CN113718199A - Noble metal structure array and preparation method and application thereof - Google Patents
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000002077 nanosphere Substances 0.000 claims abstract description 32
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000004544 sputter deposition Methods 0.000 claims abstract description 12
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 8
- 239000004793 Polystyrene Substances 0.000 claims description 33
- 239000004005 microsphere Substances 0.000 claims description 33
- 229920002223 polystyrene Polymers 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 238000005530 etching Methods 0.000 claims description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000001020 plasma etching Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 229910018503 SF6 Inorganic materials 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000001338 self-assembly Methods 0.000 claims description 4
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 4
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- 230000010354 integration Effects 0.000 claims description 3
- 238000001237 Raman spectrum Methods 0.000 claims description 2
- 238000005289 physical deposition Methods 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 4
- 235000000832 Ayote Nutrition 0.000 abstract description 2
- 235000009854 Cucurbita moschata Nutrition 0.000 abstract description 2
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- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
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- 235000015136 pumpkin Nutrition 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- -1 fluorine ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 244000020551 Helianthus annuus Species 0.000 description 2
- 235000003222 Helianthus annuus Nutrition 0.000 description 2
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- 239000002105 nanoparticle Substances 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
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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
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- 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
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- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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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
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Abstract
The invention relates to the technical field of nano materials, in particular to a noble metal structure array and a preparation method and application thereof. The noble metal structure array consists of orderly-arranged noble metal nanospheres, has long-range orderly arrangement and good structural consistency, and has high consistency in Raman signals obtained from different regions when the array is used as an SERS substrate in a test process; the top of the noble metal nanosphere is not in a protruding shape or a circular arc shape, but has a certain flatness, and the cylindrical side surface expands outwards along the radial direction to form a smooth ellipsoidal curved surface similar to a pumpkin shape; rich optical 'hot spots' provided by the rough nanosphere structure and the nanosphere gaps, and the pumpkin-shaped structure reflects more light, so that the whole SERS substrate has strong Raman activity; the noble metal nanoparticles of the present application are prepared by a physical ion sputtering method, and the particle surface does not contain any ligand, so that the substrate has no background interference signal.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a noble metal structure array and a preparation method and application thereof.
Background
The molecular detection technology based on the Surface Enhanced Raman Scattering (SERS) spectrum has the advantages of high sensitivity, quick response and fingerprint identification, and has wide application prospects in the fields of chemical analysis, biomedicine, environmental detection and the like. The nano structure of noble metal such as gold, silver and the like can provide a high-activity detection 'hot spot', and is usually used as a basic sensitive unit for constructing a sol type enhanced reagent and a solid type enhanced substrate, so as to realize trace detection of target molecules with low ppb level.
Due to the structural uniformity and abundant 'hot spots', the ordered array of the noble metal micro-nano structure generally has higher sensitivity and good signal reproducibility in SERS detection application, and has attracted general attention in recent years. For example, in a sunflower nano-array structure for enhancing SERS activity and a preparation method thereof (CN111426674A), polystyrene microspheres with two different diameters are adopted to self-assemble a single-layer sunflower array, the microspheres are etched to obtain a non-close-packed structure, and silver is sputtered and deposited to obtain stronger SERS activity. However, limited by the preparation method, such SERS substrates need further improvement in structural stability and background interference: on one hand, the polystyrene microspheres are combined with the silicon substrate and are not firm, precious metals are directly deposited on the surfaces of the polystyrene microspheres, and when a target object is detected in a dripping or soaking mode, the precious metal sensitive layer is easy to fall off, and the application of the precious metal sensitive layer is limited by the instability of the structure; on the other hand, polystyrene has a strong Raman characteristic signal, and when the thickness of the silver layer is insufficient, a strong background signal can be generated, so that interference is caused on identification and quantitative detection of a target molecule characteristic peak.
Disclosure of Invention
The invention provides a noble metal structure array and a preparation method and application thereof, aiming at overcoming the defects that particles of an SERS substrate are easy to fall off, background signals interfere Raman characteristic signals and the like in the prior art.
