CN1865936A - SERS detection method employing nano semiconductor material as substrate - Google Patents
SERS detection method employing nano semiconductor material as substrate Download PDFInfo
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- CN1865936A CN1865936A CN 200610016841 CN200610016841A CN1865936A CN 1865936 A CN1865936 A CN 1865936A CN 200610016841 CN200610016841 CN 200610016841 CN 200610016841 A CN200610016841 A CN 200610016841A CN 1865936 A CN1865936 A CN 1865936A
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Abstract
The SERS test method uses nano semiconductor material as surface enhancement of Raman scattering base, and enhances the SERS signal up to 104 times. Wherein, this invention is fit to cadmium telluride, cadmium sulphide, ZnO, ZnS, lead sulfide, TiO2, Pb3O4 or Pb2O3, and mercaptopyridine, p-aminobenzenethiol, pyridine, sulfhydrylbenzoic acid, 1,4-2[(4-pyridyl) vinyl]-benzene, 2-2bipyridyl or 4-4bipyridyl. This invention has wide application.
Description
Technical field
The invention belongs to the molecular recognition technical field, be specifically related to adopt nano semiconductor material, probe molecule is carried out the new method that Surface enhanced raman spectroscopy (SERS) detects as substrate.
Background technology
Raman spectrum belongs to molecular vibration spectrum, can reflect the feature structure of molecule.Be widely used in the state of nature of molecular recognition and bond chemisorption.But Raman scattering effect is a very weak process, and generally its light intensity only is about 10 of incident intensity
-10So Raman signal is all very weak, carries out raman study to surperficial adsorbing species and nearly all will utilize certain enhancement effect.
1974, after people such as Fleischmann carry out roughened to smooth silver electrode surface, obtain to be adsorbed on the high-quality Raman spectrum of unimolecular layer on the silver electrode surface-pyridine molecule first.Van Duyne and co-worker thereof the experiment by system is subsequently compared with the Raman scattering signal that calculates the Raman scattering signal of finding to be adsorbed on each the pyridine molecule on the coarse silver surface and the solution pyridine in mutually, strengthen about 6 orders of magnitude, and then point out that this is a kind of surperficial enhancement effect relevant with rough surface, is called as the SERS effect.10
6The enhancing of times surface signal is equivalent to people's interested monolayer surface molecules of institute (or ion) are amplified becomes 1,000,000 layers, thereby the SERS effect can avoid effectively solution mutually in the signal of same species disturb, obtain high-quality surface molecular signal easily.Be widely used very soon after the SERS effect is found in fields such as Surface Science, analysis science and bio-science, for structure and the process that deeply characterizes various surfaces (interface) (various solid-liquids, solid-gas and solid-solid interface) provides the information on the molecular level, as differentiating that molecule (ion) is at bonding, configuration and the orientation on surface and the surface structure of material etc.The more important thing is the porosint that is used for studying surface kinetics and the inapplicable high-specific surface area of many sufacings that the SERS effect can be very well.Therefore the SERS effect is one of the most promising method in Surface Science.In future, can be widely used in aspects such as advanced material, surface treatment, catalytic action, galvanochemistry, corrosion and biology sensor.
When from the experiment and in theory the SERS effect is carried out more comprehensive and careful research after, researchers recognize the same outstanding of its advantage of the existing shortcoming of SERS technology: one has strong SERS effect as the alkaline metal (as lithium, sodium etc.) that only has gold, silver, three kinds of metals of copper and the minority utmost point to be of little use.The eighties of last century the nineties confirms again: some transition metal such as Pt, Pd, Ru, Rh, Ni, Co and Fe also have the surface to be strengthened, although relatively.Rely on the state of nature and the surface roughening of metal itself, their enhancer reaches 10
2To 10
4The research of the SERS effect study being widened other system does not obtain the progress with practical significance for a long time.Its two, experimentally viewed a lot of complicated phenomenons still can't make an explanation with existing SERS theory.For example, concerning normal Raman spectroscopy, the intensity of Raman signal is directly proportional with the biquadratic of exciting light frequency, but SERS intensity is not followed this relation; Have only SERS effect etc. is just arranged in the minority substrate.
