CN104237203A - SERS sensor for quantitatively detecting concentration of mercury ions in water sample and preparation method of SERS sensor - Google Patents
SERS sensor for quantitatively detecting concentration of mercury ions in water sample and preparation method of SERS sensor Download PDFInfo
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- CN104237203A CN104237203A CN201410504871.7A CN201410504871A CN104237203A CN 104237203 A CN104237203 A CN 104237203A CN 201410504871 A CN201410504871 A CN 201410504871A CN 104237203 A CN104237203 A CN 104237203A
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Abstract
The invention discloses an SERS sensor for quantitatively detecting the concentration of mercury ions in a real water sample and a preparation method of the SERS sensor. The DNA technology is combined with the SERS technology. Firstly, a hydrogen fluoride auxiliary-etching method is adopted to prepare silicon nanowire arrays, then gold nanoparticles grow in situ to prepare gold-nanoparticle-modified silicon nanowire arrays, and finally, the SERS sensor with the gold-nanoparticle-modified silicon nanowire arrays is manufactured. The SERS sensor can complete the whole reaction process at room temperature and achieves the purpose of quickly detecting the mercury ions, and the limit of detection for the mercury ions is 1pM. The SERS sensor has good specificity, repeatability and reusability, is convenient in detection process, and can be used for detecting the real water sample with the mercury ions.
Description
Technical field
The invention belongs to biological and Raman spectrum detection technique field, relate to a kind of Surface enhanced raman spectroscopy (Surface-Enhanced Raman Scattering, be called for short in full: SERS) sensor and preparation method thereof, is specifically related to SERS sensor of a kind of quantitative detection actual water sample ion concentration of mercury and preparation method thereof.
Background technology
Mercury is that one common are malicious heavy metal, mainly with dimercurion (Hg
2+) form exists, and can produce great harm to the health of the mankind and environment.Mercury compound is relevant with the mercury quantity entered in body to the infringement of human body, and US Gov Env Protection Agency is defined in Mercury in Drinking Water ion concentration must not higher than 10nM.The harm of mercury to human body relates generally to central nervous system, digestive system and kidney, also has a certain impact in addition to respiratory system, skin, blood and eyes.Meanwhile, mercury ion has the bioconcentration of lasting contaminative, easily animal migration and height, and it can be accumulated in the environment, by food chain transport in human body, causes the various disease of human body (see Nat. Nanotechnol.2009,4,742 – 746).Therefore the detection of mercury ion is become day by day to the major issue of Environmental monitoring, research and develop novel mercury ion detecting method significant for environmental protection, prevention from suffering from the diseases, great environmental pollution monitoring.
Research finds, a mercury ion specifically with two thymine alkali bases (T) covalent bond can form stable T-Hg
2+-T structure, utilizes this principle, has established the multiple method based on fluorescence signal transition detection mercury ion, as Akira Ono etc. devises the oligonucleotide sequence that is rich in base (T), its 5 ' end is marked with quencher element, and 3 ' end is marked with fluorescein, when mercury ion exists, due to T-Hg
2+the combination of-T and make oligonucleotides form hairpin structure and cause 3 ' end and 5 ' end close cause fluorescent quenching thus to mercury ion carry out quantitative measurement (see: Angew. Chem., Int. Ed. 2004,116,4400-4402).
Surface enhanced raman spectroscopy is compared with traditional Raman signal, and in the ideal case, signal can amplify 10
12~ 10
15doubly, thus be that the detection analyzing thing under extremely low concentration condition provides feasibility, being therefore construed to is a kind of powerful analysis tool, has a wide range of applications in bio-sensing field and life science.The reported first such as Nie S. M. in 1997 Nano silver grain is to the Raman signal amplification of absorption rhodamine molecule in its surface (see Science, 1997,275,1102-1106).Subsequently, Xia Y. N. has developed the SERS substrate (see Angew. Chem., Int. Ed., 2010,49,164 – 168) based on liquid phase silver or golden nanometer particle.But material is easily assembled under solution state, reunites, thus cause its poor stability, reappearance is bad.Therefore, more make great efforts to start to be devoted to good, the high reproducible substrate of development stability.The silicon nanowires of finishing Nano silver grain; because Nano silver grain is fixed on surface of silicon nanowires very well; thus avoid the gathering of Nano silver grain very well; improve its stability; during therefore the silicon nanowires of finishing Nano silver grain is detected for various bioanalysis as SERS substrate (see: Nano Today 2010; 5,282-295; Nano Today 2011,6,122-130).
