CN106404747A - Compound type nano-structure Raman-enhanced substrate, preparation method and application - Google Patents
Compound type nano-structure Raman-enhanced substrate, preparation method and application Download PDFInfo
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Abstract
The invention discloses a compound type nano-structure Raman-enhanced substrate, a preparation method and application. The preparation method comprises the following steps: carrying out film formation of Au nano-particles and transferring to prepare an Au film-1,4-benzene dithioglycol-Au film sandwich structure by using 1,4-benzene dithioglycol as an internal standard substance, then evaporating a molybdenum trioxide layer with a thickness for isolating direct contact of inner layer metal and a detected molecule so as to prevent competitive adsorption between the internal standard molecule and the detected molecule, and thus obtaining the compound type nano-structure Raman-enhanced substrate. The compound type substrate prepared in the invention can obtain the characteristic spectrum signal of the internal standard molecule and the characteristic spectrum signal of the detected molecule at the same time, a relation between SERS relative signal strength and concentration logarithm of the detected molecule is established in a certain concentration range by using the relation strength relation between the characteristic peak of the internal standard molecule and the characteristic peak of the detected molecule, analytical means capable of expanding an SERS technology into quantitative determination is provided, and the compound type nano-structure Raman-enhanced substrate is significant in scientific research and practical application.
Description
Technical field
The present invention relates to a kind of Multi-layer composite nanostructured Raman strengthens substrate, preparation method and application in 1,4- benzene
Diformazan mercaptan, malachite green etc. carry out quantitative determination, belong to preparation and the detection applied technical field of nanostructured substrate.
Background technology
1974, Southampton University of Southampton Fleischmann etc. was carried out to silver electrode by electrochemical redox method
Roughening is processed, and obtains Pyridine Molecules and adsorbs in the high-quality Raman spectrum of coarse silver electrode surface.By Van Duyne and
Creighton et al., by detailed experiment and theoretical research, this phenomenon is defined as SERS（Surface
enhanced Raman scattering, SERS）Effect.It is found 40 for many years from this phenomenon, with nanometer technology, swash
The progress of each side such as light technology, detection technique, apparatus structure optimization, SERS is in analysis detection, interface science, environment prison
The fields such as survey, biomedicine obtain a wide range of applications.Its SERS substrate, also opens up from noble metals such as traditional gold, silver, copper
Open up transition metal, metal oxide etc.；The dimension of nanometer substrate includes zero dimension, one-dimensional, two-dimentional；The pattern of nanometer substrate includes
Spherical, cube, cuboid, bar-shaped, octahedra, triangular pyramid etc.；The structure of nanometer substrate have also been developed nucleocapsid, alloy, super group
Assembling structure etc..The detection object of SERS enumerates solid, liquid, gas, and detection architecture includes normal temperature and pressure, HTHP, very
To being ultrahigh vacuum system.Therefore, SERS has caused chemist, physicist, even biological and pharmaceutical researchers
Great interest, make the experiment of numerous scientific domains and theoretical research unprecedentedly active.
It is found that a lot of researchs to SERS are only limited to qualitative or semi-quantitative analysis at present, in quantitative analysis side
The work succeeding in face is less, and the feature of this and SERS technology itself is relevant.It is generally believed that the high enhancement effect of SERS
Have benefited from the focus of substrate surface（hot spots）If molecule is in this hot spot region, the scattered signal of molecule will be exaggerated
Several or even more than ten order of magnitude.Therefore, focus is particularly important in suprabasil uniform distribution.But due to nano junction
The complexity of structure, leads to the signal that the zones of different of substrate collects to there is very big difference, sometimes can reach several orders of magnitude,
These technical limitation make the quantitative Application of SERS be restricted.
Also some scientists are had to do more work in the Quantitative study of SERS（Referring to document：Bell
S.E.J., Sirimuthu N.M.S.Chem. Soc. Rev., 2008, 37, 1012–1024）.It is concentrated mainly on uniformly
The aspects such as the preparation of substrate, internal standard mark.In terms of homogenous substrate preparation, Gwo seminar adopts alkyl hydrosulfide as dressing agent,
Define the silver nanoparticle film of hexagonal closs packing.This film has area greatly, the feature of the homogeneity of height and high enhancing signal,
Test limit is even up to unimolecule rank, and, with crystal violet as probe molecule, result shows for they, in certain concentration range,
The signal response linear with concentration（Referring to document：Chen H.Y., Lin M.H., et.alJ. Am. Chem. Soc.
