CN106290296A - A kind of SERS substrate based on metal lattice and preparation method thereof and the method utilizing this substrate to carry out Raman detection - Google Patents
A kind of SERS substrate based on metal lattice and preparation method thereof and the method utilizing this substrate to carry out Raman detection Download PDFInfo
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- CN106290296A CN106290296A CN201610599623.4A CN201610599623A CN106290296A CN 106290296 A CN106290296 A CN 106290296A CN 201610599623 A CN201610599623 A CN 201610599623A CN 106290296 A CN106290296 A CN 106290296A
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The invention provides a kind of SERS substrate based on metal lattice, including silicon-based substrate, and the metal lattice being formed on described silicon-based substrate and be arranged on the described metal lattice hydrophobic layer with exterior domain, the material of the metal level constituting described metal lattice is gold, silver or copper.In this substrate, region beyond metal lattice has a hydrophobicity, and the metal dots position relative hydropathic of metal lattice, therefore, material to be detected can be made preferably to be enriched with in metal dots, beneficially the enhancing of Raman signal.The preparation method that present invention also offers this substrate and the method utilizing this substrate to carry out Raman detection, and a kind of SERS chip based on metal lattice.
Description
Technical field
The present invention relates to analyze detection field, particularly relate to a kind of SERS substrate based on metal lattice and preparation side thereof
Method and the method utilizing this substrate to carry out Raman detection.
Background technology
Surface enhanced raman spectroscopy technology (Surface-enhanced Raman scattering, SERS) is owing to having
The advantages such as high sensitivity, Non-Destructive Testing and in site measurement, are widely used in the table of food safety detection, medical diagnosis, material
Levy, engage in archaeological studies, the every field such as criminal investigation.Especially in harmful substance detection and material characterization field, SERS is a kind of extremely important
Analysis means.
The advantage of SERS technology is very clear and definite, but when SERS technology is released laboratory aspect, real owing to not being suitable for
Border application SERS active-substrate and limit the actual popularization of SERS technology.SERS active-substrate now includes two classes, i.e.
Solid-state and liquid, although the active substrate of solid-state has controlled periodicity hotspot location, it is ensured that the reproduction that SERS measures
Property, but this kind of substrate is to preserve for a long time, needs now to prepare when using, and then add the difficulty of partial routine；And liquid
Active substrate, although can preserve for a long time, the existing enchashment use when SERS analyzes, but when SERS analyzes, liquid substrate be received
The uncontrollable gathering of rice corpuscles can cause the poor reproducibility that SERS analyzes.And present SERS technology mostly is and utilizes merely substrate
On metal nanoparticle structure " focus ", limited to the gain effect of Raman signal.
These problems above-mentioned hinder SERS technology from research aspect march toward the marketization application paces, constrain SERS skill
The development of the actual application of art.Therefore can preserve for a long time in the urgent need to research and development one, with take with and to have high detection sensitive
The SERS active-substrate of degree.
Summary of the invention
In consideration of it, first aspect present invention provides a kind of SERS substrate based on metal lattice, the metal dots of this substrate
Region beyond Zhen has a hydrophobicity, and the metal dots position relative hydropathic of metal lattice, therefore, material to be detected can be made to exist
Preferably it is enriched with in metal dots, beneficially the enhancing of Raman signal, improves detection sensitivity.
First aspect, the invention provides a kind of SERS substrate based on metal lattice, including silicon-based substrate, and is formed
Metal lattice on described silicon-based substrate and be arranged on the described metal lattice hydrophobic layer with exterior domain, constitutes described metal dots
The material of the metal level of battle array is gold, silver or copper.
In first aspect present invention, the thickness of the metal level of described metal lattice is 0.1-1 micron, in described metal lattice
A diameter of 0.2-2 millimeter of each metal dots.Preferably, the thickness of metal level is 0.1-0.5 micron, metal dots a diameter of
0.8-1.5 millimeter.Described metal dots can be circular.
In first aspect present invention, the material of described hydrophobic layer is hydrophobic silane coupling agent, such as, can be n-pro-pyl
Trimethoxy silane (TMPS), MTMS, MTES, the thickness of described hydrophobic layer is thick with layer gold
Spend basically identical, for 0.1-1 micron.
