CN116893167A - Needle tip material of needle tip enhanced Raman spectrum, preparation method and application - Google Patents
Needle tip material of needle tip enhanced Raman spectrum, preparation method and application Download PDFInfo
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- CN116893167A CN116893167A CN202310866919.8A CN202310866919A CN116893167A CN 116893167 A CN116893167 A CN 116893167A CN 202310866919 A CN202310866919 A CN 202310866919A CN 116893167 A CN116893167 A CN 116893167A
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- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000001237 Raman spectrum Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000010931 gold Substances 0.000 claims abstract description 102
- 229910052737 gold Inorganic materials 0.000 claims abstract description 71
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002105 nanoparticle Substances 0.000 claims abstract description 61
- 239000000523 sample Substances 0.000 claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 28
- 238000000772 tip-enhanced Raman spectroscopy Methods 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 238000003384 imaging method Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 241000252506 Characiformes Species 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- -1 gold ions Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000002444 silanisation Methods 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 238000012876 topography Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000002848 electrochemical method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- 238000004630 atomic force microscopy Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000004621 scanning probe microscopy Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- KXHFTXJPJMEXKR-UHFFFAOYSA-N methanol 3-trimethoxysilylpropan-1-amine Chemical compound OC.CO[Si](OC)(OC)CCCN KXHFTXJPJMEXKR-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000004574 scanning tunneling microscopy Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- 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 a needle tip material of a needle Tip Enhanced Raman Spectrum (TERS), a preparation method and application thereof. The needle tip material of the invention is a composite structure, and is sequentially provided with an atomic force microscope silicon probe, a gold nanoparticle film and a gold layer from inside to outside. According to the invention, firstly, a dense gold nanoparticle film is coated on the surface of the AFM silicon needle tip after the surface is treated by utilizing the chemical adsorption performance of the AFM silicon needle tip, and the coated needle tip is annealed, so that the distribution of the coated needle tip on the needle tip is improved, and the coverage probability of gold nanoparticles at the tip of the needle tip is increased. An electrochemical method is used, and an extremely thin gold layer is deposited on the surface of the coated needle tip so as to increase the mechanical stability of the coated needle tip gold nanoparticle. The TERS needle point provided by the invention is simple to prepare, good in stability and mechanical strength, good in reproducibility and free from large-scale equipment; the prepared gold nanoparticle film probe has uniform surface, controllable nanoparticle size and stronger TERS enhancement effect.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a needle tip material of a needle tip enhanced Raman spectrum, a preparation method and application thereof.
Background
Tip enhanced raman spectroscopy (tert) is an emerging nanoscale surface analysis technique combining Scanning Probe Microscopy (SPM) and Surface Enhanced Raman Spectroscopy (SERS), the basic principle of which is: the needle tip of pure metal (Au, ag, etc.) or loaded metal is controlled to be very close to the surface of the sample (such as 1 nm) by an SPM control system, when the needle tip is irradiated by incident light with proper wavelength, under the combined action of surface plasmon resonance and lightning rod effect, the needle tip generates very strong localized electromagnetic field, so that the Raman signal of the sample below the needle tip is enhanced, and the sample surface can be subjected to high-spatial resolution morphological imaging and chemical information imaging after the sample is scanned. Since the first report in 2000, tip-enhanced raman spectroscopy has been widely used in the fields of catalysis, materials, biology, surface science, and the like. Scanning probe microscopy instruments for constructing tip enhanced raman spectra typically include three types: scanning Tunneling Microscopy (STM), atomic Force Microscopy (AFM), and Scanning Force Microscopy (SFM), wherein AFM-based TERS is widely applicable to various samples (e.g., non-conductive biomacromolecules), and enables measurement of various mechanical properties of the sample; in addition, the requirements on the test environment are small, a vacuum environment is not needed, and the atmospheric or liquid-phase TERS test can be carried out. AFM-Raman combination instruments are commercialized at present, and the needle tip plays a crucial role as the core of TERS.
