CN110412010B - Preparation and application of Raman enhanced substrate based on multilayer composite structure - Google Patents
Preparation and application of Raman enhanced substrate based on multilayer composite structure Download PDFInfo
- Publication number
- CN110412010B CN110412010B CN201910702289.4A CN201910702289A CN110412010B CN 110412010 B CN110412010 B CN 110412010B CN 201910702289 A CN201910702289 A CN 201910702289A CN 110412010 B CN110412010 B CN 110412010B
- Authority
- CN
- China
- Prior art keywords
- substrate
- molybdenum oxide
- raman
- composite structure
- multilayer composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention relates to the technical field of trace molecule detection, in particular to preparation and application of a Raman enhanced substrate based on a multilayer composite structure, which comprises the following steps: placing a plurality of substrates on a quartz substrate, sequentially placing a spacer and a molybdenum sheet on the upper surface of each substrate, and then placing the substrates into preheated heating equipment for thermal reaction treatment; taking out, cooling and removing the separator to obtain a molybdenum oxide substrate; SnCl with the preparation concentration of 10nmol/L2Solution and conditioning of SnCl2The pH value of the solution is 5-6; placing the prepared molybdenum oxide substrate in SnCl2And (3) placing the solution on a preheated hot table for interlayer insertion Sn ion treatment, taking out the solution, and drying the solution by using a nitrogen gun to obtain the Raman enhanced substrate based on the multilayer composite structure. The preparation method is simple and rapid, the in-layer structure of the molybdenum oxide is not changed, doping is realized by introducing interlayer ions, and the prepared substrate has stable quality and high sensitivity.
Description
Technical Field
The invention relates to the technical field of trace molecule detection, in particular to preparation and application of a Raman enhanced substrate based on a multilayer composite structure.
Background
Raman enhanced scattering is a means for detecting trace molecules, and a gold and silver nano Raman enhanced substrate is adopted in the traditional process, so that the process is complex to manufacture, the material is expensive, and the uniformity and the stability are poor. The metal oxide can realize sensitive Raman enhancement detection through regulation, but the traditional regulation method realizes enhancement by introducing material defects, so that the stability and uniformity of the metal oxide cannot be guaranteed. The two-dimensional nano material developed recently has better uniformity, but the large-area preparation process is complex, and meanwhile, a plurality of two-dimensional materials with higher Raman enhancement effect, such as compounds of sulfur, tellurium, selenium and the like, have toxicity and are not suitable for popularization. On the other hand, the enhancement effect has a strongly correlated characteristic with the thickness, and the effect is rapidly weakened along with the increase of the thickness, so that great uncertainty is brought to practical application. In addition, the growth rate of the few-layer nano material is slow, and no related method facing large-scale production exists at present, so that how to realize the simple, efficient and sensitive and stable Raman enhancement substrate is a key problem for practical application.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the preparation method of the multilayer composite structure-based Raman enhancement substrate, the preparation method is simple and quick, the in-layer structure of molybdenum oxide is not changed, defects are not introduced, doping is realized by introducing interlayer ions, and the prepared multilayer composite structure-based Raman enhancement substrate has stable quality, low cost and high sensitivity, and can be continuously prepared in a large scale.
The invention also aims to provide a Raman enhancement substrate based on a multilayer composite structure, which does not change the inner structure of molybdenum oxide, has stable quality and high sensitivity.
The invention further aims to provide an application method of the Raman enhancement substrate based on the multilayer composite structure, the application method is applied to SERS detection, the detection stability is high, the sensitivity is high, the detection limit is high, the uniformity is good, the performance can be preserved in the atmosphere for more than 6 months, and the original detection performance can be still kept for more than 98%.
