CN108982464A - A kind of high distribution density nano gap oldered array and the preparation method and application thereof - Google Patents
A kind of high distribution density nano gap oldered array and the preparation method and application thereof Download PDFInfo
- Publication number
- CN108982464A CN108982464A CN201810343957.4A CN201810343957A CN108982464A CN 108982464 A CN108982464 A CN 108982464A CN 201810343957 A CN201810343957 A CN 201810343957A CN 108982464 A CN108982464 A CN 108982464A
- Authority
- CN
- China
- Prior art keywords
- nano
- distribution density
- gap
- array
- high distribution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of high distribution density nano gap oldered arrays and the preparation method and application thereof, it is the uniform orderly columnar arrays of appearance and size, are in the not close arrangement of six sides, and homoepitaxial is in substrate；In the orderly columnar arrays, the gap between adjacent nano column is 5~30nm.Preparation method includes being placed in noble metal nano-particle array in reactive ion etching machine together with substrate to perform etching, then carry out plated film, obtains high distribution density nano gap oldered array.The high distribution density nano gap oldered array can be directly as SERS substrate, for detecting to 4-ATP.The present invention can control in the gap between adjacent nanostructures unit in optimal clearance distance, not only active site is evenly distributed, SERS high sensitivity, signal stabilization, favorable reproducibility, and preparation process it is simple, rapidly and efficiently, it is low in cost, environment friendly and pollution-free, be suitble to large-scale industrial production.
Description
Technical field
The present invention relates to surface enhanced Raman scattering substrate field of material technology more particularly to a kind of high distribution density nanometers
Gap oldered array and the preparation method and application thereof.
Background technique
Surface enhanced Raman scattering (Surface enhanced Raman scattering, SERS) effect is as a kind of
Highly sensitive spectral analysis technique can provide molecular structure finger-print information abundant, realize the inspection of unimolecule magnitude sample
It surveys, is widely used in the numerous areas such as food and drug safety, bio-medical analysis and environment measuring.
Based on the SERS substrate that noble metal nano structural unit is constructed, has and prepare simple, easily stored, active site point
The advantages that cloth controllable (in the prior art, active site normally tends at the tip of structure), and have to all polymoleculars significant
SERS reinforcing effect, therefore the extensive favor by researcher.The enhancing characteristic of this kind of SERS substrate, depends not only on institute
Using the size of nano structured unit, pattern and surrounding dielectric constant (i.e. intrinsic SPR property), and with adjacent nanostructures list
The coherent condition (such as orderly with unordered aggregation) of gap size and structural unit between member is directly related.
In the prior art, traditional SERS substrate preparation method mainly has electron beam lithography, plasma etching, single layer glue
Body crystal template method, but SERS substrate prepared by these preparation methods is all low resolution, (low distribution is close for low distribution density
Degree refers to substrate of the gap between adjacent nanostructures unit greater than 100nm), it is difficult to obtain having optimal clearance distance (most
Excellent clearance distance refer to the gap between adjacent nanostructures unit be greater than 0nm, and less than 30 nanometers) SERS substrate (have
The SERS substrate of optimal clearance distance can be described as the SERS substrate of very-high performance).
Summary of the invention
In order to solve the active site of existing SERS substrate is unevenly distributed, signal stabilization and reproducibility are poor, be difficult to by
Gap between adjacent nanostructures unit is controlled in technical problems such as optimal clearance distances, and the present invention provides a kind of high distributions
Density nano gap oldered array and the preparation method and application thereof can control the gap between adjacent nanostructures unit
Optimal clearance distance, not only active site is evenly distributed, SERS high sensitivity, signal stabilization, favorable reproducibility, but also preparation process
Simply, rapidly and efficiently, it is low in cost, environment friendly and pollution-free, be suitble to large-scale industrial production.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of high distribution density nano gap oldered array, the high distribution density nano gap oldered array is pattern ruler
Very little uniform orderly columnar arrays are in the not close arrangement of six sides, and homoepitaxial is in substrate；In the orderly columnar arrays
In, it is highly 200~800nm that the basal diameter of single nano-pillar, which is 40~150nm, the gap between adjacent nano column is 5~
30nm。
Preferably, the high distribution density nano gap oldered array is single layer noble metal nano-particle array.
Preferably, the surface of the high distribution density nano gap oldered array is coated in golden film, silverskin or copper film extremely
Few one kind.
Preferably, the substrate uses silicon wafer, quartz plate or titanium dioxide silicon wafer.
A kind of preparation method of high distribution density nano gap oldered array, comprising the following steps:
Step A, noble metal nano-particle array is placed in reactive ion etching machine together with substrate and is performed etching,
The vacuum degree of the reactive ion etching machine is 150mT, and power is 50~200w, and etch period is 2~30min, and gas flow is
CF4/O2=45/5 Sccm, so that the orderly columnar arrays template of high distribution density nano gap be made；Wherein, the noble metal is received
Rice grain array be in substrate homoepitaxial in the compact arranged orderly single layer noble metal nano-particle array of six sides, and it is expensive
The granularity of metal nanoparticle is 40~150nm；
Step B, plated film is carried out to the high orderly columnar arrays template of distribution density nano gap, to be made above-mentioned
High distribution density nano gap oldered array.
Preferably, described includes: by institute to the high orderly columnar arrays template progress plated film of distribution density nano gap
It states the orderly columnar arrays template of high distribution density nano gap and is placed in ion sputtering plating instrument and carry out ion sputtering film coating, and should
The power that instrument is plated in ion sputtering is 20mA, and plated film time is 6~8min.
