the etching liquid is 2mmol/L, and the concentration of hydrofluorite is 4.8mol/L; At P type (100) monocrystalline silicon substrate surface deposition the silver ion place is arranged, Si can be etched down, and depositing silver ion place not, Si can be retained, thereby go out the silicon nanowire array that vertical orientation is stood and arranged in surface etch, silicon nanowires in the silicon nanowire array that etches and the spacing between the silicon nanowires are 200nm～8 μ m, and silicon nanowires is about 5 μ m, and diameter is 150～250nm.
2) P type (100) monocrystalline silicon substrate of the surface etch that step 1) the is obtained silicon nanowire array that has vertical orientation to stand to arrange soaks through chloroazotic acid successively, mass concentration is after 5% the hydrofluoric acid dips, taking-up be statically placed in soak in the liquor argenti nitratis ophthalmicus that concentration is 5mmol/L 8 minutes silver-plated, standing at vertical orientation, to deposit thickness be that the pattern of 300～500nm is netted Nano silver grain film for the top of the silicon nanowire array arranged, obtain by being distributed in the silicon nanowire array that P type (100) monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and stand at the bottom of the pattern on the silicon nanowire array top of arranging is surface that netted Nano silver grain film constitutes and has the active group that strengthens Raman scattering effect at vertical orientation, it is that diameter by size comparison homogeneous is that the Nano silver grain of 250～400nm constitutes (seeing Fig. 2,3) that described pattern is netted Nano silver grain film.
3) will be by step 2) to place mass concentration at the bottom of the active group that obtains be that 1% HF soaked 20 minutes, the SiO that contains in can removing at the bottom of this active group fully
2And Ag
2O, thereby SiO in having removed at the bottom of the active group
2And Ag
2The assorted peak of O has at the bottom of enhancing Raman scattering effect and the stable high active group thereby obtain the surface the influence of Raman detection.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and rhodamine 6G is done the Raman test.(solution concentration is selected from 10 as the rhodamine 6G solution of solvent preparation variable concentrations with absolute ethyl alcohol
-8Mol/L～10
-17Among the mol/L scope), with micro syringe the rhodamine 6G drips of solution of 5 microlitre variable concentrations is added in and detects in the substrate, treat solvent evaporates after, do the Raman test.Detected the rhodamine 6G solution of variable concentrations, the raman signatures peak intensity of finding rhodamine 6G strengthens (as Fig. 6) along with the increase of rhodamine 6G solution concentration, linear in concentration and the intensity back of all taking the logarithm, thus the linear scaled curve (see figure 7) after having drawn solution concentration and rhodamine 6G raman signatures peak intensity and all taking the logarithm.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and sevin is done the Raman test.(solution concentration is selected from 10 because of solution as solvent preparation variable concentrations western little with absolute ethyl alcohol
-2Mol/L～10
-7Among the mol/L scope), with micro syringe the western little of 5 microlitre variable concentrations detected in the substrate because of drips of solution is added in, treat solvent evaporates after, do the Raman test.Detected the western little of variable concentrations because of solution, find western little because of the raman signatures peak intensity along with the little increase because of solution concentration in west strengthens, linear in concentration and the intensity back of all taking the logarithm, thus it is little because of the linear scaled curve of raman signatures peak intensity after all taking the logarithm to have drawn solution concentration and west.
Embodiment 3
1) will place the mixed solution of liquor argenti nitratis ophthalmicus and hydrofluorite to soak taking-up after 1 minute with P type (100) monocrystalline silicon substrate that hydrofluoric acid dips was cleaned, wherein the concentration of silver nitrate is 10mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; To soak pernitric acid silver and P type (100) monocrystalline silicon substrate of hydrofluorite mixed solution then places the container that fills the etching liquid that hydrogen peroxide mixes with hydrofluorite to carry out etching 30 minutes, the container that wherein fills the etching liquid that hydrogen peroxide mixes with hydrofluorite is to be placed in the water-bath, the temperature of water-bath is 45 ℃, the concentration of the hydrogen peroxide in the etching liquid is 2mmol/L, and the concentration of hydrofluorite is 4.8mol/L; At P type (100) monocrystalline silicon substrate surface deposition the silver ion place is arranged, Si can be etched down, and depositing silver ion place not, Si can be retained, thereby go out the silicon nanowire array that vertical orientation is stood and arranged in surface etch, silicon nanowires in the silicon nanowire array that etches and the spacing between the silicon nanowires are 250nm～6 μ m, and silicon nanowires is about 25 μ m, and diameter is 150～250nm.