The purpose of the invention is realized by the following technical scheme: a preparation method of a Raman enhanced substrate based on a multilayer composite structure comprises the following steps:
A. preparing a composite laminate: placing a plurality of substrates on a quartz substrate, placing an isolator on the upper surface of each substrate, and placing a molybdenum sheet on the upper surface of each isolator to obtain a plurality of composite laminates;
B. preparing a molybdenum oxide substrate: placing the quartz substrate with the plurality of composite laminates into preheated heating equipment for heat treatment; taking out the quartz substrate, cooling, and removing the separator to obtain a molybdenum oxide substrate;
C. blending SnCl2Solution: SnCl with the concentration of 10nmol/L is prepared in a glass container2Solution, then to SnCl2Adding dilute hydrochloric acid dropwise into the solution to adjust SnCl2The pH value of the solution is 5-6;
D. preparing a finished product: placing the molybdenum oxide substrate prepared in the step B in SnCl after the pH value is adjusted in the step C2In solution, and placing SnCl with a molybdenum oxide substrate2And placing the solution on a preheated hot table for interlayer insertion Sn ion treatment, taking out the molybdenum oxide substrate, and blow-drying by using a nitrogen gun to obtain the Raman enhancement substrate based on the multilayer composite structure.
The preparation method of the multilayer composite structure-based Raman enhanced substrate is simple and rapid, the in-layer structure of molybdenum oxide is not changed, defects are not introduced, and doping is realized by introducing interlayer ions, so that the prepared multilayer composite structure-based Raman enhanced substrate has stable quality, low cost, high sensitivity, high detection limit and good uniformity, can be stored in the atmosphere for more than 6 months, and still has the performance of more than 98% of the original detection performance.
In the step C, molybdenum oxide is generated by the molybdenum sheet through heat treatment reaction, and the generated molybdenum oxide is deposited in the space between the molybdenum sheet and the separator to form the molybdenum oxide with a multilayer interval structure; and the substrate deposited with the molybdenum oxide with the multilayer interval structure is placed in SnCl after the pH value is adjusted2In solution, SnCl2Sn ions in solution at a pH ofAnd 5-6, performing reduction oxidation reaction, replacing to a free state, inserting into a spacing layer of molybdenum oxide, and introducing Sn ions between layers on the basis of not changing the structure in the molybdenum oxide layer, so that the sensitivity and the detection limit of the substrate are improved. In the step C, diluted hydrochloric acid is dripped to adjust SnCl2The pH of the solution is in particular 5, 5.2, 5.5, 5.8 or 6, preferably pH 5.
The preparation method can place a plurality of substrates on the quartz substrate, and sequentially place the spacers and the molybdenum sheets on the substrates to realize mass preparation, can form a plurality of molybdenum oxide spacing layers, and introduces Sn ions between the layers to improve the sensitivity and detection limit of the substrate; and doping is realized by introducing interlayer ions, excellent stability and high sensitivity can be obtained without accurately controlling the thickness of the substrate, and the preparation is quick and simple.
Preferably, in the step a, the substrate is SiO2A substrate or a Si substrate; the cross-sectional area of the substrate is 1 × 1cm2(ii) a The cross section area of the molybdenum sheet is 1 multiplied by 1cm2。
The substrate has high stability and high strength, and can be stably combined with molybdenum oxide and tin ions to form a stable base material. The laminated structure of the substrate, the spacer and the molybdenum sheet is arranged, and preferably, the cross section area of the outermost periphery of the spacer is equal to the cross section area of the substrate and the cross section area of the molybdenum sheet, so that the periphery of the spacer is not completely closed, the admission of airflow can be ensured, the molybdenum sheet is sublimated into molybdenum oxide after reacting with oxygen, the sublimated molybdenum oxide can be deposited in the non-completely closed area in the center of the annular spacer, the formation of a molybdenum oxide spacer layer is realized, Sn ions are introduced into the molybdenum oxide spacer layer, and the sensitivity and the detection limit of the substrate are improved; and doping is realized by introducing interlayer ions, excellent stability and high sensitivity can be obtained without accurately controlling the thickness of the substrate, and the preparation is quick and simple.
