CN102020231B - Enhanced Raman scattering substrates of silicon semiconductor and a manufacturing method and application for the same - Google Patents
Enhanced Raman scattering substrates of silicon semiconductor and a manufacturing method and application for the same Download PDFInfo
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- CN102020231B CN102020231B CN 201010526155 CN201010526155A CN102020231B CN 102020231 B CN102020231 B CN 102020231B CN 201010526155 CN201010526155 CN 201010526155 CN 201010526155 A CN201010526155 A CN 201010526155A CN 102020231 B CN102020231 B CN 102020231B
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Abstract
The invention relates to enhanced Raman scattering substrates of silicon semiconductor which possessed good biological compatibility, a preparation method for the same, and the detection of rhodamine 6G molecules and 4-aminothiophenol molecules in solution with the said substrate. The invention adopts a chemical etching method to etch vertically-arranged silicon nanowire array in the surface of the monocrystalline silicon chip; then flocculent silver branches produced as by-products in the silicon nanowire array top in the etching process are removed; and a lot of Si-H bond are decorated in the nanowire surface. The enhanced Raman scattering substrates of silicon semiconductor are constituted by the vertically-arranged silicon nanowire array in the surface of the monocrystalline silicon chip and do not contain precious metal silver; the silicon nanowire surface is decorated with Si-H bonds. The invention realizes for the first time the preparation of enhanced Raman scattering substrates of silicon emiconductor which possessed good biological compatibility with only silicon materials rather than any precious metals.
Description
Technical field
The present invention relates to nano structure device based on surface enhanced Raman scattering effect; Be particularly related to Raman scattering and strengthen substrate with the compatible silicon-based semiconductor of good biological; And relate to the preparation method of this substrate and carry out the detection of the amino thiophenol molecule of rhodamine 6G molecule and 4-in the solution with this substrate.
Background technology
The target molecule SERS as a kind of chemical solution in the trace detection means of target molecule, since coming to light, received widely always and paying close attention to.Surface enhanced Raman scattering effect (SERS) needs to detect in the substrate to contain noble metal (like gold, silver, platinum) usually; Conduction electron can produce collective's resonance in the noble metal under the exciting of light field, that is, and and surface plasma body resonant vibration (Surface Particle Plasmon Resonance); Thereby cause the local electromagnetic field around the noble metal to strengthen, make the Raman scattering signal of the target molecule that is adsorbed on the noble metal surface strengthen (Baohua Zhang, Haishui Wang; Lehui Lu, Kelong Ai, Guo Zhang; And Xiaoli Cheng, Adv.Funct.Mater.18,2348 (2008).; Ming-liang Zhang, Chang-Qing Yi, Xia Fan, Kui-Qing Peng, Ning-Bew Wong, Meng-Su Yang, Rui-Qin, and Shuit-Tong Lee, Appl.Phys.Lett.92,043116 (2008) .).And noble metal has limited the application that the SERS technology detects at biomedicine field to the toxic and side effect of biosome always.
At using metal oxide (like zinc paste; Titania) substitute in the report that noble metal preparation surface has the enhancing substrate that strengthens Raman scattering effect verified: utilize the charge transfer process between metal oxide and target molecule, realized enhancing target molecule raman scattering cross section, promptly strengthen the effect (Z.H.Sun of target molecule Raman scattering signal; B.Zhao; John R.Lombardi, Appl.Phys.Lett.91,221106 (2007); Anthony Musumeci et al., J.Am.Chem.Soc.131,6040 (2009) .).And semiconductor silicon material is owing to have a good bio-compatibility, has a wide range of applications (M.J.Sailor et al., Biomaterials.30,26 (2009) .) at the device of biomedicine field aspect preparing always.Therefore, if can realize the charge transfer process between silicon nanostructure and target molecule, and applying silicon nanostructured preparation will be expected to expand the application of SERS technology in biomedicine field at the bottom of having the active group that strengthens Raman scattering effect.
Summary of the invention
The purpose of this invention is to provide a kind of Raman scattering and strengthen substrate with the compatible silicon-based semiconductor of good biological.
A purpose more of the present invention provides the method that a kind of preparation has the Raman scattering enhancing substrate of the compatible silicon-based semiconductor of good biological.
An also purpose of the present invention provides the application that the Raman scattering with the compatible silicon-based semiconductor of good biological strengthens substrate, in order to realize strengthening target molecule Raman scattering signal.