Summary of the invention
At above problem, we adopt semiconductor material to be used as Surface enhanced raman spectroscopy (SERS) substrate first, thereby the SERS base material is extended to the semiconductor category from noble metal or transition metal category, further widen the scope of SERS base material.
The purpose of this invention is to provide a kind of method, it can extend to the semiconductor material category from noble metal or transition metal category with the SERS base material, further widens the scope of SERS base material.Method of the present invention comprises the preparation of semiconductor surface modification probe molecule, is that New type of S ERS substrate is carried out SERS detection two parts to probe molecule with the semiconductor.
Use by novel substrate can obtain more multiprobe molecule and the interactional information of substrate, for the further mechanism of research SERS effect provides theory and test basis, the characterization tool that also becomes the material surface special nature for development SERS effect lays the foundation simultaneously.
Adopt mercaptopyridine (4-MPY), p-aminophenyl thiophenol (ATP), pyridine, mercaptobenzoic acid (MBA), 1,4-2[2-(4-pyridine radicals) vinyl]-benzene (BVPP), 2-2 dipyridine and 4-4 dipyridine etc. be as probe molecule, the SERS signal that detection is adsorbed onto the Nano semiconductor surface obviously strengthens than body phase molecule Raman signal, and enhancer can reach 10
2～10
4This work clearly provides semiconductor-quantum-point can produce the experimental evidence of SERS effect, and enhanced mechanism belongs to charge transfer mechanism.Nano semiconductor material is because the relevant optical property of size, is subjected to people's favor day by day as photoelectron and biomarker novel block, and its performance depends on the surface texture properties of substrate.Therefore, SERS is as the very high spectrum means of a kind of sensitivity, will become a kind of very promising characterization technique to the detection at quantum dot surface and interface.
This patent is assembled modes such as probe molecule in vain by adding probe molecule and semiconductor in the semiconductor fabrication process, successfully probe molecule is connected on the semiconductor by chemical bond-linking.The chemical bonding of probe molecule and substrate has made the ligand molecular cancellation hyperfluorescence of semiconductor material obtains the SERS signal of strong probe molecule.
Method of the present invention comprises two steps:
1, semi-conductive surface-functionalized, i.e. the preparation of the Nano semiconductor of finishing probe molecule:
The semi-conductive surface-functionalized dual mode that has: the one, introduce probe molecule in the course of reaction, another is that probe molecule is modified in the reaction back.
Introduce probe molecule in the course of reaction:
With sulfide is example, the probe molecule that in the pure water of 100ml, adds 0.02～1.0g, logical nitrogen, vigorous stirring is to dissolving fully, add Zn, the Pb of 1～10ml, 0.1M, the deionized water solution of Cd slaine, add the S that contains of 0.5～5.0ml, 0.1M behind 2～10h again
2-Deionized water solution, continue to stir 6～24h after, centrifugal washing promptly gets colloidal sol and the powder and the PbS powder of probe molecule modified ZnS, CdS particle.
The salt of the Zn described in the said method, Pb, Cd metal is zinc nitrate, zinc acetate, plumbi nitras, lead acetate, cadmium nitrate, cadmium acetate etc., probe molecule is the micromolecule that contains sulfydryl or nitrogen-atoms, as mercaptopyridine (4-MPY), p-aminophenyl thiophenol (ATP), pyridine, mercaptobenzoic acid (MBA), 1,4-2[2-(4-pyridine radicals) vinyl]-benzene (BVPP), 2-2 dipyridine and 4-4 dipyridine etc.Contain S
2-Deionized water solution be Na
2S or K
2The deionized water solution of S.
Probe molecule is modified in the reaction back:
The reaction back is modified probe molecule and is divided into two parts, at first is the preparation of nano semiconductor material, is the modification of probe molecule then.
The preparation of nano semiconductor material:
With ZnO is example, and the zinc salt of 4～5g is joined in the monoethanolamine of 0.8～1g, and heating for dissolving stirs, and makes colloidal sol, leaves standstill the formation gel, and 400～500 ℃ of roastings promptly obtain nano level ZnO powder, and yardstick is 3～100nm.
