CN114525483B - Gold nano tree dendrite and preparation method and application thereof - Google Patents
Gold nano tree dendrite and preparation method and application thereof Download PDFInfo
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- CN114525483B CN114525483B CN202111664337.9A CN202111664337A CN114525483B CN 114525483 B CN114525483 B CN 114525483B CN 202111664337 A CN202111664337 A CN 202111664337A CN 114525483 B CN114525483 B CN 114525483B
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C23C14/34—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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
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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
Abstract
The invention discloses gold nano tree dendrites and a preparation method and application thereof. The dendrite consists of branched gold nano structures positioned at the edges of the gold nano film on the surface of the conductive substrate; the gold nano-tree dendrite is composed of a trunk and various levels of branch structures; the preparation method comprises the steps of sputtering a gold particle film on a conductive substrate, forming a long and narrow gap on the gold nano film, and electrodepositing the gold film edge at the gap or the gold film edge at the edge of the conductive substrate to prepare the gold nano dendrite structure. The gold nanodendrite is micro-nano structure, has the advantages of agglomeration resistance, large specific surface area and the like, particularly has pyramid-shaped gold nanostructure with three-dimensional space distribution, can be used as an active substrate of Surface Enhanced Raman Scattering (SERS) to measure trace organic matters attached on the surface enhanced Raman scattering, and has detection concentration as low as 10 ‑12 mol/L rhodamine 6G. By adjusting electrodeposition parameters, the Local Surface Plasmon Resonance (LSPR) peak of the gold nano dendrite can be regulated and controlled to be matched with 532nm excitation light.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to gold nano dendrites and a preparation method and application thereof.
Background
The Surface Enhanced Raman Scattering (SERS) spectrum technology has wide application prospect in the fields of trace detection and the like. Strong SERS activity requires a SERS substrate (typically gold or silver nanostructures) with a large number of hot spots and suitable surface plasmon resonance (local surface plasmon resonances, LSPR) peaks. SERS spectra originate mainly at hot spots of gold or silver nanostructures. Under the excitation of incident light with a specific wavelength, the narrow gap, sharp edge and sharp tip of the noble metal nano structure can generate strong local electromagnetic field, namely hot spot. When the excitation light wavelength is matched with the LSPR absorption peak of the gold or silver nano structure, a stronger Raman spectrum enhancement effect can be obtained. Gold has more stable chemical properties than silver and is not easily oxidized, so that the SERS performance of gold is more stable. In recent years, pyramid-shaped or pyramid-shaped gold nanostructures have received attention. For example, in 2007, published in Chemistry of Materials, volume 19, pages 4551-4556 (chem. Mater.2007,19, 4551-4556), entitled "Templated Fabrication ofPeriodic Metallic NanopyramidArrays", a report was made on a method of preparing an inverted pyramid-shaped pit array on a silicon wafer by using a single-layer non-densely arranged colloidal sphere template-assisted etching method, then sputtering a thicker gold film on the surface of the pit array, and then peeling the gold film, i.e., obtaining a pyramid-shaped nano array structure on the surface of the gold film, and studying the SERS performance of the array structure. An array of pyramid or pyramid-shaped gold nanostructures was reported in 2022, volume 33, article No. 095303 (Nanotechnology, 2022,33,095303), entitled "Hexagonal arrays ofplasmonic gold nanopyramids on flexible substrates for surface-enhanced Raman scattering"; the preparation method comprises the steps of preparing an inverted pyramid-shaped pit array on a silicon wafer by using a single-layer ordered colloid sphere template auxiliary etching method, sputtering a layer of thinner gold film on the surface of the pit array, adsorbing a layer of thicker elastic polydimethylsiloxane film on the surface of the gold film, transferring the pyramid-shaped gold nanostructure array to the surface of the elastic polydimethylsiloxane film, obtaining a gold tower-shaped gold nanostructure array on the surface of an organic film, and researching SERS performance of the gold tower-shaped gold nanostructure array. However, the pyramid or pyramid-shaped gold nanostructure array prepared by the two methods has fewer pyramids and hot spots in the excitation light beam during SERS test, which limits SERS activity. Moreover, the LSPR peaks of the gold nanostructure array prepared by the method are not optimized to match the excitation wavelength. In addition, both of these preparation methods cannot overcome the above-mentioned drawbacks.
