CN110044866A - A kind of transverse direction nano-cavity array structure SERS substrate and preparation method thereof - Google Patents
A kind of transverse direction nano-cavity array structure SERS substrate and preparation method thereof Download PDFInfo
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- CN110044866A CN110044866A CN201910265560.2A CN201910265560A CN110044866A CN 110044866 A CN110044866 A CN 110044866A CN 201910265560 A CN201910265560 A CN 201910265560A CN 110044866 A CN110044866 A CN 110044866A
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Abstract
The invention belongs to nanocomposite technical fields, more particularly to a kind of lateral nano-cavity array structure SERS substrate, it is made of the internal semi-open tiny balloon for being equipped with a hollow cavity, it is provided with a lateral opening in the horizontal direction, and described its internal layer of semi-open tiny balloon is the surface modification TiO of 4-MBA probe molecule2Film, in TiO2One layer of noble metal film is also coated with outside film.It is support with the polystyrene sphere array of plasma clean, by TiO by being prepared in conjunction with template2It is obtained with noble metal through the means of inclination angle magnetron sputtering.It can not effectively construct that electric field strength is identical and the defect of current density difference electricity environment the present invention overcomes SERS substrate in the prior art, it can construct that electric field strength is identical but the different electricity environment of current density through the invention, it is theoretical to can be used for studying plasma-induced charge transfer mechanism and the enhancing of SERS physics and the intermediate state of Chemical enhancement with this.
Description
Technical field
The invention belongs to nanocomposite technical field more particularly to a kind of lateral nano-cavity array structure SERS substrates
And preparation method thereof.
Background technique
Fleischmann in 1974 et al. is when research Pyridine Molecules are adsorbed in spectrum caused by coarse silver electrode surface
Discovery earliest: it in the Raman spectrum of coarse silver electrode surface, shows and is significantly increased than same strength solution raman scattering spectrum
And clear sharp Characteristic Raman scattering spectra band.The identical system of Van Duyne in 1977 et al. system research, is eliminating
Probe molecule quantity increases factor and resonance influence after obtain: 5-6 order of magnitude pyridine probe Raman scattering of molecule signal
Enhance the surface enhanced effect from coarse electrode.This phenomenon causes the extensive concern of scientific circles, and this phenomenon is ordered
Entitled Surface enhanced Raman scattering, English name are Surface Enhanced Raman Seattering (SERS).
Surface enhanced Raman scattering (SERS) is the one mode of light and metal surface interaction, utilizes metallic surface
Plasma resonance enhances a kind of spectral technique of the Raman scattering signal of adsorbate.SERS spectra measurement have high sensitivity,
The advantages that preparation method is simple, smaller to sample damage, without aqueous interference and be widely used in Molecular Detection and identification, biology are cured
The fields such as, sensor.
Although SERS theoretical developments are rapid in recent years, since SERS is theoretical complicated, for most of experimental fact according to
Old no method interpretation, and much explain relatively fuzzyyer.Up to the present, SERS technology semiconductor enhancing mechanism is still difficult
Complete theory support is provided, significantly limits SERS theory in the application of life science.
Most important one is a little that existing SERS substrate can not effectively construct that electric field strength is identical and electric current
Density difference electricity environment, thus with existing SERS substrate be not used to research gas ions induction charge transfer mechanism and
The underlying theory of SERS physics enhancing and the intermediate state of Chemical enhancement.
Summary of the invention
The present invention is that electric field strength is identical and electric current in order to overcome SERS substrate in the prior art not construct effectively
The defect of density difference electricity environment provides a kind of lateral nano-cavity array structure SERS substrate and preparation method thereof, passes through
The SERS substrate can effectively construct electric field strength phase current density difference electricity environment, can be used for studying plasma with this and lure
Charge transfer mechanism and SERS the physics enhancing led and the intermediate state of Chemical enhancement are theoretical.
Therefore, the invention is realized by the following technical scheme:
A kind of transverse direction nano-cavity array structure SERS substrate, the lateral nano-cavity array are equipped with a hollow cavity by inside
Semi-open tiny balloon constitute, be provided with a lateral opening in the horizontal direction, the semi-open tiny balloon its
Internal layer is the surface modification TiO of 4-MBA probe molecule2Film, in TiO2One layer of noble metal film is also coated with outside film.
Lateral nano-cavity array structure SERS substrate in the present invention is entered due to its special array structure in different
Penetrating light excites the electric field strength for being able to maintain its inside under angle essentially identical, and under different angle shooting condition, structure
Internal carrier concentration, which has, obviously to be changed.Therefore, through the invention in SERS substrate can be relatively easy to structure
Build out the different special electricity environment of electric field strength same current density.Thus, the SERS underlying structure in the present invention can be used
In the further charge transfer mechanism of research gas ions induction and the bottom of SERS physics enhancing and the intermediate state of Chemical enhancement
It is theoretical.
Preferably, the noble metal film material is one of gold or silver.
Preferably, the internal diameter of the hollow cavity of the semi-open tiny balloon is 400 ~ 480nm, the transverse direction is opened
The diameter in hole is 250 ~ 350nm.
Preferably, described its TiO of semi-open tiny balloon2Film with a thickness of 5 ~ 8nm, the thickness of noble metal film
For 40 ~ 60nm.
A kind of preparation method of transverse direction nano-cavity array structure SERS substrate, the preparation method the following steps are included:
1) the close heap polystyrene sphere array mould plate of two-dimensional hexagonal is prepared using self-assembly method；
2) diameter of polystyrene sphere is reduced by plasma etching technology；
3) one layer of TiO is sputtered on polystyrene sphere array mould plate using magnetron sputtering inclination angle deposition technique2Film；
4) array is immersed in 4-MBA probe molecule alcoholic solution, makes probe molecule modification in TiO2Film surface；
5) noble metal film is sputtered on the array mould plate for modified probe molecule using magnetron sputtered deposition technology；
6) the intracorporal polystyrene sphere of chamber is removed using organic solvent, obtains TiO2/ 4-MBA/noble metal transverse direction nano-cavity battle array
Array structure.
The preparation method of lateral nano-cavity array structure SERS substrate its first step in the present invention is to prepare two-dimensional hexagonal
Then it is reduced the straight of diminution polystyrene sphere therein by plasma etching by close heap polystyrene sphere array mould plate
Diameter is the magnetron sputtering TiO in subsequent step2Film and noble metal film provide necessary space, and enable to institute
It will not be adhered between semi-open tiny balloon obtained, to be effectively formed lateral nano-cavity array structure.In the present invention
One layer of TiO is sputtered in styrene bead surface2Its table can effectively be enhanced after film and in its surface modification 4-MBA probe molecule
The Raman scattering signal intensity in face, and it has the characteristics that hot spot is controllable, stablizes, the degree of order is high.Then again in external magnetic control
One layer of noble metal film is sputtered, local surface phasmon is easier to excite, and with very big and controllable absorption and dissipates
Property is penetrated, it is total to change it by changing size, pattern, composition, charge and dielectric environment locating for it of nano material etc.
Vibration frequency, to realize the light for optionally scattering and absorbing different frequency.Array in the present invention, due to TiO2/4-MBA
Individual unit is the internal semi-open tiny balloon knot for being equipped with a hollow cavity in/noble metal transverse direction nano-cavity array structure
Structure, this special structure can be in the reinforcing effects for effectively improving its Raman enhancement factor.
Preferably, in the step 1) polystyrene sphere array mould plate the preparation method is as follows:
1.1) cleaning of silicon wafer: being put into silicon wafer in the beaker for filling ammonium hydroxide, hydrogen peroxide and deionized water, is being heated to 100
DEG C, boiling is boiled 3 ~ 10 minutes；It is stood to room temperature, uses deionized water or ethanol washing；The silicon wafer washed is put into and is contained
Have in 8 ~ 12% sodium dodecyl sulfate solution and impregnates 10 ~ 15 hours；
1.2) arrange polystyrene moulding: by polystyrene microsphere, 1:1 is mixed to get mixed solution by volume with ethanol solution, uses
Liquid-transfering gun takes mixed solution to drip on silicon wafer obtained in step 1.1), and silicon wafer is slowly put into the container for filling with deionized water
In；Polystyrene microsphere on the water surface forms disorderly arranged monofilm, then 0.5 ~ 2.5% lauryl sodium sulfate is added dropwise
Solution driving makes its surface form the monofilm that high-sequential arranges；Finally monofilm is delayed with the silicon wafer after hydrophilic treated
Slowly it picks up, extra moisture is sucked with filter paper, stand and obtain the hexagonal Mi Dui of high-sequential arrangement after spontaneously drying in air
Shape polystyrene moulding.
It is obtained by way of self assembly for polystyrene sphere array mould plate in the present invention, when polystyrene microsphere with
The mixed liquor of ethyl alcohol is put into the container for filling with deionized water, and polystyrene microsphere therein can spontaneously form one layer and be not necessarily to
The single layer polystyrene microsphere film of arrangement, after sodium dodecyl sulfate solution is added, originally unordered single layer polystyrene
Polystyrene microsphere in microballoon film is driven the structure for capableing of automatic height ordered arrangement by surface tension, it is used and is passed through
Silicon wafer after crossing hydrophilic treated just finally obtains the close heap shape polystyrene moulding of hexagonal after picking up drying.
Preferably, in the step 1.1) ammonium hydroxide, hydrogen peroxide and deionized water volume ratio be 1:(1.5 ~
2.5): (5 ~ 8).
Preferably, the diameter of polystyrene sphere is 400 ~ 480nm in the step 2).
Due to TiO2Film is attached to polystyrene sphere surface, therefore the diameter for changing polystyrene sphere just can change
Become the internal diameter of the hollow cavity of semi-open tiny balloon.
Preferably, the step 3) and 5) in magnetron sputtering specific step is as follows: by TiO2And noble metal target
It is respectively charged on the magnetic target position in magnetron sputtering cavity, the level angle of substrate is located in 85 ° of positions, setting back before starting
Boom is forced down in 1.0 × 10-6The throughput of Ar gas is arranged to control operating air pressure 10 in Pa-3Pa magnitude, TiO2Target position is with 60W
Sputtering power sputter 2min, noble metal target position sputters 10min with the sputtering power of 60W, and target is at a distance from sample substrate
It is held in 20cm.
Preferably, organic solvent is tetrahydrofuran, toluene, carbon tetrachloride, styrene or four in the step 6)
One of chloroethanes.
The organic solvent selected in the present invention can effective dissolved polystyrene, be formed with to form semi-open tiny balloon
Sharp condition.
Therefore, the invention has the following advantages:
(1) the different special electricity space environment of electric field strength same current density can be constructed, in light capture, optical detection, biography
The fields such as sensor and catalysis have a extensive future；
(2) can be used in studying plasma-induced SERS electric charge transfer bottom mechanism；
(3) it can be used in the enhancing of SERS physics and the intermediate state of Chemical enhancement be theoretical.
Detailed description of the invention
Fig. 1 is the preparation flow figure of lateral nano-cavity array structure.
Fig. 2 is the scanning electron microscope phenogram of lateral nano-cavity array structure.
Fig. 3 is lateral nanometer cavity configuration electric field strength and current density simulation calculated result figure.
Specific embodiment
The present invention is described further combined with specific embodiments below, described embodiment is only the present invention one
Divide embodiment, instead of all the embodiments.Based in the present invention being embodiment, those of ordinary skill in the art are not being done
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of transverse direction nano-cavity array structure SERS substrate, the lateral nano-cavity array is by internal for the half-open of hollow cavity
Tiny balloon composition is put, internal diameter 450nm is provided with the lateral opening that a diameter is 300nm, institute in the horizontal direction
Its internal layer of semi-open tiny balloon stated is surface modification TiO of the 4-MBA probe molecule with a thickness of 6nm2Film, in TiO2It is thin
It is 50nmAu film that a layer thickness is also coated with outside film.
Preparation method includes the following steps:
1) the close heap polystyrene sphere array mould plate of two-dimensional hexagonal is prepared using self-assembly method, it is specific the preparation method is as follows:
(1.1) cleaning of silicon wafer.Silicon wafer is put into fill ammonium hydroxide, hydrogen peroxide, deionized water (volume ratio 1:2:6) beaker
In, it is heated to 100 DEG C in ventilating kitchen and boils 5 minutes.After being stood room temperature, suitable deionized water is added or ethyl alcohol is thorough
It cleans up.Cleaned silicon wafer is put into impregnate 12 hours in the sodium dodecyl sulfate solution containing 10% and makes its surface
It is modified, there is hydrophily.
(1.2) polystyrene moulding is arranged.By polystyrene microsphere, 1:1 is mixed by volume with ethanol solution, uses liquid-transfering gun
It takes suitable solution to drip on hydrophilic silicon wafer, silicon wafer is slowly put into the container for filling with deionized water.On the water surface
Polystyrene microsphere form disorderly arranged monofilm, then be added dropwise 2% sodium dodecyl sulfate solution driving make its surface shape
The monofilm arranged at high-sequential.Finally monofilm is slowly picked up with hydrophilic silicon wafer, extra moisture filter paper
It sucks, stands the close heap shape polystyrene mould of hexagonal that can form high-sequential arrangement after spontaneously drying in air on silicon wafer
Plate.
2) the small ball's diameter as shown in Fig. 1, is contracted to by 450nm using argon oxygen plasma etch technology, is formed with bright
The polystyrene moulding in aobvious gap.
3) using magnetron sputtering inclination angle deposition technique sputtered on polystyrene sphere array mould plate with 85 ° of inclination angles with a thickness of
The TiO2 film of 6nm, the specific process is as follows: by TiO2Target is fitted on the magnetic target position in magnetron sputtering cavity, by substrate
Level angle is located in 85 ° of positions, and setting background gas pressure is lower than 1.0 × 10 before starting-6The throughput of Ar gas is arranged to control in Pa
Operating air pressure is 10-3Pa magnitude, TiO2Target position sputters 2min with the sputtering power of 60W, and target is protected at a distance from sample substrate
It holds in 20cm.
4) then array is immersed in 4-MBA probe molecule alcoholic solution 6 hours, modifies probe molecule sufficiently
TiO2 film surface, substrate three times sputtered with deionized water and ethyl alcohol circulation flushing, with being dried with nitrogen.
5) thickness is sputtered on the array mould plate for modified probe molecule with 85 ° of inclination angles using magnetron sputtering inclination angle deposition technique
Degree is the noble metal film of 50nm, the specific process is as follows: Au target is respectively charged on the magnetic target position in magnetron sputtering cavity,
The level angle of substrate is located in 85 ° of positions, setting background gas pressure is lower than 1.0 × 10 before starting-6The air-flow of Ar gas is arranged in Pa
Amount is to control operating air pressure 10-3Pa magnitude, Au target position sputter 10min with the sputtering power of 60W, target and sample substrate
Distance is held in 20cm.
6) finally the intracorporal polystyrene sphere of chamber is impregnated using tetrahydrofuran, obtains TiO2/4-MBA/Au transverse direction
Nano-cavity array structure, the corresponding scanning electron microscopic picture of this structure are as shown in Fig. 2.
Embodiment 2
A kind of transverse direction nano-cavity array structure SERS substrate, the lateral nano-cavity array is by internal for the half-open of hollow cavity
Tiny balloon composition is put, internal diameter 400nm is provided with the lateral opening that a diameter is 250nm, institute in the horizontal direction
Its internal layer of semi-open tiny balloon stated is surface modification TiO of the 4-MBA probe molecule with a thickness of 5nm2Film, in TiO2It is thin
It is 40nmAg film that a layer thickness is also coated with outside film.
Preparation method includes the following steps:
1) the close heap polystyrene sphere array mould plate of two-dimensional hexagonal is prepared using self-assembly method, it is specific the preparation method is as follows:
(1.1) cleaning of silicon wafer: silicon wafer is put into fill ammonium hydroxide, hydrogen peroxide, deionized water (volume ratio 1:1.5:5) burning
In cup, it is heated to 100 DEG C in ventilating kitchen and boils 3 minutes.After being stood room temperature, suitable deionized water is added or ethyl alcohol is thorough
Bottom cleans up.Cleaned silicon wafer, which is put into, to impregnate 10 hours in the sodium dodecyl sulfate solution containing 8% changes its surface
Property, there is hydrophily.
(1.2) arrange polystyrene moulding: by polystyrene microsphere, 1:1 is mixed by volume with ethanol solution, uses liquid-transfering gun
It takes suitable solution to drip on hydrophilic silicon wafer, silicon wafer is slowly put into the container for filling with deionized water.On the water surface
Polystyrene microsphere form disorderly arranged monofilm, then be added dropwise 0.5% sodium dodecyl sulfate solution driving make its surface
Form the monofilm of high-sequential arrangement.Finally monofilm is slowly picked up with hydrophilic silicon wafer, extra moisture is filtered
Paper sucks, and stands the close heap shape polystyrene mould of hexagonal that can form high-sequential arrangement after spontaneously drying in air on silicon wafer
Plate.
2) the small ball's diameter is contracted to by 400nm using argon oxygen plasma etch technology, is formed with the polyphenyl in obvious gap
Ethylene template.
3) using magnetron sputtering inclination angle deposition technique sputtered on polystyrene sphere array mould plate with 85 ° of inclination angles with a thickness of
The TiO2 film of 5nm, the specific process is as follows: by TiO2Target is fitted on the magnetic target position in magnetron sputtering cavity, by substrate
Level angle is located in 85 ° of positions, and setting background gas pressure is lower than 1.0 × 10 before starting-6The throughput of Ar gas is arranged to control in Pa
Operating air pressure is 10-3Pa magnitude, TiO2Target position sputters 2min with the sputtering power of 60W, and target is protected at a distance from sample substrate
It holds in 20cm.
4) then array is immersed in 4-MBA probe molecule alcoholic solution 6 hours, modifies probe molecule sufficiently
TiO2 film surface, substrate three times sputtered with deionized water and ethyl alcohol circulation flushing, with being dried with nitrogen.
5) thickness is sputtered on the array mould plate for modified probe molecule with 85 ° of inclination angles using magnetron sputtering inclination angle deposition technique
Degree is the noble metal film of 40nm, the specific process is as follows: Ag target is respectively charged on the magnetic target position in magnetron sputtering cavity,
The level angle of substrate is located in 85 ° of positions, setting background gas pressure is lower than 1.0 × 10 before starting-6The air-flow of Ar gas is arranged in Pa
Amount is to control operating air pressure 10-3Pa magnitude, Ag target position sputter 10min with the sputtering power of 60W, target and sample substrate
Distance is held in 20cm.
6) finally the intracorporal polystyrene sphere of chamber is impregnated using toluene, obtains TiO2/4-MBA/Ag transverse direction nanometer
Chamber array structure.
Embodiment 3
A kind of transverse direction nano-cavity array structure SERS substrate, the lateral nano-cavity array is by internal for the half-open of hollow cavity
Tiny balloon composition is put, internal diameter 480nm is provided with the lateral opening that a diameter is 350nm, institute in the horizontal direction
Its internal layer of semi-open tiny balloon stated is surface modification TiO of the 4-MBA probe molecule with a thickness of 8nm2Film, in TiO2It is thin
It is 60nm Ag film that a layer thickness is also coated with outside film.
Preparation method includes the following steps:
1) the close heap polystyrene sphere array mould plate of two-dimensional hexagonal is prepared using self-assembly method, it is specific the preparation method is as follows:
(1.1) cleaning of silicon wafer: silicon wafer is put into fill ammonium hydroxide, hydrogen peroxide, deionized water (volume ratio 1:2.5:8) burning
In cup, it is heated to 100 DEG C in ventilating kitchen and boils 10 minutes.After being stood room temperature, suitable deionized water or ethyl alcohol is added
Thoroughly clean up.Cleaned silicon wafer is put into impregnate 15 hours in the sodium dodecyl sulfate solution containing 12% and makes its table
Face is modified, has hydrophily.
(1.2) arrange polystyrene moulding: by polystyrene microsphere, 1:1 is mixed by volume with ethanol solution, uses liquid-transfering gun
It takes suitable solution to drip on hydrophilic silicon wafer, silicon wafer is slowly put into the container for filling with deionized water.On the water surface
Polystyrene microsphere form disorderly arranged monofilm, then be added dropwise 2.5% sodium dodecyl sulfate solution driving make its surface
Form the monofilm of high-sequential arrangement.Finally monofilm is slowly picked up with hydrophilic silicon wafer, extra moisture is filtered
Paper sucks, and stands the close heap shape polystyrene mould of hexagonal that can form high-sequential arrangement after spontaneously drying in air on silicon wafer
Plate.
2) the small ball's diameter is contracted to by 480nm using argon oxygen plasma etch technology, is formed with the polyphenyl in obvious gap
Ethylene template.
3) using magnetron sputtering inclination angle deposition technique sputtered on polystyrene sphere array mould plate with 85 ° of inclination angles with a thickness of
The TiO2 film of 8nm, the specific process is as follows: by TiO2Target is fitted on the magnetic target position in magnetron sputtering cavity, by substrate
Level angle is located in 85 ° of positions, and setting background gas pressure is lower than 1.0 × 10 before starting-6The throughput of Ar gas is arranged to control in Pa
Operating air pressure is 10-3Pa magnitude, TiO2Target position sputters 2min with the sputtering power of 60W, and target is protected at a distance from sample substrate
It holds in 20cm.
4) then array is immersed in 4-MBA probe molecule alcoholic solution 6 hours, modifies probe molecule sufficiently
TiO2 film surface, substrate three times sputtered with deionized water and ethyl alcohol circulation flushing, with being dried with nitrogen.
5) thickness is sputtered on the array mould plate for modified probe molecule with 85 ° of inclination angles using magnetron sputtering inclination angle deposition technique
Degree is the noble metal film of 60nm, the specific process is as follows: Ag target is respectively charged on the magnetic target position in magnetron sputtering cavity,
The level angle of substrate is located in 85 ° of positions, setting background gas pressure is lower than 1.0 × 10 before starting-6The air-flow of Ar gas is arranged in Pa
Amount is to control operating air pressure 10-3Pa magnitude, Ag target position sputter 10min with the sputtering power of 60W, target and sample substrate
Distance is held in 20cm.
6) finally the intracorporal polystyrene sphere of chamber is impregnated using carbon tetrachloride, obtains TiO2/4-MBA/Ag transverse direction
Nano-cavity array structure.
Embodiment 4
A kind of transverse direction nano-cavity array structure SERS substrate, the lateral nano-cavity array is by internal for the half-open of hollow cavity
Tiny balloon composition is put, internal diameter 420nm is provided with the lateral opening that a diameter is 280nm, institute in the horizontal direction
Its internal layer of semi-open tiny balloon stated is surface modification TiO of the 4-MBA probe molecule with a thickness of 7nm2Film, in TiO2It is thin
It is 45nmAu film that a layer thickness is also coated with outside film.
Preparation method includes the following steps:
1) the close heap polystyrene sphere array mould plate of two-dimensional hexagonal is prepared using self-assembly method, it is specific the preparation method is as follows:
(1.1) cleaning of silicon wafer: silicon wafer is put into fill ammonium hydroxide, hydrogen peroxide, deionized water (volume ratio 1:2:7) beaker
In, it is heated to 100 DEG C in ventilating kitchen and boils 6 minutes.After being stood room temperature, suitable deionized water is added or ethyl alcohol is thorough
It cleans up.Cleaned silicon wafer, which is put into, to impregnate 14 hours in the sodium dodecyl sulfate solution containing 9% changes its surface
Property, there is hydrophily.
(1.2) arrange polystyrene moulding: by polystyrene microsphere, 1:1 is mixed by volume with ethanol solution, uses liquid-transfering gun
It takes suitable solution to drip on hydrophilic silicon wafer, silicon wafer is slowly put into the container for filling with deionized water.On the water surface
Polystyrene microsphere form disorderly arranged monofilm, then be added dropwise 1% sodium dodecyl sulfate solution driving make its surface shape
The monofilm arranged at high-sequential.Finally monofilm is slowly picked up with hydrophilic silicon wafer, extra moisture filter paper
It sucks, stands the close heap shape polystyrene mould of hexagonal that can form high-sequential arrangement after spontaneously drying in air on silicon wafer
Plate.
2) the small ball's diameter is contracted to by 420nm using argon oxygen plasma etch technology, is formed with the polyphenyl in obvious gap
Ethylene template.
3) using magnetron sputtering inclination angle deposition technique sputtered on polystyrene sphere array mould plate with 85 ° of inclination angles with a thickness of
The TiO2 film of 7nm, the specific process is as follows: by TiO2Target is fitted on the magnetic target position in magnetron sputtering cavity, by substrate
Level angle is located in 85 ° of positions, and setting background gas pressure is lower than 1.0 × 10 before starting-6The throughput of Ar gas is arranged to control in Pa
Operating air pressure is 10-3Pa magnitude, TiO2Target position sputters 2min with the sputtering power of 60W, and target is protected at a distance from sample substrate
It holds in 20cm.
4) then array is immersed in 4-MBA probe molecule alcoholic solution 6 hours, modifies probe molecule sufficiently
TiO2 film surface, substrate three times sputtered with deionized water and ethyl alcohol circulation flushing, with being dried with nitrogen.
5) thickness is sputtered on the array mould plate for modified probe molecule with 85 ° of inclination angles using magnetron sputtering inclination angle deposition technique
Degree is the noble metal film of 45nm, the specific process is as follows: Au target is respectively charged on the magnetic target position in magnetron sputtering cavity,
The level angle of substrate is located in 85 ° of positions to open, setting background gas pressure is lower than 1.0 × 10 before beginning-6The air-flow of Ar gas is arranged in Pa
Amount is to control operating air pressure 10-3Pa magnitude, Au target position sputter 10min with the sputtering power of 60W, target and sample substrate
Distance is held in 20cm.
6) finally the intracorporal polystyrene sphere of chamber is impregnated using styrene, obtains TiO2/4-MBA/Au and laterally receives
Rice chamber array structure.
Embodiment 5
A kind of transverse direction nano-cavity array structure SERS substrate, the lateral nano-cavity array is by internal for the half-open of hollow cavity
Tiny balloon composition is put, internal diameter 470nm is provided with the lateral opening that a diameter is 320nm, institute in the horizontal direction
Its internal layer of semi-open tiny balloon stated is surface modification TiO of the 4-MBA probe molecule with a thickness of 6nm2Film, in TiO2It is thin
It is 55nm Au film that a layer thickness is also coated with outside film.
Preparation method includes the following steps:
1) the close heap polystyrene sphere array mould plate of two-dimensional hexagonal is prepared using self-assembly method, it is specific the preparation method is as follows:
(1.1) cleaning of silicon wafer: silicon wafer is put into fill ammonium hydroxide, hydrogen peroxide, deionized water (volume ratio 1:2:6) beaker
In, it is heated to 100 DEG C in ventilating kitchen and boils 5 minutes.After being stood room temperature, suitable deionized water is added or ethyl alcohol is thorough
It cleans up.Cleaned silicon wafer, which is put into, to impregnate 12 hours in the sodium dodecyl sulfate solution containing 10% changes its surface
Property, there is hydrophily.
(1.2) arrange polystyrene moulding: by polystyrene microsphere, 1:1 is mixed by volume with ethanol solution, uses liquid-transfering gun
It takes suitable solution to drip on hydrophilic silicon wafer, silicon wafer is slowly put into the container for filling with deionized water.On the water surface
Polystyrene microsphere form disorderly arranged monofilm, then be added dropwise 1.6% sodium dodecyl sulfate solution driving make its surface
Form the monofilm of high-sequential arrangement.Finally monofilm is slowly picked up with hydrophilic silicon wafer, extra moisture is filtered
Paper sucks, and stands the close heap shape polystyrene mould of hexagonal that can form high-sequential arrangement after spontaneously drying in air on silicon wafer
Plate.
2) the small ball's diameter is contracted to by 470nm using argon oxygen plasma etch technology, is formed with the polyphenyl in obvious gap
Ethylene template.
3) using magnetron sputtering inclination angle deposition technique sputtered on polystyrene sphere array mould plate with 85 ° of inclination angles with a thickness of
The TiO2 film of 6nm, the specific process is as follows: by TiO2Target is fitted on the magnetic target position in magnetron sputtering cavity, by substrate
Level angle is located in 85 ° of positions, and setting background gas pressure is lower than 1.0 × 10 before starting-6The throughput of Ar gas is arranged to control in Pa
Operating air pressure is 10-3Pa magnitude, TiO2Target position sputters 2min with the sputtering power of 60W, and target is protected at a distance from sample substrate
It holds in 20cm.
4) then array is immersed in 4-MBA probe molecule alcoholic solution 6 hours, modifies probe molecule sufficiently
TiO2 film surface, substrate three times sputtered with deionized water and ethyl alcohol circulation flushing, with being dried with nitrogen.
5) thickness is sputtered on the array mould plate for modified probe molecule with 85 ° of inclination angles using magnetron sputtering inclination angle deposition technique
Degree is the noble metal film of 55nm, the specific process is as follows: Au target is respectively charged on the magnetic target position in magnetron sputtering cavity,
The level angle of substrate is located in 85 ° of positions, setting background gas pressure is lower than 1.0 × 10 before starting-6The air-flow of Ar gas is arranged in Pa
Amount is to control operating air pressure 10-3Pa magnitude, Au target position sputter 10min with the sputtering power of 60W, target and sample substrate
Distance is held in 20cm.
6) finally the intracorporal polystyrene sphere of chamber is impregnated using tetrachloroethanes, obtains TiO2/4-MBA/Au transverse direction
Nano-cavity array structure.
Transverse direction nano-cavity array structure SERS substrate obtained in embodiment 1 is tested, by this structure
FDTD simulation is it can be seen that (see attached drawing 3), the basic phase of inside cavity electric field strength when incident light excitation angle is 20 ° 40 ° 60 °
Together, while to having with the carrier concentration that different angle excitation is inside configuration obviously change.Analog result shows electricity
The different special electricity environment of field intensity same current density, which passes through lateral nano-cavity array structure, easily to be constructed
Come, the charge transfer mechanism and the enhancing of SERS physics that can further study gas ions induction through this structure increase with chemistry
The underlying theory of strong intermediate state.