With TiO
2Be example, the mixed liquor of the organic salt (for example metatitanic acid four fourth fat, metatitanic acid isopropyl ester etc.) of 20mL titanium and 20mL absolute ethyl alcohol is added dropwise under vigorous stirring lentamente in the mixed liquor of the secondary deionized water of 80mL absolute ethyl alcohol, 40mL and 2～6ml red fuming nitric acid (RFNA) and launches hydrolysis, then continue to stir 1h, obtain flaxen transparent TiO
2Colloidal sol; Advance still with 30mL colloidal sol then, hydrothermal temperature is 140～200 ℃, and the hydro-thermal time is 6～10h, take out supernatant after going out still, 60 ℃ of vacuum drying obtain precursor, at last with precursor respectively at 350～450 ℃, 500～650 ℃, 700～800 ℃ following roasting 2h, promptly obtain TiO
2Nano particle.
With PbO is example, takes by weighing the pure water solution of the divalence lead salt (for example lead acetate, plumbi nitras etc.) of 0.01mol, and the sodium carbonate of 0.02mol after respectively it being ground with mortar, is put into mortar then together and ground.Fully grind, become thickly, and then grind about 40～60min, it is fully reacted.Water and ethanol alternately wash five times, 90 ℃ of dryings, and calcining is 4 hours under the condition of 620 ℃ of inflated with nitrogen, and natural cooling can obtain flaxen PbO powder.
With the lead orthoplumbate is example, take by weighing 10g divalence lead salt (for example plumbi nitras, lead acetate etc.), it is dissolved in the 20mL water, add 0.4～1g solid NaOH, regulator solution pH waits to dissolve complete back and adds 80mL NaClO solution between 9.0～10.0, stir, behind the about 6h of reaction about 90 ℃, the gained precipitation obtains brown PbO through washing, drying
2Sample; With synthetic PbO
2Be placed in the dried crucible of porcelain, control pyrolysis 5h down, promptly obtain cherry Pb at 420 ℃
3O
4Powder.
The semiconductor colloidal sol that obtains in the above-mentioned steps by lift, the mode of spin-coating or knifing transfers to the surface of wave carrier piece, in 300～450 ℃ of roastings, promptly gets the semi-conductor nano particles film.
The modification of probe molecule:
The Nano semiconductor nanometer powder for preparing is added 1 * 10
-9～1 * 10
-3In the aqueous solution or methanol solution of M probe molecule, vigorous stirring, room temperature lucifuge reaction 12～24h; Repeatedly clean with aqueous solution identical with the front or methanol solvate, the centrifugal not probe molecule of absorption of removing promptly gets surface-functionalized semiconductor nano powder.
Can directly add 1 * 10 for semiconductor film
-9～1 * 10
-3In the aqueous solution or methanol solution of M probe molecule, room temperature lucifuge 12～24h uses aqueous solution identical with the front or methanol solvate repeatedly to clean, and promptly gets surface-functionalized semiconductor nano film.
Can directly add 1 * 10 for semiconductor colloidal sol
-9～1 * 10
-3The aqueous solution of M probe molecule or methanol solution promptly get surface-functionalized semiconductor colloidal sol, and directly test gets final product.
The salt of the metal described in the said method is nitrate, acetate or organometallics etc. (as zinc nitrate, cadmium nitrate, plumbi nitras, zinc acetate, lead acetate, metatitanic acid four fourth fat, metatitanic acid isopropyl ester etc.), probe molecule is the micromolecule that contains sulfydryl or nitrogen-atoms, as mercaptopyridine (4-MPY), p-aminophenyl thiophenol (ATP), pyridine, mercaptobenzoic acid (MBA), 1,4-2[2-(4-pyridine radicals) vinyl]-benzene (BVPP), 2-2 dipyridine and 4-4 dipyridine etc.
2, adopt novel semiconductor nano material to carry out the SERS test as substrate
The present invention uses instrument: testing tool is the burnt Ramam spectrometer of 1000 type copolymerization that Britain Renishaw company produces; Experiment condition: excitaton source wavelength 514nm.
