CN108613959B - SERS chip and preparation method thereof - Google Patents
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- CN108613959B CN108613959B CN201810240090.XA CN201810240090A CN108613959B CN 108613959 B CN108613959 B CN 108613959B CN 201810240090 A CN201810240090 A CN 201810240090A CN 108613959 B CN108613959 B CN 108613959B
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000002086 nanomaterial Substances 0.000 claims abstract description 19
- 239000004020 conductor Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 238000001338 self-assembly Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 239000002077 nanosphere Substances 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
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- 238000003486 chemical etching Methods 0.000 claims description 4
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
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- 239000001509 sodium citrate Substances 0.000 description 5
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- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 4
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- 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
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
Abstract
The invention provides a SERS chip and a preparation method thereof, wherein the SERS chip comprises a substrate with a plurality of pits on the surface and a nano-structure unit arranged in the pits, and the nano-structure unit comprises a first part arranged in the pits and a second part positioned outside the pits. According to the invention, the first nano particles grow in the pits of the substrate, and then the second nano particles grow at the positions of the first nano particles and grow out of the pits to obtain the chip. The SERS chip prepared by the invention has the advantages of high repeatability, uniform hot spot, stable property, large-area growth, high sensitivity and capability of being recycled for multiple times, thereby saving the user cost and realizing the detection of various low-concentration organic matters.
Description
Technical Field
The invention relates to a Surface-Enhanced Raman Scattering (SERS) technology, in particular to an SERS chip and a preparation method thereof.
Background
The Raman spectroscopy is a scattering spectrum, and the Raman spectroscopy analysis is an analysis method which is used for analyzing a scattering spectrum with different incident light frequencies based on a Raman scattering effect found by indian scientists c.v. Raman (Raman) to obtain information on molecular vibration and rotation, and is applied to molecular structure research. The technology is widely applied to various fields of chemistry, physics, biology, medicine and the like because of the advantages of rapid, simple, repeatable and nondestructive qualitative and quantitative analysis, and also shows unique advantages in the aspects of pure qualitative analysis, high-degree quantitative analysis and molecular structure determination. The SERS enhancing source comprises a noble metal sol and an enhancing substrate.
In the existing SERS research, researchers are all focused on preparing controllable, repeatable and hot-spot concentrated SERS substrates with metal nanostructures. Such as patent numbers: 201610658664.6, the patent names: a method for preparing ordered silver nanosphere array includes evaporating a silver film with thickness of 10nm on surface of ordered aluminium nanometer bowl OAB array template sample, then vacuum annealing OAB template at 500 deg.C for 1h to obtain ordered silver nanometer array structure. Patent numbers: 201610327475.0, patent name: a large-area surface-enhanced Raman scattering substrate and a preparation method thereof are disclosed, wherein a template with a three-dimensional micron structure is prepared, a layer of silver is evaporated to form silver nanoparticles, then a layer of oxide is evaporated, and a layer of silver is evaporated to obtain a large-area SERS substrate. Patent numbers: 201610929950.1, patent name: a preparation method of an SERS substrate with controllable precious metal nanoparticle spacing comprises the steps of cleaning an AAO template by hydrochloric acid, then obtaining precious metal nanoparticle clusters by a physical or chemical method, and filling the whole AAO template holes. And further leading the AAO template on PMMA, carrying out heat treatment to ensure that the noble metal cluster is immersed in the PMMA, cleaning by hydrochloric acid to remove the AAO template, and drying to obtain the SERS substrate with the noble metal nanoparticles regularly distributed. The method has complicated template transfer and hydrochloric acid cleaning operations, is difficult to realize large-area preparation by transferring AAO to other templates, and has high cost.
Disclosure of Invention
The invention aims to provide an SERS chip which is low in cost, high in reproducibility, high in SERS activity, excellent in uniformity and batch reproducibility and capable of being produced in a large scale and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a SERS chip which comprises a substrate with a plurality of pits on the surface and a nano-structure unit arranged in the pits, wherein the nano-structure unit comprises a first part arranged in the pits and a second part positioned outside the pits.
In the invention, the nanostructure unit is prepared by forming a first conductive material in a pit of a substrate by a self-assembly method and then growing a second conductive material in situ on the surface of the first conductive material.
In the present invention, embodiments of the self-assembly method include, but are not limited to, solvent-volatile self-assembly, active adsorption, hydrophilic-hydrophobic repulsion and adsorption, electrostatic adsorption, and the like.
In the present invention, the second conductive material is grown by chemical deposition.
