CN108375567A - A kind of surface-enhanced Raman substrate and preparation method thereof - Google Patents
A kind of surface-enhanced Raman substrate and preparation method thereof Download PDFInfo
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- CN108375567A CN108375567A CN201810156824.6A CN201810156824A CN108375567A CN 108375567 A CN108375567 A CN 108375567A CN 201810156824 A CN201810156824 A CN 201810156824A CN 108375567 A CN108375567 A CN 108375567A
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- 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
Abstract
The present invention provides a kind of surface-enhanced Raman substrates and preparation method thereof.The Raman substrate includes Nanostructure Network and the composite construction that the nano-spherical structure on the Nanostructure Network is formed, and the metallic particles positioned at composite structure surface.The preparation method of the Raman substrate includes the following steps：(1) positive electronic beam resist and negativity electron sensitive resist are mixed, obtains mixed electronic bundle resist, the mixed electronic bundle resist is coated in substrate, the substrate after being coated；(2) nano-array pattern is formed in substrate after application, development obtains nanostructure, and the deposited metal in the nanostructure obtains the Raman substrate.Surface-enhanced Raman substrate provided by the invention has excellent surface-enhanced Raman effects and splendid detection sensitivity, can be obviously improved the homogeneity and repeatability of Raman test result.
Description
Technical field
The invention belongs to technical field of nano material, it is related to a kind of preparation method of nanostructure more particularly to a kind of table
Face enhances Raman substrate and preparation method thereof.
Background technology
Surface enhanced Raman scattering is because it is with unimolecule specific recognition, and data acquisition speed is fast, and sensitivity height etc. is excellent
Gesture and be widely used in chemistry and the unimolecule of related fields such as biomedicine and single celled detection and analyze.Wherein, it serves as a contrast
Bottom plays decisive role to enhancing effect.Discovered in recent years, the nanostructure of metal/dielectric Material cladding are more single than traditional
Metal Nano structure can bring more significant Raman enhancing effect.This is strong between light and metal/dielectric material interface
It interacts closely related.
Compared with chemical synthesis process, there is nanometer using the surface-enhanced Raman substrat structure that nanofabrication technique makes
Structure design is flexibly adjustable, the uniform nanostructure substrate that is controllable, making of nanostructure size is reusable, consistency of performance
The good, processing convenient for long-term preservation, suitable for various types of materials and preparation are easy to carry out standardization and Quantitative study and be convenient for
The advantages such as practical application.
CN106770180A discloses a kind of surface-enhanced Raman substrate and preparation method thereof.Raman substrate described in the program
The line width of the nano array structure being made of metal and dielectric material, the nano array structure is 10-25nm, preparation side
Method includes the following steps：(1) spin coating negativity electron sensitive resist, exposure, development, immersion and drying are prepared on a silicon substrate
Negativity electron sensitive resist nano array structure；(2) the electron sensitive resist nano array structure prepared to step (1) moves back
Fiery processing forms stable dielectric material；(3) dielectric material surface obtained in step (2) deposits one layer of metallic particles, to
Obtain the surface-enhanced Raman substrate.The surface-enhanced Raman for the surface-enhanced Raman substrate that the deficiency of the program is
It still needs further improvement for effect and detectivity and detection limit.
Therefore, developing a kind of surface-enhanced Raman substrate that surface-enhanced Raman effects are more excellent has this field
Important meaning.
Invention content
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of surface-enhanced Raman substrates
And preparation method thereof.Surface-enhanced Raman substrate provided by the invention has excellent surface-enhanced Raman effects and high
Detectivity and very low detection limit, detection repeatability are very high.Preparation method flow provided by the invention is simple, at low cost
It is honest and clean, it is appropriate for mass producing.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of Raman substrate, the Raman substrate includes Nanostructure Network and is located at institute
State the composite construction that the nano-spherical structure on Nanostructure Network is formed, and the metallic particles positioned at composite structure surface.
Raman substrate provided by the invention is surface-enhanced Raman substrate.This Raman substrate has unique by nano net
Shape structure and on the Nanostructure Network nano-spherical structure composition composite construction, such composite construction because
There is mutually matched netted and spherical two kinds of nanostructures simultaneously, there is higher detection spirit compared to single nanostructure
The homogeneity and repeatability of sensitivity and better test result.And positioned at the metallic particles of the composite structure surface, it is right
Also play an important roll in the raising of the Raman substrate performance.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, the Raman substrate is by Nanostructure Network and is located at the mesh nanometer
The composite construction that nano-spherical structure in structure is formed, and formed positioned at the metallic particles of composite structure surface.The present invention
In, it is only formed by Nanostructure Network and the nano-spherical structure on the Nanostructure Network when the Raman substrate
Composite construction, and positioned at composite structure surface metallic particles composition when, have the effect of more excellent.
Preferably, the Nanostructure Network is nanometer period reticular structure.
Preferably, the Raman substrate is three-dimensional matrix structure.
Preferably, the material for constituting the Nanostructure Network is dielectric material, preferably silica.
Preferably, the material for constituting the nano-spherical structure is dielectric material, preferably silica.
Preferably, the line width of the Nanostructure Network be 10nm-50nm, such as 10nm, 11nm, 15nm, 17nm,
20nm, 23nm, 32nm, 35nm, 40nm, 46nm or 50nm etc., it is not limited to cited numerical value, in the numberical range its
His unrequited numerical value is equally applicable.The line width of the Nanostructure Network does not include the metallic particles on Nanostructure Network surface
Width.
Preferably, the metallic particles is coated on Nanostructure Network and nano-spherical structure surface.
Preferably, the line width of the Nanostructure Network of metallic particles has been coated as 20nm-80nm, such as 20nm, 29nm,
35nm, 40nm, 50nm, 53nm, 60nm, 70nm or 80nm etc., it is not limited to cited numerical value, in the numberical range its
His unrequited numerical value is equally applicable.The line width of the Nanostructure Network for having coated metallic particles refers to Nanostructure Network
The total line width for the structure that metallic particles thereon is constituted.
