CN107313046B - SERS substrate and preparation method thereof - Google Patents

SERS substrate and preparation method thereof Download PDF

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CN107313046B
CN107313046B CN201710334855.1A CN201710334855A CN107313046B CN 107313046 B CN107313046 B CN 107313046B CN 201710334855 A CN201710334855 A CN 201710334855A CN 107313046 B CN107313046 B CN 107313046B
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CN107313046A (en
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王�琦
候旭
毛国明
刘凯
任晓敏
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Beijing University of Posts and Telecommunications
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not
    • 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

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Abstract

The invention provides an SERS substrate and a preparation method thereof, and relates to the technical field of Raman spectroscopy. The method comprises the following steps: s0, sequentially cleaning and hydrophilically treating the substrate; s1, forming at least one layer of self-assembled array structure in regular arrangement on the surface of the substrate by adopting monodisperse nano-spheres, nano-crystals or quantum dots; s2, depositing a metal active layer on the top of the self-assembly array structure; and S3, covering a carbon-based nano material layer on the metal active layer to obtain the SERS substrate. According to the invention, the metal active layer is deposited on the self-assembly array structure regularly arranged in a large area, the periodic metal nano structure can be formed without annealing, and then the carbon-based nano material layer is covered to isolate the metal nano structure from air so as to avoid or slow down the oxidation process, so that the SERS substrate not only has very high sensitivity, but also can maintain long-term activity.

Description

SERS substrate and preparation method thereof
Technical Field
The invention relates to the technical field of Raman spectroscopy, in particular to a SERS substrate and a preparation method thereof.
Background
The raman spectroscopy is a spectroscopic method for studying molecular vibration, and obtains characteristic peaks related to molecular vibration by means of spectroscopic analysis, thereby obtaining key information about components, structures and the like of probe molecules, and is therefore an important detection and analysis technology. However, in the conventional raman spectroscopy detection, the raman signal intensity of the probe molecules is too weak, which greatly restricts the application range of the raman detection technology. In 1974, Fleischmann et al obtained a greatly enhanced Raman scattering signal of pyridine molecules on a roughened metallic silver electrode surface for the first time (Fleischmann et al Raman spectra of pyridine adsorbed at a silver electrode. chemical Physics Letters, 1974, 26 (2): 163-. Since then, Surface Enhanced Raman Scattering (SERS) technology was established and rapidly developed. Surface increasingThe strong Raman (SERS) is Enhanced by inducing the interaction between probe molecules on or near the Surface of a metal nanostructure and the Surface of the metal, and Raman signals generated by SERS are Enhanced by 10% compared with ordinary Raman Scattering4-107And (4) doubling. The enhancing mechanism of SERS mainly includes physical enhancement and chemical enhancement, wherein the physical enhancement means that a Local Surface Plasmon Resonance (LSPR) excited by a metal surface generates a strong electromagnetic field to enhance a raman signal; chemical enhancement refers to the enhancement of Raman signals realized by the chemical action or charge transfer between a metal substrate and molecules to be detected adsorbed on the surface of the metal substrate. Compared with other spectrum detection methods, SERS has three obvious advantages of high sensitivity, high selectivity and loose detection conditions, and can be widely applied to the fields of trace analysis, single-molecule detection, biomedical detection, surface adsorption, catalytic reaction and the like.
Obviously, the preparation of the high-performance SERS substrate is one of the prerequisites for realizing SERS detection. As early as 1977, Jeanmarie et al discovered that metals with specific nanostructures (e.g., silver, gold, copper, platinum, palladium, titanium, etc.) could be used to prepare high performance SERS substrates, with silver having the best SERS properties. At present, a self-assembly method is widely used for preparing a large-area uniformly-arranged periodic metal nano structure and a corresponding SERS active substrate, and high-sensitivity SERS detection is realized by providing high-density SERS 'hot spots'.