Preferably, the first conductive material comprises one or more nanoparticles, and the particle size of the nanoparticles is 2nm to 120nm, preferably 2nm to 80nm, and more preferably 5nm to 30 nm.
Further preferably, the nanoparticles of the first conductive material are of an alloy structure or a core-shell structure. .
Further, the alloy structure comprises an alloy structure with SERS activity, such as a gold-silver alloy, a gold-copper alloy, a gold-carbon alloy, a gold-platinum alloy, a silver-platinum alloy and the like; core-shell structures include core-shell structures having two components, such as silver-coated gold, gold-coated silver, platinum-coated gold, gold-coated platinum, gold-coated ferroferric oxide, silver-coated ferroferric oxide, and the like.
Further preferably, the first conductive material and the second conductive material comprise one or more of gold, silver, copper, platinum, aluminum.
In the present invention, the first conductive material and the second conductive material are the same or different.
Preferably, the thickness of the second part is 2-200 nm.
Preferably, the first conductive material has a regular or irregular shape. For example, the shape of the nanoparticle includes a sphere, a block, a plate, a rod, or the like, and is not limited thereto.
In the present invention, the first conductive material may be used in the form of a dispersion, and the dispersion may further be a metal nanoparticle sol. The metal nanoparticles can be synthesized by a wet process, the morphology and size of the metal nanoparticles can also be conveniently regulated, and reference can be made to the following processes and conditions, but not limited to the following document 1: angew. chem. int. ed.45, 3414.
Preferably, the concentration of the metal nanoparticles in the dispersion is 1 × 1091X 10 to one/mL11one/mL.
In the present invention, the concentration of the metal nanoparticles may be adjusted by adding a solvent, and the solvent used may be a conventional solvent in the art. Preferably, the first conductive material is one of gold sol, silver sol or gold-silver mixed sol; further preferably, the first conductive material is gold sol or silver sol; more preferably, the first conductive material is gold sol.
In the present invention, the second conductive material may be obtained by growing the substrate assembled with the first conductive material in a growth liquid, and the growth liquid may be a precursor liquid capable of generating nanoparticles.
In the invention, the shape of the pit can be regular or irregular, for example, the cross section of the pit can be circular, rectangular, triangular, parallelogram, hexagonal, cross-shaped or other arbitrary shapes, etc., and the longitudinal section of the pit can be rectangular, square, triangular, U-shaped or other arbitrary shapes.
In the present invention, the shape of the first portion matches the shape of the recess.
In the present invention, the shape of the second portion may be a regular shape or an irregular shape, for example, a column shape having the same cross section as that of the dimple, an inverted hemispherical shape, or an arbitrary shape having an arc surface.
In the invention, the thickness of the second convex pits can be set according to actual requirements to meet various different use requirements, and in addition, the method for adjusting various different thicknesses can be realized by controlling preparation parameters.
In the invention, the pits are distributed at intervals on the whole surface of the substrate, namely, a gap is formed between the pits instead of being connected into a whole.
In the present invention, the substrate having a plurality of pits on the surface may be a substrate having pits of the same specification or pits of different specifications, and a substrate having pits of a plurality of specifications is preferably used.
The specifications of the pit are defined by the circumferential outline shape of the pit, the volume of the pit and the opening area of the pit, and when any one of the circumferential outline shape of the two pits, the volume of the pit and the opening area of the pit is different, the two specifications are considered.
Further preferably, the number of said pits per square centimeter of area is N, the N pits having at least N/10 gauge, still further preferably at least N/8 gauge, more preferably at least N/6 gauge, most preferably at least N/3 gauge.
According to the invention, the pits are preferably arranged on the surface of the substrate in an array manner, and the pits have various specifications, so that the SERS chip is microscopically disordered, and the conventional understanding of people on an excellent SERS substrate is broken through. As can be seen from the foregoing, since SERS substrate performance is closely related to structure, researchers have consistently strived to obtain uniform nanostructures j.phys.chem.c 111,6720 in pursuit of repeatable SERS substrates; ACS appl. Indeed, uniform nanostructures can ensure good reproducibility, but the inventors of the present application found, in long-term research and extensive practice, that energy resonance is very likely to occur between nanostructure units with similar structures, and energy accumulated at nanoparticle gaps ("hot spots") is dissipated, resulting in a great decrease in SERS activity at the "hot spots". It may be based on this factor that the SERS activity of some SERS substrates with too high structural similarity in the prior art is not prominent. The inventor of the present application makes specifications of a plurality of pits different to make the specifications of the pits as much as possible, so that sizes and/or shapes of a plurality of nano-structure units limited in the pits are not completely the same, and thus interaction between the nano-structure units with the same structure can be avoided, adverse effects on plasma localization caused by the interaction are eliminated, and SERS activity of the SERS unit when the SERS unit is applied as a SERS substrate is greatly enhanced. On the other hand, statistically, over a large area (1 μm)2) The overall performance of the nano-structure units (about 100 or more) is very close, so that the SERS chip has the characteristic of macroscopic uniformity, the SERS chip is very uniform, and the reliability of the SERS test result can be further ensured, so that the SERS chip can be well applied to quantitative detection.
