A method for measuring adsorption dynamics under enhanced relative Raman scattering cross section

Abstract

The present invention provides an adsorption dynamics measurement method for relative Raman scattering cross sections under enhanced state, comprising the following steps: adopting an immersion adsorption method to test the relationship between the Raman scattering intensity and the immersion adsorption time of different molecules, obtaining a relationship diagram between the Raman characteristic peak intensity and the adsorption time of different molecules and performing adsorption dynamics curve fitting processing to obtain the characteristic peak intensity of different molecules when a monolayer is fully adsorbed; selecting a molecule as a reference molecule, measuring its Raman characteristic peak intensity when a monolayer is fully adsorbed and using it as a reference value, and comparing the Raman characteristic peak intensity of other molecules at full coverage with the Raman characteristic peak intensity of the selected molecule at full coverage to obtain the relative Raman scattering cross section value between other molecules and the selected molecule. The present invention can solve the problem of lack of a universal semi-quantitative and quantitative analysis method in the current quantitative analysis technology of surface enhanced Raman scattering spectrum.

Description

Technical Field

[0001] The present invention relates to the technical field of quantitative analysis based on surface enhanced Raman scattering spectroscopy, and more specifically, to a method for measuring adsorption dynamics of a relative Raman scattering cross section under an enhanced state. Background Art

[0002] Surface enhanced Raman scattering (SERS) spectroscopy has become an important inelastic scattering spectroscopy analysis method with the advantages of fast speed, high sensitivity, simple sample preparation, accurate fingerprint characteristics, etc. It has broad application prospects in many fields such as biochemical detection, organic pollutant detection, pharmaceutical analysis, pesticide residues and food additives detection. From traditional precious metal (gold, silver, copper) nanostructured SERS substrates to semiconductor SERS substrates, great progress has been made in the field of substrate development, but improving the sensitivity, stability and uniformity of substrates is still a research hotspot in this field. At the same time, flexible SERS substrates, tip-enhanced Raman scattering technology (TERS), electrochemical and surface enhanced Raman scattering coupling technology are also constantly expanding the application scope of surface enhanced Raman scattering technology. Although great progress has been made in qualitative analysis based on SERS technology, SERS technology has not yet established a universal semi-quantitative and quantitative analysis method similar to X-ray diffraction or X-ray photoelectron spectroscopy in the field of semi-quantitative and quantitative analysis, mainly because for a system consisting of a given molecule and SERS substrate, the quantitative analysis of the enhancement mechanism under a determined excitation wavelength still faces many difficulties.

[0003] For SERS spectra, the spectral intensity fluctuations in actual tests are important interference factors in semi-quantitative and quantitative analysis. This interference makes the working curve relationship between the target concentration / content and the Raman scattering characteristic peak intensity not universal. The SERS spectral intensity is easily affected by factors such as fluctuations in actual test conditions, poor uniformity of SERS substrates, and differences between different batches, resulting in large fluctuations in the actual SERS spectral intensity. Chemometric analysis methods and machine learning algorithms have been used in quantitative analysis of SERS spectra. Studies have found that compared with absolute intensity, the relative intensity of surface enhanced Raman scattering spectra can effectively reduce the impact of absolute intensity fluctuations on quantitative analysis, but a universal semi-quantitative and quantitative analysis method has not yet been established. The relative sensitivity factor (RSF) based on the internal standard method is a commonly used method in semi-quantitative and quantitative analysis. For example, in X-ray photoelectron spectroscopy, the RSF of different elements can be used for quantitative analysis of sample surface elements. The relative peak intensity method currently used in the quantitative analysis of SERS spectra also uses the relative intensity internal standard method to carry out quantitative analysis, but it is still unclear how the Raman scattering cross section of molecules in the enhanced state changes with the enhancement effect of the SERS substrate.