In the said method, adopt novel semiconductor nano material to carry out the SERS test as substrate, nano semiconductor material can be the form of colloidal sol, also can be the form of powder or film.
For powder, pressed powder is placed on the carrier wave on-chip testing, be beneficial to laser focusing like this.
For film, directly test gets final product.
For colloidal sol, to be placed in the various sample cells that glass makes, sample cell can be designed to different shapes according to form, the quantity of requirement of experiment and sample.For example: kapillary, wedge scattering cell, reagent bottle etc.; For the rotatable sample pond that prevents local overheating, be applicable to the constant-temperature sample pool of biological sample etc.This group at colloidal sol SERS substrate design the U-shaped kapillary, as shown in Figure 8, wherein the each several part name is called: kapillary 1, microslide 2, sol particles 3, semiconductor colloidal sol 4, sol particles film 5, microscopical object lens 6.In when test,, focus on test with 5 corresponding to 6.
In the said method, adopt novel semiconductor nano material to carry out the SERS test as substrate, the semiconductor with SERS activity is cadmium telluride (CdTe), cadmium sulfide (CdS), zinc paste (ZnO), zinc sulphide (ZnS), vulcanized lead (PbS), titania (TiO
2), lead orthoplumbate (Pb
3O
4) and massicot (PbO) etc., these materials are to adopt the said method prepared in laboratory to obtain.Probe molecule is respectively mercaptopyridine (4-MPY), p-aminophenyl thiophenol (ATP), pyridine, mercaptobenzoic acid (MBA), 1,4-2[2-(4-pyridine radicals) vinyl]-benzene (BVPP), 2-2 dipyridine and 4-4 dipyridine etc.Probe molecule is bought, and all is that analysis is pure.Its structural formula is as follows.
4-MPY ATP pyridine mercaptobenzoic acid
BVPP
The 2-2 dipyridine
The 4-4 dipyridine
In the said method, adopt novel semiconductor nano material to carry out the SERS test as substrate, the result shows: nano semiconductor material has surperficial enhanced optical character.
In the said method, adopt novel semiconductor nano material to carry out the SERS test as substrate, the SERS spectral results is in conjunction with x-ray photoelectron power spectrum (XPS) and scanning electron microscope (SEM), and preliminary judgement causes that the reason that the SERS signal obviously strengthens is that chemistry strengthens, and belongs to charge transfer mechanism.
Among the present invention, adopt novel base material-semiconductor, probe molecule is carried out Surface enhanced raman spectroscopy (SERS) detect.Further widen the scope of SERS base material.Use by novel substrate obtains more multiprobe molecule and the interactional information of substrate.For the mechanism of further studying SERS provides test basis.Simultaneously the characterization tool that also becomes the material surface special nature for development SERS lays the foundation.
Description of drawings
Fig. 1: the uv-vis spectra of (a), back (b) before the CdTe quantum dot modification 4-MPY;
Fig. 2: the fluorescence spectrum of (a), back (b) before the CdTe quantum dot modification 4-MPY;
Fig. 3: 4-MPY is the Raman spectrum of the SERS on CdTe quantum dot (a), silver sol (b) and CdTe powder (c) and 4-MPY (d) itself respectively;
Fig. 4: 4-MPY is the Raman spectrum of the SERS on CdS nano particle (a), silver sol (b) and 4-MPY (c) itself respectively;
Fig. 5: 4-MPY is the Raman spectrum of the SERS on ZnS nano particle (a), silver sol (b) and 4-MPY (c) itself respectively;
Fig. 6: 4-MPY is the Raman spectrum of the SERS on ZnO nano particle (a), silver sol (b) and 4-MPY (c) itself respectively;
Fig. 7: BVPP and ATP be the SERS spectrum on the ZnO nano particle respectively;
Fig. 8: this patent carries out the U-shaped kapillary synoptic diagram of Test Design to the colloidal sol substrate.
Specific embodiments
Below in conjunction with embodiment the present invention is done further explaination, rather than will limit the invention with this.