In order to solve the technical problem, the technical scheme is that the noble metal structure array is composed of a plurality of noble metal nanospheres which are positioned on a silicon substrate and distributed in a close-packed hexagonal structure, the distance between every two adjacent noble metal nanospheres is 80-150nm, the gap is 2-30nm, the noble metal nanospheres are cylindrical, the side surfaces of the noble metal nanospheres are radially and outwardly expanded to form a smooth ellipsoidal curved surface, the section of each noble metal nanosphere, which is vertical to the axial direction of the noble metal nanosphere, is circular, and the diameter range of the section along the axial direction is 100-500 nm;
the sphere of the noble metal nanosphere is formed by piling up noble metal nano particles, the size of the noble metal nano particles is 5-50nm, and the particle gaps are 1-5 nm.
As a further improvement of the noble metal structure array:
preferably, the material of the noble metal nanoparticles is gold or silver.
In order to solve the technical problem of the invention, another technical scheme is that the preparation method of the noble metal structure array comprises the following steps:
s1, preparing an ordered single-layer polystyrene microsphere array on a silicon substrate by a self-assembly method;
s2, etching the polystyrene microsphere array prepared in the step S1 by using a reactive ion etching technology and taking the polystyrene microsphere array as a mask and sulfur hexafluoride and oxygen as reaction gases, stopping etching when the diameter of the polystyrene microsphere is reduced by one third to one half, and generating a downward groove on the surface of the silicon substrate;
s3, removing the polystyrene microspheres remained on the surface of the silicon substrate;
s4, performing physical deposition of the noble metal on the surface of the silicon substrate by adopting an ion sputtering method, firstly performing deposition for 3-5 minutes by adopting a small current of 5-20mA, and then performing deposition for 1-2 minutes by adopting a large current of 30-80mA to obtain the noble metal structure array.
The preparation method of the noble metal structure array is further improved as follows:
preferably, the particle size of the polystyrene microsphere in the step S1 is 80-500 nm.
Preferably, in step S2, the reactive ion etching gas flow rate is 10-30sccm, the etching power is 30-100W, the chamber pressure is 1-10Pa, and the etching time is 15-60S.
Preferably, the removing of the remaining polystyrene microspheres in step S3 is performed by annealing or chemical dissolution.
Preferably, the annealing temperature is 400-600 ℃, and the time is 1-2 h; the chemical reagent used for the chemical dissolution is dichloromethane.
In order to solve the technical problem of the invention, another technical scheme is that a noble metal structure array is used as an active substrate for surface enhanced Raman scattering.
The further technical proposal of the application of the noble metal structure array as the active substrate of the surface enhanced Raman scattering:
preferably, when the raman spectrum of the organic molecule attached to the active substrate is measured by using a laser raman spectrometer, the wavelength of excitation light of the laser raman spectrometer is 532 or 785nm, the power is 0.1-2mW, and the integration time is 1-30 s.
Compared with the prior art, the invention has the beneficial effects that:
1) the noble metal structure array consists of orderly-arranged noble metal nanospheres, has long-range orderly arrangement and good structural consistency, and has high consistency of Raman signals obtained from different regions in the test process; the top and bottom of the nanosphere are not convex or arc-shaped, but have certain flatness, and the whole nanosphere is similar to pumpkin-shaped, so that the nanosphere has the advantage of reflecting more light, and thus obtaining stronger Raman signals.
2) The noble metal structure array is used as an active substrate for surface enhanced Raman scattering, and has three optical enhancement effects: the rough nanosphere structure and the nanosphere gaps provide abundant optical 'hot spots', and the ordered array structure enhances the provided optical 'hot spots', so that the whole SERS substrate has strong Raman activity.