Raman scattering with the compatible silicon-based semiconductor of good biological of the present invention strengthens substrate; It is method through chemical etching; The monocrystalline silicon substrate Surface Vertical orientation silicon nanowire array of arranging of standing that is distributed in by etching constitutes (like Fig. 1; Fig. 2, shown in Figure 3), and do not contain any noble metal silver in the described substrate to the biosome toxic side effect; Described surface of silicon nanowires is modified with the Si-H key.
Silicon nanowires in the described silicon nanowire array and the spacing between the silicon nanowires are 150nm～8 μ m.
The diameter of the silicon nanowires in the described silicon nanowire array is about 80nm～120nm, and the length of silicon nanowires is about 20 μ m～40 μ m.
The preparation method that the Raman scattering of silicon-based semiconductor of the present invention strengthens substrate may further comprise the steps:
1) with the method for chemical etching, goes out the silicon nanowire array that vertical orientation is stood and arranged in the monocrystalline silicon substrate surface etch;
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 5～10mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L;
Ii) with step I) soak pernitric acid silver and carried out etching 25～35 minutes with the etching liquid that the monocrystalline silicon substrate of the mixed solution of hydrofluorite places oxydol to mix with hydrofluorite; At the monocrystalline silicon substrate surface deposition silver ion place is arranged; Si can be etched down, and does not deposit the silver ion place, and 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 20 μ m～40 μ m, and diameter is about 80nm～120nm, 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 oxydol in the etching liquid is 2～4mmol/L, and the concentration of hydrofluorite is 4.8mol/L～5.5mol/L.
2) remove step 1) is created on the silicon nanowire array top as accessory substance in etching process cotton-shaped silver-colored branch, and on surface of silicon nanowires is modified a large amount of Si-H keys;
The monocrystalline silicon substrate of the silicon nanowire array that the surface etch that i) step 1) is obtained has vertical orientation to stand to arrange is soaked in the chloroazotic acid, all to remove in etching process the cotton-shaped silver-colored branch that is created on the silicon nanowire array top as accessory substance; Therefore noble metal silver need be removed to guarantee the good biological at the bottom of the active group compatible to the biosome toxic side effect;
Ii) with step I) removed the silicon nanowire array of cotton-shaped silver-colored branch; Be soaked in the hydrofluorite of 3%～5% volumetric concentration; Remove the oxide layer of surface of silicon nanowires; And on surface of silicon nanowires is modified a large amount of Si-H key (after handling through hydrofluoric acid dips; The surface of silicon nanowires oxide layer will and be removed with hydrofluorite reaction, and oxide layer is removed the back will be modified the Si-H key at surface of silicon nanowires), the Raman scattering that finally obtains having the compatible silicon-based semiconductor of good biological strengthens substrate; The silicon nanowire array of removing cotton-shaped silver-colored branch is soaked in the purpose in the hydrofluorite: the one, remove the oxide layer of surface of silicon nanowires, thus be beneficial to and target molecule between physisorption; The 2nd, be on surface of silicon nanowires is modified a large amount of Si-H keys, thereby be beneficial to and target molecule between covalent bonding.
Step 1) is described with step I) to soak pernitric acid silver be 40～50 ℃ with the temperature that etching liquid that the monocrystalline silicon substrate of the mixed solution of hydrofluorite places oxydol to mix with hydrofluorite carries out etching.
Step 2) described time that is soaked in the chloroazotic acid is 60～90 minutes.
Step 2) time in the described hydrofluorite that is soaked in 3%～5% volumetric concentration is 5～10 minutes.
Described monocrystalline silicon substrate is P type (a 100) monocrystalline silicon substrate.
Raman scattering with the compatible silicon-based semiconductor of good biological of the present invention strengthens substrate; The Raman scattering that the method for utilizing physical modification or chemical modification is modified said silicon-based semiconductor with target molecule strengthens substrate surface; After target molecule physically or is chemically modified surface of silicon nanowires; Because the charge transfer process between silicon nanowires and target molecule; Make the raman scattering cross section of target molecule obviously increase, cause silicon nanowire array to strengthen the Raman scattering signal of target molecule dramatically.Charge transfer process between the target molecule that utilizes this substrate and modify has realized strengthening the effect of target molecule Raman scattering signal.
Raman scattering with the compatible silicon-based semiconductor of good biological of the present invention strengthens substrate; Utilize the intermolecular Van der Waals force of silicon nanowires and rhodamine 6G; In method through physical modification; After target molecule rhodamine 6G molecular physics is adsorbed onto surface of silicon nanowires; The intermolecular charge transfer process of target molecule rhodamine 6G on utilizing silicon nanowires and modifying has realized strengthening the effect of the Raman scattering signal of target molecule rhodamine 6G molecule, and this charge transfer process cancellation the fluorescence of target molecule rhodamine 6G make the Raman signal of target molecule rhodamine 6G be observed (shown in Fig. 4 (b)) more easily.The Raman scattering of said silicon-based semiconductor strengthens substrate can detect that concentration is 10 in the solution
-6The rhodamine 6G molecule of mol/L (shown in Fig. 4 (a)).
