CN106645087A - PDMS-base single-layer SERS substrate not requiring surface modification and preparation method thereof - Google Patents
PDMS-base single-layer SERS substrate not requiring surface modification and preparation method thereof Download PDFInfo
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- CN106645087A CN106645087A CN201611198339.2A CN201611198339A CN106645087A CN 106645087 A CN106645087 A CN 106645087A CN 201611198339 A CN201611198339 A CN 201611198339A CN 106645087 A CN106645087 A CN 106645087A
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Abstract
The invention discloses a PDMS-base single-layer SERS substrate not requiring surface modification and a preparation method thereof. The method comprises the following steps: preparing uniform metal sol particles; self-assembling a single-layer compact metal nanoparticle film in an oil-water interface; transferring the metal nanoparticle film to the surface of a PDMS not subjected to surface treatment, so as to form a compact and uniform SERS substrate. According to the method, hydrophilization treatment on the PDMS and subsequent specific group modification are cancelled, the manufacture flow is greatly simplified, the manufacture reliability is improved, the method is not required to be implemented in an ultra-clean chamber, and the requirement on the manufacture environment is reduced; the metal nanoparticle film prepared through the method is spontaneously formed, and the distance between metal nanoparticles is extremely small, so that the SERS strengthening effect and uniformity are extremely high.
Description
Technical field
The invention belongs to measure, test or detection technique field, particularly a kind of system of hydrophobic surface solid phase SERS substrate
Preparation Method.
Background technology
SERS (SERS) detection technique is a kind of highly sensitive detection method, can characterize low concentration
Analyte architectural feature；Micro-fluidic device then can the reaction such as Real Time Observation biology, chemistry in the state of flowing
Process, therefore, the microfluidic device with SERS activity is biological for research, Chemical Kinetics is significant.Poly- two
Methylsiloxane (PDMS) is the PDMS base SERS substrates for preparing material, preparing high evenness of microfluidic device the most frequently used at present
It is the basis of the SERS activity microfluidic devices for researching and developing functionalization.
Modal solid phase SERS substrate fabrication method is the metal nanoparticle colloid uniform deposition that will be prepared in base
On bottom.However, PDMS has strong-hydrophobicity, it is difficult to uniform deposition metal nanoparticle thereon.Usual way is first right
PDMS carries out surface and is modified, then some specific groups of grafting or macromolecule layer (such as modifying APTMS or PDDA) so as to surface
Positively charged, by electronegative part in adsorbing metal nano-colloid, most at last metal nanoparticle is deposited to PDMS surfaces.
As can be seen here, at present SERS substrates are made on hydrophobic PDMS surfaces and there is problems with：1. complex steps, drop
The low reliability for preparing high evenness SERS substrates, causes the uniformity to be difficult to ensure；2. the cycle is long, high cost, need to use oxygen
The main equipments such as plasma cleaner；3. the purity requirements of pair production environment are high, need to carry out surface hydrophilicity in ultra-clean chamber and change
Property；4., due to the repulsion between metal nanoparticle, the grain spacing adsorbed in substrate is larger.
Accordingly, it would be desirable to develop a kind of high side of making individual layer densification the simple of SERS substrates, reliability on PDMS
Method.
The content of the invention
Goal of the invention：Hydrophobic material (PDMS) surface not surface modification directly from the fine and close metal nano of assembling individual layer
Particle film, obtains the SERS substrates that SERS activity is good, repeatability is high.
Technical scheme：A kind of PDMS base SERS substrate preparation methods without the need for surface modification are provided, are comprised the steps：
Step 1, prepare homogeneous metal sol particle；
Step 2, in the fine and close film of metal nano-particles of water-oil interface self-assembled monolayer；
Step 3, the PDMS surfaces that film of metal nano-particles is transferred to non-surface treated simultaneously form dense uniform
SERS substrates.
Preferably, the step 1 is further included：
Step 11, the silver nitrate solution for preparing 0.2-2mol/L, are placed in boiling water and preheat；Prepare the lemon of 0.3-1.5mol/L
Lemon acid sodium solution, adjust pH value to 8.7-12, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to nitre
Sour silver measures silver nitrate solution with the mol ratio of sodium citrate for the ratio of 0.125-1.5, and silver nitrate solution is injected into lemon
In acid sodium solution, liquid to be mixed obtains seed solution into after milky；
Step 12, prepare pH be 3.5-7.5 the aqueous solution, and by the aqueous solution be placed in oil bath add boil, condense back
Stream；The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 0.5-2 hours, obtain silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 1500-5000 rev/min
Clock；Centrifugation number of times is 1-8 time；Obtain the spherical silver nanoparticle solution of 65 × (1 ± 0.07) nm.