Preferably, in the step a, the spacer is an annular spacer with a notch; the spacer is an alumina spacer.
According to the invention, the isolation piece is arranged to be of the annular structure with the notch, so that hot air of heating equipment can conveniently flow in from the notch, the molybdenum sheet is sublimated into molybdenum oxide after reacting with oxygen, and the sublimated molybdenum oxide can be deposited in the incomplete closed area in the center of the annular isolation piece, the formation of a molybdenum oxide spacing layer is realized, the generation effect and the deposition effect of the molybdenum oxide are improved, and the using amount of the molybdenum sheet is reduced; the isolating piece is made of alumina material, has good high temperature resistance, has a compact alumina diaphragm on the surface, does not participate in the reaction under the condition of 650 ℃ at 540 ℃ in the invention, does not influence the generation of molybdenum oxide, and has stable quality.
Preferably, in the step a, the thickness of the separator is 0.4-0.6mm, and the thickness of the molybdenum sheet is 0.1-0.3 mm.
According to the invention, by strictly controlling the thickness of the separator, a smaller space is provided to promote the rapid deposition of molybdenum oxide, the consumption of molybdenum sheets is reduced, and the molybdenum sheets with a certain thickness can be reused until the molybdenum sheets are completely used, so that the utilization rate of materials is improved, and the production cost is reduced. In particular, the thickness of the spacer is 0.4mm, 0.45mm, 0.5mm, 0.55mm or 0.6mm, preferably 0.5 mm; the thickness of the molybdenum oxide sheet is 0.1mm, 0.15mm, 0.20mm, 0.25mm or 0.3mm, preferably 0.2 mm.
Preferably, in the step B, the heating device is preheated to 540-650 ℃ in advance, and the heating device is a hot platform or a muffle furnace.
According to the invention, the heating equipment is preheated to 540-650 ℃ in advance, so that the generation efficiency and the deposition effect of molybdenum oxide can be improved, and the heating treatment is carried out by adopting a hot bench or a muffle furnace, so that the heating efficiency is high, the heat is stable, and the control is easy. More preferably, in the step A, the preheating temperature of the heating device is 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃ or 650 ℃, preferably 600 ℃; the temperature rise rate of preheating is 30 ℃/min.
Preferably, in the step B, the temperature of the heat treatment is 540-650 ℃, and the treatment time is 3-8 min. The molybdenum sheet can generate molybdenum oxide in the central space of the ring among the molybdenum sheet, the spacer and the substrate under the conditions of 540 ℃ and 650 ℃, and more preferably, the heat treatment temperature in the equipment is specifically 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃ or 650 ℃, preferably 600 ℃; the reaction time is specifically 3min, 4min, 5min, 6min, 7min or 8min, preferably 5 min.
Preferably, before the step C, the method further comprises removing stray molybdenum oxide, and the specific steps are as follows: and D, cooling the molybdenum oxide substrate prepared in the step B, reversely compacting the substrate on the adhesive tape, tearing off the adhesive tape, and removing the stray molybdenum oxide on the upper surface of the molybdenum oxide substrate.
According to the invention, by removing the stray molybdenum oxide on the upper surface of the molybdenum oxide substrate, the influence of the stray molybdenum oxide on the subsequent Raman spectrum measurement of the sample to be detected can be avoided, the sensitivity and the detection limit of the Raman enhanced substrate based on the multilayer composite structure are improved, and the stability is high.
Preferably, in the step D, the heating stage is preheated to 65-75 ℃ in advance, the treatment temperature of interlayer insertion Sn ion treatment is 65-75 ℃, and the treatment time is 40-70 min.