It is 10 to concentration in the solution that the Raman scattering of described silicon-based semiconductor strengthens substrate
-6The method that the rhodamine 6G molecule of mol/L detects is: the Raman scattering that will have the compatible silicon-based semiconductor of good biological strengthens substrate as the raman detection substrate, is 10 with absolute ethyl alcohol as the solvent compound concentration
-6The rhodamine 6G solution of mol/L, the Raman scattering of described silicon-based semiconductor is strengthened substrate, and to be immersed in this concentration be 10
-6In the rhodamine 6G solution of mol/L 5～8 hours, use absolute ethyl alcohol, deionized water rinsing successively after the taking-up after, do raman detection immediately after drying up with nitrogen again.
And at the silicon nanowire array of the deoxidation layer that do not eliminate with the surface when detecting substrate, be 10 in concentration
-6Can only detect the fluorescence peak of rhodamine 6G molecule under the concentration of mol/L, explain that silicon nanowires and the intermolecular charge transfer process of rhodamine 6G have been blocked in the existence of oxide layer, cause the hyperfluorescence (shown in Fig. 4 (c)) of rhodamine 6G molecule.
Raman scattering with the compatible silicon-based semiconductor of good biological of the present invention strengthens substrate; Utilize the mercapto (dehydrogenation reaction SH) in the amino thiophenol molecule of a large amount of Si-H key of surface of silicon nanowires and 4-; Through the method for chemical reflux, with the amino thiophenol molecule of 4-with the bonding mode covalent modification of Si-S key to surface of silicon nanowires; In method through chemical modification; After the amino thiophenol molecule of target molecule 4-was covalently bound to surface of silicon nanowires, the intermolecular charge transfer process of the amino thiophenol of target molecule 4-on utilizing silicon nanowires and modifying had realized strengthening the effect (shown in Fig. 5 (b)) of the Raman scattering signal of the amino thiophenol molecule of target molecule 4-.The Raman scattering of said silicon-based semiconductor strengthens substrate can detect that concentration is 10 in the solution
-3The amino thiophenol molecule of the 4-of mol/L, even can detect the b of the amino thiophenol molecule of 4-
2Mould (shown in Fig. 5 (a)).
It is 10 to concentration in the solution that the Raman scattering of described silicon-based semiconductor strengthens substrate
-3The method that the amino thiophenol molecule of the 4-of mol/L detects is: the Raman scattering that will have the compatible silicon-based semiconductor of good biological strengthens substrate as the raman detection substrate, is 10 with absolute ethyl alcohol as the solvent compound concentration
-3The amino thiophenol solution of the 4-of mol/L, the Raman scattering of described silicon-based semiconductor is strengthened substrate, and to be immersed in this concentration be 10
-3In the amino thiophenol solution of the 4-of mol/L; In temperature is 90 ℃ of following chemical refluxes 5～8 hours; Utilize mercapto in the amino thiophenol molecule of Si-H key and 4-of surface of silicon nanowires (dehydrogenation reaction SH), with the amino thiophenol molecule of 4-with the bonding mode covalent modification of Si-S key to surface of silicon nanowires; After using absolute ethyl alcohol, deionized water rinsing successively after the taking-up, do raman detection immediately after drying up with nitrogen again.
And with the powder of the amino thiophenol of 4-when detecting substrate, can only detect a of the amino thiophenol molecule of 4-usually
1Mould, and utilize the Raman scattering enhancing substrate of silicon-based semiconductor of the present invention can detect b
2Mould, intermolecular that violent charge transfer process has taken place is (verified in the model of amino thiophenol molecule of 4-and metallic substrates: b with being chemically bonded to the amino thiophenol of its surperficial 4-to prove absolutely silicon nanowires
2Mould is with respect to a
1The remarkable enhancing of mould is the positive evidence [John R.Lombardi et al., J.Phys.Chem.C.112,6093 (2008)] of charge transfer process violent between amino thiophenol molecule of 4-and metallic substrates.), thereby increased the raman scattering cross section of the amino thiophenol molecule of 4-dramatically, cause its Raman signal significantly to be strengthened.