Preferably, the step 2 is further included：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver
Nanoparticles solution, then inject oil-phase solution into the reaction vessel, stands, oil-phase solution and spherical silver nanoparticle solution
Volume ratio is 0.5-2；
Step 22, at the uniform velocity a certain amount of hydrophilic matched somebody with somebody to the water phase side injection of water-oil interface with the speed of 0.01-2ml/min
Body substituting agent, silver nano-grain is separated out in water-oil interface.
Preferably, the step 3 is further included：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with gold
The silver nano-grain single thin film of category gloss；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 0.5-5 minutes, silverskin is transferred to PDMS substrates
On, combine closely individual layer silver nanometer particle film on PDMS surfaces；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
A kind of PDMS base SERS substrate preparation methods without the need for surface modification, including：
Single-layer metal nanometer particle film is generated at water phase and an oil phase interface；Volatilization upper oil phase solvent；Will be undressed
PDMS is gently placed in film surface, and film of metal nano-particles is automatically transferred on PDMS, forms SERS substrates.
Preferably, the process for generating single-layer metal nanometer particle film at water phase and an oil phase interface specifically includes following steps：
The homogeneous metal colloidal sol of the concentration for preparing first is injected in clean glass container, density is reinjected less than water
Oil phase solvent, stands；At the uniform velocity get along to water-oil interface water at a predetermined velocity and inject metal Ion-hydrophilic Ligand substituting agent, metal nanoparticle is certainly
Send out and separated out in water-oil interface, form single-layer metal nanometer particle film.
Preferably, described oil phase solvent includes toluene, ethyl acetate and n-hexane.Metal nanoparticle includes gold nano
Particle and silver nano-grain.The metal Ion-hydrophilic Ligand substituting agent includes alcohols, red fuming nitric acid (RFNA) silver salt solution, acetone and protein solution.
The PDMS base SERS substrates obtained using the preparation method of any of the above-described embodiment.
Operation principle：Applicant's process is goed deep into and creative research discovery is grown on water-oil interface and greatly reduces
The current potential of film of metal nano-particles, adsorbed close can be produced with PDMS surfaces by strong electrostatic interaction, so as to need not
Deposit the fine and close film of metal nano-particles of individual layer by any surface modification is carried out to PDMS thereon, it is uniform so as to be formed
With high enhanced SERS substrates.
Beneficial effect：Preparation method of the present invention can prepare densification on the PDMS without any surface modification
Single-layer metal nanometer particle film, method is simple；And the film of metal nano-particles densification that this method makes is flexible,
It is tightly combined with PDMS, with high SERS enhancements and uniformity.This method is eliminated carries out hydrophilicity-imparting treatment to PDMS
And the modification of follow-up special groups, Making programme is greatly simplified, the reliability of making is improve, and without the need for super
Implement between net, reduce the requirement to production environment；Film of metal nano-particles system prepared by this method spontaneously forms, and metal is received
Rice grain spacing is minimum, thus SERS enhancing effects and uniformity are high.
Description of the drawings
Fig. 1 is the flow chart of the present invention.
Fig. 2 a and Fig. 2 b is the shape appearance figure of PDMS bases SERS substrates obtained in embodiment eight.
Fig. 3 is the SERS spectrums of the R6G of any 20 points of detections in obtained SERS substrates.
Fig. 4 is the 1510cm of R6G-1The uniformity of characteristic peak is characterized.
Fig. 5 is the shape appearance figure of PDMS bases SERS substrates obtained in example nine.
Fig. 6 is the shape appearance figure of PDMS bases SERS substrates obtained in example ten.
Specific embodiment
Loaded down with trivial details the step of prior art is present in order to solve, repeatability is low, high to the purity requirements of production environment, and
The problems such as metal nanoparticle spacing is larger, applicant proposed following scheme：
The PDMS base SERS bases preparation method without the need for surface modification of the present invention, comprises the steps：Prepare uniform gold
Category sol particle；In the film of metal nano-particles that water-oil interface self-assembled monolayer is fine and close；Film of metal nano-particles is shifted
To non-surface treated PDMS surfaces and form the SERS substrates of dense uniform.