Nevertheless, the activity of metals such as silver, titanium, bismuth, copper, etc. is strong, and the metals are easily oxidized when exposed in air, and the activity of the metal nanostructures and the corresponding SERS substrate prepared by the metals is weakened or even ineffective along with the oxidation of the metals.
Disclosure of Invention
Embodiments of the present invention provide a SERS substrate and a method of making the same that overcome or at least partially address the above-mentioned problems.
In one aspect, an embodiment of the present invention provides a method for preparing a SERS substrate, including:
s1, forming at least one layer of self-assembly array structure in regular arrangement on the surface of the substrate by adopting monodisperse nano-spheres, nano-crystals or quantum dots;
s2, depositing a metal active layer on the top of the self-assembly array structure;
s3, covering a carbon-based nano material layer on the metal active layer to obtain an SERS substrate;
wherein, before step S1, the method further includes:
s0, the substrate is sequentially cleaned and hydrophilically treated.
Wherein the carbon-based nano material layer is a graphene material layer with the thickness of 0.3-10nm or a carbon coating layer with the thickness of 1-10 nm.
The graphene material is one of graphene, Graphene Oxide (GO), reduced graphene oxide (rGO) and functionalized graphene.
The graphene material layer is covered on the metal active layer in a transfer or film forming mode.
Wherein the carbon wrapping layer is covered on the metal active layer by a pyrolysis method, a chemical vapor deposition method, a liquid phase impregnation method or an arc discharge method.
Wherein, in step S1:
at least one layer of self-assembly array structure which is regularly arranged is formed on the surface of the substrate by adopting monodisperse nano-spheres, nano-crystals or quantum dots with the diameter of 1-1000nm through spin coating, drop coating, dipping and pulling, vertical pulling or liquid level pulling.
Wherein the material of the nano-spheres, the nano-crystals or the quantum dots is Polystyrene (PS), polyaniline (PAn), polypyrrole (PPy) or silicon oxide (SiO)x) Titanium dioxide (TiO)2) Tin dioxide (SnO)2) Aluminum oxide (Al)2O3) Ferroferric oxide (Fe)3O4) Vanadium pentoxide (V)2O5) Carbon (C), silicon (Si), and a II-VI compound semiconductor.
Wherein, in step S2:
and depositing a metal active layer with the thickness of 1-300nm on the self-assembly array structure in an evaporation, sputtering, ion plating, laser-assisted deposition or chemical plating mode to form a metal nano structure.
In another aspect, an embodiment of the present invention provides a SERS substrate prepared by the above method, including: the self-organized structure comprises a substrate, a self-organized array structure regularly arranged on the surface of the substrate and a metal active layer deposited on the top of the self-organized array structure, and is characterized in that a carbon-based nano material layer covers the metal active layer.
According to the SERS substrate and the preparation method thereof provided by the embodiment of the invention, the periodic metal nano structure is covered with the carbon-based nano material layer, so that the metal nano structure is isolated from air, and the oxidation process of the metal nano structure is avoided or slowed down, and further, the SERS substrate not only has very high sensitivity, but also can maintain long-term activity.
Drawings
Fig. 1 is a flowchart of a method for preparing a SERS substrate according to an embodiment of the present invention;
fig. 2 is a schematic diagram illustrating a method for preparing a SERS substrate according to an embodiment of the present invention;
FIG. 3 is an SEM image of a self-organized array structure before and after deposition of a metal active layer according to an embodiment of the invention;
fig. 4 is a raman spectrum of a graphene oxide layer in the example according to the embodiment of the present invention;
fig. 5 is a raman spectrum of a low-concentration rhodamine 6G probe molecule measured using a SERS substrate in the example of the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments, but not all embodiments, of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is a flowchart of a method for preparing a SERS substrate according to an embodiment of the present invention, as shown in fig. 1, including: s1, forming at least one layer of self-assembly array structure in regular arrangement on the surface of the substrate by adopting monodisperse nano-spheres, nano-crystals or quantum dots; s2, depositing a metal active layer on the top of the self-assembly array structure; and S3, covering a carbon-based nano material layer on the metal active layer to obtain the SERS substrate.
