CN116728909A - High-sensitivity composite SERS substrate with self-cleaning function and preparation method thereof - Google Patents
High-sensitivity composite SERS substrate with self-cleaning function and preparation method thereof Download PDFInfo
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Classifications
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
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- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2264/1051—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/754—Self-cleaning
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Abstract
The embodiment of the application provides a high-sensitivity composite SERS substrate with a self-cleaning function and a preparation method thereof, wherein the substrate comprises the following components: a silicon substrate; self-cleaning layer: the device is arranged on the silicon substrate and is used for degrading adsorbed molecules to be detected under specific conditions; first noble metal layer: is arranged on the self-cleaning layer; a spacer layer: the first noble metal layer is arranged on the first noble metal layer and used for regulating and controlling particle gaps in the vertical direction; second noble metal layer: is arranged on the graphene layer. The SERS substrate has certain self-cleaning capability, high Raman sensitivity, good spectrum reproducibility and good stability, can be recycled and is suitable for the field of trace detection.
Description
Technical Field
The application relates to the technical field of SERS substrates in trace detection, in particular to a high-sensitivity composite SERS substrate with a self-cleaning function and a preparation method thereof.
Background
The surface enhanced Raman spectrum (Surface enhanced Raman spectroscopy technology, SERS) technology is a detection technology for extremely low-concentration pollutants, has the advantages of fingerprint identification, high sensitivity, rapidness, no damage and the like, and has great potential application value in the fields of medicine, environment, food safety, catalysis and the like. However, the preparation of an active substrate having multiple properties of high sensitivity, high stability, reproducibility, and recyclability remains a scientific problem to be solved.
Some existing SERS substrates are constructed by noble metal materials such as gold and silver, and the noble metal materials have good plasmon activity in a visible-near infrared light region due to special electrical properties and controllable local plasmon resonance properties, but have certain application limitations. For example, silver nanomaterials, while possessing good electromagnetic enhancement properties, are extremely susceptible to oxidation, which can affect the stability, sensitivity and shelf life of SERS substrates; while the chemical stability of gold nano-materials is relatively good, the plasma resonance effect is relatively weak, and the SERS substrate still cannot obtain ideal detection sensitivity. In addition, most of the existing SERS substrates have the defects of low binding degree with molecules to be detected, poor signal reproducibility, incapability of recycling and the like.
Disclosure of Invention
In order to solve one of the technical defects, the embodiment of the application provides a high-sensitivity composite SERS substrate with a self-cleaning function and a preparation method thereof.
According to a first aspect of an embodiment of the present application, there is provided a high-sensitivity composite SERS substrate having a self-cleaning function, the composite SERS substrate comprising: a silicon substrate; self-cleaning layer: the device is arranged on the silicon substrate and is used for degrading adsorbed molecules to be detected under specific conditions; first noble metal layer: is arranged on the self-cleaning layer; a spacer layer: the first noble metal layer is arranged on the first noble metal layer and used for regulating and controlling particle gaps in the vertical direction; second noble metal layer: is arranged on the graphene layer.
Preferably, the self-cleaning layer is a zinc oxide layer; the first noble metal layer is a silver nanoparticle layer; the spacing layer is a graphene film layer; the second noble metal layer is a gold nanoparticle layer.
Preferably, the spacer layer is a single layer of graphene film.
Preferably, the thickness of the zinc oxide layer is 150 nm-250 nm; the thickness of the silver nanoparticle layer is 15 nm-25 nm; the thickness of the graphene film layer is 0.3 nm-0.5 nm; the thickness of the gold nano particle layer is 3 nm-8 nm.
According to a second aspect of the embodiment of the present application, there is provided a method for preparing a high-sensitivity composite SERS substrate having a self-cleaning function, the method comprising: providing a silicon substrate; preparing a zinc oxide layer on the silicon substrate by adopting a magnetron sputtering process; preparing a silver nanoparticle layer on the zinc oxide layer by adopting a magnetron sputtering process; transferring the prepared graphene film to the silver nanoparticle layer to form a graphene film layer; and preparing a gold nanoparticle layer on the graphene layer by adopting an electron beam evaporation process.
