CN109001183A - Precious metal nanorod-precious metal nanoparticle composite structure and preparation method thereof - Google Patents
Precious metal nanorod-precious metal nanoparticle composite structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a noble metal nanorod-noble metal nanoparticle composite structure and a preparation method thereof, wherein the structure comprises the following components: the device comprises a substrate, a metal film layer, a noble metal film layer, noble metal nanorods and noble metal nanoparticles, wherein the metal film layer is at least arranged on the top surface of the substrate; the noble metal film layer is arranged on the top surface of the metal film layer; the noble metal nano-rod is arranged on the noble metal film layer; the noble metal nano particles form electric adsorption force or covalent bond bonding force through the polymer layer and are combined on the surface of the noble metal nano rod; the included angle formed by the axial direction of the noble metal nano rod and the normal direction of the surface of the substrate is 60-85 degrees. The obtained structure can be used as SERS, so that the SERS hot spot quantity of the obtained structure material can be improved.
Description
Technical field
The present invention relates to a kind of noble metal nano stick-metal nanoparticle composite constructions and preparation method thereof, belong to nanometer
Material Field.
Background technique
Surface enhanced Raman scattering technology (Surface-enhanced Raman scattering, hereinafter referred to as SERS)
It is a kind of very important analysis detection means, is widely used in the fields such as medical treatment, environment, food safety detection, especially existing
There is huge application prospect in terms of field, highly sensitive quickly biochemistry detection and trace analysis field.
When substance to be detected is adsorbed on coarse precious metal surface, due to the plasma resonance characteristic of precious metal surface,
The raman spectral signal intensity of material molecule can be significantly enhanced.These coarse noble metal structures are commonly known as SERS base
Bottom.Therefore, SERS detection sensitivity is mainly determined by the enhancing ability of SERS substrate.The surface microscopic topographic of SERS substrate is usual
It is made of the noble metal nano structure of different shape.These nanostructured morphologies play a decisive role to the enhancing of signal.Research
Show when nanotip or nano gap occurs in noble metal nano structure, enhances the available significant increase of performance.?
In SERS detection, these nanotips and nano gap are commonly known as SERS hot spot.
Existing SERS substrate processing is with across scale difficulty of processing is big, at high cost, homogeneity is poor, structure can not regulate and control, nothing
Method realizes the disadvantages of standardization processing.
Summary of the invention
A kind of noble metal nano stick-noble metal nano particles composite construction is additionally provided according to an aspect of the present invention, it should
The detection sensitivity of composite construction substrate is high, SERS signal reproducible, and preparation process is simple, cost is relatively low.
Noble metal nano stick-noble metal nano particles composite construction, comprising: substrate, metallic diaphragm, precious metal film layer, expensive
Metal nano-rod and noble metal nano particles, the metallic diaphragm are at least set on the top surface of the substrate；
The precious metal film layer is set on the top surface of the metallic diaphragm；
The noble metal nano stick is obliquely installed on the precious metal film layer；
The noble metal nano forms electrical adsorption capacity by polymeric layer and forms covalent bonding power is incorporated in your gold
Belong to nanorod surfaces；
The axial direction of the noble metal nano stick and the substrate surface normal orientation at 60 ° ~ 85 ° of angle.
According to the one aspect of the application, provide it is a kind of it is versatile, technique is controllable, low in cost, simple process
Noble metal nano stick-noble metal nano particles composite construction preparation method, the method overcome machining mode is at high cost, difficult
The disadvantages of to control, realizes being stably connected with for metal nanoparticle and noble metal nano stick structure by the way that body structure surface is modified, obtains
Obtain noble metal nano stick-metal nanoparticle composite construction.
The noble metal nano stick-nano-particles reinforcement structure preparation method, comprising the following steps:
It is sequentially depositing metal film and noble metal film in substrate surface, in the noble metal film surface inclined deposition noble metal nano
Stick obtains oblique bar material；The axial direction of the noble metal nano stick and the normal orientation angulation of the substrate surface exist
Between 60 ° ~ 85 °；；
Pass through polymer connection method carried noble metal nano particle on the oblique bar material surface and the noble metal mould surface；Institute
State polymer connection method the following steps are included:
The oblique bar material is impregnated and is taken out after reacting in a polymer solution, the positively charged modification structure in surface is obtained；
The modification structure is immersed in nano particle colloidal sol and is reacted；It include several negatively charged in the nano particle colloidal sol
Noble metal nano particles；Your gold be incorporated by covalent bonding power and electrical adsorption capacity for the noble metal nano particles
Belong to nanorod surfaces and noble metal film layer surface；
It is dried after the oblique side material for being adsorbed with noble metal nano particles is taken out, obtains noble metal nano stick-noble metal and receive
Rice grain composite construction.
Beneficial effects of the present invention include but is not limited to:
(1) noble metal nano stick provided by the present invention-noble metal nano particles composite construction preparation method, passes through polymer pair
Noble metal nano stick body structure surface is modified, and nano particle is enable to form stable electricity with noble metal nano stick body structure surface
Property absorption and/or chemical covalent key connection, in original nanostructure add sol particle realize different structure compound, gained
Noble metal nano stick-noble metal nano particles sandwich is as substrate in use, detection sensitivity is high, SERS signal
It is reproducible.
(2) noble metal nano stick provided by the present invention-noble metal nano particles composite construction preparation method, for metal
Nano material SERS enhances the characteristics of substrate manufacture, by the method for chemical modification, adds in original noble metal nano stick structure
Ghana's rice grain forms the composite construction of a kind of similar " sesame is attached on club ".Wherein noble metal nano stick structure is made
Addition for the skeleton of composite construction substrate, nano particle will not influence the distribution and arrangement of raw skeleton structure, but make base
More nano gaps and nanotip structure are generated in the skeleton structure of bottom, the electromagnetic field in these regions generates aggregation and coupling,
Substrate is set to show as the intensity and increase in density of SERS hot spot.This method can effectively improve nano particle in noble metal nano
The homogeneity on stick surface, while significantly improving the SERS enhancing ability of noble metal nano stick structural substrates.Without to existing structure
It is machined, while reducing difficulty of processing, improves the detection sensitivity of resulting structures.
