CN108226138A - A kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling - Google Patents
A kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling Download PDFInfo
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- CN108226138A CN108226138A CN201810110706.1A CN201810110706A CN108226138A CN 108226138 A CN108226138 A CN 108226138A CN 201810110706 A CN201810110706 A CN 201810110706A CN 108226138 A CN108226138 A CN 108226138A
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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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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Abstract
Hollow pipe array surface the invention discloses a kind of assembling of Ag nanometer sheets enhances Raman scattering（SERS）Substrate, the SERS active-substrate are that the hollow pipe array structure of precious metals ag nanometer sheet assembling sacrificed template and generated is served as based on semiconductor ZnO nanorod.The preparation method of the present invention uses two step galvanostatic deposition methods, using the ZnO nano-rod array substrate of Au spin coatings generated on ITO electro-conductive glass as working electrode, graphite flake is the hollow pipe array assembled to Ag nanometer sheets made from electrode, the hollow tubular structures that this active substrate is assembled by precious metals ag nanometer sheet.Preparation method advantage of the present invention is that preparation process simplicity, inexpensive, electric current is small, voltage is low.The substrate stability that this method obtains is high, structurally ordered controllable, and very high sensitivity is shown in Raman spectrum detection.
Description
Technical field
The present invention relates to micro-nano electronic technology field and nanomaterial science field, the sky of specifically a kind of Ag nanometer sheets assembling
Heart pipe array surface enhances Raman scattering substrate.
Background technology
Absorption on the metallic matrix of nanostructured the Raman scattering signal of molecule can obtain 1,000,000 times it is even more
Enhancing, this has a wide range of applications in terms of ultra trace chemical analysis.This surprising enhancing is mainly attributed to plasma
The Electromagnetic enhancement of induction, this is because the very big electric field generated in so-called hot spot region in nanoscale gap, Yi Ji
The sharp edge of nanoscale, corner and the noble metal substrate at tip, the increase of a large amount of hot spot quantity and intensity will enhance SERS
Activity.Therefore, Raman scattering (SERS) active substrate with high density 3D hot spots causes the strong interest of people.Such as
The carbon nano pipe array that the Au of vertical alignment is nano-particle modified can detect the highly sensitive SERS signal of target molecule, and examine
It surveys the limit and reaches 10-12The glass nano column of M, Ag nano island modification, because high density hot spot is located at the top and side of glass nano column
Face also shows that high enhancement factor 107.The SERS active-substrate of other 3D：Such as Ag coatings carbon nano pipe array, Au-HFO2Carbon
Nano-tube array, Ag nano-particle modified ZnO nano bores array, Au coatings TiO2The Si nanometers of nano-tube array, gold cladding
Line/nano column array since it is with highdensity 3D hot spots, also shows that high SERS activity.Nanoscale angle, edge or point
The metal structure at end has the ability of aggregation of stronger plasma induction field.Therefore, if these unique nano junctions
Structure is prepared to SERS active-substrate, then will there is heat-flash points in the gap between adjacent building block.
Invention content
The purpose of the present invention is in view of the deficiencies of the prior art and defect, provide a kind of hollow pipe battle array of Ag nanometer sheets assembling
Row surface enhanced Raman scattering substrate.
In order to achieve the above object, the technical solution adopted in the present invention is：
A kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling, it is characterised in that：Including substrate,
Substrate is made of the ZnO nano-rod array of the Au spin coatings on ITO electro-conductive glass and ITO electro-conductive glass, on ZnO nano-rod array
Ag nanometer sheets are deposited, and are all etched away ZnO nano-rod array with acid solution, the self assembly of Ag nanometer sheets is only stayed to form nanometer
Hollow tubular structures.
A kind of hollow pipe array surface enhancing Raman scattering substrate of the Ag nanometer sheets assembling, it is characterised in that：ITO
The ZnO nano-rod array of Au spin coatings on electro-conductive glass, preparation process include the following steps：
(1), layer of ZnO Seed Layer is deposited on ITO electro-conductive glass in advance using atomic layer ALD deposition method, by ITO conductions
Glass and ZnO Seed Layers thereon form ZnO seed layer substrates；
(2), using ZnO seed layer substrates made from step (1) as working electrode, zinc nitrate hexahydrate and hexamethylenetetramine
Mixed solution deposits ZnO nano-rod array by galvanostatic method as electrolyte in ZnO seed layer surfaces controllable electric；
(3) layer of Au film is deposited in ZnO nano-rod array surface vacuum by ion sputtering instrument again, so as in ITO conductions
The ZnO nano-rod array of Au spin coatings is obtained on glass.
