CN112326624A - Application of doped two-dimensional semiconductor nano material in surface Raman scattering enhancement - Google Patents
Application of doped two-dimensional semiconductor nano material in surface Raman scattering enhancement Download PDFInfo
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- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 68
- 239000004065 semiconductor Substances 0.000 title claims abstract description 26
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- 239000002135 nanosheet Substances 0.000 claims abstract description 75
- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical compound [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 claims abstract description 68
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- 229910052618 mica group Inorganic materials 0.000 claims abstract description 17
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- 238000007740 vapor deposition Methods 0.000 claims abstract description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 19
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005843 Thiram Substances 0.000 claims description 10
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 10
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- 229910052717 sulfur Inorganic materials 0.000 claims description 5
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- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
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- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 claims 2
- 238000001237 Raman spectrum Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 15
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 abstract description 10
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- 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 relates to the technical field of Raman spectrum molecular detection materials, in particular to application of a doped two-dimensional semiconductor nano material as a surface Raman scattering enhancement active substrate. Aiming at the problem that the surface enhanced Raman scattering sensitivity of a semiconductor material substrate in the prior art is relatively low, the invention provides the application of a doped two-dimensional semiconductor nano material as a surface Raman scattering enhanced active substrate, and a sulfur-doped two-dimensional layered structure tin selenide nanosheet is directly generated on a mica substrate through a vapor deposition method. The nanosheet has a good signal enhancement effect when being applied to a surface enhanced Raman spectrum, is high in detection sensitivity, simple and controllable in preparation method, large in detection range and free from reaction with probe molecules.
Description
Technical Field
The invention relates to the technical field of Raman spectrum molecular detection materials, in particular to application of a doped two-dimensional semiconductor nano material as a surface Raman scattering enhancement active substrate.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The Surface Enhanced Raman Scattering (SERS) effect refers to a phenomenon of enhancing and adsorbing a molecular Raman scattering signal on the Surface of a specially prepared substrate by utilizing a strong interaction between the substrate and a molecule. In 1974, Fieschmann et al used a roughened silver electrode surface for the first time to obtain high quality raman spectra of monolayer pyridine molecules adsorbed on the silver electrode surface. Because the surface raman enhancement effect can effectively overcome the defects of small molecular raman scattering cross section, low intensity of the obtained raman spectrum and poor sensitivity, the surface raman enhancement technology is widely used for the research of material surface research, structural analysis and the like in the fields of analytical chemistry, catalysis, biology, chemical detection and analysis and the like as an effective means for analyzing the adsorption orientation, the change of the adsorption state and the interface information of a compound on an interface at present.
The traditional surface enhanced Raman scattering effect mainly comes from the rough material surfaces of gold, silver and copper, the selection range of the substrate material is very limited, and the fine structure material involved in the practical application is also easily interfered by factors such as environment, preparation conditions, storage and the like, so that the stability is strong. Therefore, semiconductor materials with abundant varieties and chemical compositions and varied crystal structures have become one of the most important research directions in the recent exploration of novel high-performance non-metal surface enhanced raman scattering technology. However, when the compound is used as a surface-enhanced Raman scattering substrate, the chemical enhancement process which is relied on by the compound is a short-range effect, and the spatial range of the generated Raman enhancement effect is very limited. The better solution is to increase the contact area between the substrate and the adsorbed molecules through the layered material with the nanometer thickness and increase the channels for charge transfer. The two-dimensional layered material, which is a research hotspot of new materials in the world at present, becomes the most ideal material for constructing the nonmetal surface enhanced Raman scattering substrate due to the large specific surface area, stable physical properties, simple preparation and excellent photoelectric properties. However, the current research results show that the enhancement effect is weak, even a part in a thousand of the enhancement effect of the metal SERS substrate is not enough for detecting trace substances and low-concentration molecules.