The technology of the most widely used detection mercury ion is atomic absorption spectrum and atomic emission spectrum at present.But these methods require higher to the aftertreatment of sample, and accuracy of detection is lower, so be not suitable for the detection of actual water sample.Therefore exploitation one is simple, quick, highly sensitive, specific detection metal mercury ions method seems especially important.
Summary of the invention
In view of this, object of the present invention quantitatively detects SERS sensor of ion concentration of mercury in actual water sample and preparation method thereof fast providing a kind of.
For achieving the above object, DNA technique combines with Surface enhanced raman spectroscopy (SERS) technology by the present invention, first hydrogen fluoride auxiliary etch method is adopted to prepare silicon nanowire array, then golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified, and finally constructs the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
Concrete, the invention provides following technical scheme:
The preparation method of the SERS sensor of quantitative detection actual water sample ion concentration of mercury of the present invention, comprises the steps:
A () hydrogen fluoride auxiliary etch prepares silicon nanowire array
(1) first silicon wafer is carried out ultrasonic cleaning with deionized water, acetone, deionized water successively, then put into the concentrated sulphuric acid and mixed solution of hydrogen peroxide cleans further, and then by washed with de-ionized water, obtain clean silicon wafer;
Preferably, described silicon wafer is p-type or the N-shaped silicon wafer of 0.01 ~ 20 Ω * cm.
Preferably, described superoxol mass concentration is 40%, the concentrated sulphuric acid and hydrogen peroxide volume ratio=1:(0.01 ~ 100).
(2) silicon wafer that step (1) cleans up is inserted in hydrogen fluoride solution carry out oscillating reactions, obtain the silicon wafer of a large amount of silicon-hydrogen bond of surface coverage (Si-H);
Preferably, described hydrogen fluoride solution mass concentration is 1 ~ 40%.
Further, the silicon wafer that step (1) cleans up is inserted in hydrogen fluoride solution carry out oscillating reactions 1 ~ 60 minute.
(3) silicon wafer that step (2) obtains is put into silver nitrate and hydrofluoric mixed solution oscillating reactions, obtain the silicon wafer of growth in situ one deck Nano silver grain of surface uniform;
Preferably, described liquor argenti nitratis ophthalmicus concentration is 1M, and hydrogen fluoride solution mass concentration is 40%, liquor argenti nitratis ophthalmicus and hydrogen fluoride solution volume ratio=1:(0.01 ~ 100).
Further, the silicon wafer that step (2) obtains is put into silver nitrate and hydrofluoric mixed solution oscillating reactions 1 ~ 60 minute.
(4) silicon wafer that Nano silver grain step (3) obtained is modified puts into hydrogen peroxide and hydrofluoric mixed solution oscillating reactions, obtains the silicon nanowire array of silver nanoparticle deposition;
Preferably, described superoxol mass concentration is 40%, and hydrogen fluoride solution mass concentration is 40%, superoxol and hydrogen fluoride solution volume ratio=1:(0.01 ~ 100).
Further, the silicon wafer that the Nano silver grain that step (3) obtained is modified puts into hydrogen peroxide and hydrofluoric mixed solution oscillating reactions 1 ~ 60 minute.
(5) silicon nanowire array of silver nanoparticle deposition step (4) obtained is put into salpeter solution and is reacted, and the Nano silver grain on removing surface, obtains silicon nanowire array;
Preferably, the mass concentration of described salpeter solution is 1 ~ 70%.
Further, the silicon nanowire array of silver nanoparticle deposition step (4) obtained puts into salpeter solution reaction 1 ~ 60 minute.
B () golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified
(1) silicon nanowire array step (a) prepared immerses in hydrogen fluoride solution and reacts, and defines a large amount of Si-H keys on silicon nanowire array surface;
Preferably, described hydrogen fluoride solution mass concentration is 1 ~ 40%.
Further, silicon nanowire array step (a) prepared immerses in hydrogen fluoride solution and reacts 1 ~ 60 minute.
(2) silicon nanowire array that step (1) obtains is put into chlorauric acid solution to react, because Si-H key has very strong reductibility, gold ion in solution can be reduced into golden nanometer particle, growth in situ is on silicon nanowire array surface, taken out, dry up after deionized water washing, obtain the silicon nanowire array that golden nanometer particle is modified;
Preferably, the concentration of described chlorauric acid solution is 0.001 ~ 10 M.
