CN113533295A - Based on ReS2Three-dimensional SERS substrate and preparation method and application thereof - Google Patents
Based on ReS2Three-dimensional SERS substrate and preparation method and application thereof Download PDFInfo
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title description 13
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- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 48
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- 239000010408 film Substances 0.000 claims description 40
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
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- 238000007747 plating Methods 0.000 claims description 8
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- 238000007733 ion plating Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
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- 230000003247 decreasing effect Effects 0.000 claims 1
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- USWJSZNKYVUTIE-UHFFFAOYSA-N bis(sulfanylidene)rhenium Chemical compound S=[Re]=S USWJSZNKYVUTIE-UHFFFAOYSA-N 0.000 abstract description 6
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- 238000001069 Raman spectroscopy Methods 0.000 description 6
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G47/00—Compounds of rhenium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a method based on ReS2The three-dimensional SERS substrate comprises a substrate, wherein the surface of the substrate is sequentially coated with Au, ReS2 and Ag films. The existence of the Au film can effectively help the rhenium disulfide nanosheets to be adsorbed on the substrate to form a three-dimensional nano cavity, so that sufficient adsorption is provided for Ag and objects to be detectedArea, and then can show promotion SERS's sensitivity.
Description
Technical Field
The invention belongs to a Raman detection technologyField, especially relating to based on ReS2The three-dimensional SERS substrate and the preparation method and the application thereof.
Background
The statements in this section merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The Surface Enhanced Raman Spectroscopy (SERS) technology is a nondestructive and ultrasensitive analysis technology, and is used for accurately and sensitively identifying the specificity of a substance through the characteristic vibration peak of a special group in the substance. In long-term SERS research, noble metals (Au, Ag and Cu) are found to show strong SERS effect, so that the noble metals become hot spots for researching SERS substrates. However, the noble metal SERS substrate has a single function, and the development thereof is greatly limited.
Researches have proved that the composite material formed by combining the two-dimensional material and the noble metal has more excellent detection capability and diversified functions than the two-dimensional material and the noble metal material which are independent. The existing composite material consisting of two-dimensional material and noble metal is often combined by molybdenum disulfide, gold and silver. However, the above solution has several problems: the preparation process mostly needs to go through the steps of growth, centrifugation, transfer and the like, and the experiment is complicated; the transfer coating process can cause poor uniformity of the substrate and is difficult to meet the actual detection requirement; the composite material has weak interaction with the substrate, is easy to fall off and has poor stability.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method based on ReS2The three-dimensional SERS substrate and the preparation method and the application thereof. The existence of the Au film can effectively help the rhenium disulfide nanosheets to be adsorbed on the substrate to form a three-dimensional nano cavity, so that a sufficient adsorption area is provided for Ag and an object to be detected, and the sensitivity of SERS can be obviously improved.
In order to achieve the above object, one or more embodiments of the present invention provide the following technical solutions:
based on Ree2The three-dimensional SERS substrate comprises a substrate, wherein the surface of the substrate is sequentially coated with Au and ReS2And Ag thin films.
Further, the method comprises the following steps:
evaporating and plating an Au film on the substrate;
mixing ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine in deionized water to obtain a precursor solution;
heating the substrate coated with the Au thin film and the precursor liquid to obtain the substrate coated with Au/ReS2A substrate of composite nanoplatelets;
in the coating of Au/ReS2And evaporating a layer of Ag film on the substrate of the composite nanosheet to obtain the SERS substrate with the Au/ReS2/Ag composite structure.
Further, before an Au film is evaporated on the substrate, the substrate is cleaned.
Further, the evaporation plating adopts a vacuum evaporation plating method, a magnetron sputtering plating method or an ion plating method.
Further, the Au thin film is 7 nm.
Further, the concentrations of the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are all 0.1M, the volumes of the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are 0.4-1 ml, 3ml and 3ml respectively, and the volume of the deionized water is 3 ml.
Further, heating the substrate and the precursor solution which are evaporated with the Au thin film by adopting a 25-500 ml hydrothermal reaction kettle, keeping the temperature for 2-6 hours after the temperature reaches 200 ℃, and then slowly cooling to room temperature.
Further, the Ag thin film is 15 nm.
One or more embodiments provide a SERS sensor comprising the SERS substrate.