(3) noble metal nano stick provided by the present invention-noble metal nano particles composite construction preparation method, technique letter
It is single, low in cost, universality is high, be conducive to mass large-scale production.
(4) noble metal nano stick-noble metal nano particles composite construction provided by the present invention, is obtained by the above method
Composite construction substrate detection sensitivity it is high, SERS signal reproducible.The composite construction highly sensitive optical device,
All have wide practical use in terms of biochemical sensitive device.Silver nanorod-P2VPy- gold core silver shell can be made using this method
Grain composite construction (example 1), Silver nanorod-PEI- gold core silver shell particle composite structures and Silver nanorod-Argent grain composite construction
Preparation (example 2), Silver nanorod-PDA- silver nanoparticle composite construction preparation (example 3).
Detailed description of the invention
Fig. 1 is noble metal nano stick provided by the invention-noble metal nano particles composite construction preparation method process signal
Block diagram；
The model schematic of golden core silver core-shell nanoparticles in gold seeds colloidal sol obtained by Fig. 2 preferred embodiment of the present invention；
Glancing angle deposition device use state diagram used in Fig. 3 preferred embodiment of the present invention；
Glancing angle deposition Silver nanorod structure deposition process schematic diagram in Fig. 4 preferred embodiment of the present invention；
Gained Silver nanorod structural model schematic diagram after glancing angle deposition in Fig. 5 preferred embodiment of the present invention；
Silver nanorod structural substrates, which are immersed in polymer molecule solution, in Fig. 6 preferred embodiment of the present invention reacts schematic diagram；
The Silver nanorod structural schematic diagram of polymer molecule film is covered in Fig. 7 preferred embodiment of the present invention；
The Silver nanorod structure partial enlarged diagram of polymer molecule film is covered in Fig. 8 preferred embodiment of the present invention；
The Silver nanorod structure that polymer has been modified in Fig. 9 preferred embodiment of the present invention 1 is immersed in golden core silver shell particle colloidal sols
React schematic diagram；
Gained Silver nanorod-polymer-gold core silver shell particle composite structures model signal in Figure 10 preferred embodiment of the present invention 1
Figure；
Gained Silver nanorod-polymer-gold core silver shell particle composite structures model is locally put in Figure 11 preferred embodiment of the present invention 1
Big schematic diagram；
Figure 12 is the SEM of resulting structures material in the embodiment of the present invention 1 and comparative example 1 as a result, wherein (a) is to mention in comparative example 1
The Silver nanorod structural schematic diagram that supplier's method is prepared；(b) gained Silver nanorod-P2VPy- gold core silver shell in embodiment 1
Grain composite construction schematic diagram；
Figure 13 is the Raman light of resulting structures material tests various concentration 1,2- bis- (4- pyridyl group) ethylene in comparative example 1 of the present invention
Spectrogram；Wherein, (a) be with Silver nanorod structure be SERS substrate detect various concentration 1,2-di(4-pyridyl)ethylene Raman
Spectrogram (b) be with Silver nanorod structure be SERS substrate detect various concentration 1,2- bis- (4- pyridyl group) ethylene Raman spectrum
Figure is in 1570cm-1-1680cm-1Partial enlarged view；
Figure 14 is the Raman of detection various concentration 1,2- bis- (4- pyridyl group) ethylene of resulting structures material in the embodiment of the present invention 1
Spectrogram, wherein a) to be that SERS substrate detects various concentration 1 with Silver nanorod-P2VPy- gold core silver shell particle composite structures,
The Raman spectrogram of 2- bis- (4- pyridyl group) ethylene；It b) is to be with Silver nanorod-P2VPy- gold core silver shell particle composite structures
SERS substrate detects the Raman spectrogram of various concentration 1,2- bis- (4- pyridyl group) ethylene in 1570cm-1-1710cm-1Part
Enlarged drawing；
Marginal data:
100, substrate；210, angle modulation turntable；220, clamping component；230, hanging bracket；300, evaporation source；400, instrument is deposited.
Specific embodiment
The present invention is described in detail below with reference to embodiment, but the invention is not limited to these embodiments.
Referring to Fig. 1, noble metal nano stick provided by the invention-noble metal nano particles composite construction preparation method, including
Following steps:
It is sequentially depositing metal film and noble metal film in substrate surface, in the noble metal film surface inclined deposition noble metal nano
Stick obtains oblique bar material；
In the oblique bar material area load noble metal nano particles；Metal nano-rod body structure surface characteristics of plasma regulates and controls problem
It is the difficult point of this field one, the present invention is hot using the method regulation SERS of carried metal nano particle building composite S ERS substrate
Point achieves SERS signal improvement effect, while ensure that the homogeneity of substrate；
The axial direction of the noble metal nano stick and the normal orientation angulation of the substrate surface are between 60 ° ~ 85 °.
Noble metal nano structure composition of the microscopic appearance of gained SERS substrate surface by different shape, these nanostructures
Presence play a major role to the enhancing of detectable substance Molecular Raman signal.The structural factors such as material, pattern, the size of nanostructure
Influence the performances such as generation, distribution and the intensity size of Raman signal.In the region with nanotip or interstitial structure, electromagnetism
Field generates aggregation or coupling, forms localized surface plasmons resonance, and the raman scattering intensity for being adsorbed on substrate surface molecule significantly increases
By force, the position of these nanotips or nano gap is claimed into SERS hot spot.SERS hotspot's distribution, intensity and density are to substrate
The excellent degree of SERS performance plays a decisive role.Obvious substrate material used herein is silicon, glass, quartz or other polymerizations
Object.Noble metal nano particles can be carried on the noble metal nano stick surface and/or noble metal film surface of oblique bar material as needed.