[0004] In summary, there is currently a lack of a universal semi-quantitative and quantitative analysis method in SERS spectroscopy quantitative analysis technology. Summary of the invention

[0005] In view of the above discussion, the purpose of the present invention is to provide a method for measuring the adsorption dynamics of the relative Raman scattering cross section under enhanced state, so as to solve the problem that the current SERS spectroscopy quantitative analysis technology lacks a universal semi-quantitative and quantitative analysis method.

[0006] The present invention provides a method for measuring adsorption dynamics of relative Raman scattering cross section under enhanced state, comprising the following steps:

[0007] S1. Using the soaking adsorption method, the relationship between the Raman scattering intensity of different molecules and the soaking adsorption time is tested to obtain the relationship between the Raman scattering characteristic peak intensity of different molecules and the adsorption time;

[0008] S2, performing adsorption kinetic curve fitting processing on the relationship diagram between the Raman scattering characteristic peak intensity and the adsorption time of the different molecules to obtain the Raman scattering characteristic peak intensity of the different molecules at full coverage;

[0009] S3. Select the Raman scattering characteristic peak intensity of a molecule at full coverage as a reference, and compare the Raman scattering characteristic peak intensity of other molecules at full coverage with the Raman scattering characteristic peak intensity of the selected molecule at full coverage to obtain the relative Raman scattering cross-section value of the other molecules.

[0010] In addition, a preferred solution is that the relationship between the Raman scattering characteristic peak intensity and the immersion adsorption time of different molecules is tested by the immersion adsorption method, and the relationship diagram between the Raman scattering characteristic peak intensity and the adsorption time of different molecules is obtained, including:

[0011] The surface enhanced Raman scattering substrate sample is placed in different molecular solutions of preset concentrations for immersion adsorption, and samples with different adsorption amounts at different adsorption times are obtained by controlling the adsorption time of the sample;

[0012] Collecting surface enhanced Raman scattering spectra of the samples with different adsorption amounts to obtain surface enhanced Raman scattering spectra of the samples with different molecular adsorption amounts;

[0013] According to the surface enhanced Raman scattering spectra of the samples with different molecular adsorption amounts, the Raman scattering characteristic peak intensity of each molecule at different adsorption times is calculated to obtain a relationship diagram between the Raman scattering characteristic peak intensity of different molecules and the adsorption time.

[0014] In addition, a preferred scheme is that in the process of placing the surface-enhanced Raman scattering substrate samples in different molecular solutions of preset concentrations for immersion adsorption, and obtaining samples with different adsorption amounts at different adsorption times by controlling the adsorption time of the samples, the surface-enhanced Raman scattering substrate samples of the same batch are placed in different molecular solutions of preset concentrations for immersion adsorption, and obtaining samples with different adsorption amounts of each molecule by controlling the adsorption time of the samples.

[0015] In addition, a preferred solution is that the Raman scattering characteristic peak intensity of each molecule at different adsorption times is calculated according to the surface enhanced Raman scattering spectra of the samples with different molecular adsorption amounts, and the relationship diagram between the Raman scattering characteristic peak intensity of different molecules and the adsorption time is obtained, which includes:

[0016] According to the enhanced Raman scattering spectra of the different molecules on the sample surface, for each molecule, the main surface enhanced Raman scattering characteristic peak of the molecule is used as the selected Raman scattering characteristic peak;

[0017] Calculating the intensity of the selected Raman scattering characteristic peak;

[0018] The relationship between the intensity of the selected Raman scattering characteristic peak and the adsorption time is established to obtain a relationship diagram between the intensity of the selected Raman scattering characteristic peak and the adsorption time of different molecules.

[0019] In addition, a preferred scheme is that in the process of collecting surface enhanced Raman scattering spectra of the samples with different adsorption amounts to obtain surface enhanced Raman scattering spectra of samples with different molecular adsorption amounts, it also includes: removing the molecules contained in the surface residual solution of the samples taken out from different molecular solutions at different adsorption times.