Preferably, the preparing a zinc oxide layer on the silicon substrate by using a magnetron sputtering process specifically includes: placing a silicon substrate on a plane base frame of a magnetron sputtering vacuum coating machine, and adopting a radio frequency sputtering method to coat zinc oxideSputtering out target particles and depositing the target particles on the surface of the silicon substrate to form a zinc oxide layer; vacuum pumping the cavity background of the vacuum coating machine to 8 multiplied by 10 before sputtering -6 Torr, ar for sputtering gas and reaction gas, 30sccm for flow rate, 5.28X10 for sputtering pressure -3 Torr, sputtering rate ofThe reaction time was 144min.
The preparation of the silver nanoparticle layer on the zinc oxide layer by adopting a magnetron sputtering process specifically comprises the following steps:
placing a silicon substrate with a zinc oxide film on a plane base frame of a magnetron sputtering vacuum coating machine, and sputtering silver target particles by adopting a direct current sputtering method to deposit silver nano particle layers on the surface of the zinc oxide film; vacuum pumping the cavity background of the vacuum coating machine to 8 multiplied by 10 before sputtering -6 Torr, ar for sputtering gas and reaction gas, 21sccm for flow rate, 4.36×10 for sputtering pressure -3 Torr, sputtering rate of The reaction time was 325s.
Preferably, the transferring the prepared graphene film onto the silver nanoparticle layer to form a graphene film layer specifically includes: providing a graphene substrate; the structure of the graphene substrate comprises a Cu substrate, wherein the upper surface and the lower surface of the Cu substrate are respectively provided with a graphene film; spin-coating a PMMA protective layer on the surface of one graphene film, baking at 180 ℃ for 2min to solidify the PMMA protective layer, and then adhering the PMMA protective layer on a silicon oxide substrate prepared in advance; exposing the other graphene film of the graphene substrate to oxygen plasma for 10min so as to enable the graphene film to fall off from the graphene substrate; wherein the power of the treatment equipment is 300w, and the gas flow is 300sccm; placing a graphene substrate from which a layer of graphene film has been removed together with a silicon oxide substrate to which it is attachedInto FeCl 3 In an etching solution, the Cu substrate and FeCl 3 The solution reacts chemically to etch away the Cu substrate; placing a graphene substrate with only one layer of graphene film left in an acetone solution together with a silicon oxide substrate attached to the graphene substrate, and removing the PMMA protective layer; and fishing out and transferring the graphene film suspended in the solution to the silver nanoparticle layer of the substrate by using a silicon oxide substrate to form a graphene film layer.
Preferably, the preparing a gold nanoparticle layer on the graphene layer by using an electron beam evaporation process specifically includes: fixing the substrate of the prepared graphene film layer on a sample holder for evaporation so as to form a gold nanoparticle layer on the surface of the graphene film layer; vacuum pumping the cavity background of the vapor plating equipment to 9.1×10 before vapor plating -9 Torr, evaporation rate ofThe evaporation time was 400s.
The composite SERS substrate provided by the embodiment of the application adopts a bimetal nanostructure, combines the chemical stability of the gold nanomaterial and the electromagnetic enhancement characteristic of the silver nanomaterial, integrates the advantages of the gold nanomaterial and the silver nanomaterial, and introduces graphene as a spacing layer to be arranged between two layers of noble metal materials; the graphene is used as a stable novel carbonaceous material, has excellent molecular enrichment effect, can be well combined with most molecules to be detected, and meanwhile, has a unique two-dimensional honeycomb lattice structure, can effectively regulate and control particle nano or sub-nano gaps in the vertical direction, can protect silver nano materials from being oxidized, prolong the storage time of the whole substrate, improve the stability of the whole substrate, and more importantly, can enable the noble metal/graphene/noble metal composite substrate to have multiple plasma coupling effects in multi-dimensional directions between layers and in layers, so that the Raman sensitivity of the whole substrate is obviously enhanced; moreover, the substrate can uniformly adsorb molecules to be detected by adding the graphene, so that the signal reproducibility of the whole composite substrate is improved. Meanwhile, a zinc oxide self-cleaning layer is further arranged between the noble metal/graphene/noble metal composite structure and the silicon substrate, and zinc oxide is a low-cost and wide-band-gap semiconductor material, has unique light response characteristics under visible light, has certain photocatalytic performance, is more excellent after being combined with noble metal, can degrade material molecules adsorbed by a substrate under the irradiation of certain visible light, has certain self-cleaning capability, enables the substrate to be reused, and has the advantage of recycling.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute a limitation on the application. In the drawings:
FIG. 1 shows Au/G in an embodiment of the application 1 Schematic structural diagram of Ag@ZnO composite SERS substrate;
FIG. 2 shows Au/G in an embodiment of the application 1 A process flow chart of a preparation method of the Ag@ZnO composite SERS substrate;
FIG. 3 is a chart of SERS spectra of solutions adsorbed on substrates with different graphene layers when testing SERS substrates according to embodiments of the present application;
FIG. 4 shows a ZnO substrate (a), an Ag@ZnO substrate (b), a G/Ag@ZnO substrate (c), and an Au/G when the SERS substrate in the embodiment of the application is characterized 1 SEM image of the ag@zno substrate (d);
FIG. 5 shows Au/G in an embodiment of the application 1 AFM image of Ag@ZnO composite SERS substrate;
FIG. 6 shows Au/G in an embodiment of the application 1 XRD pattern of ZnO in Ag@ZnO composite SERS substrate;
FIG. 7 shows Au/G in an embodiment of the application 1 XPS energy spectrum of the Ag@ZnO composite SERS substrate;
FIG. 8 shows Au/G in an embodiment of the application 1 SERS spectrograms of the Ag@ZnO composite SERS substrate on R6G solutions with different concentrations;
FIG. 9 is a diagram of Au/G in an embodiment of the application 1 SERS spectrogram (a) of Ag@ZnO composite SERS substrate at different sites and characteristic peak at 611cm -1 Position (b), 771cm -1 Point (c) and 1648cm -1 A corresponding RSD value at (d);
FIG. 10 shows Au/G in an embodiment of the application 1 Raman spectrum (a) of R6G adsorbed on surface of Ag@ZnO composite SERS substrate before and after ultraviolet irradiation, and R6G in Au/G 1 Raman spectrum (b) of the/ag@zno composite SERS substrate (5 wash cycles);
fig. 11 shows electric field distribution of each metal nanoparticle Ag (a), au (b), and graphene with different thickness 0nm (c), 0.5nm (d), 1.5nm (e), 3nm (f) as noble metal nano-spacer layer in the Au/G/ag@zno composite SERS substrate according to the embodiment of the present application.
In the figure: 10-silicon substrate, 20-self-cleaning layer, 30-first noble metal layer, 40-spacer layer, 50-second noble metal layer.
Detailed Description
In order to make the technical solutions and advantages of the embodiments of the present application more apparent, the following detailed description of exemplary embodiments of the present application is provided in conjunction with the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present application and not exhaustive of all embodiments. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
The embodiment of the application provides a high-sensitivity composite SERS substrate with a self-cleaning function, as shown in fig. 1, which comprises the following components:
a silicon substrate 10.
Self-cleaning layer 20: is disposed on the silicon substrate 10, and is used for degrading adsorbed molecules to be detected under specific conditions.
First noble metal layer 30: is provided on the self-cleaning layer 20.
Spacer layer 40: is disposed on the first noble metal layer 30 for controlling the particle gap in the vertical direction.
Second noble metal layer 50: is disposed on the graphene layer 40.
Further: the self-cleaning layer 20 may be a zinc oxide layer; the first noble metal layer 30 may be a silver nanoparticle layer; the spacer layer 40 may be a graphene thin film layer; the second noble metal layer 50 may be a gold nanoparticle layer.
The composite SERS substrate provided by the embodiment of the application adopts a bimetal nanostructure, combines the chemical stability of the gold nanomaterial and the electromagnetic enhancement characteristic of the silver nanomaterial, integrates the advantages of the gold nanomaterial and the silver nanomaterial, and introduces graphene as a spacing layer to be arranged between two layers of noble metal materials; the graphene is used as a stable novel carbonaceous material, has excellent molecular enrichment effect, can be well combined with most molecules to be detected, and meanwhile, has a unique two-dimensional honeycomb lattice structure, can effectively regulate and control particle nano or sub-nano gaps in the vertical direction, can protect silver nano materials from being oxidized, prolong the storage time of the whole substrate, improve the stability of the whole substrate, and more importantly, can enable the noble metal/graphene/noble metal composite substrate to have multiple plasma coupling effects in multi-dimensional directions between layers and in layers, so that the Raman sensitivity of the whole substrate is obviously enhanced; moreover, the substrate can uniformly adsorb molecules to be detected by adding the graphene, so that the signal reproducibility of the whole composite substrate is improved. Meanwhile, a zinc oxide self-cleaning layer is further arranged between the noble metal/graphene/noble metal composite structure and the silicon substrate, and zinc oxide is a semiconductor material with low cost and wide band gap, has certain photocatalytic performance, is more excellent after being combined with noble metal, can degrade material molecules adsorbed by the substrate under the irradiation of certain ultraviolet and visible light, has certain self-cleaning capability, enables the substrate to be reused, and has the advantage of recycling.