Preferably, a diameter of 50nm-500nm of the nano-spherical structure, for example, 50nm, 80nm, 100nm, 160nm,
200nm, 300nm, 320nm, 400nm, 480nm or 500nm etc., it is not limited to cited numerical value, in the numberical range
Other unrequited numerical value are equally applicable.
Preferably, a diameter of 5nm-15nm of the metallic particles, such as 5nm, 8nm, 10nm, 12nm, 14nm or 15nm
Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
Preferably, the spacing of the metallic particles is 0nm-3nm, such as 0nm, 0.5nm, 1nm, 1.5nm, 2nm, 2.5nm
Or 3nm etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, the thickness of the Nanostructure Network be 30nm-300nm, such as 30nm, 60nm, 90nm, 100nm,
150nm, 200nm, 250nm or 300nm etc., it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value is equally applicable.
Preferably, the Raman substrate is located in substrate.In the present invention, substrate can be allowed close to nano-spherical structure.
Preferably, the area of the nano-array pattern in the Nanostructure Network is 100 μm2-250000μm2, such as
100μm2、500μm2、1000μm2、5000μm2、10000μm2、50000μm2、100000μm2、150000μm2、200000μm2Or
250000μm2Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.This
In invention, the nano-array pattern in Nanostructure Network refers to the lattice in Nanostructure Network, which is nanometer
Array pattern.
Preferably, the nano-array pattern in the Nanostructure Network includes triangle, quadrangle, hexagon or circle
In any one or at least two combination, preferably hexagon.
Second aspect, the present invention provide a kind of preparation method of the substrate of Raman as described in relation to the first aspect, the method includes
Following steps：
(1) positive electronic beam resist and negativity electron sensitive resist are mixed, mixed electronic bundle resist is obtained, by institute
It states mixed electronic bundle resist to be coated in substrate, the substrate after being coated；
(2) nano-array pattern is formed in substrate after application, development obtains nanostructure, in the nanostructure
Deposited metal obtains the Raman substrate.
In preparation method provided by the invention, step (1) is to positive electronic beam resist and negativity electron sensitive resist
Mixing is for obtaining provided by the invention while having Nanostructure Network and the Raman substrate of nano-spherical structure with important
Effect.Positron-electron beam resist dissolubility is different, and part negativity electron sensitive resist dissolves each other with positive electronic beam resist, separately
The dispersion in positive electronic beam resist of an outer part forms the colloid bead to suspend, these colloid beads pass through subsequent processing most
Become the nano-spherical structure in Raman substrate provided by the invention eventually.Positive electronic beam resist type, negativity electron beam are anti-
Losing agent, shared volume ratio and mixed condition all can be to positron-electron beam resists in the mixed electronic bundle resist
The ratio sum number amount of dissolve each other ratio and negativity electron sensitive resist suspension colloid bead have an impact, and then the present invention is carried
The structure and performance of the Raman substrate of confession have an impact.
As currently preferred technical solution, in step (1), the volume with the mixed electronic bundle resist is
100% meter, the volume fraction of negativity electron sensitive resist are 25%-85%, for example, 25%, 35%, 45%, 55%, 65%,
75% or 85% etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.This
It is in terms of 100% by the volume of the mixed electronic bundle resist, the volume fraction of negativity electron sensitive resist is in invention
25%-85%.If the volume fraction of negativity electron sensitive resist is too small, mesh nanometer knot can not be formed after exposure can be caused
Structure；If the volume fraction of negativity electron sensitive resist is excessive, can lead to not disperse to be formed in positive electronic beam resist
Nanoscale colloid bead, can not form nano-spherical structure after exposure.
Preferably, the mixing is with ultrasonic disperse.
Preferably, the time of the ultrasonic disperse be 2min-60min, such as 2min, 5min, 10min, 20min,
30min, 40min, 50min or 60min etc., it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value is equally applicable.In the present invention, if the time of ultrasonic disperse is too short, the negativity in positive electronic beam resist can be caused
Electron sensitive resist is unable to fully disperse, and the size distribution ranges of the nano-spherical structure obtained after exposure are big, and surface enhanced is drawn
The homogeneity and repeatability of graceful signal reduce；If the overlong time of ultrasonic disperse does not have further dispersion effect, and
And mixed electronic bundle resist solution temperature can be caused to increase, the effect of pre-exposure is played, the Nanostructure Network after exposure is made
Line width become larger, the sensitivity of surface-enhanced Raman declines.
In the present invention, positive electronic beam resist can use PMMA 950k or ZEP520, different positive electronic beams anti-
Erosion agent can be such that finally obtained Raman substrate has an impact；Negativity electron sensitive resist can use HSQ (hydrogen
Silsesquioxane, hydrogen silsesquioxane).
As currently preferred technical solution, in step (1), the method for the coating is spin coating.
Preferably, the substrate includes any one in silicon base, metal substrate and Group III-V semiconductor substrate,
Preferably silicon base.
Preferably, in step (1), the thickness for being coated in the electron sensitive resist in substrate is 50nm-500nm, such as
50nm, 100nm, 200nm, 300nm, 400nm or 500nm etc., it is not limited to cited numerical value, in the numberical range its
His unrequited numerical value is equally applicable.
As currently preferred technical solution, in step (2), the method for forming nano-array pattern is to use electronics
Beam exposure method carries out nano-array pattern direct write.
Preferably, the size of the electron beam spot of the electron beam exposure be 0.5nm-10nm, such as 0.5nm, 1nm,
2nm, 4nm, 6nm, 8nm or 10nm etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range
It is equally applicable.