A kind of hollow pipe array surface enhancing Raman scattering substrate of the Ag nanometer sheets assembling, it is characterised in that：Step
Suddenly in (2), a concentration of 25mM of the mixed solution of zinc nitrate hexahydrate and hexamethylenetetramine, in mixed solution zinc nitrate hexahydrate and
The ratio between molal quantity of hexamethylenetetramine is 1:1.
A kind of hollow pipe array surface enhancing Raman scattering substrate of the Ag nanometer sheets assembling, it is characterised in that：It will
The nano-hollow tubular structure that the self assembly of Ag nanometer sheets is formed is transferred on silicon chip, nano-hollow tubulose knot by silicon chip and thereon
Structure obtains the hollow pipe array surface enhancing Raman scattering that equally the Ag nanometer sheets with surface-enhanced Raman scattering activity assemble
Substrate.
A kind of preparation method of the hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling, feature exist
In：Using substrate as working electrode, the mixed solution of silver nitrate and citric acid is as electrolyte, by galvanostatic method in substrate
Controllable electro-deposition Ag nanometer sheets on ZnO nano-rod array, ZnO nano-rod array is all etched away, only stay Ag using electrolyte
Nanometer sheet self assembly forms nano-hollow tubular structure.
A kind of preparation method of the hollow pipe array surface enhancing Raman scattering substrate of the Ag nanometer sheets assembling, it is special
Sign is：The electrolyte is the mixed solution of silver nitrate and citric acid, concentration ratio 1:9.
A kind of preparation method of the hollow pipe array surface enhancing Raman scattering substrate of the Ag nanometer sheets assembling, it is special
Sign is：When the galvanostatic method carries out controllable electro-deposition, using reverse operation electric current, current range 100~
Between 300 μ A.
A kind of preparation method of the hollow pipe array surface enhancing Raman scattering substrate of the Ag nanometer sheets assembling, it is special
Sign is：10~30min of sedimentation time of electro-deposition.
A kind of purposes of the hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling, it is characterised in that：With
In detecting the organic molecule in solution, the detection limit of concentration is up to 10-12mol·L-1。
The purposes of the hollow pipe array surface enhancing Raman scattering substrate of the Ag nanometer sheets assembling, it is characterised in that：
The process being detected to organic molecule in solution is as follows：
The hollow pipe array surface enhancing Raman scattering substrate that Ag nanometer sheets are assembled as Raman detection substrate, with go from
Sub- water is 10 as solvent compounding high concentration-6mol·L-1, low concentration 10-12mol·L-1Rhodamine 6G organic molecule it is molten
Liquid, it is 10 that Raman detection substrate, which is cut into pieces, and is separately immersed in high concentration-6mol·L-1, low concentration 10-12mol·L-1's
In the rhodamine 6G organic molecule solution of both concentration, in the organic molecule solution of middle and high concentration soaking time for 0.5~
1h, soaking time is 3.5~5h in the organic molecule solution of low concentration, after the Raman detection substrate impregnated is pulled out, treats Luo Dan
Bright 6G solution evaporations, then do Raman detection.
The present invention proposes a kind of electro-deposition method based on sacrifice template, sacrifices template, system by building ZnO nanorod
The 3D SERS substrates of the metal nano-tube array of standby vertical arrangement.First, it is zinc nitrate hexahydrate and six methines four in electrolyte
In the mixed liquor of amine, using graphite flake as working electrode, on the ITO substrates for be coated with ZnO Seed Layers electro-deposition prepare vertical row
The ZnO nanorod of row.It then will be in Au nano particle splashes to ZnO nanorod by ion sputtering instrument, it is desirable to provide metal pattern
The nucleating point of block growth.Next, using metal ion and citric acid mixed liquor as electrolyte, pass through electro-deposition, Ag metal components
It is assembled on the nano-particle modified ZnO nanorods of Au.Meanwhile in the electrolytic solution, ZnO nanorod is in itself also gradually by citric acid
It corrodes, so as to which the hollow pipe array of Ag nanometer sheets assembling be made.Have the result shows that the hollow pipe array of Ag nanometer sheets assembling removes
Outside high surface area, abundant surface chemistries and anti-agglomeration, also with following some characteristics：First, the electromagnetism of high concentration
Generated near the tip at the angle of nanoscale, edge and single building block, these adjacent nanostructureds it
Between nano gap produce strong hot spot.Therefore, this metal nano-tube array should have highdensity three-dimensional hot spot,
It and can be as sensitive substrate.Second, metal component assemble nanometer pipe array has chemical stabilization under acid and alkaline case
Property, this characteristic has wider application in terms of environmental pollution.Third, compared to traditional noble metal nano structure, metal structure
The nano-tube array of part assembling has many advantages, such as that low-density, high surface area, cost are relatively low.Therefore, it is assembled using Ag nanometer sheets
Hollow pipe array as SERS active-substrate, can not only identify low concentration 10-14The rhodamine 6G solution molecule (R6G) of M, and
And it can also identify a concentration of 10-7The Polychlorinated biphenyls (PCBs) of M, is expected in terms of the materials such as fast detection of trace environment organic contamination
There is potential application.