2015, 137, 13698−13705）.Yao seminar is using being adsorbed with the golden nanometer particle of polyvinylpyrrolidone in gas-liquid two
Phase film forming defines large-sized gold monolayers film, up to Centimeter Level.Result shows, the SERS of this golden film activity, uniformity and steady
Qualitative all very good.（Referring to document：Guo Q.H., Xu M.M., Gu R.A., Yao J.L.Langmuir2016,
32, 4530−4537）.Lei etc. is prepared for large-area polystyrene sphere array using nanolithography, in silver sol body
In system, last layer silver is coated on polystyrene sphere array using electrophoretic techniques, form silver nanoparticle shell structurre.This structure
Diameter, surface roughness, gap are controllable.（Referring to document：Yang S.K., Cai W.P., Kong L.C., Lei Y.Adv.Funct.Mater. 2010, 20, 2527−2533）.
Internal standard method is the common method carrying out quantitative analysis in analytical chemistry.In system to be analyzed, add a certain amount of
Internal standard substance, calculate the relation between analyzed material and internal standard substance, typically two kinds of materials taking SERS as a example
The size of SERS peak relative intensity, can extrapolate the concentration of analyte.Schultz seminar combines dividing of liquid chromatogram
From the highly sensitive feature of function and SERS, achieve vitamin B1, vitamin B2 and leaf by the use of acetonitrile as internal standard molecule
The ON-LINE SEPARATION of acid and detection.（Referring to document：Nguyen A., Schultz Z. D., Analyst 2016, 141,
3630−3635）.And milk, then cleverly by the use of the Raman signal of milk itself as internal standard, detects using SERS in Lu seminar
The dicyandiamide of middle residual, result shows that its range of linearity is 10-4～10-3g·mL-1.（Referring to document：Nguyen A.,
Schultz Z. D., Analyst 2016, 141, 3630−3635）.
As can be seen here, even if there is the SERS technology difficult point of itself, scientists pass through using various methods, still carve and
How the pursuit do not given up makes SERS technology realize breaking through at quantitative aspect, to making SERS in wider scientific research field and the people
Obtain further application with field.
Content of the invention
The deficiency that the present invention exists in terms of quantitative determination for existing SERS technology, provides and a kind of has good substrate
The composite nano structure Raman of uniformity and internal standard compound stability strengthens substrate, preparation method and applications.
The technical scheme realizing the object of the invention is the preparation side providing a kind of composite nano structure Raman to strengthen substrate
Method, using prior art, first in the gas-liquid interface preparation Gold nanoparticle monofilm of the aurosol containing golden nanometer particle, then enters
The operation of row following steps：
(1) using vertical czochralski method, Gold nanoparticle monofilm is transferred on monocrystalline silicon piece, covers on the surface of monocrystalline silicon piece
Au nano particle single layer film；
（2）It is 10 that the monocrystalline silicon piece that Au nano particle single layer film is covered is immersed in concentration-2～10-3mol·dm-31,4-
Dimercaptobenzene（It is denoted as 1,4-BDT）Ethanol solution in, obtain being repaiied by Isosorbide-5-Nitrae-dimercaptobenzene on Au nano particle single layer film surface
The cover layer of decorations；
（3）Using vertical czochralski method, by step（2）The surface of the monocrystalline silicon piece obtaining covers layer of Au nano particle single layer again
Film, forms with Isosorbide-5-Nitrae-dimercaptobenzene monofilm as intermediate layer, inside and outside layer is the list of " sandwich " structural modification of Au monofilm
Crystal silicon chip；
（4）Using vacuum thermal evaporation instrument in step（3）" sandwich " body structure surface be deposited with three oxygen that a layer thickness is 2～4 nm
Change molybdenum layer, for completely cutting off the directly contact of inner layer metal and detected molecule, prevent between internal standard molecule and testing molecule
Competitive Adsorption, obtain a kind of composite nano structure Raman and strengthen substrate.