Embodiment 1:
The CdTe quantum dot is surface-functionalized:
The 80mg sodium borohydride is dissolved in the 1ml deionized water, adds 127.5mg tellurium powder, cool off with ice-water bath.System communicates with the external world by a little pin hole in course of reaction, so that discharge the hydrogen that produces.After about 8 hours, the tellurium powder of black disappears, and produces white sodium borate crystal.So NaHTe solution that obtains clarifying.
The nanocrystalline Cd that passes through of CdTe that sulfydryl is stable
2+With the NaHTe prepared in reaction.With 100ml 4-mercaptopyridine (4-MPY), mercapto-amine (2DMAET) and cadmium nitrate (Cd (NO
3)
2) the pH value of mixed solution is transferred to 5.0～6.0 with 0.1N NaOH, vigorous stirring is used N in this process
2Qi exhaustion oxygen.Add NaHTe solution then rapidly, continue to stir 10～30min, obtain the CdTe precursor solution from preparation.Wherein, Cd
2+, HTe
-, 4-MPY, 2DMAET mol ratio be 1: 0.5: 1.2: 1.2.At N
2Under the gas shiled, with the precursor solution 2h that refluxes, promptly obtain the CdTe quantum dot of used finishing probe molecule 4-MPY, scanning electron microscope (SEM) shows dimensions as about 3nm.The change of uv-vis spectra (see figure 1) peak shape and the cancellation of fluorescence (see figure 2) explanation 4-MPY have modified the surface of CdTe substrate, and fluorescent quenching simultaneously also further provides evidence for chemical mechanism.
The SERS test of surface-functionalized CdTe quantum dot:
The CdTe quantum dot that adopts preparation mentioned above is as Surface enhanced raman spectroscopy (SERS) substrate, confirm that directly the SERS signal that is adsorbed onto CdTe quantum dot surface-probe molecule 4-mercaptopyridine obviously strengthens than body phase molecule Raman signal, as shown in Figure 3, be that the 4-MPY probe molecule is respectively shown in the Raman spectrum of the SERS on silver sol, CdTe quantum dot and CdTe powder and 4-MPY.(a) being that 4-Mpy is adsorbed onto the SERS spectrum on the CdTe quantum dot, (b) is that 4-Mpy is adsorbed onto the SERS spectrum on the Ag colloidal sol, (c) is that 4-Mpy is adsorbed onto the SERS spectrum on the CdTe powder, (d) is the Raman spectrogram of 4-MPY powder.This novel quantum dot-based end, compared with the conventional metals substrate, and existing many similarities have than big difference again.
4-Mpy is adsorbed onto in the CdTe quantum dot SERS spectrum, the bands of a spectrum of existing 4-Mpy, and the while has the phonon peak of CdTe again.The bands of a spectrum of 4-Mpy (1585,1113,1013) come from the 4-Mpy of enhancing fully, rather than 4-Mpy freely in the solution.Because under identical experiment condition, the signal of the 4-Mpy of same concentrations is very weak, almost detect less than.
4-Mpy is adsorbed onto the CdTe powder surface and is adsorbed onto more similar part on CdTe quantum dot, the silver sol, have bigger difference simultaneously again.The three compares 1113cm with the Raman spectrum of Mpy itself
-1The bands of a spectrum experience is significant to be strengthened, simultaneously 717cm
-1Bands of a spectrum obviously move to low frequency.On metallic substrates, also observed this variation in the past, and thought to cause to the metal surface by the S atomic adsorption on the Mpy.Therefore, we inference Mpy arrives the CdTe surface by the S atomic adsorption.
In addition, 4-Mpy is adsorbed onto on CdTe powder surface and the absorption silver sol and has bigger difference again.Marked difference is among (a) figure, and there is very strong signal in low frequency, and this phenomenon is a unobserved phenomenon on the metallic substrates of in the past reporting.Low frequency signal occurs and enriched spectral information greatly, the semiconductor visual substrate can provide the information of the molecular vibration that enriches more.Another obvious characteristics is that SERS bands of a spectrum half-peak breadth is narrower.Usually, the half-peak breadth of SERS bands of a spectrum will be wider than the half-peak breadth of normal bands of a spectrum.Yet the spectral signal at the semiconductor-based end is not but observed this principle.We think it may is that semiconductor CdTe nano-particles size narrow distribution causes.On the semiconductor on detected bands of a spectrum frequency and the metallic substrates bands of a spectrum frequency difference bigger, some bands of a spectrum exist significantly and move.We think that different substrate shows different molecular vibration information, have reflected the interaction different with molecule.Therefore, the SERS signal of molecule depends on the essence of substrate.
