CN105755463B - The preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer - Google Patents
The preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer Download PDFInfo
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- CN105755463B CN105755463B CN201610127954.8A CN201610127954A CN105755463B CN 105755463 B CN105755463 B CN 105755463B CN 201610127954 A CN201610127954 A CN 201610127954A CN 105755463 B CN105755463 B CN 105755463B
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Abstract
The invention discloses a kind of preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer, including preparing homogeneous metal nano particle and in hydrophobic material surface uniform deposition single-layer metal nano particle, being specifically included wherein preparing homogeneous metal nano particle：Prepare metal nanoparticle seed solution；The metal nanoparticle seed solution of preparation is moved into rapidly growing environment, makes its homoepitaxial；Low-speed centrifugal chooses the spheric granules for being deposited in centrifugation bottom of the tube.The process of deposition single-layer metal nano particle specifically includes：The amount of metal nanoparticle according to needed for metal nanoparticle size calculates deposition individual layer SERS substrates；Hydrophobic material after the silanization treatment of suitable size is placed in container bottom, adds in metal nanoparticle colloid, dry out solvent is completed the uniform SERS substrates of solid phase individual layer and prepared.The present invention can prepare the SERS substrates of the very high metal nanoparticle of uniformity and tight monolayers arrangement, substantially increase and prepare the uniformity of individual layer SERS substrates on hydrophobic material surface.
Description
Technical field
The invention belongs to measure, test or detection technique field, especially a kind of uniform SERS of hydrophobic surface solid phase individual layer
The preparation method of substrate.
Background technology
Surface enhanced Raman scattering (SERS) has very high detection sensitivity, in biomedicine, environmental monitoring, food peace
It has broad application prospects in terms of complete and other industry, agricultural and scientific research.But the technology there are one it is serious not
Foot is exactly the lack of homogeneity of SERS substrate fabrications, particularly is difficult to form the uniform SERS substrates of larger area in hydrophobic surface,
Lead to the poor repeatability of experiment, reliability is not high, it is difficult to carry out quantitative detection.
Therefore, it is necessary to it is conducted further research and is improved.
Invention content
Goal of the invention：A kind of preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer is provided, to solve existing skill
The above problem existing for art.
Technical solution：A kind of preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer, including following processing step：
Step 1 prepares homogeneous metal nano particle
Step 11 prepares the uniform metal nanoparticle seed solution of pattern under the acid-base value of scheduled nucleation, at this
In step, the uniformity of metal nanoparticle size is improved by the precision of control ph；
Metal nanoparticle seed solution is transferred to growing environment by step 12, adjusts pH value, it is made unanimously to grow to and is set
Count size, in this step, the size of the big minor adjustment metal nanoparticle by adjusting pH value；
Step 13, low-speed centrifugal several times, choose the spheric granules for being deposited in centrifugation bottom of the tube, to further improve metal
Nano particle uniformity；
Step 2, in hydrophobic material surface uniform deposition single-layer metal nano particle
Step 21, the metal nanoparticle size according to acquisition calculate metal nano needed for deposition individual layer SERS substrates
The amount of grain；
Hydrophobic material after the silanization treatment of suitable size is placed in container bottom by step 22, adds in the gold calculated
Metal nano-particle colloid, rapid dry out solvent are completed the uniform SERS substrates of solid phase individual layer and are prepared.Suitable size refers to material with holding
Device is adapted to, and can be stuck in the bottom of container.
In a further embodiment：In the step 11, scheduled nucleation acid-base value refers to pH=11 ± 0.5, can
Metal nanoparticle is made to grow to 65 ± 15 nanometers；Preferably pH=11 ± 0.2 can make metal nanoparticle grow to 65 ± 5
Nanometer；Further preferably pH=11 can make metal nanoparticle grow to 65 ± 0.5 nanometers.With nucleation pH value it is accurate
Control, can be remarkably decreased the size inhomogeneities of prepared metal nanoparticle.