Raman scattering with the compatible silicon-based semiconductor of good biological of the present invention strengthens substrate, is that method with chemical etching etches the stand silicon nanowire array of arrangement of vertical orientation on monocrystalline silicon substrate; Utilize the method for modifying of physics or chemistry that target molecule is modified the silicon nanowire array surface, utilize the effect of the charge transfer process realization enhancing target molecule Raman scattering signal between the target molecule in silicon nanowires and the modification.Described physical modification method is to utilize the Van der Waals force between the big specific surface area of silicon nanowires and silicon nanowires and target molecule that the target molecule physisorption is surperficial to silicon nanowire array with the method for solution soaking; Described chemical modification method is to utilize the Si-H key of surface of silicon nanowires that the target molecule covalent modification is surperficial to silicon nanowire array with the method for chemical reflux under the high temperature.The Raman scattering of silicon-based semiconductor of the present invention strengthens substrate can detect that concentration is 10 in the solution
-6The rhodamine 6G molecule of mol/L, and concentration is 10 in the solution
-3The amino thiophenol molecule of the 4-of mol/L.The present invention has successfully realized first not using any noble metal and has only prepared the Raman scattering enhancing substrate with the compatible silicon-based semiconductor of good biological with semiconductor silicon material.
Description of drawings
Fig. 1. the Raman scattering of the silicon-based semiconductor of the embodiment of the invention 1 strengthens the positive SEM picture of substrate, and wherein the silicon nanowires diameter is 80～120nm.
Fig. 2. the Raman scattering of the silicon-based semiconductor of the embodiment of the invention 2 strengthens the side SEM picture of substrate, and silicon nanowires is about 40 μ m in the array.
Fig. 3. the Raman scattering of the silicon-based semiconductor of the embodiment of the invention 3 strengthens the side SEM picture of substrate, and silicon nanowires is about 20 μ m in the array.
Fig. 4 (a). curve a strengthens substrate as the raman detection substrate with the Raman scattering of the silicon-based semiconductor of the embodiment of the invention 1, curve b be with the surface oxide layer is arranged in the embodiment of the invention 1 silicon nanowire array as the raman detection substrate; Be 10 to concentration in the solution respectively
-6The Raman spectrum that the rhodamine 6G molecule of mol/L detects.
Fig. 4 (b). the Raman scattering of the silicon-based semiconductor of the embodiment of the invention 1, embodiment 3, embodiment 5 strengthens substrate as the raman detection substrate; Under the 532nm laser; The intermolecular charge transfer process of silicon nanometer and rhodamine 6G causes the Raman scattering signal of rhodamine 6G molecule to strengthen and fluorescent quenching.
Fig. 4 (c). the silicon nanowire array that with the surface oxide layer is arranged in the embodiment of the invention 1 is as the raman detection substrate; Under the 532nm laser; Because the oxide layer of silicon has been blocked silicon nanowires and the intermolecular charge transfer process of rhodamine 6G; Cause the rhodamine 6G molecule hyperfluorescence to occur, and flooded its Raman signal.
Fig. 5 (a). curve a is the intrinsic Raman collection of illustrative plates of the amino thiophenol powder of 4-, can only detect a
1Mould; Curve b strengthens substrate as the raman detection substrate with the Raman scattering of the silicon-based semiconductor of the embodiment of the invention 2, is 10 to concentration in the solution
-3The Raman collection of illustrative plates that the amino thiophenol molecule of the 4-of mol/L detects can obviously detect b
2Mould.
Fig. 5 (b). the Raman scattering of the silicon-based semiconductor of the embodiment of the invention 2, embodiment 4, embodiment 6 strengthens substrate as the raman detection substrate; Under the 532nm laser; The intermolecular charge transfer process of the amino thiophenol of silicon nanowires and 4-causes the Raman scattering signal of the amino thiophenol molecule of 4-to be enhanced.
Embodiment
Embodiment 1
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; P type (100) monocrystalline silicon substrate that will soak pernitric acid silver then places the container that fills the etching liquid that oxydol mixes with hydrofluorite to carry out etching 30 minutes; The container that wherein fills the etching liquid that oxydol mixes with hydrofluorite is to be placed in the water-bath; The temperature of water-bath is 50 ℃; The concentration of the oxydol 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 25 μ m, and diameter is 80～120nm.
P type (100) monocrystalline silicon substrate of the silicon nanowire array that the surface etch that 2) step 1) is obtained has vertical orientation to stand to arrange is soaked in the cotton-shaped silver-colored branch of removing the silicon nanowire array top in the chloroazotic acid in 60 minutes; Be soaked in volumetric concentration again and be in 5% the hydrofluorite 5 minutes; Remove the oxide layer of surface of silicon nanowires and modify upward a large amount of Si-H key, the Raman scattering that obtains silicon-based semiconductor strengthens substrate.As shown in Figure 1.
