CN108254355A - A kind of preparation method of salt bridge auxiliary primary battery induced growth gold nano grain surface enhanced Raman scattering substrate - Google Patents
A kind of preparation method of salt bridge auxiliary primary battery induced growth gold nano grain surface enhanced Raman scattering substrate Download PDFInfo
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Abstract
The invention belongs to silicon chip surface enhancing Raman scattering effect domain variabilities to disclose a kind of preparation method of salt bridge auxiliary primary battery induced growth gold nano grain surface enhanced Raman scattering substrate；First, golden seed crystal colloidal solution is prepared with gold chloride, sodium citrate and sodium borohydride；2nd, agar, potassium chloride are taken, distilled water is added in, is poured into after dissolving in U-tube and obtain agar-potassium chloride salt bridge；3rd, golden seed crystal colloidal solution is added drop-wise to ITO conductive glass surfaces, obtains the ITO Conducting Glass of spun golden seed crystal；4th, graphite is connect with ITO Conducting Glass with conducting wire, graphite is placed in solution of ferrous chloride, and ITO Conducting Glass is placed in deposition liquid；Agar-potassium chloride salt bridge is inserted into two kinds of solution, stands 3h；5th, by ITO Conducting Glass sputtering silvers, gold nano grain surface enhanced Raman scattering substrate is obtained.The method of the present invention is simple, preparation time is short, and the gold nano grain substrate of preparation has good SERS activity and uniformity, detection sensitivity height.
Description
Technical field
The present invention relates to silicon chip surface enhancing Raman scattering effect fields, and in particular to a kind of salt bridge auxiliary primary battery induction
Grow the preparation method of gold nano grain surface enhanced Raman scattering substrate.
Background technology
The special optical performance of gold nanoparticle is one of hot spot studied in field of nanometer material technology, since it has well
Stability, bioaffinity along with the properties such as its surface plasmon absorption, it is made all to have in various fields wide
Wealthy application prospect.Since the characteristic of the surface plasmon absorption of gold nano structure can induce stronger electromagnetic field to increase
By force, therefore, golden various structures are also widely used in Surface enhanced Raman scattering (SERS) research.
It is well known that the optical property of gold nanoparticle and size, size, shape are closely related, traditional gold nano grain
Preparation method mainly have physical method and chemical method.Physical method is using top-to-bottom method, by ontology gold directly
It is changed into nanoparticle, such as vacuum vapour deposition, laser ablation and induced with laser size abatement technology.And chemical method is to adopt
With bottom-to-top method, by generating gold atom the methods of electronation, photodissociation, pyrolysis, electrolysis, gold atom continue into
Core grows and then forms gold nanoparticle.
Two methods are compared, and chemical method operation is more simple and practicable, and the appearance and size of gold nanoparticle can
Control property is more preferable, and that is applied in the preparation of gold nano-material is more extensive.But the gold nano grain prepared by chemical method
Polydispersion in the solution, often limits the application of SERS.At present, in the SERS context of detection of chemical substance, in addition to substrate has
Standby good SERS activity, also requires the controllability of substrate and SERS uniformities.In recent years due to the development of nanometer technology,
Such as：Self-assembly method, template, photoetching process, nano print and photoetching technique etc. are gold SERS substrates for strong side
Hand.Perfect array substrate can be made with electron beam lithography, this substrate shows good SERS signal reproducibility.But,
Electron beam lithography needs equipment costly, and the SERS substrates of one piece of large area are prepared than time-consuming using it.So such as
What provides a kind of preparation method simple and practicable, preparation time is short, substrate S ERS activity is high, is that those skilled in the art need to solve
Certainly the technical issues of.
Invention content
The present invention is carried for the difficult point that complex process, preparation time are long in prior art, substrate S ERS activity is relatively low
For a kind of preparation method of salt bridge auxiliary primary battery induced growth gold nano grain surface enhanced Raman scattering substrate.