Further, the silicon nanowire array that step (1) obtains is put into chlorauric acid solution reaction 1 ~ 60 minute.
Preferably, in step (2), dry up with nitrogen after deionized water washing, obtain the silicon nanowire array that golden nanometer particle is modified.
The SERS sensor of c silicon nanowire array that () golden nanometer particle is modified builds
(1) silicon nanowire array that golden nanometer particle step (b) prepared is modified is placed in reaction vessels, adds the single stranded DNA solution submergence that are rich in thymine alkali bases;
Preferably, the described concentration being rich in the single stranded DNA of thymine alkali bases is 0.001 ~ 10M.
Preferably, the described single stranded DNA being rich in thymine alkali bases is
5’-(Cy5)-TTCTTTCTTCCCCTTGTTTGTT-SH-3’。
(2) reaction vessels is placed in constant temperature oscillation instrument stirring reaction, the single stranded DNA terminal sulfhydryl group and the golden nanometer particle covalency that are rich in thymine alkali bases form golden sulfide linkage, make the single stranded DNA being rich in thymine alkali bases be covalently attached on the silicon nanowire array of golden nanometer particle modification;
Preferably, reaction vessels is placed in constant temperature oscillation instrument 100 ~ 600RPM, reaction 1 ~ 24 hour at 25 DEG C.
(3) add salt solusion to gradation in the solution of step (2), make salt solusion ultimate density be 0.001 ~ 10M, spend the night aging;
Preferably, in the solution of step (2), the salt solusion adding 1M for 5 times is divided to add once every 2 hours.
(4) material is taken out, dry up after deionized water washing, obtain the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
Preferably, in step (4), taken out by material, after deionized water washing, nitrogen dries up.
Present invention provides a kind of SERS sensor prepared based on said method.
SERS sensor of the present invention can at room temperature complete whole course of reaction, reach the object of rapid mercury detection ion, 1pM is limited to the detection of mercury ion, and there is good specificity, reappearance, reusability, testing process is convenient, can be used for the detection of the actual water sample of mercury ion.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing for the present invention in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the principle schematic that the present invention DNA Raman technology detects mercury ion;
Fig. 2 is that the scanning electron microscope of the silicon nanowire array of the golden nanometer particle modification that the present invention prepares characterizes photo;
Fig. 3 is that the SERS sensor for preparing of the present invention is to the comparison diagram of the Raman signal of variable concentrations mercury ion;
Fig. 4 is that the SERS sensor for preparing of the present invention is to the comparison diagram of the Raman signal of same concentration different ions;
Fig. 5 is that the SERS sensor for preparing of the present invention is to the reusable picture of mercury ion detecting;
Fig. 6 is that the SERS sensor for preparing of the present invention is based on the comparison diagram of deionized water to mercury ion content detection in lake water.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is described in detail.
The present invention's raw material used freely can be buied by market, be analyze pure;
Embodiment 1
A () hydrogen fluoride auxiliary etch method prepares silicon nanowire array:
(1) silicon wafer is carried out ultrasonic cleaning with deionized water, acetone, deionized water first successively, put into the concentrated sulphuric acid again and hydrogen peroxide (concentration: 40wt%) mixed solution (volume ratio=1:0.01) cleans further, and then by washed with de-ionized water, obtain clean silicon wafer.(2) inserted by the silicon wafer cleaned up in hydrogen fluoride solution (concentration: 1wt%) and carry out silicon-hydrogenation, slowly vibration 1 minute, obtains the silicon wafer of a large amount of silicon-hydrogen bond of surface coverage (Si-H).(3) silicon wafer obtained after above-mentioned process is put into the mixed solution (volume ratio=1:0.01) of silver nitrate (concentration: 1M) and hydrogen fluoride (concentration: 40wt%), slow vibration 1 minute, enables the uniform growth in situ one deck Nano silver grain of silicon chip surface.(4) silicon wafer that the Nano silver grain obtained after above-mentioned process is modified is put into the mixed solution (volume ratio=1:0.01) of hydrogen peroxide (concentration: 40wt%) and hydrogen fluoride (concentration: 40wt%), slow vibration 1 minute, can obtain the silicon nanowire array of silver nanoparticle deposition.(5) silicon nanowire array of the silver nanoparticle deposition obtained is put into nitric acid (concentration: 1wt%) solution, the reaction time is 1 minute, and the Nano silver grain on removing silicon nanowire array surface, obtains silicon nanowire array.
B () golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified:
(1) immersed in hydrogen fluoride (concentration: 1wt%) solution by the silicon nanowire array prepared, the reaction time is 1 minute, defines a large amount of Si-H keys on silicon nanowire array surface.(2) silicon nanowire array is put into gold chloride (concentration: 0.001M) solution, because Si-H key has very strong reductibility, the gold ion in solution can be reduced into golden nanometer particle, growth in situ is on silicon nanowire array surface.(3) react after 1 minute, taken out by material, deionized water washs, and nitrogen dries up, and obtains the silicon nanowire array that golden nanometer particle is modified.
The SERS sensor of c silicon nanowire array that () golden nanometer particle is modified builds:
(1) silicon nanowire array that golden nanometer particle is modified is placed in reaction vessels, adds the solution of single stranded DNA (5 '-(Cy5)-TTCTTTCTTCCCCTTGTTTGTT-SH-3 ') (concentration: 0.001M), make solution submergence material.(2) reaction vessels is placed in constant temperature oscillation instrument, 100 rpms, 25 DEG C of constant temperature, reacts 1 hour, make DNA terminal sulfhydryl group and golden nanometer particle covalency form golden sulfide linkage, DNA is covalently attached on the silicon nanowire array of golden nanometer particle modification.(3) in solution, then divide the salt solusion adding 1M for 5 times to add once every 2 hours, make salt solusion ultimate density be 0.001M, spend the night aging.(4) taken out by material, deionized water washs, and nitrogen dries up, and obtains the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
Embodiment 2
A () hydrogen fluoride auxiliary etch method prepares silicon nanowire array:
(1) silicon wafer is carried out ultrasonic cleaning with deionized water, acetone, deionized water first successively, put into the concentrated sulphuric acid again and hydrogen peroxide (concentration: 40wt%) mixed solution (volume ratio=1:0.1) cleans further, and then by washed with de-ionized water, obtain clean silicon wafer.(2) inserted by the silicon wafer cleaned up in hydrogen fluoride solution (concentration: 5wt%) and carry out silicon-hydrogenation, slowly vibration 10 minutes, obtains the silicon wafer of a large amount of silicon-hydrogen bond of surface coverage (Si-H).(3) silicon wafer obtained after above-mentioned process is put into the mixed solution (volume ratio=1:0.1) of silver nitrate (concentration: 1M) and hydrogen fluoride (concentration: 40wt%), slow vibration 10 minutes, enables the uniform growth in situ one deck Nano silver grain of silicon chip surface.(4) silicon wafer that the Nano silver grain obtained after above-mentioned process is modified is put into the mixed solution (volume ratio=1:0.1) of hydrogen peroxide (concentration: 40wt%) and hydrogen fluoride (concentration: 40wt%), slow vibration 10 minutes, can obtain the silicon nanowire array of silver nanoparticle deposition.(5) silicon nanowire array of the silver nanoparticle deposition obtained is put into nitric acid (concentration: 10wt%) solution, the reaction time is 10 minutes, and the Nano silver grain on removing silicon nanowire array surface, obtains silicon nanowire array.
B () golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified:
(1) immersed in hydrogen fluoride (concentration: 5wt%) solution by the silicon nanowire array prepared, the reaction time is 10 minutes, defines a large amount of Si-H keys on silicon nanowire array surface.(2) silicon nanowire array is put into gold chloride (concentration: 0.01M) solution, because Si-H key has very strong reductibility, the gold ion in solution can be reduced into golden nanometer particle, growth in situ is on silicon nanowire array surface.(3) react after 10 minutes, taken out by material, deionized water washs, and nitrogen dries up, and obtains the silicon nanowire array that golden nanometer particle is modified.