Preferably, the density of the pits is 108～1010Per cm2A substrate.
Preferably, the minimum spacing distance between two adjacent pits is 1-50 nm, more preferably 5-50 nm, and still more preferably 10-30 nm.
In the present invention, the minimum spaced distance between two adjacent pits refers to a minimum distance among a plurality of distances between an arbitrary point on the upper edge of one pit and an arbitrary point on the upper edge of an adjacent one pit.
Preferably, the depth of the pits is in the range of 30nm to 300nm, preferably 40nm to 300nm, more preferably 40nm to 200 nm.
In the present invention, the depth of the dimple refers to the maximum distance from the surface of the dimple where the upper edge of the dimple is located to the bottom surface of the dimple.
Preferably, the diameter of the mouth is in the range of 30nm to 4 μm, preferably 30nm to 500nm, more preferably 40nm to 200 nm.
In the invention, the diameter of the opening part of the pit refers to the largest distance in a plurality of distances between any two points on the upper edge of the pit, and when the surface surrounded by the upper edge of the pit is circular, the diameter of the pit is the diameter of the circle; when the surface enclosed by the upper edges of the pits is square, the diameter of each pit is the diagonal line of the square; when the surface enclosed by the upper edges of the pits is triangular, the diameter of each pit is the longest side of the triangle; when the surface enclosed by the upper edge of the pit is in an ellipse shape, the diameter of the pit is the major axis of the ellipse.
According to the invention, by controlling the minimum distance between the pits and/or the density of the pits and/or the diameter of the opening of the pits, high-density stacking of the nano-structure units can be realized, and the SERS effect can be further enhanced. Furthermore, the invention can make the diameter of the pit and the metal nano particle as small as possible, thereby making the activity of the chip better and making the stability, uniformity and repeatability better.
Preferably, the pits are made by plasma etching, uv etching, chemical etching, laser etching, mechanical drilling, mechanical punching, nanosphere printing or electrochemical methods.
Further preferably, the plurality of pits have a plurality of specifications by controlling the preparation parameters.
For example, the substrate having a plurality of pits on the surface can be prepared by nanosphere printing or electrochemical method, and the following references are specifically and not limited to document 2: j.am.chem.soc.127, 3710; chem.Commun.53, 7949.
Among them, the process of electrochemically preparing a substrate having nano-pores is very easy and has been commercialized (e.g., AAO template). And the relative controllability of the nanosphere printing is stronger, and more pore structure parameters can be prepared. Compared with other nanostructure processing methods (such as EBL, nano-imprinting and the like), the two methods have the advantages of high resolution, strong operability and low cost, and are very suitable for preparing the substrate.
Preferably, the substrate includes an inorganic substrate, an organic substrate, or an inorganic/organic composite substrate, such as a metal or metal oxide substrate (e.g., an alumina template), a semiconductor material, a polymer template, single crystal silicon, a quartz plate, a glass plate, polytetrafluoroethylene, plastic, and the like, without being limited thereto.
Preferably, the substrate in the present invention is: preparing a silicon template or an aluminum oxide template by an anodic oxidation method; processing a semiconductor wafer, monocrystalline silicon, quartz, glass and a metal substrate by adopting methods such as plasma etching, laser ablation, mechanical drilling, mechanical stamping or chemical etching and the like to prepare a template; and the template such as metal, macromolecule, polymer, plastics, organic glass, etc. copied by the template.
Further preferably a silicon template or an aluminum oxide template prepared by an anodic oxidation method; the template is prepared by processing semiconductor wafers, monocrystalline silicon, quartz, glass and metal substrates by methods such as plasma etching, laser ablation, mechanical drilling, mechanical stamping or chemical etching.
More preferably an aluminum nano bowl, etched single crystal silicon, or a template with ordered nano holes prepared by nano imprinting.
The invention also provides a preparation method of the SERS chip, wherein a first conductive material is formed in the pit of the substrate by a self-assembly method, and then a second conductive material is grown in situ on the surface of the first conductive material to form the nano-structure unit.
