CN103868909A - Mushroom array type surface enhanced Raman spectrum active substrate and preparation method thereof - Google Patents
Mushroom array type surface enhanced Raman spectrum active substrate and preparation method thereof Download PDFInfo
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- CN103868909A CN103868909A CN201410096351.7A CN201410096351A CN103868909A CN 103868909 A CN103868909 A CN 103868909A CN 201410096351 A CN201410096351 A CN 201410096351A CN 103868909 A CN103868909 A CN 103868909A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a mushroom array type surface enhanced Raman spectrum active substrate and a preparation method of the mushroom array type surface enhanced Raman spectrum active substrate. The active substrate is a gold or silver mushroom nano-structure array. The preparation method comprises the following steps: impressing a through hole in a photoresist on the surface of a silicon or glass substrate with a gold film by using a nano-impressing technology; then performing electro-deposition to form the mushroom nano-structure array. The mushroom nano-structure array is mainly characterized in that the diameters of mushroom cap parts are 50-300nm; the distance between the caps is 0-50nm. According to the substrate, the enhancement effect of a Raman scattering signal can be greatly improved.
Description
Technical field
The invention belongs to Raman spectrum detection technique field, particularly the preparation method of simple, extensive, the low cost of process, high performance surface reinforced Raman active substrate.
Background technology
Nineteen twenty-eight India scientist C.V.Raman utilizes sunshine to observe the inelastic scattering phenomenon that scattered light occurrence frequency changes.This phenomenon is because incident photon and medium molecule generation energy exchange cause, and this energy exchange is relevant with electron cloud or chemical bond in molecule.Raman spectrum is broad-spectrum Non-Destructive Testing and molecular recognition technology, and it can provide chemistry and the finger print information of biomolecular structure.The discovery of Raman phenomenon has great meaning to scientific circles, but Raman signal is extremely faint, the defect of this inherent muting sensitivity had once restricted Raman spectrum of use in trace detection and Surface Science field, wanted Raman signal to study and nearly all will utilize certain enhancement effect.20 century 70 mid-terms, Fleischmann, VanDuyne, 3 seminar of Creighton leader observe respectively and have confirmed surface-enhanced Raman phenomenon, in solution, have strengthened approximately 10 than it at the Raman signal of the Pyridine Molecules of coarse silver electrode surface
6doubly.People by this due to the absorption of the species such as molecule or very near the surface with certain nanostructured, the phenomenon that its body phase molecule of its Raman signal intensity ratio significantly strengthens is called Surface enhanced raman spectroscopy (Surface enhanced Raman Scattering, SERS) effect.The discovery of SERS effect has solved the muting sensitivity problem that Raman spectrum exists in Surface Science and trace analysis effectively.The development of nanosecond science and technology has been injected new vigor to the application of SERS technology, the SERS signal of colloidal sol nanoparticle system can be amplified to 100,000,000,000,000 times, become important testing tool (the Shu MingNie et al.Science in unimolecule science, 1997,275,1102 – 1106), but the stability of colloidal sol nano particle substrate and the repeatability of preparation are poor.Therefore, prepare good stability, strengthen effective, have repeatable SRES substrate, be the emphasis of current research.In recent years, people start to attempt using nanometer embossing to prepare the SERS substrate of ordered structure, can realize like this batch, the low-cost production of SERS substrate, be well positioned to meet again the repeated requirement (Chinese patent CN103091983A) of SERS substrate to stability and preparation.But the spacing between the enhanced activity of raman spectral signal and nanostructured (or particle) has substantial connection, and along with the increase of spacing, be exponential damping.; theoretically; the spacing of nanostructured is less; enhanced activity is higher; conventionally require nanometer interval below 10 nanometers, and due to limitation (infiltration of photoresist to nanostructured, the eliminating of bubble of technology itself; maintenance of structure the etc. when demoulding), nanometer embossing cannot be prepared the array of structures of interval below 50 nanometers., utilize merely the enhancing effect of SERS substrate prepared by nanometer embossing unsatisfactory.