Noble metal includes gold, silver, copper in the present invention, naturally it is also possible to exclude copper as needed.
The method provided by the present invention is by after substrate material surface inclined deposition forms noble metal nano stick, referring to Fig. 7,
Substrate surface forms club shaped structure, and formed club shaped structure is added after nano particle, nano particle, which is attached to, to be received referring to Fig. 5
Rice stick surface, original rodlike following three variations to have occurred due to the presence of particle:
1, stick surface forms a large amount of due to for no particle, increasing more cutting-edge structures with the presence of particle
New hot spot region；
2, almost adhere to a large amount of nano particles in each nanometer rods, for agranular club shaped structure, shortens and receive
The distance between rice stick, gap shrinks further increase hot spot；
3, between the particle and particle adhered in same nanometer rods, it can also form hot spot.
A large amount of hot spots are formed in original SERS substrate material surface to realize, to improve the SERS signal of obtained device
Detection sensitivity.
Nanometer rods herein refer to that the diameter of club shaped structure is nanoscale；Nano particle refers to that the diameter of particle is nanometer
Grade.
Preferably, the angle of the axial direction of the noble metal nano stick and the substrate surface normal orientation be 60 ° ~
80°。
Preferably, the noble metal nano particles are in gold nano grain, silver nano-grain or golden core-silver core-shell nanoparticles
It is any.Referring to fig. 2, the golden core-silver shell structure is gold particle coated with uniform silver shell structure.
Preferably, described " carried noble metal nano particle " step includes: that nano particle in situ growth method or polymer connect
Connection.
Preferably, described " carried noble metal nano particle " step is nano particle in situ growth method；The nano particle
In situ synthesis includes: as reducing agent using poly-dopamine (Polydopamine, PDA) on noble metal nano stick surface
The step of nano particle in situ is grown.
Poly-dopamine is to be formed by polymer by dopamine (Dopamine) auto polymerization, and poly-dopamine (PDA) can be tight
It is close to be adhered to a variety of substrate material surfaces, form uniform clad.Meanwhile poly-dopamine is to Ag+Have strong adsorptivity and it is weak also
Originality, by the Ag of absorption+In-situ reducing is Ag nanoparticle, and is fixed on the substrate material surface with PDA coating, in material
Surface forms poly-dopamine/nano grain of silver minor structure.
Preferably, the nano particle in situ growth method is the following steps are included: configure in order the Tris solution that pH value is 8.5
With dopamine hydrochloride-Tris solution, the concentration range for adjusting dopamine hydrochloride-Tris solution is that 0.5-3mg/ml(is more excellent
Choosing, concentration 1mg/ml)；Oblique bar material is immersed in the dopamine hydrochloride-Tris Solutions Solution and is reacted, when reaction
Between be 3-10h (preferred soaking time is 8h), with ultrapure water clean after, be immersed in certain density AgNO3In, it is dense
Degree range is 3-12mg/ml, and shading reaction, the reaction time 0.5-5 days, reaction taking-up was cleaned 3 ~ 4 times with ultrapure water, is dried up.It is excellent
Gesture is that cost is relatively low, convenient for large-scale production, morphology controllable, by controlling AgNO3Concentration dopamine hydrochloride-Tris is molten
Time controls pattern when the concentration and reaction of liquid.
Preferably, described " carried noble metal nano particle " step is polymer connection method；The polymer connection method packet
It includes: oblique bar material is immersed into the polymer solution the step of reacting.
The electrical property for being improved noble metal nano stick surface using polymer can be formed effective between nano particle
Chemistry key connection, it is final to obtain noble metal nano stick-polymer-nanoparticle composite construction.
Referring to Fig. 6 ~ 8, it is preferred that the polymer connection method the following steps are included:
The oblique bar material is impregnated and is taken out after reacting in a polymer solution, obtains the positively charged modification structure in surface by S1；
Oblique bar material is impregnated and is taken out after reacting in a polymer solution, polymer concentration range 0.5mg/ml-5mg/ml, instead
1-8h (more preferably 3h) between seasonable, takes out after cleaning 3 ~ 5 times with deionized water, obtains modification structure；
The modification structure is immersed in nano particle colloidal sol and is reacted, is taken out after reaction time 3-10h.
Preferably, the polymer includes at least one group in amino group, mercapto groups or pyridine groups；More preferably
, the polymer comprising amino group includes PEI (Polyethyleneimine, polyethyleneimine, abbreviation PEI), PAH
[poly (allylamine hydrochloride), polyallylamine hydrochloride, abbreviation PAH], PAMAM
(Polyamidoamine dendrimer, polyamidoamine dendrimer, abbreviation PAMAM)), PDADMAC[poly
(diallyldimethylammonium chloride), polydiallyldimethyl ammonium chloride solution, abbreviation PDADMAC], include
The polymer of mercapto groups includes APTES[(3-aminopropyl) triethoxysilane, 3- aminopropyl-triethoxy silicon
Alkane, abbreviation APTES], the polymer comprising pyridine groups includes P2VY[poly-2-vinylpyridine, poly- (2- ethylene pyrrole
Pyridine), abbreviation P2VPy].PEI is branched chain type PEI.The structure that this method is formed is metal nano-rod-polymer-metal nanometer
Grain, operating method is more simple, and structure interval is easier.From a cost perspective, polymer cost is far below biotin-
Streptavidin cost.
The modification structure is immersed in nano particle colloidal sol and reacts by S2；Comprising several in the nano particle colloidal sol
The noble metal nano particles of negatively charged；The noble metal nano particles are described by covalent bonding and by being electrically adsorbed in
Noble metal nano stick surface and noble metal film layer surface；Covalent bonding and electrically absorption can form stability and preferably connect
It connects；
S3 dries after taking out the oblique bar material for being adsorbed with noble metal nano particles, obtains noble metal nano stick-noble metal
Nano-particles reinforcement structure.