2) P type (100) monocrystalline silicon substrate of the surface etch that step 1) the is obtained silicon nanowire array that has vertical orientation to stand to arrange soaks through chloroazotic acid successively, mass concentration is after 5% the hydrofluoric acid dips, taking-up be statically placed in soak in the liquor argenti nitratis ophthalmicus that concentration is 10mmol/L 5 minutes silver-plated, standing at vertical orientation, to deposit thickness be that the pattern of 600～800nm is netted Nano silver grain film for the top of the silicon nanowire array arranged, obtain by being distributed in the silicon nanowire array that P type (100) monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and stand at the bottom of the pattern on the silicon nanowire array top of arranging is surface that netted Nano silver grain film constitutes and has the active group that strengthens Raman scattering effect at vertical orientation, it is that diameter by size comparison homogeneous is that the Nano silver grain of 500～700nm constitutes (see figure 4) that described pattern is netted Nano silver grain film.
3) will be by step 2) to place mass concentration at the bottom of the active group that obtains be that 1% HF soaked 20 minutes, the SiO that contains in can removing at the bottom of this active group fully
2And Ag
2O, thereby SiO in having removed at the bottom of the active group
2And Ag
2The assorted peak of O has at the bottom of enhancing Raman scattering effect and the stable high active group thereby obtain the surface the influence of Raman detection.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and rhodamine 6G is done the Raman test.(solution concentration is selected from 10 as the rhodamine 6G solution of solvent preparation variable concentrations with absolute ethyl alcohol
-8Mol/L～10-
17Among the mol/L scope), with micro syringe the rhodamine 6G drips of solution of 5 microlitre variable concentrations is added in and detects in the substrate, treat solvent evaporates after, do the Raman test.Detected the rhodamine 6G solution of variable concentrations, the raman signatures peak intensity of finding rhodamine 6G strengthens along with the increase of rhodamine 6G solution concentration, linear in concentration and the intensity back of all taking the logarithm, thus the linear scaled curve after having drawn solution concentration and rhodamine 6G raman signatures peak intensity and all taking the logarithm.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and sevin is done the Raman test.(solution concentration is selected from 10 because of solution as solvent preparation variable concentrations western little with absolute ethyl alcohol
-2Mol/L～10
-7Among the mol/L scope), with micro syringe the western little of 5 microlitre variable concentrations detected in the substrate because of drips of solution is added in, treat solvent evaporates after, do the Raman test.Detected the western little of variable concentrations because of solution, find western little because of the raman signatures peak intensity along with the little increase because of solution concentration in west strengthens (see figure 8), linear in concentration and the intensity back of all taking the logarithm, thus it is little because of the linear scaled curve (see figure 9) of raman signatures peak intensity after all taking the logarithm to have drawn solution concentration and west.
Embodiment 4
1) will place the mixed solution of liquor argenti nitratis ophthalmicus and hydrofluorite to soak taking-up after 2 minutes with P type (100) monocrystalline silicon substrate that hydrofluoric acid dips was cleaned, wherein the concentration of silver nitrate is 8mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; To soak pernitric acid silver and P type (100) monocrystalline silicon substrate of hydrofluorite mixed solution then places the container that fills the etching liquid that hydrogen peroxide mixes with hydrofluorite to carry out etching 20 minutes, the container that wherein fills the etching liquid that hydrogen peroxide mixes with hydrofluorite is to be placed in the water-bath, the temperature of water-bath is 45 ℃, the concentration of the hydrogen peroxide in the etching liquid is 3mmol/L, and the concentration of hydrofluorite is 5mol/L; At P type (100) monocrystalline silicon substrate surface deposition the silver ion place is arranged, Si can be etched down, and depositing silver ion place not, Si can be retained, thereby go out the silicon nanowire array that vertical orientation is stood and arranged in surface etch, silicon nanowires in the silicon nanowire array that etches and the spacing between the silicon nanowires are 300nm～8 μ m, and silicon nanowires is about 20 μ m, and diameter is 150～250nm.