The present invention using following technical scheme in order to solve the above technical problems, realized：
Design a kind of preparation side of salt bridge auxiliary primary battery induced growth gold nano grain surface enhanced Raman scattering substrate
Method includes the following steps：
Step 1：Prepare 20mL 2.5 × 10-4The gold chloride of mol/L and 2.5 × 10-4The mixing of the sodium citrate of mol/L
Solution, then adds in the sodium borohydride aqueous solution of a concentration of 0.1mol/L of 0.6mL, and standing 2-5 hours after stirring 30min just obtains
Golden seed crystal colloidal solution；
Step 2：It adds in 3g agar in a reservoir and 97mL distilled water, heating water bath to agar is completely dissolved, then adds in
The potassium chloride of 30g is simultaneously sufficiently stirred, and potassium chloride is poured into after being completely dissolved in U-shaped glass tube, is stood and is just obtained after agar condensation
To agar-saturation potassium chloride salt bridge；
Step 3：ITO electro-conductive glass is placed on spin coating instrument, the golden seed crystal colloidal solution described in 100 μ L is taken to be added drop-wise to ITO
Conductive glass surface, spin coating 5 minutes under the rotating speed of 1300rpm repeat the ITO that spin coating just obtains spun golden seed crystal several times
Conducting Glass；
Step 4：Graphite electrode is connect with the ITO Conducting Glass of the spun golden seed crystal with conducting wire, graphite
Electrode is placed in solution of ferrous chloride, and ITO electro-conductive glass is placed in deposition liquid；Then by the agar-saturation potassium chloride salt
Bridge is inserted into two kinds of solution, stands deposition after 3 hours, by the ITO Conducting Glass of spun golden seed crystal from deposition liquid
It takes out, is rinsed with deionized water, nitrogen just obtains surface and deposits the ITO Conducting Glass for having gold nano grain after drying up；
Step 5：The ITO Conducting Glass that surface deposition has gold nano grain is placed in the chamber of sputter, true
Sputtering silver under empty condition obtains the gold nano grain surface enhanced Raman scattering substrate after sputtering.
Preferably, the preparation method of the solution of ferrous chloride is：0.45g solution of ferrous chloride is taken to be placed in container,
Then 0.7mL concentrated hydrochloric acids and 90mL deionized waters are added in, the solution of ferrous chloride can be obtained by stirring to being completely dissolved.
Preferably, the preparation method of the deposition liquid is：0.6g polyvinylpyrrolidones are taken in container, add in 29mL
Deionized water stirs to after being completely dissolved, adds the aqueous solution of chloraurate of a concentration of 30g/L of 1mL, after mixing,
Obtain the deposition liquid.
Preferably, the step three spin coating is three times.
Preferably, the current density that sputter sputters in the step five is 10A/m-2, sputtering time 90min.
The present invention provides a kind of salt bridge auxiliary primary battery induced growth gold nano grain surface enhanced Raman scattering substrate
Preparation method, advantageous effect are：
1st, method of the invention is by introducing salt bridge, by the use of ferrous ion as primary battery in cathode, spun golden seed crystal
Positive electrode of the electro-conductive glass as primary battery, grow spherical shape in the mixed solution of gold chloride and polyvinylpyrrolidone
Gold nano structure；By controlling the amount of polyvinylpyrrolidone and the amount of golden seed crystal, the uniform of this gold nano grain is realized
Growth, by gold nano grain sputtering silver further above, improving the SERS activity of substrate, being formed together with probe molecule strong
Active substrate.The enhancing effect specific surface of surface enhancing Raman scattering obtained by the method for the present invention only has single noble metal
Material it is more preferable, applicable wavelengths range is more extensive.