Disclosure of Invention
In order to solve the problems, the invention provides a doped two-dimensional layered tin selenide (SnSe)2) Application of material as surface enhanced scattering substrate, doping two-dimensional layered tin selenide (SnSe)2) Materials can be formed using selenide homofamily dopingThe characteristics of the continuously adjustable solid solution compound regulate and control the crystal lattice and the energy band structure of the two-dimensional tin selenide nanosheet by doping the sulfur element, and the purpose of enhancing the SERS activity of the intrinsic tin selenide nanomaterial is achieved. The application has the characteristics of obvious Raman signal enhancement effect, good repeatability and high analysis efficiency.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the present invention, the present invention provides an application of a doped two-dimensional semiconductor nanomaterial as a surface raman scattering enhanced active substrate, wherein the doped two-dimensional semiconductor nanomaterial is a doped two-dimensional tin selenide nanosheet. Wherein the dopant is sulfur;
further, the doped two-dimensional tin selenide nanosheet is less than 100nm thick.
Furthermore, the surface area of the doped two-dimensional tin selenide nanosheet is 1-100 μm.
Furthermore, when the doped two-dimensional semiconductor nano material is applied as a surface Raman scattering enhanced active substrate, the doped two-dimensional semiconductor nano material is positioned on the substrate for use.
In a second aspect of the present invention, the present invention provides a method for preparing a two-dimensional tin selenide doped nanosheet for use in the first aspect, the method comprising the steps of: growing by adopting a chemical vapor deposition method to obtain a doped two-dimensional layered tin selenide nanosheet;
further, the vapor deposition method comprises the following specific steps:
mixing tin iodide (SnI)2) The powder is placed in a central high-temperature area of a high-temperature closed tube furnace, sulfur powder and selenium powder in a certain ratio are placed above tin iodide powder, a substrate is placed below air flow, heating is carried out under inert atmosphere to enable the temperature of the central high-temperature area to reach 500-700 ℃, and heating is stopped after the nano sheets are grown.
In a third aspect of the present invention, the present invention provides a method for raman detection of an organic molecule, the method comprising: the doped two-dimensional semiconductor nano material is used as a surface Raman scattering enhancement active substrate to amplify the signal of the organic molecule.
Further, the detection method comprises the following steps: and dropwise adding the aqueous solution of the organic molecules to be detected to the surface of the doped two-dimensional semiconductor nano material, and detecting by a Raman spectrometer after water is volatilized.
The specific embodiment of the invention has the following beneficial effects:
the doped two-dimensional semiconductor nanomaterial in the specific embodiment of the invention is applied as a surface Raman scattering enhancement active substrate, can obtain good enhancement effect and high detection sensitivity, can effectively avoid the problem of compatibility of metal materials and biomolecules, cannot generate chemical bonds with probe molecules, and can effectively improve the measurement precision. The preparation method is simple, the equipment is cheap and efficient, the controllability is high, and the method has good popularization significance.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an atomic force scan (AFM) of different two-dimensional layered tin selenide nanoplatelets.
Wherein (a) is the two-dimensional SnSe prepared in example 11.14S0.92Nanosheet AFM map, (b) is the two-dimensional SnSe prepared in example 20.93S0.94AFM image of nanosheet, (c) is the two-dimensional SnSe prepared in comparative example 12Nanoplate AFM images.
FIG. 2 is the two-dimensional SnSe prepared in example 11.14S0.92Nanosheet EDS elemental scan.
Fig. 3 is a raman plot of differently doped two-dimensional layered tin selenide nanosheets.
FIG. 3(a) is a diagram of two-dimensional SnSe prepared in example 11.14S0.92Raman image of nanosheets, FIG. 3(b) is a two-dimensional SnSe prepared in example 20.93S0.94Nanosheet Raman plot, FIG. 3(c) is a two-dimensional SnSe prepared in comparative example2Nanoplate raman plots.