Preferably, the self-assembly method comprises dropping, spin coating, printing, injecting or spraying a dispersion containing nanoparticles onto the substrate surface, or immersing the substrate surface in the dispersion of nanoparticles, and removing the solvent of the dispersion by volatilization.
There are various immersion methods, for example, immersing the substrate in the dispersion liquid, taking out the substrate, and volatilizing the solvent; or immersing the surface of the substrate in the dispersion liquid, taking out the substrate, and volatilizing the solvent; alternatively, a layer of the dispersion is dropped on the surface of the substrate, and then the solvent is volatilized.
The spin coating refers to spin coating of the dispersion on the surface of the substrate by the apparatus.
Preferably, the preparation method further comprises the step of performing hydrophobic modification on the substrate and the first conductive material.
In the present invention, the hydrophobic modification may be performed by a hydrophobic modification method commonly used in the art.
When the spacing distance of the pits is large, it is preferable to perform hydrophobic modification so that the metal nanoparticles more conveniently enter the pits.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the first conductive material is grown in the pit of the substrate, then the second conductive material is grown at the position of the first conductive material, and the second conductive material is grown outside the pit to obtain the chip. The SERS chip prepared by the invention has the advantages of high repeatability, uniform hot spot, stable property, large-area growth and high sensitivity, thereby saving the user cost and realizing the detection of various low-concentration organic matters.
Drawings
FIG. 1 is a schematic diagram of a substrate and a resulting chip of the present invention, wherein the top view is the substrate and the bottom view is the chip;
FIG. 2 is a schematic view of a second portion of the present invention;
FIGS. 3, 4, 5 and 6 are schematic diagrams of different substrates before and after growth of different nanoparticles;
FIG. 7 is a SERS spectrum of example 4;
fig. 8 is a SERS spectrum of example 5.
Detailed Description
In order to make the present invention clearer, the present invention is further described with reference to the drawings and the embodiments, and it should be understood that the present embodiment is not intended to limit the scope of the present invention. Methods and conditions not described in detail in the present invention are conventional in the art.
Example 1
Preparing silver nano sol:
0.5mL of silver nitrate aqueous solution with the concentration of 30mg/mL and 83mL of ultrapure water are uniformly mixed and put into a 100mL three-necked flask, and the mixture is put into a water bath and heated to boiling. After which 1.5ml of aqueous trisodium citrate solution was rapidly injected. Stirring was continued for 30 min. The particle size of the obtained silver sol is about 20 nm.
The template prepared by nanoimprint lithography (pore size 70nm, pore depth 40nm, honeycomb configuration) was 5cm by 5 cm. Soaking in the Ag sol for 3h, taking out, washing with water, and drying with nitrogen.
In-situ growth of the substrate:
the SERS template loaded with the nanoparticles is placed at the bottom of a beaker, and 20ml of 0.01% chloroauric acid aqueous solution is added. 1ml of a 1% sodium citrate solution was added, followed by slowly dropping a 3-fold molar amount of a hydroxylamine hydrochloride solution with mechanical stirring. After the addition, stirring was continued for 20 min. And taking out the substrate, washing twice with ultrapure water, and blow-drying for later use.
Example 2
Preparing silver nano sol:
0.5mL of silver nitrate aqueous solution with the concentration of 30mg/mL and 83mL of ultrapure water are uniformly mixed and put into a 100mL three-necked flask, and the mixture is put into a water bath and heated to boiling. After which 1.2ml of aqueous trisodium citrate solution was rapidly injected. Stirring was continued for 30 min. The particle size of the obtained silver sol is about 30 nm.
The template prepared by nanoimprint lithography (pore size 70nm, pore depth 40nm, honeycomb configuration) was 5cm by 5 cm. Soaking in the Ag sol for 3h, taking out, washing with water, and drying with nitrogen.
In-situ growth of the substrate:
and (3) placing the SERS template loaded with the nanoparticles at the bottom of a beaker, and adding 20ml of 0.01% silver nitrate aqueous solution. 0.05ml of ammonia was added, and then an equimolar amount of a formaldehyde solution was slowly dropped under mechanical stirring. After the addition, stirring was continued for 20 min. And taking out the substrate, washing twice with ultrapure water, and blow-drying for later use.
Example 3
Preparing gold nano sol:
1mL of 10mg/mL chloroauric acid aqueous solution and 99mL ultrapure water are uniformly mixed and placed in a 100mL three-necked flask, and the mixture is placed in a water bath and heated to boiling. After which 2ml of an aqueous solution of trisodium citrate is rapidly injected. Stirring was continued for 30 min. The grain size of the obtained gold sol is about 35 nm.