Summary of the invention
The object of the invention is to overcome the shortcoming of said method, a kind of mushroom metal Nano structure array surface-enhanced Raman scattering activity substrate and preparation method thereof be provided,
Technical scheme of the present invention is as follows:
A kind of surface-enhanced Raman scattering activity substrate, is characterized in that: it is provided with mushroom-shaped nanostructured metal array for smooth basal layer, the diameter of mushroom bacteria cover is 50-300 nanometer, and the distance between cap is 0-50 nanometer.
Smooth basal layer of the present invention can have the one in the glass, silicon chip, piezoid of metal level for electro-conductive glass or surperficial evaporation.Described metal level can be one or more in gold, silver, copper.
The metal of metal Nano structure array of the present invention can be one or more in gold, silver, copper.
Another technical scheme of the present invention is:
A preparation method for surface-enhanced Raman scattering activity substrate, comprises the steps:
1) there is the smooth substrate surface such as glass, silicon chip, piezoid of metal level to apply photoresist at surperficial evaporation,
2) adopt nanometer embossing and lithographic technique on photoresist, to prepare ordered nano through-hole structure;
3) utilize electrochemical method to be deposited on nanometer through hole plated metal gold, silver or copper, and make outside its overfolw hole, form cap shape.Together with the column of through hole, overall shape is as mushroom;
4) remove nano-imprint lithography glue, obtain the surface enhanced Raman scattering substrate of orderly mushroom nanostructured metal array.
Wherein: step (2) preferably includes: use nano impression system, first adopt hot press printing technology, taking nickel template as mother matrix, by hot padding, its surface nano-structure is copied to dimethyl silicone polymer mantle surface; Then adopt ultraviolet stamping technology, use spin coating instrument, nano impression glue is spin-coated on to the silicon chip surface of gold evaporation film;
At nano impression glue surface ultraviolet stamping, obtain nano-pore structure taking dimethyl silicone polymer mantle as mother matrix; Re-use plasma etching machine and remove the cull layer after ultraviolet stamping, expose metal in the bottom of nano-pore.
Wherein, step (3) preferably includes: the effective mass mark of GOLD FROM PLATING SOLUTION is at 0.01-1%, and solution PH is 1-6, under 20-70 DEG C of condition, carry out continuous current or constant potential electro-deposition taking the nano impression glue after ultraviolet stamping as template restraining barrier, sedimentation time is 300-1200s;
Use microwave plasma resist remover to remove nano impression glue restraining barrier, finally obtain the surface enhanced Raman scattering substrate of orderly gold nano structure;
Adopt microwave plasma etching machine, after prepared by mushroom array electric deposition, remove nano impression glue restraining barrier, obtain orderly gold nano mushroom array.
Wherein, the more preferably 0.01-0.5% of effective mass mark of GOLD FROM PLATING SOLUTION, solution PH is 2-5 more preferably, and temperature is 40-50 DEG C more preferably, and sedimentation time is 400-1000s more preferably.
When continuous current, current density is 1-5mA/cm2, more preferably 1-3mA/cm2.
The voltage of constant potential is-2V-2V, more preferably-0.9V-0.6V.
Compared with prior art, tool has the following advantages in the present invention:
1, to have prepared the diameter of mushroom bacteria cover be 50-300 nanometer in the present invention, and the distance between cap is the nanostructured metal array of 0-50 nanometer.
2, preparation method of the present invention combine can be on a large scale, low cost prepares the nano impression of nano-structure array and can control the electrochemical deposition advantage of nanostructured size, both the repeatability of method and the homogeneity of array had been ensured, significantly dwindle again the spacing at metal nano interval, thereby increased substantially the enhancing effect of Raman scattering signal.The enhancer of the Surface enhanced raman spectroscopy of prepared mushroom array substrate to 4-mercaptopyridine molecule is 108.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is surface-enhanced Raman scattering activity substrate preparation technology schematic flow sheet;
Fig. 2 and Fig. 3 are the SEM photo that embodiment 2 removes nano impression glue restraining barrier after ultraviolet stamping cull;
Fig. 4 and Fig. 5 are embodiment 3 prepares surface-enhanced Raman scattering activity substrate SEM photo taking gold as deposition layer;
Fig. 6 be embodiment 4 taking 1mM4-mercaptopyridine as testing molecule, prepare surface-enhanced Raman scattering activity substrate taking gold as deposition layer, by the Portable Raman spectrometer of 785nm exciting light test obtain spectrogram;
Fig. 7 and Fig. 8 are embodiment 5 prepares surface-enhanced Raman scattering activity substrate SEM photo taking gold as deposition layer;
Fig. 9 and Figure 10 are embodiment 6 prepares surface-enhanced Raman scattering activity substrate SEM photo taking gold as deposition layer.