In first aspect present invention, the layer on surface of metal of described metal lattice is further provided with polymeric protective film, structure
Become the material of described polymeric protective film for having water solublity, and can not and the metal material of described metal lattice between formed strong
The polymer of adhesion.The present invention arranges polymeric protective film by the layer on surface of metal at metal lattice, such that it is able to protection
Substrate affects Detection results to prevent metal level oxidized, and the present invention is provided with the SERS substrate of polymeric protective film can be long-term
Preserve, with take with by, simple to operate, rapid and convenient, save the detection time, simplify detection process.Inventive polymers is protected
Polymer water solublity to be had used by cuticula, and will not pretend such as carboxyl, amino, sulfydryl and hydroxyl etc. with metal level generation
Group.Specifically, the material of polymeric protective film can be Polyethylene Glycol (PEG), it is also possible to for meeting demand of the present invention
Other polymer.This polymeric protective film directly can be rinsed well with deionized water, does not have residual.
In first aspect present invention, between described silicon-based substrate and described metal lattice, and described silicon-based substrate and institute
Stating and be provided with adhesion layer between hydrophobic layer, described adhesion layer is titanium coating or chromium metal level, and the thickness of described adhesion layer is 10-
1000 nanometers.
In first aspect present invention, described silicon-based substrate can be sheet glass, silicon chip or nitridation silicon chip.
A kind of based on metal lattice the SERS substrate that first aspect present invention provides, due to the metal dots position of metal lattice
Put relative hydropathic, and the zone hydrophobic beyond metal lattice, define the periodic structure of a series of hydrophobe, therefore can make
Material to be detected is preferably enriched with in metal dots, thus the enhancing of beneficially Raman signal, improve detection sensitivity；The present invention
Polymeric protective film is set further on the metal level of metal lattice so that SERS substrate based on metal lattice can be protected for a long time
Deposit, with take with, final save the detection time, simplify detection process.
Second aspect, the invention provides the preparation method of a kind of SERS substrate based on metal lattice, including following step
Rapid:
(1) silicon-based substrate of cleaning is provided, uses mode evaporated metal layer on described silicon-based substrate of evaporation, described gold
The material belonging to layer is gold, silver or copper；
(2) on described metal level, coat a layer photoetching glue, and use pre-designed mask plate to cover described photoetching
Glue, then forms metal lattice by etching technics on described silicon-based substrate；
(3) silicon-based substrate that surface is formed metal lattice carries out hydrophobization process, with beyond described metal lattice
Region form hydrophobic layer, then use organic solvent ultrasonic cleaning to remove described photoresist, then clean up with deionized water
Dry up with nitrogen afterwards, i.e. obtain described SERS substrate based on metal lattice.
In second aspect present invention, after step (3), may further include the layer on surface of metal of described metal lattice
On polymeric protective film is set, constitute the material of described polymeric protective film for having water solublity, and can not be with described metal dots
The polymer of strong adhesion is formed between the metal material of battle array.Specifically, the material of polymeric protective film can be Polyethylene Glycol
(PEG), it is also possible to for meeting other polymer of demand of the present invention.The layer on surface of metal of described metal lattice arranges polymerization
The operation of thing protecting film specifically may is that and drips polymer solution on the layer on surface of metal of metal lattice or by step (2)
The SERS substrate obtained is soaked in polymer solution, after drying, forms polymeric protective film.Described drying operation can be:
In thermostatic drying chamber 50-80 DEG C dry 5-60 minute.
In second aspect present invention, in step (1), described silicon-based substrate can be sheet glass, silicon chip or nitridation silicon chip.Institute
The silicon-based substrate stating cleaning can be obtained by following preprocessing process: takes silicon-based substrate, first cleans with deionized water, and nitrogen blows
After Gan, being put in acetone ultrasonic 1～30 minute, taking-up deionized water cleans, then dries up with nitrogen, to obtain final product.The metal of evaporation
The thickness of layer is 0.1-1 micron.
In step (2), described photoresist can be MMA and PMMA hybrid optical photoresist, the corrosion used in etching technics
Liquid is that the acid solution that chloroazotic acid mixes acquisition with water with volume ratio 1: 1-10 corrodes 10～600 seconds.Each gold in described metal lattice
Belong to a diameter of 0.2-2 millimeter of point.Described metal dots can be circular.
