CN105973865A - Au nano dendrites surface-reinforced Raman scattering substrate and preparation method thereof - Google Patents
Au nano dendrites surface-reinforced Raman scattering substrate and preparation method thereof Download PDFInfo
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- 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
Abstract
The invention discloses an Au nano dendrites surface-reinforced Raman scattering substrate and a preparation method thereof. The SERS active substrate is a layered micro nano structure composited by precious metal Au and a semiconductor ZnO. The preparation method employs a two-step constant current deposition method, an Au spin-coated ZnO nano rod array substrate generated on an ITO electro-conductive glass is taken as a work electrode, graphite flake is taken as a counter electrode, the Au nano dendrites can be produced. The active substrate is formed by a main part (the Au nano rod) hollow structure and a lim Au dendrite. The method has the advantages of simple process, low cost, small current, and low voltage, the Au dendrite can be transferred to a silicon chip substrate; the substrate obtained in the invention has the advantages of high stability, and ordered and controllable structure, and has high stability in the Raman spectroscopy detection.
Description
Technical field
The invention belongs to LR laser raman detection technique field and nanomaterial science, be specifically related to a kind of Au Nano dendritic crystal table
Face strengthens Raman scattering (SERS) substrate and preparation method thereof, and this active substrate is the hierarchical micro-acceptance structure array of a kind of layering.
Background technology
Owing to common Raman scattering signal is weak, weak effect, if changing dispersion effect by improving laser intensity, may
Sample can be made to produce the side effect such as certain damage and photobleaching.If surface adsorption material being detected or to be detected molecule dense
When spending relatively low, conventional Raman detection seems unable to do what one wishes, so enhancements need to be assisted by other.Therefore, surface enhanced
Raman scattering spectrum (SERS) arises at the historic moment as Raman enhancements, and SERS technology comes from trace molecules and is adsorbed in Au,
The noble metals such as Ag, Cu and electrode surface, Raman signal can strengthen 104 ~ 1015Times.Since Fleischman et al. was in 1974
Finding SERS(surface enhanced raman spectroscopy) since technology, this technology has become a kind of high-sensitive detection interfacial property and molecule
Interphase interaction, sign surface molecular adsorption behavior and the effective tool of molecular structure, in trace analysis, Molecular Detection, change
Learn the aspects such as industry, environmental science, biomedical system, nano material and sensor and have important application.Should at these
In applying with program or device, most important factor is to prepare high-quality SERS active-substrate, and its signal detection has high
SERS activity, good uniformity and preferable stability.Office from electromagnetic enhancement mechanism, SERS effect performance and substrate
Field surface plasma resonance (LSPR) is closely related, and LSPR is the surface topography by local and microstructure decision.Cause
This, SERS performance depends in suprabasil noble metal (such as gold or the silver) surface topography of micro/nano material and microstructure.?
In several years of past, the classification micro nano structure (HMNs) of layering, due in photocatalysis, super hydrophobic surface, optics, electrification
Learn sensor, etc. have potential application, therefore enjoy the concern of people.Micro-nano structure array is layered for Au, due to it
High local field enhancement effect, can be as surface enhanced raman spectroscopy (SERS) active substrate.
The effect of Surface Enhanced Raman Scattering Spectrum and substrate are very close, and the quality of substrate fabrication directly affects surface
Strengthen the effect of raman scattering spectrum.The method that conventional preparation strengthens substrate is a lot, but the classification micro nano structure of layering
The preparation of SERS active-substrate generally has two kinds of methods: has the SERS substrate of template and exempts from the SERS substrate of template.Based on SERS
Substrate template, in the past few decades in by as the most frequently used template, such as polystyrene (PS) microsphere or SiO2Colloid monolayer
Crystal.The golden ring that summer et al. makes, silver fourth finger array uses the solid substrate using alkyl hydrosulfide as mask and self assembly
Silicon dioxide microsphere is hard template.Liu et al. uses Stearyl mercaptan as corrosion protective layers, prepares gold grain model, mesh
Be vertical growing ZnO nanorod arrays under PS colloid monolayer crystal assists.Although the many advantages of template method existence, but this
The method of kind relates to many complicated steps and expensive experimental facilities.Therefore, the template auxiliary (side of cheap and simple is exempted from for one
Method) directly it is layered micro/nano structure array at the large-scale Au of ITO Grown, there is equipment cheap, operating process letter
Just, preparation method only needs two step electro-deposition, and two processes are all without any additive, auxiliary agent.The layering that this method is prepared
The advantages such as micro-nano structure SERS substrate good stability, reproducible, controllability is good.