FIG. 4 shows two samples prepared in example 1, example 2 and comparative example 1Pair of nanoplatelets 10-6Raman spectrum of R6G probe molecule water solution of M;
FIG. 5 is the two-dimensional SnSe prepared in example 10.93S0.94Nanosheet as surface-enhanced Raman scattering substrate pair 10-8-10-4Enhanced raman spectra of an aqueous solution of R6G probe molecules at M concentration.
FIG. 6 is the two-dimensional SnSe prepared in example 30.93S0.94Nanoplate pair 10-4～10-2Raman spectrum of the aqueous solution of thiram of M.
FIG. 7 is the two-dimensional SnSe prepared in example 40.93S0.94Nanoplate pair 10-5～10-2Raman spectrum of M in aqueous adenosine solution.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the defects of the prior art, an embodiment of the present invention provides an application of a doped two-dimensional semiconductor nanomaterial as a surface raman scattering enhancement active substrate, wherein the doped two-dimensional semiconductor nanomaterial is a doped two-dimensional tin selenide nanosheet, and the dopant is sulfur.
In a preferred embodiment, the doped two-dimensional tin selenide nanosheets are less than 100nm thick.
In a preferred embodiment, the doped two-dimensional tin selenide nanosheets have a surface area of 1-100 μm.
In a preferred embodiment, when the doped two-dimensional semiconductor nanomaterial is applied as a surface raman scattering enhancement active substrate, the doped two-dimensional semiconductor nanomaterial is positioned on the substrate for use;
preferably, the substrate is a layered structure; further preferably, the substrate is a monoclinic high-temperature resistant mica substrate.
In an embodiment of the present invention, a method for preparing a two-dimensional tin selenide nanosheet doped in the above application is provided, and the method for preparing the two-dimensional tin selenide nanosheet includes the following steps: growing by adopting a chemical vapor deposition method to obtain a doped two-dimensional layered tin selenide nanosheet;
the preparation method provided by the embodiment can obtain the two-dimensional tin selenide nanosheets with different sulfur doping concentrations.
In a preferred embodiment, the vapor deposition method comprises the following specific steps:
mixing tin iodide (SnI)2) The powder is placed in a central high-temperature area of a high-temperature closed tube furnace, sulfur powder and selenium powder in a certain ratio are placed above tin iodide powder, a substrate is placed below air flow, heating is carried out under inert atmosphere to enable the temperature of the central high-temperature area to reach 500-700 ℃, and heating is stopped after the nano sheets are grown.
Preferably, the furnace tube material of the tube furnace is corundum or quartz.
Preferably, the inert atmosphere adopts argon, and the stable gas flow is 10-50 sccm.
Preferably, the growth time of the nano-sheets is 5-20 min.
Preferably, the reaction temperature rise adopts a staged temperature rise mode, and the temperature rise time is 20-30 min.
Preferably, the sulfur powder and the selenium powder in a certain ratio have an S to Se atomic ratio of 1: 10-1: 1;
preferably, the tin iodide is used in an amount of: the mass ratio of the tin iodide to the selenium powder is 1: 8; .
Preferably, the content of doped S in the doped two-dimensional layered tin selenide nanosheet is 1: 20-1: 1 of S to Sn atomic ratio.
In one embodiment of the present invention, there is provided a method for raman detection of an organic molecule, the method comprising: the doped two-dimensional semiconductor nano material is used as a surface Raman scattering enhancement active substrate to amplify the signal of the organic molecule.
In a preferred embodiment, the detection method is as follows: and dropwise adding the aqueous solution of the organic molecules to be detected to the surface of the doped two-dimensional semiconductor nano material, and detecting by a Raman spectrometer after water is volatilized.
Preferably, the organic molecule is rhodamine 6G (R6G), thiram, adenosine;
it is further preferred that the concentration of the aqueous solution of R6G is higher than 10-7M；
It is further preferred that the concentration of the aqueous solution of thiram is higher than 10-4M；
It is further preferred that the concentration of the aqueous solution of adenosine is above 10-4M；。
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific examples and comparative examples.
