CN103451610B - Novel bionic Raman spectrum base and preparation method thereof - Google Patents
Novel bionic Raman spectrum base and preparation method thereof Download PDFInfo
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- CN103451610B CN103451610B CN201310396521.9A CN201310396521A CN103451610B CN 103451610 B CN103451610 B CN 103451610B CN 201310396521 A CN201310396521 A CN 201310396521A CN 103451610 B CN103451610 B CN 103451610B
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Abstract
The invention discloses a kind of novel surface and strengthen raman spectrum substrate and preparation method thereof.This substrate is prepared by following method: 1) pre-treatment of raw material: by ultrasonicly for cicada wing cleaning, removing vein, be cut into fritter, after fixing, smooth, as biological template; 2) substrate preparation: the biological template obtained after step 1) pre-treatment is put into direct-current ion sputtering instrument, under an inert atmosphere, with high-purity precious metal for target, adopt intermittent type sputtering mode by precious metal sputtering sedimentation on biological template, Novel bionic Raman spectrum base; Described high-purity precious metal refers to that purity is gold and/or the silver of >=99.99%; After described intermittent type sputtering mode refers to and often sputters 45 ~ 75s, rest 45 ~ 75s immediately, each sputtering, the process of resting are collectively referred to as one-period.The present invention with abundance, the substrate not only clean surface of draw materials conveniently, process two dimension that simple cicada wing goes out for Template preparation or three-dimensional, and enhancement factor is high, favorable reproducibility, stability are strong.
Description
Technical field
The invention belongs to Raman spectroscopy and technical field of nano material, be specifically related to a kind of Novel bionic Raman spectrum base and preparation method thereof.
Background technology
Since 20 century 70s are found mid-term, surface enhanced Raman scattering (SERS) technology, with narrow, highly sensitive, the anti-light bleaching of the bands of a spectrum of its uniqueness, original position, harmless and can provide the advantages such as finger printing information, obtains in various fields such as biomedicine, Surface Science, molecular recognition, trace detection and applies more and more widely.Raman spectrum base can significantly improve the Raman signal of molecule by Electromagnetic enhancement effect, makes to be adsorbed in strengthen suprabasil Molecular Raman signal than common molecular Raman signal enhancing about 10
4-10
7doubly; By the surface plasma resonance effect that the substrate of coupling noble metal nano produces, the detection sensitivity of single molecules level even can be reached.Prepare with low cost, method is easy, highly sensitive, that favorable reproducibility, stability are strong Raman spectrum base promotes SERS technology to further develop, realize SERS technology and be widely used in one of the key in analyzing and testing field.
Up to now, document has reported the method for multiple structure Raman spectrum base, as electrochemical activation, chemical etching, molecule assembling, nano lithography, beamwriter lithography etc.But these methods have certain limitation, as: preparation process easily pollutes environment is unfriendly, preparative-scale and cost and sensitivity, circulation ratio, stability are often difficult to take into account by the impact of many factors, therefore constrain SERS technology and apply more widely.In addition, in the Raman spectrum base reported, traditional 1D(one dimension) substrate, as colloidal sol nanoparticle and aggregate thereof, the reinforced effects produced is comparatively strong, but its signal randomness is comparatively large, circulation ratio is poor.Conventional 2D(two dimension) substrate, as nanometer ball array, nanometer stick array, nano-wire array etc., although have good signal reproducibility, Comparatively speaking its density strengthening focus has much room for improvement.The people (Nanotechnology, 2006,17,680) such as such as P.R.Stoddart utilize electron beam deposition technique gold and silver layer on cicada wing pan coating, have prepared the bionical substrate of 2D.But the plant and instrument needed for this method is expensive, preparation cost is high, and obtained substrate hotspot density is low, reinforced effects is general.Emerging 3D(is three-dimensional) substrate; as modified the silicon nano column array, glass nano post array, ZnO nano columnar arrays, carbon nano pipe array etc. of noble metal nano particles; although can provide highdensity enhancing focus and good signal reproducibility, its complex manufacturing process, cost be higher, be difficult to large-scale production.Therefore, be badly in need of the construction process of the new Raman spectrum base of development, the Raman spectrum base that prepare with low cost, excellent property, can be mass-produced, meets fast with this, demand that sensitive analysis detects, promotes SERS technology development.