Technical solution of the present invention further relates to be prepared as described above a kind of composite nano structure Raman enhancing base that method obtains
Bottom.
Technical solution of the present invention also includes the application that described composite nano structure Raman strengthens substrate, with Isosorbide-5-Nitrae-diphenyl disulfide
Alcohol is internal standard compound, and its Raman signal is used for demarcating the concentration of testing molecule, and substrate is used for the quantitative determination to testing molecule.
The concrete application that described composite nano structure Raman strengthens substrate includes：
（1）Set up 1,4- benzene dimethanethiol（It is denoted as 1,4-BDMT）Concentration is from 10-6～10-3mol·dm-3Log concentration-letter
The calibration curve of number relative intensity, substrate is used for the quantitative determination to Isosorbide-5-Nitrae-benzene dimethanethiol.
（2）Set up malachite green（It is denoted as MG）Concentration is from 10-9～10-6mol·dm-3Log concentration-signal relatively strong
The calibration curve of degree, substrate is used for the quantitative determination to malachite green.
Chinese invention patent CN103590037B discloses a kind of preparation method of Gold nanoparticle monofilm and its device；
Including steps such as the preparation of aurosol, the formation of monofilm, transfer and optimizations, first in the gas of the aurosol containing golden nanometer particle
Gold nanoparticle monofilm is prepared at liquid interface, then with vertical czochralski method, Gold nanoparticle monofilm is transferred to solid phase substrate
On.This invention, by regulating and controlling the monodispersity of aurosol, the volatilization of solvent, transfer of design interface monofilm etc., obtains institute
The Gold nanoparticle monofilm needing.The present invention using individual layer Au nanoparticles films prepared by gas-liquid two-phase method have uniformity good,
The advantages of be easily transferred to solid phase substrate, with relatively stable conventional SERS probe, Isosorbide-5-Nitrae-BDT is internal standard molecule, by adopting Au
" sandwich " mode of film-Isosorbide-5-Nitrae-BDT-Au film-Au film is it is achieved that the fixation of internal standard molecule；Meanwhile, enter on outer layer golden film surface
The controlled evaporation super thin oxide layer of row, prevents interfering between molecule, especially competitive Adsorption.After tested, this kind compound
Substrate can obtain the characteristic spectrum signal of internal standard and detected molecule simultaneously, and in certain concentration range, its characteristic peak is relatively
The size of intensity is linear with the logarithm of concentration.Quantification detection can be carried out using SERS using technical solution of the present invention.
The principle of the present invention is：Strengthen substrate by designing a kind of composite nano structure Raman, select rational internal standard
Molecule so as to be fixed between fine and close, the uniform gold monolayers film of two-layer, using the spy of characteristic peak and the tested molecule of internal standard molecule
Levy the relative intensity relation between peak, in certain concentration range, establish testing molecule SERS relative signal intensity with dense
Relation curve between degree logarithm, can be applicable to the quantitative determination with the molecule of stronger adsorption capacity, as to Isosorbide-5-Nitrae-BDMT
Can detection range be 10-6～10-3mol·dm-3, the detection range of MG molecule is 10-9～10-6mol·dm-3.
The present invention compared with prior art, has the advantage that：
1st, the present invention adopts two-layer gold monolayers film to fix internal standard molecule, so that internal standard molecule is not desorbed when testing molecule adsorbs；Adopt
With ultrathin oxide layer isolation internal standard molecule and tested molecule, two kinds of molecules are made competitive Adsorption not occur, thus ensureing that internal standard is divided
The stability of son.
2, present invention incorporates the technological means of homogenous substrate and fixing internal standard both quantification experiment, have played substrate
Uniformity and the respective advantage of internal standard stability, the quantification detection of achievable SERS.
3rd, the method for preparation enhancing Raman substrate provided by the present invention, technological process and operating procedure are fairly simple, relate to
And reaction and testing conditions gentle.The cost of manufacture of substrate is cheap, can batch making, there is popularizing application prospect.
Brief description
Fig. 1 is the SERS spectra figure that composite nano structure Raman strengthens internal standard molecule Isosorbide-5-Nitrae-BDT in substrate, and molecule assembles
Concentration is 10-3mol·dm-3.