The present invention provides one kind based on semiconductor as sacrifice template, the hollow pipe battle array of controllable preparation Ag nanometer sheets assembling
Row surface enhanced Raman scattering substrate, the technique have that equipment is cheap, flow is simple, favorable repeatability, substrate stability are good.
The present invention compared with prior art, protrude the advantages of be：
1st, the hollow pipe array substrate of Ag nanometer sheets assembling that prepared by the present invention, belongs to noble metal SERS substrates, wherein, half
Conductor serves as the effect for sacrificing template, but its SERS signal is stronger than the single noble metal SERS basal signals deposited on ITO
Much.And the SERS substrates are uniform with pattern, size adjustable, and its SRES signal is reliable, stablizes, uniformly.
2nd, deposited substrate is the ZnO nano-rod array of Au spin coatings generated on ITO electro-conductive glass, the preparation of the array
Technique includes the following steps：Prepare a tunic thickness about 15~25nm's on ITO substrates in advance using atomic layer (ALD) sedimentation
ZnO Seed Layers, the ZnO Seed Layers prepared on ITO substrates be even compact arrange.The preparation of ZnO nanorod is with ITO
The ZnO Seed Layers substrate generated on electro-conductive glass be working electrode, the mixed liquor conduct of zinc nitrate hexahydrate and hexamethylenetetramine
Electrolyte deposits ZnO nano-rod array by first step galvanostatic method in its ZnO seed layer surfaces controllable electric.To make noble metal
There are 3D tubular structures in Ag, need to ZnO nano-rod array obtained be served as sacrifice template, and pass through ion sputtering instrument on its surface
The golden film of one 13~20nm of thickness of vacuum evaporation.Therefore, the hollow pipe array surface enhancing Raman scattering of Ag nanometer sheets assembling
(SERS) preparation of substrate, need to be using the ZnO nano-rod array substrate of the Au spin coatings generated on ITO electro-conductive glass as working electrode.
3rd, the SERS substrates of the hollow pipe array of this Ag nanometer sheets assembling, depositing operation is simple, of low cost, and should
Preparation process serves as sacrifice template by semiconductor ZnO nanorod, while is related to the catalytic effect of golden film, that is, is depositing Ag nanometers
During the hollow pipe array of piece assembling, entire ZnO nanorod is eroded completely by citric acid quickly under the catalysis etching of golden film,
The nanotube that Ag nanometer sheets assemble is caused to be hollow-core construction to the greatest extent.
4th, the hollow pipe array of the Ag nanometer sheets assembling of deposition simply ultrasound can be transferred on conducting resinl or transmit electricity
On the copper mesh of mirror, its hollow tubular structures can be more subtly observed.
Preparation method advantage of the present invention is that preparation process serves as sacrifice template, technique letter using semiconductor ZnO nanorod
Just, inexpensive, electric current are small, voltage is low.The substrate stability that this method obtains is high, structurally ordered controllable, is examined in Raman spectrum
Very high sensitivity is shown in survey.
Description of the drawings
Fig. 1 is the X-ray diffractogram (XRD) of the hollow pipe array of Ag nanometer sheets assembling.
The microscope scanning figure (SEM) of hollow pipe array that Fig. 2 is ZnO nanorod and Ag nanometer sheets assemble, wherein：
Fig. 2 (a) is the Ag nanometer sheets of different enlargement ratios respectively to sacrifice template ZnO nanorod, Fig. 2 (b), (c) and (d)
The front view and sectional view of the hollow pipe array structure of assembling.
Fig. 3 is that deposition reverse current is 100~300 μ A, the concentration of electrolyte of silver nitrate and citric acid mixed liquor for 10~
30g·L-1, in the SEM figures of sample obtained by the ZnO nanorod rough surface deposition for being rotary with Au nano particles, wherein：
The sedimentation time of Fig. 3 (a) is respectively 10min, and the sedimentation time of Fig. 3 (b) is respectively 15min, the deposition of Fig. 3 (c)
Time is respectively 20min, and the sedimentation time of Fig. 3 (d) is respectively 25min.
Fig. 4 scrapes off (stripping top level product) by blade for the tube array of Ag nanometer sheets assembling and is transferred to transmission electron microscope copper
SEM figures (c) and (d) and corresponding energy spectrum diagram (e) on online TEM figures (a) and (b) and conducting resinl.