Summary of the invention
First purpose of the present invention is to provide a kind of substrate to have set for making up shortcomings and deficiencies of the prior art
Standby cheap, flow process is simple, structurally ordered Au Nano dendritic crystal surface enhanced controlled, favorable repeatability, substrate good stability draws
Graceful scattering (SERS) substrate.
Another object of the present invention is exactly to propose a kind of layering micro-nano structure that can effectively be perpendicular to substrate growth, and
Without any additive, exempt from template auxiliary, there is equipment cheap, the preparation method of the excellent specific properties such as flow process is simple.
Third object of the present invention is to provide above-mentioned Au Nano dendritic crystal surface enhanced raman spectroscopy (SERS) substrate
Purposes.
Technical scheme is as follows:
A kind of Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that: with the Au generated on ITO electro-conductive glass
The ZnO nano-rod array of spin coating is substrate, deposits Au nanometer tree branches over the substrate surface equably again by electro-deposition method
Brilliant.
Described a kind of Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that: this SERS active-substrate
Being combined, by noble metal Au and quasiconductor ZnO, the layering micro-nano structure constructed to form, ground floor is the ZnO nanorod being evenly distributed
Array, the second layer is the Au Nano dendritic crystal being evenly distributed, and the trunk of its dendrite is hollow, and the pattern of branch is controlled
's.
The preparation method of described Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that include following
Step: the ZnO nano-rod array substrate of the Au spin coating generated on ITO electro-conductive glass is as working electrode, and gold chloride is as electricity
Solve liquid, by galvanostatic method at its surface controllable electric deposition Au Nano dendritic crystal.
The preparation method of described Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that: described chlorine
Auric acid concentration of electrolyte is 0.3 ~ 0.7g L-1。
The preparation method of described Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that: described electricity
Deposition galvanostatic method uses reverse operation electric current, and its current range is between 0.2 ~ 2 mA.
The preparation method of described Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that: electro-deposition
Sedimentation time 1 ~ 2 h.
The purposes of described Au Nano dendritic crystal surface enhanced Raman scattering substrate, is characterized in that: by described Au nanotrees
Dendrite Raman spectrum base is for detecting the organic molecule in solution, and such as rhodamine (R6G), the detection limit of concentration can
Reach 10-16mol·L-1。
The purposes of described Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that: to organic in solution
The method that molecule carries out detecting is: using Au Nano dendritic crystal Raman spectrum base as Raman detection substrate, to go
Ionized water is 10 as solvent compounding high concentration-6mol·L-1, low concentration is 10-12mol·L-1、10-14mol·L-1、10- 16mol·L-1Organic molecule solution, this Raman detection substrate being cut into pieces and being separately immersed in high concentration is 10-6mol·L-1,
Low concentration is 10-12mol·L-1、10-14mol·L-1、10-16mol·L-1These several concentration organic molecule solution in, soak
Time is followed successively by high concentration 10-6mol·L-1It is 0.5 ~ 1 h, low concentration 10-12mol·L-1、10-14mol·L-1、10- 16mol·L-1It is 3.5 ~ 5 h, after the substrate soaked is pulled out, treats R6G solution evaporation, then do Raman detection.
By the Au nanometer tree branches on the ZnO nano-rod array of described Au Nano dendritic crystal surface enhanced Raman scattering substrate
Crystalline substance is transferred on silicon chip, it is thus achieved that have the Au Nano dendritic crystal surface enhanced raman spectroscopy of surface-enhanced Raman scattering activity equally
Substrate.
The preparation technology of the ZnO nano-rod array of the Au spin coating generated on described ITO electro-conductive glass includes following step
Rapid: (1) utilizes the ZnO seed that atomic layer (ALD) sedimentation deposits tunic thickness about 15 ~ 25 nm in advance on ITO substrate
Layer, it is thus achieved that ZnO Seed Layer substrate；(2) with what step (1) prepared with the substrate of generation ZnO Seed Layer on ITO electro-conductive glass it is
The mixed liquor of working electrode, zinc nitrate hexahydrate and hexamethylenetetramine is as electrolyte, by constant current electrodeposition process in ZnO kind
Sub-layer surface controllable electric deposition ZnO nano-rod array, the concentration of described mixed liquor is 25mM, zinc nitrate hexahydrate and six in mixed liquor
The ratio of the molal quantity of methine tetramine is 1:1；(3) it is deposited with one by ion sputtering instrument at ZnO nano-rod array surface vacuum again
The golden film of thickness 13 ~ 20 nm, it is thus achieved that the ZnO nano-rod array substrate of Au spin coating.