3) Etching the polystyrene microsphere array on the silicon substrate by using a reactive ion etching technology, etching the polystyrene microspheres by using active fluorine ions and oxygen plasmas to gradually reduce the size of the polystyrene microspheres, and etching the silicon at the bottom downwards by using the fluorine ions to gradually generate conical protrusions of the silicon; then removing the polystyrene microspheres remained on the surface of the silicon substrate; preparing noble metal nanoparticles by an ion sputtering method, firstly adopting a small current of 5-20mA for deposition for 3-5 minutes to generate gold nanoparticles or clusters with smaller sizes, increasing the probability of lateral nucleation growth of the gold nanoparticles while forming a film on the surface of a platform at the top of a silicon cone to obtain a pumpkin-shaped configuration with a compact and flat surface, and then adopting a large current of 30-80mA for deposition for 1-2 minutes to obtain a rough surface; compared with the traditional chemical method, the particle surface does not contain any ligand, so that the substrate has no background interference signal.
Drawings
Fig. 1 and 2 are "pumpkin-shaped" noble metal micro/nano-structure SERS substrates according to example 1 of the present invention;
FIG. 3 shows that the "pumpkin-shaped" gold micro/nano structure prepared in example 2 and the gold particle thin film are respectively used as SERS substrates with a concentration of 10-7SERS spectrum of mol/L rhodamine solution;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
The preparation method of the noble metal structure array comprises the following steps:
(1) adopting polystyrene colloid microspheres with the diameter of 120nm to obtain a single-layer colloid sphere ordered array on the surface of a silicon wafer based on a gas-liquid interface self-assembly method;
(2) placing the reaction chamber in a reaction ion chamber, and performing reactive ion etching by using sulfur hexafluoride with the flow rate of 20.0sccm and oxygen with the flow rate of 10.0sccm as working gases, wherein the pressure of the chamber is 1.0Pa, and the etching power is 50W; with the reaction, the oxygen plasma etches the polystyrene microsphere to gradually reduce the size of the polystyrene microsphere, the fluorine ions etch the silicon at the bottom downwards to gradually generate conical protrusions of the silicon, and when the etching lasts for 40 seconds, the size of the polystyrene microsphere is reduced to about 50nm, namely the etching is stopped;
(3) annealing the polystyrene microspheres in a muffle furnace at 400 ℃ for 2 hours to remove the residual polystyrene microspheres;
(4) taking gold as a target material, and carrying out ion sputtering on the surface of a silicon wafer: firstly, setting the sputtering current to be 10mA, and sputtering for 3 minutes and then sputtering for 2 minutes by using a large current of 30 mA;
(5) according to the operation, the pumpkin-shaped gold nanosphere structure array with the size of about 120nm and the spherical gap of 5nm is obtained.
Example 2
The preparation method of the noble metal structure array comprises the following steps:
(1) adopting polystyrene colloid microspheres with the diameter of 120nm to obtain a single-layer colloid sphere ordered array on the surface of a silicon wafer based on a gas-liquid interface self-assembly method;
(2) placing the polystyrene microspheres in a reaction ion cavity, taking sulfur hexafluoride with the flow rate of 20.0sccm and oxygen with the flow rate of 10.0sccm as working gases, keeping the cavity pressure at 1.0Pa and the etching power at 50W, and when the reaction ion etching is carried out for 40 seconds, reducing the size of the polystyrene microspheres to about 50nm, namely stopping the etching;
(3) annealing the polystyrene microspheres in a muffle furnace at 400 ℃ for 2 hours to remove the residual polystyrene microspheres;
(4) taking gold as a target material, and carrying out ion sputtering on the surface of a silicon wafer: firstly, sputtering for 2 minutes at 10mA, and then sputtering for 1.5 minutes at 30 mA;
(5) according to the above operation, the pumpkin-shaped gold nanospheres with the size of about 100nm and the sphere gap of 20nm are obtained.
The objective product obtained in example 1 was characterized by using a Scanning Electron Microscope (SEM), and the results are shown in fig. 1 and 2. As can be seen from fig. 1 and 2, the target product is composed of a plurality of precious metal nanospheres located on a silicon substrate and distributed in a close-packed hexagonal structure, the distance between adjacent precious metal nanospheres is 2-30nm, the precious metal nanospheres are cylindrical, the side surfaces of the precious metal nanospheres are radially and outwardly expanded to form a smooth ellipsoidal curved surface, the appearance of the precious metal nanospheres is similar to that of a pumpkin, and grooves are uniformly formed in the side surfaces of the precious metal nanospheres along the axial direction.