In order to assess the enhancing ability of CdTe quantum dot, need the gauging surface enhancer.According to the surface-functionalized CdTe quantum dot of following Equation for Calculating 4-MPY surface enhancer (Nano Lett.2003, (3): 1229-1233).
EF=(I
SERS/ I
Raman) * (M
b/ M
Ads) Mb is the concentration of body phase sample molecule, Mads is the concentration that is adsorbed onto the quantum dot surface molecular.I
SERSAnd I
RamanBe respectively intensity and the body intensity of sample Raman bands of a spectrum mutually of SERS bands of a spectrum.Therefore, determine that surperficial enhancer requires to detect the Raman spectrum of absorbing molecules and body phase molecule under identical conditions.I
SERS/ I
Raman≈ 1, [Mb]/[Mads]=1.2 * 10
4, calculate its enhancer according to following formula and can reach 10
4Huge enhancer is that the mechanism explain that strengthens of traditional metallic substrates is obstructed.
Embodiment 2:
The CdS quantum dot is surface-functionalized:
Logical nitrogen in the pure water of 100ml, the 4-MPY of adding 0.05g, vigorous stirring adds the Cd (NO of the 0.1M of 2ml to dissolving fully
3)
2Solution.The Na that adds the 0.1M of 1.8ml behind the 5h
2The S aqueous solution.After continuing to stir 12h, centrifugal washing promptly gets the CdS particle that 4-MPY modifies.
The SERS test of surface-functionalized CdS quantum dot:
The CdS quantum dot that adopts method for preparing confirms directly that as Surface enhanced raman spectroscopy (SERS) substrate the CdS quantum dot has the SERS activity, as 4-MPY among Fig. 4 respectively shown in the Raman spectrum of the SERS on silver sol, CdTe nano particle and 4-MPY.(a) being that 4-Mpy is adsorbed onto the SERS spectrum on the CdTe nano particle, (b) is that the SERS spectrum (c) that 4-Mpy is adsorbed onto on the Ag colloidal sol is the Raman spectrogram of 4-MPY powder.Compare the responsive peak 717cm of so-called X-with body phase molecule Raman spectrum in the solution
-1V (C-S) moves and 1110cm to lower wave number
-1Peak intensity significantly increases, and shows that 4-mercaptopyridine molecule forms the Cd-S key by S atom and Cd surface.Simultaneously, be adsorbed onto the SERS spectral bandwidth on CdS quantum dot surface and frequency than bigger variation is arranged on the metallic substrates.In addition, the enhancer of this New type of S ERS substrate can reach 10
3, its enhanced mechanism belongs to charge transfer mechanism.
When in the substrate of CdS nano particle, observing the 4-Mpy signal, detect fundamental frequency peak and the frequency multiplication peak of CdS itself at lower wave number.
Embodiment 3:
ZnS quantum dot surface-functionalized:
Logical nitrogen in the pure water of 100ml, the 4-MPY of adding 0.05g, vigorous stirring adds the Zn (NO of the 0.1M of 2ml to dissolving fully
3)
2Solution.The Na that adds the 0.1M of 1.8ml behind the 5h
2The S aqueous solution.After continuing to stir 12h, centrifugal washing promptly gets 4-MPY modified ZnS particle.The SERS test of surface-functionalized ZnS quantum dot:
The CdS quantum dot that adopts method for preparing confirms directly that as Surface enhanced raman spectroscopy (SERS) substrate the ZnS quantum dot has the SERS activity, as 4-MPY among Fig. 5 respectively shown in the Raman spectrum of the SERS on silver sol, ZnS nano particle and 4-MPY.(a) being that 4-Mpy is adsorbed onto the SERS spectrum on the CdTe nano particle, (b) is that the SERS spectrum (c) that 4-Mpy is adsorbed onto on the Ag colloidal sol is the Raman spectrogram of 4-MPY powder.