2nd, when nano material prepared by traditional handicraft is used for detection molecules as SERS substrates, most of can put into actually makes
All it is golden or gold-composite material, main cause is got well much for the stability silver relatively because of gold, but golden
Raman enhancing is weaker than the enhancing of silver, and in order to improve the Raman enhancing effect of the substrate, the method for the present invention continues in gold nano grain
It is upper to continue deposition of silver to improve SERS enhancing effects.With gradually increasing for silver, SERS signal is remarkably reinforced, and in the electricity of sputtering
Current density is 10A/m-2, under the conditions of sputtering 90min, the SERS enhancing effects of substrate had both been improved, have in turn ensured the SERS of substrate
Activity is more extensive by the products application obtained by the method for the present invention.
What the 3rd, the method for the present invention was creative uses ITO electro-conductive glass to solve the Jenner of chemical method preparation as substrate
The characteristics of rice grain disperses problem in the solution, and operation is simple with reference to chemical method, preparation method is not only simplified, but also widen
The SERS application ranges of gold nano grain substrate.
4th, by the composite material prepared by the method for the present invention since two kinds of metals are in terms of molecule absorption and activation is promoted
Play synergistic effect, by cooperate with resonate, the two generate simultaneously table enhancing Raman signal, by modifying probe molecule, possess
Detection sensitivity more higher than single substrate, can be widely used in the quick detection in the fields such as environment, chemistry, biology.
Description of the drawings
The present invention is described in further detail for embodiment in below in conjunction with the accompanying drawings, but does not form to the present invention's
Any restrictions.
Fig. 1 is the ITO Conducting Glass that the method for the present invention primary cells induced growth surface deposition has gold nano grain
Principle schematic；
A, b are the characterization pictures of the scanning electron microscope (SEM) of the method for the present invention products therefrom in Fig. 2；C is the present invention
The characterization picture of the transmission electron microscope (TEM) of method products therefrom；D is the XRD characterization picture of the method for the present invention products therefrom；
The SEM characterization pictures of products therefrom when Fig. 3 is the method for the present invention spin coating seed crystal number difference；
Fig. 4 obtains the SEM characterization pictures of product when being polyvinylpyrrolidone various concentration in the method for the present invention, wherein
A is 0g/L；B is 1g/L；C is 5g/L；D is 10g/L；E is 20g/L；F is 40g/L；
Fig. 5 a characterize picture for the SERS spectral lines of institute's the method for the present invention products therefrom under R6G various concentrations, and wherein I is 10- 6mol/L；II is 10-9mol/L；III is 5 × 10-10Mol/L, time of integration 5s；Fig. 5 b are the SEM characterization pictures of products therefrom；
Fig. 6 is the method for the present invention products therefrom SERS spectrums, time of integration 1s；
Fig. 7 is the SERS spectral lines characterization picture of the method for the present invention products therefrom different time shooting, and a is 0min；B is
5min；20min during c；D is 45min；E is 90min, time of integration 1s；
Fig. 8 is the SEM characterization pictures of invention of the present invention products therefrom after deposition of silver different time is continued, and a is deposition
0min；B is deposition 5min；C is deposition 20min；D is deposition 45min；E is deposition 90min, time of integration 1s；
Fig. 9 is the SERS collection of illustrative plates characterization picture of the PCB-77 of the method for the present invention products therefrom detection various concentration；Wherein I is
10-3Mol/L, II 10-4Mol/L, III 10-5mol/L；IV is the Raman spectrogram of the powder of PCB-77.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.