Wherein, the step 1 is specifically included：
Step 11, the silver nitrate solution for preparing 0.2-2mol/L, are placed in boiling water and preheat；Prepare the lemon of 0.3-1.5mol/L
Lemon acid sodium solution, adjust pH value to 8.7-12, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to nitre
Sour silver measures silver nitrate solution with the mol ratio of sodium citrate for the ratio of 0.125-1.5, and silver nitrate solution is injected into lemon
In acid sodium solution, liquid to be mixed obtains seed solution into after milky；
Step 12, prepare pH be 3.5-7.5 the aqueous solution, and by the aqueous solution be placed in oil bath add boil, condense back
Stream；The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 0.5-2 hours, obtain silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 1500-5000 rev/min
Clock；Centrifugation number of times is 1-8 time；Obtain the spherical silver nanoparticle solution of 65 × (1 ± 0.07) nm.
The step 2 is specifically included：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver
Nanoparticles solution, then inject oil-phase solution into the reaction vessel, stands, oil-phase solution and spherical silver nanoparticle solution
Volume ratio is 0.5-2；
Step 22, at the uniform velocity a certain amount of hydrophilic matched somebody with somebody to the water phase side injection of water-oil interface with the speed of 0.01-2ml/min
Body substituting agent, silver nano-grain is separated out in water-oil interface.
The step 3 is specifically included：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with gold
The silver nano-grain single thin film of category gloss；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 0.5-5 minutes, silverskin is transferred to PDMS substrates
On, combine closely individual layer silver nanometer particle film on PDMS surfaces；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
Embodiment 1
A kind of PDMS base SERS bases preparation method without the need for surface modification, comprises the steps：
Step 1, homogeneous metal sol particle is prepared, specifically included：
Step 11, the silver nitrate solution for preparing 1.6mol/L, are placed in boiling water and preheat；Prepare the sodium citrate of 1.4mol/L
Solution, adjust pH value to 12, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to silver nitrate and lemon
The mol ratio of sour sodium is that 0.13 ratio measures silver nitrate solution, and silver nitrate solution is injected in sodium citrate solution, waits to mix
Liquid is closed into after milky, seed solution is obtained；
Step 12, the aqueous solution that pH is 3.5 is prepared, and the aqueous solution is placed in add in oil bath boils, condensing reflux；Will
The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 0.5 hour, obtains silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 5000 revs/min；From
Heart number of times is 6 times；Obtain the spherical silver nanoparticle solution of 65 × (1 ± 0.07) nm.
Step 2, in the fine and close film of metal nano-particles of water-oil interface self-assembled monolayer, specifically include：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver
Nanoparticles solution, then inject oil-phase solution into the reaction vessel, stands, oil-phase solution and spherical silver nanoparticle solution
Volume ratio is 2；
Step 22, a certain amount of metal Ion-hydrophilic Ligand is at the uniform velocity injected to the water phase side of water-oil interface with the speed of 0.01ml/min
Substituting agent, silver nano-grain is separated out in water-oil interface.
Step 3, the PDMS surfaces that film of metal nano-particles is transferred to non-surface treated simultaneously form dense uniform
SERS substrates, specifically include：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with gold
The silver nano-grain single thin film of category gloss；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 5 minutes, silverskin is transferred on PDMS substrates,
PDMS combines closely on surface individual layer silver nanometer particle film；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
Embodiment 2
A kind of PDMS base SERS substrate preparation methods without the need for surface modification, comprise the steps：
Step 1, homogeneous metal sol particle is prepared, specifically included：
Step 11, the silver nitrate solution for preparing 0.6mol/L, are placed in boiling water and preheat；The sodium citrate for preparing 1mol/L is molten
Liquid, adjust pH value to 11.0, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to silver nitrate and lemon
The mol ratio of sour sodium is that 1.25 ratio measures silver nitrate solution, and silver nitrate solution is injected in sodium citrate solution, waits to mix
Liquid is closed into after milky, seed solution is obtained；
Step 12, the aqueous solution that pH is 4.5 is prepared, and the aqueous solution is placed in add in oil bath boils, condensing reflux；Will
The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 1 hour, obtains silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 4000 revs/min；From
Heart number of times is 3 times；Obtain the spherical silver nanoparticle solution of 65 × (1 ± 0.07) nm.