The mixing of internal standard 1,4-BDT that Fig. 2 provides for the embodiment of the present invention 1 and variable concentrations tested molecule 1,4-BDMT
SERS spectra figure.
Fig. 3 is 1603 cm in the embodiment of the present invention 1-1With 1064 cm-1Relative intensity and molecular solution log concentration
Graph of a relation.
The mixing SERS spectra of internal standard 1,4-BDT that Fig. 4 provides for the embodiment of the present invention 2 and variable concentrations tested molecule MG
Figure.
Fig. 5 is 1615 cm in the embodiment of the present invention 2-1With 1064 cm-1Relative intensity and molecular solution log concentration
Graph of a relation.
Specific embodiment
Embodiment 1
1st, the preparation of Au monofilm and transfer
The present embodiment presses the apparatus and method of Chinese invention patent CN103590037B offer, first in the gold containing golden nanometer particle
The gas-liquid interface preparation Gold nanoparticle monofilm of colloidal sol, then with vertical czochralski method, Gold nanoparticle monofilm is transferred to solid
In phase substrate, comprise the following steps that：
（1）The preparation of Au film of nanoparticles：100 mL are added in three-neck flask（0.25 mmol·dm-3）Chlorauric acid solution, plus
Heat, to boiling, adds 2 mL（0.01 g·mL-1）Sodium citrate solution, keeps boiling 15 min, obtains 15 nm aurosols.Take this
Colloidal sol 25 mL, is separately added into 1 mL（0.01 g·mL）Sodium citrate solution, 1 mL（0.01 g·mL）PVP solution and 20 mL
（2.5 mmol·dm-3）Hydroxylamine hydrochloride solution；Stirring is lower to use syringe pump with 1 mL min-1Speed dropping（2.5 mmol·
dm-3）Chlorauric acid solution 20 mL, obtain 50 nm aurosols.This colloidal sol is placed 10 h at 40 DEG C, can be observed to float
In gas-liquid interface, the Gold nanoparticle monofilm of fine and close light.
（2）The transfer of Au film of nanoparticles：Clean silicon wafer using 0.4 cm × 0.4 cm is inserted perpendicularly into gas-liquid interface, so
Slowly vertically lift afterwards, you can Gold nanoparticle monofilm is attached to silicon chip surface, gradually leave gas-liquid interface with silicon chip,
Full wafer silicon chip surface can be covered upper golden film.
2nd, the modification of internal standard molecule
The silicon chip being coated with golden film obtained by the method that is prepared as described above is immersed in the ethanol solution of Isosorbide-5-Nitrae-BDT, forms 1,
The monocrystalline silicon piece that the Au nano particle single layer film that 4-BDT modifies covers.
3rd, secondary transferring Au film of nanoparticles
After step 2 modifies Isosorbide-5-Nitrae-BDT, adopt and step 1 identical czochralski method, attached last layer golden film again, form two-layer gold
Film sandwiches " sandwich " structure of 1,4-BDT.
4th, vacuum thermal evaporation isolation oxide layer
Being deposited with last layer thickness using " sandwich " body structure surface that hot evaporation instrument prepares in step 3 is the three of 2～4 nm
Molybdenum oxide layer, physically can directly completely cut off inside and outside two kinds of molecules it may happen that competitive Adsorption, thus ensureing internal standard molecule
Stability.So far, composite nano structure Raman strengthens substrate preparation and completes.
5th, the SERS detection of internal standard molecule
SERS detection is carried out to the above-mentioned substrate being not added with detected molecule, the signal of internal standard Isosorbide-5-Nitrae-BDT can be obtained.Referring to accompanying drawing
1, it is the SERS spectra figure that composite nano structure Raman strengthens internal standard molecule Isosorbide-5-Nitrae-BDT in substrate, molecule assembling concentration is 10-3
mol·dm-3；As shown in figure 1, being located at 1064 cm-1The breathing vibration for phenyl ring at place, in the present embodiment, will be as feature
Peak, is compared with the characteristic peak of tested molecule.
