CN110344030A - A kind of highly sensitive base material and preparation method thereof for LR laser raman enhancing - Google Patents
A kind of highly sensitive base material and preparation method thereof for LR laser raman enhancing Download PDFInfo
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- CN110344030A CN110344030A CN201910730688.1A CN201910730688A CN110344030A CN 110344030 A CN110344030 A CN 110344030A CN 201910730688 A CN201910730688 A CN 201910730688A CN 110344030 A CN110344030 A CN 110344030A
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
The invention discloses a kind of SERS base materials of high sensitivity, it is prepared using the polymer of surface metalation and monovalence silver ion solution or tervalence gold ion solution as raw material, wherein the polymer of surface metalation refers to surface all polymer of covering metal layer or part covering metal layer, and the polymer of the surface metalation is by obtaining in polymer surfaces deposited metal layer；The metal layer of the polymer surfaces is one of layers of copper or nickel layer；The method in polymer surfaces deposited metal layer is laser direct structuring technique.The present invention also provides the preparation method of above-mentioned high sensitivity SERS base material, the method for metal is selectively deposited as LDS technique in polymer surfaces in the present invention.SERS base material disclosed by the invention can be down to 10 to the detectable concentration lower limit of rhodamine 6G‑17Mol/L, far more than the R6G detectable concentration lower limit of most tradition SERS substrates.Moreover, the preparation method of high sensitivity SERS base material of the invention is simple, SERS detection speed is fast, precision is high, stability is good and is easy to large-scale production, and the mass detection to a variety of extremely low concentration organic pollutants may be implemented.
Description
Technical field
The invention belongs to nano materials and detection technique field, and in particular to a kind of for the highly sensitive of LR laser raman enhancing
Base material and preparation method thereof.
Background technique
Surface enhanced Raman scattering (Surface-Enhanced Raman Scattering, abbreviation SERS) is that one kind can
The technology that metal surface molecule generates Raman scattering probability is significantly greatly increased.It is big that this technology makes molecule can detect raman scattering intensity
It is big to improve, so as to make original raman scattering intensity increase several orders of magnitude.The principle that SERS is utilized is: incident laser acts on one
Determine that stronger electromagnetic field can be formed in the metal substrate surface of surface roughness, and the intensity of Raman scattering with locating for molecule
Optical electric field it is square directly proportional.
SERS technology overcomes the shortcomings that traditional Raman spectrum inherent weak output signal.Therefore, it can be used for trace
Material analysis, fluidic cell etc. are measured, these are all the fields that traditional Raman can not set foot in.In SERS research, high efficiency preparation
It provides highly sensitive, high response and the stable SERS substrate of performance is always one of the hot spot in the field.Traditional SERS substrate
It is mainly prepared by the following method: precious metal sheets or foil (gold, silver, copper etc.) (1) is carried out to the rough surface of electrochemistry；
(2) deposition of noble metal nano particles；(3) nucleocapsid structure noble metal nano particles are constructed, they are usually with colloidal sol or glue
Existing for body form.Although metal-sol preparation method is simple, its synthesis condition is harsh and not easy to control, less reproducible,
Especially easily reunite after probe molecule is added, it is unstable.Therefore, develop and prepare a kind of New Solid or film SERS base
Bottom material be there is an urgent need in the art to.
In the prior art, solid-state or film SERS substrate generally use the modes such as template, offset printing, ion injection
Preparation.And mostly there is the problems such as complex for operation step, experiment condition is harsh in existing these preparation methods.It is existing in order to overcome
The deficiency of technology needs to develop a kind of preparation method and is simple and efficient, and has both the novel of excellent surface enhancing Raman effect simultaneously
SERS base material.
Summary of the invention
That the purpose of the present invention is to provide a kind of preparation methods is simple, stability is good, high sensitivity is high, is very suitable to batch
The highly sensitive base material for LR laser raman enhancing of amount production.
The present invention provides a kind of highly sensitive base material for LR laser raman enhancing, which is with surface gold
The polymer of categoryization and monovalence silver ion solution or tervalence gold ion solution be what raw material was prepared, wherein surface metalation
Polymer refers to that surface covers the polymer of metal layer completely or partially；
The polymer of the surface metalation is by obtaining in polymer surfaces deposited metal layer；The polymer table
The metal layer in face is one of layers of copper or nickel layer；The method in polymer surfaces deposited metal layer is laser direct forming
Technology (LDS).