The AFM-TERS needle tip is prepared by various methods, including a vacuum evaporation method, an electrochemical deposition method and a non-electrochemical deposition method, but the methods have the defects of large difference in appearance, low reproducibility, lack of strong interaction between the probe and the coating and low mechanical stability due to low nucleation density on the surface of the AFM probe. The metal nano particles can also be transferred onto the AFM probe tip by a bottom-up assembly method, such as sulfhydrylation of the surface of the AFM probe and self-assembly of gold nano particles (The fabrication ofgold colloidal nanoantennas by a full wet surface assembly technique, applied physics express,2019,12,064008), but the particle assembly efficiency is low, and the morphology of the prepared probe is uncontrollable; there are also AFM probes prepared by coating a silver nanocube Langmuir-Blodgett film on the surface (Colloidal Nanoantennas for Hyperspectral Chemical Mapping, ACS nano,2016,10,7523-7531), but the plasma enhanced chemical vapor deposition equipment used is expensive, and there is a lack of strong interaction between the probe and the silver nanocube, so that the mechanical stability is poor, and silver is easily oxidized in air, thereby losing TERS activity, so that the tip lifetime prepared by this method is very short. How to simply and conveniently prepare a TERS needle tip with good reproducibility, good mechanical stability, long service life and good Raman signal enhancement effect is a problem to be solved urgently.
Disclosure of Invention
In order to solve the technical problems, the invention provides a needle tip material of a needle tip enhanced Raman spectrum, and a preparation method and application thereof. The tip material for enhancing the Raman spectrum is of a composite structure, and comprises an AFM silicon probe, a compact gold nanoparticle film and an extremely thin gold layer from inside to outside. The preparation method is simple and does not need complex equipment.
The invention is realized by the following technical scheme:
the invention provides a needle point material of a needle point enhanced Raman spectrum, which has a composite structure and comprises an atomic force microscope silicon probe, a gold nanoparticle film and a gold layer from inside to outside in sequence;
the gold nanoparticle film is coated on the surface of the atomic force microscope silicon probe;
the gold layer is deposited on the surface of the gold nanoparticle film through electrochemistry.
In one embodiment of the invention, the thickness of the gold layer is 10nm or less.
In one embodiment of the invention, the gold nanoparticle film has a thickness of 20nm to 30nm.
In one embodiment of the invention, the gold nanoparticle film is prepared by the following method:
and (3) placing the gold sol into a chimney device, volatilizing for 14-16 h at the temperature of 43-45 ℃, and standing at room temperature to obtain the gold nanoparticle film formed at the gas-liquid interface.
In one embodiment of the invention, the gold nanoparticles in the gold sol have a particle size of 25nm to 55nm.
The second object of the present invention is to provide a method for preparing a tip material of the tip enhanced raman spectrum, which is characterized by comprising the following steps:
(1) Carrying out surface pretreatment on an atomic force microscope silicon probe;
(2) Coating a gold nanoparticle film on the surface of the pretreated atomic force microscope silicon probe obtained in the step (1), and annealing to obtain the coated atomic force microscope silicon probe;
(3) And (3) depositing a gold layer on the surface of the coated atomic force microscope silicon probe obtained in the step (2) by adopting an electrochemical deposition method to obtain the tip material of the tip enhanced Raman spectrum.
In one embodiment of the invention, in step (1), the surface pretreatment is obtained by:
the atomic force microscope silicon probe is obtained by sequentially treating a piranha solution and a silanization reagent solution containing amino or sulfhydryl.
In one embodiment of the present invention, in step (2), the annealing conditions are: annealing at 100-110 deg.c for 25-30 min.
In one embodiment of the invention, the method of electrochemical deposition is:
and placing the coated atomic force microscope silicon probe into an acidic electrolyte containing gold ions, and electrodepositing for 10 s-70 s under constant potential of minus 0.85V to minus 1.2V.
The third object of the invention is to provide the application of the needle tip material in morphology imaging and chemical information imaging.