For realizing second object of the present invention, the technical scheme is that and comprise the following steps: with ITO conduction glass
The ZnO nano-rod array substrate of the Au spin coating generated on glass is working electrode, is occurred by the electrolyte gold chloride in electro-deposition
Electrolysis, causes hydrion to separate out, and forms chemical bond, by the combination of chemical bond with the ZnO nanorod generation chemical reaction of negative electrode
The catalysis of ZnO nano-rod array is etched by power and gold film, just causes the shape of the classification micro nano structure that Au Nano dendritic crystal is layered
Become (see accompanying drawing 1 and accompanying drawing 2).
For realizing the 3rd purpose of the present invention, the technical scheme is that and described Au Nano dendritic crystal surface enhanced is drawn
Graceful scattering substrate is for detecting the organic molecule in solution, and such as rhodamine 6G, the detectable limit of concentration is up to 10-16mol·L-1。
The method detecting organic molecule in solution that prepared Au Nano dendritic crystal is arranged is: by Au nanotrees
Dendrite surface enhanced Raman scattering substrate is as Raman detection substrate, using deionized water as solvent compounding high concentration for 10- 6mol·L-1, low concentration is 10-12mol·L-1、10-14mol·L-1、10-16mol·L-1Organic molecule solution, by this Raman
Detection substrate is cut into pieces and is separately immersed in high concentration is 10-6mol·L-1, low concentration is 10-12mol·L-1、10-14mol·L-1、10-16mol·L-1These several concentration organic molecule solution in, soak time is followed successively by high concentration 10-6mol·L-1For
0.5 ~ 1 h, low concentration 10-12mol·L-1、10-14mol·L-1、10-16mol·L-1It is 3.5 ~ 5 h, the base soaked
After the end is pulled out, treat R6G solution evaporation, then do Raman detection (see accompanying drawing 5).
Present invention also offers a kind of Au Nano dendritic crystal Raman spectrum base, its technical scheme is by right
Require that the Au Nano dendritic crystal surface enhanced Raman scattering substrate described in 1 is cut into pieces, be placed in ethanol, R6G mixed solution
Row is ultrasonic, and purpose makes the Au Nano dendritic crystal on this SERS substrate top layer be disperseed to get off, and is then dripped on silicon chip, natural
Dry, carry out surface-enhanced Raman detection, it is thus achieved that there is the Au Nano dendritic crystal surface of surface-enhanced Raman scattering activity equally
Strengthen raman spectrum substrate.
In the present invention, we specifically have studied the sedimentation time impact (see accompanying drawing 3) on Au morphogenesis, when deposited
Between when being 30 min, Au pattern is long flocculence granule (Fig. 3 a) near ZnO nanorod tip, increases the most respectively
When being added to 40 min and 60 min, Au nano-particle is constantly being grown up and is being occurred in that the shape of thorn-like at ZnO nanorod tip
Looks (Fig. 3 b, c).The time that Au dendrite starts to occur is 1.5 h when, size and the density of dendrite smaller (
Fig. 3 d).It is interesting that electrochemical deposition process increases over time, between 1.8h and 2h, Au sedimentation products becomes layering
Dendritic morphology.In this hierarchy, the first level is ZnO nanorod, the second level be Au hollow Nano trunk and branch (
Fig. 3 e, f).According to above-mentioned result, we have proposed the possible forming process schematic diagram of Au Nano dendritic crystal (accompanying drawing 4).
Golden film on ZnO nano-rod array not only acts as the effect of etching ZnO nanorod, and it can be as catalyst, catalytic decomposition
ZnO.If not gold evaporation film, the pattern of Au Nano dendritic crystal will be can not get, and electrochemical deposition is uneven.And electrolyte gold chloride
Playing the part of the role of chelating agen in second step electro-deposition, it can precipitate metal ion (Zn rapidly2+), cause Au dendrite uniform
Be grown in ZnO nanorod film surface, thus cause the formation of Au Nano dendritic crystal layering micro/nano structure.Two processes
Being to synchronize, i.e. gold Membrane catalysis etching ZnO nanorod and the formation of Au Nano dendritic crystal, show the same of Au dendrite electro-deposition
Time, hydrion (H+) separate out, react generation H with ZnO2O, this is owing to gold film is as catalyst, can be catalyzed etching ZnO nano
Rod, and the result of water generation reaction, reaction equation is as follows:
2H+ + ZnO→Zn2+ + H2O (1)
In sum, it will be seen that be that the catalysis of ZnO nano-rod array is etched by gold film, Au Nano dendritic crystal is just caused
The formation of layering micro/nano structure.