Embodiment
Utilizing electron beam evaporation plating technology, is the circular silicon chip surface deposition layer of gold film of two inches at the diameter after standard cleaning, and its thickness is 200nm.Standard cleaning step: 1. preparation H
2sO
4: H
2o
2=1:4 solution, takes advantage of silicon chip to put into, digestion 15 minutes with quartz boat.Hot deionized water clean, after change cold washed with de-ionized water.2. silicon chip is placed in to HF solution (HF:H
2o=1:1) in, soak 30 seconds, take out backlash deionized water 15 minutes.3. with solution (NH
4oH:H
2o
2: H
2o=1:1:5) boil cleaning: first deionized water in beaker is heated to 85 DEG C, pours the NH of corresponding proportion into
4oH and H
2o
2solution, boils 15 minutes, take out for hot deionized water clean, after change cold washed with de-ionized water.4. silicon chip is placed in to the HF solution (HF:H of dilution
2o=1:20) in, soak 20 seconds, rush hot deionized water 15 minutes.5. with solution (HCl:H
2o
2: H
2o=1:1:5) boil cleaning: first deionized water is heated to 85 DEG C, pours HCl and the H of corresponding proportion into
2o
2solution, boils 15 minutes, take out for hot deionized water clean, after change cold washed with de-ionized water.6. use nitrogen the silicon wafer blow-drying of wash clean.
Adopt Temescal2000 electron beam evaporation system, with
rate of sedimentation, at the thick chromium of silicon chip surface evaporation one deck 30nm as tack coat; Then with
rate of sedimentation, at chromium layer surface evaporation one deck 200nm gold.
Embodiment 2
Adopt combined type nanometer embossing to print off ordered nano hole shape structure plan in golden film surface pressure, nano-pore structure diameter is 200nm, and its cycle is 400nm:
Use Obducat Eitre6 type nano impression system, first adopt hot press printing technology, with nano-pore diameter 200nm, two inches of nickel templates of cycle 400nm are mother matrix, by hot padding, its surface nano-structure are copied to dimethyl silicone polymer mantle surface; Then adopt ultraviolet stamping technology, use G3P-8 type spin coating instrument, TU2-170 nano impression glue is spin-coated on to the silicon chip surface of evaporation 200nm gold film, nano impression glue THICKNESS CONTROL is at 200nm, taking dimethyl silicone polymer mantle as mother matrix at nano impression glue surface ultraviolet stamping, obtaining diameter is 200nm, the nano-pore structure that the cycle is 400nm; Re-use AMS200 plasma etching machine and remove the cull layer after ultraviolet stamping, expose gold in the bottom of nano-pore.Its Electronic Speculum figure is shown in Fig. 2 and Fig. 3, and the useful area of nanostructured is about 20 square centimeters.
Embodiment 3
Utilize electrochemical method deposited gold, use galvanostatic method, control deposition electric weight, deposited gold on embodiment 2 bases, makes the gold of electro-deposition grow nano-pore, and shape, as mushroom, is specially:
Adopt the saturated sodium bisulfite solution of gold sodium sulfide, taking potassium dihydrogen phosphate (9% massfraction), sodium citrate (4% massfraction) as electroplating additive, the effective mass mark of GOLD FROM PLATING SOLUTION is 0.2%, solution PH is 4.5, under 45 DEG C of conditions, current density size is 2mA/cm2, taking the nano impression glue after ultraviolet stamping as template restraining barrier, use CHI760E to carry out continuous current electro-deposition, sedimentation time is 660s.