Semiconductor ZnS nano particle shows stronger SERS activity.Compare with metallic substrates, have bigger difference.1000cm
-1And 1150cm
-1. the relative intensity difference at two peaks is bigger between the bands of a spectrum., the former is better than the latter at semiconductor-based the end, and just the opposite on the metallic substrates.Thirdly changing is at 1200cm
-1Around the peak, show bimodally on the semiconductor, and what show on the metallic substrates is unimodal.The last point difference is that the frequency shifts of bands of a spectrum in two kinds of substrates is bigger.Though each bands of a spectrum all have corresponding component, peak position has certain moving.In addition, the enhancer of this New type of S ERS substrate can reach 10
3, its enhanced mechanism belongs to charge transfer mechanism.
Embodiment 4:
ZnO quantum dot surface-functionalized:
The zinc acetate of 4.5g is joined in the monoethanolamine of 0.87g, and heating for dissolving stirs, and makes colloidal sol, leaves standstill the formation gel, and 450 ℃ of roastings promptly obtain the ZnO powder of nanoscale yardstick.
The Nano semiconductor nano particle for preparing is added 1 * 10
-3In the deionized water solution of M probe molecule, vigorous stirring, room temperature lucifuge reaction 12h.With washed with de-ionized water 5 times, the centrifugal not probe molecule of absorption of removing promptly gets surface-functionalized semi-conductor nano particles.
The SERS test of surface-functionalized ZnO quantum dot:
The ZnO quantum dot that adopts method for preparing confirms directly that as Surface enhanced raman spectroscopy (SERS) substrate the ZnO quantum dot has the SERS activity, as 4-MPY among Fig. 6 respectively shown in the Raman spectrum of the SERS on silver sol, ZnO nano particle and 4-MPY.(a) being that 4-Mpy is adsorbed onto the SERS spectrum on the ZnO nano particle, (b) is that the SERS spectrum (c) that 4-Mpy is adsorbed onto on the Ag colloidal sol is the Raman spectrogram of 4-MPY powder.Compare the responsive peak 717cm of so-called X-with body phase molecule Raman spectrum in the solution
-1V (C-S) moves and 1116cm to lower wave number
-1Peak intensity significantly increases, and shows that 4-mercaptopyridine molecule forms the Zn-S key by S atom and Cd surface.Simultaneously, be adsorbed onto the SERS spectral bandwidth on ZnO quantum dot surface and frequency than bigger variation is arranged on the metallic substrates.In addition, the enhancer of this New type of S ERS substrate can reach 10
3, its enhanced mechanism belongs to charge transfer mechanism.
Embodiment 5:
Selecting for use BVPP and ATP to modify yardstick as probe molecule respectively is the ZnO particle of 20nm.
The ZnO quantum dot is surface-functionalized:
The zinc acetate of 4g is joined in the monoethanolamine of 1g, and heating for dissolving stirs, and makes colloidal sol, leaves standstill the formation gel, and 450 ℃ of roastings promptly get the ZnO particle of 20nm.
The Nano semiconductor nano particle for preparing is added concentration be 1 * 10
-3In the BVPP of M and the methanol solution of ATP, vigorous stirring, room temperature lucifuge reaction 12h.With washed with de-ionized water 5 times, the centrifugal not probe molecule of absorption of removing promptly gets surface-functionalized ZnO nano particle.
The SERS test of surface-functionalized ZnO quantum dot:
The ZnO quantum dot that adopts method for preparing confirms directly that as Surface enhanced raman spectroscopy (SERS) substrate the ZnO quantum dot has the SERS activity, as BVPP among Fig. 6 and ATP respectively shown in the SERS spectrum on the ZnO of 20nm particle.(a) being that BVPP is adsorbed onto the SERS spectrum on the ZnO nano particle, (b) is that ATP is adsorbed onto the SERS spectrum on the ZnO nano particle.Select different probe molecules for use, at the bottom of the zno-based, all produced the SERS signal, prove further that the ZnO nano particle has to strengthen the property.In addition, the enhancer of this New type of S ERS substrate can reach 10
3, its enhanced mechanism belongs to charge transfer mechanism.
