CN107037027A - A kind of wide area surface strengthens the preparation method of Raman scattering substrate - Google Patents
A kind of wide area surface strengthens the preparation method of Raman scattering substrate Download PDFInfo
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- CN107037027A CN107037027A CN201611008376.2A CN201611008376A CN107037027A CN 107037027 A CN107037027 A CN 107037027A CN 201611008376 A CN201611008376 A CN 201611008376A CN 107037027 A CN107037027 A CN 107037027A
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- 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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Abstract
A kind of wide area surface strengthens the preparation method of Raman scattering substrate, it is characterised in that：With polystyrene and polymethyl methacrylate mixed film in butanone/acetone/water（Volume ratio is 7/3/15）In the mixed solvent wetting removal prepare particle diameter for 78 nanometers, spacing is 80 nanometers, equally distributed high molecular nanometer structure, using high molecular nanometer structure as substrate, the surface enhanced Raman scattering substrate that area reaches 3.5cm × 3.5cm is prepared by vertically sputtering 30 nano-silver layers.The present invention is combined using macromolecule mixed film wetting removal in solvent and magnetron sputtering evaporation coating method prepare wide area surface enhancing Raman scattering substrate first, not only enrich surface enhanced Raman scattering substrate preparation method, an application approach is provided for macromolecule mixed film wetting removal, and it is simple to operate, reproducible, with potential economic and social benefit.
Description
Technical field
The present invention relates to Nanosurface and its preparing technical field, particularly a kind of wide area surface enhancing Raman scattering base
The preparation method at bottom.
Background technology
Raman spectrum is as an important modern spectral technique, and it has been widely applied to chemistry, biology, mineral
The multiple fields such as, materialogy, environmental science and archaeology.As research molecular structure, environmental pollution analyte detection, biomolecule
Detection and the important tool of material microstructure research.
Sent out from British scientist Fleischmann in 1974 et al. on the Ag electrodes of the micro nano structure of electrochemical roughening
The intensity of spectral line of existing Pyridine Molecules Raman spectrum, which has, significantly to be strengthened.This phenomenon causes the broad interest of scientific circles, and handle
This phenomenon is named as SERS, abbreviation SERS.SERS mainly originates from metal surface
Roughening is conducive to electromagnetic wave in metal surface excitating surface plasma resonance so that the electric-field intensity of metal surface is carried significantly
It is high.So, the molecule close to metal surface is excited by the electric field that greatly strengthen and generates strong Raman scattering.It can be by
Adsorb the Raman signal amplification about 10 in the molecule of material surface6Times.This causes its application and Single Molecule Detection in detector
Aspect has huge development potentiality.Therefore SERS technology be widely used to analytical chemistry, molecule sensing,
Numerous science such as molecular biology, Food Science, environmental science and industrial circle.
On the research of SERS technology, scientist is directed to researching and developing a kind of simple effective method always
To prepare large area efficient surface enhancing Raman scattering substrate.In in the past few decades.Electromagnetism around metal Nano structure
Field can be strengthened by localized surface plasmons resonance, particularly noble metal nano structure.The size and nanometer of nanostructured
Interstructural spacing influences the property of SERS substrates strongly.Although some nanoprocessing method such as nano impressions and electronics or from
Beamlet photoetching technique, has successfully prepared the SERS substrates with good nature.However, these methods are costly, take
And it is unable to large area preparation.These shortcomings limit the extensive use of these methods.
And we have developed one kind, macromolecule mixed film wetting removal combination magnetron sputtering is deposited in solvent in this patent
Method strengthens Raman scattering substrate to prepare large area efficient surface.Have no document report at present.
We utilize macromolecule mixed film wetting removal in unconventional wetting removal technology-solvent to this patent first, to make
The homogeneous nanostructured of back-up cloth；Then one layer of silverskin is simply sputtered on the nanostructure to prepare the efficient SERS bases of large area
Bottom.
The content of the invention
The present invention, which provides a kind of wide area surface, strengthens the preparation method of Raman scattering substrate, to achieve these goals,
The present invention provides one kind macromolecule mixed film wetting removal combination magnetron sputtering evaporation coating method in solvent and prepares wide area surface
Strengthen the method for Raman scattering substrate.Adopted the technical scheme that：
A. spin-coating method is utilized, polystyrene and polymethyl methacrylate monofilm and their mixed film is prepared.
Solution concentration：（2mg/ml）
Rotary rpm：4000 rpm
Solid substrate：Except the monocrystalline silicon piece of oxide layer
B. with polystyrene and polymethyl methacrylate mixed film in butanone/acetone/water（Volume ratio is 7/3/15）It is mixed
Wetting removal prepares equally distributed high molecular nanometer structure in bonding solvent.
Macromolecule thickness：8 nm
C. using high molecular nanometer structure as substrate, the surface increasing that area reaches 3.5cm × 3.5cm is prepared by vertically sputtering silver layer
Strong Raman scattering substrate.
Area of base：3.5cm×3.5cm
Silver thickness：20 nm
D. organic dyestuff weak solution is added drop-wise in the substrate prepared in c, after natural drying, tests Raman spectrum.