2) P type (100) monocrystalline silicon substrate of the surface etch that step 1) the is obtained silicon nanowire array that has vertical orientation to stand to arrange soaks through chloroazotic acid successively, mass concentration is after 5% the hydrofluoric acid dips, taking-up be statically placed in soak in the liquor argenti nitratis ophthalmicus that concentration is 20mmol/L 5 minutes silver-plated, standing at vertical orientation, to deposit thickness be that the pattern of 700～900nm is netted Nano silver grain film for the top of the silicon nanowire array arranged, obtain by being distributed in the silicon nanowire array that P type (100) monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and stand at the bottom of the pattern on the silicon nanowire array top of arranging is surface that netted Nano silver grain film constitutes and has the active group that strengthens Raman scattering effect at vertical orientation, it is that diameter by size comparison homogeneous is that the Nano silver grain of 600～800nm constitutes that described pattern is netted Nano silver grain film.With doing the Raman test as detecting substrate at the bottom of this active group, the Raman collection of illustrative plates of the detection substrate that obtains as shown in figure 10.
3) will be by step 2) to place mass concentration at the bottom of the active group that obtains be that 1% HF soaked 20 minutes, the SiO that contains in can removing at the bottom of this active group fully
2And Ag
2O, thereby SiO in having removed at the bottom of the active group
2And Ag
2The assorted peak of O has at the bottom of enhancing Raman scattering effect and the stable high active group thereby obtain the surface the influence of Raman detection.With doing the Raman test as detecting substrate at the bottom of this active group, the Raman collection of illustrative plates of the detection substrate that obtains by finding out among the figure, has been got rid of the interference at assorted peak at the bottom of the active group, thereby has been improved sensitivity as shown in figure 11 at the bottom of this active group.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and rhodamine 6G is done the Raman test.(solution concentration is selected from 10 as the rhodamine 6G solution of solvent preparation variable concentrations with absolute ethyl alcohol
-8Mol/L～10
-17Among the mol/L scope), with micro syringe the rhodamine 6G drips of solution of 5 microlitre variable concentrations is added in and detects in the substrate, treat solvent evaporates after, do the Raman test.Detected the rhodamine 6G solution of variable concentrations, the raman signatures peak intensity of finding rhodamine 6G strengthens along with the increase of rhodamine 6G solution concentration, linear in concentration and the intensity back of all taking the logarithm, thus the linear scaled curve after having drawn solution concentration and rhodamine 6G raman signatures peak intensity and all taking the logarithm.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and sevin is done the Raman test.(solution concentration is selected from 10 because of solution as solvent preparation variable concentrations western little with absolute ethyl alcohol
-2Mol/L～10
-7Among the mol/L scope), with micro syringe the western little of 5 microlitre variable concentrations detected in the substrate because of drips of solution is added in, treat solvent evaporates after, do the Raman test.Detected the western little of variable concentrations because of solution, find western little because of the raman signatures peak intensity along with the little increase because of solution concentration in west strengthens, linear in concentration and the intensity back of all taking the logarithm, thus it is little because of the linear scaled curve of raman signatures peak intensity after all taking the logarithm to have drawn solution concentration and west.