The invention strictly controls the deposition of the substrate with the molybdenum oxide spacing layer on SnCl2The reaction temperature and time in the solution can be such that SnCl2The solution is subjected to redox reaction, so that the replaced Sn ions are inserted into the molybdenum oxide spacing layer at a specific temperature, and the Sn ions are introduced between layers on the basis of not changing the in-layer structure of the molybdenum oxide, thereby improving the sensitivity and the detection limit of the substrate. Wherein the reaction temperature is 65 ℃, 68 ℃, 70 ℃, 73 ℃ or 75 ℃, preferably 70 ℃; the reaction time is specifically 40min, 50min, 60min or 70min, preferably 60 min.
The other purpose of the invention is realized by the following technical scheme: the Raman enhancement substrate based on the multilayer composite structure is prepared by the preparation method of the Raman enhancement substrate based on the multilayer composite structure, and comprises a substrate, a first molybdenum oxide layer, a first tin ion layer, a second molybdenum oxide layer, a second tin ion layer, a third molybdenum oxide layer … …, an N-1 molybdenum oxide layer, an N-1 tin ion layer and an N-molybdenum oxide layer which are sequentially connected from bottom to top.
The Raman enhanced substrate based on the multilayer composite structure, which is prepared by the invention, does not change the inner layer structure of molybdenum oxide, does not introduce defects, realizes doping by introducing interlayer ions, has stable quality, high sensitivity, high detection limit and good uniformity, can be stored in the atmosphere for more than 6 months, and still keeps the original detection performance of more than 98%. The number of the molybdenum oxide layers N is determined by the thickness of the molybdenum oxide generated by deposition, and the specific number of the layers N is equal to the thickness (nm) of the molybdenum oxide/1.4 nm.
The other purpose of the invention is realized by the following technical scheme: a method for applying a Raman-enhanced substrate based on a multilayer composite structure comprises the following steps:
placing the Raman enhancement substrate based on the multilayer composite structure in a molecular aqueous solution to be detected for 10-30min, then taking out, drying the surface to obtain a sample to be detected, and finally testing the Raman spectrum of the sample to be detected;
the Raman enhancement substrate based on the multilayer composite structure is prepared by the preparation method of the Raman enhancement substrate based on the multilayer composite structure.
The application method disclosed by the invention is applied to SERS detection, and has the advantages of high detection stability, high sensitivity, high detection limit and good uniformity, and the performance can be preserved in the atmosphere for more than 6 months and still can be kept at more than 98% of the original detection performance.
The invention has the beneficial effects that: the preparation method of the Raman enhanced substrate based on the multilayer composite structure is simple and rapid, the in-layer structure of molybdenum oxide is not changed, defects are not introduced, doping is realized by introducing interlayer ions, the prepared Raman enhanced substrate based on the multilayer composite structure has stable quality, low cost, high sensitivity, high detection limit and good uniformity, the performance can be kept for more than 6 months in the atmosphere and still can keep more than 98% of the original detection performance, the preparation method can be continuously prepared in a large scale, the multilayer molybdenum oxide layer can be formed, and tin ions are introduced between the layers, so that the sensitivity and the detection limit of the substrate are improved.
According to the Raman enhanced substrate based on the multilayer composite structure, the in-layer structure of molybdenum oxide is not changed, Sn ions are introduced between layers of the molybdenum oxide, the quality is stable, and the sensitivity is high.
The prepared Raman enhancement substrate based on the multilayer composite structure is applied to SERS detection, has high detection stability, high sensitivity, high detection limit and good uniformity, and can be stored in the atmosphere for more than 6 months and still keep the original detection performance of more than 98%.
Drawings
FIG. 1 is a schematic view of a composite laminate in vertical section according to step A of example 1 of the present invention;
FIG. 2 is an exploded view of the composite laminate of step A of example 1 of the present invention;
fig. 3 is a schematic structural diagram of a raman enhancement substrate based on a multilayer composite structure according to embodiments 2 and 3 of the present invention after a probe molecule is adsorbed on the surface;
FIG. 4 is a Raman enhancement contrast spectrum of a multilayer composite structure-based Raman enhancement substrate and molybdenum oxide with the same thickness for detecting R6 molecules in example 2 of the invention;
FIG. 5 is a Raman spectrum of a Raman-enhanced substrate based on a multilayer composite structure for detecting R6 molecules in example 2 of the invention;
fig. 6 is a raman spectrum stability test of a multilayer composite structure-based raman enhanced substrate for detecting MB molecules in example 3 of the present invention.