Gold obtained by sputtering of unetched silicon wafersThe particle thin film is used as a contrast substrate, the pumpkin-shaped gold micro/nano structure obtained in example 2 is used as an SERS substrate, the integration time of the Bidattachman portable Raman spectrometer (the excitation wavelength is 785nm) is set to be 5 seconds, the laser power is 5 percent, and the two chips are respectively soaked in a solution with the concentration of 10-7M in rhodamine solution for 10 minutes, and the SERS spectrum is collected as shown in FIG. 3. It can be seen that the "pumpkin-like" gold micro/nano-structured SERS substrate obtained a characteristic peak intensity of 16000, whereas the intensity of the comparative substrate was only 500.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (9)
1. A noble metal structure array is characterized by comprising a plurality of noble metal nanospheres which are positioned on a silicon substrate and distributed in a close-packed hexagonal structure, wherein the distance between every two adjacent noble metal nanospheres is 80-150nm, the gap is 2-30nm, the noble metal nanospheres are cylindrical, the side surfaces of the noble metal nanospheres are radially and outwardly expanded to form a smooth ellipsoidal curved surface, the section of each noble metal nanosphere, which is vertical to the axial direction of the noble metal nanosphere, is circular, and the diameter range of the section along the axial direction is 100 plus 500 nm;
the sphere of the noble metal nanosphere is formed by piling up noble metal nano particles, the size of the noble metal nano particles is 5-50nm, and the particle gaps are 1-5 nm.
2. The array of noble metal structures of claim 1, wherein the noble metal nanoparticles are gold or silver.
3. A method for preparing an array of noble metal structures according to claim 1 or 2, comprising the steps of:
s1, preparing an ordered single-layer polystyrene microsphere array on a silicon substrate by a self-assembly method;
s2, etching the polystyrene microsphere array prepared in the step S1 by using a reactive ion etching technology and taking the polystyrene microsphere array as a mask and sulfur hexafluoride and oxygen as reaction gases, stopping etching when the diameter of the polystyrene microsphere is reduced by one third to one half, and generating a downward groove on the surface of the silicon substrate;
s3, removing the polystyrene microspheres remained on the surface of the silicon substrate;
s4, performing physical deposition of the noble metal on the surface of the silicon substrate by adopting an ion sputtering method, firstly performing deposition for 3-5 minutes by adopting a small current of 5-20mA, and then performing deposition for 1-2 minutes by adopting a large current of 30-80mA to obtain the noble metal structure array.
4. The method for preparing a noble metal structure array according to claim 3, wherein the particle size of the polystyrene microsphere in step S1 is 80-500 nm.
5. The method for preparing the noble metal structure array according to claim 3, wherein the reactive ion etching in step S2 has a gas flow rate of 10-30sccm, an etching power of 30-100W, a chamber pressure of 1-10Pa, and an etching time of 15-60S.
6. The method for preparing a noble metal structure array according to claim 3, wherein the removing of the remaining polystyrene microspheres in step S3 is performed by annealing or chemical dissolution.
7. The method as claimed in claim 6, wherein the annealing temperature is 400-600 ℃ and the annealing time is 1-2 h; the chemical reagent used for the chemical dissolution is dichloromethane.
8. Use of an array of noble metal structures according to claim 1 or 2 as an active substrate for surface enhanced raman scattering.
9. Use of a noble metal structure array according to claim 8 as an active substrate for surface enhanced raman scattering, wherein the raman spectrum of an organic molecule attached to the active substrate is measured using a laser raman spectrometer with excitation light having a wavelength of 532 or 785nm, a power of 0.1-2mW and an integration time of 1-30 s.
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| CN111455319A (en) * | 2020-05-15 | 2020-07-28 | 中国科学院合肥物质科学研究院 | Gold-silver nanocone array with body-enhanced Raman scattering effect and preparation method and application thereof |
| CN111778479A (en) * | 2020-07-08 | 2020-10-16 | 安徽大学 | Cavity structure array assembled by silver nanoparticles and preparation method and application thereof |
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