[0020] In addition, a preferred solution is that the removal of molecules contained in the surface residual solution of the samples fished out from different molecular solutions at different adsorption times comprises:

[0021] When the molecules contained in the residual solution on the sample surface are in a chemical adsorption relationship with the surface enhanced Raman scattering substrate, the residual molecules are removed by washing with a solvent;

[0022] When the molecules contained in the residual solution on the sample surface are in a physical adsorption relationship with the surface enhanced Raman scattering substrate, the residual molecules are removed by reducing the thickness of the residual liquid film on the sample surface.

[0023] In addition, a preferred solution is to construct a molecular relative Raman scattering cross-section database based on any of the molecules mentioned as a reference.

[0024] It can be seen from the above technical scheme that the adsorption kinetics measurement method of the relative Raman scattering cross section under the enhanced state provided by the present invention obtains the relative Raman scattering cross section of the molecule under the same surface coverage by utilizing the molecular adsorption kinetics process. The measured relative Raman scattering cross section of the molecule is universal between surface enhanced Raman scattering substrates with the same surface properties but different geometric morphologies, and can effectively reduce the interference of factors such as surface enhanced Raman scattering substrate uniformity, batch differences, test condition fluctuations, and geometric morphology changes on quantitative analysis. Based on this, a database of relative Raman scattering cross sections between molecules can be established, so that the SERS technology can be similar to the X-ray photoelectron energy spectrum. There is no need to repeatedly establish working curves between the same type of substrates, and quantitative analysis can be directly carried out using the SERS spectrum and the molecular relative Raman scattering cross section values. It has broad application prospects and necessary basic support in the field of quantitative analysis of trace molecules.

[0025] To achieve the above and related purposes, one or more aspects of the present invention include features that will be described in detail below, and the following description and accompanying drawings describe some exemplary aspects of the present invention in detail. However, these aspects indicate only some of the various ways in which the principles of the present invention can be used. In addition, the present invention is intended to include all of these aspects and their equivalents. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] By referring to the following description in conjunction with the accompanying drawings, the present invention will be explained more comprehensively, and other objects and results of the present invention will be more clearly understood and easier to understand. In the accompanying drawings:

[0027] Figure 1 A schematic diagram of a process for measuring adsorption dynamics of a relative Raman scattering cross section under an enhanced state according to an embodiment of the present invention;

[0028] Figure 2 Surface enhanced Raman scattering spectra of different molecules on a silver nanostructure substrate according to an embodiment of the present invention;

[0029] Figure 3 1074 cm for the 4-MBA molecule according to the embodiment of the present invention -1 The relationship between the intensity of Raman scattering characteristic peak and adsorption time;

[0030] Figure 4 1,2-BDT molecule 1034 cm according to the embodiment of the present invention -1 The relationship between the intensity of Raman scattering characteristic peak and adsorption time;

[0031] Figure 5 1064cm for the 2-NAT molecule according to an embodiment of the present invention -1 The relationship between the intensity of Raman scattering characteristic peak and adsorption time.

[0032] The same reference numerals in the drawings indicate similar or corresponding features or functions. DETAILED DESCRIPTION

[0033] In the following description, for the purpose of explanation, more specific details are set forth to provide a comprehensive understanding of one or more embodiments. However, these specific details are illustrative rather than restrictive, and the present patent cannot be limited based on the specific details of the embodiments.

[0034] In response to the aforementioned problem that the current SERS spectroscopy quantitative analysis technology lacks a universal semi-quantitative and quantitative analysis method, a method for measuring the adsorption kinetics of the relative Raman scattering cross section in the enhanced state is proposed.

[0035] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0036] In order to illustrate the adsorption dynamics measurement method of the relative Raman scattering cross section under the enhanced state provided by the present invention, Figure 1 The measurement process of the relative Raman scattering cross section of a molecule in an enhanced state according to an embodiment of the present invention is shown; Figure 2 Surface enhanced Raman scattering spectra of different molecules on silver nanostructures according to an embodiment of the present invention are shown; Figure 3 The relationship between the Raman scattering characteristic peak intensity and the adsorption time of 4-MBA molecules according to an embodiment of the present invention is shown; Figure 4 The relationship between the Raman scattering characteristic peak intensity and the adsorption time of 1,2-BDT molecules according to an embodiment of the present invention is shown; Figure 5 The relationship between the Raman scattering characteristic peak intensity of 2-NAT molecules and the adsorption time according to an embodiment of the present invention is shown.