In step (3), surface is formed the silicon-based substrate of metal lattice, and to carry out the concrete operations of hydrophobization process permissible
It is: take surface and be formed with the silicon-based substrate of metal lattice and 0.01-20 milliliter hydrophobic silane coupling agent is placed in container,
90-200 DEG C keeps 20-300 minute.Described hydrophobic silane coupling agent can be n-pro-pyl trimethoxy silane (TMPS), first
Base trimethoxy silane, MTES.Described organic solvent can be acetone, and the time of described ultrasonic cleaning is permissible
It it is 1-30 minute.
In second aspect present invention, in step (1), farther included, described silica-based before being deposited with described metal level
Evaporation preparation one adhesion layer in substrate, described adhesion layer can be titanium coating or chromium metal level, and the thickness of described adhesion layer is 10-
1000 nanometers.
The preparation method that second aspect present invention provides, technique is simple, easy to operate.
The third aspect, the invention provides a kind of utilization SERS based on metal lattice substrate and carries out the side of Raman detection
Method, comprises the steps:
Take the SERS substrate based on metal lattice being not provided with polymeric protective film described in first aspect present invention, will stream
Body determinand drops in the metal dots of described metal lattice, after drying, uses Raman spectrometer to carry out SERS detection；Or
Take the SERS substrate based on metal lattice being provided with polymeric protective film described in first aspect present invention, first use
Deionized water cleans removes described polymeric protective film, after nitrogen dries up, fluid determinand drops in the gold of described metal lattice
Belong on point, after drying, use Raman spectrometer to carry out SERS detection.
Detection method, can now prepare being not provided with the SERS substrate based on metal lattice of polymeric protective film and carry out
SERS detects.Also the SERS substrate based on metal lattice being provided with polymeric protective film kept of can directly going bail for carries out SERS
Detection.The latter is more convenient, saves the detection time.
The method of the Raman detection described in third aspect present invention, farther included before carrying out SERS detection: in institute
Stating determinand surface dropping metal nanoparticle colloidal sol, the metal nanoparticle in described metal nanoparticle colloidal sol is gold, silver
Or copper nano-particle.The size of described metal nanoparticle can be 10～1000 nanometers, and shape can be spherical, taper, post
Shape and other shapes such as bar-shaped.Detection method utilizes active metal dot matrix and metal nanoparticle jointly to construct " focus "
Principle, by dripping metal nanoparticle colloidal sol further on determinand surface so that active metal point, material to be detected and
Metal nanoparticle structure " sandwich structure ", this structure has favorable reproducibility, the advantage that reinforced effects is good.This detection method
Having hypersensitivity, its detection limit can reach 10-9mol/L。
Determinand in third aspect present invention can be malachite green oxalate, rhodamine 6G, tripolycyanamide, tonyred, furan
Harmful substance in food, medicine and the environment such as oxazolone, ciprofloxacin, enrofloxacin, chloromycetin.
In third aspect present invention, described drying operation can be: in thermostatic drying chamber 50-80 DEG C dry 1-5 minute.
In third aspect present invention, the Raman spectrometer of employing is confocal Raman spectrometer, specifically, dropping is had to be measured
The substrate of thing is positioned in the XYZ automatic platform of confocal Raman spectrometer, and the microcobjective of Raman spectrometer is entered substrate
Line focusing.
Described XYZ automatic platform parameter can be X=75 millimeter, Y=50 millimeter, and XY minimum step is 0.1 micron, and Z is
A length of 0.1 micron of small step.The laser source wavelength that described confocal hand-pulled noodles spectrogrph uses is arranged according to concrete metal lattice, as
Gold, silver dot matrix can be respectively 633 nanometers and 532 nanometers, and microcobjective multiplying power can be 20,50 and 100 times.
Fourth aspect present invention provides a kind of SERS chip based on metal lattice, including silicon-based substrate, is formed at institute
State the metal lattice on silicon-based substrate and be arranged on the described metal lattice hydrophobic layer with exterior domain, and being arranged on described metal
Nitride layer to be measured in the metal dots of dot matrix and the metal nanoparticle layer being arranged in nitride layer to be measured, constitute described metal lattice
Material is gold, silver or copper, and the material of described metal nanoparticle layer is gold, silver or copper nano-particle.
In fourth aspect present invention, the thickness of the metal level of described metal lattice is 0.1-1 micron, in described metal lattice
A diameter of 0.2-2 millimeter of each metal dots.Described metal dots can be circular.