Still further, the spacer layer 40 may be a single layer of graphene film. The unique nanometer thickness of the single-layer graphene film enables the single-layer graphene film to have optimal regulation and control performance, and related verification please see the subsequent performance test part in detail.
Further, the thickness of the zinc oxide layer is 150 nm-250 nm; the thickness of the silver nanoparticle layer is 15 nm-25 nm; the thickness of the graphene film layer is 0.3 nm-0.5 nm; the thickness of the gold nano particle layer is 3 nm-8 nm. The dimensions are optimal dimensions that provide the overall composite substrate with optimal performance, as discussed in detail in the performance test section that follows.
Correspondingly, the embodiment of the application also provides a preparation method of the high-sensitivity composite SERS substrate with the self-cleaning function, which comprises the following steps:
a silicon substrate 10 is provided as shown in fig. 2 (a).
Preparing a zinc oxide layer on the silicon substrate 10 by using a magnetron sputtering process, as shown in fig. 2 (b);
preparing a silver nanoparticle layer on the zinc oxide layer by using a magnetron sputtering process, as shown in fig. 2 (c);
transferring the prepared graphene film onto the silver nanoparticle layer to form a graphene film layer, as shown in fig. 2 (d);
a gold nanoparticle layer was prepared on the graphene layer using an electron beam evaporation process, as shown in fig. 2 (e).
Further, the providing a silicon substrate 10 specifically includes:
using a silicon wafer as a supporting material, placing the silicon wafer into acetone, ultrasonically cleaning for 10-15 min, cleaning with deionized water after cleaning is finished, removing the silicon wafer, immersing the silicon wafer in absolute ethyl alcohol for 8-10 min, and finally placing the silicon wafer into a drying box for drying.
Further, the preparation of the zinc oxide layer on the silicon substrate 10 by using the magnetron sputtering process specifically includes:
placing a silicon substrate 10 on a plane base frame of a magnetron sputtering vacuum coating machine, and sputtering zinc oxide target particles by adopting a radio frequency sputtering method to deposit the zinc oxide target particles on the surface of the silicon substrate 10 to form a zinc oxide layer;
vacuum pumping the cavity background of the vacuum coating machine to 8 multiplied by 10 before sputtering -6 Torr, ar for sputtering gas and reaction gas, 30sccm for flow rate, 5.28X10 for sputtering pressure -3 Torr, sputtering rate ofThe reaction time was 144min.
Further, the preparation of the silver nanoparticle layer on the zinc oxide layer by using a magnetron sputtering process specifically comprises the following steps:
placing a silicon substrate 10 with a zinc oxide film on a plane base frame of a magnetron sputtering vacuum coating machine, and sputtering silver target particles by adopting a direct current sputtering method to deposit silver nano particle layers on the surface of the zinc oxide film;
vacuum pumping the cavity background of the vacuum coating machine to 8 multiplied by 10 before sputtering -6 Torr, ar for sputtering gas and reaction gas, 21sccm for flow rate, 4.36×10 for sputtering pressure -3 Torr, sputtering rate ofThe reaction time was 325s.