Summary of the invention
A technical problem to be solved by this invention is for the deficiencies in the prior art, provides that a kind of highly sensitive, favorable reproducibility, stability are strong, the Novel bionic surface enhanced Raman scattering substrate of clean surface.
Another technical problem to be solved of the present invention is to provide a kind of easy, cheap, environmental friendliness, can prepares the method for various dimensions Novel bionic Raman spectrum base on a large scale.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
Preparation method of the present invention comprises the following steps:
(1) pre-treatment of raw material: by ultrasonicly for cicada wing cleaning, removing vein, be cut into fritter, after fixing, smooth, as biological template;
(2) substrate preparation: the biological template obtained after step (1) pre-treatment is put into direct-current ion sputtering instrument, under protection of inert gas, with high-purity precious metal for target, adopt intermittent type sputtering mode by precious metal sputtering sedimentation on biological template, Novel bionic Raman spectrum base; Described high-purity precious metal refers to that purity is gold and/or the silver of >=99.99%; After described intermittent type sputtering mode refers to and often sputters 45 ~ 75s, rest 45 ~ 75s immediately, each sputtering, the process of resting are collectively referred to as one-period.
Further, in described step (2), the condition of sputtering is: sputtering pressure is 8 ~ 10 handkerchiefs, and sputtering current is 4 ~ 6 milliamperes, and sputter rate is 3.0 ~ 4.0 nm/minute, and the sputtering cycle is 8 ~ 20.
Further, in described step (2), described high-purity precious metal is Jin Heyin, and intermittent type sputter procedure is after first sputtering 2 ~ 4 cycle High Purity Gold, then sputters 12 ~ 14 cycle high purity silvers.
Further, in described step (2), described high-purity precious metal is silver.
Further, in described step (2), described sputter rate is 3.6 ~ 4.0 nm/minute.
The present invention has the following advantages:
1) the present invention with abundance, draw materials conveniently, process simple cicada wing for biological template, preparation enhancement factor is high, favorable reproducibility, stability strong, the Raman spectrum base of clean surface, the LASER Light Source of available wide spectrum excites, and has significant surface Raman enhancement effect to the analyte of different concns.
2) the inventive method (manufacturing cost of the substrate of every sheet 4 × 4 square millimeters is 0.5 yuan) easy and simple to handle, with low cost, environmental friendliness, efficiency higher (starting material cicada wing is prepared into complete Raman spectrum base and is no more than 1 hour), the Raman spectrum base preparation method that do not use any reagent, can be mass-produced, mass-produce the substrate of excellent property, and the favorable repeatability of preparation method, be easy to industrialization.
3) the present invention is by changing traditional continuity sputtering mode into intermittent type sputtering mode; cicada wing not only can be protected to avoid being damaged in long-time sputter procedure; and when taking argent as target, intermittent type sputtering mode can also prepare the three-dimensional bionic Raman spectrum base of high-density focus.
4) the present invention is based on cicada wing surface chitin nanometer columnar arrays, under certain sputtering condition, not only can prepare the nanometer cylindrical substrate that the gap of the precious metal bag quilt of two dimension is adjustable, also can prepare the substrate that three-dimensional high-density Nano silver grain is modified.
Accompanying drawing explanation
Fig. 1 is that cicada wing microtexture SEM schemes, wherein the corresponding SEM vertical view of a, the corresponding SEM oblique drawing of b.
Fig. 2 is Raman spectrum base SEM figure prepared by the present invention, wherein two dimension bionical substrate SEM vertical view, the sectional view of the corresponding Jin Bao quilt of a, d, two dimension bionical substrate SEM vertical view, the sectional view of the corresponding silver-colored bag quilt of b, e, the corresponding silver particles of c, f modifies three-dimensional bionic substrate SEM vertical view, sectional view.
Fig. 3 is take high purity silver as target, the bionical substrate SEM prepared under different sputtering condition schemes, wherein a is for being 6 handkerchiefs at sputtering pressure, sputtering current is the SEM sectional view that the condition of 6 milliamperes carries out that intermittent type sputters the bionical substrate of two dimension of fine silver bag quilt prepared by 8 cycles, and b is the SEM sectional view that continuity sputters the three-dimensional bionic substrate of fine silver bag quilt prepared by 14 cycles.