[0037] like Figures 1 to 5 As shown together, the method for measuring adsorption dynamics of relative Raman scattering cross section under enhanced state provided by the present invention comprises the following steps:

[0038] S1. Using the soaking adsorption method, the relationship between the Raman scattering intensity of different molecules and the soaking adsorption time is tested to obtain the relationship between the Raman scattering characteristic peak intensity of different molecules and the adsorption time.

[0039] S2. Perform adsorption kinetic curve fitting on the relationship between the Raman scattering characteristic peak intensity and adsorption time of different molecules to obtain the Raman scattering characteristic peak intensity of different molecules at full coverage;

[0040] S3. Select a Raman scattering characteristic peak intensity of a molecule at full coverage as a reference, and compare the Raman scattering characteristic peak intensity of other molecules at full coverage with the Raman scattering characteristic peak intensity of the selected molecule at full coverage to obtain the relative Raman scattering cross-section value of the other molecules.

[0041] Through the adsorption kinetics process, the molecular relative Raman scattering cross section under the same surface coverage can be tested. The measured molecular relative Raman scattering cross section is universal between SERS substrates with the same surface properties but different geometric morphologies, which can reduce the influence of factors such as SERS substrate uniformity, batch differences, test condition fluctuations, and geometric morphology changes on quantitative analysis. Based on this, a molecular relative Raman scattering cross section database can be established, so that SERS spectroscopy technology can be similar to X-ray photoelectron spectroscopy technology. It can directly use the relative Raman scattering characteristic peak intensity of SERS spectra and the molecular relative Raman scattering cross section for quantitative analysis without establishing a working curve. It has broad application prospects and important basic support in the field of quantitative analysis of trace molecules.

[0042] By means of curve fitting, the measurement accuracy of the relative Raman scattering cross section can be improved, and the impact of differences between different samples in the same batch on the test results can be reduced.

[0043] As a preferred embodiment of the present invention, the relationship between the Raman scattering characteristic peak intensity and the immersion adsorption time of different molecules is tested by immersion adsorption, and the relationship between the Raman scattering characteristic peak intensity and the adsorption time of different molecules is obtained, including:

[0044] The surface enhanced Raman scattering substrate sample is placed in different molecular solutions of preset concentrations for immersion adsorption, and samples with different adsorption amounts at different adsorption times are obtained by controlling the adsorption time of the sample;

[0045] Surface enhanced Raman scattering spectra of samples with different adsorption amounts are collected to obtain surface enhanced Raman scattering spectra of samples with different molecular adsorption amounts;

[0046] According to the surface enhanced Raman scattering spectra of samples with different molecular adsorption amounts, the Raman scattering characteristic peak intensity of each molecule at different adsorption times was calculated, and a relationship diagram between the Raman scattering characteristic peak intensity of different molecules and the adsorption time was obtained.

[0047] The SERS substrate (i.e., surface enhanced Raman scattering substrate) sample is placed in different molecular solutions of preset concentrations for immersion adsorption, and samples with different adsorption amounts are obtained by controlling the adsorption time. The samples with different adsorption amounts are subjected to SERS spectrum testing, thereby obtaining SERS spectra of samples with different adsorption amounts of each molecule, and then the Raman scattering characteristic peak intensity of each molecule at different adsorption times is calculated based on the SERS spectrum of each sample, and a relationship diagram between the Raman scattering characteristic peak intensity and adsorption time of different molecules is obtained. Among them, the preset concentration can be set according to the adsorption kinetics of different molecules, as long as the time for different molecules to adsorb a full monolayer is appropriate.