Further, transferring the prepared graphene film onto the silver nanoparticle layer to form a graphene film layer, which specifically includes:
providing a graphene substrate; the structure of the graphene substrate comprises a Cu substrate, wherein the upper surface and the lower surface of the Cu substrate are respectively provided with a graphene film;
spin-coating a PMMA protective layer on the surface of one graphene film, baking at 180 ℃ for 2min to solidify the PMMA protective layer, and then adhering the PMMA protective layer on a silicon oxide substrate prepared in advance;
exposing the other graphene film of the graphene substrate to oxygen plasma for 10min so as to enable the graphene film to fall off from the graphene substrate; wherein the power of the treatment equipment is 300w, and the gas flow is 300sccm;
placing a graphene substrate from which a layer of graphene film has been removed and a silicon oxide substrate to which the graphene substrate is attached into FeCl 3 In an etching solution, the Cu substrate and FeCl 3 The solution reacts chemically to etch away the Cu substrate;
placing a graphene substrate with only one layer of graphene film left in an acetone solution together with a silicon oxide substrate attached to the graphene substrate, and removing the PMMA protective layer;
and fishing out and transferring the graphene film suspended in the solution to the silver nanoparticle layer of the substrate by using a silicon oxide substrate to form a graphene film layer.
Further, the preparation of the gold nanoparticle layer on the graphene layer by using an electron beam evaporation process specifically comprises the following steps:
fixing the substrate of the prepared graphene film layer on a sample holder for evaporation so as to form a gold nanoparticle layer on the surface of the graphene film layer;
vacuum pumping the cavity background of the vapor plating equipment to 9.1×10 before vapor plating -9 Torr, evaporation rate of The evaporation time was 400s.
The preparation process in the embodiment of the application has the advantages of lower cost, stronger compatibility and easy integration, not only can realize batch preparation, but also can provide a certain research and reference value for the research of SERS active substrates.
The structure and the size of the embodiment of the application are that the inventor experiences numerous times of failures, and continuously performs new attempts on the basis of the failures again, continuously performs optimization, and finally determines the specific structure and the size of each functional layer by means of some fortune so that the specific structure and the size of each functional layer reach an optimal combination, and further the scheme of the application is obtained.
The corresponding performance of the composite SERS substrate in the embodiments of the present application will be tested as follows.
The composite structure with no graphene, single-layer graphene, few-layer graphene and multi-layer graphene as a spacer layer is respectively marked as Au/Ag@ZnO and Au/G 1 /Ag@ZnO、Au/G 2 Ag@ZnO and Au/G 3 Ag@ZnO. To explore the precious metal nano-component and graphene layer number pair baseThe concentration of 10 is selected in the embodiment of the application due to the influence of the bottom SERS performance -9 mol/L R6G solution is used for preparing Ag@ZnO, au/Ag@ZnO and G 1 /Ag@ZnO、G 2 /Ag@ZnO、G 3 /Ag@ZnO、Au/G 1 /Ag@ZnO、Au/G 2 Ag@ZnO and Au/G 3 Raman testing was performed on the/ag@zno composite SERS substrate. As shown in FIG. 3, the Raman characteristic peaks of R6G can be detected by various substrates, and the Raman characteristic peaks of the R6G probe molecules are clearly visible and are respectively positioned at 611, 771, 1184, 1310, 1360, 1507, 1574 and 1648cm -1 Where it is located. Notably, au/G 1 The Raman characteristic peak intensity of R6G on the Ag@ZnO substrate is highest, and compared with Ag@ZnO and G 1 /Ag@ZnO、G 2 Ag@ZnO and G 3 The Ag@ZnO SERS substrate can obviously observe that the single-layer graphene has obvious enhancement effect on the Raman signal of the substrate, so that Au/G is used below 1 The Ag@ZnO substrate was subjected to SERS and other performance tests.
First, for Au/G in the embodiment of the present application 1 Characterization of the Ag@ZnO composite SERS substrate:
(1) The morphology of the samples was characterized using a scanning electron microscope (FE-SEM, zeiss Supra 55 VP), as shown in particular in fig. 4.
(2) The surface topography of the sample was measured using an Atomic Force Microscope (AFM). The gold nano layer after thermal evaporation has uniform and flat surface structure, and the surface roughness is only less than 3nm, which proves that the gold nano layer is successfully constructed on the surface of graphene, and is shown in fig. 5.
(3) The zinc oxide crystal structure was characterized by X-ray diffraction (XRD, siemens D800) (Cu ka source, λ=0.154 nm, scan rate: 2 (°) min -1 Operating voltage: 40kV, working current: 40 mA). Fig. 6 is an XRD pattern of ZnO, and the characteristic peak shown at 2θ= 34.27 ° is a diffraction peak of a typical ZnO film.