Further, laser sensitization agent is used in the laser direct structuring technique, laser sensitization agent is selected from the oxygen of copper
Compound, the salt of copper, organic palladium, the oxide of bismuth, the sulfide of bismuth, the hydroxide of bismuth, the oxychloride of bismuth, the salt of bismuth, tungsten
Oxide, stannic oxide, tin-antiomony oxide, tin indium oxide, Fluorin doped stannic oxide, tin-antiomony oxide cladding TiO2Thin slice, oxygen
Change the splitting of tin antimony cladding, in ferrous acid zinc-nickel any one or it is two or more；
Preferably, the laser sensitization agent is selected from the oxide of copper, the salt of copper, the oxide of bismuth, the salt of bismuth, indium oxide
In tin, ferrous acid zinc-nickel any one or it is two or more.
Further, the oxide of the copper is selected from CuO, Cu2O、CuO·Cr2O3In any one or it is two or more；
The salt of the copper is selected from CuSO4、CuC2O4、Cu(acac)2、Cu2(OH)PO4, orthophosphoric acid copper, cupric pyrophosphate, Cu
(NO3)2, in hydroxy carbonate copper any one or it is two or more；
The oxide of the bismuth is selected from Bi2O3、Bi2O2、Bi2O4In any one or it is two or more；
The salt of the bismuth in bismuth nitrate, bismuth sulfate, bismuth aluminate, basic bismuth carbonate any one or it is two or more；
Further, the polymer is polyethylene, polypropylene, polycarbonate, ethylene-butene copolymer, ethylene-octene
Copolymer, polyvinylidene fluoride, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, polyvinyl chloride, ABS, propylene
Nitrile-styrol copolymer, polyurethane elastomer, polyester elastomer, polyamide elastomer, gathers acrylic styrene copolymer
Styrene, polyamide, polyphenylene oxide, polyformaldehyde, polyethylene terephthalate, polybutylene terephthalate (PBT), asphalt mixtures modified by epoxy resin
Rouge, phenolic resin, polymethyl methacrylate, ethylene-vinyl acetate copolymerization, polyimides, natural rubber, butadiene rubber,
Silicon rubber, polyphenylene sulfide, polyether-ether-ketone, polyketone, in SEBS, SEPS any one or it is two or more.
Further, the monovalence silver ion solution includes monovalence silver ion salt or the monovalence silver ion solution includes
Following components: monovalence silver ion salt, reducing agent, stabilizer, surfactant；
Wherein, monovalence silver ion salt, reducing agent, stabilizer, surfactant mass ratio be (1~30): (0~30):
(0~30): (0~30)；Preferably (1~6): (0~10): (0~7): (0~10)；
The monovalence silver ion salt, reducing agent, stabilizer, the total concentration of surfactant in a solvent are 1~35g/L；
Preferably 1~13g/L；
The monovalence silver ion salt is selected from one of silver nitrate, silver acetate, silver orthophosphate；
The reducing agent is selected from glucose, hydrogen peroxide, sodium potassium tartrate tetrahydrate, ortho phosphorous acid are received, formaldehyde, dimethyl amine boron
One of alkane, Triammonium citrate；
The stabilizer is selected from NaI, KI, gelatin, Ni2+One of salt；
The surfactant is selected from one of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone；
The solvent is selected from water, ammonium hydroxide, alcohols solvent or ammonium hydroxide/alcohol mixed solvent；Preferably water, ammonium hydroxide or ammonium hydroxide/second
The mixed solvent of glycol.
Further, the tervalence gold ion solution includes gold chloride or the tervalence gold ion solution includes with the following group
Point: gold chloride, reducing agent, pH adjusting agent, solvent；
Wherein, gold chloride, reducing agent, pH adjusting agent mass ratio be (1~10): (0~10): (0~10), preferably (1
~7): (0~5): (0~5)；
The total concentration of the gold chloride, reducing agent, pH adjusting agent in a solvent is 1~20g/L；Preferably 1~8g/L；
The reducing agent is selected from one of glucose, formaldehyde, ascorbic acid；
The pH adjusting agent is selected from one of saleratus, sodium bicarbonate, ammonium chloride, borax；
The solvent is selected from water or alcohols solvent；Preferably water.
Further, the metal layer with a thickness of 1~45 μm.