The Au dendrite that the present invention is deposited can be transferred on silicon chip.With rhodamine liquor (R6G) as probe molecule,
The Au dendrite being deposited on ZnO nanorod is transferred to the raman characteristic peak that can also detect R6G molecule on silicon chip such as figure
Shown in 6.Result above shows, the Au dendrite micro-nano structure material prepared by this experiment can be very effective as one
The substrate of surface enhanced raman spectroscopy.
Compared with prior art, its prominent advantage is the present invention:
1, the Au Nano dendritic crystal substrate that prepared by the present invention, belongs to the SERS substrate of noble metal and semiconductors coupling, and its SERS believes
Number than single on ITO the noble metal SERS basal signal of deposition much better than.And this composite S ERS substrate to have pattern homogeneous,
Size adjustable, and its SRES signal is reliable, stable, uniform.
2, deposited substrate is the ZnO nano-rod array of the Au spin coating generated on ITO electro-conductive glass, the system of this array
Standby technique comprises the following steps: preparing the ZnO Seed Layer of tunic thickness about 15 ~ 25 nm in advance on ITO substrate, it is prepared
Method is to utilize atomic layer (ALD) sedimentation, and prepared ZnO Seed Layer is evenly arranged on ITO substrate.ZnO nano
Rod preparation be on ITO electro-conductive glass generate ZnO Seed Layer substrate as working electrode, zinc nitrate hexahydrate and six methines
The mixed liquor of tetramine is as electrolyte, by first step galvanostatic method at its ZnO Seed Layer surface controllable electric deposition ZnO nanorod
Array.For making noble metal Au form the micro-nano structure of layering with quasiconductor ZnO nanorod, need to be by prepared ZnO nano-rod array
The surface golden film by ion sputtering instrument vacuum evaporation thick layer 13 ~ 20 nm.Therefore, Au Nano dendritic crystal surface enhanced draws
The preparation of graceful scattering (SERS) substrate, need to be with the ZnO nano-rod array substrate of the Au spin coating of generation on ITO electro-conductive glass as work
Make electrode.
3, the SERS substrate of this Au Nano dendritic crystal, its depositing operation is simple, with low cost, and whole preparation process without
Need template to assist, and preparation process relates to the catalytic effect of gold film, i.e. when depositing Au Nano dendritic crystal, ZnO nanorod
Most advanced and sophisticated under the catalysis etching of gold film, by a gold chloride corrosion part, causing the trunk of Au Nano dendritic crystal to the greatest extent is hollow knot
Structure.
4, the Au Nano dendritic crystal of deposition can the most ultrasonic be transferred on silicon chip, can observe the sky of its layering more subtly
Heart micro-nano structure.
Preparation method advantage of the present invention is that preparation process exempts from template auxiliary, and simple process, inexpensive, electric current are little, electric
Force down and Au dendrite can be transferred in silicon chip substrate.The substrate stability that the method obtains is high, structurally ordered controlled,
Raman spectrum detection shows the highest sensitivity.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
The X-ray diffractogram (XRD) of Fig. 1 Au Nano dendritic crystal layering micro-nano structure, result shows, electro-deposition sample
Being made up of ZnO and Au mutually, its diffraction maximum is mated with the hexagon ZnO of standard and the Au of cubic structure very much.34.4oPlace,
There is a sharp-pointed diffraction maximum, corresponding to (002) crystal face of ZnO, there is obvious preferred orientation, and 38oPlace, Au(111) brilliant
, relative to other diffraction maximum, also there is stronger advantage in face, also has obvious preferred orientation, and this has absolutely proved ZnO nano-rod array
Being perpendicular to substrate growth, the hierarchical micro-acceptance structure causing Au Nano dendritic crystal is also vertical substrates growth；