Step 2, in the fine and close film of metal nano-particles of water-oil interface self-assembled monolayer, specifically include：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver
Nanoparticles solution, then inject oil-phase solution into the reaction vessel, stands, oil-phase solution and spherical silver nanoparticle solution
Volume ratio is 1.2；
Step 22, a certain amount of metal Ion-hydrophilic Ligand is at the uniform velocity injected to the water phase side of water-oil interface with the speed of 0.5ml/min
Substituting agent, silver nano-grain is separated out in water-oil interface.
Step 3, the PDMS surfaces that film of metal nano-particles is transferred to non-surface treated simultaneously form dense uniform
SERS substrates, specifically include：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with gold
The silver nano-grain single thin film of category gloss；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 4 minutes, silverskin is transferred on PDMS substrates,
PDMS combines closely on surface individual layer silver nanometer particle film；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
Embodiment 3
A kind of PDMS base SERS bases preparation method without the need for surface modification, comprises the steps：
Step 1, homogeneous metal sol particle is prepared, specifically included：
Step 11, the silver nitrate solution for preparing 0.3mol/L, are placed in boiling water and preheat；Prepare the sodium citrate of 0.4mol/L
Solution, adjust pH value to 10.0, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to silver nitrate and lemon
The mol ratio of lemon acid sodium is that 0.8 ratio measures silver nitrate solution, and silver nitrate solution is injected in sodium citrate solution, waits to mix
Liquid is closed into after milky, seed solution is obtained；
Step 12, the aqueous solution that pH is 5.5 is prepared, and the aqueous solution is placed in add in oil bath boils, condensing reflux；Will
The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 1.5 hours, obtains silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 3000 revs/min；From
Heart number of times is 5 times；Obtain the spherical silver nanoparticle solution of 65 × (1 ± 0.07) nm.
Step 2, in the fine and close film of metal nano-particles of water-oil interface self-assembled monolayer, specifically include：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver
Nanoparticles solution, then inject oil-phase solution into the reaction vessel, stands, oil-phase solution and spherical silver nanoparticle solution
Volume ratio is 4；
Step 22, a certain amount of metal Ion-hydrophilic Ligand is at the uniform velocity injected to the water phase side of water-oil interface with the speed of 1ml/min take
For agent, silver nano-grain is separated out in water-oil interface.
Step 3, the PDMS surfaces that film of metal nano-particles is transferred to non-surface treated simultaneously form dense uniform
SERS substrates, specifically include：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with gold
The silver nano-grain single thin film of category gloss；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 3 minutes, silverskin is transferred on PDMS substrates,
PDMS combines closely on surface individual layer silver nanometer particle film；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
Embodiment 4
A kind of PDMS base SERS bases preparation method without the need for surface modification, comprises the steps：
Step 1, homogeneous metal sol particle is prepared, specifically included：
Step 11, the silver nitrate solution for preparing 1.9mol/L, are placed in boiling water and preheat；Prepare the sodium citrate of 0.4mol/L
Solution, adjust pH value to 8.7, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to silver nitrate and lemon
The mol ratio of sour sodium is that 0.15 ratio measures silver nitrate solution, and silver nitrate solution is injected in sodium citrate solution, waits to mix
Liquid is closed into after milky, seed solution is obtained；
Step 12, the aqueous solution that pH is 6.5 is prepared, and the aqueous solution is placed in add in oil bath boils, condensing reflux；Will
The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 2 hours, obtains silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 2500 revs/min；From
Heart number of times is 8 times；Obtain the spherical silver nanoparticle solution of 65 × (1 ± 0.07) nm.
Step 2, in the fine and close film of metal nano-particles of water-oil interface self-assembled monolayer, specifically include：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver
Nanoparticles solution, then inject oil-phase solution into the reaction vessel, stands, oil-phase solution and spherical silver nanoparticle solution
Volume ratio is 0.6；
Step 22, a certain amount of metal Ion-hydrophilic Ligand is at the uniform velocity injected to the water phase side of water-oil interface with the speed of 1.2ml/min
Substituting agent, silver nano-grain is separated out in water-oil interface.