Fig. 5 is the tube array forming process schematic diagram of Ag nanometer sheets assembling.
Fig. 6 be Ag nanometer sheets assembling tube array as SERS active-substrate detection R6G Raman spectrogram (laser swashs
It is 532nm, time of integration 30s to send out wavelength), wherein：
Fig. 6 (a) is high concentration 10-6The R6G solution of moL/L, Fig. 6 (b) are that low concentration is 10-12mol·L-1, R6G it is molten
Liquid.
Specific embodiment
A kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling, including substrate, substrate is led by ITO
The ZnO nano-rod array of Au spin coatings on electric glass and ITO electro-conductive glass is formed, and Ag nanometers are deposited on ZnO nano-rod array
Piece, and all etched away ZnO nano-rod array with acid solution, the self assembly of Ag nanometer sheets is only stayed to form nano-hollow tubulose knot
Structure.
The ZnO nano-rod array of Au spin coatings on ITO electro-conductive glass, preparation process include the following steps：
(1), layer of ZnO Seed Layer is deposited on ITO electro-conductive glass in advance using atomic layer ALD deposition method, by ITO conductions
Glass and ZnO Seed Layers thereon form ZnO seed layer substrates；
(2), using ZnO seed layer substrates made from step (1) as working electrode, zinc nitrate hexahydrate and hexamethylenetetramine
Mixed solution deposits ZnO nano-rod array by galvanostatic method as electrolyte in ZnO seed layer surfaces controllable electric；
(3) layer of Au film is deposited in ZnO nano-rod array surface vacuum by ion sputtering instrument again, so as in ITO conductions
The ZnO nano-rod array of Au spin coatings is obtained on glass.
In step (2), a concentration of 25mM of the mixed solution of zinc nitrate hexahydrate and hexamethylenetetramine, six in mixed solution
The ratio between molal quantity of water zinc nitrate and hexamethylenetetramine is 1:1.
The nano-hollow tubular structure that the self assembly of Ag nanometer sheets is formed is transferred on silicon chip, nanometer by silicon chip and thereon
Hollow tubular structures obtain the hollow pipe array surface that equally the Ag nanometer sheets with surface-enhanced Raman scattering activity assemble and increase
Strong Raman scattering substrate.
A kind of preparation method of the hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling, using substrate as
The mixed solution of working electrode, silver nitrate and citric acid as electrolyte, by galvanostatic method substrate ZnO nano-rod array
Upper controllable electro-deposition Ag nanometer sheets, ZnO nano-rod array is all etched away, only stay Ag nanometer sheet self assembly structures using electrolyte
Into nano-hollow tubular structure.
The concentration of electrolyte of the mixed solution of silver nitrate and citric acid is 10~30gL-1。
When galvanostatic method carries out controllable electro-deposition, using reverse operation electric current, current range is in 100~300 μ A
Between.
10~30min of sedimentation time of electro-deposition.
The purposes of the hollow pipe array surface enhancing Raman scattering substrate of a kind of Ag nanometer sheets assembling, for detecting in solution
Organic molecule, the detection limit of concentration is up to 10-12mol·L-1。
The process being detected to organic molecule in solution is as follows：
The hollow pipe array surface enhancing Raman scattering substrate that Ag nanometer sheets are assembled as Raman detection substrate, with go from
Sub- water is 10 as solvent compounding high concentration-6mol·L-1, low concentration 10-12mol·L-1Organic point of rhodamine 6G (R6G)
Sub- solution, it is 10 that Raman detection substrate, which is cut into pieces, and is separately immersed in high concentration-6mol·L-1, low concentration 10-12mol·L-1Both concentration rhodamine 6G (R6G) organic molecule solution in, soaking time in the organic molecule solution of middle and high concentration
For 0.5~1h, soaking time is 3.5~5h in the organic molecule solution of low concentration, after the Raman detection substrate impregnated is pulled out,
It treats R6G solution evaporations, then does Raman detection.
In the present invention, using the ZnO nano-rod array substrate of Au spin coatings generated on ITO electro-conductive glass as working electrode,
Under electric field action, the Ag+ in electrolyte is moved to cathode surface and reduction reaction occurs on substrate.On the other hand, in electrolyte
Citric acid be a kind of weak reductant, with a mild speed silver colloidal solution make Ag+ restore Ag20.Citric acid is in addition to can
Outside as weak reductant, be alternatively arranged as complexing agent, can precipitate metal ion (Ag+) rapidly, and metal ion Ag+ activity is higher,
It is easy to oxidation generation Ag2O, since the electro-deposition of golden film catalysis etching and Ag nanometer sheets acts on so that hydrogen ion (H+) is precipitated, with
Ag2O reaction generations H2O.Just lead to the formation of hollow tubular structures that Ag nanometer sheets assemble, as shown in Figure 1 and Figure 4.