The present invention also provides a kind of methods for preparing the above-mentioned highly sensitive base material for LR laser raman enhancing, including
Following preparation step:
The polymer of surface metalation is soaked into monovalence silver ion solution or tervalence gold ion solution and is handled, constantly
Solution is stirred, make silver or gold ion concentration keep uniformly, then take out, with deionized water clean to get；
The time of the immersion is 0.5 minute~60 minutes, preferably 1~5 minute；
The temperature of the immersion is 10 DEG C~50 DEG C, preferably 10 DEG C~35 DEG C.
Purposes the present invention also provides above-mentioned highly sensitive base material as surface enhanced Raman scattering substrate material.
In the present invention, laser direct structuring technique (LDS), which refers to, activates polymeric articles surface using laser, so
The technology for carrying out selective metal deposition to laser activation region using chemical plating afterwards, belongs to common knowledge.
Laser sensitization agent is a kind of laser additive in LDS technology, it can be formed in corresponding laser activation region
The catalytic center of inducing metal deposition.
It is demonstrated experimentally that inspection of the surface enhanced Raman scattering substrate material of high sensitivity produced by the present invention to rhodamine 6G
Surveying concentration limit can be down to 10-17Mol/L, far more than the R6G detectable concentration lower limit of most tradition SERS substrates.This hair
It is bright to provide a kind of new thinking and technological approaches to prepare solid high sensitivity SERS base material；This novel SERS
Substrate is stablized, detection sensitivity is high, has apparent technical advantage compared with the prior art, is highly susceptible to large-scale application.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
Below by way of specific embodiment, above content of the invention is described in further detail again.But it should not
This range for being interpreted as the above-mentioned theme of the present invention is only limitted to example below.All skills realized based on above content of the present invention
Art all belongs to the scope of the present invention.
Detailed description of the invention
Fig. 1 is that the SERS substrate that embodiment 17 is prepared detects the R6G progress surface-enhanced Raman of various concentration
The Raman spectrogram arrived.
Specific embodiment
Raw material that the specific embodiment of the invention uses, equipment are known product, pass through purchase commercial product and obtain.
Wherein, part material source is as follows:
Hydroxyl cupric phosphate: Merck chemical industry, Iriotec 8840 are powdered；
Tin indium oxide: great Zhan Ji Yuan new material Science and Technology Ltd., powdered, technical grade；
Basic bismuth carbonate: Shanghai Aladdin biochemical technology limited liability company, powdered, analysis level；
Ferrous acid zinc-nickel: Nanjing Ai Purui nano material Co., Ltd, it is powdered；
Rhodamine 6G (R6G): Shanghai Aladdin biochemical technology limited liability company, powdered, analysis level；
Crystal violet (CV): Chengdu Cologne Chemical Company, powdered, analysis level；
Copper oxide: Shanghai Aladdin biochemical technology limited liability company, powdered, analysis level；
Acrylonitrile-butadiene-styrene copolymer (ABS): the odd beauty in Taiwan, PA747.
Polypropylene (PP): Sinopec Lanzhou branch company, T30S.
Polycarbonate (PC): South Korea's Samsung, SC-1220R.
Polybutylene terephthalate (PBT) (PBT): Dupont, S650FR.
Polyamide 66 (PA66): the bright Sheng of Germany, A30S.
Following example 1-31 is the preparation of SERS base material of the present invention.
Embodiment 1
(1) preparation of LDS plastics: di copper powders are added in polycarbonate with 6wt%, using twin-screw extrusion
Machine blending extrusion is granulated, and by resulting mixed pellet, the direct injection molding in injection molding machine, is made standard jig, processing
Temperature in the process is controlled at 250 DEG C~290 DEG C；
(2) laser activation: laser sensitization agent is hydroxyl cupric phosphate, using the following conditions to step (1) resulting standard sample
Plate carries out laser activation: utilizing pulsed near infrared laser, wavelength 1064nm, scanning speed 2000mm/s, laser energy
Amount is 8W, laser frequency 70kHz；
(3) selective metal deposits: living to the resulting laser of step (2) according to LDS method well known in the art and technique
Standard jig after change is selectively deposited copper, obtains the plastics template of surface covering copper；
(in liquid nitrogen), electron microscope (SEM) will be scanned to cross section after the plastics template brittle failure of surface covering copper
Observation, the surface copper layer thickness measured are 13.5 μm；
(4) processing of monovalence silver ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) 3.5g silver orthophosphate, 4.5g glucose and 3g polyvinylpyrrolidone are weighed, is dissolved in 1L ammonium hydroxide；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
It is constantly stirred, 30s is handled at 35 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry is to get SERS
Substrate.