The reference signs are: 1-quartz substrate, 2-substrate, 3-spacer, 31-gap, 4-molybdenum sheet, 5-composite lamination, 6-molybdenum oxide, 7-Sn ion layer and 8-detection molecular layer.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and accompanying fig. 1 to 6, and the content of the embodiments is not intended to limit the present invention.
Example 1
A preparation method of a Raman enhanced substrate based on a multilayer composite structure comprises the following steps:
A. several cross-sectional areas of 1 x 1cm are placed on a quartz substrate 12Of each substrate 2, in the substrate 2A spacer 3 is placed on the upper surface of each of the spacers 3, and a cross-sectional area of 1X 1cm is placed on the upper surface of each of the spacers 32Obtaining a plurality of composite laminates 5 from the molybdenum sheet 4;
B. preparing a molybdenum oxide substrate: putting the quartz substrate 1 with the plurality of composite laminates 5 in preheated 600 ℃ heating equipment for heat treatment, and reacting for 5min at 600 ℃; taking out the quartz substrate 1, cooling, and removing the separator 3 to obtain a molybdenum oxide substrate;
C. blending SnCl2Solution: SnCl with the concentration of 10nmol/L is prepared in a glass container2Solution, then to SnCl2Adding dilute hydrochloric acid dropwise into the solution to adjust SnCl2The pH value of the solution is 5-6;
D. preparing a finished product: placing the molybdenum oxide substrate prepared in the step B in SnCl after the pH value is adjusted in the step C2In solution, and placing SnCl with a molybdenum oxide substrate2And placing the solution on a hot table preheated to 70 ℃ for interlayer insertion Sn ion treatment, reacting for 60min, taking out the molybdenum oxide substrate, and blow-drying by using a nitrogen gun to obtain the multilayer composite structure-based Raman enhancement substrate.
In the step A, the substrate 2 is SiO2A substrate or a Si substrate.
In the step a, the spacer 3 is an annular spacer with a notch 31; the spacer 3 is an alumina spacer.
The thickness of the separator 3 is 0.5mm, and the thickness of the molybdenum sheet 4 is 0.2 mm.
Before the step C, removing stray molybdenum oxide, and specifically comprising the following steps: and D, cooling the molybdenum oxide substrate prepared in the step B, inverting and compacting the substrate 2 on the adhesive tape, tearing off the adhesive tape, and removing the stray molybdenum oxide on the upper surface of the molybdenum oxide substrate.
The Raman enhancement substrate based on the multilayer composite structure is prepared by the preparation method of the Raman enhancement substrate based on the multilayer composite structure, and comprises a substrate 1, a first molybdenum oxide layer, a first tin ion layer, a second molybdenum oxide layer, a second tin ion layer, a third molybdenum oxide layer … …, an N-1 molybdenum oxide layer, an N-1 tin ion layer and an N-molybdenum oxide layer which are sequentially connected from bottom to top.
Example 2
A method for applying a Raman-enhanced substrate based on a multilayer composite structure comprises the following steps:
step (1): taking R6G molecule, dissolving in deionized water to prepare the solution with the concentration of 4 multiplied by 10-6Molecular solution of R6G of M;
step (2): the multilayer composite structure-based raman-enhanced substrate prepared in example 2 was placed at step (1)4 × 10-6Placing the M in an R6G molecular solution for 20min, taking out, and drying the surface by blowing to obtain a sample to be detected;
and (3): measuring the intensity of R6G molecule at 1100cm by using a micro-Raman spectrometer with excitation light of 514nm and 50 times of eyepiece, wherein the intensity of the excitation light is 0.625mW, and the integration time is 10s-1-1700cm-1The characteristic vibration of (1); and is equivalent to pure molybdenum oxide with the same thickness (100nm) for 4X 10-6The Raman enhancement effect of the R6G molecular solution of M.