Use Alpha microwave plasma resist remover to remove nano impression glue restraining barrier, finally obtain the surface enhanced Raman scattering substrate of orderly gold nano structure;
Adopt Q240Alpha microwave plasma etching machine, after prepared by mushroom array electric deposition, remove nano impression glue restraining barrier, power 300W, operation pressure 20Pa, time 2min, obtains orderly gold nano mushroom array.
The diameter of the mushroom bacteria cover that the present embodiment is prepared is about 50-300 nanometer, and the distance between cap is about 0-50 nanometer." stem " is highly about 10-200 nanometer.Its Electronic Speculum figure is shown in Fig. 4 and Fig. 5, and the useful area of mushroom array is about 20 square centimeters.
Embodiment 4
Get 5uL1mM4-mercaptopyridine aqueous solution and drop in the prepared surface enhanced Raman scattering substrate surface of embodiment 3, dry rear a large amount of ultrapure waters flushings that use, nitrogen dries up, and tests by the Portable Raman spectrometer of 785nm exciting light.It the results are shown in Figure 6, and the enhancer of the Surface enhanced raman spectroscopy of prepared mushroom array substrate to 4-mercaptopyridine molecule is 108.
Embodiment 5
Utilize electrochemical method deposited gold, use potentiostatic method, control deposition electric weight, the gold that embodiment 2 is deposited grows nano-pore, and shape, as mushroom, is specially.
Adopt the saturated sodium bisulfite solution of gold sodium sulfide, taking potassium dihydrogen phosphate (9% massfraction), sodium citrate (4% massfraction) as electroplating additive, the effective mass mark of GOLD FROM PLATING SOLUTION is 0.2%, solution PH is 4.5, under 45 DEG C of conditions, constant potential-0.9V electro-deposition, taking the nano impression glue after ultraviolet stamping as template restraining barrier, use CHI760E to carry out constant potential electro-deposition, sedimentation time is 400s.
The diameter of the mushroom bacteria cover that the present embodiment is prepared is about 50-300 nanometer, and the distance between cap is about 0-50 nanometer." stem " is highly about 10-200 nanometer.Its Electronic Speculum figure is shown in Fig. 7 and Fig. 8, and the useful area of mushroom array is about 20 square centimeters.
Embodiment 6
Basic identical with embodiment 5, difference is
Adopting the potassium auricyanide solution of 3g/L is electroplate liquid, massfraction is that 1% sodium citrate is adjuvant, solution pH value is about 4.0, the effective mass mark of GOLD FROM PLATING SOLUTION is 0.2%, under 55 DEG C of conditions, and continuous current electro-deposition, current density size is 3mA/cm2, taking the nano impression glue after ultraviolet stamping as template restraining barrier, use CHI760E to carry out continuous current electro-deposition, sedimentation time is 300s.
The diameter of the mushroom bacteria cover that the present embodiment is prepared is about 50-300 nanometer, and the distance between cap is 0-50 nanometer." stem " is highly about 10-200 nanometer.Its Electronic Speculum figure is shown in Fig. 9 and Figure 10.
Embodiment 7
Basic identical with embodiment 5, difference is
Adopting 1mM aqueous solution of chloraurate is electroplate liquid, sodium perchlorate taking massfraction as 1.5% is as adjuvant, the effective mass mark of GOLD FROM PLATING SOLUTION is 0.02%, solution pH value is about 2, under 50 DEG C of conditions, and constant potential electro-deposition, sedimentation potential is 0.6V, taking the nano impression glue after ultraviolet stamping as template restraining barrier, use CHI760E to carry out constant potential electro-deposition, sedimentation time is 560s.
The diameter of the mushroom bacteria cover that the present embodiment is prepared is about 50-300 nanometer, and the distance between cap is 0-50 nanometer." stem " is highly about 10-200 nanometer.
Embodiment 8
Basic identical with embodiment 5, difference is
Adopting 1mM aqueous solution of chloraurate is electroplate liquid, solution pH value is about 2, the effective mass mark of GOLD FROM PLATING SOLUTION is 0.02%, under 50 DEG C of conditions, continuous current electro-deposition, current density size is 1.6mA/cm2, taking the nano impression glue after ultraviolet stamping as template restraining barrier, use CHI760E to carry out continuous current electro-deposition, sedimentation time is 1000s.