Embodiment 2
The processing time of monovalence silver ion solution is 1min, and other conditions are same as Example 1.
Embodiment 3
The processing time of monovalence silver ion solution is 3min, and other conditions are same as Example 1.
Embodiment 4
The processing time of monovalence silver ion solution is 5min, and other conditions are same as Example 1.
Embodiment 5
The processing time of monovalence silver ion solution is 1h, and other conditions are same as Example 1.
Embodiment 6
(1) preparation of LDS plastics: copper oxide is added in polybutylene terephthalate (PBT) with 8wt%, using twin-screw
Extruder blending extrusion is granulated, and by resulting mixed pellet, the direct injection molding in injection molding machine, is made standard jig,
Temperature in process is controlled at 230 DEG C~250 DEG C；
(2) laser activation: laser sensitization agent be copper oxide, using the following conditions to step (1) resulting standard jig into
Row laser activation: utilizing pulsed near infrared laser, wavelength 1064nm, scanning speed 2000mm/s, and laser energy is
8W, laser frequency 60kHz；
(3) with embodiment 1；
(4) processing of monovalence silver ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) 2.5g silver acetate, 5g sodium potassium tartrate tetrahydrate, 2g KI and 2.5g polyvinyl alcohol are weighed, is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
It is constantly stirred, 30s is handled at 50 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry is to get SERS
Substrate.
Embodiment 7
The processing time of monovalence silver ion solution is 1min, and other conditions are same as Example 6.
Embodiment 8
The processing time of monovalence silver ion solution is 3min, and other conditions are same as Example 6.
Embodiment 9
The processing time of monovalence silver ion solution is 5min, and other conditions are same as Example 6.
Embodiment 10
The processing time of monovalence silver ion solution is 1h, and other conditions are same as Example 6.
Embodiment 11
(1) preparation of LDS plastics: basic bismuth carbonate is added in polyamide 66 with the dosage of 10wt%, using twin-screw
Extruder blending extrusion is granulated, and by resulting mixed pellet, the direct injection molding in injection molding machine, is made the sample of standard
Plate, the temperature in process are controlled at 230 DEG C~265 DEG C；
(2) laser activation: laser sensitization agent is basic bismuth carbonate, using the following conditions to step (1) resulting standard sample
Plate carries out laser activation: utilizing pulsed near infrared laser, wavelength 1064nm, scanning speed 2000mm/s, laser energy
Amount is 8W, laser frequency 60kHz；
(3) with embodiment 1；
(4) processing of monovalence silver ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) 3.5g silver nitrate, 4.0g polyethylene glycol are weighed, is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
It is constantly stirred, 30s is handled at 30 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry is to get SERS
Substrate.
Embodiment 12
The processing time of monovalence silver ion solution is 1min, and other conditions are identical as embodiment 11.
Embodiment 13
The processing time of monovalence silver ion solution is 3min, and other conditions are identical as embodiment 11.
Embodiment 14
The processing time of monovalence silver ion solution is 5min, and other conditions are identical as embodiment 11.
Embodiment 15
The processing time of monovalence silver ion solution is 1h, and other conditions are identical as embodiment 11.
Embodiment 16
(1) preparation of LDS plastics: tin indium oxide is added in ABS resin with the dosage of 5wt%, using twin-screw extrusion
Machine blending extrusion is granulated, and by resulting mixed pellet, the direct injection molding in injection molding machine, is made the template of standard, adds
Temperature during work is controlled at 210 DEG C~235 DEG C.
(2) laser activation: laser sensitization agent is tin indium oxide, using the following conditions to the template of standard obtained by step (1)
Carry out laser-induced activation: pulsed near infrared laser, optical maser wavelength 1064nm, scanning speed 2000mm/s, laser
Energy is 8W, laser frequency 60KHz.
(3) with embodiment 1；
(4) processing of monovalence silver ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) 2.5g silver nitrate is weighed, is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
It is constantly stirred, 30s is handled at 26 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry is to get SERS
Substrate.