Example 1
The application of the doped two-dimensional tin selenide nanosheet in R6G Raman detection:
0.05g of SnI is weighed2Powder, Se powder 0.4g and S powder 0.02g, respectively, were placed in a porcelain boat, and the boat was filled with SnI2Placing a porcelain boat of the powder in a quartz tube and in the central position of a vacuum tube furnace; respectively placing porcelain boats filled with Se powder and S powder above the air flow at a distance SnI2The powder is 13.5cm and 14 cm; placing a freshly peeled mica substrate under the air stream at a distance SnI2The source is in the range of 14-14.5cm, and the quartz tube is closed.
Pumping by using a mechanical pump until the pressure in the tube is in a vacuum state, introducing argon with the flow of 30sccm into the tube, and continuously vacuumizing for 60 minutes; then adjusting the pressure in the furnace to 1 atm; heating the central position of the furnace body to 600 ℃ at the speed of 50 ℃/min, and maintaining the state for 10 minutes; and after the growth is finished, closing the heating device to naturally cool the quartz tube to room temperature, and obtaining the sulfur-doped two-dimensional tin selenide nanosheets on the mica substrate.
Taking out the doped two-dimensional tin selenide nanosheet from the quartz tube, and observing the two-dimensional tin selenide nanosheet under an atomic force microscope to obtain a truncated-angle triangular two-dimensional layered nanosheet (shown in figure 1 a) with a regular shape and a side length of 20-30 mu m; raman test and EDS determination: the two-dimensional SnSe with good crystallization quality and uniform doping is obtained by the growth method1.14S0.92Nanosheets (fig. 2, 3 a).
The obtained sulfur-doped two-dimensional tin selenide nanosheets growing on the mica substrate are used as surface-enhanced Raman active substrates, and 2mL of the sulfur-doped two-dimensional tin selenide nanosheets with the concentration of 10 are dripped on the surfaces of the two-dimensional tin selenide nanosheets-6In the aqueous solution of M R6G, after the solution naturally volatilizes, a Raman spectrometer with an excitation wavelength of 532nm was used to test the Raman spectrum (as shown in FIG. 4).
Analyzing and testing results, and obtaining the sulfur-doped two-dimensional tin selenide nanosheet as a surface enhanced Raman active substrate at 614cm-1，774cm-1，1185cm-1，1360cm-1，1506cm-1，1650cm-1A Raman spectrum of R6G molecule with a distinct characteristic peak. The detection limit of the R6G aqueous solution can reach 10-7M (FIG. 5). The sulfur-doped two-dimensional tin selenide nanosheets prepared in the example are used as surface-enhanced Raman active substrates, and have a remarkable effect of enhancing Raman signals of R6G molecules.
Example 2
The application of the doped two-dimensional tin selenide nanosheet in R6G Raman detection:
0.05g of SnI is weighed2Powder, Se powder 0.4g and S powder 0.04g, respectively, were placed in a porcelain boat, and the boat was filled with SnI2Placing a porcelain boat of the powder in a quartz tube and in the central position of a vacuum tube furnace; respectively placing porcelain boats filled with Se powder and S powder above the air flow at a distance SnI2The powder is 13cm and 14.5 cm; placing a freshly peeled mica substrate under the air stream at a distance SnI2Source in the range of 13-14cmThe quartz tube is sealed in the enclosure.
Pumping by using a mechanical pump until the pressure in the tube is in a vacuum state, introducing argon with the flow of 40sccm into the tube, and continuously vacuumizing for 60 minutes; then adjusting the pressure in the furnace to 1 atm; heating the central position of the furnace body to 600 ℃ at the speed of 50 ℃/min, and maintaining the state for 10 minutes; and after the growth is finished, closing the heating device to naturally cool the quartz tube to room temperature, and obtaining the sulfur-doped two-dimensional tin selenide nanosheets on the mica substrate.