Preferably, if the noble metal nano-particle array is the gold goal nano-grain array of orderly single layer, the gold goal
The preparation method of nano-grain array the following steps are included:
Step A1, gold chloride, phthalic acid diethylene glycol diacrylate and hydrochloric acid are added into ethylene glycol solution, so
Afterwards using oil bath heating to 195 DEG C, 30 minutes are kept the temperature, then wet-chemical chamber is carried out using hydrochloric acid, so that monodispersed gold be made
Nanoparticle colloid solution；
Step A2, the gold nano-particle colloid solution is centrifuged, and the precipitating after centrifuge separation is divided
It is scattered in butanol solution, so that the n-butanol dispersion liquid of gold nano grain be made；
Step A3, it is carried out using n-butanol dispersion liquid of the liquid-vapor interface self-assembling method to the gold nano grain from group
Dress processing, and picked up the single layer of gold nano-grain array swum on liquid level with substrate, it dries, so that orderly single layer be made
Gold goal nano-grain array.
Preferably, the substrate uses silicon wafer, quartz plate or titanium dioxide silicon wafer.
A kind of application of high distribution density nano gap oldered array, the high distribution density nano gap of above-mentioned power is orderly
Array is directly as SERS substrate.
Preferably, by above-mentioned high distribution density nano gap oldered array directly as SERS substrate, for to ammonia
Base benzenethiol 4-ATP is detected.
As seen from the above technical solution provided by the invention, high distribution density nano gap provided by the present invention has
Sequence array be first using in substrate homoepitaxial in the compact arranged orderly single layer noble metal nano-particle array of six sides as template
Reactive ion etching is carried out, then carries out ion sputtering film coating and is prepared.The present invention passes through to noble metal before reactive ion etching
Plant capacity, reactive ion when equipment vacuum degree when the granularity of nano particle, reactive ion etching, reactive ion etching are carved
Gas flow when etch period when erosion, reactive ion etching be adjusted can accurately and efficiently control it is final obtained high
Gap between the pattern and adjacent nano column of distribution density nano gap oldered array, so as to so that adjacent nano column it
Between gap accurately and efficiently controlled this optimal clearance distance in 5~30nm, so small gap can make in array
Generate strong SERS enhancement effect between nano-pillar, especially when the gap between adjacent nano column is controlled in 5~10nm,
SPR coupling between adjacent structural units can generate synergistic effect, this can be such that its electromagnetic field redistributes, and form stronger " heat
Point " distribution, active site is evenly distributed more uniform, and local electromagnetic field intensity can significantly improve, so that SERS can be made sensitive
Degree greatly improves, thus high distribution density nano gap oldered array provided by the present invention can directly as signal stabilization, again
Existing property is good, very-high performance SERS substrate, this is not only solved, and be difficult in the prior art will be between adjacent nanostructures unit
Gap control the optimal clearance distance the technical issues of, and preparation process it is simple, rapidly and efficiently, low in cost, environmentally friendly no dirt
Dye is suitble to large-scale industrial production.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the scanning electron microscope (FESEM) of gold goal nano particle obtained in the step a1 of the embodiment of the present invention 1
Photo and transmission electron microscope (TEM) photo.
Fig. 2 is the stereoscan photograph of gold goal nano-grain array made from step c1 in the embodiment of the present invention 1.
Fig. 3 is the high power section of the final high distribution density nano gap oldered array obtained of the embodiment of the present invention 1, low power
The stereoscan photograph of section, high power inclined-plane and low power inclined-plane.
Fig. 4 is using the final high distribution density nano gap oldered array obtained of the embodiment of the present invention 1 as SERS base
The SERS map of the 4-ATP molecule of various concentration is tested measured by bottom.
Fig. 5 is the high power section of the final high distribution density nano gap oldered array obtained of the embodiment of the present invention 2, low power
The stereoscan photograph of section, high power inclined-plane and low power inclined-plane.
Fig. 6 is using the final high distribution density nano gap oldered array obtained of the embodiment of the present invention 2 as SERS base
The SERS map of the 4-ATP molecule of various concentration measured by bottom.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, belongs to protection scope of the present invention.
High distribution density nano gap oldered array provided by the present invention and the preparation method and application thereof is carried out below
Detailed description.The content being not described in detail in the embodiment of the present invention belongs to existing skill well known to professional and technical personnel in the field
Art.
A kind of high distribution density nano gap oldered array, the high distribution density nano gap oldered array is pattern ruler
Very little uniform orderly columnar arrays are in the not close arrangement of six sides, and homoepitaxial is in substrate；In the orderly columnar arrays
In, it is highly 200~800nm that the basal diameter of single nano-pillar, which is 40~150nm, the gap between adjacent nano column is 5~
30nm。
Wherein, the high distribution density nano gap oldered array is single layer noble metal nano-particle array, such as: single layer
Gold nano grain array, single layer silver nano-grain array etc..The surface of the high distribution density nano gap oldered array is coated with
At least one of golden film, silverskin or copper mold can also be coated with made of other good materials of SERS effect in the prior art
Film.The substrate is preferably with silicon wafer, quartz plate or titanium dioxide silicon wafer.