Fig. 1's the result shows that, electro-deposition sample is mutually made of Ag, and diffraction maximum matches very much with the Ag of standard.
38.2oPlace, the relatively other diffraction maximums of Ag (111) crystal face also have stronger advantage, also there is apparent preferred orientation, this fully says
Clear Ag is with lamellar growth, 44.3oPlace, 64.5oPlace is followed successively by Ag (200), Ag (220) crystal orientation, and there is no ZnO (002)
Diffraction maximum, this illustrates that ZnO nanorod is corroded completely by citric acid just.The hollow pipe array that Ag nanometer sheets is caused to assemble
It is that vertical substrates are grown, but is maintained a certain distance with substrate, this distance is the length of ZnO nanorod eroded.
As shown in Fig. 2, Fig. 2 shows that the growth of the hollow pipe array of Ag nanometer sheets assembling is received dependent on the ZnO being corroded
Rice stick array structure is all perpendicular to substrate and all preferred orientation is grown, and the nanotube of Ag nanometer sheets assembling is hanging hangs down
Directly in substrate growth.The form of the tube array structure of Ag nanometer sheets assembling, and Ag nanometer sheets can also be found out from sectional view
The nanotube of assembling is hollow, this is because the catalysis etching of golden film decomposes the reason of ZnO nanorod in acidic environment, it will
ZnO nanorod gradually erodes.
In Fig. 4 the experimental results showed that：ZnO nanorod is corroded completely by citric acid under golden film catalysis.Scheme (a), (b) and
The nanotube that the assembling of Ag nanometer sheets is seen in figure (e) is hollow-core construction, and the Au elements in figure (e) are ion sputterings in ZnO nano
Au nano particles on stick, and other than Au elements, only Ag elements, do not occur Zn, O element, this is further demonstrate,proved
Understand that ZnO nanorod is corroded completely, inherently serve as the effect for sacrificing template.
The hollow pipe array surface enhancing Raman scattering substrate that Ag nanometer sheets assemble is used to detect in solution by the present invention
Organic molecule, such as rhodamine 6G, the detectable limit of concentration is up to 10-12mol·L-1。
The method being detected to organic molecule in solution of the hollow pipe array setting of prepared Ag nanometer sheets assembling
It is：The hollow pipe array surface that Ag nanometer sheets are assembled enhances Raman scattering substrate as Raman detection substrate, with deionized water
It is 10 as solvent compounding high concentration-6mol·L-1, low concentration 10-12mol·L-1, organic molecule solution, which is examined
It is 10 that survey substrate, which is cut into pieces and is separately immersed in high concentration,-6mol·L-1, low concentration 10-12mol·L-1These types of concentration
In organic molecule solution, soaking time is followed successively by high concentration 10-6mol·L-1For 0.5~1h, low concentration 10-12mol·L-1For
3.5~5h after the substrate impregnated is pulled out, treats R6G solution evaporations, then do Raman detection, as shown in Figure 6.
Fig. 6 (a) is high concentration 10-6The R6G solution of moL/L：Substrate soaking time 30min, 50 times of object distance amplifications are total to export
Power is 15mW, and 5% general power is exported after attenuation, finds out under high concentration, the characteristic peak of R6G occur from Raman figure, is drawn
Graceful signal is remarkably reinforced, and enhances to 105Times), Fig. 6 (b) is that low concentration is 10-12mol·L-1, R6G solution：When substrate is impregnated
Between 4h, it can be seen that have R6G characteristic peaks appearance, also mean that this SERS substrates also can for the organic molecule of low concentration
It is detected, detectable limit can reach 10-12mol·L-1。
The hollow pipe array surface that Ag nanometer sheets assemble can also be enhanced the Ag blades on Raman scattering substrate by the present invention
It directly scrapes a part and is put on transmission electron microscope copper mesh and carry out carrying out microscope scanning on transmission scan or conducting resinl, can measure
Its finer appearance structure, corresponding power spectrum can more show that ZnO nanorod here is to play the role of serving as sacrificing template,
Purpose is to generate the hollow pipe array that precious metals ag nanometer sheet assembles by means of semiconductor ZnO nanorod, this is than directly generating
Precious metals ag nanotube Raman signal is strong.