The principle of the invention is as follows: coating a gold nanoparticle monolayer film on the AFM tip based on the chemisorption performance of the AFM silicon tip after the surface is treated; because the radius of curvature of the tip of the AFM silicon tip is smaller than the diameter of the gold nanoparticles, the distribution of the gold nanoparticles on the tip is improved by utilizing the gravity action of the gold nanoparticles during annealing, the coverage probability of the gold nanoparticles is increased, and an extremely thin gold layer is deposited on the surface of the coated tip by using an electrochemical method so as to increase the mechanical stability of the coated tip gold nanoparticles, so that the tip enhanced Raman spectrum tip material is obtained.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The three-layer composite needle tip material of the needle tip enhanced Raman spectrum provided by the invention has the advantages of uniform surface, controllable gold nano particle size, difficult spalling and stronger TERS enhancement effect.
(2) Compared with a simple electrochemical deposition method, the needle point material prepared by the method has controllable needle point morphology: because the surface nucleation density of the commercial AFM probe tip is low, the electrode tip with TERS enhancement effect is prepared by a pure chemical method, a thicker gold layer is required to be electrodeposited, so that the curvature radius of the tip end is larger and is uncontrollable.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
fig. 1 is an SEM image of a tip of a silicon-Au nanoparticle film provided in example 1 of the present invention;
FIG. 2 is an SEM image of a silicon-Au nanoparticle film tip provided in example 1 of the present invention without annealing;
FIG. 3 is an SEM image of a three-layer composite tip of a silicon-Au nanoparticle film-Au provided in example 1 of the present invention;
FIG. 4 is a schematic illustration of an experimental procedure for the preparation of a needle tip provided in example 1 of the present invention;
FIG. 5 is a schematic diagram of a single point test performed on a TERS needle tip prepared in example 2 of the present invention and a corresponding Raman signal diagram (PNTP for the probe molecule);
FIG. 6 is a graph showing the background signal of the coated needle tip without annealing operation and with annealing operation in comparative example 1 of the present invention;
FIG. 7 is an SEM image of a silicon-Au nanoparticle film-Au three-layer composite tip material of comparative example 2 of the present invention;
FIG. 8 is an SEM image of a silicon-Au nanoparticle film-Au three-layer composite tip material of comparative example 3 of the present invention;
fig. 9 is SEM images of different batches of silicon-Au nanoparticle films-Au three-layer composite tips prepared using the method of example 1 in the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1 preparation of a silicon-Au nanoparticle film-Au three-layer composite tip material.
The embodiment provides a preparation method of a silicon-Au nanoparticle film-Au three-layer composite needle point material, a flow chart of which is shown in fig. 4, which specifically comprises the following steps:
1. gold nanoparticle film preparation:
(1) Preparation of gold nanoparticles
100mL of 0.01% HAuCl 4 The aqueous solution is heated in an oil bath pot at 160 ℃ until steam is condensed and reflowed, 2mL of 1% sodium citrate aqueous solution is rapidly added, and gold sol with the particle size of 15nm is obtained after the reaction is completed. 25mL of the gold sol prepared above was taken and 1mL of a 1% aqueous solution of sodium citrate, 1mL of a 1% aqueous solution of PVP (molecular weight: 10000), 20mL of 0.025mol/dm were added 3 Uniformly mixing, and dropwise adding 20mL of 0.1% HAuCl at the speed of 60mL/h at normal temperature 4 The aqueous solution was stirred for half an hour after the completion of the dropping, and a gold sol having a particle diameter of 30nm was obtained.
(2) Preparation of gold nanoparticle films
Adding 4.5mL of the prepared 30nm gold sol into a centrifuge tube after ultrasonic cleaning and drying of 5mL of ethanol, volatilizing by adopting a chimney device (disclosed in CN 103590037A), standing for 14h at 43 ℃, taking out, and standing for 8h at room temperature to obtain the gold nanoparticle film formed by a gas-liquid interface.
2. Preparation of a covered needle point:
(1) Surface treatment of AFM silicon tips
And (3) carrying out surface treatment on an AFM silicon needle point (the needle point height is 14-16 mu m) in a new piranha solution (a mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide in a volume ratio of 7:3), and then cleaning and drying the surface treated surface in a 3-aminopropyl trimethoxy silane methanol solution for later use.