Fig. 4 is the enhancement factor scaling system of bionical substrate prepared by the present invention, wherein the SERS spectrogram of the corresponding different bionical substrate of a under 633 nanometer lasers excite, the enhancement factor calculation result of the corresponding different bionical substrate of b under 514,633 and 785 nanometer lasers excite.
Fig. 5 is the reproducibility test pattern of bionical substrate prepared by the present invention, wherein the bionical substrate of two dimension of a, the b corresponding Jin Bao quilt of difference and silver-colored bag quilt, and the corresponding silver particles of c modifies three-dimensional bionic substrate.
Fig. 6 is the stability test figure of bionical substrate prepared by the present invention, wherein the bionical substrate of two dimension of a, the b corresponding Jin Bao quilt of difference and silver-colored bag quilt, the three-dimensional bionic substrate that the corresponding silver particles of c is modified.
Embodiment
Embodiment 1: Jin Bao is strengthened the preparation of raman spectrum substrate by two-dimentional bionic surface
1) pre-treatment of raw material: choose totally transparent black cicada (CryptotympanaatrataFabricius) fore wing, with ultrapure water ultrasonic cleaning 5 minutes, dry rear scalpel in air cicada wing vein is removed and is cut into the fritter of 4 × 4 square millimeters, then being fixed on tweezers is stained with on the slide glass of double faced adhesive tape, brush smooth with rubber suction bulb, with this as biological template.
2) substrate preparation: prepared biological template is put into direct-current ion sputtering instrument (ETD-3000); with high-purity argon gas (99.999%) for protection gas; with High Purity Gold (99.99%) for target; sputtering pressure is 10 handkerchiefs; sputtering current is 4 milliamperes, and sputter rate is 3.0 ~ 4.0 nanometers per minute, is preferably 3.6 ~ 4.0 nanometers per minute; adopt intermittent type sputtering mode (sputtering in a minute rests for a minute subsequently), sputtering 8 ~ 20 cycles can regulate Gold plated Layer microtexture.As shown in Fig. 2 a and 2d, sputter the column two dimension bionic surface that gap that 16 all after dates prepare Jin Bao quilt is less than 10 nanometers and strengthen raman spectrum substrate (namely two-dimensional gold wraps up substrate).Institute's plated thickness is about 60 nanometers.
3) performance test: select thiophenol to be the calculating that probe molecule carries out enhancement factor (EnhancementFactor).Prepared substrate to be soaked in the thiophenol ethanolic soln that 10 mmoles often rise 12 hours, then to use straight alcohol washes clean, make substrate surface form thiophenol unimolecular layer fine and close continuously.Its calculation formula is EF=I
sERSn
bulk/ I
bulkn
sERS, wherein I
sERSand I
bulkcorrespond respectively to thiophenol molecule at 1578cm
-1the SERS spectral intensity at place and 1583cm
-1the normal Raman spectroscopy intensity at place; N
sERSand N
bulkcorrespond respectively to the molecule number in laser facula when testing SERS and normal Raman spectroscopy.Adopt Renishawinvia confocal laser microscopic Raman system in test, excitation wavelength adopts 514 nanometers, 633 nanometers, 785 nanometer laser light sources, and spot diameter is about 2.0 microns, and power used is respectively 1.5 milliwatts, 1.0 milliwatts, 25.0 milliwatts.Wherein, the SERS spectrum of made substrate unimolecular layer thiophenol excites for 633 nanometers, and all enhancement factor calculation result as shown in Figure 4.Under 785 nanometer lasers excite, Jin Bao can be reached 10 by the enhancement factor that two-dimentional bionic surface strengthens raman spectrum substrate
6level.Reproducibility test selects rhodamine 6G to be probe molecule, substrate to be soaked in the rhodamine 6G aqueous solution that 1 micromole often rises 30 minutes, dry in atmosphere after cleaning with ultrapure water, 633 nanometer lasers are adopted to excite, utilize Raman mapping function, step is 2 microns, chooses 20 × 20 points and characterizes.As shown in Figure 5 a, prepared Jin Bao is strengthened raman spectrum substrate by two-dimentional bionic surface and has good homogeneity and signal reproducibility.Prepared substrate is out placed in vacuum drying tank and preserves 1 ~ 4 week respectively by stability test, after taking-up, just substrate to be soaked in the rhodamine 6G aqueous solution that 1 micromole often rises 30 minutes, dry in atmosphere after cleaning with ultrapure water, 633 nanometer lasers are adopted to excite, the change of contrast rhodamine 6G SERS strength of signal.As shown in Figure 6 a, the substrate after preserving 4 weeks in vacuum drying tank is lost without obvious enhanced activity.Above-mentioned all test employings 50 times of object lens, the condition of 10 second time shutter and 1 integration.