6th, the SERS detection of 1,4-BDMT and the foundation of calibration curve
The present embodiment provides the method for building up of a kind of detection to Isosorbide-5-Nitrae-BDMT and calibration curve, and step is as follows：
（1）Prepare the 1,4-BDMT solution of variable concentrations：Weigh 0.017 gram of Isosorbide-5-Nitrae-BDMT, plus ethanol 10 mL dissolving, formed
Concentration is 10-2mol·dm-3Ethanol solution.Take out 1 mL from above-mentioned 10 mL solution, be diluted to 10 mL, shape with ethanol
Become 10-3mol·dm-3Ethanol solution.From 10 mL 10-3mol·dm-3Ethanol solution in draw 1 mL, diluted with ethanol
To 10 mL, form 10-4mol·dm-3Ethanol solution.From 10 mL 10-4mol·dm-3Ethanol solution in draw 1
ML, is diluted to 10 mL with ethanol, forms 10-5mol·dm-3Ethanol solution.From 10 mL 10-5mol·dm-3Ethanol
Draw 1 mL in solution, be diluted to 10 mL with ethanol, form 10-6mol·dm-3The aqueous solution.From 10 mL 10-6mol·
dm-3Ethanol solution in draw 1 mL, be diluted to 10 mL with ethanol, form 10-7mol·dm-3Ethanol solution.
（2）The composite substrate being provided using the present embodiment, by the Isosorbide-5-Nitrae-BDMT solution concentration of the various concentration of above-mentioned preparation
Adsorb successively from low to high, then carry out SERS detection respectively, obtain variable concentrations Isosorbide-5-Nitrae-BDMT solution in this composite substrate
SERS spectra, referring to accompanying drawing 2, is the mixing SERS spectra figure of internal standard Isosorbide-5-Nitrae-BDT and variable concentrations tested molecule Isosorbide-5-Nitrae-BDMT, figure
Middle curve（a）~（e）Correspond to the variable concentrations of 1,4-BDMT respectively：（a）For 10-6mol·dm-3、（b）For 10-5mol·
dm-3、（c）For 10-4mol·dm-3、（d）For 10-2mol·dm-3With（e）For 10-2mol·dm-3.Due to 10-7mol·dm-3Isosorbide-5-Nitrae-BDMT ethanol solution in the characteristic signal of this molecule cannot be detected, therefore, in Fig. 2, do not comprise below this concentration
Spectrum；Wherein, positioned at 1603 cm-1For the carbon carbon stretching vibration peak of Isosorbide-5-Nitrae-BDMT molecule phenyl ring, by 1064 cm of Isosorbide-5-Nitrae-BDT-1
1603 cm with 1,4-BDMT-1Compare, establish the pass between the logarithm of Isosorbide-5-Nitrae-BDMT concentration and two characteristic peak relative intensities
System, referring to accompanying drawing 3, Isosorbide-5-Nitrae-BDMT is 10-6～10-3mol·dm-3In the range of, the size of its characteristic peak relative intensity and concentration
Logarithm linear.
Embodiment 2
1st, the preparation of Au monofilm and transfer
（1）The preparation of Au film of nanoparticles：100 mL are added in three-neck flask（0.25 mmol·dm-3）Chlorauric acid solution, plus
Heat, to boiling, adds 2 mL（0.01 g·mL-1）Sodium citrate solution, keeps boiling 15 min, obtains 15 nm aurosols.Take this
Colloidal sol 25 mL, is separately added into 1 mL（0.01 g·mL）Sodium citrate solution, 1 mL（0.01 g·mL）PVP solution and 20 mL
（2.5 mmol·dm-3）Hydroxylamine hydrochloride solution；Stirring is lower to use syringe pump with 1 mL min-1Speed dropping（2.5 mmol·
dm-3）Chlorauric acid solution 20 mL, obtain 50 nm aurosols.This colloidal sol is placed 10 h at 40 DEG C, can be observed to float
In gas-liquid interface, the Gold nanoparticle monofilm of fine and close light.
（2）The transfer of Au film of nanoparticles：Clean silicon wafer using 0.4 cm × 0.4 cm is inserted perpendicularly into gas-liquid interface, so
Slowly vertically lift afterwards, you can Gold nanoparticle monofilm is attached to silicon chip surface, gradually leave gas-liquid interface with silicon chip,
Full wafer silicon chip surface can be covered upper golden film.