Referring to Fig. 3, it is preferred that " in the substrate surface inclined deposition noble metal nano stick " step can use existing skill
Art means are realized, such as equipment therefor includes: hanging bracket 230, clamping component 220 and the angle modulation being installed in vapor deposition instrument 400
Turntable 210, the hanging bracket 230 are set to 300 top of evaporation source；The clamping component 220 is rotationally connected with the suspension
The inside of bracket 230 simultaneously clamps the substrate 100.Referring to fig. 4, it is able to achieve in deposition process by using the device,
The normal direction of easy adjusting substrate material and the axis angulation of the evaporation source.To which deposition obtains differing tilt angles
Noble metal nano stick structure.The device has the supporting structure of adjustable-angle, it is only necessary to common electron-beam coating equipment be transformed
, keep depositional plane normal direction and evaporation source angled, to realize the inclined deposition technique in experiment.
Specifically, substrate or glass substrate can be placed in electron-beam coating equipment, one layer of chromium film is successively vertically deposited
With one layer of noble metal film (such as silverskin).Then, above-mentioned print is taken out to the surface for being pasted onto adjustable support supporting plane, is adjusted
It after angle, is mounted on and continues to be deposited at the top of electron beam equipment, will be obtained on noble metal film surface and tilt noble metal nano stick
Structure.
Preferably, the inclined deposition condition are as follows: vacuum degree is 5 × 10-4Pa, preheat gun filament 3min after up voltage extremely
8KV, evaporation rate are maintained at 1-1.5/s.
Preferably, the surfacing of the print includes the chromium film and precious metal film layer for being stacked and placed on substrate surface.Referring to figure
5, chromium film is set on substrate, silverskin is set in chromium film surface.Substrate can be silicon substrate or the substrate of glass.
Preferably, the noble metal nano particles partial size is 10-80nm.
Preferably, the precious metal film layer with a thickness of 50-500nm.
Preferably, the length of the noble metal stick is 400-1400nm.
Since the length of noble metal nano stick is larger, and there are many Nano grade gaps between nanometer rods, in order to allow
Reagent containing polymer reaches nanorod surfaces and noble metal film surface, before step S1 further include:
S01 immerses oblique bar material in the piranha solution that temperature is 80 DEG C, and ultrasonic vibration is reacted 1 hour, receives to noble metal
Rice stick surface and substrate noble metal film layer surface carry out hydrophilic treated；
S02 is cleaned after taking out oblique bar material with deionized water.
Above-mentioned steps treated tiltedly bar material increase the hydrophily of substrate surface so that the reagent containing polymer is more
It is accessible to nanorod surfaces and noble metal film surface.
Due to the planform of oblique bar material, so that noble metal granule is provided with noble metal nano stick structure when connecting
Steric hindrance, and disconnected polymer is The more the better is needed through the proportion adjustment metal surface group of polymeric reagent
Density, step S2 include:
S21, configuration concentration range are the branched chain type PEI solution of 0.5mg/ml-5mg/ml；
Long chain type PEI is added in S22 in the above solution；
S23 impregnates the oblique bar material in the above solution, and ultrasonic vibration reaction, adjusting is attached to the noble metal nano
The amino amount on stick surface and substrate noble metal film surface.
Adjust through the above steps and be attached to the number of group in substrate, obtain attachment on the surface of the substrate one layer it is uniform
Noble metal granule layer, the equally distributed SERS hot spot of acquisition.To the measurement sensitivity of the Raman substrate improved.
Referring to Figure 10 ~ 11, another aspect provides a kind of noble metal nano stick-noble metal nano particles are compound
Structure, comprising: substrate, metallic diaphragm, precious metal film layer, noble metal nano stick and noble metal nano particles, the metallic diaphragm
It is at least set on the top surface of the substrate；The precious metal film layer is at least set on the top surface of the metallic diaphragm；It is described
Noble metal nano stick is obliquely installed on the precious metal film layer；The noble metal nano particles are adsorbed on institute by polymeric layer
State noble metal nano stick surface and/or noble metal film layer surface；The axial direction of the noble metal nano stick and the substrate table
The normal orientation in face is at 60 ~ 85 ° of angle.
The noble metal nano particles herein can also be distributed in the inclination noble metal nano stick and/or your gold
Belong to film surface.Between noble metal nano particles and metal nano-rod surface and noble metal nano particles and precious metal film layer table
By chemical bond joining and Electrostatic Absorption between face, specific preparation method is referring to embodiment 3；Noble metal nano particles and gold
Belong between nanorod surfaces and pass through Polymer adsorption between noble metal nano particles and noble metal film layer surface, mainly ties
The Covalent bonding together on structure surface also has electrostatic simultaneously, and electrically absorption combines.Specific preparation method is referring to embodiment 1.Behaviour of the invention
It is more simple to make method, structure interval is easier, and polymer cost is far below biotin-streptavidin cost.
Preferably, the noble metal nano particles partial size is 10-80nm.
Preferably, the precious metal film layer with a thickness of 50-500nm.
Preferably, the length of the noble metal stick is 400-1400nm.
Preferably, the noble metal nano stick and the substrate material surface are angled 60 ° ~ 80 °.
Below in conjunction with specific embodiments of the present invention, technical solution of the present invention is described in detail.
Unless otherwise instructed, the raw material in the embodiment of the present invention and catalyst are bought by commercial sources, wherein
P2VPY is purchased in Sigma-Aldrich company, analyzes pure P2VPy 159K, Mw 159000, Mn 152000.
SERS substrate can be divided into three kinds: the first is solid SERS substrate (or becoming metal Nano structure substrate)；
Second is metal nanometer sol SERS substrate, and substrate macroscopic form is liquid；It is the third shown in the embodiment of the present invention, solid-state
Substrate and colloidal sol combine the composite S ERS substrate of composition.