Influence of the sedimentation time to Ag morphogenesis is specifically had studied in the present invention, as shown in figure 3, Fig. 3 (a) only exists
ZnO nanorod tip nearby grows some fritters Ag nanometer sheets, and Fig. 3 (b) and 3 (c) as time went on, start from ZnO nano
Stick top grows the Ag nanometer sheets of some bulks along ear of maize from top to bottom, while ZnO nanorod is cut in gradually, and Fig. 3 (d) exists
The hollow pipe array structure of Ag nanometer sheets assembling is grown after deposition 25min, ZnO nanorod is corroded completely at this time；
When being 10min between when deposited, some fritters Ag nanometer sheets (Fig. 3 a) are grown near ZnO nanorod tip, with
When the time and increasing respectively to 15min and 20min, start to grow some from top to bottom from ZnO nanorod top along ear of maize big
The Ag nanometer sheets of block, while ZnO nanorod is cut in gradually, (Fig. 3 b, c).It is interesting that electrochemical deposition process is with the time
Increase, grown after 25min is deposited Ag nanometer sheets assembling hollow pipe array structure, at this time ZnO nanorod corroded completely.
According to it is above-mentioned as a result, it is of the invention propose Ag nanometer sheets assembling the possible forming process schematic diagram of hollow pipe such as
Shown in Fig. 5.Golden film on ZnO nano-rod array not only acts as the effect of etching ZnO nanorod, and it can be used as catalyst,
ZnO is catalytically decomposed.If golden film is not deposited, the pattern of the hollow pipe array of Ag nanometer sheets assembling, and electrochemical deposition will be cannot get
It is uneven.And the citric acid in electrolyte plays the part of the role of chelating agent in second step electro-deposition, it can precipitate rapidly metal
Ion (Zn2+、Ag+), Ag nanometer sheets is caused equably to be grown in the frame surface for sacrificing template (ZnO nanorod), so as to cause
The formation of the hollow pipe array of Ag nanometer sheets assembling.Two processes are synchronous, i.e., golden film catalysis etching ZnO nanorod and Ag receive
The formation of the hollow pipe array of rice piece assembling, shows during the two there is hydrogen ion (H+) be precipitated, and metal ion Ag
+ activity is higher, is easy to oxidation generation Ag2O, with Ag2O reaction generations H2O.Meanwhile the H+ of precipitation occurs instead again with ZnO nanorod
H should be generated2O, reaction equation are as follows：
2H++Ag2O→2Ag++H2O (1)
Ag++e→Ag0 (2)
2H++ZnO→Zn2++H2O (3)
It can be seen that, it is that golden film etches the catalysis of ZnO nano-rod array, just leads to what Ag nanometer sheets assembled in summary
The formation of hollow pipe array.
The hollow pipe array of Ag nanometer sheets assembling that the present invention is deposited, since the ZnO nanorod in ZnO Seed Layers exists
It being etched completely in citric acid, this is equivalent to the hollow pipe array that Ag nanometer sheets assemble being transferred directly in ZnO Seed Layers,
The Au nano particles that original is sputtered on ZnO nanorod also while are catalyzed etching ZnO nanorod, there remains a small amount of Au nanometers
Grain.With rhodamine liquor (R6G) for probe molecule, the hollow pipe array of this pure Ag nanometer sheets assembling can also detect R6G
The raman characteristic peak of molecule is as shown in Figure 6.
The above result shows that the hollow pipe array of the Ag nanometer sheets assembling prepared by this experiment can be used as one kind have very much
The substrate of the Surface enhanced Raman scattering of effect.
With reference to embodiments, the present invention is further illustrated.Following explanation is but this hair in a manner of enumerating
Bright protection domain is not limited thereto.