As shown in fig.1, a kind of salt bridge auxiliary primary battery induced growth gold nano grain surface-enhanced Raman of the present invention
The preparation method of substrate is scattered, is included the following steps：
Step 1：Prepare 20mL 2.5 × 10-4The gold chloride of mol/L and 2.5 × 10-4The mixing of the sodium citrate of mol/L
Solution, then adds in the sodium borohydride aqueous solution of a concentration of 0.1mol/L of 0.6mL, and standing 3 hours after stirring 30min just obtains gold
Seed crystal colloidal solution；
Step 2：It adds in 3g agar in a reservoir and 97mL distilled water, heating water bath to agar is completely dissolved, then adds in
The potassium chloride of 30g is simultaneously sufficiently stirred, and potassium chloride is poured into after being completely dissolved in U-shaped glass tube, is stood and is just obtained after agar condensation
To agar-saturation potassium chloride salt bridge；
Step 3：ITO electro-conductive glass is placed on spin coating instrument, the golden seed crystal colloidal solution described in 100 μ L is taken to be added drop-wise to ITO
Conductive glass surface, spin coating 5 minutes under the rotating speed of 1300rpm, the ITO that repetition spin coating just obtains spun golden seed crystal three times are led
Electric glass substrate；
Step 4：Graphite electrode is connect with the ITO Conducting Glass of the spun golden seed crystal with conducting wire, graphite
Electrode is placed in solution of ferrous chloride, and ITO electro-conductive glass is placed in deposition liquid；Then by the agar-saturation potassium chloride salt
Bridge is inserted into two kinds of solution, stands deposition after 3 hours, by the ITO Conducting Glass of spun golden seed crystal from deposition liquid
It takes out, is rinsed with deionized water, nitrogen just obtains surface and deposits the ITO Conducting Glass for having gold nano grain after drying up；
Step 5：The ITO Conducting Glass that surface deposition has gold nano grain is placed in the chamber of sputter, true
Sputtering silver under empty condition obtains the gold nano grain surface enhanced Raman scattering substrate after sputtering.
The preparation method of the solution of ferrous chloride is：0.45g solution of ferrous chloride is taken to be placed in container, is then added in
0.7mL concentrated hydrochloric acids and 90mL deionized waters, the solution of ferrous chloride can be obtained by stirring to being completely dissolved.
The preparation method of the deposition liquid is：0.6g polyvinylpyrrolidones are taken in container, add in 29mL deionizations
Water stirs to after being completely dissolved, adds the aqueous solution of chloraurate of a concentration of 30g/L of 1mL, after mixing, can obtain institute
The deposition liquid stated.
The current density that sputter sputters in the step five is 10A/m-2, sputtering time 90min.
Verification experimental verification
1st, the basic pattern and structure of product
Obtained product carries out related pattern and structure detection after implementing according to above-described embodiment.Testing result is refering to figure
Shown in 2, a-c is the scanning of prepared sample and transmission electron microscope picture in Fig. 2, it can be seen that prepared gold nano grain
For uniform spheric granules, diameter 100nm or so, these spheric granules are dispersed on electro-conductive glass on a large scale.Such as d in Fig. 2
Shown, we can obtain the structure and ingredient of sample, and five diffraction maximums correspond to (111) of face-centred cubic Au respectively,
(200), (220), (311) and (222) face, space group are Fm3m (JCPDS).
2nd, during seed crystal spin coating number difference products therefrom influence
Implement according to above-described embodiment, wherein seed crystal difference 0 time, 1 time and 3 times obtained product of spin coating of step 3,
Then related pattern and structure detection are carried out respectively.Refering to shown in attached drawing 3, a, b are the picture of spin coating 0 time in Fig. 3；C, d is rotation
Apply the picture of 1 time；E, f is the picture of spin coating 3 times, without gold seed crystal in the case of, it is impossible to obtain ball in electro-conductive glass substrate
The gold nano grain of shape；With the increase of silver-colored seed crystal spin coating number, the distribution density of spherical gold nano grain gradually increases.Spin coating
Golden seed crystal on to ITO electro-conductive glass acts as heterogeneous nucleation site, and the electronics of galvanic interaction constantly reaches just from cathode
Pole surface, the gold chloride in mixed solution is constantly reduced to gold atom, and Preferential Nucleation is grown on golden seed crystal.Due to gold
Seed crystal is uniformly distributed on ITO conductive glass surfaces, therefore obtained product also can be uniform in ITO conductive glass surfaces
Distribution.Increase with the distribution density of golden seed crystal, obtained spherical gold nano grain also constantly increases.Utilize seed crystal control
Pelleting distribution density on substrate has a critically important influence in terms of SERS, during distribution density increase, between particle between
Gap significantly increases, and SERS active sites constantly increase, and SERS activity can also increased.