As shown in fig. 4, compared with a raman enhancement spectrum of a molybdenum oxide with the same thickness for detecting R6 molecules, the enhancement effect of the multilayer composite structure-based raman enhancement substrate of embodiment 3 is far better than that of pure molybdenum oxide, which indicates that the multilayer composite structure-based raman enhancement substrate of the present invention has high sensitivity, high detection limit, and good uniformity.
As shown in fig. 5, it is shown that the raman spectrum of the R6G molecule adsorbed on the raman-enhanced substrate with the multilayer composite structure is substantially unchanged after 207 days, and still maintains 98.9% of the original intensity, which indicates that the raman-enhanced substrate with the multilayer composite structure prepared by the present invention has higher stability.
Example 3
A method for applying a Raman-enhanced substrate based on a multilayer composite structure comprises the following steps:
step (1): dissolving MB molecules in deionized water to obtain the final product with concentration of 4 × 10-3M、4×10-4M、4×10-5M、4×10-6M、4×10-7M、1×10-7M、6×10-8M、2×10-8MB molecule solution of M;
step (2): the multilayer composite structure-based raman-enhanced substrates prepared in example 2 were placed at the concentrations of 4 × 10 in step (1), respectively-3M、4×10-4M、4×10-5M、4×10-6M、4×10-7M、1×10-7M、6×10-8M、2×10-8Placing the M MB molecular solution for 20min, taking out, and drying the surface to obtain a sample to be detected;
and (3): measuring MB molecule at 1100cm by using a micro-Raman spectrometer with excitation light wavelength of 633nm and 50-fold eyepiece, wherein the excitation light intensity is 0.945mW, the integration time is 10s-1-1700cm-1Characteristic vibration of (2).
The test result is shown in FIG. 6, and the detection limit of the Raman enhanced substrate based on the multilayer composite structure on the MB molecular solution can reach 2 x 10-8M shows that the multilayer composite structure Raman enhanced substrate prepared by the invention has high detection limit and high sensitivity.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (8)
1. A preparation method of a Raman enhanced substrate based on a multilayer composite structure is characterized by comprising the following steps: the method comprises the following steps:
A. preparing a composite laminate: placing a plurality of substrates on a quartz substrate, placing an isolator on the upper surface of each substrate, and placing a molybdenum sheet on the upper surface of each isolator to obtain a plurality of composite laminates;
B. preparing a molybdenum oxide substrate: placing the quartz substrate with the plurality of composite laminates into preheated heating equipment for heat treatment; taking out the quartz substrate, cooling, and removing the separator to obtain a molybdenum oxide substrate;
C. blending SnCl2Solution: prepared in a glass container at a concentration of 10nmol/LSnCl2Solution, then to SnCl2Adding dilute hydrochloric acid dropwise into the solution to adjust SnCl2The pH value of the solution is 5-6;
D. preparing a finished product: placing the molybdenum oxide substrate prepared in the step B in SnCl after the pH value is adjusted in the step C2In solution, and placing SnCl with a molybdenum oxide substrate2Placing the solution on a preheated hot table for interlayer insertion Sn ion treatment, taking out the molybdenum oxide substrate, and blow-drying by using a nitrogen gun to prepare the Raman enhancement substrate based on the multilayer composite structure;
in the step B, the temperature of the heat treatment is 540-650 ℃, and the treatment time is 3-8 min;
in the step D, the hot stage is preheated to 65-75 ℃ in advance, the treatment temperature of interlayer insertion Sn ion treatment is 65-75 ℃, and the treatment time is 40-70 min.
