WO2020155751A1 - 一种基于二维材料的拉曼增强基底及其制备方法和应用 - Google Patents

一种基于二维材料的拉曼增强基底及其制备方法和应用 Download PDF

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WO2020155751A1
WO2020155751A1 PCT/CN2019/117266 CN2019117266W WO2020155751A1 WO 2020155751 A1 WO2020155751 A1 WO 2020155751A1 CN 2019117266 W CN2019117266 W CN 2019117266W WO 2020155751 A1 WO2020155751 A1 WO 2020155751A1
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substrate
dimensional material
raman
dimensional
material layer
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French (fr)
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张文静
宋秀菊
曼尼什·乔瓦拉
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Shenzhen University
Rutgers State University of New Jersey
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Rutgers State University of New Jersey
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/28—Deposition of only one other non-metal element
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • 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

Definitions

  • the present invention claims the priority of the prior application of the application number 201910078937.3 with the title of "a Raman reinforced substrate based on two-dimensional material and its preparation method and application” filed on January 28, 2019, and the content of the foregoing prior application Incorporated into this text by way of introduction.
  • the invention relates to the field of detection technology, in particular to a Raman enhanced substrate based on a two-dimensional material, and a preparation method and application thereof.
  • SERS Surface enhanced Raman Scattering
  • the present invention provides a Raman-enhanced substrate based on a two-dimensional material, in which the resonance of the Raman signal is realized through charge transfer between the two-dimensional material layer provided on the substrate and the molecules of the substance to be detected. Enhancement; the two-dimensional material is directly combined with the substrate, eliminating the use of precious metal layers, reducing preparation costs, reducing process flow, conducive to large-scale production, and avoiding the problem of signal complexity caused by intermolecular reactions with the substance to be detected, making The detection has good repeatability and high stability, and has broad application prospects in surface enhanced Raman spectroscopy technology.
  • the present invention provides a Raman-enhanced substrate based on a two-dimensional material, including a substrate and a two-dimensional material layer disposed on the substrate.
  • the material of the two-dimensional material layer includes graphene, black phosphorus, and At least one of transition metal chalcogenides.
  • the two-dimensional material layer may be a single-layer structure obtained by a single preparation process, or may be a multi-layer structure obtained by multiple preparation processes, which is not limited.
  • the transition metal chalcogenide compound includes titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, technetium, rhenium, cobalt, rhodium, iridium, nickel, palladium, platinum corresponding sulfides and selenides , At least one of tellurides.
  • the transition metal chalcogenide compound includes titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, technetium, rhenium, cobalt, rhodium, iridium, nickel, palladium and/or platinum corresponding sulfides and selenides And/or telluride.
  • the sulfides corresponding to titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, technetium, rhenium, cobalt, rhodium, iridium, nickel, palladium, and platinum may be titanium disulfide, zirconium disulfide, At least one of hafnium disulfide, vanadium sulfide, niobium disulfide, tantalum disulfide, molybdenum disulfide, tungsten disulfide, technetium disulfide, rhenium disulfide, cobalt disulfide, rhodium sulfide, iridium disulfide, and nickel disulfide .
  • the transition metal chalcogenide compound includes at least one of niobium disulfide and 1T-phase molybdenum disulfide.
  • the thickness of the two-dimensional material layer is 0.5 nm-500 nm. Further, the thickness of the two-dimensional material layer is 1 nm-450 nm. Furthermore, the thickness of the two-dimensional material layer is 10 nm-400 nm. Specifically, the thickness of the two-dimensional material layer may be, but not limited to, 100 nm, 150 nm, 220 nm, 330 nm, or 370 nm.
  • the two-dimensional material layer completely or partially covers the substrate.
  • the two-dimensional material layer is composed of one or more sub-two-dimensional material layers.
  • the two sub-two-dimensional material layers are arranged on the substrate at intervals.
  • a plurality of the sub-two-dimensional material layers may be, but not limited to, arranged on the substrate at even intervals or randomly arranged on the substrate.
  • the Raman-enhanced substrate based on two-dimensional materials is used to detect substances in the visible light region of the resonance laser.
  • the wavelength range of the visible light region is within 380nm-780nm.
  • the substrate and the two-dimensional material layer are combined by at least one of intermolecular force, covalent bond and ionic bond.
  • the material of the substrate includes at least one of silicon wafer, quartz, conductive glass, and sapphire.
  • the silicon wafer has a silicon oxide layer.
  • the thickness of the silicon oxide layer is 90 nm-300 nm.
  • Raman-enhanced substrates all have a precious metal layer (such as gold and silver), and precious metal nanoparticles form an electric field on the surface of the substrate to enhance the Raman cross-sectional area, thereby achieving the effect of enhancing Raman signals; however, precious metal nano-particles can As a catalyst for many redox reactions, when the molecule of the substance to be detected is in contact with it, the molecule of the substance to be detected may undergo reactions such as distortion, carbonization, optical drift, plasma catalysis, etc., which will complicate the Raman signal, which is not conducive to substance Detection, high preparation cost and complicated process.
  • precious metal layer such as gold and silver
  • the two-dimensional material is directly combined with the substrate to prepare a Raman-enhanced substrate based on the two-dimensional material.
  • the charge transfer between the two-dimensional material layer and the molecules of the substance to be detected enhances the detection signal, thereby reducing
  • the use of precious metal layer has good repeatability, high stability and short detection time.
  • the present invention provides a method for preparing a Raman reinforced substrate based on a two-dimensional material, including:
  • a substrate is provided, and a two-dimensional material layer is formed on the substrate to obtain a Raman enhanced substrate based on the two-dimensional material.