One or more embodiments provide a SERS sensor system including the SERS sensor.
The above one or more technical solutions have the following beneficial effects:
the technical scheme provides the Au/ReS2/Ag three-dimensional composite material substrate, wherein the existence of the Au film can effectively help the rhenium disulfide nanosheets to be adsorbed on the substrate to form a three-dimensional nano cavity, so that a sufficient adsorption area is provided for Ag and an object to be detected, and the sensitivity of SERS can be obviously improved;
the large-area and high-quality ReS2 nanosheets are compounded with Ag nanoparticles, so that the service life of hot electrons is effectively prolonged.
The characteristic that the ReS2 nanosheets deform under the change of environmental temperature can realize hot spot regulation of the SERS substrate.
When the preparation method is used, the Au modified pyramid silicon wafer is placed in a hydrothermal reaction kettle, after heating is completed, a layer of Ag is plated on the surface of the substrate, and the Au/ReS2/Ag composite material with large area and high quality can be obtained.
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 a scanning electron microscope image of the novel SERS substrate of Au/ReS2/Ag thin film provided by the invention;
FIG. 2 is a Raman spectrum of the Au/ReS2/Ag thin film novel SERS substrate prepared according to the embodiment of the invention;
FIG. 3 is a comparison of Raman enhancement effects of the Au/ReS2/Ag thin film novel SERS substrate comparison substrate prepared according to the embodiment of the invention on rhodamine 6G molecules;
FIG. 4 is a temperature response Raman spectrum of the Au/ReS2/Ag thin film novel SERS substrate prepared according to the embodiment of the invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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 invention 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 exemplary embodiments according to the invention. 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.
The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
Rhenium disulfide (ReS2) is a novel transition metal double-halogenated hydrocarbon material, has the characteristics of stable chemical property, large surface area, high carrier mobility and the like, and has proved that the ReS2 film has a remarkable Raman enhancement effect. However, the current research has not fully applied the ReS2 to Raman detection to explore its potential for development in this area.
One or more embodiments of the invention provide a three-dimensional SERS substrate based on ReS2, which comprises a substrate, wherein the surface of the substrate is sequentially coated with gold, rhenium disulfide and a silver film. The characteristic that the ReS2 nanosheets deform under the change of environmental temperature can realize hot spot regulation of the SERS substrate. Ag nanoparticles are adsorbed on the ReS2 nanosheets, and the sensitivity of SERS can be remarkably improved.
The preparation method of the three-dimensional SERS substrate comprises the following steps:
evaporating and plating an Au film on the substrate;
mixing ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine in deionized water to obtain a precursor solution;
heating the substrate coated with the Au thin film and the precursor liquid to obtain the substrate coated with Au/ReS2A substrate of composite nanoplatelets;
in the coating of Au/ReS2And evaporating a layer of Ag film on the substrate of the composite nanosheet to obtain the SERS substrate with the Au/ReS2/Ag composite structure.
Wherein, the evaporation coating can adopt a vacuum evaporation coating method, a magnetron sputtering coating method or an ion coating method.
Example 1
The embodiment provides a preparation method of a three-dimensional SERS substrate based on ReS2, which specifically comprises the following steps:
(1) cleaning the substrate:
the method comprises the following steps of (1) putting a substrate made of a monocrystalline silicon material into acetone, and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; then putting the substrate into ethanol and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; finally, the substrate is further placed into deionized water to be ultrasonically cleaned in an ultrasonic machine for fifteen minutes, and the clean substrate is obtained. The substrate is made of pyramidal silicon.
(2) Preparing a gold film:
and (2) putting the cleaned substrate obtained by cleaning in the step (1) into vacuum evaporation coating equipment, wherein an evaporation source adopts a gold rake with the purity of 99.99%, vacuumizing to 8 x 10 < -6 > Torr (Torr), controlling the rate of current for evaporation, and depositing an Au film with the thickness of about 7nm on the cleaned and flat substrate.
(3) Preparing a precursor solution:
weighing certain mass of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine powder by a one-ten-thousandth balance and putting into a container. Deionized water is taken by a liquid transfer gun and is injected into a container containing the mixed powder to prepare precursor liquid. And then putting the precursor solution into an ultrasonic machine for ultrasonic treatment for 20 minutes to crush the mixed powder and form a uniform solution. Specifically, the concentrations of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine are all 0.1M, the volumes of the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are respectively 0.4-1 ml, 3ml and 3ml, and the volume of deionized water is 3 ml.