The SERS sensor of c silicon nanowire array that () golden nanometer particle is modified builds:
(1) silicon nanowire array that golden nanometer particle is modified is placed in reaction vessels, adds the solution of single stranded DNA (5 '-(Cy5)-TTCTTTCTTCCCCTTGTTTGTT-SH-3 ') (concentration: 0.01M), make solution submergence material.(2) reaction vessels is placed in constant temperature oscillation instrument, 200 rpms, 25 DEG C of constant temperature, reacts 4 hours, make DNA terminal sulfhydryl group and golden nanometer particle covalency form golden sulfide linkage, DNA is covalently attached on the silicon nanowire array of golden nanometer particle modification.(3) in solution, then divide the salt solusion adding 1M for 5 times to add once every 2 hours, make salt solusion ultimate density be 0.01M, spend the night aging.(4) taken out by material, deionized water washs, and nitrogen dries up, and obtains the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
Embodiment 3
A () hydrogen fluoride auxiliary etch method prepares silicon nanowire array:
(1) silicon wafer is carried out ultrasonic cleaning with deionized water, acetone, deionized water first successively, put into the concentrated sulphuric acid again and hydrogen peroxide (concentration: 40wt%) mixed solution (volume ratio=1:1) cleans further, and then by washed with de-ionized water, obtain clean silicon wafer.(2) inserted by the silicon wafer cleaned up in hydrogen fluoride solution (concentration: 10wt%) and carry out silicon-hydrogenation, slowly vibration 20 minutes, obtains the silicon wafer of a large amount of silicon-hydrogen bond of surface coverage (Si-H).(3) silicon wafer obtained after above-mentioned process is put into the mixed solution (volume ratio=1:1) of silver nitrate (concentration: 1M) and hydrogen fluoride (concentration: 40wt%), slow vibration 20 minutes, enables the uniform growth in situ one deck Nano silver grain of silicon chip surface.(4) silicon wafer that the Nano silver grain obtained after above-mentioned process is modified is put into the mixed solution (volume ratio=1:1) of hydrogen peroxide (concentration: 40wt%) and hydrogen fluoride (concentration: 40wt%), slow vibration 20 minutes, can obtain the silicon nanowire array of silver nanoparticle deposition.(5) silicon nanowire array of the silver nanoparticle deposition obtained is put into nitric acid (concentration: 20wt%) solution, the reaction time is 20 minutes, and the Nano silver grain on removing silicon nanowire array surface, obtains silicon nanowire array.
B () golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified:
(1) immersed in hydrogen fluoride (concentration: 10wt%) solution by the silicon nanowire array prepared, the reaction time is 20 minutes, defines a large amount of Si-H keys on silicon nanowire array surface.(2) silicon nanowire array is put into gold chloride (concentration: 0.1M) solution, because Si-H key has very strong reductibility, the gold ion in solution can be reduced into golden nanometer particle, growth in situ is on silicon nanowire array surface.(3) react after 20 minutes, taken out by material, deionized water washs, and nitrogen dries up, and obtains the silicon nanowire array that golden nanometer particle is modified.
The SERS sensor of c silicon nanowire array that () golden nanometer particle is modified builds:
(1) silicon nanowire array that golden nanometer particle is modified is placed in reaction vessels, adds the solution of single stranded DNA (5 '-(Cy5)-TTCTTTCTTCCCCTTGTTTGTT-SH-3 ') (concentration: 0.1M), make solution submergence material.(2) reaction vessels is placed in constant temperature oscillation instrument, 300 rpms, 25 DEG C of constant temperature, reacts 8 hours, make DNA terminal sulfhydryl group and golden nanometer particle covalency form golden sulfide linkage, DNA is covalently attached on the silicon nanowire array of golden nanometer particle modification.(3) in solution, then divide the salt solusion adding 1M for 5 times to add once every 2 hours, make salt solusion ultimate density be 0.1M, spend the night aging.(4) taken out by material, deionized water washs, and nitrogen dries up, and obtains the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
Embodiment 4
A () hydrogen fluoride auxiliary etch method prepares silicon nanowire array:
(1) silicon wafer is carried out ultrasonic cleaning with deionized water, acetone, deionized water first successively, put into the concentrated sulphuric acid again and hydrogen peroxide (concentration: 40wt%) mixed solution (volume ratio=1:10) cleans further, and then by washed with de-ionized water, obtain clean silicon wafer.(2) inserted by the silicon wafer cleaned up in hydrogen fluoride solution (concentration: 20wt%) and carry out silicon-hydrogenation, slowly vibration 30 minutes, obtains the silicon wafer of a large amount of silicon-hydrogen bond of surface coverage (Si-H).(3) silicon wafer obtained after above-mentioned process is put into the mixed solution (volume ratio=1:10) of silver nitrate (concentration: 1M) and hydrogen fluoride (concentration: 40wt%), slow vibration 30 minutes, enables the uniform growth in situ one deck Nano silver grain of silicon chip surface.(4) silicon wafer that the Nano silver grain obtained after above-mentioned process is modified is put into the mixed solution (volume ratio=1:10) of hydrogen peroxide (concentration: 40wt%) and hydrogen fluoride (concentration: 40wt%), slow vibration 30 minutes, can obtain the silicon nanowire array of silver nanoparticle deposition.(5) silicon nanowire array of the silver nanoparticle deposition obtained is put into nitric acid (concentration: 40wt%) solution, the reaction time is 30 minutes, and the Nano silver grain on removing silicon nanowire array surface, obtains silicon nanowire array.
B () golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified:
(1) immersed in hydrogen fluoride (concentration: 20wt%) solution by the silicon nanowire array prepared, the reaction time is 30 minutes, defines a large amount of Si-H keys on silicon nanowire array surface.(2) silicon nanowire array is put into gold chloride (concentration: 1M) solution, because Si-H key has very strong reductibility, the gold ion in solution can be reduced into golden nanometer particle, growth in situ is on silicon nanowire array surface.(3) react after 30 minutes, taken out by material, deionized water washs, and nitrogen dries up, and obtains the silicon nanowire array that golden nanometer particle is modified.
The SERS sensor of c silicon nanowire array that () golden nanometer particle is modified builds:
(1) silicon nanowire array that golden nanometer particle is modified is placed in reaction vessels, adds the solution of single stranded DNA (5 '-(Cy5)-TTCTTTCTTCCCCTTGTTTGTT-SH-3 ') (concentration: 1M), make solution submergence material.(2) reaction vessels is placed in constant temperature oscillation instrument, 400 rpms, 25 DEG C of constant temperature, reacts 12 hours, make DNA terminal sulfhydryl group and golden nanometer particle covalency form golden sulfide linkage, DNA is covalently attached on the silicon nanowire array of golden nanometer particle modification.(3) in solution, then divide the salt solusion adding 1M for 5 times to add once every 2 hours, make salt solusion ultimate density be 1M, spend the night aging.(4) taken out by material, deionized water washs, and nitrogen dries up, and obtains the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
Embodiment 5
A () hydrogen fluoride auxiliary etch method prepares silicon nanowire array:
(1) silicon wafer is carried out ultrasonic cleaning with deionized water, acetone, deionized water first successively, put into the concentrated sulphuric acid again and hydrogen peroxide (concentration: 40wt%) mixed solution (volume ratio=1:50) cleans further, and then by washed with de-ionized water, obtain clean silicon wafer.(2) inserted by the silicon wafer cleaned up in hydrogen fluoride solution (concentration: 30wt%) and carry out silicon-hydrogenation, slowly vibration 40 minutes, obtains the silicon wafer of a large amount of silicon-hydrogen bond of surface coverage (Si-H).(3) silicon wafer obtained after above-mentioned process is put into the mixed solution (volume ratio=1:50) of silver nitrate (concentration: 1M) and hydrogen fluoride (concentration: 40wt%), slow vibration 40 minutes, enables the uniform growth in situ one deck Nano silver grain of silicon chip surface.(4) silicon wafer that the Nano silver grain obtained after above-mentioned process is modified is put into the mixed solution (volume ratio=1:50) of hydrogen peroxide (concentration: 40wt%) and hydrogen fluoride (concentration: 40wt%), slow vibration 40 minutes, can obtain the silicon nanowire array of silver nanoparticle deposition.(5) silicon nanowire array of the silver nanoparticle deposition obtained is put into nitric acid (concentration: 50wt%) solution, the reaction time is 40 minutes, and the Nano silver grain on removing silicon nanowire array surface, obtains silicon nanowire array.
B () golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified:
(1) immersed in hydrogen fluoride (concentration: 30wt%) solution by the silicon nanowire array prepared, the reaction time is 40 minutes, defines a large amount of Si-H keys on silicon nanowire array surface.(2) silicon nanowire array is put into gold chloride (concentration: 5M) solution, because Si-H key has very strong reductibility, the gold ion in solution can be reduced into golden nanometer particle, growth in situ is on silicon nanowire array surface.(3) react after 40 minutes, taken out by material, deionized water washs, and nitrogen dries up, and obtains the silicon nanowire array that golden nanometer particle is modified.