In step S1, the size of the nanospheres, nanocrystals or quantum dots is in the nanometer scale range, and after the metal active layer is deposited thereon, the metal nanostructures are correspondingly formed. The material of the nano-spheres, the nano-crystals or the quantum dots is Polystyrene (PS), polyaniline (PAn), polypyrrole (PPy) or silicon oxide (SiO)x) Titanium dioxide (TiO)2) Tin dioxide (SnO)2) Aluminum oxide (Al)2O3) Ferroferric oxide (Fe)3O4) Vanadium pentoxide (V)2O5) Carbon (C), silicon (Si), and a II-VI compound semiconductor.
Specifically, at least one layer of self-assembled array structure which is regularly arranged is formed on the surface of the substrate by adopting monodisperse nano-spheres, nano-crystals or quantum dots with the diameter of 1-1000nm through spin coating, drop coating, dip drawing, vertical drawing or liquid level drawing.
In step S2, the metal is one of silver (Ag), gold (Au), copper (Cu), platinum (Pt), palladium (Pd), titanium (Ti), and bismuth (Bi), or an alloy of a plurality of them. Wherein the alloy is obtained by simultaneously depositing two or more metals, or by depositing a single metal layer by layer.
Specifically, a metal active layer with the thickness of 1-300nm is deposited on the self-assembly array structure in an evaporation, sputtering, ion plating, laser-assisted deposition or chemical plating mode to form a metal nano structure. In specific implementation, the thickness of the metal active layer needs to be selected according to the diameter of the nanospheres, the nanocrystals or the quantum dots and the raman enhancement effect of the SERS substrate.
In step S3, the carbon-based nanomaterial layer is a graphene material layer with a thickness of 0.3-10nm or a carbon-coated layer with a thickness of 1-10 nm. The graphene material is one of graphene, Graphene Oxide (GO), reduced graphene oxide (rGO) and functionalized graphene. The graphene material exists in a film form, the thickness of the graphene material is less than 10 carbon atom layers, the graphene material can be tightly attached to the metal active layer, and large-area continuous coverage is realized, so that the metal active layer is effectively protected. In addition, graphene and graphene derivatives, Graphene Oxide (GO) and reduced graphene oxide (rGO), also have the SERS effect, and the enhancement mechanism thereof is chemical enhancement caused by charge transfer. Therefore, the graphene material with the chemical enhancement effect is introduced to serve as a protective layer and is combined with the metal nano structure with the electromagnetic enhancement, so that the stability of the SERS substrate is better, and the Raman enhancement effect of the SERS substrate is higher. In addition, a carbon nano shell (carbon shell) can be coated on the metal active layer of the SERS substrate, namely the metal nano structure, the carbon shell can be used for confining metal materials, adverse effects of air contact on metal activity are avoided or weakened, and the problem that metal with strong activity cannot be placed in the air for a long time is solved.
Specifically, the graphene material layer is covered on the metal active layer through a transfer or film forming mode. The carbon wrapping layer is covered on the metal active layer through a pyrolysis method, a chemical vapor deposition method, a liquid phase impregnation method or an arc discharge method. In specific implementation, the thickness of the carbon-based nanomaterial layer needs to be selected according to the raman enhancement effect and the SERS substrate stability of the SERS substrate.
In the above embodiment, before step S1, the method further includes: s0, the substrate is sequentially cleaned and hydrophilically treated.
In step S0, the hydrophilic treatment is performed on the substrate to facilitate the self-assembly of the monodisperse nano-spheres, nanocrystals or quantum dots on the substrate in S2. The substrate material includes, but is not limited to, metal, polymer, glass, ceramic, filter paper, silicon oxide (SiO)xX is more than 0 and less than or equal to 2), Indium Tin Oxide (ITO), Si, Ge, GaAs, SOI, GeOI, GaN, AlN, InN, ZnO, MgO, LiAlO2、LiGaO2、MgAl2O4、SiC、Al2O3GaAs, InP, GaP, InAs, or GaSb.