(4) Transfer of precursor solution:
and (4) transferring the precursor solution prepared in the step (3) into a hydrothermal reaction kettle of 25-500 ml by using a liquid transfer gun.
(5) Heating to obtain Au/ReS2Substrate:
and (5) placing the hydrothermal reaction kettle obtained in the step (4) into a thermostat to heat, and keeping the temperature for 2 hours after the temperature reaches 200 ℃. After which the oven was slowly cooled to room temperature. Taking out from the hydrothermal reaction kettle to obtain 70nm Au/ReS2A substrate.
(6) Vapor deposition treatment to obtain Au/ReS2Ag film novel SERS substrate:
the Au/ReS obtained in the step (5) is added2Putting the substrate into vacuum evaporation coating equipment, adopting a silver rake with the purity of 99.99 percent as an evaporation source,vacuumizing to 8 multiplied by 10 < -6 > Torr (Torr), controlling the rate of current for evaporation, and depositing a layer of Ag with the thickness of about 15nm on a clean and flat substrate to obtain the novel SERS substrate of the Au/ReS2/Ag film.
Example 2
The embodiment provides a preparation method of a three-dimensional SERS substrate based on ReS2, which specifically comprises the following steps:
(1) cleaning the substrate:
the method comprises the following steps of (1) putting a substrate made of a monocrystalline silicon material into acetone, and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; then putting the substrate into ethanol and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; finally, the substrate is further placed into deionized water to be ultrasonically cleaned in an ultrasonic machine for fifteen minutes, and the clean substrate is obtained. The substrate is made of pyramidal silicon.
(2) Preparing a gold film:
and (2) putting the cleaned substrate obtained by cleaning in the step (1) into vacuum evaporation coating equipment, wherein an evaporation source adopts a gold rake with the purity of 99.99%, vacuumizing to 8 x 10 < -6 > Torr (Torr), controlling the rate of current for evaporation, and depositing an Au film with the thickness of about 7nm on the cleaned and flat substrate.
(3) Preparing a precursor solution:
weighing certain mass of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine powder by a one-ten-thousandth balance and putting into a container. Deionized water is taken by a liquid transfer gun and is injected into a container containing the mixed powder to prepare precursor liquid. And then putting the precursor solution into an ultrasonic machine for ultrasonic treatment for 20 minutes to crush the mixed powder and form a uniform solution. Specifically, the concentrations of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine are all 0.1M, the volumes of the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are respectively 0.4-1 ml, 3ml and 3ml, and the volume of deionized water is 3 ml.
(4) Transfer of precursor solution:
and (4) transferring the precursor solution prepared in the step (3) into a hydrothermal reaction kettle of 25-500 ml by using a liquid transfer gun.
(5) Heating to obtain Au/ReS2Substrate:
putting the hydrothermal reaction kettle obtained in the step (4) into a thermostat for heating until the temperature reachesAfter reaching 200 ℃, the temperature is kept constant for 6 hours. After which the oven was slowly cooled to room temperature. Taking out from the hydrothermal reaction kettle to obtain 70nm Au/ReS2A substrate.
(6) Vapor deposition treatment to obtain Au/ReS2Ag film novel SERS substrate:
the Au/ReS obtained in the step (5) is added2Putting the substrate into vacuum evaporation coating equipment, vacuumizing an evaporation source to 8 x 10 < -6 > Torr (Torr) by adopting a silver rake with the purity of 99.99%, controlling the rate of current for evaporation, and depositing a layer of Ag with the thickness of about 15nm on a clean and flat substrate to obtain the novel SERS substrate of the Au/ReS2/Ag film.
Example 3
The embodiment discloses a preparation method of a three-dimensional SERS substrate based on ReS2, which specifically comprises the following steps:
(1) cleaning the substrate:
the method comprises the following steps of (1) putting a substrate made of a monocrystalline silicon material into acetone, and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; then putting the substrate into ethanol and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; finally, the substrate is further placed into deionized water to be ultrasonically cleaned in an ultrasonic machine for fifteen minutes, and the clean substrate is obtained. The substrate is made of pyramidal silicon.
