CN106770157A - 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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- CN106770157A CN106770157A CN201611046796.XA CN201611046796A CN106770157A CN 106770157 A CN106770157 A CN 106770157A CN 201611046796 A CN201611046796 A CN 201611046796A CN 106770157 A CN106770157 A CN 106770157A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides a kind of preparation method of surface enhanced Raman substrate, the described method comprises the following steps：Silverskin is prepared on substrate, silver-plated substrate is obtained；The silver-plated substrate is carried out into plasma dry etch, the surface enhanced Raman substrate of loose structure is obtained.The method can prepare the adjustable silver-colored loose structure of granularity size, and without any mask, manufacture craft is simple, process control, reproducible, can large area prepare.Silver nano-grain loose structure prepared by the present invention can be used as the efficient detection substrate of surface Raman enhancement, and significantly, detection substrate consistency of performance is good, and sensitivity is high for Raman enhancement effect.
Description
Technical field
The present invention relates to micro-nano material processing technique field, and in particular to surface enhanced Raman substrate and preparation method thereof.
Background technology
SERS (SERS) Detection Techniques have very big in fields such as chemistry, biological medicine, environment measurings
Actual application value.Meanwhile, what SERS was given is molecular level information, it is not necessary to which UHV condition, sensitivity is high, selectivity
It is good, and with nondestructive photon as probe signals, sensitivity is high, and detection process is simple, low cost, it is easy in practical application
Middle realization.Up to 10 can be realized on the surface such as coarse noble metal Au, Ag, Cu6Enhancement effect, compared to other surfaces detect skill
Art has unique advantage.In numerous metals and precious metal material, Ag typically exhibits optimal enhancing effect.
Nano Silver is because of unique physicochemical property such as its surface-active higher and good catalytic performance, being widely used in
The industries such as work, medical science, optics, electronics.Argent grain, due to its high-sensitivity characteristic, can be used for as a kind of conventional probe material
SERS Detection Techniques, are widely applied in fields such as chemistry, biological and medical science, are capable of achieving hypersensitive or even unimolecule inspection
Survey.The shortcomings of nm of gold, Ag colloid particle have repeatability and stability difference, Ag films have preferably repeatability, but
There is chemical property to be not sufficiently stable, the shortcoming of easy sulfidation-oxidation.Therefore, how effectively to control the size of Argent grain, spacing and
Structure is to realize the key of its surface-enhanced Raman efficient detection, thus in widespread attention and further investigation.
In recent years, silver nanostructured technology of preparing is developed rapidly, for example chemical reduction method, chemical deposition, electrochemistry
Sedimentation, sonochemical method, go alloyage.Wherein, chemical method is versatile and flexible, easy to operate, but there are shortcomings, such as produces
Product purity is low, particle size is difficult to control to, complex process, power consumption, pollution environment etc..Wherein magnetron sputtering method, electron beam steam method
Simple Deng physical preparation method principle, impurity in products is few, quality is high, but is hardly formed silver nanoparticle loose structure, and this nanometer
Loose structure is often efficiently to detect desired ideal structure.
CN 102759520A prepare a kind of with big ratio when SERS substrates are prepared, first with hydro-thermal corrosion technology
The nano-structure porous silicon columnar arrays of surface area, then with chemical vapour deposition technique in nano-silicon Grown II-VI group compound
Semiconductor (such as zinc oxide, titanium dioxide, cadmium sulfide, cadmium selenide, cadmium telluride) nano thread structure, finally using chemical reduction method
Noble metal (e.g., gold, silver, copper etc.) nano particle is prepared thereon obtains active base material.Not only technique is cumbersome for whole process,
And cost is larger, and be not suitable for large-scale industrial production.
The content of the invention
In view of problems of the prior art, an object of the present invention is to provide a kind of surface enhanced Raman substrate
Preparation method, the described method comprises the following steps：
(1) silverskin is prepared on substrate, silver-plated substrate is obtained；
(2) silver-plated substrate described in step (1) is carried out into plasma dry etch, obtains the surface enhanced of loose structure
Raman substrate.