Disclosure of Invention
The invention aims to overcome the defects that pyramid-shaped hot spots in an excitation light beam are fewer and LSPR peaks are not matched with excitation wavelength in a SERS test of a pyramid-shaped or pyramid-shaped gold nanostructure array in the prior art, and provides a gold nanodendrite and a preparation method and application thereof.
In order to solve the technical problem of the invention, the adopted technical scheme is that the gold nano dendrite is positioned at the edge of the gold nano film connected with the conductive substrate, and the gold nano film is positioned on the conductive substrate; the gold nano dendrite is made of gold and consists of a trunk and branch structures at all levels extending from the trunk, each branch structure comprises a primary branch structure extending from the trunk and a secondary branch structure extending from the primary branch structure, and the shape and the extending direction of the trunk are consistent with those of each branch structure.
As a further improvement of gold nanotree dendrites:
preferably, the each stage of branching structure further comprises a tertiary branching structure extending from the secondary stage of branching structure.
Preferably, the trunk and each level of branch structure are similar to a quadrangular prism, the extending ends of the similar quadrangular prism are protruded forwards along the extending direction to form a similar quadrangular pyramid, and the included angle between each level of branch structure and the trunk or the upper level of branch structure at the branch node is 30-80 degrees.
Preferably, the length of the trunk of the gold nano dendrite is 3-20 μm, and the length of each level of branch structure is 0.5-10 μm and does not exceed the length of the trunk or the upper level of branch structure.
In order to solve the technical problem of the invention, another technical scheme adopted is that the preparation method of the gold nano dendrite comprises the following steps:
s1, sputtering a gold nano film with the thickness of 5-20nm on the surface of a conductive substrate;
s2, scribing the gold nano film to form a long and narrow gap penetrating through the gold nano film;
s3, placing the conductive substrate prepared in the step S2 into a gold electrolyte to serve as a cathode, and taking a graphite sheet as an anode, wherein the temperature is 100-700 mu A/cm at room temperature 2 And (3) electrodepositing gold on the conductive substrate for 8-16h under constant current density, then taking out, soaking in deionized water, cleaning for multiple times, and drying by using inert gas to obtain the gold nano dendrite.
The preparation method of the gold nano dendrite is further improved:
preferably, the method of sputtering the gold nano-film in the step S1 is an ion sputtering method or a magnetron sputtering method.
Preferably, the method of scribing the gold nano-film in step S2 is scribing with a sharp object or etching with lithography/electron beam.
Preferably, the gold electrolyte in the step S3 is an aqueous solution containing 0.1-10g/L chloroauric acid, 0.1-1g/L ferroferric oxide and 0.5-50g/L polyvinylpyrrolidone.
In order to solve the technical problem of the invention, the adopted technical scheme is that the gold nano-dendrite is used as an active substrate for surface enhanced Raman scattering, and a laser Raman spectrometer is used for measuring the rhodamine 6G content attached to the gold nano-dendrite.
The use as gold nanodendrites is further improved:
preferably, the wavelength of the excitation light of the laser Raman spectrometer is 532nm, the power is 0.05-1mW, and the integration time is 0.1-120s.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the prepared gold nano dendrite is of a micro-nano hierarchical structure, and has the advantages of agglomeration resistance, large specific surface area and the like, so that a target product has a very high specific surface area; numerous pyramid gold nanostructure units are clustered together in three dimensions to provide high density of hot spots and high SERS activity in an excitation beam (typically 1-5 μm in diameter). The prepared target product is used as an SERS active substrate, and is subjected to repeated and multi-batch test under different concentrations of rhodamine 6G (R6G), when the concentration of the measured object R6G is as low as 10 -12 The detection of the molecular weight of the fluorescent dye can still be effectively performed at the mol/L.