Preferably, the exposure dose of the electron beam exposure is 20000 μ C/cm2-200000μC/cm2, such as 20000 μ C/
cm2、40000μC/cm2、60000μC/cm2、80000μC/cm2、100000μC/cm2、150000μC/cm2Or 200000 μ C/cm2
Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
Preferably, the layout design line width of the nano-array pattern be 0nm-10nm and include 0nm, such as 0.1nm,
1nm, 3nm, 5nm, 7nm or 10nm etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range
It is equally applicable.
Preferably, the area of the nano-array pattern is 100 μm2-250000μm2, such as 100 μm2、500μm2、1000
μm2、5000μm2、10000μm2、50000μm2、100000μm2、150000μm2、200000μm2Or 250000 μm2Deng, but not
It is only limitted to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
Preferably, the nano-array pattern include in triangle, quadrangle, hexagon or circle any one or extremely
Few two kinds of combination, preferably hexagon.
As currently preferred technical solution, in step (2), the method for the development is with negativity electron sensitive resist
Developer solution and the developer solution of positive electronic beam resist develop.
Preferably, in step (2), the developer solution of the negativity electron sensitive resist includes NaOH solution.
Preferably, in the NaOH solution, the mass fraction of NaOH is 0.5wt%-3wt%, such as 0.5wt%,
1wt%, 2wt% or 3wt% etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are same
Sample is applicable in, preferably 1wt%.
Preferably, in step (2), the developer solution of the positive electronic beam resist includes isobutyl acetate or by 4- first
The mixing developer solution of base -2 pentanone and isopropanol composition.
Preferably, in the mixing developer solution being made of 4-methyl-2 pentanone and isopropanol, 4-methyl-2 pentanone and
The volume ratio of isopropanol is 1:2-1:4, such as 1:2、1:2.5、1:3、1:3.5 or 1:4 etc., it is not limited to cited number
Value, other interior unrequited numerical value of the numberical range are equally applicable, and preferably 1:3.
Preferably, step (2) further includes：Substrate is cleaned after development.
Preferably, the cleaning solution of the cleaning includes water and/or acetone.In the present invention, the water and/or acetone refer to can
Think water, or acetone can also be the combination of water and acetone.
Preferably, step (2) further includes：It is fixed with fixer after development.
Preferably, the fixer is isopropanol.
Preferably, step (2) further includes：After development substrate is dried with inert gas.
Preferably, when step (2) includes fixing, substrate is dried with inert gas after fixing.
Preferably, the inert gas includes nitrogen.
Preferably, the development is developed for substep, and the method for the substep development is：First use negativity electron sensitive resist
Developer solution develops, then is developed with the developer solution of positive electronic beam resist.
Preferably, the developing time to be developed with the developer solution of negativity electron sensitive resist is 0.5min-2min, such as
0.5min, 0.8min, 1min, 1.5min or 2min etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable, preferably 1min.
Preferably, the developing time to be developed with the developer solution of positive electronic beam resist is 0.5min-2.5min, example
Such as 0.5min, 1min, 2min or 2.5min, it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value it is equally applicable, preferably 1min.
Preferably, it after being developed with the developer solution of negativity electron sensitive resist, washes with water substrate and uses absolute ethyl alcohol
Impregnate substrate.
Preferably, the time of the cleaning is 2min.
Preferably, the time of the immersion is 10min.
Preferably, showing after being developed with the developer solution of negativity electron sensitive resist and with positive electronic beam resist
After shadow liquid is developed, substrate is dried with inert gas.
As currently preferred technical solution, in step (2), the nanostructure includes Nanostructure Network and is located at
The composite construction that nano-spherical structure on the Nanostructure Network is formed.
Preferably, a diameter of 50nm-500nm of the nano-spherical structure, for example, 50nm, 80nm, 100nm, 160nm,
200nm, 300nm, 320nm, 400nm, 480nm or 500nm etc., it is not limited to cited numerical value, in the numberical range
Other unrequited numerical value are equally applicable.
Preferably, the line width of the Nanostructure Network be 10nm-50nm, such as 10nm, 11nm, 15nm, 17nm,
20nm, 23nm, 32nm, 35nm, 40nm, 46nm or 50nm etc., it is not limited to cited numerical value, in the numberical range its
His unrequited numerical value is equally applicable.
Preferably, the Nanostructure Network is nanometer period reticular structure.
As currently preferred technical solution, in step (2), the metal includes appointing in gold, platinum, silver, copper or aluminium
Anticipate a kind of or at least two combinations, typical but be non-limiting combination and have a combination of gold and platinum, the combination of Jin Heyin, silver and
The combination etc. of the combination of copper, copper and aluminium.
Preferably, in step (2), the method for the deposited metal includes hot evaporation, electron beam evaporation plating, magnetron sputtering or original
Sublayer deposition in any one or at least two combination.
Preferably, in step (2), the thickness of the metal of deposition is 1nm-50nm, for example, 1nm, 5nm, 10nm, 20nm,
30nm, 40nm or 50nm etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally suitable
With.
Preferably, in step (2), the deposition rate of deposited metal isSuch as OrDeng it is not limited to cited numerical value, other are not arranged in the numberical range
The numerical value of act is equally applicable.
Preferably, in step (2), the line width that the Nanostructure Network of metal is deposited in the Raman substrate is 20nm-
80nm, such as 20nm, 29nm, 35nm, 40nm, 50nm, 53nm, 60nm, 70nm or 80nm etc., it is not limited to cited
Numerical value, other interior unrequited numerical value of the numberical range are equally applicable.The line width of the Nanostructure Network that deposited metal
It refer to the total line width for the structure that Nanostructure Network and the metallic particles deposited thereon are constituted.
Preferably, in step (2), the metal for being deposited on nanostructured surface is made of metallic particles.