Step 3, the PDMS surfaces that film of metal nano-particles is transferred to non-surface treated simultaneously form dense uniform
SERS substrates, specifically include：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with gold
The silver nano-grain single thin film of category gloss；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 2 minutes, silverskin is transferred on PDMS substrates,
PDMS combines closely on surface individual layer silver nanometer particle film；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
Embodiment 5
A kind of PDMS base SERS bases preparation method without the need for surface modification, comprises the steps：
Step 1, homogeneous metal sol particle is prepared, specifically included：
Step 11, the silver nitrate solution for preparing 0.2mol/L, are placed in boiling water and preheat；Prepare the sodium citrate of 0.3mol/L
Solution, adjust pH value to 11.0, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to silver nitrate and lemon
The mol ratio of lemon acid sodium is that 0.6 ratio measures silver nitrate solution, and silver nitrate solution is injected in sodium citrate solution, waits to mix
Liquid is closed into after milky, seed solution is obtained；
Step 12, the aqueous solution that pH is 7.5 is prepared, and the aqueous solution is placed in add in oil bath boils, condensing reflux；Will
The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 1.5 hours, obtains silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 2000 revs/min；From
Heart number of times is 6 times；Obtain the spherical silver nanoparticle solution of 65 × (1 ± 0.07) nm.
Step 2, in the fine and close film of metal nano-particles of water-oil interface self-assembled monolayer, specifically include：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver
Nanoparticles solution, then inject oil-phase solution into the reaction vessel, stands, oil-phase solution and spherical silver nanoparticle solution
Volume ratio is 1.5；
Step 22, a certain amount of metal Ion-hydrophilic Ligand is at the uniform velocity injected to the water phase side of water-oil interface with the speed of 2ml/min take
For agent, silver nano-grain is separated out in water-oil interface.
Step 3, the PDMS surfaces that film of metal nano-particles is transferred to non-surface treated simultaneously form dense uniform
SERS substrates, specifically include：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with gold
The silver nano-grain single thin film of category gloss；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 1 minute, silverskin is transferred on PDMS substrates,
PDMS combines closely on surface individual layer silver nanometer particle film；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
Embodiment 6
A kind of PDMS base SERS bases preparation method without the need for surface modification, comprises the steps：
Step 1, homogeneous metal sol particle is prepared, specifically included：
Step 11, the silver nitrate solution for preparing 0.8mol/L, are placed in boiling water and preheat；Prepare the sodium citrate of 1.1mol/L
Solution, adjust pH value to 11.0, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to silver nitrate and lemon
The mol ratio of lemon acid sodium is that 0.65 ratio measures silver nitrate solution, and silver nitrate solution is injected in sodium citrate solution, is treated
Mixed liquor obtains seed solution into after milky；
Step 12, the aqueous solution that pH is 4.5 is prepared, and the aqueous solution is placed in add in oil bath boils, condensing reflux；Will
The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 1.5 hours, obtains silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 1500 revs/min；From
Heart number of times is 5 times；Obtain the spherical silver nanoparticle solution of 65 × (1 ± 0.07) nm.
Step 2, in the fine and close film of metal nano-particles of water-oil interface self-assembled monolayer, specifically include：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver
Nanoparticles solution, then inject oil-phase solution into the reaction vessel, stands, oil-phase solution and spherical silver nanoparticle solution
Volume ratio is 0.6；
Step 22, a certain amount of metal Ion-hydrophilic Ligand is at the uniform velocity injected to the water phase side of water-oil interface with the speed of 1.0ml/min
Substituting agent, silver nano-grain is separated out in water-oil interface.
Step 3, the PDMS surfaces that film of metal nano-particles is transferred to non-surface treated simultaneously form dense uniform
SERS substrates, specifically include：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with gold
The silver nano-grain single thin film of category gloss；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 0.5 minute, silverskin is transferred on PDMS substrates,
Combine closely individual layer silver nanometer particle film on PDMS surfaces；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
Embodiment 7：The currently preferred PDMS base individual layer SERS substrate fabrications method without the need for surface modification includes following
Three steps：
The first step：Homogeneous metal sol particle is prepared, following steps are specifically included：
A, take 0.5418g sodium citrates and be dissolved in the water of 4ml, adjust its pH value for 11, be placed among boiling water and preheat,
And it is ultrasonic to be placed on ultrasonic machine the inside；The silver nitrate for taking 0.051g is dissolved in the water of 1ml, is placed in boiling water and is preheated；To be obtained
Silver nitrate aqueous solution injection pH value be after solution is creamy white, to obtain seed solution in 11 sodium citrate solution；
B, the water for taking 295ml are placed in three neck round bottom flask, adjust its pH value for 4.5, and oil bath heating is boiled, and is condensed back
Stream；The seed solution obtained in step A is rapidly injected in the aqueous solution that pH value is 4.5, continues to keep after heating stirring 1.5h,
Natural cooling in stirring, completes silver nano-grain preparation；
C, obtained silver nano-grain is repeatedly centrifuged, 2500 revs/min of centrifugal speed, extraction is deposited in centrifuge tube
The silver nano-grain of bottom, Jing after 6 centrifugations, obtains the spherical silver nanoparticle that 65nm or so, relative standard deviation are only 7%
Grain.