Secondly, the structural parameters of the prepared gold nano dendrites can be regulated and controlled. The regulation and control of LSPR peaks of gold nano dendrites are realized by regulating electrodeposition parameters, so that the gold nano dendrites are matched with 532nm excitation light, and the SERS sensitivity of the gold nano dendrites is optimized.
Thirdly, the preparation method is scientific and effective. The gold nano dendrite is prepared at the edge of the gold nano film with the gap by using an electrodeposition method, and the method is simple, convenient and easy to implement and has high repeatability. The method not only prepares the target product with high pyramid gold nanostructure density and high SERS hot spot density, but also has higher SERS sensitivity, and is more convenient for simply and cheaply preparing gold nanostructures with stable performance which are highly matched with the excitation light wavelength in batches, so that the target product can be used as an active substrate of SERS to measure trace organic matters attached on the target product.
Fourth, because of the adjustability of the structure and SERS performance, the light can be matched with the excitation wavelength at 532nm, so that the performance is optimized, and the light has important application prospects in the fields of organic molecule detection and the like.
Drawings
FIG. 1 is one of the results of characterization of the objective gold nanodendrites of example 1 of the present invention using Scanning Electron Microscopy (SEM).
FIG. 2 is one of the results of SEM characterization of the gold nanodendrites of the product of interest in example 1 of the present invention.
FIG. 3 is a graph showing one of the results of scanning electron microscope characterization of the target product gold nanodendrites of example 2 of the present invention.
FIG. 4 shows the detection of the presence of 10 by confocal laser Raman spectroscopy using the products of examples 1 and 2 of the present invention as substrates for enhanced Raman scattering -11 mol/L (curves 1) and 10 -12 One of the results of rhodamine 6G in mol/L (curve 2).
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention based on the examples in the present invention.
The preferred mode of the present invention will be described in further detail with reference to the accompanying drawings.
First, from commercial sources or by itself:
selecting ferroferric oxide powder with the grain diameter of 200nm-5 mu m;
a monocrystalline silicon wafer as a conductive substrate;
example 1
The embodiment provides a preparation method of gold nano tree dendrites, which comprises the following specific steps:
step 1: ion sputtering a gold nano film with the thickness of 10nm on the surface of the conductive substrate; then, a sharp tip is utilized to score the gold nano film to form a long and narrow gap;
step 2: and (2) placing the conductive substrate prepared in the step (1) into a gold electrolyte to serve as a cathode, taking a rectangular graphite sheet as an anode, and preparing a mixed solution containing 1g/L chloroauric acid, 0.3g/L ferroferric oxide powder with the particle size of 200nm-5 mu m and 10g/L polyvinylpyrrolidone serving as a solvent to serve as the gold electrolyte. At 300. Mu.A/cm 2 Electrodepositing gold on a conductive substrate at room temperature for 8h;
step 3: and (3) soaking the conductive substrate prepared in the step (2) in deionized water, repeatedly cleaning for a plurality of times, and drying the product by using inert gas to obtain the gold nano dendrite.
The objective product was characterized by Scanning Electron Microscopy (SEM) and the results are shown in fig. 1 and 2. As can be seen from fig. 1 and 2, the target product is a gold nanodendrite structure (fig. 1) located at the edge of the gold nano film, and the tops of the trunk and branches of the gold nanodendrite structure are mostly quadrangular-like, and the gold nanodendrite consists of a trunk, a primary branch, a secondary branch and even a tertiary branch structure; the end face of the similar quadrangular prism, which faces the extending direction, protrudes to form a similar quadrangular pyramid, the height of the similar quadrangular prism is 300-1000nm, and the height of the similar quadrangular pyramid along the extending direction is 10-100nm; the cross section of the branch structure perpendicular to the extending direction is approximately square, and the side length of the square is 0.5-1 mu m.
And measuring a dark field scattering spectrum of the gold nano dendrite structure to obtain the LSPR with the peak at about 515 nm. The prepared target product is used as an SERS active substrate, and is tested for multiple times and multiple batches under different concentrations of rhodamine 6G, when the concentration of the measured object R6G is as low as 10 -11 At mol/L, it can still be detected efficiently (FIG. 4, curve 1).