Taking out the sulfur-doped two-dimensional tin selenide nanosheets from the quartz tube, and observing under an atomic force microscope to obtain rounded triangular two-dimensional layered nanosheets (as shown in figure 1 b) with regular shapes and side lengths of 20-30 mu m; raman testing: the two-dimensional SnSe grown by the method has good crystallization quality and uniform doping0.93S0.94Nanoplatelets (fig. 3 b).
The obtained sulfur-doped two-dimensional tin selenide nanosheets growing on the mica substrate are used as surface-enhanced Raman active substrates, and 2mL of the sulfur-doped two-dimensional tin selenide nanosheets with the concentration of 10 are dripped on the surfaces of the two-dimensional tin selenide nanosheets-6In the aqueous solution of M R6G, after the solution naturally volatilizes, a Raman spectrometer with an excitation wavelength of 532nm was used to test the Raman spectrum (as shown in FIG. 4).
Analysis and test results show that the sulfur-doped two-dimensional tin selenide nanosheets serve as a surface-enhanced Raman active substrate to obtain an R6G molecular Raman spectrum with an obvious characteristic peak, and the effect of the sulfur-doped two-dimensional tin selenide nanosheets prepared in the embodiment serving as the surface-enhanced Raman active substrate on the enhancement of the Raman signal of the R6G molecule is more obvious than that of the embodiment 1.
Example 3
The doped two-dimensional tin selenide nanosheets are applied to Raman detection of thiram aqueous solution:
0.05g of SnI is weighed2Powder, Se powder 0.4g and S powder 0.04g, respectively, were placed in a porcelain boat, and the boat was filled with SnI2Placing a porcelain boat of the powder in a quartz tube and in the central position of a vacuum tube furnace; respectively placing porcelain boats filled with Se powder and S powder above the air flow at a distance SnI2The powder is 13cm and 14.5 cm; freshly peeled mica substratePlaced under the gas flow by a distance SnI2The quartz tube was closed within a source range of 13-14 cm.
Pumping by using a mechanical pump until the pressure in the tube is in a vacuum state, introducing argon with the flow of 40sccm into the tube, and continuously vacuumizing for 60 min; then adjusting the pressure in the furnace to 1 atm; heating the central position of the furnace body to 600 ℃ at the speed of 50 ℃/min, and maintaining the state for 10 min; and after the growth is finished, closing the heating device to naturally cool the quartz tube to room temperature, and obtaining the sulfur-doped two-dimensional tin selenide nanosheets on the mica substrate.
Taking out the sulfur-doped two-dimensional tin selenide nanosheet from the quartz tube, and obtaining the two-dimensional SnSe with good crystallization quality and uniform doping by utilizing an atomic force microscope and Raman test0.93S0.94Nanosheets.
The obtained sulfur-doped two-dimensional tin selenide nanosheets growing on the mica substrate are used as surface-enhanced Raman active substrates, and 2mL of 10-concentration tin selenide nanosheets are respectively dripped on the surfaces of the two-dimensional tin selenide nanosheets-4M、10-3M、10-2M in a solution of thiram, and after the solution was allowed to evaporate naturally, the Raman spectrum was measured using a Raman spectrometer with an excitation wavelength of 532nm (as shown in FIG. 6).
Analyzing and testing results, and taking the sulfur-doped two-dimensional tin selenide nanosheet as a surface enhanced Raman active substrate, wherein the concentration of the sulfur-doped two-dimensional tin selenide nanosheet in the thiram aqueous solution is as low as 10-4The thiram Raman spectrum with an obvious characteristic peak can be obtained during M, which shows that the sulfur-doped two-dimensional tin selenide nanosheet prepared by the embodiment has an obvious effect of enhancing the thiram Raman signal when being used as a surface-enhanced Raman active substrate.