In step 12, pH value is adjusted to 3.5, and metal nanoparticle grows to 75 ± 0.5 nanometers；PH value is adjusted to 4.5,
Metal nanoparticle grows to 65 ± 0.5 nanometers；PH value is adjusted to 5.5, metal nanoparticle grows to 55 ± 0.5 nanometers.It is logical
The pH value of growth phase is overregulated, the metal nanoparticle of preparation can be made to grow to design size.
It in step 13, centrifuges 4~8 times, rotating speed is 2200~2700 revs/min, and centrifugation time is 35~45 minutes, excellent
Centrifugation 6 times is selected as, rotating speed is 2500 revs/min, and the time is 40 minutes.
In a further embodiment, the metal nanoparticle includes gold nano grain and silver nano-grain.
A kind of preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer, including following processing step：
Step 1：Prepare uniform metal nanoparticle colloid：
Step 11 takes 0.5418g sodium citrates to be dissolved in the water of 4ml, and it is 11 to adjust pH value, places it among boiling water in advance
Heat, and be placed in ultrasonic machine and be ultrasonically treated；The silver nitrate of 0.051g is taken to be dissolved in the water of 1ml, places it in boiling water and preheats；It will
Silver nitrate aqueous solution injection pH value obtained is in 11 sodium citrate solution, after solution is creamy white, obtains seed solution；
Step 12 takes the water of 295ml to be placed in three neck round bottom flask, and it is 4.5 to adjust its pH value, and oil bath heating is boiled, cold
Solidifying reflux；The seed solution obtained in step 11 is rapidly injected in the aqueous solution that pH value is 4.5, continues to keep heating stirring
After 1.5h, natural cooling in stirring is completed silver nano-grain and is prepared；
Step 13 centrifuges silver nano-grain obtained, 2500 revs/min of centrifugal speed, and extraction is deposited in centrifugation
The silver nano-grain of bottom of the tube after 6 centrifugations, obtains uniform, spherical silver nano-grain；
Step 2：Uniform monolayers film of metal nano-particles is prepared on hydrophobic material surface, is as follows：
After step 21, plasma cleaning PDMS substrates 40s, place it in rapidly in the ethanol solution of 5% (V/V) APTMS,
Temperature is 65 DEG C of holding 6h, and PDMS substrates are taken out, is rinsed repeatedly with absolute ethyl alcohol, removes extra APTMS；
Step 22, will through step 21, treated that PDMS is cut into suitable size, bottom of the beaker is placed it in, according to silver obtained
Nanoparticle size calculates the amount for the elargol that densely covered bottom of the beaker needs, and is added into beaker, 50 DEG C of dry out solvent, completes
It is prepared by uniform SERS substrates；
Step 23 in SERS substrates obtained does SERS detections at optional 10 points using rhodamine 6G as probe molecule, tests
The result shows that the relative standard deviation of the uniform SERS substrates of solid phase individual layer made from hydrophobic material PDMS surfaces be only 11 ±
0.5%.
Advantageous effect：The present invention can prepare the very high metal nanoparticle of uniformity and the SERS of tight monolayers arrangement
Substrate, the relative standard deviation of metal nanoparticle up to 7%, SERS substrates relative standard deviation up to 11%, the present invention
It substantially increases and prepares the uniformity of individual layer SERS substrates on hydrophobic material surface.
Description of the drawings
Fig. 1 a and Fig. 1 b are respectively silver nano-grain transmission electron microscope picture (TEM) obtained and particle diameter distribution statistics.
The scanning electron microscope (SEM) photograph (SEM) of SERS substrates prepared by Fig. 2 PDMS surfaces.
Fig. 3 a and Fig. 3 b are respectively SERS spectrums and homogeneity statistical.
Fig. 4：There is the Spectral Extinction of elargol that pH value regulates and controls and prepared without pH value regulation and control.
Fig. 5：Nucleation stage pH value is 11, and growth phase pH value is respectively the delustring of 7.4 and 4.5 elargol prepared
Spectrum.