The above-mentioned Raman scattering with the compatible silicon-based semiconductor of good biological that obtains is strengthened substrate as the raman detection substrate, and being soaked in absolute ethyl alcohol is 10 as the solvent compound concentration
-6In the rhodamine 6G solution of mol/L 5 hours, utilize the intermolecular Van der Waals force of silicon nanowires and rhodamine 6G, target molecule rhodamine 6G molecular physics is adsorbed onto surface of silicon nanowires; Take out the back and use absolute ethyl alcohol; Deionized water washes successively; After drying up with nitrogen again; Do raman detection (optical maser wavelength of micro confocal laser Raman spectrometer is selected 532nm for use), the intermolecular charge transfer process of target molecule rhodamine 6G (shown in Fig. 4 (b)) on utilizing silicon nanowires and modifying realizes strengthening the effect of target molecule rhodamine 6G Raman scattering of molecule signal, detects the characteristic peak of rhodamine 6G significantly.Shown in Fig. 4 (a) curve a.
Strengthening substrate when the silicon nanowire array that oxide layer is arranged with the surface replaces the Raman scattering of this silicon-based semiconductor, is 10 to concentration in the solution
-6When the rhodamine 6G molecule of mol/L detects,, and flooded its Raman signal because silicon nanowires has been blocked in the existence of oxide layer and the intermolecular charge transfer process of target molecule rhodamine 6G (shown in Fig. 4 (c)) causes the rhodamine 6G molecule hyperfluorescence to occur.Shown in Fig. 4 (a) curve b.
Embodiment 2
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 8mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; P type (100) monocrystalline silicon substrate that will soak pernitric acid silver then places the container that fills the etching liquid that oxydol mixes with hydrofluorite to carry out etching 35 minutes; The container that wherein fills the etching liquid that oxydol mixes with hydrofluorite is to be placed in the water-bath; The temperature of water-bath is 40 ℃; The concentration of the oxydol 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 150nm～8 μ m, and silicon nanowires is about 40 μ m, and diameter is 80～120nm.
P type (100) monocrystalline silicon substrate of the silicon nanowire array that the surface etch that 2) step 1) is obtained has vertical orientation to stand to arrange is soaked in the cotton-shaped silver-colored branch of removing the silicon nanowire array top in the chloroazotic acid in 90 minutes; Be soaked in volumetric concentration again and be in 3% the hydrofluorite l0 minute; Remove the oxide layer of surface of silicon nanowires and modify upward a large amount of Si-H key, the Raman scattering that obtains silicon-based semiconductor strengthens substrate.As shown in Figure 2.
The above-mentioned Raman scattering with the compatible silicon-based semiconductor of good biological that obtains is strengthened substrate as the raman detection substrate, and being soaked in absolute ethyl alcohol is 10 as the solvent compound concentration
-3In the amino thiophenol solution of the 4-of mol/L; Chemical reflux is 5 hours under 90 ℃ of constant temperature; Utilize the dehydrogenation reaction between the mercapto in the amino thiophenol molecule of Si-H key and 4-of surface of silicon nanowires, with the amino thiophenol molecule of 4-with the bonding mode covalent modification of Si-S key to surface of silicon nanowires; Take out the back and use absolute ethyl alcohol; Deionized water washes successively; After drying up with nitrogen again; Do raman detection (optical maser wavelength of micro confocal laser Raman spectrometer is selected 532nm for use), the amino intermolecular charge transfer process of thiophenol of target molecule 4-(shown in Fig. 5 (b)) on utilizing silicon nanowires and modifying realizes strengthening the effect of the amino thiophenol Raman scattering of molecule of target molecule 4-signal, detects the characteristic peak of the amino thiophenol of 4-significantly.Shown in Fig. 5 (a) curve b.
Embodiment 3
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 10mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; P type (100) monocrystalline silicon substrate that will soak pernitric acid silver then places the container that fills the etching liquid that oxydol mixes with hydrofluorite to carry out etching 25 minutes; The container that wherein fills the etching liquid that oxydol mixes with hydrofluorite is to be placed in the water-bath; The temperature of water-bath is 45 ℃; The concentration of the oxydol 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 150nm～8 μ m, and silicon nanowires is about 20 μ m, and diameter is 80～120nm.
P type (100) monocrystalline silicon substrate of the silicon nanowire array that the surface etch that 2) step 1) is obtained has vertical orientation to stand to arrange is soaked in the cotton-shaped silver-colored branch of removing the silicon nanowire array top in the chloroazotic acid in 80 minutes; Be soaked in volumetric concentration again and be in 5% the hydrofluorite 7 minutes; Remove the oxide layer of surface of silicon nanowires and modify upward a large amount of Si-H key, the Raman scattering that obtains silicon-based semiconductor strengthens substrate.As shown in Figure 3.