[0048] As a preferred embodiment of the present invention, in the process of placing the surface enhanced Raman scattering substrate samples in different molecular solutions of preset concentrations for immersion adsorption, and obtaining samples with different adsorption amounts at different adsorption times by controlling the adsorption time of the samples, the surface enhanced Raman scattering substrate samples of the same batch are placed in different molecular solutions of preset concentrations for immersion adsorption, and obtaining samples with different adsorption amounts of each molecule by controlling the adsorption time of the samples.

[0049] Selecting SERS substrate samples from the same batch can reduce the impact of differences between SERS substrate samples from different batches on the test results during the test process.

[0050] As a preferred embodiment of the present invention, according to the surface enhanced Raman scattering spectra of samples with different molecular adsorption amounts, the Raman scattering characteristic peak intensity of each molecule at different adsorption times is calculated, and the relationship diagram between the Raman scattering characteristic peak intensity of different molecules and the adsorption time is obtained, including:

[0051] According to the enhanced Raman scattering spectra of different molecules on the sample surface, for each molecule, the main surface enhanced Raman scattering characteristic peak of the molecule is used as the selected Raman scattering characteristic peak;

[0052] Calculate the intensity of the selected Raman scattering characteristic peak;

[0053] The relationship between the intensity of the selected Raman scattering characteristic peak and the adsorption time is established, and the relationship diagram between the intensity of the selected Raman scattering characteristic peak and the adsorption time of different molecules is obtained.

[0054] As a preferred embodiment of the present invention, in the process of collecting surface enhanced Raman scattering spectra of samples with different adsorption amounts to obtain surface enhanced Raman scattering spectra of samples with different molecular adsorption amounts, the process also includes:

[0055] The samples taken out from different molecular solutions at different adsorption times are treated to remove the molecules contained in the surface residual solution, thereby reducing the influence of the molecules contained in the surface residual solution on the SERS spectrum test results.

[0056] As a preferred embodiment of the present invention, the removal of molecules contained in the surface residual solution of samples taken out from different molecular solutions at different adsorption times includes:

[0057] When the molecules contained in the residual solution on the sample surface are in a chemical adsorption relationship with the surface-enhanced Raman scattering substrate, the residual molecules are removed by solvent washing;

[0058] When the molecules contained in the residual solution on the sample surface are in a physical adsorption relationship with the surface enhanced Raman scattering substrate, the residual molecules are removed by reducing the thickness of the residual liquid film on the sample surface.

[0059] Different removal methods are used for molecules with different adsorption modes on the SERS substrate surface to reduce the influence of the molecules contained in the residual solution on the SERS substrate surface on the test results. When the molecules are chemically adsorbed on the surface, the sample can be rinsed with a solvent after immersion to remove the influence of the residual molecules in the surface liquid film. When the molecules are physically adsorbed on the surface, the influence of the residual molecules in the surface liquid film can be reduced by selecting a lower solution concentration and reducing the thickness of the residual liquid film on the sample surface after immersion.

[0060] As a preferred embodiment of the present invention, it also includes:

[0061] Construct a molecular relative Raman scattering cross-section database based on a selected molecule as a reference.

[0062] The relative Raman scattering cross section of molecules when adsorbed in one monolayer determined by this method can be directly used for quantitative analysis of the relative coverage of surface adsorbed molecules. It is an intrinsic characteristic parameter of the system composed of molecules and SERS substrates. For the same type of SERS substrates, a database of molecular Raman scattering characteristics can be constructed.

[0063] The relative Raman scattering cross section of molecules in the enhanced state measured by the method provided by the present invention can be used for quantitative analysis of the relative coverage of surface adsorbed molecules and quantitative analysis of the molecular content.

[0064] In order to better illustrate the method for measuring the relative Raman scattering cross section of molecules in the enhanced state provided by the present invention, the following specific embodiments are provided.