In fourth aspect present invention, the material of described hydrophobic layer is hydrophobic silane coupling agent, such as, can be n-pro-pyl
Trimethoxy silane (TMPS), MTMS, MTES, the thickness of described hydrophobic layer is thick with layer gold
Spend basically identical, for 0.1-1 micron.
In fourth aspect present invention, the layer on surface of metal of described metal lattice is further provided with polymeric protective film, structure
Become the material of described polymeric protective film for having water solublity, and can not and the metal material of described metal lattice between formed strong
The polymer of adhesion.Specifically, the material of polymeric protective film can be Polyethylene Glycol (PEG), it is also possible to for meeting this
Other polymer of bright demand.
In fourth aspect present invention, between described silicon-based substrate and described metal lattice, and described silicon-based substrate and institute
Stating and be provided with adhesion layer between hydrophobic layer, described adhesion layer is titanium coating or chromium metal level, and the thickness of described adhesion layer is 10-
1000 nanometers.
In fourth aspect present invention, described silicon-based substrate can be sheet glass, silicon chip or nitridation silicon chip.
In fourth aspect present invention, the size of described metal nanoparticle can be 10～1000 nanometers, and shape can be
Spherical, taper, cylindricality and other shapes such as bar-shaped.
The SERS chip based on metal lattice that fourth aspect present invention provides, utilizes active metal dot matrix and metal nano
Particle constructs the principle of " focus " jointly, by arranging metal nanoparticle layer further on determinand surface so that activity gold
Belonging to point, material to be detected and metal nanoparticle structure " sandwich structure ", this structure has favorable reproducibility, and reinforced effects is good
Advantage.Using this chip structure to carry out SERS detection, have hypersensitivity, its detection limit can reach 10-9mol/L。
Advantages of the present invention will partly illustrate, and a part is apparent according to description
, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the gold point system of battle formations of embodiment of the present invention SERS based on gold point battle array substrate；
Fig. 2 is the preparation technology flow chart of embodiment of the present invention SERS based on gold point battle array substrate；
Fig. 3 is the flow chart using embodiment of the present invention SERS based on gold point battle array substrate to carry out Raman detection；
Fig. 4 is to use embodiment of the present invention SERS based on the gold point battle array substrate testing result to malachite green oxalate.
Detailed description of the invention
The following stated is the preferred implementation of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of without departing from embodiment of the present invention principle, it is also possible to make some improvements and modifications, these improve
With the protection domain that retouching is also considered as the embodiment of the present invention.
Embodiment 1
The preparation method of a kind of SERS substrate based on gold point battle array, comprises the following steps:
(1) take a sheet glass, first clean with deionized water, then dry up with nitrogen, then put the most ultrasonic 10 minutes,
Then take out and clean up with deionized water, finally dry up with nitrogen stand-by；The mode using evaporation is deposited with one on the glass sheet
Thickness is the titanium coating of 10 nanometers, and on titanium coating, evaporation preparation one thickness is the layer gold of 100 nanometers the most again；
(2) with the dot matrix mask plate of CAD design good a series of 4 × 4, a diameter of 1 millimeter of each gold point, in layer gold
Photoresist in spin coating, covers in layer gold by the mask plate designed, and is positioned in litho machine, utilizes configuration good and the volume ratio of water
Be 1: 3 chloroazotic acid layer gold is corroded 300 seconds, on titanium coating, i.e. define a series of gold point, obtain gold point battle array；Such as figure
Shown in 1,1 is the sheet glass being attached with titanium coating, and 2 is gold point battle array.
(3) the titanium part beyond gold point battle array is carried out hydrophobization process, i.e. take step (2) gained substrate and 5 milliliters
N-pro-pyl trimethoxy silane (TMPS) is placed in container, heats 100 minutes, then take out, put water in acetone at 134 DEG C
Bathe ultrasonic 5 minutes, after repeatedly clean with deionized water, then dry up with nitrogen, wash away photoresist；Thus beyond gold point battle array
Define the hydrophobic layer that thickness is 0.2 micron on titanium coating, i.e. obtain SERS substrate based on gold point battle array, in this substrate, gold
Dot matrix and hydrophobic layer occupied area are than about 1:7.