After dry etching, a kind of silver nano-grain loose structure is formed.It is adjustable that the method can prepare granularity size
Silver-colored loose structure, without any mask, manufacture craft is simple, process control, reproducible, can large area prepare.Of the invention
The loose structure substrate for arriving can be used as the efficient detection substrate of surface Raman enhancement, and Raman enhancement effect significantly, is detected basilar
Energy uniformity is good, and sensitivity is high.
Used as currently preferred technical scheme, substrate described in step (1) of the present invention includes silicon chip, glass, titanium dioxide
Any a kind or at least 2 kinds of combination in silicon or silicon nitride, preferably silicon chip.The insensitive base in the substrate plasma source
Piece, the substrate example but without limitation, the substrate is silicon chip, glass, silicon nitride or silica.
Of the present invention " including ", it is intended that it can also include other components, these other components in addition to the component
Assign the surface enhanced Raman substrate different characteristics.In addition, of the present invention " including ", may be replaced by envelope
" being " of enclosed or " by ... constitute ".
The substrate of the present invention gas that can not be etched is etched, and can be selected to according to actual needs and nanometer
The substrate of pore structure collaboration enhancing Raman enhancement effect, can further improve surface-enhanced Raman effects.
Used as currently preferred technical scheme, the method that silverskin is prepared described in step (1) of the present invention is splashed including magnetic control
Penetrate and/or electron beam evaporation.
Preferably, the magnetron sputtering is silver target sputtering.
Used as currently preferred technical scheme, the thickness of silverskin described in step (1) of the present invention is 20~1000nm, example
As 20nm, 30nm, 50nm, 90nm, 110nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm,
950nm or 1000nm, preferably 100~800nm.
According to the thickness of silverskin, corresponding pore structure can be obtained by adjusting process, this silver film thickness depends on actual
Need.
Used as currently preferred technical scheme, plasma dry etch is in plasma described in step (2) of the present invention
Carried out in body etching machine.
Preferably, the working gas of the plasma dry etch process includes Cl2.Dry plasma etch process
In, excite the gas in work atmosphere to produce plasma, carry out dry etching.
Preferably, the working gas includes Cl2With auxiliary gas, the auxiliary gas include Ar, N2, He or containing chlorine
Any a kind or at least 2 kinds of combination in body.
Preferably, Cl in the working gas2It is (1~9) with the volume ratio of auxiliary gas:(9~1), preferably (3~7):
(7~3).
Example but without limitation, the etching gas can have any a kind in following composition：
Cl2；Volume ratio is 1:9 Cl2And BCl3；Volume ratio is 2:8 Cl2And Ar；Volume ratio is 2.5:7.5 Cl2With
He；Volume ratio is 3:3:4 Cl2, Ar and N2；Volume ratio is 4:3:3 Cl2, He and BCl3；Volume ratio is 9:1 Cl2And He.
The method that using plasma of the present invention carries out dry etching, etching area is big, and etching structure is uniform, in high vacuum
The pollution problem for avoiding liquid phase chemical lithographic method from bringing is carried out in equipment, causes differing as Raman enhancing substrate performance
Cause, it is impossible to use.Further, since Ag can form dystectic silver chlorate with chlorine reaction, these silver chlorates are made in etching
For micro- mask that autoreaction is formed so that Argent grain pore structure may finally be obtained.Furthermore, this method can be by controlling work
The composition of gas and the pattern and structure of Flow-rate adjustment product.
Cl2It is the active gases in working gas, using auxiliary gas and Cl2Can realize etching efficiency and etching effect
Regulation.
Used as currently preferred technical scheme, plasma dry etch is in plasma described in step (2) of the present invention
Carried out in body etching machine, its working gas is passed through with the flow of 1~1000sccm, the flow of such as working gas is 1sccm,
2sccm、4sccm、5sccm、10sccm、20sccm、50sccm、100sccm、200sccm、220sccm、300sccm、
380sccm、400sccm、450sccm、490sccm、510sccm、560sccm、620sccm、680sccm、730sccm、
790sccm, 830sccm, 900sccm, 950sccm or 1000sccm etc.；Regulation chamber pressure is 0.2~2Pa, for example
0.25Pa, 0.5Pa, 0.8Pa, 1.2Pa, 1.4Pa, 1.7Pa or 1.9Pa etc.；Setting upper electrode power is 50~2000W, for example
60W、80W、100W、150W、190W、220W、300W、400W、500W、600W、700W、800W、900W、1000W、1200W、
1500W, 1700W, 1800W, 1900W or 2000W etc.；Setting lower electrode power be 5~500W, such as 6W, 10W, 20W, 50W,
70W, 90W, 100W, 140W, 150W, 170W, 200W, 220W, 300W, 320W, 380W, 400W, 450W, 480W, 490W or
500W etc.；Etching 5~200s, such as 5s, 6s, 7s, 8s, 9s, 10s, 15s, 20s, 30s, 40s, 50s, 80s, 90s, 100s,
120s, 130s, 150s, 170s, 190s or 200s.