(2) Silicon needle tip coating and annealing
Dipping the surface-treated silicon needle tip in the prepared gold nanoparticle film twice, washing with ethanol, drying, and annealing at 105 ℃ for 25-30 min, wherein an SEM image of the annealed coated needle tip is shown in fig. 1, and for comparison, fig. 2 is an unannealed needle tip.
As can be seen from fig. 1 and fig. 2, the annealing operation can further improve the distribution of gold nanoparticles on the surface of the probe, so that the empty space occupied by no gold nanoparticles is occupied by gold nanoparticles, which greatly increases the probability that the tip of the probe is covered by gold nanoparticles, which is important for whether the prepared coated needle tip has tert activity.
3. Preparation of a silicon-Au nanoparticle film-Au three-layer composite needle point material:
placing the coated needle tip at 5×10 -3 mmol/dm 3 HAuCl 4 0.1mol/dm 3 H 2 SO 4 In the electrolyte of (1) and (2), electrodepositing for 10s under the constant potential of-1.2V, so that Au is quickly nucleated on the surface of the coated probe, and electrodepositing for 60s under the constant potential of-0.85V, thus obtaining the silicon-Au nanoparticle film-Au three-layer composite needle point material, wherein the SEM image is shown in figure 3, the appearance of gold nanoparticles on the surface of the needle point is uniform and the coverage is high, and the thickness of the gold layer is smaller than 10nm. The radius of curvature of the tip of the needle tip is between 20nm and 40 nm.
Example 2
The silicon-Au nanoparticle film-Au three-layer composite needle tip material prepared in example 1 is subjected to single-point test, a schematic diagram and a corresponding Raman signal diagram are shown in FIG. 5, a substrate adopts a gold sheet with p-nitrophenol (PNTP) molecules adsorbed on the surface, and when the prepared three-layer composite TERS needle tip contacts the gold sheet with PNTP molecules adsorbed on the surfaceUnder the irradiation of 0.15mW and 618 nm laser, PNTP molecules can be detected to be located at 1081cm -1 、1339cm -1 、1576cm -1 The three characteristic peaks of the three-layer composite TERS needle tip prepared by the invention are proved to have good Raman enhancement activity.
Comparative example 1
The preparation method of the silicon-Au nanoparticle film-Au three-layer composite needle tip material of the comparative example is similar to that of example 1, and the difference is that:
the preparation step (2) of the coated needle tip is not annealed.
As can be seen from FIG. 6, the background signal of the non-annealed and annealed coated needle tips is 1100cm -1 ～1600cm -1 Where stronger background signal interference is generated.
Comparative example 2
The preparation method of the silicon-Au nanoparticle film-Au three-layer composite needle tip material of the comparative example is similar to that of example 1, and the difference is that:
in the preparation step of the silicon-Au nanoparticle film-Au three-layer composite needle point material, HAuCl is contained in the electrolyte 4 Is 0.2mmol/dm 3 。
The prepared needle tip material is shown in fig. 7, and as can be seen from fig. 7, the radius of curvature of the tip of the prepared TERS needle tip is remarkably increased by about 200nm, and the imaging resolution is low.
Comparative example 3
The preparation method of the silicon-Au nanoparticle film-Au three-layer composite needle tip material of the comparative example is similar to that of example 1, and the difference is that:
and (3) annealing for 90min in the preparation step (2) of the coated needle tip.
As shown in FIG. 8, when the annealing time is too long, the gold nanoparticles are easy to aggregate at the tip of the needle tip, so that the radius of curvature of the tip of the needle tip is increased by about 150nm, and the TERS enhancement effect of the needle tip is lost.