The above-mentioned Raman scattering with the compatible silicon-based semiconductor of good biological that obtains is strengthened substrate as the raman detection substrate, and being soaked in absolute ethyl alcohol is 10 as the solvent compound concentration
-6In the rhodamine 6G solution of mol/L 8 hours, utilize the intermolecular Van der Waals force of silicon nanowires and rhodamine 6G, target molecule rhodamine 6G molecular physics is adsorbed onto surface of silicon nanowires; Take out the back and use absolute ethyl alcohol; Deionized water washes successively; After drying up with nitrogen again; Do raman detection (optical maser wavelength of micro confocal laser Raman spectrometer is selected 532nm for use), the intermolecular charge transfer process of target molecule rhodamine 6G (shown in Fig. 4 (b)) on utilizing silicon nanowires and modifying realizes strengthening the effect of target molecule rhodamine 6G Raman scattering of molecule signal, detects the characteristic peak of rhodamine 6G significantly.
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 6mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; P type (100) monocrystalline silicon substrate that will soak pernitric acid silver then places the container that fills the etching liquid that oxydol mixes with hydrofluorite to carry out etching 30 minutes; The container that wherein fills the etching liquid that oxydol mixes with hydrofluorite is to be placed in the water-bath; The temperature of water-bath is 50 ℃; The concentration of the oxydol in the etching liquid is 4mmol/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 150nm～8 μ m, and silicon nanowires is about 25 μ m, and diameter is 80～120nm.
P type (100) monocrystalline silicon substrate of the silicon nanowire array that the surface etch that 2) step 1) is obtained has vertical orientation to stand to arrange is soaked in the cotton-shaped silver-colored branch of removing the silicon nanowire array top in the chloroazotic acid in 90 minutes; Be soaked in volumetric concentration again and be in 4% the hydrofluorite 8 minutes; Remove the oxide layer of surface of silicon nanowires and modify upward a large amount of Si-H key, the Raman scattering that obtains silicon-based semiconductor strengthens substrate.
The above-mentioned Raman scattering with the compatible silicon-based semiconductor of good biological that obtains is strengthened substrate as the raman detection substrate, and being soaked in absolute ethyl alcohol is 10 as the solvent compound concentration
-3In the amino thiophenol solution of the 4-of mol/L; Chemical reflux is 8 hours under 90 ℃ of constant temperature; Utilize the dehydrogenation reaction between the mercapto in the amino thiophenol molecule of Si-H key and 4-of surface of silicon nanowires, with the amino thiophenol molecule of 4-with the bonding mode covalent modification of Si-S key to surface of silicon nanowires; Take out the back and use absolute ethyl alcohol; Deionized water washes successively; After drying up with nitrogen again; Do raman detection (optical maser wavelength of micro confocal laser Raman spectrometer is selected 532nm for use), the amino intermolecular charge transfer process of thiophenol of target molecule 4-(shown in Fig. 5 (b)) on utilizing silicon nanowires and modifying realizes strengthening the effect of the amino thiophenol Raman scattering of molecule of target molecule 4-signal, detects the characteristic peak of the amino thiophenol of 4-significantly.
Embodiment 5
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; P type (100) monocrystalline silicon substrate that will soak pernitric acid silver then places the container that fills the etching liquid that oxydol mixes with hydrofluorite to carry out etching 25 minutes; The container that wherein fills the etching liquid that oxydol mixes with hydrofluorite is to be placed in the water-bath; The temperature of water-bath is 45 ℃; The concentration of the oxydol in the etching liquid is 2mmol/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 150nm～8 μ m, and silicon nanowires is about 30 μ m, and diameter is 80～120nm.
P type (100) monocrystalline silicon substrate of the silicon nanowire array that the surface etch that 2) step 1) is obtained has vertical orientation to stand to arrange is soaked in the cotton-shaped silver-colored branch of removing the silicon nanowire array top in the chloroazotic acid in 70 minutes; Be soaked in volumetric concentration again and be in 3% the hydrofluorite 9 minutes; Remove the oxide layer of surface of silicon nanowires and modify upward a large amount of Si-H key, the Raman scattering that obtains silicon-based semiconductor strengthens substrate.