(2) Preparing a gold film:
and (2) putting the cleaned substrate obtained by cleaning in the step (1) into a magnetron sputtering coating device, vacuumizing an evaporation source to 8 x 10 < -6 > Torr (Torr) by adopting a gold rake with the purity of 99.99%, controlling the rate of current for evaporation, and depositing an Au film with the thickness of about 7nm on the cleaned and flat substrate.
(3) Preparing a precursor solution:
weighing certain mass of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine powder by a one-ten-thousandth balance and putting into a container. Deionized water is taken by a liquid transfer gun and is injected into a container containing the mixed powder to prepare precursor liquid. And then putting the precursor solution into an ultrasonic machine for ultrasonic treatment for 20 minutes to crush the mixed powder and form a uniform solution. Specifically, the concentrations of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine are all 0.1M, the volumes of the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are respectively 0.4-1 ml, 3ml and 3ml, and the volume of deionized water is 3 ml.
(4) Transfer of precursor solution:
and (4) transferring the precursor solution prepared in the step (3) into a hydrothermal reaction kettle of 25-500 ml by using a liquid transfer gun.
(5) Heating to obtain Au/ReS2Substrate:
and (5) placing the hydrothermal reaction kettle obtained in the step (4) into a thermostat to heat, and keeping the temperature for 2 hours after the temperature reaches 200 ℃. After which the oven was slowly cooled to room temperature. Taking out from the hydrothermal reaction kettle to obtain 70nm Au/ReS2A substrate.
(6) Vapor deposition treatment to obtain Au/ReS2Ag film novel SERS substrate:
the Au/ReS obtained in the step (5) is added2Putting the substrate into a magnetron sputtering coating device, vacuumizing an evaporation source to 8 x 10 < -6 > Torr (Torr) by adopting a silver rake with the purity of 99.99%, controlling the rate of current for evaporation, and depositing a layer of Ag with the thickness of about 15nm on a clean and flat substrate to obtain the novel SERS substrate of the Au/ReS2/Ag film.
Example 4
The embodiment discloses a preparation method of a three-dimensional SERS substrate based on ReS2, which specifically comprises the following steps:
(1) cleaning the substrate:
the method comprises the following steps of (1) putting a substrate made of a monocrystalline silicon material into acetone, and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; then putting the substrate into ethanol and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; finally, the substrate is further placed into deionized water to be ultrasonically cleaned in an ultrasonic machine for fifteen minutes, and the clean substrate is obtained. The substrate is made of pyramidal silicon.
(2) Preparing a gold film:
and (2) putting the cleaned substrate obtained by cleaning in the step (1) into a magnetron sputtering coating device, vacuumizing an evaporation source to 8 x 10 < -6 > Torr (Torr) by adopting a gold rake with the purity of 99.99%, controlling the rate of current for evaporation, and depositing an Au film with the thickness of about 7nm on the cleaned and flat substrate.
(3) Preparing a precursor solution:
weighing certain mass of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine powder by a one-ten-thousandth balance and putting into a container. Deionized water is taken by a liquid transfer gun and is injected into a container containing the mixed powder to prepare precursor liquid. And then putting the precursor solution into an ultrasonic machine for ultrasonic treatment for 20 minutes to crush the mixed powder and form a uniform solution. Specifically, the concentrations of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine are all 0.1M, the volumes of the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are respectively 0.4-1 ml, 3ml and 3ml, and the volume of deionized water is 3 ml.
(4) Transfer of precursor solution:
and (4) transferring the precursor solution prepared in the step (3) into a hydrothermal reaction kettle of 25-500 ml by using a liquid transfer gun.
(5) Heating to obtain Au/ReS2Substrate:
and (5) placing the hydrothermal reaction kettle obtained in the step (4) into a thermostat to heat, and keeping the temperature for 6 hours after the temperature reaches 200 ℃. After which the oven was slowly cooled to room temperature. Taking out from the hydrothermal reaction kettle to obtain 70nm Au/ReS2A substrate.