[0065] First, through the immersion adsorption experiment, the relationship curve between the Raman scattering characteristic peak intensity and the adsorption time of different molecules was tested. The Raman scattering characteristic peak intensity when the molecule adsorbed a full monolayer under the enhanced state was further fitted by the adsorption kinetic equation and the relative Raman scattering cross-section value between molecules was calculated, so as to further study the relationship between the relative Raman scattering cross-section of molecules and the geometric morphology and surface properties of the SERS substrate nanostructure. Three drug intermediate molecules were selected, including 4-mercaptobenzoic acid (4-MBA), 1,2-benzenedithiol (1,2-BDT), and 2-naphthol (2-NAT). By placing a series of precious metal silver nanorod structure SERS substrates at a preset concentration (5×10 -7 mol / L) solution for different time periods and tested its SERS spectra. The surface enhanced Raman scattering spectra of the three molecules are shown in Figure 2 As shown, the Raman scattering characteristic peaks of the three molecules were selected at 1074 cm -1 (4-MBA), 1034cm -1 (1,2-BDT), 1064 cm -1 (2-NAT), as marked by the dotted line in the figure.

[0066] The relationship curve between the characteristic peak intensity of the three molecules and the immersion adsorption time is as follows: Figures 3 to 5 As shown in the figure, the Raman scattering characteristic peak intensity when adsorbed to one monolayer can be obtained by fitting the adsorption kinetic equation. The 1074 cm -1 The characteristic peaks are used as references to obtain the relative Raman scattering cross-section values ​​of 1,2-BDT and 2-NAT molecules. Similarly, the relative Raman scattering cross-sections of each molecule on silver nanostructure SERS substrates with different geometric morphologies can be tested. Table 1 shows the relative Raman scattering cross-sections of molecules measured on silver SERS substrates with different structures:

[0067]

[0068] Table 1

[0069] It can be seen from Table 1 that the relative Raman scattering cross section of the molecule when adsorbing a monolayer does not change with the nanostructure morphology of the SERS substrate and is an intrinsic parameter of the system composed of the molecule and the SERS substrate.

[0070] Furthermore, for gold nanostructures, Table 2 shows the molecular relative Raman scattering cross sections measured by gold SERS substrates with different structures:

[0071]

[0072] Table 2

[0073] It can be seen from Table 2 that for different gold nanostructured SERS substrates, the relative Raman scattering cross sections of each molecule remain unchanged.

[0074] By comparing Table 1 and Table 2, it can be found that the molecular relative Raman scattering cross sections corresponding to different surface properties are different. Therefore, in the enhanced state, for the system composed of SERS substrates and molecules with the same surface properties but different nanostructure geometric morphologies, there is a stable molecular relative Raman scattering cross section; while for the system composed of SERS substrates and molecules with different surface properties, there are different molecular relative Raman scattering cross sections.

[0075] It can be seen from the above specific embodiments that the method for measuring the relative Raman scattering cross section of molecules under the enhanced state provided by the present invention utilizes the adsorption process of molecules to obtain the relative Raman scattering cross section of molecules under the same surface coverage. The measured relative Raman scattering cross section of molecules is universal between SERS substrates with the same surface properties but different geometric morphologies, and can reduce the interference of factors such as uniformity of surface enhanced Raman scattering substrates, batch differences, fluctuations in test conditions, and changes in geometric morphology on quantitative analysis. Thus, a molecular relative Raman scattering cross section database can be constructed, so that the SERS technology can be similar to technologies such as X-ray photoelectron spectroscopy, and the measured parameters can be directly used to carry out quantitative analysis based on SERS spectra. It has broad application prospects and an important basic supporting role in the field of quantitative analysis of trace molecules.

[0076] As described above with reference to the accompanying drawings, the adsorption kinetics measurement method of the relative Raman scattering cross section in the enhanced state proposed by the present invention is described in an exemplary embodiment. However, those skilled in the art should understand that various improvements can be made to the adsorption kinetics measurement method of the relative Raman scattering cross section in the enhanced state proposed by the present invention without departing from the content of the present invention. Therefore, the protection scope of the present invention should be determined by the content of the attached claims.