Embodiment 17
The processing time of monovalence silver ion solution is 1min, and other conditions are identical as embodiment 16.
Embodiment 18
The processing time of monovalence silver ion solution is 3min, and other conditions are identical as embodiment 16.
Embodiment 19
The processing time of monovalence silver ion solution is 5min, and other conditions are identical as embodiment 16.
Embodiment 20
The processing time of monovalence silver ion solution is 1h, and other conditions are identical as embodiment 16.
Embodiment 21
(1) preparation of LDS plastics: ferrous acid zinc-nickel is added in polypropylene with the dosage of 11wt%, using twin-screw extrusion
Machine blending extrusion is granulated, and by resulting mixed pellet, the direct injection molding in injection molding machine, is made the template of standard, adds
Temperature during work is controlled at 180 DEG C~230 DEG C.
(2) laser activation: laser sensitization agent is ferrous acid zinc-nickel, using the following conditions to the template of standard obtained by step (1)
Carry out laser-induced activation: pulsed near infrared laser, optical maser wavelength 1064nm, scanning speed 2000mm/s, laser
Energy is 8W, laser frequency 60KHz.
(3) with embodiment 1；
(4) processing of monovalence silver ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) weigh 3.5g silver nitrate, 5.5g ortho phosphorous acid is received, be dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
It is constantly stirred, 30s is handled at 28 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry is to get SERS
Substrate.
Embodiment 22
The processing time of monovalence silver ion solution is 1min, and other conditions are identical as embodiment 21.
Embodiment 23
The processing time of monovalence silver ion solution is 3min, and other conditions are identical as embodiment 21.
Embodiment 24
The processing time of monovalence silver ion solution is 5min, and other conditions are identical as embodiment 21.
Embodiment 25
The processing time of monovalence silver ion solution is 1h, and other conditions are identical as embodiment 21.
Embodiment 26
(1) with embodiment 16；
(2) with embodiment 16；
(3) with embodiment 16；
(4) processing of tervalence gold ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) 3g gold chloride, 2.5g glucose, 1.5g saleratus are weighed, is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
It is constantly stirred, 30s is handled at 20 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry is to get SERS
Substrate.
Embodiment 27
(1) with embodiment 16；
(2) with embodiment 16；
(3) with embodiment 16；
(4) processing of tervalence gold ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) 2.5g gold chloride, 3.5g ascorbic acid, 2g ammonium chloride are weighed, is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
Constantly be stirred, 1min handled at 15 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry to get
SERS substrate.
Embodiment 28
(1) with embodiment 16；
(2) with embodiment 16；
(3) with embodiment 16；
(4) processing of tervalence gold ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) 3.5g gold chloride is weighed, 4.5g formalin (content of formaldehyde: 37%), is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
Constantly be stirred, 3min handled at 15 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry to get
SERS substrate.
Embodiment 29
(1) with embodiment 16；
(2) with embodiment 16；
(3) with embodiment 16；
(4) processing of tervalence gold ion solution: handling the plastics template for the surface covering copper that step (3) obtains,
Steps are as follows:
A) 3g gold chloride, 5g borax are weighed, is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
Constantly be stirred, 5min handled at 10 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry to get
SERS substrate.
Embodiment 30
(1) preparation of LDS plastics: tin indium oxide is added in ABS resin with the dosage of 5wt%, using twin-screw extrusion
Machine blending extrusion is granulated, and by resulting mixed pellet, the direct injection molding in injection molding machine, is made the template of standard, adds
Temperature during work is controlled at 210 DEG C~235 DEG C.
(2) laser activation: laser sensitization agent is tin indium oxide, using the following conditions to the template of standard obtained by step (1)
Carry out laser-induced activation: pulsed near infrared laser, optical maser wavelength 1064nm, scanning speed 2000mm/s, laser
Energy is 8W, laser frequency 60KHz.
(3) selective metal deposits: living to the resulting laser of step (2) according to LDS method well known in the art and technique
Standard jig after change is selectively deposited copper, first obtains the plastics template of surface covering copper；Then, according still further to this field
Method and technique well known to nickel plating are learned, the Direct precipitation metallic nickel in the surface layers of copper of plastics template finally obtains surface covering
The plastics template of nickel.