2. The method of claim 1, wherein the raman-enhanced substrate comprises a multilayer composite structure comprising: in the step A, the substrate is SiO2A substrate or a Si substrate; the cross-sectional area of the substrate is 1 × 1cm2(ii) a The cross section area of the molybdenum sheet is 1 multiplied by 1cm2。
3. The method of claim 1, wherein the raman-enhanced substrate comprises a multilayer composite structure comprising: in the step A, the spacer is an annular spacer with a notch; the spacer is an alumina spacer.
4. The method of claim 1, wherein the raman-enhanced substrate comprises a multilayer composite structure comprising: in the step A, the thickness of the separator is 0.4-0.6mm, and the thickness of the molybdenum sheet is 0.1-0.3 mm.
5. The method of claim 1, wherein the raman-enhanced substrate comprises a multilayer composite structure comprising: in the step B, the heating equipment is preheated to 540-650 ℃ in advance, and the heating equipment is a hot platform or a muffle furnace.
6. The method of claim 1, wherein the raman-enhanced substrate comprises a multilayer composite structure comprising: before the step C, removing stray molybdenum oxide, and specifically comprising the following steps: and D, cooling the molybdenum oxide substrate prepared in the step B, reversely compacting the substrate on the adhesive tape, tearing off the adhesive tape, and removing the stray molybdenum oxide on the upper surface of the molybdenum oxide substrate.
7. A raman-enhanced substrate based on a multilayer composite structure, characterized in that: the Raman enhancement substrate based on the multilayer composite structure is prepared by the preparation method of the Raman enhancement substrate based on the multilayer composite structure, which comprises a substrate, a first molybdenum oxide layer, a first tin ion layer, a second molybdenum oxide layer, a second tin ion layer, a third molybdenum oxide layer … …, an N-1 molybdenum oxide layer, an N-1 tin ion layer and an N-molybdenum oxide layer which are sequentially connected from bottom to top.
8. An application method of a Raman enhanced substrate based on a multilayer composite structure is characterized in that: the method comprises the following steps:
placing the Raman enhancement substrate based on the multilayer composite structure in a molecular aqueous solution to be detected for 10-30min, then taking out, drying the surface to obtain a sample to be detected, and finally testing the Raman spectrum of the sample to be detected;
the multilayer composite structure-based raman-enhanced substrate is produced by the method for producing a multilayer composite structure-based raman-enhanced substrate according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910702289.4A CN110412010B (en) | 2019-07-31 | 2019-07-31 | Preparation and application of Raman enhanced substrate based on multilayer composite structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910702289.4A CN110412010B (en) | 2019-07-31 | 2019-07-31 | Preparation and application of Raman enhanced substrate based on multilayer composite structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110412010A CN110412010A (en) | 2019-11-05 |
| CN110412010B true CN110412010B (en) | 2020-02-21 |
Family
ID=68364815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910702289.4A Active CN110412010B (en) | 2019-07-31 | 2019-07-31 | Preparation and application of Raman enhanced substrate based on multilayer composite structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110412010B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112577943B (en) * | 2020-12-11 | 2021-08-10 | 广东食品药品职业学院 | Array type surface Raman enhanced substrate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426610A (en) * | 2000-04-26 | 2003-06-25 | 三洋电机株式会社 | Lithium secondary battery-use electrode and lithium secondary battery |
| CN101776604A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Production method of basement for enhancing raman scattering of molecule |