Second step：The fine and close film of metal nano-particles of water-oil interface self-assembled monolayer, as shown in Figure 1, specifically includes
Following steps：
A) prepare one, the beaker processed with Piranha solution of 10ml, inject in the 2ml first steps thereto make first
The fulmargin for obtaining reinjects 2ml oil-phase solution B as solution A, stands；
B) a certain amount of solution C, boundary are at the uniform velocity injected to water-oil interface (water phase side) with the speed of 1ml/min with syringe pump
Face acutely disturbs, and silver nano-grain is constantly separated out in water-oil interface, until interface is completely covered by metal film.
3rd step：Film of metal nano-particles is transferred to into the PDMS surfaces of non-surface treated and dense uniform is formed
SERS substrates, comprise the steps：
A) upper solution B is removed, until volatilizing completely, the fine and close flexible silver nanoparticle with metallic luster is formed on the water surface
Granular cell layer film；
B) PDMS substrates are gently placed in the silver nanometer particle film of densification, or so half a minute, silverskin spontaneously turns completely
Move on PDMS substrates, combine closely individual layer silver nanometer particle film on PDMS surfaces, as shown in Figure 2；
C) PDMS for being coated with film of metal nano-particles is taken out into washing, nitrogen is dried up, then PDMS bases individual layer SERS substrates
Preparation is completed；
D) SERS Activity determinations：Obtained SERS substrates are immersed in into 1.0 × 10-63h in M R6G solution, takes out, and Jing goes
Ionized water is rinsed, and optional 20 points carry out SERS detections after nitrogen is dried up.
Example 8：
Taking the elargol that in scheme prepared by the first step carries out centrifugal concentrating so that the Spectral Extinction peak intensity of concentrate solution is 1.Take dense
The fulmargin 2ml of contracting is placed in the beaker processed with Piranha solution of 10ml, adds the toluene solution of 2ml, is stood point
Layer.A certain amount of ethanol solution, Yin Na are at the uniform velocity injected to water/toluene interface (water phase side) with the speed of 1ml/min with syringe pump
Rice grain is constantly separated out and captured by interface, until the particle for separating out is paved with beaker bore and stops injection ethanol.With toluene
Volatilization, the Argent grain of precipitation is shrunk to the silverskin of a densification, shown in the TEM such as accompanying drawings 2 (a) of silverskin.Silverskin is transferred to
Shown in the pattern such as accompanying drawing 2 (b) of the SERS substrates formed on PDMS surfaces.Obtained SERS substrates are immersed in into 1.0 × 10-6M
3h in R6G solution, takes out, Jing deionized water rinsings, and optional 20 points carry out SERS detections after nitrogen is dried up, and SERS spectrums are shown graphically in the attached figures
In 3, enhancer is 1.7 × 107；With 1510cm-1The uniformity of the SERS substrates is analyzed at peak, and relative standard deviation is RSD=
7.2%, as shown in Figure 4.
Example 9：
Taking the elargol that in scheme prepared by the first step carries out centrifugal concentrating so that the Spectral Extinction peak intensity of concentrate solution is 1.Take dense
The fulmargin 2ml of contracting is placed in the beaker processed with Piranha solution of 10ml, adds the hexane solution of 2ml, is stood
Layering.A certain amount of ethanol solution is at the uniform velocity injected to water/n-hexane interface (water phase side) with the speed of 1ml/min with syringe pump,
Silver nano-grain is constantly separated out and captured by interface, until the particle for separating out is paved with beaker bore and stops injection ethanol.With just
The volatilization of hexane, the Argent grain of precipitation is shrunk to a silverskin, and silverskin is transferred to into the SERS substrates of formation on PDMS surfaces
Pattern.As shown in Figure 5.