(6) Vapor deposition treatment to obtain Au/ReS2Ag film novel SERS substrate:
the Au/ReS obtained in the step (5) is added2Putting the substrate into a magnetron sputtering coating device, performing evaporation coating by using a silver rake with the purity of 99.99 percent and controlling the current rate after vacuumizing to 8 multiplied by 10 < -6 > Torr, and depositing a layer of Ag with the thickness of about 15nm on a clean and flat substrate to obtain Au/ReS2The Ag film novel SERS substrate.
Example 5
The embodiment discloses that the embodiment provides a method based on the ReS2The preparation method of the three-dimensional SERS substrate specifically comprises the following steps:
(1) cleaning the substrate:
the method comprises the following steps of (1) putting a substrate made of a monocrystalline silicon material into acetone, and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; then putting the substrate into ethanol and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; finally, the substrate is further placed into deionized water to be ultrasonically cleaned in an ultrasonic machine for fifteen minutes, and the clean substrate is obtained. The substrate is made of pyramidal silicon.
(2) Preparing a gold film:
putting the cleaned substrate obtained by cleaning in the step (1) into ion plating equipment, vacuumizing an evaporation source to 8 x 10 < -6 > Torr (Torr) by adopting a gold rake with the purity of 99.99%, controlling the rate of current for evaporation, and depositing an Au film with the thickness of about 7nm on the cleaned and flat substrate.
(3) Preparing a precursor solution:
weighing certain mass of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine powder by a one-ten-thousandth balance and putting into a container. Deionized water is taken by a liquid transfer gun and is injected into a container containing the mixed powder to prepare precursor liquid. And then putting the precursor solution into an ultrasonic machine for ultrasonic treatment for 20 minutes to crush the mixed powder and form a uniform solution. Specifically, the concentrations of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine are all 0.1M, the volumes of the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are respectively 0.4-1 ml, 3ml and 3ml, and the volume of deionized water is 3 ml.
(4) Transfer of precursor solution:
and (4) transferring the precursor solution prepared in the step (3) into a hydrothermal reaction kettle of 25-500 ml by using a liquid transfer gun.
(5) Heating to obtain Au/ReS2Substrate:
and (5) placing the hydrothermal reaction kettle obtained in the step (4) into a thermostat to heat, and keeping the temperature for 2 hours after the temperature reaches 200 ℃. After which the oven was slowly cooled to room temperature. Taking out from the hydrothermal reaction kettle to obtain 70nm Au/ReS2A substrate.
(6) Vapor deposition treatment to obtain Au/ReS2Ag film novel SERS substrate:
the Au/ReS obtained in the step (5) is added2Putting the substrate into ion plating equipment, performing evaporation plating by using a silver rake with the purity of 99.99 percent and controlling the current rate after vacuumizing to 8 multiplied by 10 < -6 > Torr, and depositing a layer of Ag with the thickness of about 15nm on a clean and flat substrate to obtain Au/ReS2The Ag film novel SERS substrate.
Example 6
The embodiment discloses that the embodiment provides a method based on the ReS2The preparation method of the three-dimensional SERS substrate specifically comprises the following steps:
(1) cleaning the substrate:
the method comprises the following steps of (1) putting a substrate made of a monocrystalline silicon material into acetone, and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; then putting the substrate into ethanol and ultrasonically cleaning the substrate in an ultrasonic machine for fifteen minutes; finally, the substrate is further placed into deionized water to be ultrasonically cleaned in an ultrasonic machine for fifteen minutes, and the clean substrate is obtained. The substrate is made of pyramidal silicon.
(2) Preparing a gold film:
putting the cleaned substrate obtained by cleaning in the step (1) into ion plating equipment, vacuumizing an evaporation source to 8 x 10 < -6 > Torr (Torr) by adopting a gold rake with the purity of 99.99%, controlling the rate of current for evaporation, and depositing an Au film with the thickness of about 7nm on the cleaned and flat substrate.
(3) Preparing a precursor solution:
weighing certain mass of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine powder by a one-ten-thousandth balance and putting into a container. Deionized water is taken by a liquid transfer gun and is injected into a container containing the mixed powder to prepare precursor liquid. And then putting the precursor solution into an ultrasonic machine for ultrasonic treatment for 20 minutes to crush the mixed powder and form a uniform solution. Specifically, the concentrations of ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine are all 0.1M, the volumes of the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are respectively 0.4-1 ml, 3ml and 3ml, and the volume of deionized water is 3 ml.