Specifically, the substrate material is selected from common Si, and the cleaning and hydrophilic treatment processes of the Si substrate are as follows: sequentially carrying out ultrasonic cleaning on a Si substrate in acetone, alcohol and deionized water, then washing with the deionized water and using N2Drying; and then bombarding the Si substrate by oxygen plasma for 5-10min, so that the surface of the Si substrate obtains excellent hydrophilicity.
In the process of preparing the SERS substrate, the substrate material is Si, and the monodisperse nanospheres, nanocrystals or quantum dots are SiO2The nano-spheres are characterized in that the metal active layer is made of Ag, and the carbon-based nano-material is graphene oxide. It should be noted that the materials selected in the present example are only used for illustrating the specific implementation process of the present invention, and the present invention is not limited thereto. The method comprises the following steps:
s10, ultrasonic cleaning the Si substrate in acetone, alcohol and deionized water in sequence, washing with deionized water and drying with N2; and then bombarding the Si substrate with oxygen plasma for 5-10min to obtain the Si substrate with excellent hydrophilicity.
S11, using SiO with the concentration of 5-15% wt and the diameter of 200-600nm2Forming SiO in single layer arrangement on the surface of the substrate by the nano-bead solution in an inclined dripping way2A self-assembled nano-bead array structure.
Specifically, a Si substrate with excellent hydrophilicity is placed in an environment with the temperature of 40-50 ℃ and is placed in an inclined manner at the angle of 7-20 degrees; taking SiO with the concentration of 10 wt% and the diameter of 200-600nm2Mixing the nano-bead solution (alcohol is used as a solvent) with absolute ethyl alcohol and ethylene glycol in an equal volume ratio to form a colloid mixed solution, and performing ultrasonic treatment for 30-60 min; a micro-sampler is used for taking a proper amount of colloid mixed liquid to be dripped to the upper end of the Si substrate which is obliquely arranged, the environment temperature is controlled to regulate and control the evaporation rate of the solvent, and after the solvent is completely volatilized, large-area SiO arranged in a single layer is formed2The structure of the self-assembled nano-bead array is shown in FIG. 3 a.
And S12, putting the self-assembly array structure into a magnetron sputtering coating system, and depositing an Ag active layer with the thickness of 20-120nm on the self-assembly array by using an Ag target as a sputtering target to form an Ag nano structure.
Specifically, the SiO obtained in S112Placing the nano-bead self-assembly array into a magnetron sputtering coating system, and depositing an Ag active layer with the thickness of 60nm, wherein the sputtering target is a silver target with the purity of 99.99 percent, and the vacuum degree is lower than 4.5 multiplied by 10-4Pa, current 0.12A. As shown in FIG. 3b, the scanning electron microscope test shows that the SiO2Cluster-shaped Ag nano structures are formed on the spherical crown of the nano-spheres.
S13, spin-coating the graphene oxide layer with uniform thickness on the metal active layer for 20-40S at the rotating speed of 1500-3000 r/min by adopting the graphene oxide aqueous solution with the concentration of 0.05-0.3g g/ml.
Specifically, a certain amount of Graphene Oxide (GO) is ultrasonically dissolved in deionized water to prepare a GO aqueous solution with the concentration of 0.1 g/ml; and (3) carrying out spin coating on the substrate prepared in S13 by taking a proper amount of GO aqueous solution, (the rotating speed is 2000 rpm, and the spin coating time is 30S), so as to obtain a uniform GO layer. As shown in FIG. 4, Raman testing using a test laser source at 523nm wavelength and 30 μ W power indicated that the GO layer had covered with an active layer of metallic Ag.