Example 10：
Taking the elargol that in scheme prepared by the first step carries out centrifugal concentrating so that the Spectral Extinction peak intensity of concentrate solution is 1.Take dense
The fulmargin 2ml of contracting is placed in the beaker processed with Piranha solution of 10ml, adds the toluene solution of 2ml, is stood point
Layer.A certain amount of red fuming nitric acid (RFNA) silver salt is at the uniform velocity injected to water/toluene interface (water phase side) with the speed of 1ml/min with syringe pump molten
Liquid, silver nano-grain is constantly separated out and captured by interface, until the particle for separating out is paved with beaker bore and stops injection red fuming nitric acid (RFNA) silver
Salting liquid.With the volatilization of toluene, the Argent grain of precipitation is shrunk to a silverskin, and silverskin is transferred to into what is formed on PDMS surfaces
The pattern of SERS substrates is as shown in Figure 6.
From above-described embodiment, the program can deposit single-layer metal nanometer on the PDMS without any surface treatment
Grain film, forms uniform SERS substrates.The method is simple, and SERS enhancing effects are good, and different molten by selecting
Liquid group, can obtain the SERS substrates of different consistency.
Embodiment 11
Other steps in the embodiment are similar to the above embodiments, it is preferred that emphasis is：
Taking the elargol that in scheme prepared by the first step carries out centrifugal concentrating so that the Spectral Extinction peak intensity of concentrate solution is 0.6-
0.7.The fulmargin 2ml for taking concentration is placed in and adds the n-hexane of 2ml molten in the beaker processed with Piranha solution of 10ml
Liquid, stratification.At the uniform velocity inject 1-1.5ml's to water/n-hexane interface (water phase side) with the speed of 1ml/min with syringe pump
Ethanol solution, silver nano-grain is constantly separated out and captured by interface, until the particle for separating out is paved with beaker bore and stops injection second
Alcohol.With the volatilization of n-hexane, the Argent grain of precipitation is shrunk to a silverskin, and silverskin is transferred to into what is formed on PDMS surfaces
The pattern of SERS substrates.
Find in an experiment, elargol delustring spectral intensity changes to 0.9 from 0.15, into silverskin it is increasing, due to container
Bore is limited, and silverskin is more and more closeer, and delustring spectral intensity even multilayer particle occurs more than 0.7, so optimal elargol Spectral Extinction is strong
Degree should be near 0.6-0.7.
When elargol concentration is 0.65, ethanol injection amount is respectively 0,0.5,1,1.5,2,2.5,3,3.5ml, and silverskin first increases
After reduce, in the ethanol injection amount of 1-1.5ml, silverskin is maximum.
Elargol concentration is 0.65, using different speed (0.05,0.25,0.5,1,1.5,1.75,2ml/min) Xiang Shuixiang
The ethanol of middle injection equal amount (1.5ml), the easy multilayer of little speed, the easy silverskin rupture of big speed, so speeds control exists
1ml/min。
In a word, the invention discloses a kind of PDMS base individual layer SERS substrate preparation methods without the need for surface modification, are included in
Water phase and an oil phase interface generates single-layer metal nano thin-film and the film is transferred on the PDMS without any surface treatment, shape
Into PDMS base individual layer SERS substrates.Wherein water phase and an oil phase interface generates concretely comprising the following steps for single-layer metal nano thin-film：Successively
The metal-sol and density of concentration are added in a reservoir less than the oil phase solvent of water, then it is hydrophilic in the injection of getting along of the nearly water of two-phase interface
Ligand substituting agent, then metal nanoparticle is spontaneous separates out to form film at water-oil interface；The metal nanometer thin film for generating is turned
Move on the PDMS without any surface treatment, form PDMS base individual layer SERS substrates, specifically include the whole oil phases of standing volatilization
Solvent, then will gently be placed in the film of metal nano-particles of generation without the PDMS of any process, then the film is spontaneously shifted
To PDMS, PDMS base individual layer SERS substrates are formed.Present invention greatly simplifies preparing the making stream of PDMS base SERS substrates
Journey, reduces preparation environmental requirement, and the SERS base metal nano particle spacing for preparing is minimum, and uniformity is very high, has both
High SERS enhancements and repeatability.
The several embodiments of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Several selections, the present invention range of the technology design in, various equivalents can be carried out to technical scheme, this
A little equivalents belong to protection scope of the present invention.
Claims (10)
1. a kind of PDMS base SERS substrate preparation methods without the need for surface modification, it is characterised in that comprise the steps：
Step 1, prepare homogeneous metal sol particle；
Step 2, in the fine and close film of metal nano-particles of water-oil interface self-assembled monolayer；
Step 3, the SERS that film of metal nano-particles is transferred to the PDMS surfaces of non-surface treated and dense uniform is formed
Substrate.