(4) processing of monovalence silver ion solution: the surface that step (3) obtains is covered at the plastics template of nickel copper
Reason, steps are as follows:
A) 2.5g silver nitrate is weighed, is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) copper is immersed in the prepared solution of step a), simultaneously
Constantly be stirred, 1min handled at 26 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry to get
SERS substrate.
Embodiment 31
(1) preparation of LDS plastics: tin indium oxide is added in ABS resin with the dosage of 5wt%, using twin-screw extrusion
Machine blending extrusion is granulated, and by resulting mixed pellet, the direct injection molding in injection molding machine, is made the template of standard, adds
Temperature during work is controlled at 210 DEG C~235 DEG C.
(2) laser activation: laser sensitization agent is tin indium oxide, using the following conditions to the template of standard obtained by step (1)
Carry out laser-induced activation: pulsed near infrared laser, optical maser wavelength 1064nm, scanning speed 1000mm/s, laser
Energy is 3W, laser frequency 40KHz.
(3) selective metal deposits: living to the resulting laser of step (2) according to LDS method well known in the art and technique
Standard jig after change directly carries out disposable selective deposition nickel, obtains the plastics template of surface covering nickel.
(4) processing of monovalence silver ion solution: handling the plastics template for the surface covering nickel that step (3) obtains,
Steps are as follows:
A) 2.5g silver nitrate is weighed, is dissolved in 1L deionized water；
B) the plastics template of the covering of surface obtained in step (3) nickel is immersed in the prepared solution of step a), simultaneously
Constantly be stirred, 1min handled at 26 DEG C, sufficiently cleaned after taking-up with deionized water, then naturally dry to get
SERS substrate.
The following are the comparative examples of the preparation method of SERS base material.
Comparative example 1
Pure polycarbonate is granulated through double screw extruder, and the standard jig of comparison is then prepared using injection molding machine, is added
Temperature control is at 250 DEG C~290 DEG C during work.
Gained comparison standard jig according in embodiment 2 the same terms carry out monovalence silver ion solution processing to get
Compare SERS base material.
Comparative example 2
Pure polybutylene terephthalate (PBT) is granulated through double screw extruder, then prepares comparison using injection molding machine
Standard jig, temperature control is at 230 DEG C~250 DEG C in process.
Gained comparison standard jig according in embodiment 7 the same terms carry out monovalence silver ion solution processing to get
Compare SERS base material.
Comparative example 3
Pure polyamide 66 is granulated through double screw extruder, and the standard jig of comparison is then prepared using injection molding machine, is added
Temperature control is at 230 DEG C~265 DEG C during work.
Gained comparison standard jig according in embodiment 12 the same terms carry out monovalence silver ion solution processing to get
Compare SERS base material.
Comparative example 4
Pure ABS resin is granulated through double screw extruder, and the standard jig of comparison is then prepared using injection molding machine, processing
Temperature control is at 210 DEG C~235 DEG C in the process.
Gained comparison standard jig according in embodiment 27 the same terms carry out tervalence gold ion solution processing to get
Compare SERS base material.
Comparative example 5
Pure polypropylene is granulated through double screw extruder, and the standard jig of comparison is then prepared using injection molding machine, processing
Temperature control is at 180 DEG C~230 DEG C in the process.
Gained comparison standard jig according in embodiment 22 the same terms carry out monovalence silver ion solution processing to get
Compare SERS base material.
Comparative example 6
(1) pure ABS resin is granulated through double screw extruder, and the standard jig of comparison is then prepared using injection molding machine,
Temperature control is at 210 DEG C~235 DEG C in process.
(2) according to well known frosting general chemistry copper coating and technique, to the standard jig of gained comparison into
The copper coating of row plastics；
(3) processing of monovalence silver ion solution: step is identical as embodiment 17 to get control SERS base material.
Comparative example 7
Step is identical as comparative example 6, is a difference in that the metal layer of polymer surfaces is nickel layer.
Comparative example 8
Step is identical as comparative example 6, and the method for being a difference in that polymer surfaces deposition copper is vacuum evaporation.
Comparative example 9
Step is identical as comparative example 6, and the method for being a difference in that polymer surfaces deposition copper is plating.
Comparative example 10
Step is identical as embodiment 16, is a difference in that the plastics template of surface covering copper without monovalence silver ion solution
Processing.
Comparative example 11
Step is identical as embodiment 31, is a difference in that the plastics template of surface covering nickel without monovalence silver ion solution
Processing.