Fig. 6：Growth phase pH value is 4.5, and nucleation stage pH value is respectively 12,11,9.7 and 8.7 elargol prepared
Spectral Extinction.
Fig. 7 a to Fig. 7 f are respectively the transmission electron microscope picture (TEM) of elargol and corresponding to be received after centrifuging 0,4,6 time about silver
The frequency statistics of rice grain diameter.
Fig. 8 a and Fig. 8 b are respectively the scanning electron microscope (SEM) photograph that quantitative solvent evaporation and self-assembly method prepare SERS substrates
(SEM)。
Specific embodiment
It is rich applicant carried out deep creatively to study in order to solve the above problem of the existing technology.Shen
It asks someone to find：The poor difficulty for being firstly because uniform metal nanoparticle preparation of SERS substrate uniformities is larger, especially
Uniform silver nano-grain.And the uniform noble metal nano particles of pattern prepared by existing many chemical methodes are all to pass through package
One layer of other substance or its particular growth is controlled by adding surfactant, these all can greatly influence the later stage
SERS is applied.In addition, the difficulty that particle is equably adsorbed onto in hydrophobic substrate is also bigger, and due between metallic particles
Electrostatic repulsion, particle are difficult to tighten solid matter cloth in substrate.
For this purpose, applicant proposed following schemes：
The preparation method of the currently preferred uniform SERS substrates of hydrophobic surface solid phase individual layer, including following two step：
The first step：Uniform metal nanoparticle colloid is prepared, specifically includes following steps：
A 0.5418g sodium citrates) is taken to be dissolved in the water of 4ml, adjust its pH value as 11, places it among boiling water and preheats,
And it is placed on ultrasound inside ultrasonic machine；The silver nitrate of 0.051g is taken to be dissolved in the water of 1ml, places it in boiling water and preheats；It will be made
Silver nitrate aqueous solution injection pH value be 11 sodium citrate solution in, after solution is creamy white, obtain seed solution；
B the water of 295ml) is taken to be placed in three neck round bottom flask, it is 4.5 to adjust its pH value, and oil bath heating is boiled, and is condensed back to
Stream；The seed solution obtained in step A is rapidly injected in the aqueous solution that pH value is 4.5, continued after keeping heating stirring 1.5h,
Natural cooling in stirring is completed silver nano-grain and is prepared；
C) silver nano-grain obtained is repeatedly centrifuged, 2500 revs/min of centrifugal speed, extraction is deposited in centrifuge tube
The silver nano-grain of bottom after 6 centrifugations, obtains 65nm or so, uniform, spherical shape silver nano-grain, relative standard deviation
Only 7% or so, as shown in attached drawing 1a and Fig. 1 b.
Second step：Uniform monolayers film of metal nano-particles is prepared on hydrophobic material (PDMS) surface, is as follows：
A) after plasma cleaning PDMS substrates 40s, 5% (V/V) APTMS ethanol solutions, temperature 65 are placed it in rapidly
DEG C keep 6h, PDMS substrates are taken out, is rinsed repeatedly with absolute ethyl alcohol, removes extra APTMS；
B the size of bottom of the beaker can be just stuck in by) being cut into the PDMS after processing of step A, be placed in bottom of the beaker, according to
Silver nano-grain size obtained in one step, calculates the amount for the elargol that densely covered bottom of the beaker needs, and is added into beaker, 50
DEG C dry out solvent is completed uniform SERS substrates and is prepared, as shown in Figure 2.
C) in SERS substrates obtained SERS detections, test result table are done at optional 10 points using rhodamine 6G as probe molecule
The relative standard deviation of the uniform SERS substrates of solid phase individual layer made from bright hydrophobic material PDMS surfaces is only 11% or so, such as attached drawing
Shown in 3a and Fig. 3 b.