The common manufacturing process of solid SERS substrate (metal Nano structure substrate) includes focused-ion-beam lithography, electronics
Beam photoetching, nano impression, nanosphere lithography etc..These technologies generally use precision equipment and are processed, high degree of automation, base
Controllability, homogeneity and repeatability prepared by bottom is superior.But it due to having used precision instrument, just inevitably improves
The technology difficulty and processing cost of substrate preparation.
The typical structure of metal nanoparticle colloidal sol substrate includes gold/silver nano-grain, core-shell structure particles etc..These are molten
Glue particle is using being chemically synthesized, and simple process, preparation cost is low, but substrate hot spot emerged be it is random, will be from root
Cause the SERS hot spot of substrate that cannot repeat to construct in sheet.
Composite S ERS substrate is that metal nanoparticle is supported on metallic nanostructured surface, adjusts and enhances original
Substrate surface plasma characteristics, simple process and low cost are a kind of highly sensitive SERS substrate building sides of great potential
Method.
1 SERS of table enhances the comparative analysis of substrate performance
The method that embodiment 1 prepares Silver nanorod-P2VPy- gold core silver shell particle composite structures
1, the nano particle of golden core-silver shell is prepared
The preparation process of 1.1 gold seeds colloidal sols
Experiment flow is as follows: the gold chloride that 2ml concentration is 1% being added in 200ml water, addition when being heated with stirring to 100 DEG C
1.4ml sodium citrate, mixing speed 900rpm observe the variation of solution colour: colourless-black-black and blue color-darkviolet, solution
It is whole penetrating.With the variation of solution colour, gold seeds complete the process for being nucleated and growing up.It is kept stirring and fluidized state,
Stirring at normal temperature 45min after reaction 15min, constant volume to 400ml, shading are stored refrigerated spare after the reaction was completed.
The preparation process of 1.2 gold medal core silver shell colloidal sols
Above-mentioned solution 200ml is taken, is stirred again, 900 rpm of mixing speed is heated to the sodium citrate of addition 2ml after boiling
(1g/ml) and 2ml silver nitrate (0.18g/ml), the permeability decline of solution is obvious under visible light, color slightly deepen it is graying,
The reaction that silver nitrate is restored under sodium citrate high temperature has occurred, in one layer of gold seeds particle outer layer covers silver-colored shell.To Jin Heyin
Shell particle colloidal sols carry out centrifugation and redisperse to remove unreacted solution.Centrifuge speed is 6500rpm, and centrifugation time is
5min.Centrifugation removes supernatant later, will be deposited on the golden core silver shell particle of bottom.It is re-dispersed into 200ml secondary distilled water
In.
2, Silver nanorod structure is prepared
The preparation process flow of Silver nanorod structure includes pretreatment, vertical vapor deposition, orientation patch and the glancing angle deposition of substrate
Four processing steps.
The pretreatment of 2.1 substrates
It takes 3 cun of silicon substrates as substrate, is successively immersed in acetone, ethyl alcohol, is cleaned by ultrasonic 15 minutes in deionized water, then 80
DEG C " Piranha " solution (H2O2/H2SO4=1:4 (v/v)) middle immersion one hour, it is cleaned three times with deionized water, is stored in ethyl alcohol
In it is spare, using preceding with being dried with nitrogen.
2.2 vertical vapor depositions
Vertical evaporation process refer to by substrate be adhered to coating machine evaporated on top source surface and with horizontal plane keeping parallelism.
Ensure that evaporation source air-flow vertical deposition is successively deposited 200 in sample surfaces for the adhesiveness and SERS performance for improving bottom silverskin
Chromium film and 2000 silverskin, thickness of metal film controls by film thickness gauge.The technological parameter of vapor deposition process is as follows, vacuum degree 5
×10-4Pa, coating speed are 1 ~ 1.5/s, voltage 8KV.
2.3 orientation patches
Pretreated substrate is pasted onto the surface of angle-adjustable support supporting plane with high temperature gummed tape, each substrate is in same
One height, and ensure substrate surface and supporting plane surface gapless.
2.4 glancing angle deposition
Glancing angle deposition technique mainly includes the installation of adjustable support, keeps vacuum environment, the fusing of target Argent grain, Yin Na
The formation of rice stick layer, this cooling five key steps.After the sample cooling for completing vertical evaporation process, opens vapor deposition and set
It is standby, silicon substrate is set up in right above evaporation source, and the angle of silicon substrate is adjusted by ring flange, it is ensured that evaporative air is with default
Angle deposition is in substrate surface.The parameter setting for tilting nanometer rods depositing operation is as follows: vacuum degree is 5 × 10-4Pa, coating speed
For 1 ~ 1.5/s, voltage 8KV.It is 800nm that film thickness gauge, which controls film thickness, supports that planar depositions angle is 86.Tilt nanometer rods with
Substrate surface angulation is 73 °.
3, Silver nanorod body structure surface is modified
Silver nanorod structural substrates are immersed in the P2VPy of volumetric concentration 1mg/ml referring to Fig. 9 ~ 11 by the implementation process of step 3 ~ 4
It in solution, takes out after reacting 3h, is cleaned 3 ~ 5 times with deionized water, Silver nanorod body structure surface has been modified one layer of P2VPy points
Son.
4, Silver nanorod-P2VPy- gold core silver shell Particles dispersed nanostructure is prepared
The substrate of surface modification P2VPy is immersed in the colloidal solution of freshly prepd golden core silver shell particle, is taken after reacting 6h
Out, it is cleaned 4 times with deionized water, is dried with nitrogen after removing not connected golden core silver shell particle, obtain Silver nanorod-P2VPy-
Golden core silver shell Particles dispersed nanostructure substrate.Products therefrom structure is as shown in figure 11.By analog result in figure as it can be seen that in silverskin
P2VPy molecule film layer is arranged in surface；P2VPy molecule film layer coats silver nanometer column simultaneously；Golden core silver core-shell nanoparticles are with P2VPy points
Sub- film layer is binder, is supported on silver nanometer column surface.