The diameter of the mushroom bacteria cover that the present embodiment is prepared is about 50-300 nanometer, and the distance between cap is 0-50 nanometer." stem " is highly about 10-200 nanometer.
Finally explanation, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, with reference to embodiment, the present invention is had been described in detail, and those of ordinary skill in the art is to be understood that.Technical scheme of the present invention is modified or is equal to replacement, and do not depart from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (10)
1. a surface-enhanced Raman scattering activity substrate, is characterized in that: it is provided with mushroom-shaped nanostructured metal array for smooth basal layer, and the diameter of mushroom bacteria cover is 50-300 nanometer, and the distance between cap is 0-50 nanometer.
2. by surface-enhanced Raman scattering activity substrate claimed in claim 1, it is characterized in that: described smooth basal layer is the one in electro-conductive glass or the surperficial evaporation glass that has metal level, silicon chip, piezoid.
3. by surface-enhanced Raman scattering activity substrate claimed in claim 1, it is characterized in that: the metal of described metal Nano structure array is one or more in gold, silver, copper.
4. a preparation method for surface-enhanced Raman scattering activity substrate, comprises the steps:
1) there is the smooth substrate surface of metal level to apply photoresist at surperficial evaporation,
2) adopt nanometer embossing and lithographic technique on photoresist, to prepare ordered nano through-hole structure;
3) utilize electrochemical method at nanometer through hole plated metal gold, silver or copper, and make outside its overfolw hole, form cap shape, together with the column of through hole, overall shape is as mushroom;
4) remove nano-imprint lithography glue, obtain the surface enhanced Raman scattering substrate of orderly mushroom nanostructured metal array.
5. the preparation method of a kind of surface-enhanced Raman scattering activity substrate as claimed in claim 4, it is characterized in that: step (2) comprising: use nano impression system, first adopt hot press printing technology, taking nickel template as mother matrix, by hot padding, its surface nano-structure is copied to dimethyl silicone polymer mantle surface; Then adopt ultraviolet stamping technology, use spin coating instrument, nano impression glue is spin-coated on to the silicon chip surface of gold evaporation film;
At nano impression glue surface ultraviolet stamping, obtain nano-pore structure taking dimethyl silicone polymer mantle as mother matrix; Re-use plasma etching machine and remove the cull layer after ultraviolet stamping, expose metal in the bottom of nano-pore.
6. the preparation method of a kind of surface-enhanced Raman scattering activity substrate as claimed in claim 4, it is characterized in that: step (3) comprising: for the effective mass mark of the GOLD FROM PLATING SOLUTION of electro-deposition at 0.01-1%, solution PH is 1-6, under 20-70 DEG C of condition, carry out continuous current or constant potential electro-deposition taking the nano impression glue after ultraviolet stamping as template restraining barrier, sedimentation time is 300-1200s;
Use microwave plasma resist remover to remove nano impression glue restraining barrier, finally obtain the surface enhanced Raman scattering substrate of orderly gold nano structure;
Adopt microwave plasma etching machine, after prepared by mushroom array electric deposition, remove nano impression glue restraining barrier, obtain orderly gold nano mushroom array.
7. by the preparation method of surface-enhanced Raman scattering activity substrate claimed in claim 6, it is characterized in that: when continuous current, current density is 1-5mA/cm2.
8. by the preparation method of surface-enhanced Raman scattering activity substrate claimed in claim 6, it is characterized in that: the voltage of constant potential is-2V-2V.
9. by the preparation method of surface-enhanced Raman scattering activity substrate claimed in claim 4, it is characterized in that: described smooth basal layer is the one in electro-conductive glass or the surperficial evaporation glass that has metal level, silicon chip, piezoid.
10. by the preparation method of surface-enhanced Raman scattering activity substrate claimed in claim 4, it is characterized in that: the metal of described metal Nano structure array is one or more in gold, silver, copper.
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| PCT/CN2015/073856 WO2015135450A1 (en) | 2014-03-14 | 2015-03-09 | Mushroom array type surface enhanced raman spectrum active substrate and preparation method |
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