The SERS sensor of c silicon nanowire array that () golden nanometer particle is modified builds:
(1) silicon nanowire array that golden nanometer particle is modified is placed in reaction vessels, adds the solution of single stranded DNA (5 '-(Cy5)-TTCTTTCTTCCCCTTGTTTGTT-SH-3 ') (concentration: 5M), make solution submergence material.(2) reaction vessels is placed in constant temperature oscillation instrument, 500 rpms, 25 DEG C of constant temperature, reacts 18 hours, make DNA terminal sulfhydryl group and golden nanometer particle covalency form golden sulfide linkage, DNA is covalently attached on the silicon nanowire array of golden nanometer particle modification.(3) in solution, then divide the salt solusion adding 1M for 5 times to add once every 2 hours, make salt solusion ultimate density be 5M, spend the night aging.(4) taken out by material, deionized water washs, and nitrogen dries up, and obtains the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
Embodiment 6
A () hydrogen fluoride auxiliary etch method prepares silicon nanowire array:
(1) silicon wafer is carried out ultrasonic cleaning with deionized water, acetone, deionized water first successively, put into the concentrated sulphuric acid again and hydrogen peroxide (concentration: 40wt%) mixed solution (volume ratio=1:100) cleans further, and then by washed with de-ionized water, obtain clean silicon wafer.(2) inserted by the silicon wafer cleaned up in hydrogen fluoride solution (concentration: 40wt%) and carry out silicon-hydrogenation, slowly vibration 60 minutes, obtains the silicon wafer of a large amount of silicon-hydrogen bond of surface coverage (Si-H).(3) silicon wafer obtained after above-mentioned process is put into the mixed solution (volume ratio=1:100) of silver nitrate (concentration: 1M) and hydrogen fluoride (concentration: 40wt%), slow vibration 60 minutes, enables the uniform growth in situ one deck Nano silver grain of silicon chip surface.(4) silicon wafer that the Nano silver grain obtained after above-mentioned process is modified is put into the mixed solution (volume ratio=1:100) of hydrogen peroxide (concentration: 40wt%) and hydrogen fluoride (concentration: 40wt%), slow vibration 60 minutes, can obtain the silicon nanowire array of silver nanoparticle deposition.(5) silicon nanowire array of the silver nanoparticle deposition obtained is put into nitric acid (concentration: 70wt%) solution, the reaction time is 60 minutes, and the Nano silver grain on removing silicon nanowire array surface, obtains silicon nanowire array.
B () golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified:
(1) immersed in hydrogen fluoride (concentration: 40wt%) solution by the silicon nanowire array prepared, the reaction time is 60 minutes, defines a large amount of Si-H keys on silicon nanowire array surface.(2) silicon nanowire array is put into gold chloride (concentration: 10M) solution, because Si-H key has very strong reductibility, the gold ion in solution can be reduced into golden nanometer particle, growth in situ is on silicon nanowire array surface.(3) react after 60 minutes, taken out by material, deionized water washs, and nitrogen dries up, and obtains the silicon nanowire array that golden nanometer particle is modified.
The SERS sensor of c silicon nanowire array that () golden nanometer particle is modified builds:
(1) silicon nanowire array that golden nanometer particle is modified is placed in reaction vessels, adds the solution of single stranded DNA (5 '-(Cy5)-TTCTTTCTTCCCCTTGTTTGTT-SH-3 ') (concentration: 10M), make solution submergence material.(2) reaction vessels is placed in constant temperature oscillation instrument, 600 rpms, 25 DEG C of constant temperature, reacts 24 hours, make DNA terminal sulfhydryl group and golden nanometer particle covalency form golden sulfide linkage, DNA is covalently attached on the silicon nanowire array of golden nanometer particle modification.(3) in solution, then divide the salt solusion adding 1M for 5 times to add once every 2 hours, make salt solusion ultimate density be 10M, spend the night aging.(4) taken out by material, deionized water washs, and nitrogen dries up, and obtains the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
What Fig. 6 represented is that simple lake water and deionized water sample directly detect with SERS sensor prepared by the present invention the data result obtained, and analyzes data and can learn in simple lake water containing a certain amount of mercury ion (Hg
2+).Now by contrasting with the data of Fig. 3, can find, the concentration of mercury ion the chances are 10pM in simple lake water.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
In addition, be to be understood that, although this instructions is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of instructions is only for clarity sake, those skilled in the art should by instructions integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (10)