  • the material of the two-dimensional material layer includes at least one of graphene, black phosphorus, and transition metal chalcogenidekind.
  • the specific operation of forming a two-dimensional material layer on the substrate is: forming a two-dimensional material layer on the substrate using a chemical vapor deposition method or a chemical peeling method, or forming a two-dimensional material layer on an auxiliary substrate After peeling and transferring, the two-dimensional material layer is separated from the auxiliary substrate and combined with the substrate.
  • the two-dimensional material can be grown directly on the substrate, or the auxiliary substrate can be used for growth and then transferred to the substrate, which can be selected according to the properties of the two-dimensional material, which is not limited.
  • the transition metal chalcogenide compound includes titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, technetium, rhenium, cobalt, rhodium, iridium, nickel, palladium, platinum corresponding sulfides and selenides , At least one of tellurides. Further, the transition metal chalcogenide compound includes at least one of niobium disulfide and 1T-phase molybdenum disulfide.
  • the thickness of the two-dimensional material layer is 0.5 nm-500 nm. Further, the thickness of the two-dimensional material layer is 1 nm-450 nm. Furthermore, the thickness of the two-dimensional material layer is 10 nm-400 nm. Specifically, the thickness of the two-dimensional material layer may be, but not limited to, 100 nm, 150 nm, 220 nm, 330 nm, or 370 nm.
  • the two-dimensional material layer completely or partially covers the substrate.
  • the two-dimensional material layer is composed of one or more sub-two-dimensional material layers.
  • the two sub-two-dimensional material layers are arranged on the substrate at intervals.
  • a plurality of the sub-two-dimensional material layers may be, but not limited to, arranged on the substrate at even intervals or randomly arranged on the substrate.
  • the Raman-enhanced substrate based on two-dimensional materials is used to detect substances in the visible light region of the resonance laser.
  • the substrate and the two-dimensional material layer are combined by at least one of intermolecular force, covalent bond and ionic bond.
  • the material of the substrate includes at least one of silicon wafer, quartz, conductive glass, and sapphire.
  • the silicon wafer has a silicon oxide layer.
  • the thickness of the silicon oxide layer is 90 nm-300 nm.
  • the peeling includes at least one of chemical peeling, mechanical peeling, and liquid phase peeling.
  • the preparation method may be but not limited to:
  • the niobium metal powder is placed in a quartz tube and oxidized after the temperature is raised to obtain partially oxidized niobium oxide powder. Take the partially oxidized niobium oxide powder and sodium chloride, mix and stir evenly, spread it flat in an alumina boat, place the cleaned substrate on top of the powder, and place the alumina boat in a high-temperature tube furnace. The temperature of the reaction chamber is 800°C-850°C. Place the sulfur powder in an alumina boat.
  • a hydrogen/argon mixture of 100 sccm-220 sccm (in which the hydrogen content is 10%) is passed into the reaction chamber, the furnace body is heated to the temperature of the reaction chamber, and the reaction chamber temperature is maintained for 13-20 minutes to grow two-dimensional niobium disulfide. Then turn off the heating power and cool to room temperature naturally. After the sample is taken out and cleaned, a Raman enhanced substrate with two-dimensional niobium disulfide material can be obtained.
  • the preparation method may be but not limited to:
  • the n-butyllithium solution was added to the molybdenum disulfide powder, and the reaction was refluxed in an argon atmosphere, followed by cleaning. Disperse the reacted mixture in water, perform ultrasonic and centrifugal treatment to remove lithium ions and molybdenum disulfide that has not been stripped. Disperse the 1T-phase molybdenum disulfide in water after centrifugation, and then filter the 1T-phase molybdenum disulfide solution with filter paper so that the 1T-phase molybdenum disulfide adheres to the filter paper.
  • the filter paper with 1T phase molybdenum disulfide attached to the substrate is laminated and pressed, and then the filter membrane is removed with acetone to obtain a Raman reinforced substrate with 1T phase molybdenum disulfide two-dimensional material.
  • the preparation method may be but not limited to:
  • the graphene layer and the auxiliary substrate are peeled off by a peeling technique, and the graphene layer is combined with the substrate, and after cleaning, a Raman enhanced substrate with a two-dimensional graphene material is obtained.
  • peeling the graphene layer from the auxiliary substrate by using a peeling technique, and combining the graphene layer with the substrate may be, but not limited to:
  • the second aspect of the present invention provides a method for preparing a Raman reinforced substrate based on a two-dimensional material.
  • the preparation method is relatively simple, the process flow is short, the controllability is strong, the preparation cost is low, and large-scale production is possible.
  • the present invention provides the application of the Raman-enhanced substrate based on the two-dimensional material as described in the first aspect in detecting substances in the visible light region of resonance laser.
  • the Raman-enhanced substrate based on two-dimensional materials provided by the present invention can perform qualitative and/or quantitative detection of substances in the visible light region by resonance laser; qualitative detection can be judged based on the characteristic peaks of the substance to be detected; quantitative detection can be detected first Standard substances of substances are prepared at different concentrations for inspection, and a standard curve is made for inspection.
  • the Raman enhanced substrate based on two-dimensional materials is used to detect anthocyanins. Specifically, it can be used but not limited to the detection of red wine quality and classification.
  • the invention provides a Raman enhanced substrate based on a two-dimensional material.
  • the two-dimensional material layer can be directly combined with the substrate, and the resonance enhancement of the Raman signal is realized through the charge transfer between the two-dimensional material layer and the substance molecules to be detected.