3rd, during the amount difference of polyvinylpyrrolidone products therefrom influence
Implement according to above-described embodiment, wherein product obtained during polyvinylpyrrolidone various concentration in deposition liquid,
Then related pattern and structure detection are carried out.Refering to shown in attached drawing 4a, in the presence of no polyvinylpyrrolidone, also there is gold
Nanoparticle growth, but these products are interconnected to film, and pattern is nor very uniform.With polyvinylpyrrolidone
The increase of concentration, what is obtained is the nano particle of gold being separated from each other, but when polyvinylpyrrolidoneconcentration concentration is relatively low, ruler
It is very little be not it is very uniform, in addition to the spherical nanoparticle of gold, also some rodlike or sheet products (as shown in Fig. 4 b-c).
As polyvinylpyrrolidoneconcentration concentration further increases, such as during 20g/L, the pattern of product is only minimal amount of than more uniform
Rodlike or sheet output is inside (as shown in fig 4e).Polyvinylpyrrolidone can not only be given birth to as surfactant in nucleation
The long stage inhibits the reunion of product, and it can control the growth of pattern.
4th, the SERS characterizations of product
Obtained product carries out SERS characterization detections after implementing according to above-described embodiment, with 10-6The R6G solution of mol/L
For molecular detection, refering to as shown in attached drawing 5a, three characteristic peaks in SERS spectrograms, 612cm-1,775cm-1,1361cm-1Respectively
Beam mode in the face of corresponding R6G phenyl ring and outside face, the extension vibration mode of aromatic hydrocarbon.From the picture of attached drawing 5b
As can be seen that there is a large amount of gap for being less than 10nm between gold nano grain, when this gap, is advantageous to SERS activity and carries
High.
Obtained product carries out SERS characterization detections after implementing according to above-described embodiment, refering to shown in attached drawing 6, to bit
Levy peak 611cm-1The intensity value at place finds that the SERS signal uniformity of substrate is fine, and relative deviation illustrates to prepare within 5%
Substrate uniformity it is fine.In general, it is well many for golden stability silver relatively, but the Raman enhancing of gold is weaker than
Silver enhancing, in order to improve the Raman enhancing effect of the substrate, we using continue on gold nano grain continuation deposition of silver come
Improve SERS enhancing effects.
Implement according to above-described embodiment, gold nano grain substrate continue deposit different time silver after gained product into
Row SERS spectrums are shot and the SEM of corresponding product detections, refering to shown in Fig. 7-Fig. 8.By after comparing deposition of silver
SERS spectrograms are found, with gradually increasing for silver, (referring to shown in Fig. 7 a-d) is remarkably reinforced mainly due to silver in SERS signal
Caused by amount increases；Compare simultaneously the silver after deposition different time SEM (refering to shown in Fig. 8 a-d) picture can be seen that with
The increase of silver, particle constantly become larger, and have bulk particle to generate (refering to shown in Fig. 7 d.As sedimentation time becomes 90min
When, signal slightly declines (referring to shown in 7e), and this is active with there is more bulk particles to generate (referring to shown in 8e) SERS in product
Point, which reduces, relationship.
With the increase of deposition of silver time, the signal of SERS also constantly enhances, by contrast scans picture can be seen that with
The difference of sedimentation time, variation constantly occurs for the pattern of product, and silver is constantly deposited on the surface of gold nano grain, even
Grow up to bigger particle.Although SERS signal can significantly be improved by continuing deposition of silver, but non-uniform depositional mode,
So that the uniformity of signal cannot ensure.