Claims

1. A method for measuring adsorption dynamics of relative Raman scattering cross sections under enhanced conditions, characterized in that: The steps include: S1. Using the soaking adsorption method, the relationship between the Raman scattering intensity of different molecules and the soaking adsorption time is tested to obtain the relationship between the Raman scattering characteristic peak intensity of different molecules and the adsorption time. It includes: The surface enhanced Raman scattering substrate sample is placed in different molecular solutions of preset concentrations for immersion adsorption, and samples with different adsorption amounts at different adsorption times are obtained by controlling the adsorption time of the sample; Collecting surface enhanced Raman scattering spectra of the samples with different adsorption amounts to obtain surface enhanced Raman scattering spectra of the samples with different molecular adsorption amounts; According to the surface enhanced Raman scattering spectra of the samples with different molecular adsorption amounts, the Raman scattering characteristic peak intensity of each molecule at different adsorption times is calculated to obtain a relationship diagram between the Raman scattering characteristic peak intensity of different molecules and the adsorption time; S2, performing adsorption kinetic curve fitting processing on the relationship diagram between the Raman scattering characteristic peak intensity and the adsorption time of the different molecules to obtain the Raman scattering characteristic peak intensity of the different molecules at full coverage; S3. Select the Raman scattering characteristic peak intensity of a molecule at full coverage as a reference, and compare the Raman scattering characteristic peak intensity of other molecules at full coverage with the Raman scattering characteristic peak intensity of the selected molecule at full coverage to obtain the relative Raman scattering cross-section value of the other molecules.

2. The method for measuring adsorption dynamics of relative Raman scattering cross section under enhanced state according to claim 1, characterized in that: In the process of placing the surface enhanced Raman scattering substrate samples in different molecular solutions of preset concentrations for immersion adsorption, and obtaining samples with different adsorption amounts at different adsorption times by controlling the adsorption time of the samples, the surface enhanced Raman scattering substrate samples of the same batch are placed in different molecular solutions of preset concentrations for immersion adsorption, and obtaining samples with different adsorption amounts of each molecule by controlling the adsorption time of the samples.

3. The method for measuring adsorption dynamics of relative Raman scattering cross section under enhanced state according to claim 1, characterized in that: The step of calculating the Raman scattering characteristic peak intensity of each molecule at different adsorption times according to the surface enhanced Raman scattering spectra of the samples with different molecular adsorption amounts, and obtaining a relationship diagram between the Raman scattering characteristic peak intensity of different molecules and the adsorption time comprises: According to the enhanced Raman scattering spectra of the different molecules on the sample surface, for each molecule, the main surface enhanced Raman scattering characteristic peak of the molecule is used as the selected Raman scattering characteristic peak; Calculating the intensity of the selected Raman scattering characteristic peak; The relationship between the intensity of the selected Raman scattering characteristic peak and the adsorption time is established to obtain a relationship diagram between the intensity of the selected Raman scattering characteristic peak and the adsorption time of different molecules.

4. The method for measuring adsorption dynamics of relative Raman scattering cross section under enhanced state according to claim 1, characterized in that: In the process of collecting surface enhanced Raman scattering spectra of the samples with different adsorption amounts to obtain surface enhanced Raman scattering spectra of samples with different molecular adsorption amounts, the process also includes: The samples taken out from different molecular solutions at different adsorption times are treated to remove the molecules contained in the surface residual solution.

5. The method for measuring adsorption dynamics of relative Raman scattering cross section under enhanced state according to claim 4, characterized in that: The removing of molecules contained in the surface residual solution of the samples fished out from different molecular solutions at different adsorption times comprises: When the molecules contained in the residual solution on the sample surface are in a chemical adsorption relationship with the surface enhanced Raman scattering substrate, the residual molecules are removed by washing with a solvent; When the molecules contained in the residual solution on the sample surface are in a physical adsorption relationship with the surface enhanced Raman scattering substrate, the residual molecules are removed by reducing the thickness of the residual liquid film on the sample surface.

6. The method for measuring adsorption dynamics of relative Raman scattering cross section in enhanced state according to claim 1, characterized in that: Also includes: Construct a molecular relative Raman scattering cross section database based on any molecule as a reference.

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