A kind of hollow pipe array surface enhancing Raman scattering (SERS) substrate of 1 Ag nanometer sheets of embodiment assembling and its preparation
Method includes the following steps：
A, the preparation of ZnO nano-rod array substrate, includes the following steps：(1) pass through atomic layer on ITO substrates in advance
(ALD) the ZnO Seed Layers of one tunic thickness about 15-25nm of deposition method, can obtain ZnO Seed Layer substrates；(2) with step (1)
Substrate obtained to generate ZnO Seed Layers on ITO electro-conductive glass as working electrode, zinc nitrate hexahydrate and hexamethylenetetramine
Mixed liquor is described mixed in ZnO seeds layer surface by constant current electrodeposition process electro-deposition ZnO nano-rod array as electrolyte
A concentration of 25mM of liquid is closed, the ratio between molal quantity of zinc nitrate hexahydrate and hexamethylenetetramine is 1 in mixed liquor:1；(3) it is received in ZnO
Rice stick array surface by the golden film of one 13~20nm of thickness of ion sputtering process vacuum evaporation, obtains the ZnO nano of Au spin coatings again
Stick array substrate；
B, 50ml AgNO are added in the electrolytic cell of 100ml3(2.0g·L-1) and citric acid (18gL-1) mixing it is molten
Liquid is electrolyte, is inserted into the ZnO nano-rod array substrate of the Au spin coatings generated on ITO electro-conductive glass prepared by small pieces step A
In electrolytic cell, as working electrode, the live part for immersing electrolyte is 2.5cm × 0.8cm, using graphite flake as to electricity
Pole, open reverse operation electric current, and adjust to the hollow pipe array that 150 μ A, Ag nanometer sheets assemble Au spin coatings ZnO nanorod
Array substrate surface is grown, and electric current is closed after 20min, rinses the hollow pipe array base that Ag nanometer sheets assemble with alcohol, water successively
Piece dries and just obtains SERS active-substrate,
Surface obtained above had into the active substrate of SERS effects as Raman detection substrate, with rhodamine liquor
(R6G) it is probe molecule, deionized water is 10 as solvent difference compounding high concentration-6mol·L-1, low concentration 10-12mol·
L-1Organic molecule solution, which is cut into pieces and is separately immersed in high concentration as 10-6mol·L-1, low concentration
It is 10-12mol·L-1Both concentration organic molecule solution in, soaking time is followed successively by high concentration 10-6mol·L-1For
0.5h, low concentration 10-12mol·L-1For 4h, after the substrate impregnated is pulled out, R6G solution evaporations are treated, then do Raman detection
(RenishawinVia Reflex Raman spectrometers, excitation wavelength 532nm), it will be apparent that observe the characteristic peak of R6G (see attached
Fig. 6).
Embodiment 2
A, it is identical with the step A of embodiment 1；
B, 50ml AgNO are added in the electrolytic cell of 100ml3(2.0g·L-1) and citric acid (18gL-1) mixing it is molten
Liquid is electrolyte, is inserted into the ZnO nano-rod array substrate of the Au spin coatings generated on ITO electro-conductive glass prepared by small pieces step A
In electrolytic cell, as working electrode, the live part for immersing electrolyte is 2.5cm × 0.8cm, using graphite flake as to electricity
Pole, open reverse operation electric current, and adjust to the hollow pipe array that 150 μ A, Ag nanometer sheets assemble Au spin coatings ZnO nanorod
Array substrate surface is grown, and electric current is closed after 25min, rinses the hollow pipe array base that Ag nanometer sheets assemble with alcohol, water successively
Piece dries and just obtains SERS active-substrate,
Surface obtained above had into the active substrate of SERS effects as Raman detection substrate, using R6G as probe
Molecule does Raman detection by the method in embodiment 1, it will be apparent that observes the characteristic peak of R6G, Raman signal intensity is close in fact
Apply example 1.
Embodiment 3
A, it is identical with the step A of embodiment 1；
B, 50ml AgNO are added in the electrolytic cell of 100ml3(2.0g·L-1) and citric acid (18gL-1) mixing it is molten
Liquid is electrolyte, is inserted into the ZnO nano-rod array substrate of the Au spin coatings generated on ITO electro-conductive glass prepared by small pieces step A
In electrolytic cell, as working electrode, the live part for immersing electrolyte is 2.5cm × 0.8cm, using graphite flake as to electricity
Pole, open reverse operation electric current, and adjust to the hollow pipe array that 170 μ A, Ag nanometer sheets assemble Au spin coatings ZnO nanorod
Array substrate surface is grown, and electric current is closed after 20min, rinses the hollow pipe array base that Ag nanometer sheets assemble with alcohol, water successively
Piece dries and just obtains SERS active-substrate,
Surface obtained above had into the active substrate of SERS effects as Raman detection substrate, using R6G as probe
Molecule does Raman detection by the method in embodiment 1, it will be apparent that observes the characteristic peak of R6G, Raman signal intensity is with implementing
Example 1 is suitable.
Embodiment 4
A, it is identical with the step A of embodiment 1；
B, 50ml AgNO are added in the electrolytic cell of 100ml3(2.0g·L-1) and citric acid (18gL-1) mixing it is molten
Liquid is electrolyte, is inserted into the ZnO nano-rod array substrate of the Au spin coatings generated on ITO electro-conductive glass prepared by small pieces step A
In electrolytic cell, as working electrode, the live part for immersing electrolyte is 2.5cm × 0.8cm, using graphite flake as to electricity
Pole, open reverse operation electric current, and adjust to the hollow pipe array that 170 μ A, Ag nanometer sheets assemble Au spin coatings ZnO nanorod
Array substrate surface is grown, and electric current is closed after 30min, rinses the hollow pipe array base that Ag nanometer sheets assemble with alcohol, water successively
Piece dries and just obtains SERS active-substrate,
Surface obtained above had into the active substrate of SERS effects as Raman detection substrate, using R6G as probe
Molecule does Raman detection by the method in embodiment 1, it will be apparent that observes the characteristic peak of R6G, Raman signal intensity is with implementing
Example 1 is suitable.