Embodiment 2: silver bag is strengthened the preparation of raman spectrum substrate by two-dimentional bionic surface
1) pre-treatment of raw material: with step 1) in embodiment 1.
2) substrate preparation: sputtering condition and mode are with step 2 in embodiment 1) described in.First intermittent type sputters the layer gold in 2 cycles, then uses high purity silver (99.99%) target, sputters 12 ~ 14 cycles to regulate silvered film microtexture.As shown in Fig. 2 b and 2e, the gap of preparing silver-colored bag quilt after sputtering 13 cycle silver is less than the column two dimension bionic surface enhancing raman spectrum substrate (i.e. two dimension silver parcel substrate) of 10 nanometers.Comparatively speaking, be 6 handkerchiefs at sputtering pressure, sputtering current is under the condition of 6 milliamperes, carries out intermittent type and sputters two-dimentional bionic surface enhancing raman spectrum substrate (i.e. the bionical substrate of the two dimension of fine silver bag quilt) that 8 cycles also can prepare fine silver bag quilt, as shown in Figure 3 a.But under this condition, the repeatability of its operation and the controllability of microtexture thereof are compared poor, should not adopt.
3) performance test: enhancement factor calculates with embodiment 1, and acquired results as shown in Figure 4 b.Under 633 and 785 nanometer lasers excite, silver bag has all been exceeded 10 by the enhancement factor that two-dimentional bionic surface strengthens raman spectrum substrate
6, and all comparatively Jin Bao is wanted high by two-dimentional bionic surface enhancing raman spectrum substrate.Reproducibility test is with embodiment 1, and acquired results as shown in Figure 5 b.Stability test is with embodiment 1, and acquired results as shown in Figure 6 b.Data show that prepared silver bag is strengthened raman spectrum substrate by two-dimentional bionic surface and has good homogeneity, signal reproducibility and stability.
Embodiment 3: silver particles modifies the preparation of three-dimensional bionic Raman spectrum base
1) pre-treatment of raw material: with step 1) in embodiment 1.Cicada wing surface due to black cicada has quasi-regular chitin nanometer column array junctions, and its chitin pillar is wide at the top and narrow at the bottom, top diameter about 60 nanometer, base diameter about 120 nanometer, height about 180 nanometer, gap about 80 nanometer between two pillar tops.In the process of the three-dimensional bionic Raman spectrum base of preparation silver particles modification, this special microtexture contributes to the formation of silver particles.
2) substrate preparation: sputtering condition and mode are with step 2 in embodiment 1) described in.8 ~ 20 cycles of the silver-colored target as sputter of direct use can regulate nano grain of silver sublayer microtexture.As shown in Fig. 2 c and 2f, after the silver in 14 cycles of sputtering, can prepare nano grain of silver sublayer modify columnar arrays, form island structure at chitin nano-pillar sidewall and form flower-like structure on its top, the gap of silver particles is less than 10 nanometers, forms three-dimensional bionic Raman spectrum base (namely three-dimensional silver particle modifies substrate).Comparatively speaking, under identical sputtering condition, adopt the sputtering mode of continous way, the island structure formed at chitin nano-pillar sidewall is less, flower-like structure (being the three-dimensional bionic substrate of the fine silver bag quilt that this continous way sputtering mode obtains as shown in Figure 3 b) is not formed on its top yet, and Comparatively speaking the nano gap formed also will lack, therefore, the SERS reinforced effects produced is more weak.Therefore, we adopt the sputtering mode of interval type to form more highdensity Nano silver grain in chitin nano-pillar, prepare highly active three-dimensional bionic Raman spectrum base with this.