Example one：
The silver nitrate of 0.051g is taken to be dissolved in the water of 5ml and obtains silver nitrate solution；0.5418g sodium citrates is taken to be placed in three mouthfuls
In round-bottomed flask, the deionized water of 295ml is added in, oil bath heating is boiled, and is stirred energetically, condensing reflux.Nitric acid is added in after boiling
Silver-colored solution continues to keep heating stirring 1.5h, stop working, natural cooling in stirring, then prepared by elargol completes.The elargol of preparation disappears
Spectrum is as shown in figure 4, absorb peak position in 413nm or so, halfwidth 95nm or so.
And the Spectral Extinction of elargol prepared in above-mentioned preferred method, peak position is absorbed in 415nm or so, and halfwidth 78nm is left
It is right.Since the peak position of Spectral Extinction is determined by the size of particle, and halfwidth is determined by the uniformity of particle, so there is pH value regulation and control
The silver nano-grain of preparation is dimensionally got well greatly, than in uniformity than silver nano-grain prepared by the regulation and control of no pH value.
Example two：
0.5418g sodium citrates is taken to be dissolved in the water of 4ml, add in a certain amount of sodium hydroxide solution, adjusting its pH value is
11, it places it among boiling water and preheats, and be placed on ultrasound inside ultrasonic machine；The silver nitrate of 0.051g is taken to be dissolved in the water of 1ml, it will
It is placed in boiling water and preheats.With needle tubing by among silver nitrate solution injection sodium citrate solution, after solution is creamy white, incite somebody to action
The seed solution arrived takes out inside ultrasonic machine；The water of 295ml is taken to be placed in three neck round bottom flask, oil bath heating is boiled, energetically
Stirring, condensing reflux after solution boiling, obtained silver-colored seed solution are disposably rapidly injected in flask with needle tubing, after continuation of insurance
After holding heating stirring 1.5h, stop working, natural cooling in stirring, then prepared by elargol completes.The Spectral Extinction of the elargol of preparation such as Fig. 5 institutes
Show, absorb peak position in 405nm or so.
And the Spectral Extinction of the elargol prepared in above-mentioned preferred method, peak position is absorbed in 415nm or so.Due to the peak of Spectral Extinction
Position is determined by the size of particle, so the pH value (pH=4.5) in growth phase regulates and controls the size bigger so that particle.
Example three：
0.5418g sodium citrates is taken to be dissolved in the water of 4ml, add in a certain amount of sodium hydroxide solution, adjust its pH value point
Not Wei 12,11,9.7,8.7, place it among boiling water and preheat, and be placed on ultrasound inside ultrasonic machine；Take the silver nitrate of 0.051g
It is dissolved in the water of 1ml, places it in boiling water and preheat.With needle tubing by among silver nitrate solution injection sodium citrate solution, treat molten
After liquid is creamy white, obtained seed solution is taken out inside ultrasonic machine；The water of 295ml is taken to be placed in three neck round bottom flask,
A certain amount of salpeter solution is added in, it is 4.5 to adjust its pH value, and oil bath heating is boiled, and is stirred energetically, condensing reflux, solution boiling
Afterwards, obtained silver-colored seed solution with needle tubing is disposably rapidly injected in flask, continues after keeping heating stirring 1.5h, stop working,
Natural cooling in stirring, then prepared by elargol completes.The Spectral Extinction of the elargol of preparation as shown in fig. 6, nucleation stage pH value be 12,
11st, 9.7,8.7, growth phase pH value all for 4.5, the absorption peak of corresponding elargol be respectively 416nm, 415nm, 415nm,
416nm, but halfwidth is respectively 92nm, 78nm, 97nm, 126nm.Since the peak position of Spectral Extinction is determined by the size of particle,
And halfwidth is determined by the uniformity of particle, so the adjoining dimensions of these four silver nano-grains, and during nucleation stage pH=11
Uniformity it is best.
Example four：
The elargol that multiple low-speed centrifugal prepares, 2500 turns of centrifugal speed, centrifugation time 40min are straight with dropper every time
The bottom for reaching centrifuge tube is connect, draws the silver nano-grain for being deposited in bottom.