Preferably, a diameter of 5nm-15nm of the metallic particles, such as 5nm, 8nm, 10nm, 12nm, 14nm or 15nm
Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
Preferably, the spacing of the metallic particles is 0nm-3nm, such as 0nm, 0.5nm, 1nm, 1.5nm, 2nm, 2.5nm
Or 3nm etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
As the further preferred technical solution of preparation method of the present invention, the described method comprises the following steps：
(1) positive electronic beam resist and negativity electron sensitive resist are mixed, ultrasonic disperse 2min-60min is mixed
Electron sensitive resist is closed, on a silicon substrate by the mixed electronic bundle resist spin coating, the mixed electronic bundle resist of coating is thick
Degree is 50nm-500nm, the substrate after being coated；
(2) in the substrate after step (1) described coating hexagon nano-array pattern is carried out with electron beam exposure method
Direct write is written the substrate of nano-array pattern；The size of the electron beam spot of the electron beam exposure is 0.5nm-10nm,
The exposure dose of the electron beam exposure is 20000 μ C/cm2-200000μC/cm2, the layout design of the nano-array pattern
Line width is 0nm-10nm and does not include 0nm, and the area of the nano-array pattern is 100 μm2-250000μm2；
(3) first use the developer solution of negativity electron sensitive resist to the substrate of step (2) said write nano-array pattern into
Row development, developing time 1min, wash with water substrate 2min and use soaked in absolute ethyl alcohol substrate 10min, with nitrogen drying base
Bottom, then developed with the developer solution of positive electronic beam resist, developing time 1min is fixed with isopropanol, dry with nitrogen
Dry substrate, obtains nanostructure；
(4) step (3) nanostructured surface withDeposition rate deposition thickness be 1nm-
The metal of 50nm obtains the Raman substrate；The metal includes any one or at least two in gold, platinum, silver, copper or aluminium
Combination, be deposited on nanostructured surface metal be metallic particles.
Compared with the prior art, the present invention has the advantages that：
(1) surface-enhanced Raman substrate provided by the invention has excellent surface-enhanced Raman effects and splendid detection
Sensitivity can be obviously improved the homogeneity and repeatability of Raman test result；
(2) Raman substrate fabrication method provided by the invention can neatly adjust surface-enhanced Raman by adjusting technique
The structure and performance of substrate, flow is short, at low cost, favorable repeatability, is appropriate for mass producing.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram piece for the nanostructure that 1 step of the embodiment of the present invention (3) obtains；
Fig. 2 is the scanning electron microscope side view of 1 finally obtained surface-enhanced Raman substrate of the embodiment of the present invention；
Fig. 3 be 1 finally obtained surface-enhanced Raman substrate of the embodiment of the present invention (include ball/net composite nanostructure) and
The 2,2'- bipyridyls for the surface-enhanced Raman substrate (only with network nano structure without chondritic) that comparative example 1 obtains
Molecular Raman enhanced spectrum figure, wherein ball/net is compound in the spectrum corresponding diagram for the surface-enhanced Raman substrate that embodiment 1 obtains
The curve of nanostructure, the curve of network nano structure in the spectrum corresponding diagram for the surface-enhanced Raman substrate that comparative example 1 obtains.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.But following embodiments are only
The simple example of the present invention does not represent or limits the scope of the present invention, and the scope of the present invention is with claim
Subject to book.
Embodiment 1
The present embodiment provides a kind of preparation method of surface-enhanced Raman substrate, specific method is：
(1) silicon (100) substrate is cleaned, negativity electron sensitive resist HSQ and positive electronic beam resist PMMA 950k are pressed
According to volume ratio 1:1 mixing, by mixed resist solution ultrasonic disperse 30min, spin coating thickness is 250nm's on a silicon substrate
The electron sensitive resist, the substrate after being coated.
(2) in the substrate after step (1) described coating, use beam spot diameter, anti-for the electron beam exposure electron beam of 6nm
Agent is lost, adjusting exposure dose is 190000 μ C/cm2Direct write hexagon nano-array pattern, is written nano-array pattern
The area of substrate, nano-array pattern is 150 μm of 150 μ m, and the layout design line width of nano-array pattern is 6nm.
(3) use the NaOH solution that mass percentage is 1% aobvious to the substrate of step (2) said write nano-array pattern
Shadow 1min, later use pure water rinsing 2min, then use soaked in absolute ethyl alcohol substrate 10min, nitrogen drying substrate.Then volume ratio is used
1:3 4-methyl-2 pentanone and aqueous isopropanol development PMMA positive electronic beam resists, developing time 1min, isopropanol are fixed
Shadow, nitrogen dry substrate, obtain nanostructure.The ingredient of the nanostructure is silica.
(4) use electron beam evaporation that the chromium of 1nm thickness is deposited in step (3) described nanostructure, later again in chromium
The silver of upper electron beam evaporation plating 36nm thickness, chromium and golden deposition rate are respectivelyWithObtain surface-enhanced Raman
Substrate, the substrate have silver/ball-compound nanostructure of net silica.
The surface-enhanced Raman substrate that the present embodiment is prepared by Nanostructure Network and be located at the mesh nanometer
The composite construction that nano-spherical structure in structure is formed, and formed positioned at the metallic particles of composite structure surface, that is, have
Silver/ball-compound the nanostructure of net silica, Nanostructure Network are period reticular structure, and line width is before deposited metal
21nm is 35nm, a diameter of 95nm-470nm of nano-spherical structure, a diameter of 7nm of silver nano-grain, silver after deposited metal
The spacing of nano particle is 2.7nm, and the thickness of Nanostructure Network is 110nm.
Fig. 1 is the scanning electron microscope diagram piece for the nanostructure that the present embodiment step (3) obtains, as can be seen from this figure
The two-layer composite being made of nano net and nanosphere, lower layer of the nanosphere in Nanostructure Network have been obtained after exposure imaging
And close to substrate, a diameter of 80nm-400nm of the nanoscale chondritic obtained after development, hexagon period netted electronics
The line width of beam resist structure is 21nm.