The above-mentioned Raman scattering with the compatible silicon-based semiconductor of good biological that obtains is strengthened substrate as the raman detection substrate, and being soaked in absolute ethyl alcohol is 10 as the solvent compound concentration
-6In the rhodamine 6G solution of mol/L 6 hours, utilize the intermolecular Van der Waals force of silicon nanowires and rhodamine 6G, target molecule rhodamine 6G molecular physics is adsorbed onto surface of silicon nanowires; Take out the back and use absolute ethyl alcohol; Deionized water washes successively; After drying up with nitrogen again; Do raman detection (optical maser wavelength of micro confocal laser Raman spectrometer is selected 532nm for use), the intermolecular charge transfer process of target molecule rhodamine 6G (shown in Fig. 4 (b)) on utilizing silicon nanowires and modifying realizes strengthening the effect of target molecule rhodamine 6G Raman scattering of molecule signal, detects the characteristic peak of rhodamine 6G significantly.
Embodiment 6
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 8mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; P type (100) monocrystalline silicon substrate that will soak pernitric acid silver then places the container that fills the etching liquid that oxydol mixes with hydrofluorite to carry out etching 30 minutes; The container that wherein fills the etching liquid that oxydol mixes with hydrofluorite is to be placed in the water-bath; The temperature of water-bath is 50 ℃; The concentration of the oxydol 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 150nm～8 μ m, and silicon nanowires is about 35 μ m, and diameter is 80～120nm.
P type (100) monocrystalline silicon substrate of the silicon nanowire array that the surface etch that 2) step 1) is obtained has vertical orientation to stand to arrange is soaked in the cotton-shaped silver-colored branch of removing the silicon nanowire array top in the chloroazotic acid in 60 minutes; Be soaked in volumetric concentration again and be in 5% the hydrofluorite 6 minutes; Remove the oxide layer of surface of silicon nanowires and modify upward a large amount of Si-H key, the Raman scattering that obtains silicon-based semiconductor strengthens substrate.
The above-mentioned Raman scattering with the compatible silicon-based semiconductor of good biological that obtains is strengthened substrate as the raman detection substrate, and being soaked in absolute ethyl alcohol is 10 as the solvent compound concentration
-3In the amino thiophenol solution of the 4-of mol/L; Chemical reflux is 6 hours under 90 ℃ of constant temperature; Utilize the dehydrogenation reaction between the mercapto in the amino thiophenol molecule of Si-H key and 4-of surface of silicon nanowires, with the amino thiophenol molecule of 4-with the bonding mode covalent modification of Si-S key to surface of silicon nanowires; Take out the back and use absolute ethyl alcohol; Deionized water washes successively; After drying up with nitrogen again; Do raman detection (optical maser wavelength of micro confocal laser Raman spectrometer is selected 532nm for use), the amino intermolecular charge transfer process of thiophenol of target molecule 4-(shown in Fig. 5 (b)) on utilizing silicon nanowires and modifying realizes strengthening the effect of the amino thiophenol Raman scattering of molecule of target molecule 4-signal, detects the characteristic peak of the amino thiophenol of 4-significantly.
Claims (10)
1. the Raman scattering of a silicon-based semiconductor strengthens substrate; It is characterized in that: described substrate is to constitute by being distributed in the monocrystalline silicon substrate Surface Vertical orientation silicon nanowire array of arranging of standing; Utilize silicon nanowires and be modified at the charge transfer process between the target molecule on the silicon nanowires, realize strengthening the effect of target molecule Raman scattering signal; Do not contain noble metal in the described substrate; Described surface of silicon nanowires is modified with the Si-H key.
2. the Raman scattering of silicon-based semiconductor according to claim 1 strengthens substrate, and it is characterized in that: silicon nanowires in the described silicon nanowire array and the spacing between the silicon nanowires are 150nm～8 μ m.
3. the Raman scattering of silicon-based semiconductor according to claim 1 and 2 strengthens substrate, and it is characterized in that: the diameter of the silicon nanowires in the described silicon nanowire array is 80nm～120nm, and the length of silicon nanowires is 20 μ m～40 μ m.
4. one kind strengthens the preparation method of substrate according to the Raman scattering of any described silicon-based semiconductor of claim 1～3, and it is characterized in that: this preparation method may further comprise the steps:
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 5～10mmol/L in the mixed solution, and the concentration of hydrofluorite is 4.8mol/L; To soak pernitric acid silver then and carry out etching 25～35 minutes with the etching liquid that the monocrystalline silicon substrate of the mixed solution of hydrofluorite places oxydol to mix with hydrofluorite; Go out the silicon nanowire array that vertical orientation is stood and arranged in the monocrystalline silicon substrate surface etch; Wherein the concentration of the oxydol in the etching liquid is 2～4mmol/L, and the concentration of hydrofluorite is 4.8mol/L～5.5mol/L;
The monocrystalline silicon substrate of the silicon nanowire array that the surface etch that 2) step 1) is obtained has vertical orientation to stand to arrange is soaked in the chloroazotic acid, to remove in etching process the cotton-shaped silver-colored branch that is created on the silicon nanowire array top as accessory substance; With the silicon nanowire array of removing cotton-shaped silver-colored branch, be soaked in again in the hydrofluorite of 3%～5% volumetric concentration, remove the oxide layer of surface of silicon nanowires, and on surface of silicon nanowires is modified the Si-H key, the Raman scattering that obtains silicon-based semiconductor strengthens substrate.