Preferably, the flow of the work atmosphere is 5~100sccm.
Preferably, the chamber pressure is 1~1.5Pa.
Preferably, the upper electrode power is 200~1000W.
Preferably, the lower electrode power is 20~150W.
Preferably, the etch period is 8~60s.Etch period extension Argent grain tends to assembling, and particle diameter increases
Plus.
Used as the preferred technical solution of the present invention, the preparation method of surface enhanced Raman substrate of the present invention includes following step
Suddenly：
(1) silverskin that thickness is 100~800nm is prepared by magnetron sputtering and/or electron beam evaporation on silicon chip, is obtained
Silver-plated substrate；
(2) silver-plated substrate described in step (1) is carried out into plasma dry etch, process in plasma etching machine
In working gas Cl is passed through with the flow of 5~100sccm2And/or auxiliary gas, regulation chamber pressure is 1~1.5Pa, is set
Upper electrode power is 200~1000W, and setting lower electrode power is 20~150W, etches 5~200s；Obtain the table of loose structure
Face strengthens Raman substrate.
The second object of the present invention is to provide a kind of surface enhanced Raman substrate, is increased as the surface as described in the first purpose
The preparation method of strong Raman substrate is prepared.
Used as currently preferred technical scheme, surface enhanced Raman substrate of the present invention includes that Nano Silver is porous thin
Film.
" porous " of the present invention refers to the two dimension or three-dimensional structure assembled in the plane by a large amount of polygonal holes and formed, category
In clear statement.
Preferably, the nano-Ag particles median particle diameter in the Nano Silver porous membrane be 10~300nm, such as 10nm,
15nm、18nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、95nm、98nm、100nm、110nm、
150nm, 200nm, 220nm, 250nm, 280nm or 290nm etc., preferably 20~100nm.
Compared with prior art, the present invention at least has the advantages that：
The method of the invention forms a kind of silver nano-grain loose structure after dry etching.The method can not by
The adjustable silver-colored loose structure of granularity size is prepared in any substrate of etching gas etching, without any mask, manufacture craft
Simply, process control, reproducible, can large area prepare.The loose structure that the present invention is obtained can be used as surface Raman enhancement
Substrate is efficiently detected, and Ramam effect can be further enhanced by selecting suitable substrate, sensitivity reaches Single Molecule Detection
Level.
Brief description of the drawings
Fig. 1 is the front SEM figures of the gained surface enhanced Raman substrate of embodiment 1.
Fig. 2 is the section SEM figures of the gained surface enhanced Raman substrate of embodiment 1
Fig. 3 is that the gained surface enhanced Raman substrate of embodiment 1 is 10 to concentration-7The Raman of the rhodamine 6G molecule of mol/L
Enhanced spectrum figure.
Fig. 4 is the front SEM figures of the gained surface enhanced Raman substrate of embodiment 2.
Fig. 5 is the section SEM figures of the gained surface enhanced Raman substrate of embodiment 2.
Fig. 6 is the front SEM figures of the gained surface enhanced Raman substrate of embodiment 3.
Fig. 7 is the section SEM figures of the gained surface enhanced Raman substrate of embodiment 3.
Fig. 8 is the front SEM figures of the gained surface enhanced Raman substrate of embodiment 4.
Fig. 9 is the section SEM figures of the gained surface enhanced Raman substrate of embodiment 4.
Figure 10 is the front SEM figures of the gained surface enhanced Raman substrate of embodiment 5.
Figure 11 is the section SEM figures of the gained surface enhanced Raman substrate of embodiment 5.