Claims (10)
1. a kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling, it is characterised in that：Including substrate,
Substrate is made of the ZnO nano-rod array of the Au spin coatings on ITO electro-conductive glass and ITO electro-conductive glass, on ZnO nano-rod array
Ag nanometer sheets are deposited, and are all etched away ZnO nano-rod array with acid solution, the self assembly of Ag nanometer sheets is only stayed to form nanometer
Hollow tubular structures.
2. a kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling according to claim 1,
It is characterized in that：The ZnO nano-rod array of Au spin coatings on ITO electro-conductive glass, preparation process include the following steps：
（1）, using atomic layer ALD deposition method in advance on ITO electro-conductive glass deposit layer of ZnO Seed Layer, by ITO electro-conductive glass
And ZnO Seed Layers thereon form ZnO seed layer substrates；
（2）, with step（1）ZnO seed layer substrates obtained be working electrode, the mixing of zinc nitrate hexahydrate and hexamethylenetetramine
Solution deposits ZnO nano-rod array by galvanostatic method as electrolyte in ZnO seed layer surfaces controllable electric；
（3）Layer of Au film is deposited in ZnO nano-rod array surface vacuum by ion sputtering instrument again, so as in ITO electro-conductive glass
The upper ZnO nano-rod array for obtaining Au spin coatings.
3. a kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling according to claim 2,
It is characterized in that：Step（2）In, a concentration of 25mM of the mixed solution of zinc nitrate hexahydrate and hexamethylenetetramine, in mixed solution
The ratio between molal quantity of zinc nitrate hexahydrate and hexamethylenetetramine is 1:1.
4. a kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling according to claim 1,
It is characterized in that：The nano-hollow tubular structure that the self assembly of Ag nanometer sheets is formed is transferred on silicon chip, receiving by silicon chip and thereon
Rice hollow tubular structures obtain the hollow pipe array surface that equally the Ag nanometer sheets with surface-enhanced Raman scattering activity assemble
Enhance Raman scattering substrate.
5. the preparation side of hollow pipe array surface enhancing Raman scattering substrate that Ag nanometer sheets described in a kind of claim 1 assemble
Method, it is characterised in that：Using substrate as working electrode, the mixed solution of silver nitrate and citric acid passes through permanent electricity as electrolyte
Stream method controllable electro-deposition Ag nanometer sheets on the ZnO nano-rod array of substrate are all carved ZnO nano-rod array using electrolyte
Eating away only stays the self assembly of Ag nanometer sheets to form nano-hollow tubular structure.
6. a kind of system of the hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling according to claim 5
Preparation Method, it is characterised in that：The electrolyte is the mixed solution of silver nitrate and citric acid, concentration ratio 1:9.
7. a kind of system of the hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling according to claim 5
Preparation Method, it is characterised in that：When the galvanostatic method carries out controllable electro-deposition, using reverse operation electric current, electric current
Range is between 100 ~ 300 μ A.
8. a kind of system of the hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling according to claim 5
Preparation Method, it is characterised in that：10 ~ 30min of sedimentation time of electro-deposition.
9. the purposes of hollow pipe array surface enhancing Raman scattering substrate that Ag nanometer sheets described in a kind of claim 1 assemble,
It is characterized in that：For detecting the organic molecule in solution, the detection limit of concentration is up to 10-12mol·L-1。
10. the purposes of the hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling according to claim 9,
It is characterized in that：The process being detected to organic molecule in solution is as follows：
The hollow pipe array surface that Ag nanometer sheets are assembled enhances Raman scattering substrate as Raman detection substrate, with deionized water
It is 10 as solvent compounding high concentration-6mol·L-1, low concentration 10-12mol·L-1Rhodamine 6G organic molecule solution, will
It is 10 that Raman detection substrate, which is cut into pieces and is separately immersed in high concentration,-6mol·L-1, low concentration 10-12mol·L-1Both
In the rhodamine 6G organic molecule solution of concentration, soaking time is 0.5 ~ 1 h in the organic molecule solution of middle and high concentration, low dense
Soaking time is 3.5 ~ 5 h in the organic molecule solution of degree, after the Raman detection substrate impregnated is pulled out, treats that rhodamine 6G is molten
Liquid volatilizees, then does Raman detection.
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