Organic dyestuff：R6G, CV and ATP
Organic dyestuff concentration：10-6 -10-8mol/l
The composition of the present invention：A kind of wide area surface strengthens the preparation method of Raman scattering substrate, it is characterised in that：With polyphenyl second
Alkene and polymethyl methacrylate mixed film come in butanone/acetone/water volume ratio for 7/3/15 in the mixed solvent wetting removal
It is 78 nanometers to prepare particle diameter, and spacing is 80 nanometers, equally distributed high molecular nanometer structure, using high molecular nanometer structure as base
Bottom, the surface enhanced Raman scattering substrate that area reaches 3.5cm × 3.5cm is prepared by vertically sputtering 30 nano-silver layers.
Beneficial effects of the present invention：The present invention is deposited using macromolecule mixed film wetting removal combination magnetron sputtering in solvent
Method prepares wide area surface enhancing Raman scattering substrate, and SERS substrates prepared by this method have higher surface-enhanced Raman
Scattering effect, area is big, reproducible, and substrate stability is high, and cost is low, simple operation and other advantages.
Brief description of the drawings
Fig. 1 is present invention process flow chart,
Fig. 2 is that three kinds of different dyes concentration are 10-6Mol/l is in silver-plated smooth silicon base and Raman produced herein enhancing substrate
On Raman spectrum.
Embodiment
Embodiment 1：A kind of wide area surface strengthens the preparation method of Raman scattering substrate, can utilize simple method system
Standby SERS areas of base can reach 3.5cm × 3.5cm,.Specific method comprises the following steps：
1）Polystyrene powder（48 kg/mol, decentralization is 1.02）Toluene is dissolved in, 2mg/ml mixed solution is configured.Use glass
Glass knife cuts into circular single crystal silicon chip the square silicon wafer of 3.5cm × 3.5cm sizes；Silicon chip after cutting is placed in by 80%
H2SO4、30% H2O2In the cleaning fluid for the certain volume being made into deionized water by 100/35/15 volume ratio, at 80 DEG C
Boil 30 minutes；Then, rinsed well, be put into plastic beaker with deionized water, add 20% hydrofluoric acid and deionized water mixing
Solution, volume ratio is 1：1；The oxide layer in silicon base is removed with hydrofluoric acid；Finally, rinsed well with deionized water, with high-purity
Nitrogen drying is standby.
Silicon chip is placed on desk-top sol evenning machine, the mixing macromolecule toluene solution configured is dripped on silicon chip, spin-coated thin film
Sample.
Solution concentration：2mg/ml
Rotary rpm：4000 rpm
Solid substrate：Except the monocrystalline silicon piece of oxide layer
2）Obtained film sample is placed in vacuum drying chamber, kept in a vacuum at least 12 hours, to remove residual
Organic solvent；Then film thickness is measured with ellipsometer.
3) in the mixed solvent that macromolecule mixed film is put into butanone/acetone/water is annealed, and volume ratio is 7/3/15, system
The macromolecule surface that standby nanostructured is evenly distributed.
4）In the substrate of nanostructured, one layer of silverskin of sputtering obtains wide area surface enhancing Raman scattering substrate.
Embodiment 2：A kind of wide area surface strengthens the preparation method of Raman scattering substrate, can be prepared using simple method
SERS areas of base can reach 3.5cm × 3.5cm,.Specific method comprises the following steps：
1）Polymethylmethacrylate powder（The kg/mol of molecular weight 50, decentralization is 1.1) to be dissolved in toluene, configuration 2mg/ml's
Mixed solution.Circular single crystal silicon chip is cut into the square silicon wafer of 3.5cm × 3.5cm sizes with glass cutter；After cutting
Silicon chip is placed in by 80% H2SO4、30% H2O2The certain volume being made into deionized water by 100/35/15 volume ratio
In cleaning fluid, boiled at 80 DEG C 30 minutes；Then, rinsed well, be put into plastic beaker with deionized water, add 20% hydrogen
Fluoric acid and deionized water mixed solution, volume ratio is 1：1；The oxide layer in silicon base is removed with hydrofluoric acid；Finally, deionization is used
Water is rinsed well, is dried up with high pure nitrogen standby.
Silicon chip is placed on desk-top sol evenning machine, the mixing macromolecule toluene solution configured is dripped on silicon chip, spin-coated thin film
Sample.
Solution concentration：2mg/ml
Rotary rpm：4000 rpm
Solid substrate：Except the monocrystalline silicon piece of oxide layer
2）Obtained film sample is placed in vacuum drying chamber, kept in a vacuum at least 12 hours, to remove residual
Organic solvent；Then film thickness is measured with ellipsometer.
3) in the mixed solvent that macromolecule mixed film is put into butanone/acetone/water is annealed, and volume ratio is 7/3/15, system
The macromolecule surface that standby nanostructured is evenly distributed.
4）In the substrate of nanostructured, one layer of silverskin of sputtering obtains wide area surface enhancing Raman scattering substrate.