The remarkable result of SERS base material of the present invention is proved below by way of experimental evaluation.
SERS base material tests the detectable concentration lower limit of probe molecule:
1, experimental method
The detectable concentration lower limit test to probe molecule of method 1, each SERS base material:
A) rhodamine 6G and crystal violet solution (10 of various concentration gradient are prepared-1M~10-19M)；
B) by SERS base material made from embodiment 1-31, comparative example 1-11 respectively in various concentration rhodamine 6G and knot
It is protected from light in crystalviolet and impregnates 12h, cleaned after taking-up with coordinative solvent and dried for several times and in air；
C) LR laser raman confocal spectroscopic instrument (U.S., the Thermo Fisher of 20X times of mirror and 532nm wavelength are selected
Scientific) do Raman test, and record respectively rhodamine 6G and crystal violet probe molecule can be detected it is minimum dense
Degree, test result are shown in Table 1.
SERS substrate prepared by method 2, embodiment 17 detects the surface-enhanced Raman of the R6G of various concentration:
The SERS base material that embodiment 17 is prepared carries out surface-enhanced Raman detection to the R6G of various concentration,
Testing result is shown in Fig. 1.
2, experimental result
The preparation process and comparison of test results of the SERS base material of table 1, Examples 1 to 31 and comparative example 1~11
Above-mentioned table 1 the result shows that, in comparative example polymer surfaces method for metallising prepare SERS substrate compared with, this hair
In bright embodiment using monovalence silver ion solution or tervalence gold ion solution as raw material, be based on LDS selective metallization process system
Standby SERS base material has SERS substrate material made from extraordinary SERS signal enhancement effect, especially embodiment 17
Material, the R6G probe molecule concentration lower limit that can detecte is down to 10-17M (M=mol/L), detection sensitivity is high.
From Fig. 1 it can also be seen that when R6G probe molecule concentration is 10-17When M, using made from the embodiment of the present invention 17
SERS substrate remains to detect R6G spectral signal, and obtained raman spectrum still has preferable signal-to-noise ratio.
To sum up, the present invention is using monovalence silver ion solution or tervalence gold ion solution as raw material, using selective deposition metal
LDS technique, highly sensitive surface enhanced Raman scattering substrate material has been made.Detection of the base material to rhodamine 6G
Concentration limit can be down to 10-17Mol/L, far more than the R6G detectable concentration lower limit of most tradition SERS substrates.Moreover, this
The preparation method for inventing high sensitivity SERS base material is simple, and SERS detection speed is fast, precision is high, stability is good and is easy to
The mass detection to a variety of extremely low concentration organic pollutants may be implemented in large-scale production.
Claims (9)
1. a kind of highly sensitive base material for LR laser raman enhancing, it is characterised in that: the base material is with surface metal
The polymer and monovalence silver ion solution or tervalence gold ion solution of change are what raw material was prepared, and wherein surface metalation is poly-
It closes object and refers to that surface covers the polymer of metal layer completely or partially；
The polymer of the surface metalation is by obtaining in polymer surfaces deposited metal layer；The polymer surfaces
Metal layer is one of layers of copper or nickel layer；The method in polymer surfaces deposited metal layer is laser direct forming skill
Art.
2. the highly sensitive base material according to claim 1 for LR laser raman enhancing, it is characterised in that: the laser
Laser sensitization agent is used in straight forming technology, laser sensitization agent is selected from the oxygen of the oxide of copper, the salt of copper, organic palladium, bismuth
Compound, the sulfide of bismuth, the hydroxide of bismuth, the oxychloride of bismuth, the salt of bismuth, the oxide of tungsten, stannic oxide, tin oxide
The TiO that antimony, tin indium oxide, Fluorin doped stannic oxide, tin-antiomony oxide coat2Splitting, the ferrous acid of thin slice, tin-antiomony oxide cladding
In zinc-nickel any one or it is two or more；
Preferably, the laser sensitization agent is selected from the oxide of copper, the salt of copper, the oxide of bismuth, the salt of bismuth, tin indium oxide, iron
In sour zinc-nickel any one or it is two or more.