Figure 12 is the front SEM figures of the gained surface enhanced Raman substrate of embodiment 6.
Figure 13 is the section SEM figures of the gained surface enhanced Raman substrate of embodiment 6.
The present invention is described in more detail below.But following examples are only simple example of the invention, are not represented
Or the scope of the present invention is limited, protection scope of the present invention is defined by claims.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
For the present invention is better described, technical scheme is readily appreciated, it is as follows that the present invention enumerates embodiment.Ability
Field technique personnel it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to concrete restriction of the invention.
Embodiment 1
1) one layer of silverskin of 200nm of magnetron sputtering is used on silicon chip, silver-plated silicon chip is obtained；
2) 1) gained plating silverskin silicon chip is put into inductively coupled plasma etching machine ICP chambers, is passed through 30sccm's
Working gas, wherein working gas are 2 by volume ratio:1 Cl2With Ar compositions, regulation chamber pressure is 0.4Pa, electricity in setting
Pole power is 500W, and setting lower electrode power is 60W, maintains 30s, obtains surface enhanced Raman substrate.
Can see the surface enhanced Raman substrate surface that embodiment 1 obtains and formed from Fig. 1 and Fig. 2 and be about by median particle diameter
The nano-Ag particles of 30nm are dispersed in silicon chip surface composition porous nano Ag films.
Print is taken out, rhodamine 6G molecule is modified：10-715h is soaked in the rhodamine 6G solution of mol/L, taking-up is dried
Afterwards as the active substrate of SERS, it is 514nm to use wavelength, the laser irradiation of the about 0.005mW of power 0.05%, and the time of integration is
10s, obtains the Raman scattering features peak of rhodamine 6G, as shown in Figure 3.With sensitivity higher, Single Molecule Detection is capable of achieving.
Comparative example 1 is differed only in embodiment 1：Save step 2).
The silverskin of the gained substrate surface of comparative example 1 does not have pore structure, and the drawing of rhodamine 6G is not obtained for Single Molecule Detection
Man Sanshetezhengfeng.
Embodiment 2
1) one layer of silverskin of 500nm of magnetron sputtering is used on silicon chip, silver-plated silicon chip is obtained；
2) 1) gained plating silverskin silicon chip is put into inductively coupled plasma etching machine ICP chambers, is passed through 50sccm's
Cl2, chamber pressure is 1Pa, and setting upper electrode power is 1000W, and setting lower electrode power is 100W, maintains 15s, the table for obtaining
Face enhancing Raman substrate has sensitivity higher, is capable of achieving Single Molecule Detection.
Embodiment 3 differs only in etch period for 30s with embodiment 2.
Can see the surface enhanced Raman substrate surface that embodiment 3 obtains and formed from Fig. 4 and Fig. 5 and be about by median particle diameter
The nano-Ag particles of 40nm are dispersed in silicon chip surface composition porous nano Ag films.This surface enhanced Raman substrate have compared with
Sensitivity high, is capable of achieving Single Molecule Detection.
Embodiment 4 differs only in etch period for 60s with embodiment 2.
Can see the surface enhanced Raman substrate surface that embodiment 4 obtains and formed from Fig. 6 and Fig. 7 and be about by median particle diameter
The dispersed nano-silver particles of 80nm constitute porous nano Ag films in silicon chip surface, the particle diameter uneven distribution of silver nano-grain in
In the range of 10~300nm.
Embodiment 5 differs only in etch period for 120s with embodiment 2.
The surface enhanced Raman substrate surface that embodiment 5 obtains being can see from Fig. 8 and Fig. 9 and forming Argent grain be dispersed in silicon
Piece surface composition porous nano Ag films, Argent grain is in irregular pattern, has Argent grain particle diameter to reach 932.7nm.
Comparing embodiment 2,3,4 and 5 understands, in the case of other conditions identical, when etch period extends to more than 60s
When, Argent grain is gradually reunited, and Argent grain particle diameter becomes big.