5. preparation method according to claim 4 is characterized in that: step 2) the described time that is soaked in the chloroazotic acid is 60～90 minutes.
6. preparation method according to claim 4 is characterized in that: step 2) time in the described hydrofluorite that is soaked in 3%～5% volumetric concentration is 5～10 minutes.
7. application that strengthens substrate according to the Raman scattering of any described silicon-based semiconductor of claim 1～3; It is characterized in that: utilize the intermolecular Van der Waals force of silicon nanowires and rhodamine 6G; In method through physical modification; After target molecule rhodamine 6G molecular physics was adsorbed onto surface of silicon nanowires, the intermolecular charge transfer process of target molecule rhodamine 6G on utilizing silicon nanowires and modifying realized strengthening the effect of target molecule rhodamine 6G Raman scattering of molecule signal; The Raman scattering of said silicon-based semiconductor strengthens substrate can detect that concentration is 10 in the solution
-6The rhodamine 6G molecule of mol/L.
8. application according to claim 7 is characterized in that: it is 10 to concentration in the solution that the Raman scattering of silicon-based semiconductor strengthens substrate
-6The method that the rhodamine 6G molecule of mol/L detects is: as the raman detection substrate, is 10 with absolute ethyl alcohol as the solvent compound concentration with described substrate
-6The rhodamine 6G solution of mol/L, it is 10 that described substrate is immersed in this concentration
-6In the rhodamine 6G solution of mol/L, use absolute ethyl alcohol, deionized water rinsing successively after the taking-up after, do raman detection after drying up with nitrogen again.
9. application that strengthens substrate according to the Raman scattering of any described silicon-based semiconductor of claim 1～3; It is characterized in that: utilize the Si-H key of surface of silicon nanowires and the dehydrogenation reaction between the mercapto in the amino thiophenol molecule of 4-; Through the method for chemical reflux, with the amino thiophenol molecule of 4-with the bonding mode covalent modification of Si-S key to surface of silicon nanowires; In method through chemical modification; After the amino thiophenol molecule of target molecule 4-was covalently bound to surface of silicon nanowires, the intermolecular charge transfer process of the amino thiophenol of target molecule 4-on utilizing silicon nanowires and modifying realized strengthening the effect of the amino thiophenol Raman scattering of molecule of target molecule 4-signal; The Raman scattering of said silicon-based semiconductor strengthens substrate can detect that concentration is 10 in the solution
-3The amino thiophenol molecule of the 4-of mol/L.
10. application according to claim 9 is characterized in that: it is 10 to concentration in the solution that the Raman scattering of silicon-based semiconductor strengthens substrate
-3The method that the amino thiophenol molecule of the 4-of mol/L detects is: as the raman detection substrate, is 10 with absolute ethyl alcohol as the solvent compound concentration with described substrate
-3The amino thiophenol solution of the 4-of mol/L, it is 10 that described substrate is immersed in this concentration
-3In the amino thiophenol solution of the 4-of mol/L; In temperature is 90 ℃ of following chemical refluxes; Utilize the dehydrogenation reaction between the mercapto in the amino thiophenol molecule of Si-H key and 4-of surface of silicon nanowires, with the amino thiophenol molecule of 4-with the bonding mode covalent modification of Si-S key to surface of silicon nanowires; After using absolute ethyl alcohol, deionized water rinsing successively after the taking-up, do raman detection after drying up with nitrogen again.
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| CN102928391B (en) * | 2012-10-11 | 2014-10-15 | 中国科学院理化技术研究所 | Silicon nanowire ordered array-based pH fluorescence sensor and manufacturing method and application thereof |
| CN104155277A (en) * | 2014-08-27 | 2014-11-19 | 中国科学院理化技术研究所 | Preparation method of sulfur ion fluorescent chemical sensor based on silicon nanowire or silicon nanowire array |
| CN108318473A (en) * | 2018-01-12 | 2018-07-24 | 暨南大学 | A kind of surface-enhanced Raman scattering activity substrate and its preparation method and application |
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