CN109060762A - Composite and flexible surface enhanced Raman substrate based on silver nano-grain and preparation method thereof - Google Patents
Composite and flexible surface enhanced Raman substrate based on silver nano-grain and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of composite and flexible surface enhanced Raman substrate and preparation method thereof based on silver nano-grain.The silver colloid containing a large amount of silver nano-grains (AgNPs) is prepared first with chemical reduction method；Secondly it is mixed to form suspension by silver colloid and with the dimethyl silicone polymer (PDMS) of dilution with toluene, suspension is added dropwise on hard substrate surface, be heating and curing the PDMS film to be formed and include a large amount of silver nano-grains, removing；One layer of silver nano-grain is finally shifted on the film prepared with infusion process, prepares the composite and flexible surface enhanced Raman substrate based on silver nano-grain.Experiment shows, highly sensitive SERS detection can be realized by surface enhanced Raman scattering substrate prepared by this method, Raman signal is uniform, while having good mechanical stability and flexibility, and SERS signal is not decayed or even increased substantially under large-scale elongation strain.The method of the present invention is simple and efficient, inexpensive, can large area repetition preparation.
Description
Technical field
The invention belongs to nano material and optical technical field, in particular to a kind of composite and flexible based on silver nano-grain
Surface enhanced Raman substrate and preparation method thereof.
Background technique
Surface enhanced Raman scattering (SERS) is the light of a kind of highly sensitive detection interfacial characteristics and intermolecular interaction
Spectrum means, it by the distinctive vibration mode of molecule can realize Single Molecule Detection level, thus medical diagnosis, environmental protection,
The fields such as food safety and national defense safety receive significant attention.In SERS detection, researcher relies primarily on metal nano knot
The plasma resonance (LSPR) that structure surface generates goes to realize the enhancing of electromagnetic field.Some hardness substrates are used to deposit these nanometers
Structure is simultaneously used as Raman active substrate.But in many cases, traditional rigid substrate is not suitable for direct detection body surface
Molecule, especially in out-of-flatness or the surface contacted is not easy, so various flexibility Raman active substrates are come into being.Close
Nian Zhong, researcher provide supplementary mode mainly using straight polymer material as template, for directly analysis surface molecular.While this
The most of main complicated technologies of a little substrates, production cost is higher, limits them in public life and commercial field
Large area preparation and popularization.
PDMS because have good biocompatibility, optical transparence, flexibility, nontoxicity, hydrophobicity, produceability,
High oxygen permeability and low cost the advantages that, bio-microelectromechanical, hydrophobic protective coating, in terms of be used widely.
Patent CN201611198339.2 discloses a kind of PDMS base single layer SERS substrate and its system without surface modification
Preparation Method, the above-mentioned base the PDMS base SERS preparation method without surface modification, includes the following steps: to prepare homogeneous metal colloidal sol
Particle；In the film of metal nano-particles of water-oil interface self-assembled monolayer densification；By film of metal nano-particles be transferred to without
The surface PDMS of surface treatment and the SERS substrate for forming dense uniform.But it is to be improved to the reinforcing effect of SERS signal.
Summary of the invention
In order to overcome above-mentioned deficiency, the present invention provides a kind of composite and flexible surface-enhanced Raman base based on silver nano-grain
Bottom and preparation method thereof.Method provided by the invention is simple and fast, inexpensive, can large area repeat prepare, while prepare
The high sensitivity of surface enhanced Raman scattering substrate, uniformity is good, and mechanical stability is strong, the SERS under large-scale elongation strain
Signal is not decayed or even is increased substantially, and the surface that can be applied to various substances carries out the detection and identification of molecule,
And Raman active substrate or decaying SERS signal will not be damaged.