1. quantitatively detect a preparation method for the SERS sensor of water sample ion concentration of mercury, it is characterized in that, comprise the steps:
A () hydrogen fluoride auxiliary etch prepares silicon nanowire array
(1) first silicon wafer is carried out ultrasonic cleaning with deionized water, acetone, deionized water successively, then put into the concentrated sulphuric acid and mixed solution of hydrogen peroxide cleans further, and then by washed with de-ionized water, obtain clean silicon wafer;
(2) silicon wafer that step (1) cleans up is inserted in hydrogen fluoride solution carry out oscillating reactions, obtain the silicon wafer of a large amount of silicon-hydrogen bond of surface coverage;
(3) silicon wafer that step (2) obtains is put into silver nitrate and hydrofluoric mixed solution oscillating reactions, obtain the silicon wafer of growth in situ one deck Nano silver grain of surface uniform;
(4) silicon wafer that Nano silver grain step (3) obtained is modified puts into hydrogen peroxide and hydrofluoric mixed solution oscillating reactions, obtains the silicon nanowire array of silver nanoparticle deposition;
(5) silicon nanowire array of silver nanoparticle deposition step (4) obtained is put into salpeter solution and is reacted, and the Nano silver grain on removing surface, obtains silicon nanowire array;
B () golden nanometer particle growth in situ prepares the silicon nanowire array that golden nanometer particle is modified
(1) silicon nanowire array step (a) prepared immerses in hydrogen fluoride solution and reacts, and defines a large amount of Si-H keys on silicon nanowire array surface;
(2) silicon nanowire array that step (1) obtains is put into chlorauric acid solution to react, taken out, dry up after deionized water washing, obtain the silicon nanowire array that golden nanometer particle is modified;
The SERS sensor of c silicon nanowire array that () golden nanometer particle is modified builds
(1) silicon nanowire array that golden nanometer particle step (b) prepared is modified is placed in reaction vessels, adds the single stranded DNA solution submergence that are rich in thymine alkali bases;
(2) reaction vessels is placed in constant temperature oscillation instrument stirring reaction, makes the single stranded DNA being rich in thymine alkali bases be covalently attached on the silicon nanowire array of golden nanometer particle modification;
(3) add salt solusion to gradation in the solution of step (2), make salt solusion ultimate density be 0.001 ~ 10M, spend the night aging;
(4) material is taken out, dry up after deionized water washing, obtain the SERS sensor of the silicon nanowire array that golden nanometer particle is modified.
2. preparation method according to claim 1, is characterized in that: in the step (1) of step (a), and described silicon wafer is p-type or the N-shaped silicon wafer of 0.01 ~ 20 Ω * cm.
3. preparation method according to claim 1, it is characterized in that: in the step (3) of step (a), described liquor argenti nitratis ophthalmicus concentration is 1M, and hydrogen fluoride solution mass concentration is 40%, liquor argenti nitratis ophthalmicus and hydrogen fluoride solution volume ratio=1:(0.01 ~ 100), the reaction time is 1 ~ 60 minute.
4. preparation method according to claim 1, it is characterized in that: in the step (4) of step (a), described superoxol mass concentration is 40%, hydrogen fluoride solution mass concentration is 40%, superoxol and hydrogen fluoride solution volume ratio=1:(0.01 ~ 100), the reaction time is 1 ~ 60 minute.
5. preparation method according to claim 1, is characterized in that: in the step (1) of step (b), described hydrogen fluoride solution mass concentration is 1 ~ 40%, and the reaction time is 1 ~ 60 minute.
6. preparation method according to claim 1, is characterized in that: in the step (2) of step (b), and the concentration of described chlorauric acid solution is 0.001 ~ 10 M, and the reaction time is 1 ~ 60 minute.
7. preparation method according to claim 1, is characterized in that: in the step (1) of step (c), the described concentration being rich in the single stranded DNA of thymine alkali bases is 0.001 ~ 10M.
8. preparation method according to claim 1, is characterized in that: in the step (2) of step (c), reaction vessels is placed in constant temperature oscillation instrument 100 ~ 600RPM, reaction 1 ~ 24 hour at 25 DEG C.
9. preparation method according to claim 1, it is characterized in that: in the step (3) of step (c), in the solution of step (2), divide the salt solusion adding 1M for 5 times to add once every 2 hours, in final solution, concentration of salt solution is 0.001 ~ 10M, spends the night aging.
10. the SERS sensor of the quantitative detection water sample ion concentration of mercury prepared by the preparation method described in any one of claim 1 ~ 9.
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