(4) The chemical composition of the substrate was analyzed by X-ray photoelectron spectroscopy (XPS, thermo esclab 250 Xi). Coexistence of five elements C, O, ag, au and Zn was observed on the XPS full spectrum curve, as shown in fig. 7.
Then, in the embodiment of the applicationAu/G of (2) 1 Performance test is carried out on the Ag@ZnO composite SERS substrate:
(1) Sensitivity test
At room temperature, 0.144G of R6G powder (molecular weight is 479.01G/mol) is measured, dissolved in 30mL of deionized water, magnetically stirred for 10 minutes at 1600R/min, and prepared to obtain the powder with the concentration of 10 -2 The mol/L R6G solution is diluted to obtain a series of concentration gradient R6G solutions (10 -8 -10 -14 mol/L)。
2mL of R6G solution with specific concentration is dripped on the surface of the prepared substrate, the substrate is dried in a dark place at room temperature, and the Raman spectrum of R6G under different concentrations is measured by using a laser micro-confocal Raman spectrometer (an excitation light source with 532nm, irradiation time of 10s, laser energy of 1mW and an objective lens magnification of 100 times).
The characteristic peak Raman intensity of R6G decreases with the decrease of the concentration of the solution, and the concentration of the solution decreases to 10 -14 At mol/L, the Raman characteristic peak of R6G can not be detected, but at a concentration of 10 -13 The weak characteristic peak can be seen in the R6G solution with mol/L, which proves that the composite substrate has ultra-sensitive detection limit as low as 10 -13 mol/L. The raman spectral detection is shown in fig. 8.
(2) Signal reproducibility test
At room temperature, 2mL of the solution was taken to have a concentration of 10 -11 The mol/L R6G solution is dripped on the surface of the prepared substrate, 20 different sites are randomly selected on the surface of the substrate for Raman spectrum detection after the substrate is dried, and the Raman spectrum detection is particularly shown in figure 9.
From the figure, the SERS spectra of the 20 test points are substantially uniform. Calculation of Raman intensity at 611cm -1 、771cm -1 And 1648cm -1 The Relative Standard Deviation (RSD) values of the three characteristic peaks are 13.7%, 11.4% and 12.1%, respectively, and the relative standard deviation of the three characteristic peaks is less than 15%, which indicates that the composite substrate has good spectral reproducibility (signal reproducibility) for SERS detection.
(3) Photocatalytic degradation test
Soaking the substrate at room temperature at a concentration of 10 -6 In a mol/L R6G solution for 20min to ensure that adsorption equilibrium is reached, thenThe substrate was removed and dried for raman spectroscopy. And then, immersing the tested substrate in deionized water, placing a xenon lamp above the substrate for photocatalytic degradation, taking out the irradiated part of the substrate every 30min, washing the substrate with deionized water, drying the substrate at room temperature, and carrying out Raman test. After 30min of irradiation, the raman signal of R6G was significantly reduced. The irradiation time was further prolonged, and when 120min was reached, the raman signal of R6G was almost absent, which means that it was thoroughly degraded under uv-vis irradiation, as shown in fig. 10 (a).
(4) Self-cleaning performance test
Soaking the substrate at room temperature at a concentration of 10 -6 The molar/L R6G solution was allowed to stand for 20 minutes to ensure that adsorption equilibrium was reached, and then the substrate was removed and dried for Raman spectroscopy. Then, the tested substrate is soaked in deionized water, a xenon lamp is placed above the substrate for photocatalysis self-cleaning, the substrate is thoroughly rinsed with the deionized water after 120min, and the substrate is dried at room temperature and then repeatedly used for Raman testing, and the self-cleaning SERS detection period is adopted. After five continuous self-cleaning experiments, the SERS substrate still maintains good SERS performance, and the R6G Raman signal is not obviously attenuated. The results show that the SERS substrate has good self-cleaning properties, as shown in fig. 10 (b).
Finally, performing time domain finite difference (FDTD) simulation on the Au/G/Ag@ZnO composite SERS substrate in the embodiment of the application to explore electromagnetic enhancement effects excited by different noble metal materials and influence of different graphene thicknesses on electromagnetic enhancement:
(1) Electromagnetic enhancement effect excited by different noble metal materials
And establishing a corresponding geometric model according to an SEM image, wherein a silver nano layer is arranged at the bottom layer, the particle size is 24nm, the inter-particle distance is 5nm, graphenes with different thicknesses are paved above the silver nano layer to serve as nano spacing layers, and finally, a gold nano layer is arranged at the top layer, the particle size is 5nm, and the inter-particle distance is 2nm. Fig. 11 (a) shows the electric field distribution of Ag nanoparticles, and it is understood that the electric field is excited only around Ag nanoparticles and at the particle gaps, and the electric field excited at the particle gaps is strongest. Fig. 11 (b) shows the distribution of the electric field of the Au nanoparticles, and the electric field is greatly enhanced around the Au nanoparticles and at the gaps, and the electromagnetic enhancement is mainly generated near the noble metal nanoparticles and at the gaps of the nanoparticles as proved by the FDTD theoretical simulation.
(2) Influence of different graphene thickness on electromagnetic enhancement
The sizes and the distances of the noble metal Ag and Au nanoparticles are not changed, and the thicknesses of the graphene are respectively 0nm, 0.5nm, 1.5nm and 3nm, so that simulation is carried out to explore the influence condition of the graphene as a nano spacer layer on the multiple electric field coupling of the composite structure. Fig. 11 (c-f) are electric field distribution diagrams of different graphene thicknesses, respectively, and it can be seen that there is an obvious longitudinal electric field coupling condition between the gold nano layer and the silver nano layer in the composite structure with the graphene thicknesses of 0nm and 0.5nm, and it can be found that the graphene (single-layer graphene) with the thickness of 0.5nm is more intense, the hot spot area is relatively more, and along with the thickening of the graphene, the multiple electric field coupling condition between the two metal layers is not observed in the two diagrams of fig. 11 (e and f). Simulation results further prove that the graphene component is used as a noble metal nano spacer layer, a good noble metal resonance coupling effect is provided for the substrate, and the nano thickness special for single-layer graphene is the most beneficial space required by the noble metal resonance coupling.
The high-sensitivity composite SERS substrate with the self-cleaning function prepared by the embodiment of the application has the advantages that the graphene chemical enhancement and metal particle electromagnetic enhancement synergistic mechanism is beneficial to further improving the SERS detection sensitivity, and the Raman signal detection sensitivity is effectively enhanced; the noble metal nano material with electromagnetic enhancement characteristic is combined with the photocatalytic semiconductor, and the SERS substrate with high sensitivity, high biocompatibility and recyclability is prepared by utilizing the synergistic effect of the noble metal nano material and the photocatalytic semiconductor, so that the problems of low detection sensitivity, poor reproducibility and poor recyclability at present are solved, and the SERS substrate has outstanding substantive characteristics and remarkable progress.
In the description of the present application, it should be understood that the orientation or positional relationship indicated by the terms "thickness", "upper", etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element in question must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present application.
In the present application, unless explicitly stated and limited otherwise, the terms "disposed," "having," and the like are to be construed broadly, and may be fixedly connected, detachably connected, or integrally formed, for example; may be mechanically connected, may be electrically connected or may communicate with each other; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. A high-sensitivity composite SERS substrate with a self-cleaning function is characterized in that: comprising the following steps:
a silicon substrate (10);
self-cleaning layer (20): the device is arranged on the silicon substrate (10) and is used for degrading adsorbed molecules to be detected under specific conditions;
first noble metal layer (30): is arranged on the self-cleaning layer (20);
spacer layer (40): the first noble metal layer (30) is arranged on the first noble metal layer and used for regulating and controlling particle gaps in the vertical direction;
second noble metal layer (50): is disposed on the graphene layer (40).
2. The high sensitivity composite SERS substrate having a self-cleaning function according to claim 1, wherein:
the self-cleaning layer (20) is a zinc oxide layer;
the first noble metal layer (30) is a silver nanoparticle layer;
the spacing layer (40) is a graphene film layer;
the second noble metal layer (50) is a gold nanoparticle layer.
3. The high sensitivity composite SERS substrate having a self-cleaning function according to claim 2, wherein: the spacer layer (40) is a single layer of graphene film.
4. A high sensitivity composite SERS substrate having a self cleaning function according to claim 3, wherein:
the thickness of the zinc oxide layer is 150 nm-250 nm;
the thickness of the silver nanoparticle layer is 15 nm-25 nm;
the thickness of the graphene film layer is 0.3 nm-0.5 nm;
the thickness of the gold nano particle layer is 3 nm-8 nm.
5. A method for preparing a high-sensitivity composite SERS substrate having a self-cleaning function as claimed in claim 2, wherein: comprising the following steps:
providing a silicon substrate (10);
preparing a zinc oxide layer on the silicon substrate (10) by adopting a magnetron sputtering process;
preparing a silver nanoparticle layer on the zinc oxide layer by adopting a magnetron sputtering process;
transferring the prepared graphene film to the silver nanoparticle layer to form a graphene film layer;
and preparing a gold nanoparticle layer on the graphene layer by adopting an electron beam evaporation process.
6. The method for preparing the high-sensitivity composite SERS substrate with the self-cleaning function according to claim 5, wherein the method is characterized by comprising the following steps: the preparation of the zinc oxide layer on the silicon substrate (10) by the magnetron sputtering technology specifically comprises the following steps:
placing a silicon substrate (10) on a plane base frame of a magnetron sputtering vacuum coating machine, and sputtering zinc oxide target particles by adopting a radio frequency sputtering method to deposit the zinc oxide target particles on the surface of the silicon substrate (10) to form a zinc oxide layer;
vacuum pumping the cavity background of the vacuum coating machine to 8 multiplied by 10 before sputtering -6 Torr, ar for sputtering gas and reaction gas, 30sccm for flow rate, 5.28X10 for sputtering pressure -3 Torr, sputtering rate ofReaction time was 144min.
7. The method for preparing the high-sensitivity composite SERS substrate with the self-cleaning function according to claim 5, wherein the method is characterized by comprising the following steps: the preparation of the silver nanoparticle layer on the zinc oxide layer by adopting a magnetron sputtering process specifically comprises the following steps:
placing a silicon substrate (10) with a zinc oxide film on a plane base frame of a magnetron sputtering vacuum coating machine, and sputtering silver target particles by adopting a direct current sputtering method to deposit silver target particles on the surface of the zinc oxide film to form a silver nanoparticle layer;
vacuum pumping the cavity background of the vacuum coating machine to 8 multiplied by 10 before sputtering -6 Torr, ar for sputtering gas and reaction gas, 21sccm for flow rate, 4.36×10 for sputtering pressure -3 Torr, sputtering rate ofReaction time was 325s.
8. The method for preparing the high-sensitivity composite SERS substrate with the self-cleaning function according to claim 5, wherein the method is characterized by comprising the following steps: transferring the prepared graphene film onto the silver nanoparticle layer to form a graphene film layer, wherein the method specifically comprises the following steps of:
providing a graphene substrate; the structure of the graphene substrate comprises a Cu substrate, wherein the upper surface and the lower surface of the Cu substrate are respectively provided with a graphene film;
spin-coating a PMMA protective layer on the surface of one graphene film, baking at 180 ℃ for 2min to solidify the PMMA protective layer, and then adhering the PMMA protective layer on a silicon oxide substrate prepared in advance;
exposing the other graphene film of the graphene substrate to oxygen plasma for 10min so as to enable the graphene film to fall off from the graphene substrate; wherein the power of the treatment equipment is 300w, and the gas flow is 300sccm;
placing a graphene substrate from which a layer of graphene film has been removed and a silicon oxide substrate to which the graphene substrate is attached into FeCl 3 In an etching solution, the Cu substrate and FeCl 3 The solution reacts chemically to etch away the Cu substrate;
placing a graphene substrate with only one layer of graphene film left in an acetone solution together with a silicon oxide substrate attached to the graphene substrate, and removing the PMMA protective layer;
and fishing out and transferring the graphene film suspended in the solution to the silver nanoparticle layer of the substrate by using a silicon oxide substrate to form a graphene film layer.
9. The method for preparing the high-sensitivity composite SERS substrate with the self-cleaning function according to claim 5, wherein the method is characterized by comprising the following steps: the preparation of the gold nanoparticle layer on the graphene layer by using an electron beam evaporation process specifically comprises the following steps:
fixing the substrate of the prepared graphene film layer on a sample holder for evaporation so as to form a gold nanoparticle layer on the surface of the graphene film layer;
vacuum pumping the cavity background of the vapor plating equipment to 9.1×10 before vapor plating -9 Torr, evaporation rate of And/s, the evaporation time is 400s.
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