After the SERS substrate is prepared through S10-S13, rhodamine 6G is used as a probe molecule to evaluate the Raman enhancement characteristic and the long-term stability of the GO-protected SERS substrate. As shown in FIG. 5, a test laser light source with the wavelength of 523nm and the power of 30 μ W and the prepared SERS substrate are used for detecting probe molecules, and a test result shows that the detection limit of the prepared SERS substrate on rhodamine 6G can reach 10-16M (as shown in fig. 5 a); the prepared SERS substrate is placed in the air for 15 days and then aligned with the SERS substrate 10-6Raman testing is carried out on M rhodamine 6G, and the result shows that the strength of the Raman characteristic peak of the rhodamine 6G measured by the SERS substrate is not obviously reduced, and the peak position and the peak shape of the characteristic peak are not obviously changed (as shown in figure 5 b). The experimental results show that the SERS substrate prepared by the method has higher sensitivity and better long-term performanceAnd (4) stability.
According to the preparation method of the SERS substrate provided by the embodiment of the invention, the periodic metal nano structure is covered with the carbon-based nano material layer, so that the metal nano structure is isolated from air, and the oxidation process of the metal nano structure is avoided or slowed down, and further, the SERS substrate not only has very high sensitivity, but also can maintain long-term activity.
An embodiment of the present invention provides a SERS substrate prepared by the above method, including: the self-organized structure comprises a substrate, a self-organized array structure regularly arranged on the surface of the substrate and a metal active layer deposited on the top of the self-organized array structure, and is characterized in that a carbon-based nano material layer covers the metal active layer.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. The SERS substrate and the preparation method thereof are characterized by comprising the following steps:
s1, forming at least one layer of self-assembly array structure in regular arrangement on the surface of the substrate by using monodisperse nano-spheres, nano-crystals or quantum dots with the diameter of 1-1000 nm;
s2, depositing a metal active layer with the thickness of 1-300nm on the top of the self-assembly array structure;
s3, covering a carbon-based nano material layer on the metal active layer to obtain an SERS substrate;
the carbon-based nano material layer is a graphene material layer with the thickness of 0.3-10nm or a carbon coating layer with the thickness of 1-10 nm.
2. The method according to claim 1, further comprising, before step S1:
s0, the substrate is sequentially cleaned and hydrophilically treated.
3. The method of claim 1, wherein the graphene material is one of graphene, Graphene Oxide (GO), reduced graphene oxide (rGO), and functionalized graphene.
4. The method according to claim 1, wherein the graphene material layer is coated on the metal active layer by means of transfer or film formation.
5. The method of claim 1 wherein the carbon wrapping is applied to the metal active layer by pyrolysis, chemical vapor deposition, liquid phase impregnation or arc discharge.
6. The method according to claim 1, wherein in step S1:
the monodisperse nano-spheres, nano-crystals or quantum dots form at least one layer of self-assembled array structure which is regularly arranged on the surface of the substrate in the modes of spin coating, drop coating, dipping and pulling, vertical pulling or liquid level pulling.
7. The method of claim 6, wherein the material of the nano-spheres, nano-crystals or quantum dots is Polystyrene (PS), polyaniline (PAn), polypyrrole (PPy), silicon oxy-Silicate (SiO)x) Titanium dioxide (TiO)2) Tin dioxide (SnO)2) Aluminum oxide (Al)2O3) Ferroferric oxide (Fe)3O4) Vanadium pentoxide (V)2O5) Carbon (C), silicon (Si), and a II-VI compound semiconductor.
8. The method according to claim 1, wherein in step S2:
and depositing a metal active layer with the thickness of 1-300nm on the self-assembly array structure in an evaporation, sputtering, ion plating, laser-assisted deposition or chemical plating mode to form a metal nano structure.
9. A SERS substrate prepared by the method of any one of claims 1-8, comprising: the self-assembled solar cell comprises a substrate, a self-assembled array structure regularly arranged on the surface of the substrate and a metal active layer deposited on the top of the self-assembled array structure, and is characterized in that a carbon-based nano material layer covers the metal active layer.
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