Example 2
The embodiment provides a preparation method of gold nano tree dendrites, which comprises the following specific steps:
step 1: ion sputtering a gold nano film with the thickness of 20nm on the surface of the conductive substrate; then etching the gold nano film by using an electron beam etching method to form a long and narrow slit;
step 2: and (2) placing the conductive substrate prepared in the step (1) into a gold electrolyte to serve as a cathode, taking a rectangular graphite sheet as an anode, and preparing a mixed solution containing 2g/L chloroauric acid, 1g/L ferroferric oxide powder with the particle size of 1-3 mu m and 5g/L polyvinylpyrrolidone serving as a solvent to serve as the gold electrolyte. At 200. Mu.A/cm 2 Electrodepositing gold on a conductive substrate at room temperature for 12h;
step 3: and (3) soaking the conductive substrate prepared in the step (2) in deionized water, repeatedly cleaning for a plurality of times, and drying the product by using inert gas to obtain the gold nano dendrite.
The obtained objective product was characterized by using a Scanning Electron Microscope (SEM), and the result is shown in fig. 3. As can be seen from fig. 3, the length of the gold nano-dendrite structure trunk can reach 30 μm; high magnification SEM electron microscopy of the surface showed a microstructure similar to that of figures 1 and 2;
and measuring a dark field scattering spectrum of the gold nano dendrite structure to obtain the LSPR with the peak at about 530 nm. The prepared target product is used as an SERS active substrate, and is tested for multiple times and multiple batches under different concentrations of rhodamine 6G, when the concentration of the measured object R6G is as low as 10 -12 And the detection of the molecular weight of the product can still be effectively carried out when the molecular weight of the product is mol/L (fig. 4 and curve 2), which shows that the LSPR peak position and the SERS activity of the product can be regulated and controlled by regulating parameters such as electrodeposition time and the like.
Example 3
The embodiment provides a preparation method of gold nano tree dendrites, which comprises the following specific steps:
step 1: ion sputtering a gold nano film with the thickness of 5nm on the surface of the conductive substrate; then, a micron-sized sharp tip is utilized to score the gold nano film to form a long and narrow slit;
step 2: and (2) placing the conductive substrate prepared in the step (1) into a gold electrolyte to serve as a cathode, taking a rectangular graphite sheet as an anode, and preparing a mixed solution containing 0.1g/L chloroauric acid, 0.1g/L ferroferric oxide powder with the particle size of 0.2-1 mu m and 0.5g/L polyvinylpyrrolidone serving as a solvent to serve as the gold electrolyte. At 100. Mu.A/cm 2 Electrodepositing gold on a conductive substrate at room temperature for 16h;
step 3: and (3) soaking the conductive substrate prepared in the step (2) in deionized water, repeatedly cleaning for a plurality of times, and drying the product by using inert gas to obtain the gold nano dendrite.
The resulting target product was characterized using a Scanning Electron Microscope (SEM) and the results were approximated as shown in fig. 2. And measuring a dark field scattering spectrum of the gold nano dendrite structure to obtain the LSPR with peak at 490 nm. The prepared target product is used as an SERS active substrate, and is tested for multiple times and multiple batches under different concentrations of rhodamine 6G, when the concentration of the measured object R6G is as low as 10 -10 The detection of the catalyst can still be effectively carried out in mol/L,612cm -1 the characteristic peak intensity was 300 count units.
Example 4
The embodiment provides a preparation method of gold nano tree dendrites, which comprises the following specific steps:
step 1: ion sputtering a gold nano film with the thickness of 15nm on the surface of the conductive substrate; then, a micron-sized sharp tip is utilized to score the gold nano film to form a long and narrow slit;
step 2: and (2) placing the conductive substrate prepared in the step (1) into a gold electrolyte to serve as a cathode, taking a rectangular graphite sheet as an anode, and preparing a mixed solution containing 10g/L chloroauric acid, 10g/L ferroferric oxide powder with the particle size of 2-5 mu m and 50g/L polyvinylpyrrolidone serving as a solvent to serve as the gold electrolyte. At 700. Mu.A/cm 2 Electrodepositing gold on a conductive substrate at room temperature for 8h;
step 3: and (3) soaking the conductive substrate prepared in the step (2) in deionized water, repeatedly cleaning for a plurality of times, and drying the product by using inert gas to obtain the gold nano dendrite.