Fig. 2 is the scanning electron microscope side view of the finally obtained surface-enhanced Raman substrate of the present embodiment, from the figure
It can be seen that line width ratio Fig. 2 of hexagon period reticular structure is dramatically increased, being deposited on silica by electron beam evaporation plating receives
The a diameter of 7nm of silver nano-grain in rice structure, this deposited the line width of the hexagon period network nano structure of metallic particles
For 35nm, a diameter of 95nm-470nm of nano-spherical structure after deposited metal.
The properties of product test method of the present embodiment is to be immersed in the surface-enhanced Raman substrate prepared by the present embodiment
A concentration of 10-5It is taken out after 4h in the aqueous solution of 2, the 2'- bipyridyl molecules of mol/L, with Raman spectrometer to this after natural drying
Substrate is tested.In test result such as Fig. 3 label be ball/net composite nanostructure " curve shown in.
The excellent surface-enhanced Raman effects of surface-enhanced Raman substrate and splendid detection that the present embodiment obtains are sensitive
Degree.
Embodiment 2
The present embodiment provides a kind of preparation method of surface-enhanced Raman substrate, specific method is：
(1) clean silicon (100) substrate, by negativity electron sensitive resist HSQ and positive electronic beam resist ZEP520 according to
Volume ratio 3:2 mixing, by mixed resist solution ultrasonic disperse 5min, spin coating thickness is being somebody's turn to do for 400nm on a silicon substrate
Electron sensitive resist, the substrate after being coated.
(2) in the substrate after step (1) described coating, use beam spot diameter, anti-for the electron beam exposure electron beam of 4nm
Agent is lost, adjusting exposure dose is 120000 μ C/cm2Direct write hexagon nano-array pattern, is written nano-array pattern
The area of substrate, nano-array pattern is 250 μm of 250 μ m, and the layout design line width of nano-array pattern is 4nm.
(3) use the NaOH solution that mass percentage is 1% aobvious to the substrate of step (2) said write nano-array pattern
Shadow 1min, later use pure water rinsing 2min, then use soaked in absolute ethyl alcohol substrate 10min, nitrogen drying substrate.Then use acetic acid different
Butyl ester development ZEP520 positive electronic beam resists, developing time 1min, isopropanol fixing, nitrogen drying substrates obtain nanometer
Structure.The ingredient of the nanostructure is silica.
(4) use electron beam evaporation that the chromium of 1nm thickness is deposited in step (3) described nanostructure, later again in chromium
The gold of upper electron beam evaporation plating 18nm thickness, chromium and golden deposition rate are respectivelyWithObtain surface-enhanced Raman
Substrate, the substrate have gold/ball-compound nanostructure of net silica.
The surface-enhanced Raman substrate that the present embodiment is prepared by Nanostructure Network and be located at the mesh nanometer
The composite construction that nano-spherical structure in structure is formed, and formed positioned at the metallic particles of composite structure surface, that is, have
Gold/ball-compound the nanostructure of net silica, Nanostructure Network are period reticular structure, and line width is before deposited metal
11nm, is 29nm, a diameter of 200nm-500nm of nano-spherical structure, a diameter of 9nm of gold nano grain after deposited metal,
The spacing of gold nano grain is 1.8nm, and the thickness of Nanostructure Network is 260nm.
The properties of product test method of the present embodiment is to be immersed in the surface-enhanced Raman substrate prepared by the present embodiment
A concentration of 10-5It is taken out after 15h in the aqueous solution of the rhodamine 6G molecule of mol/L, with Raman spectrometer to the lining after natural drying
Bottom is tested.
The excellent surface-enhanced Raman effects of surface-enhanced Raman substrate and splendid detection that the present embodiment obtains are sensitive
Degree.
Embodiment 3
The present embodiment provides a kind of preparation method of surface-enhanced Raman substrate, specific method is：
(1) silicon (100) substrate is cleaned, negativity electron sensitive resist HSQ and positive electronic beam resist PMMA 950k are pressed
According to volume ratio 1:3 mixing, by mixed resist solution ultrasonic disperse 2min, spin coating thickness is 4800nm's on a silicon substrate
The electron sensitive resist, the substrate after being coated.
(2) in the substrate after step (1) described coating, use beam spot diameter, anti-for the electron beam exposure electron beam of 1nm
Agent is lost, adjusting exposure dose is 200000 μ C/cm2Direct write triangle nano-array pattern, is written nano-array pattern
The area of substrate, nano-array pattern is 10 μm of 10 μ m, and the layout design line width of nano-array pattern is 1nm.
(3) use the NaOH solution that mass percentage is 0.5% to the substrate of step (2) said write nano-array pattern
Develop 2min, later use pure water rinsing 2min, then use soaked in absolute ethyl alcohol substrate 10min, nitrogen drying substrate.Then volume is used
Than 1:2 4-methyl-2 pentanone and aqueous isopropanol development PMMA positive electronic beam resists, developing time 0.5min, isopropyl
Alcohol is fixed, and nitrogen drying substrates obtain nanostructure.The ingredient of the nanostructure is silica.
(4) use electron beam evaporation that the chromium of 1nm thickness is deposited in step (3) described nanostructure, later again in chromium
The gold of upper electron beam evaporation plating 50nm thickness, chromium and golden deposition rate are respectivelyWithObtain surface-enhanced Raman
Substrate, the substrate have gold/ball-compound nanostructure of net silica.
The surface-enhanced Raman substrate that the present embodiment is prepared by Nanostructure Network and be located at the mesh nanometer
The composite construction that nano-spherical structure in structure is formed, and formed positioned at the metallic particles of composite structure surface, that is, have
Gold/ball-compound the nanostructure of net silica, Nanostructure Network are period reticular structure, and line width is before deposited metal
45nm, is 75nm, a diameter of 50nm-250nm of nano-spherical structure, a diameter of 15nm of gold nano grain after deposited metal,
The spacing of gold nano grain is 3nm, and the thickness of Nanostructure Network is 80nm.
The excellent surface-enhanced Raman effects of surface-enhanced Raman substrate and splendid detection that the present embodiment obtains are sensitive
Degree.