Embodiment 5
1) will place the mixed solution of liquor argenti nitratis ophthalmicus and hydrofluorite to soak taking-up after 2 minutes with P type (100) monocrystalline silicon substrate that hydrofluoric acid dips was cleaned, wherein the concentration of silver nitrate is 5mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; To soak pernitric acid silver and P type (100) monocrystalline silicon substrate of hydrofluorite mixed solution then places the container that fills the etching liquid that hydrogen peroxide mixes with hydrofluorite to carry out etching 25 minutes, the container that wherein fills the etching liquid that hydrogen peroxide mixes with hydrofluorite is to be placed in the water-bath, the temperature of water-bath is 50 ℃, the concentration of the hydrogen peroxide in the etching liquid is 3mmol/L, and the concentration of hydrofluorite is 5.5mol/L; At P type (100) monocrystalline silicon substrate surface deposition the silver ion place is arranged, Si can be etched down, and depositing silver ion place not, Si can be retained, thereby go out the silicon nanowire array that vertical orientation is stood and arranged in surface etch, silicon nanowires in the silicon nanowire array that etches and the spacing between the silicon nanowires are 150nm～5 μ m, and silicon nanowires is about 30 μ m, and diameter is 150～250nm.
2) P type (100) monocrystalline silicon substrate of the surface etch that step 1) the is obtained silicon nanowire array that has vertical orientation to stand to arrange soaks through chloroazotic acid successively, mass concentration is after 5% the hydrofluoric acid dips, taking-up be statically placed in soak in the liquor argenti nitratis ophthalmicus that concentration is 30mmol/L 2 minutes silver-plated, standing at vertical orientation, to deposit thickness be that the pattern of 700～900nm is netted Nano silver grain film for the top of the silicon nanowire array arranged, obtain by being distributed in the silicon nanowire array that P type (100) monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and stand at the bottom of the pattern on the silicon nanowire array top of arranging is surface that netted Nano silver grain film constitutes and has the active group that strengthens Raman scattering effect at vertical orientation, it is that diameter by size comparison homogeneous is that the Nano silver grain of 650～850nm constitutes that described pattern is netted Nano silver grain film.
3) will be by step 2) to place mass concentration at the bottom of the active group that obtains be that 1% HF soaked 20 minutes, the SiO that contains in can removing at the bottom of this active group fully
2And Ag
2O, thereby SiO in having removed at the bottom of the active group
2And Ag
2The assorted peak of O has at the bottom of enhancing Raman scattering effect and the stable high active group thereby obtain the surface the influence of Raman detection.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and rhodamine 6G is done the Raman test.(solution concentration is selected from 10 as the rhodamine 6G solution of solvent preparation variable concentrations with absolute ethyl alcohol
-8Mol/L～10
-17Among the mol/L scope), with micro syringe the rhodamine 6G drips of solution of 5 microlitre variable concentrations is added in and detects in the substrate, treat solvent evaporates after, do the Raman test.Detected the rhodamine 6G solution of variable concentrations, the raman signatures peak intensity of finding rhodamine 6G strengthens along with the increase of rhodamine 6G solution concentration, linear in concentration and the intensity back of all taking the logarithm, thus the linear scaled curve after having drawn solution concentration and rhodamine 6G raman signatures peak intensity and all taking the logarithm.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and sevin is done the Raman test.(solution concentration is selected from 10 because of solution as solvent preparation variable concentrations western little with absolute ethyl alcohol
-2Mol/L～10
-7Among the mol/L scope), with micro syringe the western little of 5 microlitre variable concentrations detected in the substrate because of drips of solution is added in, treat solvent evaporates after, do the Raman test.Detected the western little of variable concentrations because of solution, find western little because of the raman signatures peak intensity along with the little increase because of solution concentration in west strengthens, linear in concentration and the intensity back of all taking the logarithm, thus it is little because of the linear scaled curve of raman signatures peak intensity after all taking the logarithm to have drawn solution concentration and west.