Embodiment 2
The preparation method of a kind of SERS substrate based on gold point battle array, comprises the following steps:
(1) take a sheet glass, first clean with deionized water, then dry up with nitrogen, then put the most ultrasonic 10 minutes,
Then take out and clean up with deionized water, finally dry up with nitrogen stand-by；The mode using evaporation is deposited with one on the glass sheet
Thickness is the titanium coating of 100 nanometers, and on titanium coating, evaporation preparation one thickness is the layer gold of 500 nanometers the most again；
(2) with the dot matrix mask plate of CAD design good a series of 4 × 4, a diameter of 0.6 millimeter of each gold point, in layer gold
Photoresist in upper spin coating, covers in layer gold by the mask plate designed, and is positioned in litho machine, utilizes configuration good and the volume of water
Layer gold is corroded 600 seconds than the chloroazotic acid being 1: 3, on titanium coating, i.e. define a series of gold point, obtain gold point battle array；
(3) the titanium part beyond gold point battle array is carried out hydrophobization process, i.e. take step (2) gained substrate and 10 milliliters
N-pro-pyl trimethoxy silane (TMPS) is placed in container, heats 200 minutes, then take out, put water in acetone at 130 DEG C
Bathe ultrasonic 5 minutes, after repeatedly clean with deionized water, then dry up with nitrogen, wash away photoresist, thus beyond gold point battle array
The hydrophobic layer that thickness is 500 nanometers is defined on titanium coating；
(4) Polyethylene Glycol liquid is dropped in step (3) gained substrate, be put in afterwards in thermostatic drying chamber 30 minutes, dry
Taking out after Gan, i.e. obtain SERS substrate based on gold point battle array, in this substrate, gold point battle array and hydrophobic layer occupied area are than about 1:7.
Fig. 2 is the preparation technology flow chart of the present embodiment SERS based on gold point battle array substrate, and in figure, 101 is substrate of glass,
102 is titanium coating, and 103 is layer gold, and 104 is photoresist layer, and 105 is hydrophobic layer, and 106 is Polyethylene Glycol layer.
Embodiment 3
The preparation method of a kind of SERS substrate based on silver point battle array, comprises the following steps:
(1) take a sheet glass, first clean with deionized water, then dry up with nitrogen, then put the most ultrasonic 10 minutes,
Then take out and clean up with deionized water, finally dry up with nitrogen stand-by；The mode using evaporation is deposited with one on the glass sheet
Thickness is the titanium coating of 10 nanometers, and on titanium coating, evaporation preparation one thickness is the silver layer of 100 nanometers the most again；
(2) with the dot matrix mask plate of CAD design good a series of 4 × 4, a diameter of 0.2 millimeter of each silver point, in layer gold
Photoresist in upper spin coating, covers on silver layer by the mask plate designed, and is positioned in litho machine, utilizes configuration good and the volume of water
Silver layer is corroded 200 seconds than the chloroazotic acid being 1: 3, on titanium coating, i.e. define a series of silver point, obtain silver point battle array；
(3) the titanium part beyond silver point battle array is carried out hydrophobization process, i.e. take step (2) gained substrate and 1 milliliter
N-pro-pyl trimethoxy silane (TMPS) is placed in container, heats 100 minutes, then take out, put water in acetone at 134 DEG C
Bathe ultrasonic 5 minutes, after repeatedly clean with deionized water, then dry up with nitrogen, wash away photoresist, thus beyond silver point battle array
The hydrophobic layer that thickness is 200 nanometers is defined on titanium coating；
(4) the silver point battle array substrate of step (3) gained is immersed in Polyethylene Glycol (PEG) 30 minutes, takes out and be positioned over constant temperature
In drying baker 30 minutes, take out after drying, i.e. obtain SERS substrate based on silver point battle array.
Embodiment 4
The preparation method of a kind of SERS substrate based on copper dot matrix, comprises the following steps:
(1) take a sheet glass, first clean with deionized water, then dry up with nitrogen, then put the most ultrasonic 10 minutes,
Then take out and clean up with deionized water, finally dry up with nitrogen stand-by；The mode using evaporation is deposited with one on the glass sheet
Thickness is the titanium coating of 10 nanometers, and on titanium coating, evaporation preparation one thickness is the layers of copper of 1 micron the most again；
(2) with the dot matrix mask plate of CAD design good a series of 4 × 4, a diameter of 1 millimeter of each silver point, in layer gold
Photoresist in spin coating, covers in layers of copper by the mask plate designed, and is positioned in litho machine, utilizes configuration good and the volume ratio of water
Be 1: 3 chloroazotic acid layers of copper is corroded 300 seconds, on titanium coating, i.e. define a series of copper point, obtain copper dot matrix；
(3) the titanium part beyond copper dot matrix is carried out hydrophobization process, i.e. take step (2) gained substrate and 20 milliliters
N-pro-pyl trimethoxy silane (TMPS) is placed in container, heats 300 minutes, then take out, put water in acetone at 134 DEG C
Bathe ultrasonic 5 minutes, after repeatedly clean with deionized water, then dry up with nitrogen, wash away photoresist, thus beyond copper dot matrix
The hydrophobic layer that thickness is 1 micron is defined on titanium coating；
(4) the copper dot matrix substrate of step (3) gained is immersed in Polyethylene Glycol (PEG) 5～30 minutes, takes out and be positioned over perseverance
Temperature drying baker in 30 minutes, after drying take out, i.e. obtain SERS substrate based on copper dot matrix.