Example 4
The application of the doped two-dimensional tin selenide nanosheet in the Raman detection of adenosine aqueous solution comprises the following steps:
0.05g of SnI is weighed2Powder, Se powder 0.4g and S powder 0.04g, respectively, were placed in a porcelain boat, and the boat was filled with SnI2Placing a porcelain boat of the powder in a quartz tube and in the central position of a vacuum tube furnace; respectively placing porcelain boats filled with Se powder and S powder above the air flow at a distance SnI2The powder is 13cm and 14.5 cm; will freshly stripped cloudsThe mother substrate being placed under the gas flow at a distance SnI2The quartz tube was closed within a source range of 13-14 cm.
Pumping by using a mechanical pump until the pressure in the tube is in a vacuum state, introducing argon with the flow of 40sccm into the tube, and continuously vacuumizing for 60 min; then adjusting the pressure in the furnace to 1 atm; heating the central position of the furnace body to 600 ℃ at the speed of 50 ℃/min, and maintaining the state for 10 min; and after the growth is finished, closing the heating device to naturally cool the quartz tube to room temperature, and obtaining the sulfur-doped two-dimensional tin selenide nanosheets on the mica substrate.
Taking out the two-dimensional tin selenide doped nanosheet from the quartz tube, and obtaining two-dimensional SnSe with good crystallization quality and uniform doping by utilizing an atomic force microscope, Raman test and EDS (enhanced dispersive Spectroscopy) determination0.93S0.94Nanosheets.
The obtained sulfur-doped two-dimensional tin selenide nanosheets growing on the mica substrate are used as surface-enhanced Raman active substrates, and 2mL of 10-concentration tin selenide nanosheets with the concentration of 10 are respectively dripped on the surfaces of the two-dimensional tin selenide nanosheets-4M、10-3M、10-2M in an aqueous solution of adenosine, after the solution spontaneously volatilized, a raman spectrum was measured using a raman spectrometer with an excitation wavelength of 532nm (as shown in fig. 7).
Analyzing and testing results, and taking the sulfur-doped two-dimensional tin selenide nanosheet as a surface enhanced Raman active substrate, wherein the concentration of the substrate in an adenosine aqueous solution is as low as 10-4And the adenosine molecular Raman spectrum with an obvious characteristic peak can be obtained when M is used, which shows that the sulfur-doped two-dimensional tin selenide nanosheets prepared by the embodiment have an obvious effect of enhancing the Raman signal of the adenosine molecule when being used as a surface-enhanced Raman active substrate.
Comparative example 1
Application of pure two-dimensional tin selenide nanosheets in R6G Raman detection:
0.05g of SnI is weighed2Powder, 0.4g Se powder, put into porcelain boat respectively, will be filled with SnI2Placing a porcelain boat of the powder in a quartz tube and in the central position of a vacuum tube furnace; placing Se powder over the SnI distance of the gas flow213.5cm of powder; placing a freshly peeled mica substrate under the air stream at a distance SnI2The source is in the range of 14-14.5cm, and the quartz tube is closed.
Pumping by using a mechanical pump until the pressure in the tube is in a vacuum state, introducing argon with the flow of 30sccm into the tube, and continuously vacuumizing for 60 minutes; then, the pressure in the furnace was adjusted to 1 atm. Heating the central position of the furnace body to 600 ℃ at the speed of 50 ℃/min, and maintaining the state for 10 minutes; and after the growth is finished, closing the heating device to naturally cool the quartz tube to room temperature, and obtaining the pure two-dimensional tin selenide nanosheets on the mica substrate.
Taking out the two-dimensional tin selenide nanosheet from the quartz tube, and observing under an atomic force microscope to obtain a triangular two-dimensional layered nanosheet (shown in figure 1 c) with a regular shape and a side length of 20-30 μm; through Raman test: the two-dimensional SnSe with good crystallization quality and no impurities is obtained by the growth of the method2Nanoplatelets (fig. 3 c).