Specifically, the present invention in high distribution density nano gap oldered array preparation method the following steps are included:
(1) step A, noble metal nano-particle array is placed in reactive ion etching machine together with substrate and is carved
Erosion, the vacuum degree of the reactive ion etching machine are 150mT, and power is 50~200w, and etch period is 2~30min, gas flow
For CF4/O2(i.e. gas uses FC to=45/5Sccm4With O2Mixed gas, and FC4Flow velocity be 45Sccm, O2Gas stream
Speed is 5Sccm), so that the orderly columnar arrays template of high distribution density nano gap be made.
Wherein, the substrate is preferably with silicon wafer, quartz plate or titanium dioxide silicon wafer.The noble metal nano-particle array is
Homoepitaxial is in the compact arranged orderly single layer noble metal nano-particle array of six sides, and noble metal nano particles in substrate
Granularity be 40~150nm.The noble metal nano-particle array can be the gold nano grain array of orderly single layer, orderly list
The silver nano-grain array etc. of layer.The preparation method of the noble metal nano-particle array can use your gold in the prior art
Prepared by metal nano-particle array preparation method, but when the gold goal nanometer that the noble metal nano-particle array is orderly single layer
When array of particles, the gold goal nano-grain array of the orderly single layer can be prepared using following steps:
Step A1, gold chloride, phthalic acid diethylene glycol diacrylate and hydrochloric acid are added into ethylene glycol solution, so
Afterwards using oil bath heating to 195 DEG C, 30 minutes are kept the temperature, then wet-chemical chamber is carried out using hydrochloric acid, so that monodispersed gold be made
Ball nanoparticle colloid solution.
Step A2, the gold goal nanoparticle colloid solution is centrifuged, centrifuge separation revolving speed be 10000~
12000 revs/min, the centrifuging treatment time be 10~30 minutes, remove the supernatant liquid of centrifuge tube, repeat three times from
Heart separation, then the precipitating after centrifuge separation is distributed in butanol solution, so that the n-butanol point of gold goal nano particle be made
Dispersion liquid.
Step A3, it is carried out certainly using n-butanol dispersion liquid of the liquid-vapor interface self-assembling method to the gold goal nano particle
Assembling processing, and picked up the single layer gold goal nano-grain array swum on liquid level with substrate, it dries, to be made orderly single
The gold goal nano-grain array of layer.
(2) step B, the high orderly columnar arrays template of distribution density nano gap is placed in ion sputtering plating instrument into
Row ion sputtering film coating, and the power of ion sputtering plating instrument is 20mA, and plated film time is 6~8min, to be made above-mentioned
High distribution density nano gap oldered array.Wherein, gold, silver, copper etc. can be used in the target of the ion sputtering film coating
The good material of SERS effect, so that the surface of the high distribution density nano gap oldered array be allow to be coated with golden film, silver
Film made of film, copper mold or other good materials of SERS effect, this helps to improve final high distribution density obtained and receives
The SERS effect of rice gap oldered array.
Compared with prior art, high distribution density nano gap oldered array provided by the present invention and preparation method thereof is extremely
It has the advantage that less
(1) high distribution density nano gap oldered array provided by the present invention be homoepitaxial in substrate in six sides
The uniform orderly columnar arrays of the appearance and size of not close arrangement, the gap between adjacent nano column is 5~30nm, so small
Gap can make to generate strong SERS enhancement effect between the nano-pillar in array, especially between adjacent nano column
When gap is 5~10nm, the SPR coupling between adjacent structural units can generate synergistic effect, this can be such that its electromagnetic field redistributes,
Stronger " hot spot " distribution is formed, active site is evenly distributed more uniform, and local electromagnetic field intensity can significantly improve, thus
SERS sensitivity can be made to greatly improve, therefore high distribution density nano gap oldered array provided by the present invention can be directly as
Signal stabilization, favorable reproducibility, the SERS substrate of very-high performance.
(2) preparation method of high distribution density nano gap oldered array provided by the present invention is by carving reactive ion
Lose before noble metal nano particles granularity, reactive ion etching when equipment vacuum degree, reactive ion etching when plant capacity,
Gas flow when etch period when reactive ion etching, reactive ion etching is adjusted and can accurately and efficiently control most
Gap in high distribution density nano gap oldered array made from end between adjacent nano column between 5~30nm, that is,
Say, the preparation method of high distribution density nano gap oldered array provided by the present invention can by adjacent nanostructures unit it
Between gap be effectively controlled optimal clearance distance, to solve, be difficult in the prior art will be between adjacent nanostructures unit
Gap control the optimal clearance distance the problem of, and preparation process it is simple, rapidly and efficiently, it is low in cost, environment friendly and pollution-free,
It is suitble to large-scale industrial production.
(3) high distribution density nano gap oldered array provided by the present invention be homoepitaxial in substrate in six sides
The basal diameter of the uniform orderly columnar arrays of the appearance and size of not close arrangement, single nano-pillar is 40~150nm, is individually received
The height of meter Zhu is 200~800nm, and being adjusted by the size to noble metal nano particles before reactive ion etching can have
Effect controls the basal diameter of single nano-pillar, and when equipment vacuum degree when by reactive ion etching, reactive ion etching
Plant capacity, reactive ion etching when etch period, reactive ion etching when gas flow be adjusted can be effective
The height of single nano-pillar is controlled, this facilitates using the high distribution density nano gap oldered array as guarantor when SERS substrate
Demonstrate,prove signal stabilization, favorable reproducibility.
(4) high distribution density nano gap oldered array provided by the present invention has superelevation when as SERS substrate
SERS activity, to dye molecule 4-ATP (i.e. p-aminophenyl thiophenol) have very good detection effect, can exist to concentration
10-13~10-64-ATP between mol/L is detected, i.e., can be down to 10 to the detection limit of 4-ATP molecule-13Mol/L, can
The detection that unimolecule magnitude sample is realized to 4-ATP molecule can be used for food and drug safety, bio-medical analysis, environment inspection
The numerous areas such as survey.
To sum up, the embodiment of the present invention can control in the gap between adjacent nanostructures unit in optimal clearance gap
From not only active site is evenly distributed, SERS high sensitivity, signal stabilization, favorable reproducibility, but also preparation process is simple, quick
Efficiently, low in cost, environment friendly and pollution-free, it is suitble to large-scale industrial production.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
The high distribution density nano gap oldered array and the preparation method and application thereof in the present invention is described in detail in body embodiment.
Embodiment 1
A kind of high distribution density nano gap oldered array, preparation method includes the following steps:
Step a1, into ethylene glycol solution be added gold chloride, phthalic acid diethylene glycol diacrylate (PDDA) and
Hydrochloric acid keeps the temperature 30 minutes then using oil bath heating to 195 DEG C, then carries out wet-chemical chamber using a small amount of hydrochloric acid, to be made
Monodispersed gold goal nanoparticle colloid solution.
Step b1, the gold goal nanoparticle colloid solution is centrifuged, centrifuge separation revolving speed be 10000~
12000 revs/min, the centrifuging treatment time be 10~30 minutes, remove the supernatant liquid of centrifuge tube, repeat three times from
Heart separation, then the precipitating after centrifuge separation is distributed in butanol solution, so that the n-butanol point of gold goal nano particle be made
Dispersion liquid.
Step c1, it is carried out certainly using n-butanol dispersion liquid of the liquid-vapor interface self-assembling method to the gold goal nano particle
Assembling processing, and picked up the single layer gold goal nano-grain array swum on liquid level with substrate, it dries, to be made orderly single
The gold goal nano-grain array of layer.
Step d1, by the gold goal nano-grain array of orderly single layer described in step c1 together with substrate be placed in reaction from
It is performed etching in sub- etching machine (RIE), the vacuum degree of the reactive ion etching machine (RIE) is 150mT, power 200w, etching
Time is 6min, gas flow CF4/O2=45/5Sccm, so that it is orderly that the smooth high distribution density nano gap in surface is made
Columnar arrays template.
Step e1, the high orderly columnar arrays template of distribution density nano gap is placed in ion sputtering plating instrument and is carried out
Ion sputtering film coating, and the power of ion sputtering plating instrument is 20mA, plated film time 6min, so that high distribution density be made
Nano gap oldered array.
Embodiment 2
A kind of high distribution density nano gap oldered array, preparation method includes the following steps:
Step a2, into ethylene glycol solution be added gold chloride, phthalic acid diethylene glycol diacrylate (PDDA) and
Hydrochloric acid keeps the temperature 30 minutes then using oil bath heating to 195 DEG C, then carries out wet-chemical chamber using a small amount of hydrochloric acid, to be made
Monodispersed gold goal nanoparticle colloid solution.
Step b2, the gold goal nanoparticle colloid solution is centrifuged, centrifuge separation revolving speed be 10000~
12000 revs/min, the centrifuging treatment time be 10~30 minutes, remove the supernatant liquid of centrifuge tube, repeat three times from
Heart separation, then the precipitating after centrifuge separation is distributed in butanol solution, so that the n-butanol point of gold goal nano particle be made
Dispersion liquid.
Step c2, it is carried out certainly using n-butanol dispersion liquid of the liquid-vapor interface self-assembling method to the gold goal nano particle
Assembling processing, and picked up the single layer gold goal nano-grain array swum on liquid level with substrate, it dries, to be made orderly single
The gold goal nano-grain array of layer.
Step d2, by the gold goal nano-grain array of orderly single layer described in step c2 together with substrate be placed in reaction from
It is performed etching in sub- etching machine (RIE), the vacuum degree of the reactive ion etching machine (RIE) is 150mT, power 100w, etching
Time is 20min, gas flow CF4/O2=45/5Sccm, so that the smooth high distribution density nano gap in surface, which is made, to be had
Sequence columnar arrays template.
Step e2, the high orderly columnar arrays template of distribution density nano gap is placed in ion sputtering plating instrument and is carried out
Ion sputtering film coating, and the power of ion sputtering plating instrument is 20mA, plated film time 8min, so that high distribution density be made
Nano gap oldered array.
Pattern and performance detection
Following morphology observations, constituent analysis and performance detection are carried out in the implementation process of the embodiments of the present invention 1 and 2:
(1) using scanning electron microscope and transmission electron microscope respectively to being made in the step a1 of the embodiment of the present invention 1
Gold goal nano particle carry out morphology observations, thus obtain scanning electron microscope as shown in Figure 1 (FESEM) photo and thoroughly
Penetrate electron microscope (TEM) photo；Wherein, Fig. 1 a is gold goal nano particle obtained in the step a1 of the embodiment of the present invention 1
FESEM photo, Fig. 1 b are the TEM photo of gold goal nano particle obtained in the step a1 of the embodiment of the present invention 1, can be with by Fig. 1
Find out: gold goal nano particle pattern obtained is uniform in the step a1 of the embodiment of the present invention 1, size uniformity, diameter about 60nm.
(2) using scanning electron microscope to gold goal nano-grain array obtained in the step c1 of the embodiment of the present invention 1
Morphology observations are carried out, to obtain scanning electron microscope as shown in Figure 2 (FESEM) photo；Wherein, Fig. 2 a is that the present invention is real
The high power FESEM photo of gold goal nano-grain array obtained in the step c1 of example 1 is applied, Fig. 2 a is the step of the embodiment of the present invention 1
The low power FESEM photo of gold goal nano-grain array obtained in rapid c1.As seen from Figure 2: the step of the embodiment of the present invention 1
Gold goal nano-grain array pattern obtained is uniform in c1, and six side's close-packed arrays structures are presented.
(3) scanning electron microscope high distribution density nano gap obtained final to the embodiment of the present invention 1 respectively is used
Oldered array carries out morphology observations, to obtain scanning electron microscope as shown in Figure 1 (FESEM) photo；Wherein, Fig. 3 a is
The inclined-plane high power FESEM photo of the final high distribution density nano gap oldered array obtained of the embodiment of the present invention 1, Fig. 3 b is this
The inclined-plane low power FESEM photo of the final high distribution density nano gap oldered array obtained of inventive embodiments 1, Fig. 3 c is this hair
The section high power FESEM photo of the bright final high distribution density nano gap oldered array obtained of embodiment 1, Fig. 3 d is the present invention
The section low power FESEM photo of the final high distribution density nano gap oldered array obtained of embodiment 1.As seen from Figure 3:
The final high distribution density nano gap oldered array appearance and size obtained of the embodiment of the present invention 1 is uniform, and it is not close that six sides are presented
Arrangement architecture, and a large amount of tiny and coarse gold nano grains are distributed in its surface, and the basal diameter of single nano-pillar is about
65nm, the height of single nano-pillar are about 430nm, and the gap between adjacent nano column is about 12nm, just because of such high score
Cloth density and the nano column array with nano gap, therefore between the final high distribution density nanometer obtained of the embodiment of the present invention 1
Gap oldered array has extraordinary SERS effect.
(4) using the final high distribution density nano gap oldered array obtained of the embodiment of the present invention 1 directly as SERS
Substrate carries out trace detection to the dye molecule 4-ATP (i.e. p-aminophenyl thiophenol) of various concentration, to obtain as shown in Figure 4
Surface-enhanced Raman map (i.e. SERS map).As seen from Figure 4: the final high distribution density obtained of the embodiment of the present invention 1
When as SERS substrate, the SERS activity with superelevation has dye molecule 4-ATP very good nano gap oldered array
Good detection effect, can be to concentration 10-13~10-64-ATP between mol/L is detected, i.e. the detection to 4-ATP molecule
Limit can be down to 10-13Mol/L can realize the detection of unimolecule magnitude sample to 4-ATP molecule, be expected to be widely used in eating
The numerous areas such as product medicine safety, bio-medical analysis, environment measuring.
(5) scanning electron microscope high distribution density nano gap obtained final to the embodiment of the present invention 2 respectively is used
Oldered array carries out morphology observations, to obtain scanning electron microscope as shown in Figure 5 (FESEM) photo；Wherein, Fig. 5 a is
The inclined-plane high power FESEM photo of the final high distribution density nano gap oldered array obtained of the embodiment of the present invention 2, Fig. 5 b is this
The inclined-plane low power FESEM photo of the final high distribution density nano gap oldered array obtained of inventive embodiments 2, Fig. 5 c is this hair
The section high power FESEM photo of the bright final high distribution density nano gap oldered array obtained of embodiment 2, Fig. 5 d is the present invention
The section low power FESEM photo of the final high distribution density nano gap oldered array obtained of embodiment 2.As seen from Figure 5:
The final high distribution density nano gap oldered array appearance and size obtained of the embodiment of the present invention 2 is uniform, and it is not close that six sides are presented
Arrangement architecture, and a large amount of tiny and coarse gold nano grains are distributed in its surface, and the basal diameter of single nano-pillar is about
60nm, the height of single nano-pillar are about 480nm, and the gap between adjacent nano column is about 10nm, just because of such high score
Cloth density and the nano column array with nano gap, therefore between the final high distribution density nanometer obtained of the embodiment of the present invention 2
Gap oldered array has extraordinary SERS effect.
(6) using the final high distribution density nano gap oldered array obtained of the embodiment of the present invention 2 directly as SERS
Substrate carries out trace detection to the dye molecule 4-ATP (i.e. p-aminophenyl thiophenol) of various concentration, to obtain as shown in FIG. 6
Surface-enhanced Raman map (i.e. SERS map).As seen from Figure 6: the final high distribution density obtained of the embodiment of the present invention 2
When as SERS substrate, the SERS activity with superelevation has dye molecule 4-ATP very good nano gap oldered array
Good detection effect, can be to concentration 10-13~10-64-ATP between mol/L is detected, i.e. the detection to 4-ATP molecule
Limit can be down to 10-13Mol/L can realize the detection of unimolecule magnitude sample to 4-ATP molecule, be expected to be widely used in eating
The numerous areas such as product medicine safety, bio-medical analysis, environment measuring.
To sum up, the embodiment of the present invention can control in the gap between adjacent nanostructures unit in optimal clearance gap
From not only active site is evenly distributed, SERS high sensitivity, signal stabilization, favorable reproducibility, but also preparation process is simple, quick
Efficiently, low in cost, environment friendly and pollution-free, it is suitble to large-scale industrial production.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (10)
1. a kind of high distribution density nano gap oldered array, which is characterized in that the high orderly battle array of distribution density nano gap
Column are the uniform orderly columnar arrays of appearance and size, are in the not close arrangement of six sides, and homoepitaxial is in substrate；
In the orderly columnar arrays, it is highly 200~800nm that the basal diameter of single nano-pillar, which is 40~150nm, phase
Gap between adjacent nano-pillar is 5~30nm.
2. high distribution density nano gap oldered array according to claim 1, which is characterized in that the high distribution density
Nano gap oldered array is single layer noble metal nano-particle array.
3. high distribution density nano gap oldered array according to claim 1 or 2, which is characterized in that the high distribution
The surface of density nano gap oldered array is coated at least one of golden film, silverskin or copper film.
4. high distribution density nano gap oldered array according to claim 1 or 2, which is characterized in that the substrate is adopted
With silicon wafer, quartz plate or titanium dioxide silicon wafer.
5. a kind of preparation method of high distribution density nano gap oldered array, which comprises the following steps:
Step A, noble metal nano-particle array is placed in reactive ion etching machine together with substrate and is performed etching, this is anti-
The vacuum degree for answering ion etching machine is 150mT, and power is 50~200w, and etch period is 2~30min, gas flow CF4/O2
=45/5Sccm, so that the orderly columnar arrays template of high distribution density nano gap be made；
Wherein, the noble metal nano-particle array be in substrate homoepitaxial in the compact arranged orderly expensive gold of single layer of six sides
Metal nano-particle array, and the granularity of noble metal nano particles is 40~150nm；
Step B, plated film is carried out to the high orderly columnar arrays template of distribution density nano gap, is wanted so that aforesaid right be made
High distribution density nano gap oldered array described in asking any one of 1 to 4.
6. the preparation method of high distribution density nano gap oldered array according to claim 5, which is characterized in that described
Carrying out plated film to the high orderly columnar arrays template of distribution density nano gap includes: by the high distribution density nano gap
Orderly columnar arrays template, which is placed in ion sputtering plating instrument, carries out ion sputtering film coating, and the power of ion sputtering plating instrument is
20mA, plated film time are 6~8min.
7. the preparation method of high distribution density nano gap oldered array according to claim 5 or 6, which is characterized in that
If the noble metal nano-particle array is the gold goal nano-grain array of orderly single layer, the system of the gold goal nano-grain array
Preparation Method the following steps are included:
Step A1, gold chloride, phthalic acid diethylene glycol diacrylate and hydrochloric acid are added into ethylene glycol solution, then adopts
With oil bath heating to 195 DEG C, 30 minutes are kept the temperature, then wet-chemical chamber is carried out using hydrochloric acid, so that monodispersed gold nano be made
Particle colloid solution；
Step A2, the gold nano-particle colloid solution is centrifuged, and the precipitating after centrifuge separation is distributed to
In butanol solution, so that the n-butanol dispersion liquid of gold nano grain be made；
Step A3, it is carried out at self assembly using n-butanol dispersion liquid of the liquid-vapor interface self-assembling method to the gold nano grain
Reason, and picked up the single layer of gold nano-grain array swum on liquid level with substrate, it dries, so that the gold goal of orderly single layer be made
Nano-grain array.
8. the preparation method of high distribution density nano gap oldered array according to claim 5 or 6, which is characterized in that
The substrate uses silicon wafer, quartz plate or titanium dioxide silicon wafer.
9. a kind of application of high distribution density nano gap oldered array, which is characterized in that will appoint in the claims 1 to 4
High distribution density nano gap oldered array is directly as SERS substrate described in one.
10. the application of high distribution density nano gap oldered array according to claim 9, which is characterized in that will be above-mentioned
High distribution density nano gap oldered array described in any one of Claims 1-4 is directly as SERS substrate, for right
Aminothiophenol 4-ATP is detected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810343957.4A CN108982464A (en) | 2018-04-17 | 2018-04-17 | A kind of high distribution density nano gap oldered array and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810343957.4A CN108982464A (en) | 2018-04-17 | 2018-04-17 | A kind of high distribution density nano gap oldered array and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108982464A true CN108982464A (en) | 2018-12-11 |
Family
ID=64541870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810343957.4A Pending CN108982464A (en) | 2018-04-17 | 2018-04-17 | A kind of high distribution density nano gap oldered array and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108982464A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111122543A (en) * | 2019-12-27 | 2020-05-08 | 无锡物联网创新中心有限公司 | Roughened silicon column array structure and preparation method thereof |
| CN114346235A (en) * | 2022-01-17 | 2022-04-15 | 华东师范大学重庆研究院 | Self-assembled spherical-hexagonal gold nanoparticle assembly and preparation method thereof |
Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060038990A1 (en) * | 2004-08-20 | 2006-02-23 | Habib Youssef M | Nanowire optical sensor system and methods for making and using same |
| JP2009236830A (en) * | 2008-03-28 | 2009-10-15 | Sumitomo Precision Prod Co Ltd | Analyte carrier and its manufacturing method |
| CN101832933A (en) * | 2010-01-21 | 2010-09-15 | 厦门大学 | Method for enhancing Raman spectrum by using shell isolated nano particles |
| CN102233424A (en) * | 2010-05-07 | 2011-11-09 | 国家纳米科学中心 | Silver nano superstructure array, and preparation method and application thereof |
| CN102262083A (en) * | 2011-01-29 | 2011-11-30 | 中国科学院合肥物质科学研究院 | Dynamic surface enhanced Raman spectroscopy detection method |
| CN102398041A (en) * | 2010-09-15 | 2012-04-04 | 吉林师范大学 | Method for assembling silver nanoparticle film by using gas-liquid interface |
| CN102628809A (en) * | 2012-04-20 | 2012-08-08 | 吉林大学 | Surface enhanced raman detection test paper and application thereof |
| CN102735676A (en) * | 2012-07-02 | 2012-10-17 | 中国科学院合肥物质科学研究院 | Surface-enhanced Raman scattering spectroscopy detection method based on capillary |
| CN102747320A (en) * | 2012-07-31 | 2012-10-24 | 武汉大学 | Preparation method of noble metal nano-particle array |
| CN102774807A (en) * | 2012-07-05 | 2012-11-14 | 上海大学 | Method for preparing core shell type nanowire array raman scattering reinforcement substrate |
| CN102923647A (en) * | 2012-11-22 | 2013-02-13 | 武汉大学 | Method for preparing ordered array of metal nano-particles with adjustable space and appearance |
| CN103048307A (en) * | 2012-12-23 | 2013-04-17 | 吉林大学 | Enhanced Raman detection substrate based on natural biology super-hydrophobic structure surface and preparation method thereof |
| KR101272316B1 (en) * | 2011-11-29 | 2013-06-07 | 한국과학기술원 | Sers substrate and manufacture method thereof comprising plasmonic nanopillar arrays with high density hot spots |
| CN103409750A (en) * | 2013-08-15 | 2013-11-27 | 南京邮电大学 | Arrayed silver nanorods with surface-modifying gold nanoparticles and preparation method thereof |
| CN103451610A (en) * | 2013-09-03 | 2013-12-18 | 华中农业大学 | Novel bionic surface-enhanced Raman spectrum base and preparation method thereof |
| CN103590037A (en) * | 2013-11-20 | 2014-02-19 | 苏州大学 | Gold nanoparticle monofilm preparation method and device thereof |
| CN104251852A (en) * | 2014-08-28 | 2014-12-31 | 苏州佳因特光电科技有限公司 | Surface enhanced Raman scattering substrate constructed by electroless deposition and preparation method and application thereof |
| CN104555910A (en) * | 2014-12-31 | 2015-04-29 | 吉林大学 | Method for preparing thin film ordered microstructure based on a reaction ion beam etching technology |
| CN105731370A (en) * | 2016-02-22 | 2016-07-06 | 中国科学院合肥物质科学研究院 | Large-area two-dimensional ordered gold nanoparticle array and preparation method thereof |
| CN107425053A (en) * | 2017-07-28 | 2017-12-01 | 西安交通大学 | A kind of method that the concentric more iron heterojunction arrays of nucleocapsid three-dimensional manometer are built with ALD |
| CN107543813A (en) * | 2017-08-22 | 2018-01-05 | 中国工程物理研究院化工材料研究所 | A kind of preparation method and applications of surface-enhanced Raman ordered composite array chip |
| CN107607516A (en) * | 2017-09-11 | 2018-01-19 | 电子科技大学 | A kind of chemical sensor of Raman enhancing and preparation method thereof |
-
2018
- 2018-04-17 CN CN201810343957.4A patent/CN108982464A/en active Pending
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060038990A1 (en) * | 2004-08-20 | 2006-02-23 | Habib Youssef M | Nanowire optical sensor system and methods for making and using same |
| JP2009236830A (en) * | 2008-03-28 | 2009-10-15 | Sumitomo Precision Prod Co Ltd | Analyte carrier and its manufacturing method |
| CN101832933A (en) * | 2010-01-21 | 2010-09-15 | 厦门大学 | Method for enhancing Raman spectrum by using shell isolated nano particles |
| CN102233424A (en) * | 2010-05-07 | 2011-11-09 | 国家纳米科学中心 | Silver nano superstructure array, and preparation method and application thereof |
| CN102398041A (en) * | 2010-09-15 | 2012-04-04 | 吉林师范大学 | Method for assembling silver nanoparticle film by using gas-liquid interface |
| CN102262083A (en) * | 2011-01-29 | 2011-11-30 | 中国科学院合肥物质科学研究院 | Dynamic surface enhanced Raman spectroscopy detection method |
| KR101272316B1 (en) * | 2011-11-29 | 2013-06-07 | 한국과학기술원 | Sers substrate and manufacture method thereof comprising plasmonic nanopillar arrays with high density hot spots |
| CN102628809A (en) * | 2012-04-20 | 2012-08-08 | 吉林大学 | Surface enhanced raman detection test paper and application thereof |
| CN102735676A (en) * | 2012-07-02 | 2012-10-17 | 中国科学院合肥物质科学研究院 | Surface-enhanced Raman scattering spectroscopy detection method based on capillary |
| CN102774807A (en) * | 2012-07-05 | 2012-11-14 | 上海大学 | Method for preparing core shell type nanowire array raman scattering reinforcement substrate |
| CN102747320A (en) * | 2012-07-31 | 2012-10-24 | 武汉大学 | Preparation method of noble metal nano-particle array |
| CN102923647A (en) * | 2012-11-22 | 2013-02-13 | 武汉大学 | Method for preparing ordered array of metal nano-particles with adjustable space and appearance |
| CN103048307A (en) * | 2012-12-23 | 2013-04-17 | 吉林大学 | Enhanced Raman detection substrate based on natural biology super-hydrophobic structure surface and preparation method thereof |
| CN103409750A (en) * | 2013-08-15 | 2013-11-27 | 南京邮电大学 | Arrayed silver nanorods with surface-modifying gold nanoparticles and preparation method thereof |
| CN103451610A (en) * | 2013-09-03 | 2013-12-18 | 华中农业大学 | Novel bionic surface-enhanced Raman spectrum base and preparation method thereof |
| CN103590037A (en) * | 2013-11-20 | 2014-02-19 | 苏州大学 | Gold nanoparticle monofilm preparation method and device thereof |
| CN104251852A (en) * | 2014-08-28 | 2014-12-31 | 苏州佳因特光电科技有限公司 | Surface enhanced Raman scattering substrate constructed by electroless deposition and preparation method and application thereof |
| CN104555910A (en) * | 2014-12-31 | 2015-04-29 | 吉林大学 | Method for preparing thin film ordered microstructure based on a reaction ion beam etching technology |
| CN105731370A (en) * | 2016-02-22 | 2016-07-06 | 中国科学院合肥物质科学研究院 | Large-area two-dimensional ordered gold nanoparticle array and preparation method thereof |
| CN107425053A (en) * | 2017-07-28 | 2017-12-01 | 西安交通大学 | A kind of method that the concentric more iron heterojunction arrays of nucleocapsid three-dimensional manometer are built with ALD |
| CN107543813A (en) * | 2017-08-22 | 2018-01-05 | 中国工程物理研究院化工材料研究所 | A kind of preparation method and applications of surface-enhanced Raman ordered composite array chip |
| CN107607516A (en) * | 2017-09-11 | 2018-01-19 | 电子科技大学 | A kind of chemical sensor of Raman enhancing and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FENG SHAO 等: ""Hierarchical Nanogaps within Bioscaffold Arrays as a High-Performance SERS Substrate for Animal Virus Biosensing"", 《ACS APPLIED MATERIALS & INTERFACES 》 * |
| 邵锋 等: ""基于"热点"结构的表面增强拉曼散射基底构建策略"", 《分析科学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111122543A (en) * | 2019-12-27 | 2020-05-08 | 无锡物联网创新中心有限公司 | Roughened silicon column array structure and preparation method thereof |
| CN114346235A (en) * | 2022-01-17 | 2022-04-15 | 华东师范大学重庆研究院 | Self-assembled spherical-hexagonal gold nanoparticle assembly and preparation method thereof |
| CN114346235B (en) * | 2022-01-17 | 2024-01-26 | 华东师范大学重庆研究院 | Self-assembled spherical-hexagonal gold nanoparticle assembly and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104792766B (en) | Surface enhanced raman scattering substrate and preparation method thereof | |
| Tang et al. | Silver nanodisks with tunable size by heat aging | |
| George et al. | Flexible superhydrophobic SERS substrates fabricated by in situ reduction of Ag on femtosecond laser-written hierarchical surfaces | |
| KR101448111B1 (en) | A substrate for surface-enhanced Raman scattering spectroscopy and a preparing method thereof | |
| Liu et al. | Large-area fabrication of highly reproducible surface enhanced Raman substrate via a facile double sided tape-assisted transfer approach using hollow Au–Ag alloy nanourchins | |
| CN108872185B (en) | Preparation method of SERS chip | |
| CN108277484A (en) | A kind of preparation method of hollow Ag-Au alloys composite construction micro-nano array | |
| CN107688015B (en) | Preparation method of transparent dielectric microsphere flexible film for enhancing Raman scattering light intensity | |
| CN110987901B (en) | Au-Au dimer array structure and preparation method and application thereof | |
| CN105842227A (en) | Preparation method for surface-enhanced Raman substrate and surface-enhanced Raman substrate structure | |
| CN108971510A (en) | Silver nanowires and preparation method thereof, silver nanowires film and laminated film | |
| CN108982464A (en) | A kind of high distribution density nano gap oldered array and the preparation method and application thereof | |
| CN105136768A (en) | Preparation method of surface-enhanced Raman scattering (SERS) substrate polarized by metal nano particle array | |
| Yan et al. | Fabrication of polymer colloidal/Au composite nanofilms for stable and reusable SERS-active substrates with highly-dense hotspots | |
| Purwidyantri et al. | Plasmonic nanomaterial structuring for SERS enhancement | |
| CN107101988A (en) | A kind of high density nanometer pinpoint array of golden film covering and its application | |
| CN111426674B (en) | Sunflower nano array structure for enhancing SERS activity and preparation method thereof | |
| CN112014375A (en) | Metal circular ring inner hexagram trimer nano array and preparation method and application thereof | |
| Wang et al. | Surface-enhanced Raman scattering on a hierarchical structural Ag nano-crown array in different detection ways | |
| Chang et al. | Optimizing pyramidal silicon substrates through the electroless deposition of Ag nanoparticles for high-performance surface-enhanced Raman scattering | |
| CN108872184B (en) | Preparation method of SERS chip | |
| CN114014258B (en) | Preparation method of three-dimensional asymmetric metal-medium functional nano array structure | |
| Zou et al. | Fabrication of novel biological substrate based on photolithographic process for surface enhanced Raman spectroscopy | |
| Wang et al. | Surface-enhanced Raman spectroscopy based on ordered nanocap arrays | |
| CN111349892B (en) | Silver-superposed triangular nanoparticle array and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181211 |