Embodiment 6
1) silver-plated silicon chip is obtained using the Ag films of one layer of 400nm of magnetron sputtering on silicon chip；
2) 1) gained plating silverskin silicon chip is put into inductively coupled plasma etching machine ICP chambers, is passed through 20sccm's
Working gas, wherein working gas by volume ratio be 1:3 Cl2And BCl3Composition, regulation chamber pressure is 0.2Pa, in setting
Electrode power is 200W, and setting lower electrode power is 20W, maintains 90s, the surface enhanced Raman substrate for obtaining to have spirit higher
Sensitivity, is capable of achieving Single Molecule Detection.
Embodiment 7 is differed only in embodiment 6：Etch period is 120s.
The surface enhanced Raman substrate surface that embodiment 7 obtains is can see from Figure 10 and Figure 11 to be formed by nano-Ag particles
Be dispersed in silicon chip surface composition porous nano Ag films, the particle diameter uneven distribution of nano particle in the range of 10~150nm, and
The silverskin that internal layer still has thickness about 100nm does not almost etch vestige.
Embodiment 8
1) one layer of silverskin of 800nm of magnetron sputtering is used on silicon chip, silver-plated silicon chip is obtained；
2) 1) gained plating silverskin silicon chip is put into inductively coupled plasma etching machine ICP chambers, is passed through 150sccm's
Working gas, wherein working gas are 2 by volume ratio:1 Cl2And N2Composition, regulation chamber pressure is 2Pa, sets Top electrode work(
Rate is 700W, and setting lower electrode power is 150W, maintains 120s, the surface enhanced Raman substrate for obtaining to have higher sensitive
Degree, is capable of achieving Single Molecule Detection.
The surface enhanced Raman substrate surface that embodiment 8 obtains is can see from Figure 12 and Figure 13 to be formed by nano-Ag particles
Be dispersed in silicon chip surface composition porous nano Ag films, the particle diameter uneven distribution of silver nano-grain in the range of 10~200nm,
And the silverskin that internal layer still has thickness about 520nm does not etch vestige.
Embodiment 9
1) one layer of silverskin of 20nm of magnetron sputtering is used on titanium dioxide silicon chip, silver-plated titanium dioxide silicon chip is obtained；
2) 1) gained plating silverskin silicon chip is put into inductively coupled plasma etching machine ICP chambers, is passed through the work of 1sccm
Make gas, wherein working gas is 9 by volume ratio:1 Cl2And N2Composition, regulation chamber pressure is 1.6Pa, sets Top electrode work(
Rate is 50W, and setting lower electrode power is 5W, maintains 500s, obtains surface enhanced Raman substrate titanium dioxide silicon chip surface composition many
Hole nano silver film, this surface enhanced Raman substrate has sensitivity higher, is capable of achieving Single Molecule Detection.
Embodiment 10
1) one layer of silverskin of 1000nm of magnetron sputtering is used on nitridation silicon chip, obtains silver-plated nitridation silicon chip；
2) 1) gained plating silverskin silicon chip is put into inductively coupled plasma etching machine ICP chambers, is passed through 1000sccm
Working gas, wherein working gas by volume ratio be 1:9 Cl2And NCl3Composition, regulation chamber pressure is 1.5Pa, in setting
Electrode power is 2000W, and setting lower electrode power is 500W, maintains 200s, the surface enhanced Raman substrate for obtaining to have higher
Sensitivity, be capable of achieving Single Molecule Detection.
Embodiment 11
1) one layer of silverskin of 600nm of electron beam evaporation plating is used on the glass sheet, obtains silvered glass piece；
2) 1) gained plating silverskin silicon chip is put into inductively coupled plasma etching machine ICP chambers, is passed through 500sccm's
Working gas, wherein working gas are 4 by volume ratio:3:3 Cl2, Ar and BCl3Composition, regulation chamber pressure is 0.8Pa, if
Upper electrode power is put for 380W, setting lower electrode power is 300W, maintain 8s, the surface enhanced Raman substrate for obtaining to have higher
Sensitivity, be capable of achieving Single Molecule Detection.
Embodiment 12
1) one layer of silverskin of 300nm of electron beam evaporation plating is used on silicon chip, silver-plated silicon chip is obtained；
2) 1) gained plating silverskin silicon chip is put into inductively coupled plasma etching machine ICP chambers, is passed through 100sccm's
Working gas, wherein working gas are 3 by volume ratio:3:4 Cl2, Ar and N2Composition, regulation chamber pressure is 0.5Pa, is set
Upper electrode power is 800W, and setting lower electrode power is 125W, maintains 100s, the surface enhanced Raman substrate for obtaining to have higher
Sensitivity, be capable of achieving Single Molecule Detection.