The TEM figures and the statistical distribution to silver nano-grain diameter that Fig. 7 a and Fig. 7 b are the elargol directly prepared,
As shown in Fig. 7 b, the average-size of Argent grain is between 60-70nm, relative standard deviation 13.31%.
The TEM figures and the system to silver nano-grain diameter that Fig. 7 c and Fig. 7 d have centrifuged the elargol after 4 times for the method
Score cloth, as shown in Fig. 7 d, the average-size of Argent grain is between 60-65nm, relative standard deviation 10.40%.
The TEM figures and the system to silver nano-grain diameter that Fig. 7 e and Fig. 7 f have centrifuged the elargol after 6 times for the method
Score cloth, as shown in Fig. 7 f, the average-size of Argent grain is in 65nm or so, relative standard deviation 7.8%.In addition, along with
Centrifuge number increase, rodlike silver nano-grain from the beginning account for total particle 2.18%, to centrifugation 6 times after, rodlike silver
Nano particle accounts for the 0.29% of total particle.
Example five：
The PDMS for having modified amino is immersed in fulmargin prepared by above-mentioned preferred method, soaked overnight passes through ammonia
Base captures silver nano-grain, and the scanning electron microscope (SEM) photograph of the SERS substrates of preparation is as shown in Figure 8 b.It can be seen that it is directly captured by amino
Argent grain, due to the electrostatic repulsion between Argent grain, the spacing of particle cannot accomplish densification.And the SERS prepared in preferred method
Substrate can accomplish fine and close grain spacing, as shown in Figure 8 a.
From above-described embodiment：
The present invention separates nucleation (seed solution) with growth course, and being conducive to growth, there is the uniform of certain size to receive
Rice grain.And the two processes are not strictly separated by the prior art, therefore, it is difficult to control the pH value of growth phase, growth is received
The uniformity of rice grain is also bad.The nano particle only grown up to certain size just has preferable SERS activity.
Since PDMS is hydrophobic, it is difficult to combined with the silver nano-grain in aqueous solution, oxygen plasma of the invention+
APTMS processing so that it is easy to be combined with silver nano-grain.
Amount of the present invention according to needed for the particle size (Electronic Speculum result) grown calculates monolayer alignment, by treated
PDMS is placed in container bottom, adds in the nano particle calculated in container, rapid dry out solvent, completes individual layer dense uniform
The preparation of SERS substrates.Method is simple, works well.It is used with the prior art and PDMS is placed in self assembly deposition in fulmargin
Nanometer particle film is compared, and of the invention is with obvious effects more preferable.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of equivalents can be carried out to technical scheme of the present invention, this
A little equivalents all belong to the scope of protection of the present invention.
Claims (6)
1. a kind of preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer, which is characterized in that including following processing step：
Step 1 prepares homogeneous metal nano particle
Step 11 prepares the uniform metal nanoparticle seed solution of pattern under the acid-base value of scheduled nucleation, in the step
In, the uniformity of metal nanoparticle size is improved by the precision of control ph；The scheduled nucleation acid-base value refers to pH
=11 ± 0.5, metal nanoparticle is made to grow to 65 ± 15 nanometers；
Metal nanoparticle seed solution is transferred to growing environment by step 12, adjusts pH value, it is made unanimously to grow to design ruler
It is very little, in this step, the size of the big minor adjustment metal nanoparticle by adjusting pH value；
Step 13, low-speed centrifugal several times, choose the spheric granules for being deposited in centrifugation bottom of the tube, to further improve metal nano
Particle uniformity；
Step 2, in hydrophobic material surface uniform deposition single-layer metal nano particle
Step 21, the metal nanoparticle size according to acquisition calculate metal nanoparticle needed for deposition individual layer SERS substrates
Amount；
Hydrophobic material after the silanization treatment of suitable size is placed in container bottom by step 22, is added in the metal calculated and is received
Rice grain colloid is in container, rapid dry out solvent, completes the uniform SERS substrates of solid phase individual layer and prepares.