Embodiment 5
A kind of method utilizing SERS substrate based on gold point battle array to carry out Raman detection, comprises the steps:
Get out 10-4～10-7The malachite green solution of mol/L concentration；
The SERS substrate based on gold point battle array of Example 1 preparation, takes the variable concentrations of 0.5 microlitre respectively with pipettor
Malachite green solution drops on gold point, is positioned in thermostatic drying chamber 10 minutes, and after drying, the XYZ being put in Raman spectrometer moves
On moving platform, the Raman microcobjective choosing 20 multiplying powers focuses on, and chooses the laser of 633 nano wave lengths as light source, carries out Raman
Scattering detection, Raman detection result shows: SERS based on the gold point battle array substrate of this embodiment has higher sensitivity, and it detects limit
Reach 10-7mol/L。
Embodiment 6
A kind of method utilizing SERS substrate based on gold point battle array to carry out Raman detection, comprises the steps:
Get out 10-5～10-9The malachite green solution of mol/L concentration；
The SERS substrate based on gold point battle array of Example 2 preparation, washes except PEG protecting film with deionized water, uses nitrogen
Air-blowing is done, and the malachite green solution of the variable concentrations then taking 0.5 microlitre with pipettor respectively drops on gold point, is positioned over constant temperature
In drying baker 10 minutes, after drying, then the golden nanometer particle colloidal sol prepared is dropped on gold point, be put in thermostatic drying chamber 10 points
Clock, after drying, is put on the XYZ mobile platform of Raman spectrometer, and the Raman microcobjective choosing 20 multiplying powers focuses on, and chooses 633
The laser of nano wave length, as light source, carries out Raman scattering detection.Fig. 3 is to use the embodiment of the present invention 1 based on gold point battle array
SERS substrate carries out the flow chart of Raman detection, and in figure, 107 is determinand malachite green solution, and 108 is golden nanometer particle.Fig. 4
For Raman scattering testing result.
Embodiment 7
A kind of method utilizing SERS substrate based on silver point battle array to carry out Raman detection, comprises the steps:
Get out 10-5～10-9The malachite green solution of mol/L concentration；
The SERS substrate based on silver point battle array of Example 3 preparation, washes except PEG protecting film with deionized water, uses nitrogen
Air-blowing is done, and the malachite green solution of the variable concentrations then taking 0.5 microlitre with pipettor respectively drops on silver point, is positioned over constant temperature
In drying baker 10 minutes, after drying, then the Nano silver grain colloidal sol prepared is dropped on silver point, be put in thermostatic drying chamber 10 points
Clock, after drying, is put on the XYZ mobile platform of Raman spectrometer, and the Raman microcobjective choosing 20 multiplying powers focuses on, and chooses 532
The laser of nano wave length, as light source, carries out Raman scattering detection, and Raman detection result shows: this embodiment is based on silver point battle array
SERS substrate has hypersensitivity, and its detection limit can reach 10-10mol/L。
Claims (10)
1. a SERS substrate based on metal lattice, it is characterised in that include silicon-based substrate, and be formed at described silica-based base
Metal lattice at the end and be arranged on the described metal lattice hydrophobic layer with exterior domain, constitutes the metal level of described metal lattice
Material is gold, silver or copper.
2. SERS substrate as claimed in claim 1, it is characterised in that the thickness of the metal level of described metal lattice is 0.1-1
Micron, a diameter of 0.2-2 millimeter of each metal dots in described metal lattice.
3. SERS substrate as claimed in claim 1, it is characterised in that the material of described hydrophobic layer is hydrophobic silane coupling
Agent, the thickness of described hydrophobic layer is 0.1-1 micron.