To achieve the goals above, the present invention adopts the following technical scheme:
An object of the present invention there is provided a kind of composite and flexible surface enhanced Raman substrate based on silver nano-grain
Preparation method, comprising:
The PDMS host agent of liquid is uniformly mixed with curing agent, is dissolved in toluene solution, forms the toluene of PDMS prepolymer
Solution；
The colloidal solution of silver nano-grain is uniformly mixed with the toluene solution of PDMS prepolymer, forms suspension；
Above-mentioned suspension is added drop-wise on hard substrate surface, be heating and curing the PDMS to be formed and include a large amount of silver nano-grains
Film, removing, obtains fexible film；
Loaded on fexible film using infusion process one layer of silver nano-grain to get.
In some embodiments, infusion process refers to: will include the PDMS film of a large amount of silver nano-grains in silver nano-grain
Colloidal solution impregnate 10~15s, take out, dry to get.
In order to guarantee to be covered with dimethyl siloxane-elargol mixed structure flexible substrates of Silver nano-particle layer or more interlayer
The coupling of electromagnetic field can occur, effectively to enhance SERS signal；The application selection includes silver nano-grain in PDMS film,
Compared with silver nanowires, more uniformly spreading, orderly for the silver nano-grain that includes will not be because of silver nanowires arragement direction not
Lead to the decrease of the coupling effect of flexible substrates or more interlayer electromagnetic field with randomness, meanwhile, preparation method is also more simple, steady
It is fixed, it is conducive to industrialized production.
In order to enhance hydrophobic " dimethyl silicone polymer-elargol composite construction flexible substrates " as surface-enhanced Raman
The performance of substrate, the application attempt to load one layer of silver nano-grain on it, but silver nanoparticle layer surface is hydrophily, can damage base
The hydrophobicity at bottom hinders the enrichment of testing molecule.For this purpose, the application system research silver nano-grain is in polydimethylsiloxanes
The surface chemistry and its correlation of growth behavior, the two in alkane-elargol composite construction flexible substrates, are touched by many experiments
Suo Faxian: using infusion process in silver nanoparticles loaded in dimethyl silicone polymer-elargol composite construction flexible substrates, Yin Na
Rice grain can relative distribution, equably grow, form uniform, orderly silver nanoparticle layer (the silver nano-grain size of grain spacing
For 70-80nm, particulate interspaces 4-7nm)；To make " the composite and flexible surface enhanced Raman substrate based on silver nano-grain " table
Face still has preferably hydrophobicity, is conducive to the enrichment of testing molecule；Meanwhile silver nano-grain it is orderly, be uniformly distributed respectively
It ensure that the coupling that electromagnetic field occurs between lower layer's nano particle, upper layer nano particle, upper layer and lower layer's nano particle, favorably
In raising SERS signal.
In some embodiments, the Yin Na being deposited in dimethyl silicone polymer-elargol composite construction flexible substrates
Rice grain is having a size of 70-80nm, particulate interspaces 4-7nm, it is ensured that between the hydrophobicity and upper and lower level silver nano-grain of substrate
The coupling of resonant frequency.
In some embodiments, the colloidal solution of the silver nano-grain is the dispersion liquid of silver nano-grain in water.
In some embodiments, the silver nano-grain the preparation method comprises the following steps: under agitation, by ethylene glycol solution plus
When heat is to 70-80 DEG C, polyvinylpyrrolidone (PVP) is added thereto, when continuing to be heated to 130-140 DEG C, to mixed solution
Middle addition silver nitrate (AgNO3), mixed solution is formed, is persistently stirred 1-2 hours, when solution to be mixed becomes bright yellow,
Mixed solution is cooled to room temperature addition acetone, is then centrifuged to obtain solid precipitating, this precipitating is silver nano-grain.
In some embodiments, the mass concentration of the colloidal solution of the silver nano-grain is 1.0-1.3g/ml；
In some embodiments, silver nano-grain is having a size of 70-80nm, particulate interspaces 4-7nm.Silver nano-grain gap
When less than 4nm, continue to reduce grain spacing, not only operation difficulty is higher, and the hydrophobicity for also resulting in substrate is bad, works as silver nanoparticle
When particulate interspaces are greater than 7nm, continue to increase grain spacing, will lead to SERS signal reinforcing effect variation.
In some embodiments, the mass ratio of the PDMS host agent of the liquid and curing agent is 10: 1.