Embodiment 4
The present embodiment provides a kind of preparation method of surface-enhanced Raman substrate, specific method is：
(1) silicon (100) substrate is cleaned, negativity electron sensitive resist HSQ and positive electronic beam resist PMMA 950k are pressed
According to volume ratio 17:3 mixing, by mixed resist solution ultrasonic disperse 60min, spin coating thickness is 50nm's on a silicon substrate
The electron sensitive resist, the substrate after being coated.
(2) in the substrate after step (1) described coating, use beam spot diameter, anti-for the electron beam exposure electron beam of 10nm
Agent is lost, adjusting exposure dose is 20000 μ C/cm2Direct write quadrangle nano-array pattern, is written the base of nano-array pattern
The area at bottom, nano-array pattern is 500 μm of 500 μ m, and the line width of nano-array pattern is 10nm.
(3) use the NaOH solution that mass percentage is 3% aobvious to the substrate of step (2) said write nano-array pattern
Shadow 0.5min, later use pure water rinsing 2min, then use soaked in absolute ethyl alcohol substrate 10min, nitrogen drying substrate.Then volume is used
Than 1:4 4-methyl-2 pentanone and aqueous isopropanol development PMMA positive electronic beam resists, developing time 2.5min, isopropyl
Alcohol is fixed, and nitrogen drying substrates obtain nanostructure.The ingredient of the nanostructure is silica.
(4) use electron beam evaporation that the chromium of 1nm thickness is deposited in step (3) described nanostructure, later again in chromium
The silver of upper electron beam evaporation plating 18nm thickness, chromium and silver-colored deposition rate are respectivelyWithObtain surface-enhanced Raman
Substrate, the substrate have silver/ball-compound nanostructure of net silica.
The surface-enhanced Raman substrate that the present embodiment is prepared by Nanostructure Network and be located at the mesh nanometer
The composite construction that nano-spherical structure in structure is formed, and formed positioned at the metallic particles of composite structure surface, that is, have
Silver/ball-compound the nanostructure of net silica, Nanostructure Network are period reticular structure, and line width is before deposited metal
10nm, is 20nm, a diameter of 400nm-500nm of nano-spherical structure, a diameter of 5nm of silver nano-grain after deposited metal,
The spacing of silver nano-grain is 1nm, and the thickness of Nanostructure Network is 48nm.
The excellent surface-enhanced Raman effects of surface-enhanced Raman substrate and splendid detection that the present embodiment obtains are sensitive
Degree.
Comparative example 1
This comparative example uses the surface only with Nanostructure Network and the metallic particles positioned at Nanostructure Network surface
Enhance Raman substrate, the surface-enhanced Raman substrate is in addition to without nano-spherical structure, the product of other features and embodiment 1
Identical, i.e. the enhancing Raman substrate of this comparative example is made of single Nanostructure Network and the metallic particles positioned at its surface
, this comparative example enhances the network nano structure line width of Raman substrate, network nano structure thickness, the shape of nano-array pattern
And area, metal deposit thickness, metallic particles grain size and the parameters such as spacing and metallic particles type all with the product phase of embodiment 1
Together.Performance test methods same as Example 1 are used to the surface-enhanced Raman substrate described in this comparative example, test result is such as
In Fig. 3 label be network nano structure " curve shown in.
Fig. 3 is the single reticular nanostructure substrate of comparative example 1 and the nanostructure compound with ball/net of embodiment 1
Product Raman enhanced spectrum figure.Ball/net is compound in the spectrum corresponding diagram for the surface-enhanced Raman substrate that embodiment 1 obtains receives
The curve of rice structure, the curve of network nano structure in the spectrum corresponding diagram for the surface-enhanced Raman substrate that comparative example 1 obtains.From
It can be seen from the figure that, with comparative example 1 single reticular nanostructured surface enhancing Raman substrate compared with, embodiment 1 prepare ball/
The principal character peak such as 1360cm of the 2,2'- bipyridyl molecules of net composite nanostructure surface-enhanced Raman substrate-1Intensity
The promotion for having an order of magnitude illustrates that surface-enhanced Raman substrate provided by the invention significantly enhances surface-enhanced Raman
Sensitivity.
Comparative example 2
This comparative example uses the surface only with Nanostructure Network and the metallic particles positioned at Nanostructure Network surface
Enhance Raman substrate, the surface-enhanced Raman substrate is in addition to without nano-spherical structure, the product of other features and embodiment 2
Identical, i.e. the enhancing Raman substrate of this comparative example is made of single Nanostructure Network and the metallic particles positioned at its surface
, this comparative example enhances the network nano structure line width of Raman substrate, network nano structure thickness, the shape of nano-array pattern
And area, metal deposit thickness, metallic particles grain size and the parameters such as spacing and metallic particles type all with the product phase of embodiment 2
Together.Use performance test methods same as Example 2, test result aobvious surface-enhanced Raman substrate described in this comparative example
Show：The compound Molecular Raman intensity that measures of nanostructured surface enhancing Raman substrate of ball/net prepared by embodiment 2 is approximately comparison
8 times of the raman scattering intensity that the surface-enhanced Raman substrate of example 2 measures.
Comparative example 3
This comparative example prepares surface-enhanced Raman substrate, this comparative example using the method for the embodiment 3 of CN106770180A
The nano array structure that obtained surface-enhanced Raman substrate is made of metal and dielectric material, the size of nano-array pattern are
The line width of 500 500 μm of μ ms, hexagon nano-array pattern is 8.7nm, and silica nano junction is deposited on by electron beam evaporation plating
Gold thin film on structure is at Nanoparticulate, a diameter of 12.9nm.Compared to the product of the embodiment of the present invention 2, the production of this comparative example
Do not have nano-spherical structure in product.