5th, SERS detections are carried out using products therefrom
Tetrachloro biphenyl (PCB-77) is detected with above-described embodiment obtained product.By PCB-77 be dissolved in just oneself
In alkane, then it is added dropwise on 10 microlitres of PCB-77 to SERS substrates, and dry.Refering to shown in attached drawing 9, can be clearly seen that,
Positioned at 677cm-1, 1033cm-1, 1246cm-1, 1596cm-1The enhancing Raman peaks of the PCB-77 at place can be with PCB-77 powder standards
Peak is corresponding.Using array detection PCB-77,10 are detected-5The PCB-77 of mol/L.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of salt bridge auxiliary primary battery induced growth gold nano grain surface enhanced Raman scattering substrate, special
Sign is, includes the following steps：
Step 1：Prepare 20mL 2.5 × 10-4The gold chloride of mol/L and 2.5 × 10-4The mixed solution of the sodium citrate of mol/L,
Then the sodium borohydride aqueous solution of a concentration of 0.1mol/L of 0.6mL is added in, standing 2-5 hours after stirring 30min just obtains golden seed
Brilliant colloidal solution；
Step 2：It adds in 3g agar in a reservoir and 97mL distilled water, heating water bath to agar is completely dissolved, then add in 30g
Potassium chloride and be sufficiently stirred, potassium chloride is poured into after being completely dissolved in U-shaped glass tube, stand after agar condensation after just obtain fine jade
Fat-saturation potassium chloride salt bridge；
Step 3：ITO electro-conductive glass is placed on spin coating instrument, the golden seed crystal colloidal solution described in 100 μ L is taken to be added drop-wise to ITO conductions
Glass surface, spin coating 5 minutes under the rotating speed of 1300rpm repeat the ITO conductions that spin coating just obtains spun golden seed crystal several times
Glass substrate；
Step 4：Graphite electrode is connect with the ITO Conducting Glass of the spun golden seed crystal with conducting wire, graphite electrode
It is placed in solution of ferrous chloride, ITO electro-conductive glass is placed in deposition liquid；Then the agar-saturation potassium chloride salt bridge is inserted
Enter in two kinds of solution, stand deposition after 3 hours, the ITO Conducting Glass of spun golden seed crystal is taken out from deposition liquid,
It is rinsed with deionized water, nitrogen just obtains surface and deposits the ITO Conducting Glass for having gold nano grain after drying up；
Step 5：The ITO Conducting Glass that surface deposition has gold nano grain is placed in the chamber of sputter, in vacuum item
Sputtering silver under part obtains the gold nano grain surface enhanced Raman scattering substrate after sputtering.
2. a kind of salt bridge auxiliary primary battery induced growth gold nano grain Surface enhanced Raman scattering according to claim 1
The preparation method of substrate, which is characterized in that the preparation method of the solution of ferrous chloride is：Take 0.45g solution of ferrous chloride
It is placed in container, then adds in 0.7mL concentrated hydrochloric acids and 90mL deionized waters, the chlorination can be obtained by stirring to being completely dissolved
Ferrous iron solution.
3. a kind of salt bridge auxiliary primary battery induced growth gold nano grain Surface enhanced Raman scattering according to claim 1
The preparation method of substrate, which is characterized in that the preparation method of the deposition liquid is：0.6g polyvinylpyrrolidones are taken in container
In, 29mL deionized waters are added in, stirs to after being completely dissolved, adds the aqueous solution of chloraurate of a concentration of 30g/L of 1mL, are mixed
After uniformly, the deposition liquid can be obtained.
4. a kind of salt bridge auxiliary primary battery induced growth gold nano grain Surface enhanced Raman scattering according to claim 1
The preparation method of substrate, which is characterized in that the optimal spin coating number of the step three is three times.
5. a kind of salt bridge auxiliary primary battery induced growth gold nano grain Surface enhanced Raman scattering according to claim 1
The preparation method of substrate, which is characterized in that the current density that sputter sputters in the step five is 10A/m-2, sputtering time
For 90min.
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