In some embodiments, in the toluene solution of above-mentioned PDMS prepolymer, toluene and PDMS be 0.5 by volume~
2:1。
In some embodiments, the specific steps being heating and curing are as follows: 60-100 DEG C of temperature, toast 3-6 hour.
The second object of the present invention is to provide the composite and flexible based on silver nano-grain of any above-mentioned method preparation
Surface enhanced Raman substrate.
The third object of the present invention there is provided a kind of composite and flexible surface enhanced Raman substrate based on silver nano-grain,
Include:
Include the PDMS film of a large amount of silver nano-grains；
The silver nanoparticle layer being supported on the PDMS film for including a large amount of silver nano-grains.
There is provided above-mentioned composite and flexible surface enhanced Raman substrates in SERS detection for the fourth object of the present invention
Using.
Beneficial effects of the present invention
(1) present invention is no longer substrate preparation flexibility Raman substrate using straight polymer, will be with the poly dimethyl of dilution with toluene
Siloxanes is mixed with silver colloid, forms the flexible substrates of mixed structure.Since PDMS has good optical transparence, laser is very
It readily accesses the silver nano-grain wrapped up and generates the enhancing that LSPR effect realizes electromagnetic field.The substrate can not only serve as system
The tool of standby flexibility Raman substrate, can also be directly used as Raman active substrate.To further increase silver nano-grain resonance frequency
The coupling of rate and the hydrophobicity for keeping base material, present invention infusion process are flexible in dimethyl siloxane-elargol mixed structure
One layer of uniform silver nano-grain is covered above substrate.Therefore, lower layer's nano particle, upper layer nano particle, upper layer and lower layer receive
The coupling that electromagnetic field occurs between rice grain is conducive to improve SERS signal.In addition, the good flexibility of PDMS makes the drawing
Graceful active substrate mechanical stability is strong, it can be achieved that SERS under tensile strain is detected.Meanwhile preparation method of the invention is easy
Fast, inexpensive, can large area repeat to prepare, can be promoted in a wide range of.
(2) preparation method of the present invention is simple, detection efficiency is high, practical, easy to spread.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the flow diagram of composite and flexible surface enhanced Raman substrate of the present invention preparation based on silver nano-grain.
Fig. 2 (a) is dimethyl silicone polymer-elargol mixed structure flexible substrates scanning electron microscope diagram in the present invention
Picture.
Fig. 2 (b) is dimethyl silicone polymer-elargol mixed structure flexible substrates energy spectrum diagram in the present invention.
Fig. 3 is the scanning electron microscopy of composite and flexible surface enhanced Raman substrate of the present invention preparation based on silver nano-grain
Mirror image.
Fig. 4 is that composite and flexible surface enhanced Raman substrate of the present invention preparation based on silver nano-grain detects R6G molecule
Raman spectrogram: 10-9—10-13The Raman spectrogram of the R6G molecule of concentration.
Fig. 5 is that the present invention prepares the composite and flexible surface enhanced Raman substrate based on silver nano-grain in a stretched state
Schematic diagram and optical imagery.
Fig. 6 is that present invention composite and flexible surface enhanced Raman substrate of the preparation based on silver nano-grain is strained in different stretch
10 are detected under (percentage of the film length of stretching and its raw films length)-7The Raman spectrogram of the R6G molecule of concentration.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
The present invention provides a kind of composite and flexible surface enhanced Raman substrate and preparation method thereof based on silver nano-grain, packet
It includes:
Dimethyl silicone polymer-elargol composite construction flexible substrates；
The silver nano-grain being deposited in dimethyl silicone polymer-elargol composite construction flexible substrates；
Wherein, PDMS polymer is mixed with silver colloid, shifts, is formed by curing fexible film, be direct detection object table
The probe molecule in face provides advantageous platform.
To further enhance surface-enhanced raman scattering effect, one layer of silver nanoparticle is shifted on the film prepared with infusion process
Particle.
Compared to the flexible Raman substrate that traditional straight polymer is template, dimethyl silicone polymer-silver provided by the invention
A large amount of silver nano-grains of glue mixed structure flexible substrates, package can provide highdensity hot spot, serve not only as spy
The tool for surveying Raman spectrum, can also improve the Raman scattering efficiency of probe molecule.
Above-mentioned dimethyl silicone polymer-elargol mixed structure flexible substrates have good hydrophobic property, can sufficiently assemble
Probe molecule makes the vibration frequency of probe molecule and surface plasma body resonant vibration frequency reach efficient coupling, effectively improves
SERS signal.
Preferably, in the dimethyl silicone polymer-elargol mixed structure flexible substrates, elargol volume density is 1.0-
1.3g/ml。
Preferably, it is flexible to be distributed in dimethyl silicone polymer-elargol mixed structure uniform sequentially for the silver nano-grain
Above substrate.
Preferably, the silver nano-grain ruler being deposited in dimethyl silicone polymer-elargol composite construction flexible substrates
Very little is 70-80nm, particulate interspaces 4-7nm.
Compared to tradition using straight polymer as the flexible Raman substrate of substrate, surface enhanced Raman scattering substrate tool of the invention
It has the advantage that
1. the coupling of electromagnetic field occurs between lower layer's nano particle, upper layer nano particle, upper layer and lower layer's nano particle,
Effectively realize the enhancing of electromagnetic field.
2. silver nano-grain gap is small, the hot spot of acquisition is intensive, significantly improves LSPR effect.
3. mechanical stability is strong, flexibility is good, and the surface for being conducive to Raman active substrate and test substance is especially uneven
Surface that is whole or being not easy to contact is come into full contact with, and surface enhanced Raman substrate can be made sensitiveer.
4. even the surface enhanced Raman scattering substrate of preparation has certain hydrophobic property covering one layer of silver nanoparticle
Under conditions of grain, be conducive to the enrichment of testing molecule, can sufficiently be adsorbed onto silver nano-grain surface, is conducive to improve Raman scattering
Intensity.
The preparation method of the present invention also provides a kind of composite and flexible surface enhanced Raman substrate based on silver nano-grain,
The following steps are included:
(1) silver colloid containing a large amount of silver nano-grains (AgNPs) is prepared using chemical reduction method；
(2) it is mixed to form suspension by silver colloid and with the dimethyl silicone polymer (PDMS) of dilution with toluene, suspension
Be added dropwise on hard substrate surface, heating evaporation solvent is formed by curing the PDMS film for including a large amount of silver nano-grains, by its from
Hard substrate is removed on surface；
(3) one layer of silver nano-grain is shifted on the film prepared with infusion process.
Further, in step (1) silver colloid of silver nano-grain the preparation method comprises the following steps: 20ML ethylene glycol solution is continued
Uniform stirring when being heated to 70-80 DEG C from room temperature, is added 0.25g polyvinylpyrrolidone (PVP) into ethylene glycol solution, adds
When heat is to 130-140 DEG C, 0.05g silver nitrate (AgNO is added into mixed solution3), continuous uniform stirs 1-2 hours, to be mixed
When solution becomes bright yellow, mixed solution is cooled to room temperature, 40-60ml acetone is added, be then centrifuged to obtain solid
Precipitating, this precipitating is silver nano-grain, is washed with deionized 3-5 times, is finally scattered in 0.3-1.0ml deionized water,
Obtain the colloid of silver nano-grain.
Preferably, the colloid density of above-mentioned silver nano-grain is 1.0-1.3g/ml.