Claims (10)
1. a kind of transverse direction nano-cavity array structure SERS substrate, which is characterized in that the lateral nano-cavity array is set by inside
There is the semi-open tiny balloon an of hollow cavity to constitute, is provided with a lateral opening in the horizontal direction, described half
Its internal layer of open hollow microballoon is the surface modification TiO of 4-MBA probe molecule2Film, in TiO2One layer is also coated with outside film
Noble metal film.
2. a kind of lateral nano-cavity array structure SERS substrate according to claim 1, which is characterized in that described is half-open
The internal diameter for putting the hollow cavity of tiny balloon is 400 ~ 480nm, and the diameter of the lateral opening is 250 ~ 350nm.
3. a kind of lateral nano-cavity array structure SERS substrate according to claim 1 or 2, which is characterized in that described
Its TiO of semi-open tiny balloon2Film with a thickness of 5 ~ 8nm, noble metal film with a thickness of 40 ~ 60nm.
4. a kind of preparation method of the lateral nano-cavity array structure SERS substrate as described in claim 1 ~ 3, feature exist
In, the preparation method the following steps are included:
1) the close heap polystyrene sphere array mould plate of two-dimensional hexagonal is prepared using self-assembly method；
2) diameter of polystyrene sphere is reduced by plasma etching technology；
3) one layer of TiO is sputtered on polystyrene sphere array mould plate using magnetron sputtering inclination angle deposition technique2Film；
4) array is immersed in 4-MBA probe molecule alcoholic solution, makes probe molecule modification in TiO2 film surface；
5) noble metal film is sputtered on the array mould plate for modified probe molecule using magnetron sputtered deposition technology；
6) the intracorporal polystyrene sphere of chamber is removed using organic solvent, obtains lateral nano-cavity array structure.
5. a kind of preparation method of lateral nano-cavity array structure SERS substrate according to claim 1, which is characterized in that
In the step 1) polystyrene sphere array mould plate the preparation method is as follows:
1.1) cleaning of silicon wafer: being put into silicon wafer in the beaker for filling ammonium hydroxide, hydrogen peroxide and deionized water, is being heated to 100
DEG C, boiling is boiled 3 ~ 10 minutes；It is stood to room temperature, uses deionized water or ethanol washing；The silicon wafer washed is put into and is contained
Have in 8 ~ 12% sodium dodecyl sulfate solution and impregnates 10 ~ 15 hours；
1.2) arrange polystyrene moulding: by polystyrene microsphere, 1:1 is mixed to get mixed solution by volume with ethanol solution, uses
Liquid-transfering gun takes mixed solution to drip on silicon wafer obtained in step 1.1), and silicon wafer is slowly put into the container for filling with deionized water
In；Polystyrene microsphere on the water surface forms disorderly arranged monofilm, then 0.5 ~ 2.5% lauryl sodium sulfate is added dropwise
Solution driving makes its surface form the monofilm that high-sequential arranges；Finally monofilm is delayed with the silicon wafer after hydrophilic treated
Slowly it picks up, extra moisture is sucked with filter paper, stand and obtain the hexagonal Mi Dui of high-sequential arrangement after spontaneously drying in air
Shape polystyrene moulding.
6. a kind of preparation method of lateral nano-cavity array structure SERS substrate according to claim 5, which is characterized in that
The volume ratio of ammonium hydroxide, hydrogen peroxide and deionized water is 1:(1.5 ~ 2.5 in the step 1.1)): (5 ~ 8).
7. a kind of preparation method of lateral nano-cavity array structure SERS substrate according to claim 4, which is characterized in that
The diameter of polystyrene sphere is 400 ~ 480nm in the step 2).
8. a kind of preparation method of lateral nano-cavity array structure SERS substrate according to claim 4, which is characterized in that
The step 3) and 5) in magnetron sputtering specific step is as follows: by TiO2Magnetron sputtering chamber is respectively charged into noble metal target
On magnetic target position in body, the level angle of substrate is located in 85 ° of positions, setting background gas pressure is lower than 1.0 × 10 before starting- 6The throughput of Ar gas is arranged to control operating air pressure 10 in Pa-3Pa magnitude, TiO2Target position is sputtered with the sputtering power of 60W
2min, noble metal target position sputter 10min with the sputtering power of 60W, and target is held in 20cm at a distance from sample substrate.
9. a kind of preparation method of lateral nano-cavity array structure SERS substrate according to claim 4, which is characterized in that
Organic solvent is one of tetrahydrofuran, toluene, carbon tetrachloride, styrene or tetrachloroethanes in the step 6).
10. a kind of application of transverse direction nano-cavity array structure SERS substrate in light capture, optical detection, sensor or catalytic field.
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