The obtained two-dimensional layered tin selenide nanosheet growing on the mica substrate is used as a surface enhanced Raman active substrate, and 2mL of the two-dimensional layered tin selenide nanosheet is dripped on the surface of the two-dimensional layered tin selenide nanosheet with the concentration of 10-6In the aqueous solution of M R6G, after the solution naturally volatilizes, a Raman spectrometer with an excitation wavelength of 532nm was used to test the Raman spectrum (as shown in FIG. 4).
Analyzing and testing results, and taking the sulfur-free two-dimensional tin selenide nanosheet as a surface enhanced Raman active substrate to obtain a Raman spectrum with a characteristic peak of R6G molecules, wherein the Raman signal is more than 10-6M concentration R6G molecules the two-dimensional layered tin selenide nanoplatelets prepared in example 1 and example 2 were much weaker as surface enhanced raman active substrates.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The application of the doped two-dimensional semiconductor nano material as a surface Raman scattering enhanced active substrate is characterized in that the doped two-dimensional semiconductor nano material is a doped two-dimensional tin selenide nanosheet, wherein the dopant is sulfur.
2. The use of claim 1, wherein the doped tin selenide nanoplatelets have a thickness of less than 100 nm.
3. The use of claim 1, wherein the doped tin selenide nanoplatelets have a surface area of 1-100 μm.
4. The use according to claim 1, wherein the doped two-dimensional semiconductor nanomaterial is used on a substrate when the doped two-dimensional semiconductor nanomaterial is used as a surface raman scattering enhancing active substrate.
5. The use of claim 4, wherein the substrate is a layered structure; preferably, the substrate is a monoclinic high-temperature resistant mica substrate.
6. The use of claim 1, wherein the doped two-dimensional tin selenide nanosheets are prepared by growing the doped two-dimensional tin selenide nanosheets using a chemical vapor deposition process;
the vapor deposition method comprises the following specific steps:
the method comprises the steps of placing tin iodide powder in a central high-temperature area of a high-temperature closed tube furnace, placing sulfur powder and selenium powder in a certain ratio above the tin iodide powder, placing a substrate below air flow, heating in an inert atmosphere to enable the temperature of the central high-temperature area to reach 500-700 ℃, and stopping heating after the nano sheets are grown.
7. The use according to claim 6, wherein the tube material of the tube furnace is corundum or quartz;
or the inert atmosphere adopts argon, and the stable gas flow is 10-50 sccm;
or the growth time of the nano-sheets is 5-20 min;
or, the reaction temperature rise adopts a staged temperature rise mode, and the temperature rise time is 20-30 min;
or the sulfur powder and the selenium powder in a certain ratio have an S to Se atomic ratio of 1: 10-1: 1;
or the dosage of the tin iodide is as follows: the mass ratio of the tin iodide to the selenium powder is 1: 8;
or the content of S doped in the two-dimensional layered tin selenide nanosheet is 1: 20-1: 1 of S to Sn atomic ratio.
8. A method for raman detection of an organic molecule, the method comprising: the doped two-dimensional semiconductor nano material is used as a surface Raman scattering enhancement active substrate to amplify the signal of the organic molecule.
9. The method for raman detection of an organic molecule according to claim 8, wherein said method for detection is: and dropwise adding the aqueous solution of the organic molecules to be detected to the surface of the doped two-dimensional semiconductor nano material, and detecting by a Raman spectrometer after water is volatilized.
10. The organic molecule raman detection method of claim 8, wherein said organic molecule comprises rhodamine 6G, thiram, and adenosine;
preferably, the concentration of the aqueous solution of R6G is higher than 10-7M；
Alternatively, the concentration of the aqueous solution of thiram is higher than 10-4M；
Alternatively, the concentration of the aqueous solution of R6G is higher than 10-4M。
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