| CN103575721A (en) * | 2013-11-07 | 2014-02-12 | 无锡英普林纳米科技有限公司 | Multilayer structure surface enhanced Raman scattering base and preparation method thereof |
-
2019
- 2019-07-31 CN CN201910702289.4A patent/CN110412010B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426610A (en) * | 2000-04-26 | 2003-06-25 | 三洋电机株式会社 | Lithium secondary battery-use electrode and lithium secondary battery |
| CN101776604A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Production method of basement for enhancing raman scattering of molecule |
| CN103575721A (en) * | 2013-11-07 | 2014-02-12 | 无锡英普林纳米科技有限公司 | Multilayer structure surface enhanced Raman scattering base and preparation method thereof |
Non-Patent Citations (7)
| Title |
|---|
| 《Noble metal-comparable SERS enhancement from semiconducting metal oxides by making oxygen vacancies》;Shan Cong等;《NATURE COMMUNICATIONS》;20150717;全文 * |
| 《Rapid preparation of large size, few-layered MoO3 by anisotropic etching》;Qiulan Chen等;《Materials Letters》;20180710;全文 * |
| 《Surfactant-Free Nonaqueous Synthesis of Plasmonic Molybdenum Oxide Nanosheets with Enhanced Catalytic Activity for Hydrogen Generation from Ammonia Borane under Visible Light》;Hefeng Cheng等;《Angew. Chem. Int. Ed.》;20141231;第53卷;全文 * |
| 《基于核壳型结构纳米粒子的SERS活性基底研究进展》;温海滨等;《分析测试学报》;20160831;第35卷(第8期);全文 * |
| 《基于芯片实验室技术的表面增强光谱学在分析科学中的应用》;张浩等;《光谱学与光谱分析》;20170228;第37卷(第2期);全文 * |
| 《拉曼光谱技术在药物分析领域的研究进展》;曹露等;《光散射学报》;20190630;第31卷(第2期);全文 * |
| 《纳米氧化钼的制备和拉曼增强特性研究》;浮钰等;《第十九届全国光散射学术会议·广州》;20171231;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110412010A (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Deng et al. | Toward mass production of CVD graphene films | |
| US4181751A (en) | Process for the preparation of low temperature silicon nitride films by photochemical vapor deposition | |
| JP2011136414A (en) | Isotope-doped nano-material, method for producing the same, and labeling method | |
| CN110412010B (en) | Preparation and application of Raman enhanced substrate based on multilayer composite structure | |
| CN104803372B (en) | Graphene film, and making method and use thereof | |
| CN101824603A (en) | Method for manufacturing composite film gas sensor | |
| CH713453A1 (en) | Process for producing a substrate with a boron-doped surface. | |
| CN105319242A (en) | Application of tungsten oxide-vanadium oxide heterojunction nanowire array as gas sensitive material | |
| Fryček et al. | Thin organic layers prepared by MAPLE for gas sensor application | |
| JP2007062305A (en) | Transparent gas barrier substrate | |
| CN106979943B (en) | The preparation method of high-sensitivity surface enhancing Raman scattering substrate | |
| CN110054791B (en) | MOFs-noble metal ordered composite material and preparation method and application thereof | |
| US11261093B2 (en) | Method for nitrogen doping of solid materials | |
| JP2006156995A5 (en) | ||
| CN101798183A (en) | Preparation method of Al-Doped ZnO film | |
| CN102642822B (en) | Method for separating metal-type and semiconductor-type single-walled carbon nanotube arrays | |
| CN109400641B (en) | Colloidal quantum dot modification method | |
| CN114563388A (en) | Compound SERS substrate based on carbon six-membered ring structure and preparation method and application thereof | |
| JP5434056B2 (en) | Method for evaluating metal contamination of semiconductor substrates | |
| CN106950213B (en) | Preparation method of nano heterojunction surface enhanced Raman active substrate | |
| TW201912574A (en) | Surface-enhanced raman scattering sensing substrate having graphite oxide composite film and manufacturing method thereof | |
| CN108609614A (en) | A kind of preparation method of blue, purple fluorescent single nitrogen-doped graphene | |
| WO2013185440A1 (en) | Method for manufacturing gas sensor based on dye-sensitized tio2 film | |
| Carbone | Adsorption of formic acid on Si (111) 7× 7 at room temperature: a valence band photoemission and Si2p photodesorption study | |
| Horvath et al. | Investigation of SnO2 thin film evolution by thermoanalytical and spectroscopic methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |