CN110261365A - A kind of period crescent nano gap array and preparation method thereof with raising Surface enhanced Raman scattering performance - Google Patents
A kind of period crescent nano gap array and preparation method thereof with raising Surface enhanced Raman scattering performance Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
It is a kind of with the period crescent nano gap array and preparation method thereof for increasing substantially Surface enhanced Raman scattering performance, the invention belongs to Surface enhanced Raman scattering technical fields.This method is related to colloid lithographic method, metal Aided Wet etching, physical gas-phase deposite method, nanometer cutting method etc..Whole process is easy to operation, and controllability is high, process low consumption, and does not require expensive instrument and gnotobasis, has universality.By controlling etch period, the crescent nano gap array of different cycles can be prepared；By the thickness for controlling middle layer, the crescent nano gap array with different gap width can be prepared, realize the coupling of multiple hot spot, enhance the electromagnetic field of structure, to improve Surface enhanced Raman scattering performance, specific effect can be played in the fields such as plasma, nonlinear optics, Single Molecule Detection, photoelectronics and Meta Materials.
Description
Technical field
The invention belongs to Surface enhanced Raman scattering technical fields, and in particular to one kind, which has, increases substantially surface enhanced
Period crescent nano gap array of Raman scattering performance and preparation method thereof.
Background technique
Surface enhanced Raman scattering (SERS) layer in substrate has attracted the attraction of numerous people, because it
In plasma[1,2], nonlinear optics[3], Single Molecule Detection[4,5], photoelectronics[6]And Meta Materials[7]It is played in equal fields
Biggish effect.A large amount of adjacent particulates of receiving[8], nano wire[9]With some more complex nano-micro structures[4-6]Between gap,
Or the cuspidated nano-micro structure of tool all shows the performance of good Surface enhanced Raman scattering.
But has the noble metal nano-micro structure at gap and tip considerably less simultaneously, and generally use electron beam lithography and gather
Pyrophosphate ion beam etching etc., expensive equipment needed for these complicated techniques, time-consuming, and has lower flux, limit its into
The application of one step.So a kind of pervasive and controllable preparation method how to be selected to become current exploration hot spot.
[1]Ward,D.R.；Hueser,F.；Pauly,F.；Carlos Cuevas,J.；Natelson,D.Nature
Nanotechnology 2010,5,732-736.
[2]Kim,S.；Jin,J.；Kim,Y.J.；Park,I.Y.；Kim,Y.；Kim,S.W.Nature 2008,453,
757-760.
[3]Danckwerts,M.；Novotny,L.Physical review letters 2007,98,026104.
[4]Chirumamilla,M.；Toma,A.；Gopalakrishnan,A.；Das,G.；Zaccaria,R.P.；
Krahne,R.；Rondanina,E.；Leoncini,M.；Liberale,C.；De Angelis,F.；Di Fabrizio,
E.Adv.Mater.2014,26,2353-2358.
[5]Shi,X.；Verschueren,D.；Pud,S.；Dekker,C.Small 2017,1703307.
[6]Dong,Z.；Asbahi,M.；Lin,J.；Zhu,D.；Wang,Y.M.；Hippalgaonkar,K.；Chu,
H.S.；Goh,W.P.；Wang,F.；Huang,Z.；Yang,J.K.W.Nano Lett.2015,15,5976-5981.
[7]S.P.Burgos,R.de Waele,A.Polman,H.A.Atwater,Nat.Mater.2010,9,407.
[8]Z.Dong,M.Asbahi,J.Lin,D.Zhu,Y.M.Wang,K.Hippalgaonkar,H.S.Chu,
W.P.Goh,F.Wang,Z.Huang,J.K.Yang,Nano Lett.2015,15,5976.
[9]Z.Zhou,Z.Zhao,Y.Yu,B.Ai,R.C.Chiechi,J.K.W.Yang,G.Zhang,
Adv.Mater.2016,28,2956。
Summary of the invention
The object of the present invention is to provide a kind of with the crescent nanometer for increasing substantially Surface enhanced Raman scattering performance
Gap array and preparation method thereof.
The present invention uses colloid lithographic method, metal Aided Wet etching, physical gas-phase deposite method, nanometer cutting method
Deng whole process is easy to operation, and controllability is high.By controlling etch period, the crescent nanometer of different cycles can be prepared
Gap array；By controlling the thickness of middle layer, the crescent nano gap array with different gap width can be prepared, is realized
The coupling of multiple hot spot, to increase substantially Surface enhanced Raman scattering performance.
It is of the present invention a kind of with the crescent nano gap battle array for increasing substantially Surface enhanced Raman scattering performance
The preparation method of column, the specific steps are as follows:
1) by the mixed liquor for the hydrogen peroxide that silicon base is put into the concentrated sulfuric acid of mass fraction 98% and mass fraction is 30%
In (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7:3), 70~90 DEG C are heated to, 3~8h is kept；It places to room temperature, by silicon substrate
Bottom is rinsed after taking out with a large amount of deionized water and ethyl alcohol, and nitrogen is dry, and recycling oxygen plasma cleaning silicon substrate surface 2~
5min obtains hydrophilic and uniform surface；
2) in the deionization moisture for the polystyrene microsphere that 1~5mL, concentration are 1~20wt%, diameter is 500~900nm
2~5mL deionized water is added in dispersion liquid and is centrifuged 8~15min, the solid-state obtained after centrifugation under 6000~10000rpm revolving speed
2~5mL deionized water is added in object, and 8~15min is centrifuged under 6000~10000rpm revolving speed；Repeat be added deionized water and
Centrifugal process 3~5 times；The ethyl alcohol and deionized water that 2~5mL volume ratio is 1:1 are added in being finally centrifuged obtained solid
Mixed liquor, 8~15min is centrifuged under 6000~10000rpm revolving speed, add 2 in the solid obtained after centrifugation~
5mL ethyl alcohol and the mixed liquor of deionized water are centrifuged 8~15min under 6000~10000rpm revolving speed；It repeats that ethyl alcohol is added and goes
Ion water mixed liquid and centrifugal process 6~10 times；2~5mL ethyl alcohol and deionized water are added in the solid finally obtained
Mixed liquor obtains the ethyl alcohol and deionized water dispersion liquid for the hydrophobic polystyrene microballoon that mass percent is 1~10%；With primary
Property syringe draw 0.1~0.5mL hydrophobic polystyrene microballoon ethyl alcohol and deionized water dispersion liquid, be added drop-wise to and fill deionization
In the culture dish of water, hydrophobic polystyrene microballoon is arranged as single layer in air-deionized water gas-liquid interface, add 50~
120 μ L, mass concentration make hydrophobic polystyrene microballoon for the aqueous solution of the dodecyl sodium sulfate surfactant of 1~10wt%
Close-packed arrays, the silicon base crossed with the hydrophilic treated that step 1) obtains by the compact arranged hydrophobic polystyrene microballoon of single layer gently
Hold up, be placed on 40~60 degree inclined filter paper and spontaneously dry, thus obtain on a silicon substrate the diameter of sequential 2 D for 500~
The compact arranged hydrophobic polystyrene micro-sphere array of 900nm single layer；
It 3) is the compact arranged hydrophobic polyphenyl second of 500~900nm single layer by the diameter of sequential 2 D obtained in step 2)
Alkene micro-sphere array substrate is placed in reactive plasma etching machine, etching air pressure be 5~10mTorr, etching temperature 10
~25 DEG C, oxygen gas flow rate be 10~50sccm, radio frequency (RF) power is 20~100W, inductively coupled plasma body (ICP) power
To etch 90~120s under the conditions of 200~400W, polystyrene microsphere is etched in etching process and diameter gradually becomes smaller；
4) polystyrene microsphere and silicon base etched in step 3) are placed on to the sample of vacuum thermal evaporation filming equipment
In sample platform, the angle of substrate normal and deposition direction is 0 °, and deposition velocity isThe silver film thickness of deposition be 20~
40nm；The substrate for depositing silverskin is put into 2~5min of ultrasound in toluene, ultrasonic power is 30~50W, removes polystyrene microsphere
And its silverskin covered above, obtain the silver nanoparticle pore membrane array substrate that the period is 500~900nm, aperture is 200~500nm；
5) silver nanoparticle pore membrane array substrate obtained in step 4) is soaked into 10~15mL etching liquid (hydrofluoric acid, peroxide
The volume ratio for changing hydrogen and water is 1:1:2) metal Aided Wet 5~10min of etching is carried out, etched substrate is picked up and uses ethyl alcohol
It rinses, it is dry with nitrogen, it is (5~10): 1 silicon column array (wet etching in the draw ratio that silicon substrate surface obtains large area
Be the silicon base remained in below silverskin, so being still etched and being collapsed by the silicon base part that silverskin covers, that is, form silicon
Column array)；
6) silicon column array substrate obtained in step 5) is put into vacuum desiccator, it is chloro- that three is added dropwise in drier
(1H, 1H, 2H, 2H- perfluoro capryl) silane is put into 50~80 DEG C of baking oven modified 2~5h；The substrate being modified is put into culture dish
In, by configured dimethyl silicone polymer (PDMS) prepolymer, (mass ratio of polydimethylsiloxaneresins resins and curing agent is
10:1) pour into culture dish, culture dish be put into 50~80 DEG C of 2~5h of drying of baking oven, by silicon column array substrate from flexibility poly- two
It is removed in methylsiloxane substrate；Epoxy is poured into the flexible polydimethylsiloxane prepolymer object substrate of obtained structuring again
Resin prepolymer (volume ratio of epoxy resin and curing agent is 15:2), makes epoxy prepolymer that the poly- of structuring be completely covered
Dimethyl siloxane (PDMS) prepolymer；50~80 DEG C of 2~5h of drying in baking oven are placed into, by the asphalt mixtures modified by epoxy resin of obtained structuring
It gently removes at aliphatic radical bottom；
7) the epoxy resin substrate of structuring obtained in step 6) is placed on to the sample stage of vacuum evaporation coating film device
On, the angle of substrate normal and deposition direction is 25~40 °, and deposition velocity is3 layers of metal of successive sedimentation, 3 layers of gold
The thickness of category is 80~120nm of golden film, 1~8nm of aluminium film, 80~120nm of golden film respectively；
8) substrate obtained in step 7) is put into mold, and infusion epoxy resin prepolymer；Obtained substrate is put
In the fixed appliance for entering ultramicrotome (Leica EM UC 7), using ultra-thin diamond cutter along be parallel to the direction of substrate into
Row slice (chip rate is set as 0.6~1.0mm/s, and slice thickness is 80~150nm), then it is golden with 60~100nm is deposited with
The silicon base of film collects drying after slice in water phase, then small together in the dilute hydrochloric acid solution of slice immersion 2M thereon 1~3
When, for removing the aluminium film among 3 layers of metal；Be placed in reactive plasma etching machine, etching air pressure be 5~
10mTorr, etching temperature are 10~25 DEG C, oxygen gas flow rate is 10~50sccm, radio frequency (RF) power is 60~100W, inductance coupling
It closes under the conditions of plasma (ICP) power is 200~300W and etches 120~200s, remove all extra epoxy resin, thus
It is obtained in golden film substrate of the present invention a kind of with the wide with different gap of raising Surface enhanced Raman scattering performance
The period crescent nano gap array of degree；
The epoxy resin substrate of structuring obtained in step 6) is separately taken to be placed on the sample stage of vacuum evaporation coating film device
On, the angle of substrate normal and deposition direction is 25~40 °, carries out the golden film of one layer of 80~120nm of thermal evaporation deposition, will obtain
Sample be put into mold, and infusion epoxy resin prepolymer；It is then placed in ultramicrotome along the side for being parallel to substrate
To being sliced (chip rate is set as 0.6~1.0mm/s, and slice thickness is 80~150nm), with being deposited with 60~100nm
The silicon base of golden film collects drying after slice in water phase；Be placed in reactive plasma etching machine, etching air pressure
For 5~10mTorr, etching temperature be 10~25 DEG C, oxygen gas flow rate is 10~50sccm, radio frequency (RF) power be 60~100W,
Inductively coupled plasma body (ICP) power etches 120~200s under the conditions of being 200~300W, removes all extra asphalt mixtures modified by epoxy resin
Rouge obtains crescent Crystal structure, as reference sample；
The crescent nano gap array and the moon with different gap width in golden film substrate prepared by step 8)
Tooth form nano wire is individually positioned on the sample stage of high-resolution excitation Raman spectrometer, is tested its Raman spectrum, is analyzed its surface
Enhance Raman scattering performance.
The each step operation of the present invention is simple, and controllability is strong, in the crescent nanometer with different gap width of preparation
On the array of gap, and with the reduction of gap width, the feature peak intensity of Raman spectrum is gradually increased, and is 1nm in gap width
When raman scattering intensity reach maximum, obtain with the period crescent nano gap battle array for improving Surface enhanced Raman scattering performance
Column, can be applied in the practical applications such as photoelectric device.
Detailed description of the invention
Fig. 1 is the flow chart for preparing epoxy resin column array mould plate, and the various materials utilized and main behaviour are denoted in figure
Make step；Wherein, 1,700nm polystyrene microsphere；Substrate 2, silicon base；3, silver nanoparticle pore membrane；4, dimethyl silicone polymer；5,
Epoxy resin column array；
Fig. 2A is that the scanning electron microscope (SEM) of the polystyrene microsphere array after etching obtained in step 3) is shone
Piece；Fig. 2 B is scanning electron microscope (SEM) photo (top view) for the silicon column array that wet etching obtains in step 5)；Fig. 2 C
For scanning electron microscope (SEM) photo (30 ° of side views) of silicon column array obtained in step 5)；Fig. 2 D is to obtain in step 5)
Scanning electron microscope (SEM) photo (cross-sectional view) of the silicon column array arrived；Scale is 1 μm；
Fig. 3 is the flow chart for preparing crescent nano gap array；Corresponding step 7 and 8；Various utilize is denoted in figure
Material and main operational steps；Wherein, 5 be epoxy resin column array；
Fig. 4 A be crescent nano gap array structural parameters schematic diagram (H represents the height of crescent nano gap
(100nm), W represent the thickness (80nm) of golden film, and G represents the width (1~8nm, the thickness of aluminium film) of nano gap, and P represents the moon
The period (i.e. original polystyrene Microsphere Size 700nm) of thread form nano gap；Figure B~F is the moon with different gap width
Scanning electron microscope (SEM) photo of thread form nano gap array；B is the crescent nano gap battle array that gap width is 1nm
The top view of column；C is the top view for the crescent nano gap array that gap width is 2nm；D is the moon that gap width is 3nm
The top view of thread form nano gap array；E is the top view for the crescent nano gap array that gap width is 5nm；F is gap
Width is the top view of the crescent nano gap array of 8nm；
Fig. 5 is the Raman spectrogram that high-resolution laser Raman spectrometer measures.
Fig. 5 A is the Raman spectrogram of the crescent nano gap array of different gap width, is from top to bottom followed successively by gap
Width is the Raman spectrogram of 1nm, and gap width is the Raman spectrogram of 2nm, and gap width is the Raman spectrogram of 3nm,
Gap width is the Raman spectrogram of 5nm, and gap width is the Raman spectrogram of 8nm, illustrates the reduction with gap width, Raman
Intensity tool has greatly improved, and has good Surface enhanced Raman scattering performance；
Fig. 5 B is the crescent nano gap array of different gap width in 1077cm-1The raman scattering intensity and gap width at place
Graph of relation, with the reduction of nano gap, raman scattering intensity is in monotonic increase trend, illustrates that crescent nano gap array has
There is good Surface enhanced Raman scattering performance；
Fig. 5 C is Raman spectrogram (corresponding step 8), the feature peak intensity of crescent nanowires of gold of crescent nanowires of gold
Degree is substantially reduced compared to the selenodont nano-wire array with gap in figure A, illustrates that gap is improved surface-enhanced Raman and dissipated
Important role is penetrated；
Fig. 5 D is to randomly select 16 positions on the crescent nano gap array with 1nm gap width, passes through height
The Raman spectrogram that resolution laser Raman spectrometer measures, Raman spectrum map contour is essentially identical, and the structure illustrated has
Good homogeneity.
Specific embodiment
Embodiment 1: the preparation of hydrophilic silicon base
It is 2 × 2cm that silicon wafer, which is cut out, with glass cutter2Size is put into the concentrated sulfuric acid (mass fraction 98%) and hydrogen peroxide
(30%) 80 DEG C are heated in mixed liquor (volume ratio is the concentrated sulfuric acid: hydrogen peroxide=7:3), 5h is kept to put to room temperature, with big
It measures deionized water to rinse to get hydrophilic silicon wafer is arrived, silicon wafer is rinsed with ethyl alcohol later, is dried with nitrogen, oxygen plasma machine is utilized
Clean surface 3min is to obtain hydrophilic and uniform surface.
Embodiment 2: the preparation of hydrophobic polystyrene microballoon
At room temperature, 1mL, 5wt%, diameter be 700nm polystyrene microsphere aqueous dispersions in be added 3mL deionization
Water carries out ultrasound 10min, is centrifuged 10min with 8900rpm revolving speed, draws supernatant liquor, add 3mL in the solid left
Deionized water ultrasound is simultaneously centrifuged again, hereafter repeats this process 4 times.After last time draws supernatant liquor, in solid-state
The mixed liquor (ethyl alcohol: the volume ratio of deionized water is 1:1) of 3mL ethyl alcohol and deionized water is added in object, with 8900rpm revolving speed from
Heart 10min draws supernatant liquor, and the mixed liquor ultrasound of 3mL ethyl alcohol and deionized water is then added in the solid left
And be centrifuged again, this process is hereafter repeated 8 times, after last time draws supernatant liquor, by remaining solid 30
DEG C baking oven in 8h dried, polystyrene microsphere is configured to point of 5wt% by the mixed liquor that ethyl alcohol and deionized water is added
Dispersion liquid is stand-by.
The preparation of the closelypacked single layer polystyrene colloid crystal of 3: six side of embodiment
The hydrophobic polystyrene microballoon that the diameter prepared in 0.2mL embodiment 2 is 700nm is drawn with disposable syringe
Ethyl alcohol and deionized water dispersion liquid are slowly dripped to it using instrument on air-deionized water interface of culture dish, along training
The aqueous solution for supporting the lauryl sodium sulfate that 80 μ L are added in ware side, mass concentration is 10wt%, stands a moment, and polystyrene is micro-
Club forms the closelypacked form of six side of single layer on air-deionized water interface.The hydrophilic silicon base obtained with embodiment 1
For, the water surface is deep into hereinafter, being slowly lifted up below close single layer polystyrene microsphere, being placed in inclined-plane is
It is spontaneously dried on 60 ° of filter paper, i.e., forms the closelypacked polystyrene of six side of single layer that diameter is 700nm on a silicon substrate
Colloidal crystal.
Embodiment 4: the preparation of silver nanoparticle hole membrane array
The closelypacked polystyrene colloid of six side of sequential 2 D single layer for being 700nm by the diameter prepared in embodiment 3
The silicon base of crystal array is placed in the storehouse of reactive plasma etching machine, is 10mTorr, etching temperature in etching air pressure
It is 20 DEG C, oxygen gas flow rate 50sccm, under conditions of radio frequency (RF) power 30W, inductively coupled plasma body (ICP) power 300W
It etches 120s (such as Fig. 2A)；The polystyrene microsphere array that etched diameter becomes smaller is placed on to the sample of vacuum coating equipment
On platform, the angle of sample normal and deposition direction is 0 °, and the speed of thermal evaporation deposition isThe silver film thickness of deposition is
20nm；The substrate that golden film will be deposited with immerses ultrasound 4min, power 40w in toluene, and removing after microballoon is to obtain the period to be
700nm, aperture are the silver nanoparticle pore membrane array substrate of 350nm；
Embodiment 5: the preparation of large area high length-diameter ratio silicon column array
Silver nanoparticle pore membrane array substrate obtained in embodiment 4 is immersed into etching liquid (hydrofluoric acid: hydrogen peroxide: deionization
The volume ratio of water is 1:1:2) in, 10min is etched, the silicon base under silverskin is gradually etched, the piece ethyl alcohol that will have been etched
Rinse, be dried with nitrogen to get to the period be 700nm, the silicon column array that the draw ratio that diameter is 350nm is 6:1, corresponding diagram 2B,
2C,2D；
Embodiment 6: epoxy resin column array processed is turned over
Silicon column array substrate obtained in embodiment 5 is put into vacuum desiccator, it is chloro- that 2 drops three are added dropwise in drier
(1H, 1H, 2H, 2H- perfluoro capryl) silane is put into 60 DEG C of baking oven modified 3h；；The substrate being modified is put into culture dish, is matched
The polydimethylsiloxane prepolymer object set pours into culture dish, is put into 60 DEG C of drying 3h of baking oven, by silicon column array substrate from soft
It is removed in property dimethyl silicone polymer substrate；Epoxy prepolymer is poured into the flexible substrates of obtained structuring, is put into
60 DEG C of drying 3h, the epoxy resin substrate of obtained structuring is gently removed in baking oven, is placed stand-by；
Embodiment 7: three-layer metal gold/aluminium/gold successive sedimentation
The epoxy resin substrate turned over after making obtained in embodiment 6 is placed on the sample stage of vacuum vapor plating, sample
The angle (incidence angle) of product normal and deposition direction is 35 °, is with deposition velocityCarry out 3 layers of metal of thermal evaporation deposition
Gold/aluminium/gold, deposition thickness are respectively five kinds of samples of 80nm/1,2,3,5,8nm/80nm；
Embodiment 8: the preparation of crescent nano gap array
Sample obtained in embodiment 7 is cut into 2 × 2mm2Square, be put into mold and pour more epoxy resin
Prepolymer；Obtained sample is put into the fixed appliance of ultramicrotome (Leica EM UC 7), using diamond tool along
The direction for being parallel to substrate is sliced (chip rate is set as 0.8mm/s, and the thickness of slice is 100nm), later with deposition
There is the silicon base of 80nm thick gold membrane to collect continuous slice in water phase, it is dry；The slice gathered is immersed to the dilute hydrochloric acid of 2M
It is impregnated two hours in solution, for removing middle layer aluminium layer, ethyl alcohol drying, drying at room temperature；It is subsequently placed to reactive plasma
It is 10mTorr in etching air pressure, etching temperature is 20 DEG C, oxygen gas flow rate 50sccm, radio frequency (RF) function in the storehouse of body etching machine
180s is etched under conditions of rate 60W, inductively coupled plasma body (ICP) power 200W and removes epoxy resin, in golden film substrate
Obtain crescent nano gap array, corresponding diagram 4；
Embodiment 9: the method for the SERS enhancing performance of detection crescent nano gap array
Crescent nano gap array obtained in embodiment 8 is placed on to the sample stage of high-resolution excitation Raman spectrometer
On, test its Raman spectrum；Optical maser wavelength is 663nm, in 800~1800cm-1In the range of test its reflectance spectrum, it was demonstrated that
Crescent nano gap array has stronger Raman-enhancing energy, corresponds to Fig. 5 A；And with the reduction of gap width, Raman
Intensity is incremented by (Fig. 5 B) in monotonicity, by comparing (Fig. 5 C) with crescent nanowires of gold, it was demonstrated that gap enhances Raman
Decisive role is played.16 positions are randomly selected on the crescent nano gap array with 1nm gap width, pass through height
The Raman spectrogram that resolution laser Raman spectrometer measures finds that its Raman spectrum profile is essentially identical, the structure illustrated
With good homogeneity, correspond to Fig. 5 D.
The above described is only a preferred embodiment of the present invention, not making any form to method scheme of the invention
On limitation.Any simple modification substantially to the above embodiments of all methods according to the present invention equally changes and repairs
Decorations, fall within the protection scope of the present invention.
Claims (8)
1. a kind of preparation method with the period crescent nano gap array for improving Surface enhanced Raman scattering performance, step
It is rapid as follows:
1) silicon base for taking hydrophilic treated to cross, the diameter that sequential 2 D is prepared in substrate is that 500~900nm single layer is close
The hydrophobic polystyrene micro-sphere array of arrangement；
It 2) is that the compact arranged hydrophobic polystyrene of 500~900nm single layer is micro- by the diameter of sequential 2 D obtained in step 1)
Ball array substrate is placed in 90~120s of etching in reactive plasma etching machine；In the process, polystyrene microsphere is carved
It loses and diameter gradually becomes smaller；Etched sample is placed on later on the sample stage of vacuum evaporation coating film device, sample normal
Angle with deposition direction is 0 °, and the silver film thickness of deposition is 20~40nm；The substrate of thermal evaporation deposition silverskin is put into toluene
Middle ultrasonic 2~5 minutes, ultrasonic power was 30~50W, obtained the period after removing polystyrene microsphere as 500~900nm, aperture
For the silver nanoparticle pore membrane array substrate of 200~500nm；
3) silver nanoparticle pore membrane array substrate obtained in step 2) is soaked into 10~15mL etching liquid and carries out metal Aided Wet
5~10min is etched, substrate is picked up and is rinsed with ethyl alcohol, nitrogen is dry, is (5 in the draw ratio that silicon substrate surface obtains large area
~10): 1 silicon column array；
4) silicon column array substrate obtained in step 3) is put into vacuum desiccator, it is chloro- that three is added dropwise in drier
(1H, 1H, 2H, 2H- perfluoro capryl) silane is put into 50~80 DEG C of baking oven modified 2~5h；The substrate being modified is put into culture dish
In, configured polydimethylsiloxane prepolymer object pours into culture dish, 50~80 DEG C of 2~5h of drying of baking oven is put into, by silicon column
Array substrate is removed from flexible dimethyl silicone polymer substrate；Epoxy resin is poured into the flexible substrates of obtained structuring
Prepolymer is put into 50~80 DEG C of 2~5h of drying in baking oven, the epoxy resin substrate of obtained structuring is gently removed；
5) the epoxy resin substrate of structuring obtained in step 4) is placed on the sample stage of vacuum evaporation coating film device, base
The angle of bottom normal and deposition direction is 25~40 °, 3 layers of metal of successive sedimentation, the thickness of 3 layers of metal be respectively golden film 80~
120nm, 1~8nm of aluminium film, 80~120nm of golden film；
6) substrate obtained in step 5) is put into mold and pours epoxy prepolymer；Obtained substrate is utilized ultra-thin
Slicer is sliced along the direction for being parallel to substrate, and slice is collected in water phase with golden film substrate later；
7) slice obtained in step 6) is immersed into 1~3h in the dilute hydrochloric acid solution of 2M, for removing middle layer aluminium film；Postposition
In reactive plasma etching machine, 120~200s of etching removes extra epoxy resin, obtains having and improves surface enhanced
The period crescent nano gap array of Raman scattering performance.
2. as described in claim 1 a kind of with the period crescent nano gap battle array for improving Surface enhanced Raman scattering performance
The preparation method of column, it is characterised in that: be in the polystyrene that 1~5mL, concentration are 1~20wt%, diameter is 500~900nm
The deionized water of 2~5mL is added in the deionized water dispersion liquid of microballoon, 8~15 points are centrifuged under 6000~10000rpm revolving speed
Clock adds 2~5mL deionized water ultrasound in the solid obtained after centrifugation and is centrifuged again, repeat to be added go from
Sub- water and centrifugal process 3~5 times；The ethyl alcohol and go that 2~5mL volume ratio is 1:1 are added in being finally centrifuged obtained solid
The mixed liquor of ionized water is centrifuged 8~15 minutes under 6000~10000rpm revolving speed, repeats that ethyl alcohol and deionized water mixing is added
Liquid and centrifugal process 6~10 times add ethyl alcohol and go that 2~5mL volume ratio is 1:1 in being finally centrifuged obtained solid
The mixed liquor of ionized water, to obtain the ethyl alcohol and deionized water dispersion liquid of hydrophobic polystyrene microballoon；Use disposable syringe
The ethyl alcohol and deionized water dispersion liquid for drawing 0.1~0.5mL hydrophobic polystyrene microballoon, are added drop-wise to the container for filling deionized water
In, hydrophobic polystyrene microballoon is arranged as single layer in air-deionized water gas-liquid interface, adds 50~120 μ L, concentration is
The dodecyl sodium sulfate surfactant of 1~10wt% makes hydrophobic polystyrene microballoon close-packed arrays each other, uses hydrophilic treated
The substrate crossed holds up the compact arranged hydrophobic polystyrene microballoon of single layer, is placed on inclined surface and spontaneously dries, thus in substrate
On obtain sequential 2 D diameter be the compact arranged hydrophobic polystyrene micro-sphere array of 500~900nm single layer.
3. as described in claim 1 a kind of with the period crescent nano gap battle array for improving Surface enhanced Raman scattering performance
The preparation method of column, it is characterised in that: reactive plasma etching etching air pressure be 5~10mTorr, etching temperature 10
~25 DEG C, oxygen gas flow rate be 10~50sccm, etching power be radio-frequency power be 20~100W, inductively coupled plasma body power
For 200~400W.
4. as described in claim 1 a kind of with the period crescent nano gap battle array for improving Surface enhanced Raman scattering performance
The preparation method of column, it is characterised in that: the vacuum degree of vacuum vapor plating is 5 × 10-4~1 × 10-3Pa, deposition velocity are
5. as described in claim 1 a kind of with the period crescent nano gap battle array for improving Surface enhanced Raman scattering performance
The preparation method of column, it is characterised in that: the hydrophilic treated of substrate be silicon base is put into mass fraction 30% hydrogen peroxide and
In the mixed solution of the sulfuric acid of mass fraction 98%, the volume ratio of hydrogen peroxide and sulfuric acid is 3:7；70~90 DEG C are heated to, is held
Continuous 3~8h, places to room temperature, is cleaned with a large amount of deionized waters and ethyl alcohol, places for use, and nitrogen is dry, recycles oxygen plasma
Clean 2~5min of silicon substrate surface.
6. as described in claim 1 a kind of with the period crescent nano gap battle array for improving Surface enhanced Raman scattering performance
The preparation method of column, it is characterised in that: the etching liquid that wet etching uses is hydrofluoric acid, hydrogen peroxide and deionized water, volume
Than silver nanoparticle pore membrane being soaked into the etching liquid of 10~15mL, wet etching 5-10min is rinsed, nitrogen with ethyl alcohol for 1:1:2
Air-blowing is dry.
7. as described in claim 1 a kind of with the period crescent nano gap battle array for improving Surface enhanced Raman scattering performance
The preparation method of column, it is characterised in that: chip rate is set as 0.6~1.0mm/s, and slice thickness is 80~150nm.
8. a kind of with the period crescent nano gap array for improving Surface enhanced Raman scattering performance, it is characterised in that: be
The method as described in any one of claim 1~7 is prepared.
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