  • the preparation method is relatively simple and the process flow is short. The controllability is strong, the preparation cost is low, and it can be mass-produced, which is beneficial to its application in detecting substances in the visible light region of resonance laser.
  • Figure 1 is an optical microscope image of a Raman-enhanced substrate based on a two-dimensional material prepared in Example 1 of the present invention, in which Figure 1 (a) is an optical microscope image of a Raman-enhanced substrate based on a two-dimensional material, in Figure 1 (b) is an optical microscope image of a niobium disulfide layer on a Raman-enhanced substrate based on two-dimensional materials;
  • Example 2 is an optical microscope image of a Raman enhanced substrate based on two-dimensional materials prepared in Example 2 of the present invention
  • Example 3 is an optical microscope image of a Raman-enhanced substrate based on a two-dimensional material prepared in Example 4 of the present invention
  • Fig. 4 is a surface enhanced Raman spectrum diagram of the effect embodiment 1 of the present invention.
  • Fig. 5 is a graph showing the results of high performance liquid chromatography in Example 1 of the effect of the present invention.
  • Fig. 6 is a surface enhanced Raman spectrogram in Example 2 of the effect of the present invention.
  • Fig. 7 is a surface-enhanced Raman spectrum diagram in a comparative example of the present invention.
  • a method for preparing a Raman reinforced substrate based on a two-dimensional material includes:
  • Step 1 Place the silicon wafers in acetone and isopropanol in order for ultrasonic cleaning for 15 minutes, and dry them with argon.
  • Step 3 Take 0.7g of NbOx powder and 0.15g of sodium chloride, mix and stir evenly, spread it flat in an alumina boat, place the cleaned silicon wafer 1cm above the powder, and place the alumina boat on a 1-inch high-temperature tube In the furnace, the temperature of the reaction chamber is 800°C. Place 1g of sulfur powder in an alumina boat, 15cm away from NbOx, at a temperature of 200°C.
  • Step 4 Inject a mixture of 140 sccm hydrogen and argon gas (where the hydrogen content is 10%) into the reaction chamber, and perform a scrubbing process for 15 minutes so as to exhaust the air in the quartz tube.
  • the furnace body was set to rise to the temperature of the reaction chamber within 16 minutes, and the two-dimensional niobium disulfide was grown at the temperature of the reaction chamber for 13 minutes. Then turn off the heating power and cool to room temperature naturally. Take out the sample and clean the surface layer of sodium chloride with deionized water, and dry it with argon to obtain a Raman-enhanced substrate based on two-dimensional materials. The obtained Raman-enhanced substrate based on two-dimensional materials was inspected by optical microscope.
  • FIG. 1 The dark triangular area in Figure 1 (a) is the deposited niobium disulfide layer, and the light-colored area is silicon
  • the niobium disulfide layer on the Raman-enhanced substrate based on the two-dimensional material covers a part of the silicon wafer; in Figure 1 (b), the niobium disulfide completely covers the silicon wafer.
  • a method for preparing a Raman reinforced substrate based on a two-dimensional material includes:
  • Step 1 Put the copper foil in the polishing liquid (75% phosphoric acid, 25% ethylene glycol), set the polishing voltage to 2V, electrochemically polish for 30 minutes, take out the copper foil and rinse the polishing liquid with deionized water, argon gas Blow dry.
  • Step 2 Put the copper foil in a 1-inch quartz tube and set the temperature of the reaction chamber to 1020°C. Pass a mixture of hydrogen and argon at 200sccm (with a hydrogen content of 10%) into the reaction chamber for 30 minutes, then adjust the gas flow to a mixture of hydrogen and argon at 30sccm (with a hydrogen content of 10%), and Start the reaction program to increase the temperature.
  • 10 sccm methane gas is introduced to grow graphene, and the growth time is 10 minutes. After the graphene growth is over, turn off the methane and heating program, keep a 20cccm hydrogen and argon mixed gas, and cool to room temperature to take out the sample.
  • Step 3 Suspend a 300nm PMMA film on the graphene layer and suspend it in a 1mol/L ammonium persulfate solution.
  • the copper foil reacts with the ammonium persulfate solution to dissolve, and the PMMA film is picked up with a silicon wafer and deionized Rinse three times in water, pick up with clean silicon wafers, and dry naturally. Place it in acetone for 2 hours to remove the PMMA film on the surface of the graphene to obtain a Raman enhanced substrate based on two-dimensional materials.
  • the obtained Raman-enhanced substrate based on two-dimensional materials was inspected by an optical microscope, and the result is shown in FIG. 2.
  • the graphene layer on the two-dimensional material-based Raman enhanced substrate covers a part of the silicon wafer.
  • a method for preparing a Raman reinforced substrate based on a two-dimensional material includes:
  • Step 1 Add 3 ml of n-butyl lithium solution (1.6 mol/L) to 0.3 g of MoS 2 solid powder, and reflux for 48 hours in an argon atmosphere. The reaction mixture was filtered, and the excess n-butyl lithium and other organic matters were washed away with n-hexane.
  • Step 2 Disperse the processed mixture in water (concentration of 1.5 mg/mL), sonicate for 1 h, and then centrifuge at 10000 r/min to remove lithium ions and molybdenum sulfide that has not been stripped.
  • the centrifugated 1T phase molybdenum disulfide is dispersed in water, and then the 1T phase molybdenum disulfide solution is suction filtered with filter paper so that the 1T phase molybdenum sulfide adheres to the filter paper.
  • the filter paper with 1T phase molybdenum sulfide attached to the silicon wafer with a silicon oxide layer is laminated and pressed for 2 hours, and then the filter membrane is removed with acetone to obtain a Raman enhanced substrate of a two-dimensional material.