Microscope scanning figure (SEM) of the hierarchical micro-acceptance structure of Fig. 2 ZnO nanorod and the layering of Au Nano dendritic crystal, they are
The front view of the hierarchical micro-acceptance structure of the Au Nano dendritic crystal of different enlargement ratios and sectional view, this shows that ordered structure has kept
Whole without damaged, the growth of dendrite depends on the array structure of ZnO nanorod, is all perpendicular to substrate and all preferred orientations are raw
Long.We can also find out the form of the hierarchical layered micro-nano structure of ordered structure array Au Nano dendritic crystal from sectional view,
And the trunk of Au Nano dendritic crystal is hollow, its stem shape is upper coarse and lower fine, and this is still due to the catalysis etching point of gold film
Solve the reason of ZnO nanorod, the tip of ZnO nanorod is gradually eroded, along with the prolongation of electrodeposition time, causes close
The dendrite trunk that ZnO top end grows is relatively thick, the thinnest along ZnO nanorod.Early-stage Study was detection, Di Xiayi
Length (about 1200nm) when the length (about 1000nm) of layer ZnO nanorod does not deposits Au Nano dendritic crystal before comparing shortens
, this results from the catalysis etching effect of gold film；
It is 0.2 ~ 2 mA that Fig. 3 deposits reverse current, and the concentration of HAuCl4 is 0.5 g/L, and sedimentation time is respectively as follows: (a)
When 30 min, (b) 40 min, (c) 60 min, (d) 1.5 h, (e) 1.8 h and (f) 2 h, coarse at ITO
The SEM figure of surface deposition gained sample, figure (a) simply grows some Au nano-particle near ZnO nanorod tip, figure
B () and (c) as time went on, starts to grow from top to bottom along ear of maize the Au nanometer of some wedge angles from ZnO nanorod top
Thorn, figure (d) grows Au Herba Agrimoniae club shaped structure after deposition 1.5 h, and figure (e) dendritic structure occurs after deposition 1.8 h, figure
F () is 2 h at sedimentation time, its dendritic structure becomes apparent from, and generates the hierarchical micro-acceptance structure of layering；
Fig. 4 Au dendrite forming process schematic diagram；
Fig. 5 Au dendrite as SERS active substrate detection R6G Raman spectrogram (laser excitation wavelength is 633 nm,
The time of integration is 30 s)；Fig. 5 (a) is high concentration 10-6The R6G solution of moL/L: substrate soak time 30 min, 50 times of object distances
Amplifying, gross output is 15 mW, exports the general power rate of 5%, find out, under high concentration, R6G occur from Raman figure after decay
Characteristic peak, its Raman signal is remarkably reinforced, strengthen to 105Times), Fig. 5 (b), (c) and (d) they are that low concentration is followed successively by 10- 12mol·L-1、10-14mol·L-1、10-16mol·L-1R6G solution: substrate soak time 4 h, it can be seen that three kinds of concentration are all
There is R6G characteristic peak to occur, also imply that this SERS substrate also is able to be detected for the organic molecule of low concentration, detection
The limit can reach 10-16mol·L-1；
Raman light when ultrasonic (stripping top level product) transfers to silicon chip surface after Fig. 6 Au dendrite surface adsorption R6G molecule
Spectrogram (a) sweeps figure (b), scanning figure (c) and energy spectrogram (d) with corresponding arteries and veins, surveys the exciting light of Raman spectrum here, its excitation wavelength
Being 633 nm, the time of integration is 30 s.Early-stage Study shows: the shape of ZnO nanorod is not pointed, and this is due to gold film
Catalytic etching effect.Seeing that the trunk of Au dendrite is hollow-core construction in figure (c) and figure (d), the Cu element in figure (d) is transmission
Electronic Speculum surveys the copper mesh that energy time spectrum is used, for high concentration 10-6mol·L-1R6G solution, R6G characteristic peak there is, and SERS letter
Number it is remarkably reinforced.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.Description below is in the way of enumerating, but this
Bright protection domain is not limited thereto.