Resulting structures material tests are in the Raman spectrogram of various concentration 1,2-di(4-pyridyl)ethylene, and acquired results are such as
Shown in Figure 14.
The method that embodiment 2 prepares Silver nanorod-PEI- gold core silver shell particle composite structures
The preparation process of 1.1 gold seeds colloidal sols
Experiment flow is as follows: the gold chloride that 2ml concentration is 1% being added in 200ml water, addition when being heated with stirring to 100 DEG C
1.4ml sodium citrate, mixing speed 900rpm observe the variation of solution colour: colourless-black-black and blue color-darkviolet, solution
It is whole penetrating.With the variation of solution colour, gold seeds complete the process for being nucleated and growing up.It is kept stirring and fluidized state,
Stirring at normal temperature 45min after reaction 15min, constant volume to 400ml, shading are stored refrigerated spare (Fig. 2) after the reaction was completed.
The preparation process of 1.2 gold medal core silver shell colloidal sols
Above-mentioned solution 200ml is taken, is stirred again, 900 rpm of mixing speed is heated to the sodium citrate of addition 2ml after boiling
(1g/ml) and 2ml silver nitrate (0.18g/ml), the permeability decline of solution is obvious under visible light, color slightly deepen it is graying,
The reaction that silver nitrate is restored under sodium citrate high temperature has occurred, in one layer of gold seeds particle outer layer covers silver-colored shell.To Jin Heyin
Shell particle colloidal sols carry out centrifugation and redisperse to remove unreacted solution.Centrifuge speed is 6500rpm, and centrifugation time is
5min.Centrifugation removes supernatant later, and the golden core silver shell grains for being deposited on bottom are re-dispersed into 200ml second distillation
In water.
2, the preparation of Silver nanorod structure
The preparation process flow of Silver nanorod structure includes pretreatment, vertical vapor deposition, orientation patch and the glancing angle deposition of substrate
Four processing steps.
The pretreatment of 2.1 substrates
It takes 3 cun of silicon substrates as substrate, is successively immersed in acetone, ethyl alcohol, is cleaned by ultrasonic 15 minutes in deionized water, then 80
DEG C " Piranha " solution (H2O2/H2SO4=1:4 (v/v)) middle immersion one hour, it is cleaned three times with deionized water, is stored in ethyl alcohol
In it is spare, using preceding with being dried with nitrogen.
2.2 vertical vapor depositions
Vertical evaporation process refer to by substrate be adhered to coating machine evaporated on top source surface and with horizontal plane keeping parallelism.
Ensure that evaporation source air-flow vertical deposition is successively deposited 200 in sample surfaces for the adhesiveness and SERS performance for improving bottom silverskin
Chromium film and 2000 silverskin, thickness of metal film controls by film thickness gauge.The technological parameter of vapor deposition process is as follows, vacuum degree 5
×10-4Pa, coating speed are 1 ~ 1.5/s, voltage 8KV.
2.3 orientation patches
Pretreated substrate is pasted onto the surface of angle-adjustable support supporting plane with high temperature gummed tape, each substrate is in same
One height, and ensure substrate surface and supporting plane surface gapless.
2.4 glancing angle deposition
Equipment therefor such as Fig. 3, glancing angle deposition technique mainly include equipment therefor installation, keep vacuum environment, target Argent grain
Fusing, the formation of Silver nanorod layer, this cooling five key steps.The sample for completing vertical evaporation process is cooling
Afterwards, evaporated device is opened, the bracket of angle adjustable is mounted on right above evaporation source, and variable-angle branch is adjusted by ring flange
Support the angle of plane, it is ensured that evaporative air is deposited on substrate surface (Fig. 4) with predetermined angle.The parameter of glancing angle deposition technique is set
Set as follows: vacuum degree is 5 × 10-4Pa, coating speed are 1 ~ 1.5/s, voltage 8KV.It is 800nm that film thickness gauge, which controls film thickness,
Support that planar depositions angle is 86.Silver nanorod structure obtained is as shown in Figure 5.
3, Silver nanorod body structure surface is modified
Configuration concentration is the PEI aqueous solution of 1mg/ml, and Silver nanorod structure SERS substrate is cut into having a size of 3mm × 3mm's
Size is separately immersed in the above PEI aqueous solution, is taken out after reacting 3h, is cleaned 3 ~ 5 times with deionized water.
4, the preparation of Silver nanorod-PEI-- gold core silver shell Particles dispersed nanostructure
The above substrate is immersed in the colloidal solution of freshly prepd golden core silver shell particle, is taken out after reacting 6h, use deionized water
Cleaning 4 times, is dried with nitrogen after removing not connected golden core silver shell particle, obtains Silver nanorod-PEI- gold core silver shell Particles dispersed
Nanostructure substrate.
The method that embodiment 3 prepares the golden core silver shell particle composite structures of Silver nanorod-poly-dopamine (PDA)-
1, the preparation of Silver nanorod structure
The preparation process flow of Silver nanorod structure includes pretreatment, vertical vapor deposition, orientation patch and the glancing angle deposition of substrate
Four processing steps.
The pretreatment of 1.1 substrates
It takes 3 cun of silicon substrates as substrate, is successively immersed in acetone, ethyl alcohol, is cleaned by ultrasonic 15 minutes in deionized water, then 80
DEG C " Piranha " solution (H2O2/H2SO4=1:4 (v/v)) middle immersion one hour, it is cleaned three times with deionized water, is stored in ethyl alcohol
In it is spare, using preceding with being dried with nitrogen.
1.2 vertical vapor depositions
Vertical evaporation process refer to by substrate be adhered to coating machine evaporated on top source surface and with horizontal plane keeping parallelism.