2. the preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer as described in claim 1, which is characterized in that described
In step 11, pH=11 ± 0.2 makes metal nanoparticle grow to 65 ± 5 nanometers.
3. the preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer as described in claim 1, which is characterized in that in step
In rapid 12, pH value is adjusted to 3.5, metal nanoparticle grows to 75 ± 0.5 nanometers；Alternatively,
PH value is adjusted to 4.5, metal nanoparticle grows to 65 ± 0.5 nanometers；Alternatively,
PH value is adjusted to 5.5, metal nanoparticle grows to 55 ± 0.5 nanometers.
4. the preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer as described in claim 1, which is characterized in that in step
It in rapid 13, centrifuges 4~8 times, rotating speed is 2200~2700 revs/min, and centrifugation time is 35~45 minutes, is centrifuged 6 times, and rotating speed is
2500 revs/min, the time is 40 minutes.
5. the preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer as described in claim 1, which is characterized in that described
Metal nanoparticle is gold nano grain or silver nano-grain.
6. a kind of preparation method of the uniform SERS substrates of hydrophobic surface solid phase individual layer, which is characterized in that including following processing step：
Step 1：Prepare uniform metal nanoparticle colloid：
Step 11 takes 0.5418g sodium citrates to be dissolved in the water of 4ml, and it is 11 to adjust pH value, places it among boiling water and preheats,
And it is placed in ultrasonic machine and is ultrasonically treated；The silver nitrate of 0.051g is taken to be dissolved in the water of 1ml, places it in boiling water and preheats；It will system
The silver nitrate aqueous solution injection pH value obtained is in 11 sodium citrate solution, after solution is creamy white, obtains seed solution；
Step 12 takes the water of 295ml to be placed in three neck round bottom flask, and it is 4.5 to adjust its pH value, and oil bath heating is boiled, and is condensed back to
Stream；The seed solution obtained in step 11 is rapidly injected in the aqueous solution that pH value is 4.5, continues to keep heating stirring 1.5h
Afterwards, natural cooling in stirring is completed silver nano-grain and is prepared；
Step 13 centrifuges silver nano-grain obtained, 2500 revs/min of centrifugal speed, and extraction is deposited in centrifuge tube bottom
The silver nano-grain in portion after 6 centrifugations, obtains uniform, spherical silver nano-grain；
Step 2：Uniform monolayers film of metal nano-particles is prepared on hydrophobic material surface, is as follows：
After step 21, plasma cleaning PDMS substrates 40s, place it in rapidly in the ethanol solution of 5%APTMS, temperature 65
DEG C keep 6h, PDMS substrates are taken out, is rinsed repeatedly with absolute ethyl alcohol, removes extra APTMS；__
Step 22, will through step 21, treated that PDMS is cut into suitable size, bottom of the beaker is placed it in, according to silver nanoparticle obtained
Particle size calculates the amount for the elargol that densely covered bottom of the beaker needs, and is added into beaker, 50 DEG C of dry out solvent, completes uniform
It is prepared by SERS substrates；
Step 23 in SERS substrates obtained does SERS detections, test result at optional 10 points using rhodamine 6G as probe molecule
The relative standard deviation for showing the uniform SERS substrates of solid phase individual layer made from hydrophobic material PDMS surfaces is 11 ± 0.5%.
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| CN108226135B (en) * | 2018-01-26 | 2020-12-29 | 江南大学 | Composite membrane sensor and method for detecting vibrio parahaemolyticus by using same |
| CN110511418B (en) * | 2019-07-11 | 2021-10-29 | 宁波大学 | Silver-gold nanowire PDMS composite film material for SERS detection and preparation method and application thereof |
| CN111299606B (en) * | 2020-03-19 | 2021-08-13 | 中国科学院高能物理研究所 | Preparation method of nano-gold coffee ring and application of nano-gold coffee ring in SERS detection |
| CN115582537B (en) * | 2022-10-08 | 2023-05-16 | 温州医科大学 | Preparation method and application of large-size uniform nano noble metal film |
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