The preparation method of 1 one kinds of Au Nano dendritic crystal surface enhanced Raman scattering substrates of embodiment, comprises the following steps:
A, the preparation of the ZnO nano-rod array substrate of the Au spin coating of generation on ITO electro-conductive glass, comprise the following steps: (1)
Atomic layer (ALD) sedimentation is utilized to deposit the ZnO Seed Layer of the thick about 15-25 nm of a tunic in advance on ITO substrate, it is thus achieved that ZnO
Seed Layer substrate；(2) with step (1) prepare to generate the substrate of ZnO Seed Layer on ITO electro-conductive glass as working electrode,
The mixed liquor of zinc nitrate hexahydrate and hexamethylenetetramine is as electrolyte, by constant current electrodeposition process on ZnO Seed Layer surface
Controllable electric deposition ZnO nano-rod array, the concentration of described mixed liquor is 25mM, zinc nitrate hexahydrate and six methines four in mixed liquor
The ratio of the molal quantity of amine is 1:1；(3) again by ion sputtering instrument ZnO nano-rod array surface vacuum evaporation thick layer 13 ~
The golden film of 20 nm, it is thus achieved that the ZnO nano-rod array substrate of Au spin coating；
B, in the electrolysis bath of 100ml add 80ml HAuCl4(0.5 g L-1) solution is electrolyte, inserts small pieces A step
The ZnO nano-rod array substrate of the Au spin coating generated on ITO electro-conductive glass of rapid preparation is in electrolysis bath, as work electricity
Pole, the live part immersing electrolyte is 2.5 cm × 0.8 cm, using graphite flake as to electrode, opens reverse operation electric current,
And regulate to 1mA, Au Nano dendritic crystal in the ZnO nano-rod array substrate surface growth of Au spin coating, close electric current after 2 h,
Rinse the ZnO nano-rod array substrate of Au spin coating successively with ethanol, water, dry and just obtain SERS active substrate, obtain above-mentioned
To surface there is the active substrate of SERS effect as Raman detection substrate, with rhodamine liquor (R6G) as probe molecule,
Deionized water is 10 as solvent compounding high concentration respectively-6mol·L-1, low concentration is 10-12mol·L-1、10-14mol·L-1、
10-16mol·L-1Organic molecule solution, this Raman detection substrate being cut into pieces and being separately immersed in high concentration is 10-6mol·
L-1, low concentration is 10-12mol·L-1、10-14mol·L-1、10-16mol·L-1These several concentration organic molecule solution in,
Soak time is followed successively by high concentration 10-6mol·L-1It is 0.5 h, low concentration 10-12mol·L-1、10-14mol·L-1、10- 16mol·L-1It is 4 h, after the substrate soaked is pulled out, treats R6G solution evaporation, then be Raman detection (RenishawinVia
Reflex Raman spectrometer, excitation wavelength is 633 nm), it will be apparent that observe the characteristic peak (see accompanying drawing 5) of R6G.
Embodiment 2
A, identical with the step A of embodiment 1；
B, in the electrolysis bath of 100ml add 80ml HAuCl4(0.5 g L-1) solution is electrolyte, inserts small pieces A step
The ZnO nano-rod array substrate of the Au spin coating generated on ITO electro-conductive glass of rapid preparation is in electrolysis bath, as work electricity
Pole, the live part immersing electrolyte is 2.5 cm × 0.8 cm, using graphite flake as to electrode, opens reverse operation electric current,
And regulate to 1mA, Au Nano dendritic crystal in the ZnO nano-rod array substrate surface growth of Au spin coating, close electric current after 1.5 h,
Rinse the ZnO nano-rod array substrate of Au spin coating successively with ethanol, water, dry and just obtain SERS active substrate.
Surface obtained above is had the active substrate of SERS effect as Raman detection substrate, using R6G as spy
Pin molecule, does Raman detection by the method in embodiment 1, it will be apparent that observe the characteristic peak of R6G, and its Raman signal intensity connects
Nearly embodiment 1.
Embodiment 3
A, identical with the step A of embodiment 1；
B, in the electrolysis bath of 100ml add 80ml HAuCl4(0.5 g L-1) solution is electrolyte, inserts small pieces A step
The ZnO nano-rod array substrate of the Au spin coating generated on ITO electro-conductive glass of rapid preparation is in electrolysis bath, as work electricity
Pole, the live part immersing electrolyte is 2.5 cm × 0.8 cm, using graphite flake as to electrode.Open reverse operation electric current,
And regulate to 2 mA, Au Nano dendritic crystal grows at the ZnO nano-rod array substrate surface of Au spin coating, closes electric current after 1 h,
Rinse the ZnO nano-rod array substrate of Au spin coating successively with ethanol, water, dry and just obtain SERS active substrate.
Surface obtained above is had the active substrate of SERS effect as Raman detection substrate, using R6G as spy
Pin molecule, does Raman detection by the method in embodiment 1, it will be apparent that observe the characteristic peak of R6G, its Raman signal intensity with
Embodiment 1 is suitable.