Ensure that evaporation source air-flow vertical deposition is successively deposited 200 in sample surfaces for the adhesiveness and SERS performance for improving bottom silverskin
Chromium film and 2000 silverskin, thickness of metal film controls by film thickness gauge.The technological parameter of vapor deposition process is as follows, vacuum degree 5
×10-4Pa, coating speed are 1 ~ 1.5/s, voltage 8KV.
1.3 orientation patches
Pretreated substrate is pasted onto the surface of angle-adjustable support supporting plane with high temperature gummed tape, each substrate is in same
One height, and ensure substrate surface and supporting plane surface gapless.
1.4 glancing angle deposition
Common electron-beam coating equipment is transformed in the supporting structure for devising adjustable-angle, makes depositional plane normal direction and evaporation source
It is angled, to realize the inclined deposition technique in experiment.Glancing angle deposition technique mainly includes the peace of adjustable support
Dress keeps vacuum environment, the fusing of target Argent grain, the formation of Silver nanorod layer, this cooling five key steps.
After the sample cooling for completing vertical evaporation process, evaporated device is opened, the bracket of angle adjustable is mounted on evaporation
Right above source, and pass through the angle of ring flange adjustment variable-angle supporting plane, it is ensured that evaporative air is deposited on predetermined angle
Substrate surface.The parameter setting of glancing angle deposition technique is as follows: vacuum degree is 5 × 10-4Pa, coating speed are 1 ~ 1.5/s, electricity
Pressure is 8KV.It is 800nm that film thickness gauge, which controls film thickness, supports that planar depositions angle is 86.
2, Silver nanorod composite construction is prepared based on poly-dopamine
2.1 configuration trishydroxymethylaminomethane (Tris)-HCl buffer solutions
1. the Tris for weighing 12.11g is placed in 100ml beaker.
2. 80ml ultrapure water is added, dissolution is sufficiently stirred.
3. it is 8.5 that dense HCl, which is added, and adjusts PH.
4. by solution constant volume to 100ml after regulating PH.
5. sealing is placed on refrigerator and saves for use.
The configuration of 2.2 dopamine hydrochlorides/Tris solution
At room temperature, dopamine hydrochloride is slowly dissolved in Tris solution, configures dopamine hydrochloride/Tris solution 20ml,
Concentration is 1mg/ml.
The preparation of 2.3 Silver nanorod-PDA- silver nanoparticle composite constructions
Substrate with Silver nanorod structure is immersed in the solution of above-mentioned dopamine hydrochloride/Tris solution configuration and is reacted
8h is cleaned after taking-up with ultrapure water, and being immersed in volume is 10ml, and concentration is the AgNO of 10mg/ml3In, shading takes after reacting 3 days
It is cleaned 3 ~ 4 times, is dried with nitrogen with ultrapure water out.Obtain Silver nanorod-PDA- gold core silver shell composite structure.
The method that embodiment 4 prepares Silver nanorod-PEI- gold core silver shell particle composite structures
The difference from example 2 is that: the noble metal nano stick and the SERS substrate material surface are angled 73 °.It is expensive
Metal nanoparticle partial size is 10nm.Precious metal film layer with a thickness of 500nm, the length of noble metal nano stick is 400nm.It is described
Polymer solution concentration range is 5mg/ml.Inclined deposition condition are as follows: evaporation rate is maintained at 1.5/s.
The method that embodiment 5 prepares Silver nanorod-PEI- gold core silver shell particle composite structures
The difference from example 2 is that: the axial direction of the noble metal nano stick and the normal orientation of the surface of silicon
It is 85 ° angled.Noble metal nano particles partial size is 50nm.Precious metal film layer with a thickness of 50nm.The length of noble metal nano stick
For 1400nm.The polymer solution concentration range is 0.5mg/ml.Inclined deposition condition are as follows: evaporation rate is maintained at 1/s.
The method that embodiment 6 prepares the golden core silver shell particle composite structures of Silver nanorod-poly-dopamine (PDA)-
Difference with embodiment 3 is: the concentration range of dopamine hydrochloride-Tris solution is 0.5mg/ml；Surface is tilted
The SERS base material of depositing noble metal nanometer rods, which is immersed in the dopamine hydrochloride-Tris Solutions Solution, to react, reaction
Time is 3h, after being cleaned with ultrapure water, is immersed in AgNO3In solution, the AgNO3The concentration range of solution is 12mg/ml,
Shading reaction, the reaction time 0.5 day.
The method that embodiment 7 prepares the golden core silver shell particle composite structures of Silver nanorod-poly-dopamine (PDA)-
Difference with embodiment 3 is: the concentration range of dopamine hydrochloride-Tris solution is 3mg/ml；Surface inclination is heavy
The SERS base material of product noble metal nano stick is immersed in the dopamine hydrochloride-Tris Solutions Solution and reacts, when reaction
Between be 10h, with ultrapure water clean after, be immersed in AgNO3In solution, the AgNO3The concentration range of solution is 3mg/ml, is hidden
Light reaction, the reaction time 5 days.
The method that comparative example 1 prepares Silver nanorod structure
The difference from embodiment 1 is that not being surface modified and loading nano particle step.Only carry out inclined deposition step.
The SEM result of 1 resulting materials of the embodiment of the present invention 1 and comparative example is referring to Figure 12.As seen from Figure 12, using the present invention
Noble metal nano stick-noble metal nano particles composite structure surface that providing method is prepared, with a large amount of nanometer
Particle covering.And products therefrom surface does not have any nano particle to cover in documents 1, and club shaped structure uniformity is poor.