The resulting target product was characterized using a Scanning Electron Microscope (SEM) and the results were close to the samples shown in fig. 3. And measuring a dark field scattering spectrum of the gold nano dendrite structure to obtain the LSPR with the peak at about 560 nm. The prepared target product is used as an SERS active substrate, and is tested for multiple times and multiple batches under different concentrations of rhodamine 6G, when the concentration of the measured object R6G is as low as 10 -11 Can still effectively detect the water at mol/L of 612cm -1 The characteristic peak intensity was 350 count units.
Example 5
The embodiment provides a preparation method of gold nano tree dendrites, which comprises the following specific steps:
step 1: ion sputtering a gold nano film with the thickness of 20nm on the surface of the conductive substrate; then, a micron-sized sharp tip is utilized to score the gold nano film to form a long and narrow slit;
step 2: placing the conductive substrate obtained in the step 1 into gold electrolyte as a cathode, taking rectangular graphite sheets as an anode, and preparing water as a solvent, wherein the conductive substrate contains 5g/L chloroauric acid and 2g/L particle sizeA mixture of 0.2-1 μm ferroferric oxide powder and 2g/L polyvinylpyrrolidone was used as the gold electrolyte. At 300. Mu.A/cm 2 Electrodepositing gold on a conductive substrate at room temperature for 12h;
step 3: and (3) soaking the conductive substrate prepared in the step (2) in deionized water, repeatedly cleaning for a plurality of times, and drying the product by using inert gas to obtain the gold nano dendrite.
The resulting target product was characterized using a Scanning Electron Microscope (SEM) and the results were close to the samples shown in fig. 3. The measurement structure shows that the LSPR peak of the gold nano-dendrite structure is located near 550 nm. The prepared target product is used as an SERS active substrate, and is tested for multiple times and multiple batches under different concentrations of rhodamine 6G, when the concentration of the measured object R6G is as low as 10 - 11 Can still effectively detect the molecular weight of the polymer at mol/L, and has a spectrum of 612cm -1 The characteristic peak intensity was 520 count units.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. It should be noted that many variations and modifications can be made by those skilled in the art, and all variations and modifications which do not depart from the scope of the invention as defined in the appended claims are intended to be protected.
Claims (9)
1. The preparation method of the gold nano dendrite is characterized in that the gold nano dendrite is positioned at the edge of the gold nano film connected with the conductive substrate, and the gold nano film is positioned on the conductive substrate; the gold nano dendrite is made of gold and consists of a trunk and branch structures at all levels extending from the trunk, each branch structure comprises a primary branch structure extending from the trunk and a secondary branch structure extending from the primary branch structure, and the shape and the extending direction of the trunk are consistent with those of each branch structure;
the preparation method comprises the following steps:
s1, sputtering a gold nano film with the thickness of 5-20nm on the surface of a conductive substrate;
s2, scribing the gold nano film to form a long and narrow gap penetrating through the gold nano film;
s3, placing the conductive substrate prepared in the step S2 into a gold electrolyte to serve as a cathode, and taking a graphite sheet as an anode, wherein the temperature is 100-700 mu A/cm at room temperature 2 And (3) electrodepositing gold on the conductive substrate for 8-16h under constant current density, then taking out, soaking in deionized water, cleaning for multiple times, and drying by using inert gas to obtain the gold nano dendrite.
2. The method of preparing gold nanodendrites of claim 1 wherein each level of branching structure further comprises a tertiary branching structure extending from a secondary level of branching structure.
3. The method for preparing gold nano dendrite according to claim 1 or 2, wherein the trunk and each level of branch structure are shaped like a quadrangular prism, the extending end of the quadrangular prism protrudes forward along the extending direction to form a quadrangular pyramid, and the included angle between each level of branch structure and the trunk or the upper level of branch structure at the branch node is 30-80 degrees.