Embodiment 4
A, identical with the step A of embodiment 1；
B, in the electrolysis bath of 100ml add 80ml HAuCl4(0.5 g L-1) solution is electrolyte, inserts small pieces A step
The ZnO nano-rod array substrate of the Au spin coating generated on ITO electro-conductive glass of rapid preparation is in electrolysis bath, as work electricity
Pole, the live part immersing electrolyte is 2.5 cm × 0.8 cm, using graphite flake as to electrode.Open reverse operation electric current,
And regulate to 2 mA, Au Nano dendritic crystal grows at the ZnO nano-rod array substrate surface of Au spin coating, closes electricity after 1.8 h
Stream, rinses the ZnO nano-rod array substrate of Au spin coating successively, dries and just obtain SERS active substrate with ethanol, water.
Surface obtained above is had the active substrate of SERS effect as Raman detection substrate, using R6G as spy
Pin molecule, does Raman detection by the method in embodiment 1, it will be apparent that observe the characteristic peak of R6G, its Raman signal intensity with
Embodiment 1 is suitable.
Embodiment 5
On the ZnO nano-rod array substrate of the Au spin coating to generate on ITO electro-conductive glass, obtain Au according to embodiment 1 to receive
Rice dendrite, through the most ultrasonic, is transferred on silicon chip, detects substrate in this, as active Raman, using R6G as probe
Molecule, is 10 as solvent by its compound concentration with deionized water-6mol·L-1Organic molecule solution, by this Raman detection base
The end cut into pieces be immersed in this 10-6mol·L-1In the organic molecule solution of concentration, soak time is 0.5 h, the base soaked
After the end is pulled out, treat R6G solution evaporation, then do Raman detection (RenishawinVia Reflex Raman spectrometer, excitation wavelength
It is 633 nm), it will be apparent that observe the characteristic peak (Fig. 6) of R6G.
Claims (10)
1. an Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that: with generate on ITO electro-conductive glass
The ZnO nano-rod array of Au spin coating is substrate, deposits Au nanotrees over the substrate surface equably again by electro-deposition method
Dendrite.
2. according to the Au Nano dendritic crystal surface enhanced Raman scattering substrate described in claim 1, it is characterised in that: this SERS
Active substrate is combined, by noble metal Au and quasiconductor ZnO, the hierarchical layered micro-nano structure constructed and forms, and ground floor is that distribution is equal
Even ZnO nano-rod array, the second layer is the Au Nano dendritic crystal hierarchy being evenly distributed, and the trunk of its dendrite is hollow
, the pattern of branch is controlled.
3. a preparation method for Au Nano dendritic crystal surface enhanced Raman scattering substrate as claimed in claim 1, its feature
It is, comprises the following steps: the ZnO nano-rod array substrate of the Au spin coating of generation is as working electrode on ITO electro-conductive glass,
Gold chloride is as electrolyte, by galvanostatic method at its surface controllable electric deposition Au Nano dendritic crystal.
4. according to the preparation method of the Au Nano dendritic crystal surface enhanced Raman scattering substrate described in claim 3, its feature
It is: described gold chloride concentration of electrolyte is 0.3 ~ 0.7 g L-1。
5. according to the preparation method of the Au Nano dendritic crystal surface enhanced Raman scattering substrate described in claim 3, its feature
It is: described electro-deposition galvanostatic method uses reverse operation electric current, and its current range is between 0.2 ~ 2 mA.
6. according to the preparation method of the Au Nano dendritic crystal surface enhanced Raman scattering substrate described in claim 3, its feature
It is: sedimentation time 1 ~ 2 h of electro-deposition.
7. a purposes for the Au Nano dendritic crystal surface enhanced Raman scattering substrate as described in claim 1, is characterized in that:
Described Au Nano dendritic crystal Raman spectrum base is used for the organic molecule detecting in solution, such as rhodamine (R6G),
The detection of concentration limits up to 10-16mol·L-1。
8. according to the purposes of the Au Nano dendritic crystal surface enhanced Raman scattering substrate described in claim 7, it is characterised in that:
The method detecting organic molecule in solution is: Au Nano dendritic crystal Raman spectrum base examined as Raman
Survey substrate, using deionized water as solvent compounding high concentration for 10-6mol·L-1, low concentration is 10-12mol·L-1、10- 14mol·L-1、10-16mol·L-1Organic molecule solution, this Raman detection substrate is cut into pieces and is separately immersed in high concentration
It is 10-6mol·L-1, low concentration is 10-12mol·L-1、10-14mol·L-1、10-16mol·L-1This several concentration organic
In molecular solution, soak time is followed successively by high concentration 10-6mol·L-1It is 0.5 ~ 1 h, low concentration 10-12mol·L-1、10- 14mol·L-1、10-16mol·L-1It is 3.5 ~ 5 h, after the substrate soaked is pulled out, treats R6G solution evaporation, then do Raman
Detection.