Claims (7)
1, adopting nano semiconductor material is that the method that SERS detects is carried out in substrate, the preparation and the employing semiconductor nano material that comprise the Nano semiconductor of finishing probe molecule carry out two steps of SERS test as substrate, it is characterized in that: the probe molecule that in the pure water of 100ml, adds 0.02～1.0g, logical nitrogen, vigorous stirring is to dissolving fully, add Zn, the Pb of 1～10ml, 0.1M or the deionized water solution of Cd slaine, add the S that contains of 0.5～5.0ml, 0.1M behind 2～10h again
2-Deionized water solution, after continuing to stir 6～24h, centrifugal washing, promptly get colloidal sol or the powder and the PbS powder of probe molecule modified ZnS or CdS particle, and then the employing Raman spectroscopy is that the SERS detection is carried out in substrate with the semiconductor material, the SERS signal that detection is adsorbed onto the Nano semiconductor surface obviously strengthens than body phase molecule Raman signal, and enhancer reaches 10
2～10
4
2, employing nano semiconductor material as claimed in claim 1 is that the method that SERS detects is carried out in substrate, and it is characterized in that: Zn, Pb or Cd slaine are nitrate or acetate.
3, employing nano semiconductor material as claimed in claim 1 is that the method that SERS detects is carried out in substrate, it is characterized in that: probe molecule is mercaptopyridine, p-aminophenyl thiophenol, pyridine, mercaptobenzoic acid, 1,4-2[2-(4-pyridine radicals) vinyl]-benzene, 2-2 dipyridine or 4-4 dipyridine.
4, employing nano semiconductor material as claimed in claim 1 is that the method that SERS detects is carried out in substrate, it is characterized in that: contain S
2-Deionized water solution be Na
2S or K
2The deionized water solution of S.
5, adopting nano semiconductor material is that the method that SERS detects is carried out in substrate, the preparation and the employing semiconductor nano material that comprise the Nano semiconductor of finishing probe molecule carry out two steps of SERS test as substrate, it is characterized in that: prepare nano semiconductor material earlier, then the Nano semiconductor nano particle for preparing is added 1 * 10
-9～1 * 10
-3In the aqueous solution or methanol solution of M probe molecule, vigorous stirring, room temperature lucifuge reaction 12～24h uses aqueous solution identical with the front or methanol solvate repeatedly to clean, and the centrifugal not probe molecule of absorption of removing promptly gets surface-functionalized semi-conductor nano particles; Maybe the semiconductor film of preparing is directly added 1 * 10
-9～1 * 10
-3In the aqueous solution or methanol solution of M probe molecule, room temperature lucifuge 12～24h uses aqueous solution identical with the front or methanol solvate repeatedly to clean, and promptly gets surface-functionalized semiconductor nano film; Maybe the semiconductor colloidal sol of preparing is directly added 1 * 10
-9～1 * 10
-3The aqueous solution of M probe molecule or methanol solution; And then to adopt Raman spectroscopy be that substrate is carried out SERS and detected with the semiconductor material, detects the SERS signal that is adsorbed onto the Nano semiconductor surface and obviously strengthen than body phase molecule Raman signal, and enhancer reaches 10
2～10
4
6, employing nano semiconductor material as claimed in claim 5 is that the method that SERS detects is carried out in substrate, and it is characterized in that: nano semiconductor material is cadmium telluride, cadmium sulfide, zinc paste, zinc sulphide, vulcanized lead, titania, lead orthoplumbate or massicot.
7, employing nano semiconductor material as claimed in claim 5 is that the method that SERS detects is carried out in substrate, it is characterized in that: probe molecule is mercaptopyridine, p-aminophenyl thiophenol, pyridine, mercaptobenzoic acid, 1,4-2[2-(4-pyridine radicals) vinyl]-benzene, 2-2 dipyridine or 4-4 dipyridine.
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