The most common method for preparing AFM-TERS needle tips is to deposit metal on the surface of commercial AFM needle tips by using a vacuum evaporation method, but the AFM-TERS needle tips prepared by different groups by adopting the method have different morphologies, so that the TERS enhancement factors of the needle tips have great difference and have low reproducibility, and the reason is that each parameter of the vacuum evaporation (such as evaporation rate, temperature, distance between a substrate and a heat source, vacuum degree, a heater, a target source, the placement position of the substrate and the like) is difficult to control, while the method can realize uniform coverage of the surface of a probe without large complex instruments and harsh conditions by using gold nanoparticles with determined sizes, so that the method has better reproducibility, which can be demonstrated by SEM images (figure 9) of silicon-Au nanoparticle film-Au three-layer composite needle tip materials prepared by different batches by using the method of example 1.
The AFM-TERS needle tip prepared by the traditional vacuum evaporation method has the further disadvantage of poor mechanical stability, because a stronger interaction is lacking between the metal coating and the needle tip, and the invention assembles a layer of APTMS between the gold nano particles and the needle tip, so that the metal coating and the needle tip are connected through chemical bonds, the AFM-TERS needle tip has stronger interaction, a thin gold layer is electroplated, the acting force between the nano particles is enhanced, and the TERS can improve the mechanical stability of the probe to a certain extent under the combined action of the two means.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The needle point material is characterized by being of a composite structure and sequentially comprising an atomic force microscope silicon probe, a gold nanoparticle film and a gold layer from inside to outside;
the gold nanoparticle film is coated on the surface of the atomic force microscope silicon probe;
the gold layer is deposited on the surface of the gold nanoparticle film through electrochemistry.
2. The needle tip material according to claim 1, wherein the thickness of the gold layer is 10nm or less.
3. The needle tip material according to claim 1, wherein the gold nanoparticle film has a thickness of 20nm to 30nm.
4. The needle tip material according to claim 1, wherein the gold nanoparticle film is prepared by the following method:
and (3) placing the gold sol into a chimney device, volatilizing for 14-16 h at the temperature of 43-45 ℃, and standing at room temperature to obtain the gold nanoparticle film formed at the gas-liquid interface.
5. The needle tip material according to claim 4, wherein the gold nanoparticles in the gold sol have a particle diameter of 25nm ～ 55nm。
6. The method for preparing a tip material for tip enhanced raman spectroscopy according to any one of claims 1 to 5, comprising the steps of:
(1) Carrying out surface pretreatment on an atomic force microscope silicon probe;
(2) Coating a gold nanoparticle film on the surface of the pretreated atomic force microscope silicon probe obtained in the step (1), and annealing to obtain the coated atomic force microscope silicon probe;
(3) And (3) depositing a gold layer on the surface of the coated atomic force microscope silicon probe obtained in the step (2) by adopting an electrochemical deposition method to obtain the tip material of the tip enhanced Raman spectrum.
7. The method of claim 6, wherein in step (1), the surface pretreatment is obtained by:
the atomic force microscope silicon probe is obtained by sequentially treating a piranha solution and a silanization reagent solution containing amino or sulfhydryl.
8. The method according to claim 6, wherein in the step (2), the annealing conditions are: annealing at 100-110 deg.c for 25-30 min.
9. The method of claim 6, wherein in step (3), the electrochemical deposition method is as follows:
and placing the coated atomic force microscope silicon probe into an acidic electrolyte containing gold ions, and electrodepositing for 10 s-70 s under constant potential of minus 0.85V to minus 1.2V.
10. Use of the needle tip material of any one of claims 1 to 5 for topography imaging and chemical information imaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310866919.8A CN116893167A (en) | 2023-07-14 | 2023-07-14 | Needle tip material of needle tip enhanced Raman spectrum, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310866919.8A CN116893167A (en) | 2023-07-14 | 2023-07-14 | Needle tip material of needle tip enhanced Raman spectrum, preparation method and application |
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| Publication Number | Publication Date |
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| CN116893167A true CN116893167A (en) | 2023-10-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310866919.8A Pending CN116893167A (en) | 2023-07-14 | 2023-07-14 | Needle tip material of needle tip enhanced Raman spectrum, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116893167A (en) |
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- 2023-07-14 CN CN202310866919.8A patent/CN116893167A/en active Pending
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