9. an Au Nano dendritic crystal surface enhanced Raman scattering substrate, it is characterised in that: the Au described in claim 1 is received
Au Nano dendritic crystal on the ZnO nano-rod array of rice dendrite surface enhanced Raman scattering substrate is transferred on silicon chip, it is thus achieved that
There is the Au Nano dendritic crystal Raman spectrum base of surface-enhanced Raman scattering activity equally.
10. according to a kind of Au Nano dendritic crystal surface enhanced Raman scattering substrate described in claim 1, it is characterised in that
The preparation technology of the ZnO nano-rod array of the Au spin coating generated on described ITO electro-conductive glass comprises the following steps: (1) utilizes
Atomic layer (ALD) sedimentation deposits the ZnO Seed Layer of tunic thickness about 15 ~ 25 nm in advance on ITO substrate, it is thus achieved that ZnO kind
Sublayer substrate；(2) with step (1) prepare to generate the substrate of ZnO Seed Layer on ITO electro-conductive glass as working electrode, six
The mixed liquor of water zinc nitrate and hexamethylenetetramine, can on ZnO Seed Layer surface by constant current electrodeposition process as electrolyte
Control electro-deposition ZnO nano-rod array, the concentration of described mixed liquor is 25mM, zinc nitrate hexahydrate and hexamethylenetetramine in mixed liquor
The ratio of molal quantity be 1:1；(3) it is deposited with thick layer 13 ~ 20 by ion sputtering instrument at ZnO nano-rod array surface vacuum again
The golden film of nm, it is thus achieved that the ZnO nano-rod array substrate of Au spin coating.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841158A (en) * | 2016-12-27 | 2017-06-13 | 上海应用技术大学 | A kind of method of bacillus class biomarker Sensitive Detection |
| CN108072641A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院化学研究所 | The method of preparation method and the gas detection of surface enhanced Raman scattering substrate material |
| CN108132239A (en) * | 2018-02-22 | 2018-06-08 | 合肥工业大学 | Multilayered structure surface enhanced Raman substrate construct and its control accurate of performance |
| CN108226138A (en) * | 2018-02-05 | 2018-06-29 | 中国科学院合肥物质科学研究院 | A kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling |
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| CN110711610A (en) * | 2019-10-17 | 2020-01-21 | 桂林理工大学 | Preparation method of super-hydrophobic/super-hydrophilic mixed pattern microarray dendritic gold chip |
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| CN114507849A (en) * | 2022-02-16 | 2022-05-17 | 南京理工大学 | Surface-enhanced Raman substrate with stability and Raman intensity taken into consideration and preparation method thereof |
| CN114525483A (en) * | 2021-12-31 | 2022-05-24 | 安徽大学 | Gold nano dendrite and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181891A (en) * | 2011-04-08 | 2011-09-14 | 温州大学 | Silver nanodendrite surface enhanced Raman scattering (SERS) substrate, and preparation method and application thereof |
| CN103058132A (en) * | 2012-12-26 | 2013-04-24 | 中国科学院合肥物质科学研究院 | Ordered porous gold nanorod array and preparation method and application thereof |
| CN104297224A (en) * | 2014-09-26 | 2015-01-21 | 中国工程物理研究院化工材料研究所 | SERS substrate material and hotspot excitation method and representation thereof |
-
2016
- 2016-01-29 CN CN201610074099.9A patent/CN105973865A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181891A (en) * | 2011-04-08 | 2011-09-14 | 温州大学 | Silver nanodendrite surface enhanced Raman scattering (SERS) substrate, and preparation method and application thereof |
| CN103058132A (en) * | 2012-12-26 | 2013-04-24 | 中国科学院合肥物质科学研究院 | Ordered porous gold nanorod array and preparation method and application thereof |
| CN104297224A (en) * | 2014-09-26 | 2015-01-21 | 中国工程物理研究院化工材料研究所 | SERS substrate material and hotspot excitation method and representation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张海宝: "基于ZnO纳米薄膜的贵金属（Au, Ag）SERS基底的制备及SERS特性研究", 《万方学位论文数据库》 * |
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