The present invention carries out SERS map measurement according to the following steps:
(1) firstly, the laboratory sample for the 0.00182g that weighs with scale, is dissolved in the ethanol solution of 10ml, 10 are configured to-3M's
BPE ethanol solution；
(2) sample of step 1 is diluted according to ten times of concentration gradients, configures in order out concentration as solvent using ethyl alcohol
It is 10-4M、10-5M、10-6M、10-7M、10-8The BPE ethanol solution of M；
(3) silver nanometer column structure SERS substrate is divided into the fritter of about 3mm × 3mm, respectively takes the BPE ethyl alcohol of 5 μ l various concentrations
Solution and ethanol solution are added drop-wise to substrate surface respectively, and wherein ethyl alcohol is tested after natural air drying as blank control group；
(4) print is sequentially placed under the microscope of Portable Raman spectrometer, is opened laser, is brought into focus, and dark current is collected
Afterwards, SERS detection, the parameter of SERS detection are directly carried out are as follows: excitation wavelength 785nm, measured power 30mW, time of integration 10s,
Integral number of times 1 time.The spectrogram presented is through smooth and deduction back end processing.
Acquired results are as shown in Figure 13 ~ 14, and as shown in Figure 13, gained Silver nanorod structure is substrate in comparative example 1, with 1,
2- bis- (4- pyridyl group) ethylene (1,2-bis (4-pyridyl) ethylene, BPE) is probe molecule, determines the lowest detection limit
It is 10-6M；Display is using gained Silver nanorod composite construction is substrate in embodiment 1 in Figure 14, with 1,2-di(4-pyridyl)ethylene
(1,2-bis (4-pyridyl) ethylene, BPE) is probe molecule, determines that the lowest detection limit is 10-8M, it can be seen that, it adopts
The detection sensitivity of gained base material can be effectively provided with the method provided by the present invention, structure obtained by the method provided by the present invention
Gained underlying structure improves two orders of magnitude, significant effect in remolding sensitivity comparative example 1.
The above is only several embodiments of the present invention, not any type of limitation is done to the present invention, although this hair
It is bright to be disclosed as above with preferred embodiment, however be not intended to limit the invention, any person skilled in the art, it is not taking off
In the range of technical solution of the present invention, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of noble metal nano stick-noble metal nano particles composite construction characterized by comprising substrate, metallic diaphragm,
Precious metal film layer, noble metal nano stick and noble metal nano particles, the metallic diaphragm are at least set to the top surface of the substrate
On；
The precious metal film layer is set on the top surface of the metallic diaphragm；
The noble metal nano stick is obliquely installed on the precious metal film layer；
The noble metal nano particles form electrical adsorption capacity by polymeric layer and covalent bonding power is incorporated in your gold
Belong to nanorod surfaces；
The axial direction of the noble metal nano stick and the substrate surface normal orientation at 60 ° ~ 85 ° of angle.
2. noble metal nano stick-noble metal nano particles composite construction according to claim 1, which is characterized in that described
Noble metal nano particles partial size is 10-50nm；The length of the noble metal nano stick is 400-1400nm, the precious metal film layer
With a thickness of 50-500nm.
3. noble metal nano stick-noble metal nano particles composite construction according to claim 1, which is characterized in that formed
The material of the polymeric layer is used to form electropositive on noble metal nano stick surface, includes amino group, mercapto groups
Or in pyridine groups at least one group polymer.
4. noble metal nano stick-noble metal nano particles composite construction according to claim 3, which is characterized in that include
The polymer of amino group is PEI, PAH, PAMAM, PDADMAC, and the polymer comprising mercapto groups includes APTES, includes pyrrole
The polymer of piperidinyl group includes P2VY.
5. a kind of noble metal nano stick-noble metal nano particles composite construction preparation method, which is characterized in that including following step
It is rapid:
It is sequentially depositing metal film and noble metal film in substrate surface, in the noble metal film surface inclined deposition noble metal nano
Stick obtains oblique bar material；
Pass through polymer connection method carried noble metal nano particle on the oblique bar material surface and the noble metal mould surface；Institute
State polymer connection method the following steps are included:
The oblique bar material is impregnated and is taken out after reacting in a polymer solution, the positively charged modification structure in surface is obtained；
The modification structure is immersed in nano particle colloidal sol and is reacted；It include several negatively charged in the nano particle colloidal sol
Noble metal nano particles；The noble metal nano particles are by the attraction of positive and negative charge and the covalently bonded of formation together in institute
State noble metal nano stick surface and noble metal film layer surface；
It is dried after the oblique bar material for being adsorbed with noble metal nano particles is taken out, obtains noble metal nano stick-noble metal and receive
Rice grain composite construction.
6. noble metal nano stick according to claim 5-noble metal nano particles composite construction preparation method, feature exist
In before the oblique bar material is impregnated the step of reacting in a polymer solution further include:
Oblique bar material is immersed in the piranha solution that temperature is 80 DEG C, ultrasonic vibration is reacted 1 hour, to noble metal nano stick
Surface and substrate noble metal film layer surface carry out hydrophilic treated；
It is cleaned after oblique bar material is taken out with deionized water.
7. noble metal nano stick according to claim 5 or 6-noble metal nano particles composite construction preparation method, special
Sign is that the polymer includes at least one group in amino group, mercapto groups or pyridine groups.
8. noble metal nano stick according to claim 7-noble metal nano particles composite construction preparation method, feature exist
In the polymer comprising amino group is PEI, PAH, PAMAM, PDADMAC, and the polymer comprising mercapto groups is APTES, packet
Polymer containing pyridine groups is P2VY.
9. noble metal nano stick according to claim 8-noble metal nano particles composite construction preparation method, feature exist
In the oblique bar material, which is impregnated the step of reacting in a polymer solution, includes:
Configuration concentration range is the branched chain type PEI solution of 0.5mg/ml-5mg/ml；
Long chain type PEI is added in the above solution；
The oblique bar material is impregnated in the above solution, ultrasonic vibration reaction, adjusting is attached to the noble metal nano stick table
The amino amount in face and substrate noble metal film surface.
10. noble metal nano stick according to claim 5-noble metal nano particles composite construction preparation method, feature
It is, the noble metal nano particles are any one of gold nano grain, silver nano-grain or golden core-silver core-shell nanoparticles.
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