3) performance test: enhancement factor calculates with embodiment 1, and acquired results as shown in Figure 4.Under three kinds of laser excitation, the golden and silver-colored bag of the silver particles enhancement factor of three-dimensional bionic Raman spectrum base of modifying will at least one order of magnitude of height by two-dimentional bionic surface enhancing raman spectrum substrate.Even under 785 nanometer lasers excite, the enhancement factor of the three-dimensional bionic Raman spectrum base that silver particles is modified can reach 5 × 10
7more than level, the result reported than people (Nanotechnology, 2006,17,680) such as P.R.Stoddart before wants high more than 50 times.Reproducibility test is with embodiment 1, and acquired results as shown in Figure 5 c.Stability test is with embodiment 1, and acquired results as fig. 6 c.Data show that the three-dimensional bionic Raman spectrum base that prepared silver particles is modified has good homogeneity, signal reproducibility and stability.
Claims (4)
1. a preparation method for Novel bionic surface enhanced Raman scattering substrate, is characterized in that: comprise the steps:
1) pre-treatment of raw material: by ultrasonicly for cicada wing cleaning, removing vein, be cut into fritter, after fixing, smooth, as biological template;
2) substrate preparation: by through step 1) biological template that obtains after pre-treatment puts into direct-current ion sputtering instrument, under protection of inert gas, with high-purity precious metal for target, adopt intermittent type sputtering mode by precious metal sputtering sedimentation on biological template, Novel bionic Raman spectrum base; Described high-purity precious metal refers to that purity is gold and/or the silver of >=99.99%; After described intermittent type sputtering mode refers to and often sputters 45 ~ 75s, rest 45 ~ 75s immediately, each sputtering and the process of resting are collectively referred to as one-period; The condition of sputtering is: sputtering pressure is 8 ~ 10 handkerchiefs, and sputtering current is 4 ~ 6 milliamperes, and sputter rate is 3.0 ~ 4.0 nm/minute, and the sputtering cycle is 8 ~ 20.
2. the preparation method of Novel bionic surface enhanced Raman scattering substrate according to claim 1, it is characterized in that: described step 2) in, described high-purity precious metal is Jin Heyin, and intermittent type sputter procedure is after first sputtering 2 ~ 4 cycle High Purity Gold, then sputters 12 ~ 14 cycle high purity silvers.
3. the preparation method of a kind of Novel bionic surface enhanced Raman scattering substrate according to claim 2, is characterized in that: described step 2) in, described high-purity precious metal is silver.
4. the preparation method of a kind of Novel bionic surface enhanced Raman scattering substrate according to claim 1 and 2, is characterized in that: described step 2) in, sputter rate is 3.6 ~ 4.0 nm/minute.
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| CN105331943B (en) * | 2015-11-09 | 2017-10-27 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method for obtaining Raman enhancing substrate is modified based on cosputtering post-etching |
| CN105821398B (en) * | 2016-03-21 | 2019-01-11 | 上海交通大学 | The preparation method and applications of the periodical metal material of connection structure in co-continuous |
| CN105954254B (en) * | 2016-04-26 | 2019-02-19 | 中国科学院生态环境研究中心 | A kind of preparation method of surface enhanced Raman substrate |
| CN107101992A (en) * | 2017-06-01 | 2017-08-29 | 中国农业大学 | A kind of preparation method of D-type optical fiber surface-enhanced Raman probe |
| CN107937957B (en) * | 2017-11-23 | 2020-05-26 | 华中农业大学 | Preparation method of surface-enhanced Raman substrate and application of substrate in detection of animal viruses |
| CN107991281B (en) * | 2017-11-23 | 2020-05-26 | 华中农业大学 | Preparation method of flexible SERS substrate and application of flexible SERS substrate in specificity detection of PAT |
| CN108982464A (en) * | 2018-04-17 | 2018-12-11 | 中国科学院合肥物质科学研究院 | A kind of high distribution density nano gap oldered array and the preparation method and application thereof |
| CN109161849B (en) * | 2018-07-19 | 2019-10-11 | 西安交通大学 | A kind of ordered porous array and preparation method thereof of silver tantalum composite material building |
| CN111257300B (en) * | 2020-02-29 | 2022-04-01 | 重庆大学 | Bionic nano microstructure chip based endotoxin SERS quantitative detection system, method and application |
| CN113715361A (en) * | 2021-08-30 | 2021-11-30 | 南通大学 | Gold-silver alloy film SERS substrate based on polymer nano-pillar array structure and preparation method thereof |
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