4. The method for preparing gold nanodendrites according to claim 1 or 2, wherein the length of the trunk of the gold nanodendrites is 3 to 20 μm and the length of each of the branched structures is 0.5 to 10 μm and does not exceed the length of the trunk or the upper branched structure.
5. The method for preparing gold nanodendrite according to claim 1, wherein the method for sputtering gold nano-film in step S1 is an ion sputtering method or a magnetron sputtering method.
6. The method of preparing gold nanodendrites according to claim 1, wherein the method of scribing the gold nano-film in step S2 is scribing with a sharp object or etching with lithography/electron beam.
7. The method for preparing gold nanodendrite according to claim 1, wherein the gold electrolyte in step S3 is an aqueous solution containing 0.1 to 10g/L chloroauric acid, 0.1 to 1g/L ferroferric oxide, and 0.5 to 50g/L polyvinylpyrrolidone.
8. Use of gold nanodendrites prepared by the preparation method of any one of claims 1 to 7 as an active substrate for surface enhanced raman scattering, for measuring the content of rhodamine 6G attached thereto using a laser raman spectrometer.
9. The use of gold nanodendrites according to claim 8, characterized in that the laser raman spectrometer has excitation light with a wavelength of 532nm, a power of 0.05-1mW and an integration time of 0.1-120s.
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| WO2007100297A1 (en) * | 2006-03-03 | 2007-09-07 | Richard Furberg | Porous layer |
| KR20110003076A (en) * | 2009-07-03 | 2011-01-11 | 이화여자대학교 산학협력단 | The method for the preparation of gold nanostructure using galvanic displacement reaction and gold nanostructure with improved surface enhanced raman scattering |
| CN105973865A (en) * | 2016-01-29 | 2016-09-28 | 中国科学院合肥物质科学研究院 | Au nano dendrites surface-reinforced Raman scattering substrate and preparation method thereof |
| CN106498464A (en) * | 2016-10-24 | 2017-03-15 | 电子科技大学 | A kind of metal receives a micron preparation method for dendrite oldered array |
| CN108179392A (en) * | 2017-12-28 | 2018-06-19 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of processing method of metal nano network flexible glass |
| CN113279027A (en) * | 2021-04-29 | 2021-08-20 | 安徽大学 | Silver microparticle array and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9080980B2 (en) * | 2011-07-27 | 2015-07-14 | Hewlett-Packard Development Company, L.P. | Surface enhanced raman spectroscopy employing a nanorod in a surface indentation |
| US20150049332A1 (en) * | 2013-07-30 | 2015-02-19 | The Curators Of The University Of Missouri | Gold nanoisland arrays |
| EP3497432A4 (en) * | 2016-08-11 | 2020-03-18 | Queen's University At Kingston | Reconfigurable surface enhanced raman spectroscopy device and method therefor |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007100297A1 (en) * | 2006-03-03 | 2007-09-07 | Richard Furberg | Porous layer |
| KR20110003076A (en) * | 2009-07-03 | 2011-01-11 | 이화여자대학교 산학협력단 | The method for the preparation of gold nanostructure using galvanic displacement reaction and gold nanostructure with improved surface enhanced raman scattering |
| CN105973865A (en) * | 2016-01-29 | 2016-09-28 | 中国科学院合肥物质科学研究院 | Au nano dendrites surface-reinforced Raman scattering substrate and preparation method thereof |
| CN106498464A (en) * | 2016-10-24 | 2017-03-15 | 电子科技大学 | A kind of metal receives a micron preparation method for dendrite oldered array |
| CN108179392A (en) * | 2017-12-28 | 2018-06-19 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of processing method of metal nano network flexible glass |
| CN113279027A (en) * | 2021-04-29 | 2021-08-20 | 安徽大学 | Silver microparticle array and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 金属纳米颗粒/微纳结构金属膜增强拉曼研究进展;易明芳;;安庆师范学院学报(自然科学版)(04);第48-53页 * |
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