Further, preparation described in step (2) includes the specific method of the PDMS film of a large amount of silver nano-grains
Are as follows:
(1) the PDMS host agent of liquid is mixed with curing agent in mass ratio 10: 1, is sufficiently stirred, sonic oscillation goes degasification
Bubble, is configured to liquid PDMS prepolymer；
(2) by toluene, 0.5~2:1 is mixed by volume with prepared PDMS, is sufficiently stirred, sonic oscillation makes PDMS
Dilution；
(3) by the silver colloid prepared with the PDMS of dilution with toluene, 1~10:1 is mixed by volume, be sufficiently stirred, surpass
Sound oscillation forms suspension；
(4) suspension is added dropwise on hard substrate, covers entire hard substrate surface, coating thickness can be 50um-
100um；
(5) hard substrate for being covered with suspension is placed on heating platform, 60-100 DEG C of temperature setting, baking 3-6
Hour, solidify suspension；
(6) hard substrate by the cured completion of surface suspension is cooled to room temperature, including a large amount of silver nano-grains
PDMS film is stripped down from substrate, completes the preparation of mixed structure fexible film.
Preferably, above-mentioned rigid substrate material can be quartz or silicon wafer；Hard substrate material requirements smooth surface.
Preferably, above silver nano-grain uniform sequential ground distributed rendering structural flexibility substrate described in step (3)；
Silver nano-grain is having a size of 70-80nm, particulate interspaces 4-7nm.
The present invention also provides the above-mentioned composite and flexible surface enhanced Raman substrate based on silver nano-grain is in elongation strain
Under SERS detection.
Embodiment 1
1) by 20ML ethylene glycol (C2H6O2, 99.0%) and solution is added in 100ml flask, continuous uniform stirring, from room temperature
When being heated to 70 DEG C, 0.25g polyvinylpyrrolidone (PVP, Mw=55000) is added into ethylene glycol solution, is heated to 135 DEG C
When, 0.05g silver nitrate (AgNO is added into mixed solution3), continuous uniform stirs 1 hour, and solution to be mixed becomes bright
When yellow, mixed solution is cooled to room temperature, 60ml acetone is added, is then centrifuged to obtain solid precipitating, this precipitating is silver
Nano particle is washed with deionized 3 times, is finally scattered in the colloid that silver nano-grain is arrived in 0.5ml deionized water
2) by the PDMS host agent of liquid (184 silicone elastomer base of Sylgard) and curing agent
(184 silicone elastomer curing agent of Sylgard) in mass ratio 10: 1 is mixed, and is sufficiently stirred, ultrasound vibration
Bubble removing is swung, liquid PDMS prepolymer is configured to；By toluene, 1:1 is mixed by volume with prepared PDMS prepolymer
It closes, is sufficiently stirred, sonic oscillation dilutes PDMS；By the silver colloid prepared and with the PDMS of dilution with toluene 5:1 by volume
Mixing, is sufficiently stirred, sonic oscillation, forms suspension；Suspension is added dropwise on quartz plate, entire quartz plate surface is covered,
Coating thickness can be 50um-100um；The quartz plate for being covered with suspension is placed on heating platform, 80 DEG C of temperature setting, is dried
5 hours are baked, suspension is solidified；The quartz plate of the cured completion of surface suspension is cooled to room temperature, including a large amount of silver
The PDMS film of nano particle is stripped down from quartz plate, completes the preparation of mixed structure fexible film.
3) above-mentioned fexible film is immersed in the colloid 10s of the silver nano-grain of step 1), takes out, dry to get arriving
Surface enhanced Raman scattering substrate, through measuring: the static contact angle of the substrate is 91 °.
Fig. 2 (a) is dimethyl silicone polymer-elargol mixed structure flexible substrates scanning electron microscope diagram in the present invention
Picture, from Fig. 2 (a) as can be seen that the substrate is relatively uniform, smooth surface；Fig. 2 (b) is polydimethylsiloxanes in the present invention
Alkane-elargol mixed structure flexible substrates energy spectrum diagram can from Fig. 2 (b) although the substrate does not see the distribution of silver nano-grain
To find out, which includes silver nano-grain abundant.
Fig. 3 is the scanning electron microscopy of composite and flexible surface enhanced Raman substrate of the present invention preparation based on silver nano-grain
Mirror image, from figure 3, it can be seen that successfully covering one layer above dimethyl silicone polymer-elargol mixed structure flexible substrates
The uniform silver nano-grain of particle size；Silver nano-grain arrangement simultaneously is intensive, with the narrow nano gap of ultra-narrow.