4. the SERS substrate as described in any one of claim 1-3, it is characterised in that the layer on surface of metal of described metal lattice enters
One step is provided with polymeric protective film, constitutes the material of described polymeric protective film for having water solublity, and can not be with described gold
Belong to the polymer forming strong adhesion between the metal material of dot matrix.
5. the preparation method of a SERS substrate based on metal lattice, it is characterised in that comprise the following steps:
(1) silicon-based substrate of cleaning is provided, uses mode evaporated metal layer on described silicon-based substrate of evaporation, described metal level
Material be gold, silver or copper；
(2) on described metal level, coat a layer photoetching glue, and use pre-designed mask plate to cover described photoresist, so
On described silicon-based substrate, metal lattice is formed afterwards by etching technics；
(3) silicon-based substrate that surface is formed metal lattice carries out hydrophobization process, with the district beyond described metal lattice
Territory forms hydrophobic layer, then uses organic solvent ultrasonic cleaning to remove described photoresist, then uses after cleaning up with deionized water
Nitrogen dries up, and i.e. obtains described SERS substrate based on metal lattice.
6. the preparation method of SERS substrate as claimed in claim 5, it is characterised in that after step (3), bag the most further
Including and arrange polymeric protective film on the layer on surface of metal of described metal lattice, the material constituting described polymeric protective film is tool
Have a water solublity, and can not and the metal material of described metal lattice between form the polymer of strong adhesion.
7. one kind utilizes the method that SERS substrate based on metal lattice carries out Raman detection, it is characterised in that include walking as follows
Rapid:
Take the SERS substrate based on metal lattice as described in any one of claim 1-3, fluid determinand is dropped in described gold
Belong in the metal dots of dot matrix, after drying, use Raman spectrometer to carry out SERS detection；Or
Take SERS substrate based on metal lattice as claimed in claim 4, first clean with deionized water and remove described polymer
Protecting film, after nitrogen dries up, drops in fluid determinand in the metal dots of described metal lattice, after drying, uses Raman spectrum
Instrument carries out SERS detection.
8. the method for Raman detection as claimed in claim 7, it is characterised in that carrying out the bag that takes a step forward of SERS detection
Include: drip metal nanoparticle colloidal sol, the metal nanoparticle in described metal nanoparticle colloidal sol on described determinand surface
For gold, silver or copper nano-particle.
9. the method for Raman detection as claimed in claim 8, it is characterised in that the size of described metal nanoparticle is 10-
1000 nanometers.
10. a SERS chip based on metal lattice, it is characterised in that include silicon-based substrate, be formed at described silicon-based substrate
On metal lattice and be arranged on the described metal lattice hydrophobic layer with exterior domain, and be arranged on the metal of described metal lattice
Nitride layer to be measured on point and the metal nanoparticle layer being arranged in nitride layer to be measured, the material constituting described metal lattice is gold,
Silver or copper, the material of described metal nanoparticle layer is gold, silver or copper nano-particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610599623.4A CN106290296B (en) | 2016-07-27 | 2016-07-27 | SERS substrate based on metal dot matrix, preparation method thereof and method for performing Raman detection by using substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610599623.4A CN106290296B (en) | 2016-07-27 | 2016-07-27 | SERS substrate based on metal dot matrix, preparation method thereof and method for performing Raman detection by using substrate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107064107A (en) * | 2017-04-11 | 2017-08-18 | 中山大学 | Super hydrophobic surface enhancing Raman substrate prepared by a kind of utilization silicon nanometer dielectric material and preparation method thereof |
| CN107290331A (en) * | 2017-06-08 | 2017-10-24 | 北京航空航天大学 | A kind of hydrophobicity composite high-molecular film is used for the method for Raman detection |