(4) Transfer of precursor solution:
and (4) transferring the precursor solution prepared in the step (3) into a hydrothermal reaction kettle of 25-500 ml by using a liquid transfer gun.
(5) Heating to obtain Au/ReS2Substrate:
and (5) placing the hydrothermal reaction kettle obtained in the step (4) into a thermostat to heat, and keeping the temperature for 6 hours after the temperature reaches 200 ℃. After which the oven was slowly cooled to room temperature. Taking out from the hydrothermal reaction kettle to obtain 70nm Au/ReS2A substrate.
(6) Vapor deposition treatment to obtain Au/ReS2Ag film novel SERS substrate:
the Au/ReS obtained in the step (5) is added2Putting the substrate into ion plating equipment, performing evaporation plating by using a silver rake with the purity of 99.99 percent and controlling the current rate after vacuumizing to 8 multiplied by 10 < -6 > Torr, and depositing a layer of Ag with the thickness of about 15nm on a clean and flat substrate to obtain Au/ReS2The Ag film novel SERS substrate.
Fig. 1 is a scanning electron microscope image of a SERS substrate, and it can be seen that: (1) three-dimensional Au/ReS2The Ag film is closely attached to the surface of the substrate; (2) the prepared Ag nano-particles are dense and uniform in size.
Fig. 2 is a raman spectrum of the SERS substrate, from which it can be seen that: (1) presence of ReS2Further proves that Au/ReS is successfully prepared by the embodiment2The Ag/film composite material.
FIG. 3 shows Au/ReS prepared according to an embodiment of the present invention2The novel SERS substrate of the Ag film is compared with the Raman enhancement effect of the substrate on rhodamine 6G molecules, and the Au/ReS2/Ag film substrate is found to have an excellent SERS enhancement effect.
FIG. 4 shows Au/ReS prepared according to an embodiment of the present invention2The temperature response Raman spectrogram of the novel/Ag thin film SERS substrate shows that the Au/ReS2/Ag thin film substrate has the strongest SERS response at the ambient temperature of 45 ℃.
Au/ReS constructed in one or more of the above examples2The Au thin film can effectively help the rhenium disulfide nanosheets to be adsorbed on the substrate to form a three-dimensional nano cavity, so that a sufficient adsorption area is provided for Ag and an object to be detected, and the SERS can be remarkably improved. With respect to the sensitivity to temperature, the temperature response behavior of SERS can further promote the application and popularization of SERS in practice.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. Based on Ree2The three-dimensional SERS substrate is characterized by comprising a substrate, wherein the surface of the substrate is coated with Au and ReS in sequence2And Ag thin films.
2. A method of preparing the three-dimensional SERS substrate according to claim 1, comprising the steps of:
evaporating and plating an Au film on the substrate;
mixing ammonium perrhenate, hydroxylamine hydrochloride and L-cysteine in deionized water to obtain a precursor solution;
heating the substrate coated with the Au thin film and the precursor liquid to obtain the substrate coated with Au/ReS2A substrate of composite nanoplatelets;
in the coating of Au/ReS2Evaporating a layer of Ag film on the substrate of the composite nanosheet to obtain Au/ReS2The SERS substrate with the/Ag composite structure.
3. The method of claim 2, wherein the substrate is cleaned prior to the deposition of the Au film thereon.
4. The method of claim 2, wherein the evaporation is performed by vacuum evaporation, magnetron sputtering or ion plating.
5. The method of claim 2, wherein the Au thin film is 7 nm.
6. The method according to claim 2, wherein the ammonium perrhenate, the hydroxylamine hydrochloride and the L-cysteine are each at a concentration of 0.1M, and have a volume of 0.4 to 1ml, 3ml and 3ml, respectively, and the deionized water has a volume of 3 ml.
7. The method according to claim 2, wherein the substrate coated with the Au thin film and the precursor solution are heated in a 25-500 ml hydrothermal reaction kettle, and after the temperature reaches 200 ℃, the temperature is maintained for 2-6 hours, and then the temperature is slowly decreased to room temperature.
8. The method according to claim 2, wherein the Ag thin film is 15 nm.
9. A SERS sensor comprising the SERS substrate of claim 1.
10. A SERS sensor system comprising the SERS sensor of claim 9.
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