  • the reinforced substrate includes a silicon wafer and a 1T-phase molybdenum sulfide layer disposed on the silicon wafer.
  • a method for preparing a Raman reinforced substrate based on a two-dimensional material includes:
  • Step 1 Clean the copper foil after polishing, and dry it with nitrogen.
  • Step 2 Put the copper foil in a 1-inch quartz tube and set the temperature of the reaction chamber to 1050°C. Pass 100sccm hydrogen and argon mixed gas (in which the hydrogen content is 10%) into the reaction chamber for 20 minutes, adjust the gas flow to 20sccm hydrogen and argon mixed gas (in which the hydrogen content is 10%), and Start the reaction program to increase the temperature. When the furnace temperature reaches the set temperature of the reaction chamber, 20 sccm methane gas is introduced for graphene growth, and the growth time is 30 minutes. After the growth is over, turn off the methane and heating program, maintain a 10 cccm hydrogen and argon mixed gas, and naturally cool to room temperature to take out the sample.
  • 100sccm hydrogen and argon mixed gas in which the hydrogen content is 10%
  • Step 3 Suspend a 400nm PMMA film on the graphene layer and suspend it in ammonium persulfate solution.
  • the copper foil reacts with the ammonium persulfate solution to dissolve, and the PMMA film is picked up with a silicon wafer and washed in deionized water. Pick up with a clean silicon wafer and let it dry naturally.
  • the PMMA film on the surface of the graphene is removed by placing it in acetone to obtain a Raman enhanced substrate based on two-dimensional materials.
  • the prepared Raman-enhanced substrate based on two-dimensional materials was examined by optical microscope. The result is shown in Figure 3.
  • the graphene layer on the two-dimensional material-based Raman-enhanced substrate completely covers the silicon wafer, and the arrow in the figure shows The dark part refers to the two-layer graphene layer.
  • sample 1 (Cabernet Sauvignon), sample 2 (Pinot Noir), sample 3 (Merlot), sample 4 (Shiraz) and control group (Pinot Gris) were analyzed for anthocyanin by high performance liquid chromatography Detect and compare the intensity of the characteristic peak of Raman spectrum at 1500cm -1 .
  • Figure 5 It can be seen that the anthocyanin content and the characteristic peak of Raman spectrum in the HPLC analysis results of the four samples and the control group The intensity at 1500cm -1 is consistent, indicating that the type of red wine can be distinguished by analyzing the content of anthocyanins by Raman spectrum analysis.
  • Raman-enhanced substrate of the two-dimensional material can quickly, simply and accurately detect the anthocyanin content in various red wines, and can quickly distinguish the types of red wine, which proves that the Raman-enhanced substrate based on the two-dimensional material provided by the present invention can be very effective. Good for use in surface enhanced Raman spectroscopy technology.
  • Raman-enhanced substrates based on two-dimensional materials prepared in Example 2 Take five Raman-enhanced substrates based on two-dimensional materials prepared in Example 2 and perform the same experiment as Effect Example 1, and set the laser to 514 nm, focus the laser to collect Raman spectra, and the results are shown in Figure 6.
  • the asterisk represents the Raman peak of graphene. It can be seen that the intensity of the characteristic peak of the Raman spectrum at 1500 cm -1 is the same as the HPLC detection result in Figure 5, indicating that the type of red wine can be distinguished by analyzing the content of anthocyanins by the Raman spectrum.
  • the Raman-enhanced substrate based on two-dimensional materials provided by the invention can be well used in surface-enhanced Raman spectroscopy technology, especially for detecting substances in the visible light region of resonant lasers.
  • Silver nanoparticles with a diameter of 50nm were selected and deposited on the substrate to form a Raman enhanced substrate, and placed in red wine.
  • the two-dimensional material-based Raman enhanced substrates prepared in Example 1 and Example 2 were respectively Put it in the same red wine, soak for the same time, take it out, clean the surface with absolute ethanol, dry it with nitrogen, set the laser to 514nm after observation under an optical microscope, focus the laser to collect Raman spectra, the result is shown in the figure 7 shown.
  • the Raman-enhanced substrate prepared by the comparative example has no peak at the characteristic peak of the Raman spectrum at 1500 cm -1 , and cannot detect the anthocyanins in red wine; while the Raman-enhanced substrate prepared in Example 1 and Example 2
  • the Raman-enhanced substrate based on two-dimensional materials has a peak at 1500 cm -1 , which can detect anthocyanins in red wine, and the detection effect is better than that of the Raman-enhanced substrate prepared in the comparative example, indicating that the application adopts
  • the Raman enhancement effect of the two-dimensional material is better than that of silver nanoparticles.

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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

一种基于二维材料的拉曼增强基底，包括基底以及设置在基底上的二维材料层，二维材料层的材质包括石墨烯、黑磷和过渡金属硫族化合物中的至少一种。还提供了一种基于二维材料的拉曼增强基底的制备方法及其在检测共振激光在可见光区的物质中的应用。

Description

一种基于二维材料的拉曼增强基底及其制备方法和应用
本发明要求2019年1月28日递交的发明名称为“一种基于二维材料的拉曼增强基底及其制备方法和应用”的申请号201910078937.3的在先申请优先权，上述在先申请的内容以引入的方式并入本文本中。
技术领域
本发明涉及检测技术领域，特别涉及一种基于二维材料的拉曼增强基底及其制备方法和应用。
背景技术
表面增强拉曼光谱技术(Surface enhanced Raman Scattering，SERS)是一种高灵敏的检测吸附物种指纹振动信息的光谱技术，被认为是最具实际应用潜力的快速无损表征手段，可实现单分子水平的检测并提供分子结构指纹信息，为拉曼光谱在生物监测、食品分析、环境污染、疾病检测等方面提供了诱人的前景。但是SERS技术在实际生活中的应用仍然面临很多挑战。常见的拉曼增强基底主要为粗糙的金膜、银膜、及金、银纳米颗粒等，但是这些贵金属基底具有价格昂贵、制备过程繁琐、重复性差、基底容易变质失活、不易于长期保存等问题。鉴于此，需要寻找一种制备方法简单、重复性好、稳定性好、价格低廉的拉曼增强基底。
发明内容
有鉴于此，本发明提供了一种基于二维材料的拉曼增强基底，其中，设置在基底上的二维材料层与待检测物质分子之间通过电荷的转移，实现了拉曼信号的共振增强；二维材料与基底直接结合，省去了贵金属层的使用，降低制备成本，减少工艺流程，有利于规模化生产，且避免了与待检测物质分子间反应引起信号复杂化的问题，使得检测的重复性好、稳定性高，在表面增强拉曼光谱技术中具有广泛的应用前景。
第一方面，本发明提供了一种基于二维材料的拉曼增强基底，包括基底以及设置在所述基底上的二维材料层，所述二维材料层的材质包括石墨烯、黑磷和过渡金属硫族化合物中的至少一种。
在本发明中，所述二维材料层可以为一次制备工艺制得的单层结构，也可以为多次制备工艺制得的多层结构，对此不作限定。
可选的，所述过渡金属硫族化合物包括钛、锆、铪、钒、铌、钽、钼、钨、锝、铼、钴、铑、铱、镍、钯、铂对应的硫化物、硒化物、碲化物中的至少一种。即，所述过渡金属硫族化合物包括钛、锆、铪、钒、铌、钽、钼、钨、锝、铼、钴、铑、铱、镍、钯和/或铂对应的硫化物、硒化物和/或碲化物。具体的，所述钛、锆、铪、钒、铌、钽、钼、钨、锝、铼、钴、铑、铱、镍、钯、铂对应的硫化物可以为二硫化钛、二硫化锆、二硫化铪、硫化钒、二硫化铌、二硫化钽、二硫化钼、二硫化钨、二硫化锝、二硫化铼、二硫化钴、硫化铑、二硫化铱、二硫化镍中的至少一种。
进一步的，所述过渡金属硫族化合物包括二硫化铌、1T相的二硫化钼中的至少一种。
可选的，所述二维材料层的厚度为0.5nm-500nm。进一步的，所述二维材料层的厚度为1nm-450nm。更进一步的，所述二维材料层的厚度为10nm-400nm。具体的，所述二维材料层的厚度可以但不限于为100nm、150nm、220nm、330nm或370nm。
可选的，所述二维材料层完全或部分覆盖所述基底，当所述二维材料层部分覆盖所述基底时，所述二维材料层由一个或多个子二维材料层组成，多个所述子二维材料层间隔设置在所述基底上。具体的，多个所述子二维材料层可以但不限于为均匀间隔设置在所述基底上或无规则设置在所述基底上。
可选的，所述基于二维材料的拉曼增强基底用于检测共振激光在可见光区的物质。其中，可见光区的波长范围在380nm-780nm内。
可选的，所述基底与所述二维材料层通过分子间作用力、共价键和离子键中的至少一种方式结合。
可选的，所述基底的材质包括硅片、石英、导电玻璃、蓝宝石中的至少一种。进一步的，所述硅片具有氧化硅层。更进一步的，所述氧化硅层的厚度为 90nm-300nm。
在现有技术中，拉曼增强基底均具有贵金属层(例如金、银)，贵金属纳米颗粒在基底表面形成电场，增强拉曼截面积，从而实现增强拉曼信号的作用；但是，贵金属纳米可以作为很多氧化还原反应的催化剂，在待检测物质分子与其接触时，待检测物质分子可能会发生扭曲变形、碳化、光漂泊、等离子体催化等反应，从而导致拉曼信号复杂化，不利于物质的检测，且制备成本高，工艺复杂。而在本发明中，采用二维材料与基底直接结合，制得基于二维材料的拉曼增强基底，通过二维材料层与待检测物质分子之间的电荷转移，增强检测信号，从而减少了贵金属层的使用，且检测的重复性好、稳定性高、检测时间短。
第二方面，本发明提供了一种基于二维材料的拉曼增强基底的制备方法，包括：
提供基底，在所述基底上形成二维材料层，即得到基于二维材料的拉曼增强基底，所述二维材料层的材质包括石墨烯、黑磷、过渡金属硫族化合物中的至少一种。
可选的，在所述基底上形成二维材料层的具体操作为：采用化学气相沉积法或化学剥离法，在所述基底上形成二维材料层，或在辅助基底上形成二维材料层，经剥离和转移使所述二维材料层与所述辅助基底分离，并与所述基底结合。
在本发明中，二维材料可以直接在基底上生长，也可以利用辅助基底进行生长后转移至基底上，可以根据二维材料的性质进行选择，对此不作限定。
可选的，所述过渡金属硫族化合物包括钛、锆、铪、钒、铌、钽、钼、钨、锝、铼、钴、铑、铱、镍、钯、铂对应的硫化物、硒化物、碲化物中的至少一种。进一步的，所述过渡金属硫族化合物包括二硫化铌、1T相的二硫化钼中的至少一种。
可选的，所述二维材料层的厚度为0.5nm-500nm。进一步的，所述二维材料层的厚度为1nm-450nm。更进一步的，所述二维材料层的厚度为10nm-400nm。具体的，所述二维材料层的厚度可以但不限于为100nm、150nm、220nm、330nm或370nm。
可选的，所述二维材料层完全或部分覆盖所述基底，当所述二维材料层部分覆盖所述基底时，所述二维材料层由一个或多个子二维材料层组成，多个所述子二维材料层间隔设置在所述基底上。具体的，多个所述子二维材料层可以但不限于为均匀间隔设置在所述基底上或无规则设置在所述基底上。
可选的，所述基于二维材料的拉曼增强基底用于检测共振激光在可见光区的物质。
可选的，所述基底与所述二维材料层通过分子间作用力、共价键和离子键中的至少一种方式结合。
可选的，所述基底的材质包括硅片、石英、导电玻璃、蓝宝石中的至少一种。进一步的，所述硅片具有氧化硅层。更进一步的，所述氧化硅层的厚度为90nm-300nm。
可选的，所述剥离包括化学剥离、机械剥离、液相剥离中的至少一种。
具体的，当制备具有二硫化铌二维材料的拉曼增强基底时，所述制备方法可以但不限于为：
将铌金属粉末置于石英管中，升温后进行氧化，获得部分氧化的氧化铌粉末。取部分氧化的氧化铌粉末与氯化钠混合搅拌均匀，平铺于氧化铝舟中，将清洗干净的基底放置在粉末上方，将氧化铝舟置于高温管式炉中，反应腔的温度为800℃-850℃。将硫粉放置于氧化铝舟中。向反应腔通入100sccm-220sccm氢气/氩气混合气(其中氢气含量为10％)，炉体升温至反应腔温度，在反应腔温度维持13min-20min进行二维二硫化铌的生长。随后关闭加热电源，自然冷却至室温。将样品取出清洗后即可获得具有二硫化铌二维材料的拉曼增强基底。
具体的，当制备具有1T相的二硫化钼二维材料的拉曼增强基底时，所述制备方法可以但不限于为：
将正丁基锂溶液加入二硫化钼粉末中，在氩气的气氛中回流反应后，进行清洗。将反应的混合物分散在水中，进行超声和离心处理，除去锂离子与没有被剥离的二硫化钼。将离心后的1T相的二硫化钼分散在水中，随后将1T相的二硫化钼溶液用滤纸进行抽滤，使得1T相的二硫化钼附着在滤纸上。将附着有1T相的二硫化钼的滤纸与基底贴合进行压制，再用丙酮除去滤膜即可获得具有1T相的二硫化钼二维材料的拉曼增强基底。
具体的，当制备具有石墨烯二维材料的拉曼增强基底时，所述制备方法可以但不限于为：
将清洗干净的辅助基底放于石英管中，设定反应腔温度为1020℃-1070℃。向反应腔内通入100sccm-220sccm氢气/氩气(其中氢气含量为10％)进行洗气10min-30min后，将气流调至10sccm-30sccm氢气/氩气(其中氢气含量为10％)，并启动反应程序进行升温。当炉温达到反应腔设置温度，通入5sccm-30sccm甲烷气体进行石墨烯生长，生长时间为10min-30min。石墨烯生长结束后关闭甲烷及加热程序，保持氢气/氩气为10sccm-30sccm，自然冷却至室温取出样品。采用剥离技术将所述石墨烯层与所述辅助基底进行剥离，并使所述石墨烯层与基底结合，经清洗后得到具有石墨烯二维材料的拉曼增强基底。
具体的，采用剥离技术将所述石墨烯层与所述辅助基底进行剥离，并使所述石墨烯层与基底结合可以但不限于为：
在石墨烯层上悬涂200nm-300nmPMMA膜，将其置于可以与辅助基底发生反应的溶液中，使辅助基底反应溶解；将PMMA膜用基底捞起，清洗后置于丙酮中，将石墨烯层上的PMMA膜除去，即可获得与基底结合的石墨烯层。
本发明第二方面提供了一种基于二维材料的拉曼增强基底的制备方法，制备方法较为简单，工艺流程简短，可控性较强，制备成本低，可进行大规模生产。
第三方面，本发明提供了如第一方面所述的基于二维材料的拉曼增强基底在检测共振激光在可见光区的物质中的应用。
本发明提供的基于二维材料的拉曼增强基底可以对共振激光在可见光区的物质进行定性检测和/或定量检测；定性检测可以根据待检测物质的特征峰进行判断；定量检测可先对待检测物质的标准品配制不同浓度进行检查，制作标准曲线进行检查。
可选的，所述基于二维材料的拉曼增强基底用于检测花青素。具体的，可以但不限于用于红酒品质和分类的检测。
本发明的有益效果：
本发明提供了一种基于二维材料的拉曼增强基底，二维材料层能够与基底直接结合，通过二维材料层与待检测物质分子之间的电荷转移，实现了拉曼信 号的共振增强，从而减少了贵金属层的使用，避免了与待检测物质分子间反应引起信号复杂化的问题，且检测的重复性好、稳定性高、检测时间短，其制备方法较为简单，工艺流程简短，可控性较强，制备成本低，可进行大规模生产，有利于其在检测共振激光在可见光区的物质中的应用。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
图1为本发明实施例1制得的基于二维材料的拉曼增强基底的光学显微镜图，其中图1中(a)为基于二维材料的拉曼增强基底的光学显微镜图，图1中(b)为基于二维材料的拉曼增强基底上二硫化铌层的光学显微镜图；
图2为本发明实施例2制得的基于二维材料的拉曼增强基底的光学显微镜图；
图3为本发明实施例4制得的基于二维材料的拉曼增强基底的光学显微镜图；
图4为本发明效果实施例1中的表面增强拉曼光谱图；
图5为本发明效果实施例1中的高效液相色谱结果图；
图6为本发明效果实施例2中的表面增强拉曼光谱图；
图7为本发明对比例中的表面增强拉曼光谱图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种基于二维材料的拉曼增强基底的制备方法，包括：
步骤1：将硅片依次放置于丙酮、异丙醇中超声清洗15min，用氩气吹干。
步骤2：将2g铌粉置于石英管中(石英管两端敞口)，15min升温至680℃，在680℃氧化3min，关闭加热电源，降至室温将其取出，获得部分氧化的氧化铌粉末，以NbOx表示，x＝1～2.5。
步骤3：取0.7gNbOx粉末与0.15g氯化钠混合搅拌均匀，平铺于氧化铝舟中，将清洗干净的硅片放置在粉末上方1cm处，将氧化铝舟置于1英寸的高温管式炉中，反应腔的温度为800℃。将1g硫粉放置于氧化铝舟中，距离NbOx15cm处，温度为200℃。
步骤4：向反应腔通入140sccm氢气和氩气的混合气体(其中氢气含量为10％)，维持15min进行洗气过程以便于将石英管中的空气排出。设定16min内炉体升温至反应腔温度，在反应腔温度维持13min进行二维二硫化铌的生长。随后关闭加热电源，自然冷却至室温。将样品取出并用去离子水清洗表层氯化钠，用氩气吹干即可获得基于二维材料的拉曼增强基底。对制得的基于二维材料的拉曼增强基底进行光学显微镜检测，结果如图1所示，其中图1中(a)的深色三角形区域为沉积的二硫化铌层，浅色区域为硅片，即该基于二维材料的拉曼增强基底上的二硫化铌层覆盖部分硅片；图1中(b)中二硫化铌完全覆盖硅片。
实施例2
一种基于二维材料的拉曼增强基底的制备方法，包括：
步骤1：将铜箔放于抛光液中(75％磷酸，25％乙二醇)，设定抛光电压为2V，电化学抛光30min，取出铜箔并用去离子水将抛光液冲洗干净，氩气吹干。
步骤2：将铜箔放于1英寸石英管中，设定反应腔温度为1020℃。向反应腔内通入200sccm氢气和氩气的混合气体(其中氢气含量为10％)进行洗气30min后，将气流调至30sccm氢气和氩气的混合气体(其中氢气含量为10％)，并启动反应程序进行升温。当炉温达到反应腔设置温度，通入10sccm甲烷气体进行石墨烯生长，生长时间为10min。石墨烯生长结束后关闭甲烷及加热程序，保持20cccm氢气和氩气的混合气体，自然冷却至室温取出样品。
步骤3：在石墨烯层上悬涂300nm PMMA膜，并悬浮于于1mol/L过硫酸铵溶液中，铜箔与过硫酸铵溶液反应溶解，将PMMA膜用硅片捞起，并在去离子水中清洗三遍，用干净硅片捞起，自然晾干。放置于丙酮中2h，将石墨烯表层 的PMMA膜除去，即可获得基于二维材料的拉曼增强基底。对制得的基于二维材料的拉曼增强基底进行光学显微镜检测，结果如图2所示，该基于二维材料的拉曼增强基底上的石墨烯层覆盖部分硅片。
实施例3
一种基于二维材料的拉曼增强基底的制备方法，包括：
步骤1：将3ml正丁基锂溶液(1.6mol/L)加入0.3g MoS 2固体粉末，在氩气的气氛中回流反应48h。将反应混合物过滤，用正己烷清洗掉多余的正丁基锂及其他有机物。
步骤2：将处理好的混合物分散在水中(浓度为1.5mg/mL)，超声1h，然后10000r/min离心除去锂离子与没有被剥离的硫化钼。将离心后的1T相的二硫化钼分散在水中，随后将1T相的二硫化钼溶液用滤纸进行抽滤，使得1T相的硫化钼附着在滤纸上。将附着有1T相的硫化钼的滤纸与具有氧化硅层的硅片贴合进行压制2h，再用丙酮除去滤膜即可获得二维材料的拉曼增强基底，该基于二维材料的拉曼增强基底包括了硅片以及设置在硅片上的1T相的硫化钼层。
实施例4
一种基于二维材料的拉曼增强基底的制备方法，包括：
步骤1：将铜箔抛光后清洗干净，用氮气吹干。
步骤2：将铜箔放于1英寸石英管中，设定反应腔温度为1050℃。向反应腔内通入100sccm氢气和氩气的混合气体(其中氢气含量为10％)进行洗气20min后，将气流调至20sccm氢气和氩气的混合气体(其中氢气含量为10％)，并启动反应程序进行升温。当炉温达到反应腔设置温度，通入20sccm甲烷气体进行石墨烯生长，生长时间为30min。待生长结束后关闭甲烷及加热程序，保持10cccm氢气和氩气的混合气体，自然冷却至室温取出样品。
步骤3：在石墨烯层上悬涂400nm PMMA膜，并悬浮于于过硫酸铵溶液中，铜箔与过硫酸铵溶液反应溶解，将PMMA膜用硅片捞起，并在去离子水中清洗三遍，用干净硅片捞起，自然晾干。放置于丙酮中将石墨烯表层的PMMA膜除去，即可获得基于二维材料的拉曼增强基底。对制得的基于二维材料的拉曼增强基底进行光学显微镜检测，结果如图3所示，该基于二维材料的拉曼增强基底上的石墨烯层完全覆盖硅片，且图中箭头所指的深色部分为双层石墨烯层。
为了证明本发明的有益效果，进行以下效果实施例：
效果实施例1
取5片实施例1制得的基于二维材料的拉曼增强基底，分别置于样品1(赤霞珠)、样品2(黑比诺)、样品3(梅洛)、样品4(西拉子)的4种红酒中以及对照组(灰皮诺)的白葡萄酒中，放置10h后将基于二维材料的拉曼增强基底取出，用无水乙醇清洗表面，用氮气吹干，置于光学显微镜下观察后再设置激光为514nm，聚焦激光进行拉曼谱图采集，结果如图4所示。同时，将样品1(赤霞珠)、样品2(黑比诺)、样品3(梅洛)、样品4(西拉子)以及对照组(灰皮诺)通过高效液相色谱进行花青素检测，并比对拉曼图谱特征峰1500cm -1处的强度，结果如图5所示，可以看出四种样品和对照组的高效液相分析结果中花青素含量与拉曼图谱特征峰1500cm -1处的强度一致，表明红酒的种类可以通过拉曼图谱分析花青素的含量而进行区分。红酒的常用检测方法为质谱法、气相-质谱联用法，中红外光谱法等，但是这些方法所用仪器价格昂贵，检测过程复杂，耗时较长，常量分析准确率低，而本发明提供的基于二维材料的拉曼增强基底可以快速、简单、准确地检测到各类红酒中花青素含量，对红酒种类就行快速区分，证明了本发明提供的基于二维材料的拉曼增强基底可以很好的用于表面增强拉曼光谱技术中。
效果实施例2
取5片实施例2制得的基于二维材料的拉曼增强基底，进行与效果实施例1相同的实验，并设置激光为514nm，聚焦激光进行拉曼谱图采集，结果如图6所示，其中星号表示石墨烯的拉曼峰。可以看出拉曼图谱特征峰1500cm -1处的强度与图5中高效液相色谱检测结果相同，表明红酒的种类可以通过拉曼图谱分析花青素的含量而进行区分，同时也证明了本发明提供的基于二维材料的拉曼增强基底可以很好的用于表面增强拉曼光谱技术中，尤其是检测共振激光在可见光区的物质。
对比例
选取直径为50nm银纳米颗粒，使其沉积至基底，形成拉曼增强基底，并将其置于红酒中，同时将实施例1和实施例2制得的基于二维材料的拉曼增强基底分别置于相同的红酒中，浸泡相同的时间取出，用无水乙醇清洗表面，用氮 气吹干，置于光学显微镜下观察后再设置激光为514nm，聚焦激光进行拉曼谱图采集，结果如图7所示。可以看出，对比例制得的拉曼增强基底在拉曼图谱特征峰1500cm -1处没有峰值，对红酒中的花青素不能起到检测作用；而实施例1和实施例2制得的基于二维材料的拉曼增强基底在1500cm -1处均出现峰值，可以对红酒中的花青素起到检测作用，且检测效果优于对比例制得的拉曼增强基底，表明本申请采用的二维材料的拉曼增强效果优于银纳米颗粒。
以上所述是本发明的优选实施方式，但并不能因此而理解为对本发明专利范围的限制。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。

Claims (10)

  1. 一种基于二维材料的拉曼增强基底，其特征在于，包括基底以及设置在所述基底上的二维材料层，所述二维材料层的材质包括石墨烯、黑磷和过渡金属硫族化合物中的至少一种。
  2. 如权利要求1所述的基于二维材料的拉曼增强基底，其特征在于，所述过渡金属硫族化合物包括钛、锆、铪、钒、铌、钽、钼、钨、锝、铼、钴、铑、铱、镍、钯、铂对应的硫化物、硒化物、碲化物中的至少一种。
  3. 如权利要求2所述的基于二维材料的拉曼增强基底，其特征在于，所述过渡金属硫族化合物包括二硫化铌、1T相的二硫化钼中的至少一种。
  4. 如权利要求1所述的基于二维材料的拉曼增强基底，其特征在于，所述二维材料层的厚度为0.5nm-500nm。
  5. 如权利要求1所述的基于二维材料的拉曼增强基底，其特征在于，所述二维材料层完全或部分覆盖所述基底，当所述二维材料层部分覆盖所述基底时，所述二维材料层由一个或多个子二维材料层组成，多个所述子二维材料层间隔设置在所述基底上。
  6. 如权利要求1所述的基于二维材料的拉曼增强基底，其特征在于，所述基于二维材料的拉曼增强基底用于检测共振激光在可见光区的物质。
  7. 如权利要求1所述的基于二维材料的拉曼增强基底，其特征在于，所述基底与所述二维材料层通过分子间作用力、共价键和离子键中的至少一种方式结合。
  8. 一种基于二维材料的拉曼增强基底的制备方法，其特征在于，包括：
    提供基底，在所述基底上形成二维材料层，即得到基于二维材料的拉曼增强基底，所述二维材料层的材质包括石墨烯、黑磷、过渡金属硫族化合物中的至少一种。
  9. 如权利要求8所述的制备方法，其特征在于，在所述基底上形成二维材料层的具体操作为：采用化学气相沉积法或化学剥离法，在所述基底上形成二维材料层，或在辅助基底上形成二维材料层，经剥离和转移使所述二维材料层与所述辅助基底分离，并与所述基底结合。
  10. 如权利要求1-7任一项所述的基于二维材料的拉曼增强基底在检测共振激光在可见光区的物质中的应用。
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