Applicant states that the present invention illustrates detailed construction feature of the invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute
Category those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of part selected by the present invention
And increase, the selection of concrete mode of accessory etc., within the scope of all falling within protection scope of the present invention and disclosing.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (9)
1. a kind of preparation method of surface enhanced Raman substrate, it is characterised in that the described method comprises the following steps：
(1) silverskin is prepared on substrate, silver-plated substrate is obtained；
(2) silver-plated substrate described in step (1) is carried out into plasma dry etch, obtains the surface-enhanced Raman of loose structure
Substrate.
2. the preparation method of surface enhanced Raman substrate as claimed in claim 1, it is characterised in that base described in step (1)
Piece includes any a kind in silicon chip, glass, silica or silicon nitride, preferably silicon chip.
3. the preparation method of surface enhanced Raman substrate as claimed in claim 1 or 2, it is characterised in that described in step (1)
The method for preparing silverskin includes magnetron sputtering and/or electron beam evaporation；
Preferably, the magnetron sputtering is silver target sputtering.
4. the preparation method of the surface enhanced Raman substrate as described in claim any one of 1-3, it is characterised in that step (1)
Described in silverskin thickness be 20~1000nm, preferably 100~800nm.
5. the preparation method of the surface enhanced Raman substrate as described in claim any one of 1-4, it is characterised in that step (2)
Described in plasma dry etch carried out in plasma etching machine；
Preferably, the working gas of the plasma dry etch process includes Cl2；
Preferably, the working gas includes Cl2With auxiliary gas, the auxiliary gas include Ar, N2, in He or chlorine-containing gas
Any a kind or at least 2 kinds of combination；
Preferably, Cl in the working gas2It is (1~9) with the volume ratio of auxiliary gas:(9~1), preferably (3~7):(7~
3)。
6. the preparation method of surface enhanced Raman substrate as claimed in claim 5, it is characterised in that described in step (2) etc.
Gas ions are carried out in being dry-etched in plasma etching machine, and its working gas is passed through with the flow of 1~1000sccm, adjust chamber
Body pressure be 0.2~2Pa, settings upper electrode power be 50~2000W, settings lower electrode power be 5~500W, etch 5~
200s；
Preferably, the flow of the work atmosphere is 5~100sccm；
Preferably, the chamber pressure is 1~1.5Pa；
Preferably, the upper electrode power is 200~1000W；
Preferably, the lower electrode power is 20~150W；
Preferably, the etch period is 8~60s.
7. the preparation method of the surface enhanced Raman substrate as described in claim any one of 1-6, it is characterised in that methods described
Comprise the following steps：
(1) silverskin that thickness is 100~800nm is prepared by magnetron sputtering and/or electron beam evaporation on silicon chip, obtains silver-plated
Substrate；
(2) silver-plated substrate described in step (1) is carried out into plasma dry etch in plasma etching machine, during with
The flow of 5~100sccm is passed through working gas Cl2And/or auxiliary gas, regulation chamber pressure is 1~1.5Pa, electricity in setting
Pole power is 200~1000W, and setting lower electrode power is 20~150W, etches 5~200s；The surface for obtaining loose structure increases
Strong Raman substrate.
8. a kind of surface enhanced Raman substrate, it is characterised in that drawn as the surface enhanced as described in any one of claim 1~7
The preparation method of graceful substrate is prepared.
9. surface enhanced Raman substrate as claimed in claim 8, it is characterised in that the surface enhanced Raman substrate includes receiving
The silver-colored porous membrane of rice；
Preferably, the nano-Ag particles median particle diameter in the Nano Silver porous membrane is 10~300nm, preferably 20~100nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108588645A (en) * | 2018-05-18 | 2018-09-28 | 杭州电子科技大学信息工程学院 | A kind of preparation method of surface enhanced Raman scattering substrate |
| CN114507846A (en) * | 2022-01-25 | 2022-05-17 | 中国科学院海洋研究所 | Preparation method of SERS substrate with silver nanoparticles loaded on surface |
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