Embodiment 6
1) will place the mixed solution of liquor argenti nitratis ophthalmicus and hydrofluorite to soak taking-up after 3 minutes with P type (100) monocrystalline silicon substrate that hydrofluoric acid dips was cleaned, wherein the concentration of silver nitrate is 5mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; To soak pernitric acid silver and P type (100) monocrystalline silicon substrate of hydrofluorite mixed solution then places the container that fills the etching liquid that hydrogen peroxide mixes with hydrofluorite to carry out etching 25 minutes, the container that wherein fills the etching liquid that hydrogen peroxide mixes with hydrofluorite is to be placed in the water-bath, the temperature of water-bath is 50 ℃, the concentration of the hydrogen peroxide in the etching liquid is 3mmol/L, and the concentration of hydrofluorite is 4.8mol/L; At P type (100) monocrystalline silicon substrate surface deposition the silver ion place is arranged, Si can be etched down, and depositing silver ion place not, Si can be retained, thereby go out the silicon nanowire array that vertical orientation is stood and arranged in surface etch, silicon nanowires in the silicon nanowire array that etches and the spacing between the silicon nanowires are 150nm～8 μ m, and silicon nanowires is about 30 μ m, and diameter is 150～250nm.
2) P type (100) monocrystalline silicon substrate of the surface etch that step 1) the is obtained silicon nanowire array that has vertical orientation to stand to arrange soaks through chloroazotic acid successively, mass concentration is after 5% the hydrofluoric acid dips, taking-up be statically placed in soak in the liquor argenti nitratis ophthalmicus that concentration is 50mmol/L 1 minute silver-plated, standing at vertical orientation, to deposit thickness be that the pattern of 1 μ m～1.2 μ m is netted Nano silver grain film for the top of the silicon nanowire array arranged, obtain by being distributed in the silicon nanowire array that P type (100) monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and stand at the bottom of the pattern on the silicon nanowire array top of arranging is surface that netted Nano silver grain film constitutes and has the active group that strengthens Raman scattering effect at vertical orientation, it is that the Nano silver grain that diameter by size comparison homogeneous is about 1 μ m constitutes (see figure 5) that described pattern is netted Nano silver grain film.
3) will be by step 2) to place mass concentration at the bottom of the active group that obtains be that 1% HF soaked 20 minutes, the SiO that contains in can removing at the bottom of this active group fully
2And Ag
2O, thereby SiO in having removed at the bottom of the active group
2And Ag
2The assorted peak of O has at the bottom of enhancing Raman scattering effect and the stable high active group thereby obtain the surface the influence of Raman detection.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and rhodamine 6G is done the Raman test.(solution concentration is selected from 10 as the rhodamine 6G solution of solvent preparation variable concentrations with absolute ethyl alcohol
-8Mol/L～10
-17Among the mol/L scope), with micro syringe the rhodamine 6G drips of solution of 5 microlitre variable concentrations is added in and detects in the substrate, treat solvent evaporates after, do the Raman test.Detected the rhodamine 6G solution of variable concentrations, the raman signatures peak intensity of finding rhodamine 6G strengthens along with the increase of rhodamine 6G solution concentration, linear in concentration and the intensity back of all taking the logarithm, thus the linear scaled curve after having drawn solution concentration and rhodamine 6G raman signatures peak intensity and all taking the logarithm.
The surface that step 3) is obtained has at the bottom of the active group that strengthens Raman scattering effect together to construct as Raman detection substrate coupling Raman spectrometer becomes silicon nanowire sensor, and sevin is done the Raman test.(solution concentration is selected from 10 because of solution as solvent preparation variable concentrations western little with absolute ethyl alcohol
-2Mol/L～10
-7Among the mol/L scope), with micro syringe the western little of 5 microlitre variable concentrations detected in the substrate because of drips of solution is added in, treat solvent evaporates after, do the Raman test.Detected the western little of variable concentrations because of solution, find western little because of the raman signatures peak intensity along with the little increase because of solution concentration in west strengthens, linear in concentration and the intensity back of all taking the logarithm, thus it is little because of the linear scaled curve of raman signatures peak intensity after all taking the logarithm to have drawn solution concentration and west.