Fig. 4 is that composite and flexible surface enhanced Raman substrate of the present invention preparation based on silver nano-grain detects R6G molecule
Raman spectrogram: 10-9—10-13The Raman spectrogram of the R6G molecule of concentration, from fig. 4, it can be seen that Raman prepared by the present invention
Active substrate has high sensitivity, can carry out limit detection to testing molecule.
Fig. 5 is that the present invention prepares the composite and flexible surface enhanced Raman substrate based on silver nano-grain in a stretched state
Schematic diagram and optical imagery, from optical imagery as can be seen that Raman active substrate prepared by the present invention has good flexibility
And mechanical stability, it is advantageously implemented the Molecular Detection work on arbitrary substance surface.
Fig. 6 is that present invention composite and flexible surface enhanced Raman substrate of the preparation based on silver nano-grain is strained in different stretch
Lower detection R6The Raman spectrogram of G molecule, from fig. 6, it can be seen that Raman active substrate prepared by the present invention can bear it is very strong
Without damaging, SERS signal occurs significantly increasing on the contrary in a stretched state there is no decaying for elongation strain
(this may be primarily due to flexible substrates and the spacing of silver nanoparticle layer in drawing process and reduces, and produce reinforcing effect) by force, this
Basis is provided in practical applications for the substrate, it will be for fields such as sensing, strain detector, plasma filled waveguide and optical Limitings
Using opening up the new gate of a fan.
In addition, research also shows: when elongation strain is 80%, the reinforcing effect of SERS signal is best.
In detection R6When G molecule, arbitrarily selects 3 regions as detection zone, choose 16 active hot spots as signal
The proof of repeatability.The results showed that the surface enhanced Raman scattering substrate of preparation of the embodiment of the present invention has weight well
Renaturation, standard deviation is 6% or so.
Embodiment 2
By 20ML ethylene glycol (C2H6O2, 99.0%) solution is added in 100ml flask, continuous uniform stirring, from room temperature plus
When heat is to 80 DEG C, 0.25g polyvinylpyrrolidone (PVP, Mw=55000) is added into ethylene glycol solution, is heated to 130 DEG C
When, 0.05g silver nitrate (AgNO is added into mixed solution3), continuous uniform stirs 1.5 hours, and solution to be mixed becomes bright
Yellow when, mixed solution is cooled to room temperature, 60ml acetone is added, be then centrifuged to obtain solid precipitating, this precipitating is
Silver nano-grain is washed with deionized 3 times, is finally scattered in the colloid that silver nano-grain is arrived in 0.8ml deionized water
The PDMS host agent of liquid is mixed with curing agent in mass ratio 10: 1, is sufficiently stirred, sonic oscillation removes bubble removing, matches
Liquid PDMS prepolymer is made；By toluene, 2:1 is mixed by volume with prepared PDMS, is sufficiently stirred, sonic oscillation makes
PDMS dilution；By the silver colloid prepared with the PDMS of dilution with toluene, 4:1 is mixed by volume, be sufficiently stirred, sonic oscillation,
Form suspension；Suspension is added dropwise on quartz plate, covers entire quartz plate surface, coating thickness can be 50um-
100um；It will be covered with outstanding
The quartz plate of turbid is placed on heating platform, 100 DEG C of temperature setting, is toasted 4 hours, is solidified suspension；
The quartz plate of the cured completion of surface suspension is cooled to room temperature, including the PDMS films of a large amount of silver nano-grains from quartz
On piece strips down, and completes the preparation of mixed structure fexible film.
One layer of silver nano-grain is shifted on the fexible film prepared with infusion process to dissipate to get to surface-enhanced Raman
Penetrate substrate.
Embodiment 3
By 20ML ethylene glycol (C2H6O2, 99.0%) solution is added in 100ml flask, continuous uniform stirring, from room temperature plus
When heat is to 80 DEG C, 0.25g polyvinylpyrrolidone (PVP, Mw=55000) is added into ethylene glycol solution, is heated to 140 DEG C
When, 0.05g silver nitrate (AgNO is added into mixed solution3), continuous uniform stirs 1 hour, and solution to be mixed becomes bright
When yellow, mixed solution is cooled to room temperature, 60ml acetone is added, is then centrifuged to obtain solid precipitating, this precipitating is silver
Nano particle is washed with deionized 3 times, is finally scattered in the colloid that silver nano-grain is arrived in 1ml deionized water
The PDMS host agent of liquid is mixed with curing agent in mass ratio 10: 1, is sufficiently stirred, sonic oscillation removes bubble removing, matches
Liquid PDMS prepolymer is made；By toluene, 1:1 is mixed by volume with prepared PDMS, is sufficiently stirred, sonic oscillation makes
PDMS dilution；By the silver colloid prepared with the PDMS of dilution with toluene, 5:1 is mixed by volume, be sufficiently stirred, sonic oscillation,
Form suspension；Suspension is added dropwise on polished silicon slice, covers entire silicon chip surface, coating thickness can be 50um-
100um；The silicon wafer for being covered with suspension is placed on heating platform, 100 DEG C of temperature setting, toasts 4 hours, consolidate suspension
Change；The silicon wafer of the cured completion of surface suspension is cooled to room temperature, including the PDMS films of a large amount of silver nano-grains from silicon
On piece strips down, and completes the preparation of mixed structure fexible film.
One layer of silver nano-grain is shifted on the fexible film prepared with infusion process to dissipate to get to surface-enhanced Raman
Penetrate substrate.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of preparation method of the composite and flexible surface enhanced Raman substrate based on silver nano-grain characterized by comprising
The PDMS host agent of liquid is uniformly mixed with curing agent, is dissolved in toluene solution, forms the toluene solution of PDMS prepolymer；
The colloidal solution of silver nano-grain is uniformly mixed with the toluene solution of PDMS prepolymer, forms suspension；
Above-mentioned suspension is added drop-wise on hard substrate surface, be heating and curing to be formed include a large amount of silver nano-grains PDMS it is thin
Film, removing, obtains fexible film；
Loaded on fexible film using infusion process one layer of silver nano-grain to get.
2. the method as described in claim 1, which is characterized in that the colloidal solution of the silver nano-grain is that silver nano-grain exists
Dispersion liquid in water.
3. method according to claim 2, which is characterized in that the silver nano-grain the preparation method comprises the following steps: in stirring condition
Under, when ethylene glycol solution is heated to 70-80 DEG C, polyvinylpyrrolidone PVP is added thereto, continues to be heated to 130-140
DEG C when, into mixed solution be added silver nitrate AgNO3, mixed solution is formed, is persistently stirred 1-2 hours, solution to be mixed becomes
When bright yellow, mixed solution is cooled to room temperature addition acetone, is then centrifuged to obtain solid precipitating, this precipitating is
Silver nano-grain.
4. the method as described in claim 1, which is characterized in that the mass concentration of the colloidal solution of the silver nano-grain is
1.0-1.3g/ml；Silver nano-grain is having a size of 70-80nm, particulate interspaces 4-7nm.
5. the method as described in claim 1, which is characterized in that the mass ratio of the PDMS host agent of the liquid and curing agent is 10
∶1。
6. the method as described in claim 1, which is characterized in that in the toluene solution of above-mentioned PDMS prepolymer, toluene with
PDMS is 0.5~2:1 by volume.
7. the method as described in claim 1, which is characterized in that the specific steps being heating and curing are as follows: 60-100 DEG C of temperature, baking
3-6 hour.
8. the composite and flexible surface-enhanced Raman base based on silver nano-grain of the described in any item method preparations of claim 1-7
Bottom.
9. a kind of composite and flexible surface enhanced Raman substrate based on silver nano-grain characterized by comprising
Include the PDMS film of a large amount of silver nano-grains；
The silver nanoparticle layer being supported on the PDMS film for including a large amount of silver nano-grains.
10. application of the composite and flexible surface enhanced Raman substrate described in claim 8 or 9 in SERS detection.
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