2nd, the modification of internal standard molecule
The silicon chip being coated with golden film obtained by step 1 is immersed in the ethanol solution of Isosorbide-5-Nitrae-BDT, forms Isosorbide-5-Nitrae-BDT and modify
Au nano particle single layer film cover monocrystalline silicon piece.
3rd, secondary transferring Au film of nanoparticles
After the completion of step 2 modifies Isosorbide-5-Nitrae-BDT, using identical czochralski method in step 1, attached last layer golden film again, form two
Layer golden film sandwiches " sandwich " structure of 1,4-BDT.
4th, vacuum thermal evaporation isolation oxide layer
Using the molybdenum trioxide layer of " sandwich " body structure surface evaporation last layer 2～4 nm in step 3 for the hot evaporation instrument, can be from thing
In reason directly completely cut off inside and outside two kinds of molecules it may happen that competitive Adsorption, thus ensureing the stability of internal standard molecule.So far, it is combined
Type nanostructured Raman strengthens substrate preparation to be completed.
5th, the SERS detection of internal standard molecule
The substrate that the method for being prepared as described above is obtained carries out SERS detection under conditions of being not added with detected molecule, can obtain interior
The signal of mark Isosorbide-5-Nitrae-BDT, as shown in Figure 1, positioned at 1064 cm-1The breathing vibration for phenyl ring at place, the present embodiment will be as
Characteristic peak, is compared with the characteristic peak of tested molecule.
6th, the SERS detection of MG and the foundation of calibration curve
The present embodiment provides the method for building up of a kind of detection to MG and calibration curve, and step is as follows：
（1）The preparation of variable concentrations MG molecular solution：Weigh 0.0365 gram of MG, add water 10 mL dissolvings, and forming concentration is 10-2
mol·dm-3The aqueous solution.Take out 10 μ L from above-mentioned 10 mL solution, be diluted with water to 10 mL, form 10-5mol·dm-3The aqueous solution.From 10 mL 10-5mol·dm-3The aqueous solution in draw 1 mL, be diluted with water to 10 mL, form 10-6
mol•dm-3The aqueous solution.From 10 mL 10-6mol•dm-3The aqueous solution in draw 1 mL, be diluted with water to 10 mL, formed
10-7mol·dm-3The aqueous solution.From 10 mL 10-7mol·dm-3The aqueous solution in draw 1 mL, be diluted with water to 10 mL,
Form 10-8mol·dm-3The aqueous solution.From 10 mL 10-8mol·dm-3The aqueous solution in draw 1 mL, be diluted with water to 10
ML, forms 10-9mol·dm-3The aqueous solution.
According to GB GB/T 19857-2005《Aquatic products Malachite Green and the mensure of crystal violet residual quantity》, its requirement
Detectable concentration be 1 ppb, and through concentration conversion, 10-9mol·dm-3For 0.364 ppb, already below GB, therefore join
System 10-9mol·dm-3For minimum cut-off concentration.
（2）Using this composite substrate, the MG solution concentration of the various concentration of above-mentioned preparation is adsorbed from low to high successively, so
Carry out SERS detection afterwards respectively, obtain variable concentrations MG solution SERS spectra in this composite substrate, referring to accompanying drawing 4, in figure, song
Line（a）~（e）It is respectively variable concentrations, correspond to（a）10-9mol·dm-3、（b）10-8mol·dm-3、（c）10-7mol·
dm-3、（d）10-6mol·dm-3With（e）10-5mol·dm-3.Wherein, positioned at 1615 cm-1For MG molecular carbon carbon stretching vibration
Peak, by 1064 cm of Isosorbide-5-Nitrae-BDT-11615 cm with MG-1Compare, establish MG log concentration relatively strong with two characteristic peaks
Relation between degree, referring to accompanying drawing 5, MG is 10-9～10-6mol·dm-3In the range of, the size of its characteristic peak relative intensity with
Log concentration is linear.
Claims (5)
1. a kind of composite nano structure Raman strengthens the preparation method of substrate, in the gas-liquid of the aurosol containing golden nanometer particle
Interface preparation Gold nanoparticle monofilm is it is characterised in that carry out the operation of following steps again：
(1) using vertical czochralski method, Gold nanoparticle monofilm is transferred on monocrystalline silicon piece, covers on the surface of monocrystalline silicon piece
Au nano particle single layer film；
(2) monocrystalline silicon piece covering Au nano particle single layer film is immersed in concentration is 10-2～10-3mol·dm-31,4-
In the ethanol solution of dimercaptobenzene, obtain the cover layer modified by Isosorbide-5-Nitrae-dimercaptobenzene on Au nano particle single layer film surface；
(3) adopt vertical czochralski method, the surface of the monocrystalline silicon piece that step (2) is obtained covers layer of Au nano particle single layer again
Film, forms with Isosorbide-5-Nitrae-dimercaptobenzene monofilm as intermediate layer, inside and outside layer is the list of " sandwich " structural modification of Au monofilm
Crystal silicon chip；
(4) three oxygen that a layer thickness is 2～4 nm are deposited with " sandwich " body structure surface of step (3) using vacuum thermal evaporation instrument
Change molybdenum layer, obtain a kind of composite nano structure Raman and strengthen substrate.
2. strengthen substrate by a kind of composite nano structure Raman that claim 1 preparation method obtains.
3. composite nano structure Raman described in claim 2 strengthen substrate application it is characterised in that：With 1,4- diphenyl disulfide
Alcohol is internal standard compound, and its Raman signal is used for demarcating the concentration of testing molecule, and substrate is used for the quantitative determination to testing molecule.
4. composite nano structure Raman according to claim 3 strengthen substrate application it is characterised in that：Set up 1,4-
Benzene dimethanethiol concentration is from 10-6～10-3mol·dm-3Log concentration-signal relative intensity calibration curve, substrate is used
In the quantitative determination to 1,4- benzene dimethanethiol.
5. composite nano structure Raman according to claim 3 strengthen substrate application it is characterised in that：Set up peacock
Malachite green concentration is from 10-9～10-6mol·dm-3Log concentration-signal relative intensity calibration curve, substrate is used for device to hole
The quantitative determination of sparrow malachite green.
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| CN107598182A (en) * | 2017-07-24 | 2018-01-19 | 西北工业大学 | Gold nano grain molybdenum disulfide gold hypersensitive SERS base materials and preparation method |
| CN109142319A (en) * | 2018-10-31 | 2019-01-04 | 大连民族大学 | A kind of field fast detection method of shellfish aquatic products surface malachite green |
| CN110308136A (en) * | 2019-06-25 | 2019-10-08 | 中国计量大学 | A kind of noble metal and MoO3The preparation method and application of self-assembled material |
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| CN107389655A (en) * | 2017-07-26 | 2017-11-24 | 福州大学 | Method based on Au AgNPs composites detection malachite green |
| CN109142319A (en) * | 2018-10-31 | 2019-01-04 | 大连民族大学 | A kind of field fast detection method of shellfish aquatic products surface malachite green |
| CN111208110A (en) * | 2018-11-22 | 2020-05-29 | 国家纳米科学中心 | Flexible Raman enhanced substrate and preparation method and application thereof |
| CN110308136A (en) * | 2019-06-25 | 2019-10-08 | 中国计量大学 | A kind of noble metal and MoO3The preparation method and application of self-assembled material |
| CN110308136B (en) * | 2019-06-25 | 2021-07-30 | 中国计量大学 | Preparation method and application of noble metal and MoO3 self-assembly material |
| CN112391347A (en) * | 2019-08-13 | 2021-02-23 | 高丽大学校产学协力团 | Magneto-optical composite nanostructures, methods of making same, and methods of detecting, separating, or imaging analytes |
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| CN112391347B (en) * | 2019-08-13 | 2024-02-20 | 高丽大学校产学协力团 | Magneto-optical composite nanostructures, methods of making the same, and methods of detecting, separating, or imaging analytes |
| CN110726710A (en) * | 2019-10-28 | 2020-01-24 | 山东师范大学 | SERS sensor based on Au-Se interface for ultra-sensitive high-fidelity biomolecule quantitative detection |
| CN112285089A (en) * | 2020-09-23 | 2021-01-29 | 嘉兴学院 | Method for introducing internal standard molecules into surface enhanced Raman scattering substrate, substrate prepared by method and application of substrate |
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