Performance test methods same as Example 2, test are used to the surface-enhanced Raman substrate described in this comparative example
As a result it shows：The nanostructured surface that ball/net of the preparation of embodiment 2 is compound enhances the Molecular Raman intensity phase that Raman substrate measures
The raman scattering intensity that the surface-enhanced Raman substrate of mesh nanometer array structure thickness more identical than in comparative example 3 measures has the order of magnitude
It is promoted.
Based on the above embodiments with comparative example it is found that surface-enhanced Raman substrate provided by the invention is because have nano net
Shape structure and the nano-spherical structure on the Nanostructure Network, thus excellent surface-enhanced Raman effects can be obtained
With splendid detection sensitivity.Comparative example does not have scheme using the present invention, does not contain nano-spherical structure, thus can not obtain
The effect of the present invention.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of Raman substrate, which is characterized in that the Raman substrate include Nanostructure Network and be located at the mesh nanometer
The composite construction that nano-spherical structure in structure is formed, and the metallic particles positioned at composite structure surface.
2. Raman substrate according to claim 1, which is characterized in that the Raman substrate is by Nanostructure Network and is located at
The composite construction that nano-spherical structure on the Nanostructure Network is formed, and the metallic particles positioned at composite structure surface
Composition；
Preferably, the Nanostructure Network is nanometer period reticular structure；
Preferably, the Raman substrate is three-dimensional matrix structure；
Preferably, the material for constituting the Nanostructure Network is dielectric material, preferably silica；
Preferably, the material for constituting the nano-spherical structure is dielectric material, preferably silica；
Preferably, the line width of the Nanostructure Network is 10nm-50nm；
Preferably, the metallic particles is coated on Nanostructure Network and nano-spherical structure surface；
Preferably, the line width for having coated the Nanostructure Network of metallic particles is 20nm-80nm；
Preferably, a diameter of 50nm-500nm of the nano-spherical structure；
Preferably, a diameter of 5nm-15nm of the metallic particles；
Preferably, the spacing of the metallic particles is 0nm-3nm；
Preferably, the thickness of the Nanostructure Network is 30nm-300nm；
Preferably, the Raman substrate is located in substrate；
Preferably, the area of the nano-array pattern in the Nanostructure Network is 100 μm2-250000μm2；
Preferably, the nano-array pattern in the Nanostructure Network includes in triangle, quadrangle, hexagon or circle
Any one or at least two combination, preferably hexagon.
3. the preparation method of Raman substrate according to claim 1 or 2, which is characterized in that the method includes following steps
Suddenly：
(1) positive electronic beam resist and negativity electron sensitive resist are mixed, obtains mixed electronic bundle resist, it will be described mixed
It closes electron sensitive resist to be coated in substrate, the substrate after being coated；
(2) nano-array pattern is formed in substrate after application, development obtains nanostructure, deposited in the nanostructure
Metal obtains the Raman substrate.
4. preparation method according to claim 3, which is characterized in that in step (1), with the mixed electronic bundle resist
Volume be 100% meter, the volume fraction of negativity electron sensitive resist is 25%-85%；
Preferably, the mixing is with ultrasonic disperse；
Preferably, the time of the ultrasonic disperse is 2min-60min.
5. preparation method according to claim 3 or 4, which is characterized in that in step (1), the method for the coating is rotation
It applies；
Preferably, the substrate includes any one in silicon base, metal substrate and Group III-V semiconductor substrate, preferably
For silicon base；
Preferably, in step (1), the thickness for being coated in the electron sensitive resist in substrate is 50nm-500nm.
6. according to claim 3-5 any one of them preparation methods, which is characterized in that in step (2), the formation nanometer battle array
The method of row pattern is to carry out nano-array pattern direct write with electron beam exposure method；
Preferably, the size of the electron beam spot of the electron beam exposure is 0.5nm-10nm；
Preferably, the exposure dose of the electron beam exposure is 20000 μ C/cm2-200000μC/cm2；
Preferably, the layout design line width of the nano-array pattern is 0nm-10nm and does not include 0nm；
Preferably, the area of the nano-array pattern is 100 μm2-250000μm2；
Preferably, the nano-array pattern includes any one in triangle, quadrangle, hexagon or circle or at least two
The combination of kind, preferably hexagon.
7. according to claim 3-6 any one of them preparation methods, which is characterized in that in step (2), the method for the development
To be developed with the developer solution of the developer solution of negativity electron sensitive resist and positive electronic beam resist；
Preferably, in step (2), the developer solution of the negativity electron sensitive resist includes NaOH solution；
Preferably, in the NaOH solution, the mass fraction of NaOH is 0.5wt%-3wt%, preferably 1wt%；
Preferably, in step (2), the developer solution of the positive electronic beam resist includes isobutyl acetate or by 4- methyl -2-
The mixing developer solution of pentanone and isopropanol composition；
Preferably, in the mixing developer solution being made of 4-methyl-2 pentanone and isopropanol, 4-methyl-2 pentanone and isopropyl
The volume ratio of alcohol is 1:2-1:4, preferably 1:3；
Preferably, step (2) further includes：Substrate is cleaned after development；
Preferably, the cleaning solution of the cleaning includes water and/or acetone；
Preferably, step (2) further includes：It is fixed with fixer after development；
Preferably, the fixer is isopropanol；
Preferably, step (2) further includes：After development substrate is dried with inert gas；
Preferably, when step (2) includes fixing, substrate is dried with inert gas after fixing；
Preferably, the inert gas includes nitrogen；
Preferably, the development is developed for substep, and the method for the substep development is：First use the development of negativity electron sensitive resist
Liquid develops, then is developed with the developer solution of positive electronic beam resist；
Preferably, the developing time to be developed with the developer solution of negativity electron sensitive resist is 0.5min-2min, preferably
1min；
Preferably, the developing time to be developed with the developer solution of positive electronic beam resist is 0.5min-2.5min, preferably
1min；
Preferably, it after being developed with the developer solution of negativity electron sensitive resist, washes with water substrate and uses soaked in absolute ethyl alcohol
Substrate；
Preferably, the time of the cleaning is 2min；
Preferably, the time of the immersion is 10min；
Preferably, after being developed with the developer solution of negativity electron sensitive resist and with the developer solution of positive electronic beam resist
After being developed, substrate is dried with inert gas.