The template (pore diameter 80nm, pore depth 60nm, honeycomb configuration) prepared by laser etching 5cm by 5cm was placed on a spin coater. The concentrated Au sol was applied to the template and slowly rotated at 500 rpm for 8 minutes at 20 rpm. And taking down the product for later use.
In-situ growth of the substrate:
the SERS template loaded with the nanoparticles is placed at the bottom of a beaker, and 20ml of 0.01% chloroauric acid aqueous solution is added. 1ml of a 1% sodium citrate solution was added, and then a 3-fold molar amount of a hydroxylamine hydrochloride solution was slowly dropped with mechanical stirring. After the addition, stirring was continued for 20 min. And taking out the substrate, washing twice with ultrapure water, and blow-drying for later use.
Example 4
5 pieces of the substrate of example 1 were soaked in Sudan red I of different concentrations, wherein a is
10-4mol/L, b is 10-5mol/L, c is 10-6mol/L, d is 10-7mol/L, and e is blank; after 20min, the sample is taken out and dried, and a Raman test is carried out, the result is shown in figure 7, the peaks of the spectral lines corresponding to a and b are obvious from the figure 7, and the chip can detect the Sudan I with the concentration at least as low as 10-5 mol/L.
Example 5
5 pieces of the substrate in example 2 are taken and respectively soaked in urotropine with different concentrations, wherein a is 10-3mol/L, b is 10-4mol/L, c is 10-5mol/L, d is 10-6mol/L, e is 10-7mol/L, the substrate is taken out and dried after 20min, and a Raman test is carried out, and the result is shown in figure 8, and as can be seen from figure 8, peaks still exist for the urotropine with the concentration of 10-7mol/L, the chip can detect the urotropine with the concentration as low as 10-7 mol/L.
Claims (12)
1. A SERS chip, comprising: the SERS chip comprises a substrate with a plurality of pits on the surface and a nano-structure unit arranged in the pits, wherein the nano-structure unit comprises a first part arranged in the pits and a second part positioned outside the pits; the nano-structure unit is prepared by forming a first conductive material in a pit of a substrate by a self-assembly method and then growing a second conductive material in situ on the surface of the first conductive material, wherein the first conductive material is a plurality of nano-particles formed by self-assembly; the particle size range of the nano particles is 2 nm-120 nm; the diameter range of the opening part of the pit is 30 nm-4 mu m; the density of the pits is 108~1010Per cm2The minimum spacing distance between two adjacent pits is 1-50 nm; the self-assembly method comprises the steps of immersing the surface of the substrate into a dispersion liquid of nano particles, and removing a solvent of the dispersion liquid through volatilization.
2. The SERS chip according to claim 1, wherein: the particle size range of the nano particles is 2-80 nm.
3. The SERS chip according to claim 2, wherein: the particle size range of the nano particles is 5-30 nm.
4. The method for preparing the SERS chip according to claim 2, wherein: the nano particles of the first conductive material are of an alloy structure or a core-shell structure.
5. The SERS chip according to any of claims 1 to 4, wherein: the first and second conductive materials comprise one or more of gold, silver, copper, platinum, aluminum.
6. The SERS chip according to any of claims 1 to 4, wherein: the thickness of the second part is 2-200 nm.
7. The SERS chip according to any of claims 1 to 4, wherein: the depth range of the pits is 30 nm-300 nm, and the diameter range of the opening part is 30 nm-500 nm; the minimum spacing distance between two adjacent pits is 5-50 nm.
8. The SERS chip according to claim 7, wherein: the depth range of the pits is 40 nm-300 nm, and the diameter range of the opening part is 40 nm-200 nm; the minimum spacing distance between two adjacent pits is 10-30 nm.
9. The SERS chip according to claim 8, wherein: the depth range of the pits is 40 nm-200 nm.
10. The SERS chip according to any of claims 1 to 4, wherein: the pits are made by plasma etching, ultraviolet etching, chemical etching, laser etching, mechanical drilling, mechanical stamping, nanosphere printing or electrochemical methods.
11. The SERS chip according to any of claims 1 to 4, wherein: the substrate comprises an inorganic base material, an organic base material or an inorganic/organic composite base material.
12. A method of preparing the SERS chip according to any of claims 1 to 11, wherein: forming a first conductive material in the pits of the substrate by a self-assembly method, and then growing a second conductive material in situ on the surface of the first conductive material to form the nanostructure units; the self-assembly method comprises the steps of immersing the surface of the substrate into a dispersion liquid of nano particles, and removing a solvent of the dispersion liquid through volatilization.
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