Claims (9)
1. silicon nanowire sensor based on surface enhanced Raman scattering effect, it is when with Raman spectrometer the organism target molecule being done to detect, with at the bottom of the active group as the Raman detection substrate; It is characterized in that: this silicon nanowire sensor is at the bottom of the described active group of coupling and Raman spectrometer together is built into;
Be that the surface has at the bottom of the active group that strengthens Raman scattering effect at the bottom of the described active group, it is by being distributed in the silicon nanowire array that monocrystalline silicon substrate Surface Vertical orientation is stood and arranged, and is netted Nano silver grain film and constitutes at the stand pattern on the silicon nanowire array top of arranging of vertical orientation.
2. the silicon nanowire sensor based on surface enhanced Raman scattering effect according to claim 1 is characterized in that: SiO is not contained in having at the bottom of the active group that strengthens Raman scattering effect in described surface
2And Ag
2O.
3. the silicon nanowire sensor based on surface enhanced Raman scattering effect according to claim 1 is characterized in that: described surface is prepared by following method at the bottom of having the active group that strengthens Raman scattering effect:
1) will place the mixed solution of liquor argenti nitratis ophthalmicus and hydrofluorite to soak with the monocrystalline silicon substrate that hydrofluoric acid dips is crossed 1～3 minute, wherein the concentration of silver nitrate is 5mmol/L～10mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; To soak the silver-colored etching liquid that places hydrogen peroxide to mix with the monocrystalline silicon substrate of hydrofluorite mixed solution of pernitric acid then with hydrofluorite, at etching temperature is to carry out etching under 40～50 ℃ 15～35 minutes, goes out the silicon nanowire array that vertical orientation is stood and arranged in the monocrystalline silicon substrate surface etch; Wherein the concentration of the hydrogen peroxide in the etching liquid is 2mmol/L～4mmol/L, and the concentration of hydrofluorite is 4.8mol/L～5.5mol/L;
2) monocrystalline silicon substrate of the surface etch that step 1) the is obtained silicon nanowire array that has vertical orientation to stand to arrange successively through chloroazotic acid soak, after the hydrofluoric acid dips, be statically placed in and soaked in the liquor argenti nitratis ophthalmicus that concentration is 1mmol/L～50mmol/L silver-plated 1～15 minute, deposit pattern and be netted Nano silver grain film on the stand top of the silicon nanowire array arranged of vertical orientation, obtain described surface and have at the bottom of the active group that strengthens Raman scattering effect.
4. the silicon nanowire sensor based on surface enhanced Raman scattering effect according to claim 3, it is characterized in that: described surface has that further to place mass concentration at the bottom of the active group that strengthens Raman scattering effect be that 1～5% HF soaks, with the SiO that contains in removing at the bottom of this active group
2And Ag
2O.
5. according to claim 1,2,3 or 4 described silicon nanowire sensors based on surface enhanced Raman scattering effect, it is characterized in that: it is to be that the Nano silver grain of 150nm～1 μ m constitutes by particle diameter that the pattern at the bottom of the described formation active group is netted Nano silver grain film.
6. the silicon nanowire sensor based on surface enhanced Raman scattering effect according to claim 5 is characterized in that: the thickness that described pattern is netted Nano silver grain film is 100nm～1.2 μ m.
7. according to claim 1,2,3 or 4 described silicon nanowire sensors based on surface enhanced Raman scattering effect, it is characterized in that: silicon nanowires in the silicon nanowire array at the bottom of the described formation active group and the spacing between the silicon nanowires are 150nm～8 μ m;
The length of described silicon nanowires is 5～35 μ m, and diameter is 150～250nm.
8. application according to any described silicon nanowire sensor based on surface enhanced Raman scattering effect of claim 1～7, it is characterized in that: described silicon nanowire sensor based on surface enhanced Raman scattering effect is used for the detection by quantitative to the organism target molecule solution of unknown concentration, the calibration curve of the raman signatures peak intensity by drawing organism target molecule solution concentration and detected organism target molecule is determined the concentration of organism target molecule detected in the solution by the intensity of the detected feature Raman peaks of silicon nanowire sensor.
9. the application of the silicon nanowire sensor based on surface enhanced Raman scattering effect according to claim 8, it is characterized in that: described organism target molecule is rhodamine 6G or sevin.
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