8. according to claim 3-7 any one of them preparation methods, which is characterized in that in step (2), the nanostructure packet
Include the composite construction of Nanostructure Network and the nano-spherical structure formation on the Nanostructure Network；
Preferably, a diameter of 50nm-500nm of the nano-spherical structure；
Preferably, the line width of the Nanostructure Network is 10nm-50nm；
Preferably, the Nanostructure Network is nanometer period reticular structure.
9. according to claim 3-8 any one of them preparation methods, which is characterized in that in step (2), the metal includes
In gold, platinum, silver, copper or aluminium any one or at least two combination；
Preferably, in step (2), the method for the deposited metal includes hot evaporation, electron beam evaporation plating, magnetron sputtering or atomic layer
In deposition any one or at least two combination；
Preferably, in step (2), the thickness of the metal of deposition is 1nm-50nm；
Preferably, in step (2), the deposition rate of deposited metal is
Preferably, in step (2), the line width that the Nanostructure Network of metal is deposited in the Raman substrate is 20nm-80nm；
Preferably, in step (2), the metal for being deposited on nanostructured surface is made of metallic particles；
Preferably, a diameter of 5nm-15nm of the metallic particles；
Preferably, the spacing of the metallic particles is 0nm-3nm.
10. according to claim 3-9 any one of them preparation methods, which is characterized in that the described method comprises the following steps：
(1) positive electronic beam resist and negativity electron sensitive resist are mixed, ultrasonic disperse 2min-60min, obtains mixing electricity
Beamlet resist, on a silicon substrate by the mixed electronic bundle resist spin coating, the mixed electronic bundle resist thickness of coating is
50nm-500nm, the substrate after being coated；
(2) hexagon nano-array pattern direct write is carried out with electron beam exposure method in the substrate after step (1) described coating,
It is written the substrate of nano-array pattern；The size of the electron beam spot of the electron beam exposure is 0.5nm-10nm, described
The exposure dose of electron beam exposure is 20000 μ C/cm2-200000μC/cm2, the layout design line width of the nano-array pattern
For 0nm-10nm and do not include 0nm, the area of the nano-array pattern is 100 μm2-250000μm2；
(3) first the substrate of step (2) said write nano-array pattern is shown with the developer solution of negativity electron sensitive resist
Shadow, developing time 1min wash with water substrate 2min and with soaked in absolute ethyl alcohol substrate 10min, substrate are dried with nitrogen, then
Developed with the developer solution of positive electronic beam resist, developing time 1min is fixed with isopropanol, and base is dried with nitrogen
Bottom obtains nanostructure；
(4) step (3) nanostructured surface withDeposition rate deposition thickness be 1nm-50nm
Metal obtains the Raman substrate；The metal includes the group of any one or at least two in gold, platinum, silver, copper or aluminium
It closes, the metal for being deposited on nanostructured surface is metallic particles.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109802301A (en) * | 2019-03-05 | 2019-05-24 | 金华伏安光电科技有限公司 | A kind of electric drive surface Raman enhancement light source |
| CN110306159A (en) * | 2019-08-09 | 2019-10-08 | 浙江工业大学 | Surface-enhanced Raman substrate and preparation method thereof based on the film modified Al nanostructure of ultra-thin tetrahedral carbon |
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| CN106770180A (en) * | 2017-02-23 | 2017-05-31 | 国家纳米科学中心 | A kind of surface-enhanced Raman substrate and preparation method thereof |
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| CN107091809A (en) * | 2017-06-19 | 2017-08-25 | 江苏师范大学 | A kind of Silver nanorod array surface strengthens the cleaning method of Raman scattering substrate |
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2018
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Patent Citations (10)
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| US8953159B2 (en) * | 2008-10-03 | 2015-02-10 | The Board Of Trustees Of The University Of Illinois | Surface enhanced raman spectroscopy nanodome biosensors and methods of manufacturing the same |
| US9080981B2 (en) * | 2009-12-02 | 2015-07-14 | Lawrence Livermore National Security, Llc | Nanoscale array structures suitable for surface enhanced raman scattering and methods related thereto |
| US9013690B1 (en) * | 2010-05-21 | 2015-04-21 | The Trustees Of Princeton University | Highly sensitive detection of biomarkers for diagnostics |
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| CN105271103A (en) * | 2015-10-20 | 2016-01-27 | 国家纳米科学中心 | Nano-structure array and manufacturing method and application thereof |
| CN105954253A (en) * | 2016-04-23 | 2016-09-21 | 上海大学 | Glucose SERS detection substrate based on Ag@Ag nanodot hierarchical galaxy array and preparation method thereof |
| CN106567119A (en) * | 2016-10-19 | 2017-04-19 | 华中科技大学 | Polymer based nanometer cone structure SERS substrate and preparation method |
| CN106770180A (en) * | 2017-02-23 | 2017-05-31 | 国家纳米科学中心 | A kind of surface-enhanced Raman substrate and preparation method thereof |
| CN106929807A (en) * | 2017-03-15 | 2017-07-07 | 安徽农业大学 | The preparation method of the polyacrylonitrile nano post array film SERS substrates of Nano silver piece modification |
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| CN109802301A (en) * | 2019-03-05 | 2019-05-24 | 金华伏安光电科技有限公司 | A kind of electric drive surface Raman enhancement light source |
| CN109802301B (en) * | 2019-03-05 | 2020-07-24 | 深圳网联光仪科技有限公司 | Electrically-driven surface Raman enhanced light source |
| CN110306159A (en) * | 2019-08-09 | 2019-10-08 | 浙江工业大学 | Surface-enhanced Raman substrate and preparation method thereof based on the film modified Al nanostructure of ultra-thin tetrahedral carbon |
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