| CN108872183A (en) * | 2018-03-22 | 2018-11-23 | 苏州天际创新纳米技术有限公司 | A kind of preparation of SERS chip, preservation and upper quadrat method |
| CN109342398A (en) * | 2018-11-27 | 2019-02-15 | 浙江工业大学 | The SERS detection method of trace Ciprofloxacin in a kind of flesh of fish |
| CN109975271A (en) * | 2019-04-24 | 2019-07-05 | 西南交通大学 | The base material and its application method of high reproducibility Surface enhanced Raman scattering |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1650420A (en) * | 2002-07-12 | 2005-08-03 | 赋权新加坡私人有限公司 | Method and wafer for maintaining ultra clean bonding pads on a wafer |
| KR20120017362A (en) * | 2010-08-18 | 2012-02-28 | 한양대학교 산학협력단 | Gold patterned immunoassay microarray for image measurement of surface-enhanced raman scattering and immunoassay using the same |
| CN102621128A (en) * | 2012-04-11 | 2012-08-01 | 中国科学院半导体研究所 | Preparation method of large-area sequential controllable surface-enhanced Raman active substrate |
| CN102954956A (en) * | 2011-08-25 | 2013-03-06 | 福州高意光学有限公司 | Enhanced Raman spectroscopy test piece device and test piece manufacturing method |
| CN104730059A (en) * | 2015-03-18 | 2015-06-24 | 苏州大学 | Point-array surface enhanced raman substrate and preparation method |
| CN104792766A (en) * | 2015-04-15 | 2015-07-22 | 江苏理工学院 | Surface enhanced raman scattering substrate and preparation method thereof |
-
2016
- 2016-07-27 CN CN201610599623.4A patent/CN106290296B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1650420A (en) * | 2002-07-12 | 2005-08-03 | 赋权新加坡私人有限公司 | Method and wafer for maintaining ultra clean bonding pads on a wafer |
| KR20120017362A (en) * | 2010-08-18 | 2012-02-28 | 한양대학교 산학협력단 | Gold patterned immunoassay microarray for image measurement of surface-enhanced raman scattering and immunoassay using the same |
| CN102954956A (en) * | 2011-08-25 | 2013-03-06 | 福州高意光学有限公司 | Enhanced Raman spectroscopy test piece device and test piece manufacturing method |
| CN102621128A (en) * | 2012-04-11 | 2012-08-01 | 中国科学院半导体研究所 | Preparation method of large-area sequential controllable surface-enhanced Raman active substrate |
| CN104730059A (en) * | 2015-03-18 | 2015-06-24 | 苏州大学 | Point-array surface enhanced raman substrate and preparation method |
| CN104792766A (en) * | 2015-04-15 | 2015-07-22 | 江苏理工学院 | Surface enhanced raman scattering substrate and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107064107A (en) * | 2017-04-11 | 2017-08-18 | 中山大学 | Super hydrophobic surface enhancing Raman substrate prepared by a kind of utilization silicon nanometer dielectric material and preparation method thereof |
| CN107064107B (en) * | 2017-04-11 | 2019-11-19 | 中山大学 | A kind of super hydrophobic surface enhancing Raman substrate and preparation method thereof using the preparation of silicon nanometer dielectric material |
| CN107290331A (en) * | 2017-06-08 | 2017-10-24 | 北京航空航天大学 | A kind of hydrophobicity composite high-molecular film is used for the method for Raman detection |
| CN108872183A (en) * | 2018-03-22 | 2018-11-23 | 苏州天际创新纳米技术有限公司 | A kind of preparation of SERS chip, preservation and upper quadrat method |
| WO2019179006A1 (en) * | 2018-03-22 | 2019-09-26 | 苏州天际创新纳米技术有限公司 | Method for preparing, saving and loading sers chip |
| CN108872183B (en) * | 2018-03-22 | 2024-05-07 | 苏州纳微生命科技有限公司 | SERS chip preparation, preservation and sample loading method |
| CN109342398A (en) * | 2018-11-27 | 2019-02-15 | 浙江工业大学 | The SERS detection method of trace Ciprofloxacin in a kind of flesh of fish |
| CN109975271A (en) * | 2019-04-24 | 2019-07-05 | 西南交通大学 | The base material and its application method of high reproducibility Surface enhanced Raman scattering |
| CN111299606A (en) * | 2020-03-19 | 2020-06-19 | 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 |
| CN113281324A (en) * | 2021-06-29 | 2021-08-20 | 江苏大学 | Characteristic information extraction method of small molecule volatile matter and portable detection system |
| WO2023272749A1 (en) * | 2021-06-29 | 2023-01-05 | 江苏大学 | Feature information extraction method and portable detection system for small molecule volatile substance |
| CN114377736A (en) * | 2022-01-11 | 2022-04-22 | 中科新芯纳米技术(常州)有限公司 | Hydrophilic and hydrophobic patterned array chip, preparation method and application thereof |
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