3. the highly sensitive base material according to claim 2 for LR laser raman enhancing, it is characterised in that: the copper
Oxide is selected from CuO, Cu2O、CuO·Cr2O3In any one or it is two or more；
The salt of the copper is selected from CuSO4、CuC2O4、Cu(acac)2、Cu2(OH)PO4, orthophosphoric acid copper, cupric pyrophosphate, Cu (NO3)2、
In hydroxy carbonate copper any one or it is two or more；
The oxide of the bismuth is selected from Bi2O3、Bi2O2、Bi2O4In any one or it is two or more；
The salt of the bismuth in bismuth nitrate, bismuth sulfate, bismuth aluminate, basic bismuth carbonate any one or it is two or more.
4. the highly sensitive base material according to claim 1-3 for LR laser raman enhancing, it is characterised in that:
The polymer is polyethylene, polypropylene, polycarbonate, ethylene-butene copolymer, ethylene-octene copolymer, gathers inclined difluoro second
Alkene, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, polyvinyl chloride, ABS, acrylonitritrile-styrene resin,
Acrylic styrene copolymer, polyester elastomer, polyamide elastomer, polystyrene, polyamide, gathers polyurethane elastomer
Phenylate, polyformaldehyde, polyethylene terephthalate, polybutylene terephthalate (PBT), epoxy resin, phenolic resin, poly- first
Base methyl acrylate, ethylene-vinyl acetate copolymerization, polyimides, natural rubber, butadiene rubber, silicon rubber, polyphenylene sulfide,
Polyether-ether-ketone, polyketone, in SEBS, SEPS any one or it is two or more.
5. the highly sensitive base material according to claim 1-4 for LR laser raman enhancing, it is characterised in that:
The monovalence silver ion solution includes monovalence silver ion salt or the monovalence silver ion solution includes following components: monovalence silver from
Alite, reducing agent, stabilizer, surfactant；
Wherein, monovalence silver ion salt, reducing agent, stabilizer, surfactant mass ratio be (1~30): (0~30): (0~
30): (0~30)；Preferably (1~6): (0~10): (0~7): (0~10)；
The monovalence silver ion salt, reducing agent, stabilizer, the total concentration of surfactant in a solvent are 1~35g/L；It is preferred that
For 1~13g/L；
The monovalence silver ion salt is selected from one of silver nitrate, silver acetate, silver orthophosphate；
The reducing agent is selected from glucose, hydrogen peroxide, sodium potassium tartrate tetrahydrate, ortho phosphorous acid are received, formaldehyde, dimethyamine borane, lemon
One of lemon three ammoniums of acid；
The stabilizer is selected from NaI, KI, gelatin, Ni2+One of salt；
The surfactant is selected from one of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone；
The solvent is selected from water, ammonium hydroxide, alcohols solvent or ammonium hydroxide/alcohol mixed solvent；Preferably water, ammonium hydroxide or ammonium hydroxide/ethylene glycol
Mixed solvent.
6. the highly sensitive base material according to claim 1-4 for LR laser raman enhancing, it is characterised in that:
The tervalence gold ion solution includes gold chloride or the tervalence gold ion solution includes following components: gold chloride, reducing agent,
PH adjusting agent, solvent；
Wherein, gold chloride, reducing agent, pH adjusting agent mass ratio be (1~10): (0~10): (0~10), preferably (1~
7): (0~5): (0~5)；
The total concentration of the gold chloride, reducing agent, pH adjusting agent in a solvent is 1~20g/L；Preferably 1~8g/L；
The reducing agent is selected from one of glucose, formaldehyde, ascorbic acid；
The pH adjusting agent is selected from one of saleratus, sodium bicarbonate, ammonium chloride, borax；
The solvent is selected from water or alcohols solvent；Preferably water.
7. the highly sensitive base material according to claim 1 for LR laser raman enhancing, it is characterised in that: the metal
Layer with a thickness of 1~45 μm.
8. a kind of method prepared described in claim any one of 1-7 for the highly sensitive base material of LR laser raman enhancing,
It is characterized in that: including following preparation step:
The polymer of surface metalation is soaked into monovalence silver ion solution or tervalence gold ion solution and is handled, constantly to molten
Liquid is stirred, make silver or gold ion concentration keep uniformly, then take out, with deionized water clean to get；
The time of the immersion is 0.5 minute~60 minutes, preferably 1~5 minute；
The temperature of the immersion is 10 DEG C~50 DEG C, preferably 10 DEG C~35 DEG C.
9. purposes of any one of the claim 1-7 highly sensitive base material as surface enhanced Raman scattering substrate material.
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