2. as claimed in claim 1 without the need for the PDMS base SERS substrate preparation methods of surface modification, it is characterised in that the step
Rapid 1 further includes：
Step 11, the silver nitrate solution for preparing 0.2-2mol/L, are placed in boiling water and preheat；Prepare the citric acid of 0.3-1.5mol/L
Sodium solution, adjust pH value to 8.7-12, be placed in boiling water preheat, and be placed in ultrasonic machine carry out it is ultrasonically treated；According to silver nitrate
Silver nitrate solution is measured for the ratio of 0.125-1.5 with the mol ratio of sodium citrate, and silver nitrate solution is injected into sodium citrate
In solution, liquid to be mixed obtains seed solution into after milky；
Step 12, prepare pH be 3.5-7.5 the aqueous solution, and by the aqueous solution be placed in oil bath add boil, condensing reflux；Will
The seed solution that step 11 is obtained is injected in the aqueous solution, continues to heat 0.5-2 hours, obtains silver nanoparticle solution；
Step 13, the silver nanoparticle solution to step 12 acquisition are centrifuged, and centrifugation rate is 1500-5000 rev/min；From
Heart number of times is 1-8 time；Obtain 65 ×（1±0.07）The spherical silver nanoparticle solution of nm.
3. as claimed in claim 2 without the need for the PDMS base SERS substrate preparation methods of surface modification, it is characterised in that the step
Rapid 2 further include：
Step 21, with Piranha solution process reaction vessel, in the reaction vessel implantation step 13 obtain spherical silver nanoparticle
Particle solution, then inject oil-phase solution into the reaction vessel, stands, the volume of oil-phase solution and spherical silver nanoparticle solution
Than for 0.5-2；
Step 22, a certain amount of metal Ion-hydrophilic Ligand is at the uniform velocity injected to the water phase side of water-oil interface with the speed of 0.01-2ml/min take
For agent, silver nano-grain is separated out in water-oil interface.
4. as claimed in claim 3 without the need for the PDMS base SERS substrate preparation methods of surface modification, it is characterised in that the step
Rapid 3 further include：
Step 31, upper oil phase solution is removed, the surface of spherical silver nanoparticle solution forms fine and close flexible with metal light
The silver nano-grain single thin film in pool；
Step 32, PDMS substrates are gently placed in silver nanometer particle film, 0.5-5 minutes, silverskin is transferred on PDMS substrates,
PDMS combines closely on surface individual layer silver nanometer particle film；
Step 33, the PDMS that will be coated with film of metal nano-particles take out, washing, and are dried up with nitrogen.
5. a kind of PDMS base SERS substrate preparation methods without the need for surface modification, it is characterised in that comprise the steps：
Single-layer metal nanometer particle film is generated at water phase and an oil phase interface；
Volatilization upper oil phase solvent；
Undressed PDMS is gently placed in into film surface, film of metal nano-particles is automatically transferred on PDMS, is formed
SERS substrates.
6. as claimed in claim 5 without the need for the PDMS base SERS substrate preparation methods of surface modification, it is characterised in that in water oil
Two-phase interface generates the process of single-layer metal nanometer particle film and specifically includes following steps：
The homogeneous metal colloidal sol of the concentration for preparing first is injected in clean glass container, oil phase of the density less than water is reinjected
Solvent, stands；
At the uniform velocity get along to water-oil interface water at a predetermined velocity and inject metal Ion-hydrophilic Ligand substituting agent, metal nanoparticle is spontaneous in Shui Youjie
Face separates out, and forms single-layer metal nanometer particle film.
7. as claimed in claim 5 without the need for the PDMS base SERS substrate preparation methods of surface modification, it is characterised in that described
Oil phase solvent includes toluene, ethyl acetate and n-hexane.
8. as claimed in claim 5 without the need for the PDMS base SERS substrate preparation methods of surface modification, it is characterised in that metal is received
Rice grain includes gold nano grain and silver nano-grain.
9. as claimed in claim 6 without the need for the PDMS base SERS substrate preparation methods of surface modification, it is characterised in that the parent
The agent of water ligand substituting includes alcohols, red fuming nitric acid (RFNA) silver salt solution, acetone and protein buffer solution.
10. the PDMS base SERS for being prepared using the method described in any one of Claims 1-4 or any one of claim 5 to 9
Substrate.
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| CN109520992A (en) * | 2018-11-08 | 2019-03-26 | 南京光声超构材料研究院有限公司 | A kind of SERS substrate of bromination silver nanowires and preparation method thereof |
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