Embodiment 3：A kind of wide area surface strengthens the preparation method of Raman scattering substrate, can be prepared using simple method
SERS areas of base can reach 3.5cm × 3.5cm,.Specific method comprises the following steps：
1）Polymethylmethacrylate powder（1.1) and Polystyrene powder the kg/mol of molecular weight 50, decentralization is（48 kg/
Mol, decentralization is 1.02）In mass ratio 2：8 mixing are dissolved in toluene, configure 2mg/ml mixed solution.With glass cutter by circle
Monocrystalline silicon piece cuts into the square silicon wafer of 3.5cm × 3.5cm sizes；Silicon chip after cutting is placed in by 80% H2SO4、30%
H2O2In the cleaning fluid for the certain volume being made into deionized water by 100/35/15 volume ratio, 30 points are boiled at 80 DEG C
Clock；Then, rinsed well, be put into plastic beaker with deionized water, add 20% hydrofluoric acid and deionized water mixed solution, body
Product is than being 1：1；The oxide layer in silicon base is removed with hydrofluoric acid；Finally, rinsed well, dried up with high pure nitrogen with deionized water
It is standby.
Silicon chip is placed on desk-top sol evenning machine, the mixing macromolecule toluene solution configured is dripped on silicon chip, spin-coated thin film
Sample.
Solution concentration：2mg/ml
Rotary rpm：4000 rpm
Solid substrate：Except the monocrystalline silicon piece of oxide layer
2）Obtained film sample is placed in vacuum drying chamber, kept in a vacuum at least 12 hours, to remove residual
Organic solvent；Then film thickness is measured with ellipsometer.
3) in the mixed solvent that macromolecule mixed film is put into butanone/acetone/water is annealed, and volume ratio is 7/3/15, system
The macromolecule surface that standby nanostructured is evenly distributed.
4）In the substrate of nanostructured, one layer of silverskin of sputtering obtains wide area surface enhancing Raman scattering substrate.
Embodiment 4：A kind of wide area surface strengthens the preparation method of Raman scattering substrate, can be prepared using simple method
SERS areas of base can reach 3.5cm × 3.5cm,.Specific method comprises the following steps：
1）Polymethylmethacrylate powder（1.1) and Polystyrene powder the kg/mol of molecular weight 50, decentralization is（48 kg/
Mol, decentralization is 1.02）In mass ratio 8：2 mixing are dissolved in toluene, configure 2mg/ml mixed solution.With glass cutter by circle
Monocrystalline silicon piece cuts into the square silicon wafer of 3.5cm × 3.5cm sizes；Silicon chip after cutting is placed in by 80% H2SO4、30%
H2O2In the cleaning fluid for the certain volume being made into deionized water by 100/35/15 volume ratio, 30 points are boiled at 80 DEG C
Clock；Then, rinsed well, be put into plastic beaker with deionized water, add 20% hydrofluoric acid and deionized water mixed solution, body
Product is than being 1：1；The oxide layer in silicon base is removed with hydrofluoric acid；Finally, rinsed well, dried up with high pure nitrogen with deionized water
It is standby.
Silicon chip is placed on desk-top sol evenning machine, the mixing macromolecule toluene solution configured is dripped on silicon chip, spin-coated thin film
Sample.
Solution concentration：2mg/ml
Rotary rpm：4000 rpm
Solid substrate：Except the monocrystalline silicon piece of oxide layer
2）Obtained film sample is placed in vacuum drying chamber, kept in a vacuum at least 12 hours, to remove residual
Organic solvent；Then film thickness is measured with ellipsometer.
3) in the mixed solvent that macromolecule mixed film is put into butanone/acetone/water is annealed, and volume ratio is 7/3/15, system
The macromolecule surface that standby nanostructured is evenly distributed.
4）In the substrate of nanostructured, one layer of silverskin of sputtering obtains wide area surface enhancing Raman scattering substrate.
Embodiment 5：A kind of wide area surface strengthens the preparation method of Raman scattering substrate, can be prepared using simple method
SERS areas of base can reach 3.5cm × 3.5cm,.Specific method comprises the following steps：
1）Polymethylmethacrylate powder（1.1) and Polystyrene powder the kg/mol of molecular weight 50, decentralization is（48 kg/
Mol, decentralization is 1.02）In mass ratio 1：1 mixing is dissolved in toluene, configures 2mg/ml mixed solution.With glass cutter by circle
Monocrystalline silicon piece cuts into the square silicon wafer of 3.5cm × 3.5cm sizes；Silicon chip after cutting is placed in by 80% H2SO4、30%
H2O2In the cleaning fluid for the certain volume being made into deionized water by 100/35/15 volume ratio, boiled at 80 DEG C 30 minutes；
Then, rinsed well, be put into plastic beaker with deionized water, add 20% hydrofluoric acid and deionized water mixed solution, volume ratio
For 1：1；The oxide layer in silicon base is removed with hydrofluoric acid；Finally, rinsed well, dried up with high pure nitrogen standby with deionized water
With.
Silicon chip is placed on desk-top sol evenning machine, the mixing macromolecule toluene solution configured is dripped on silicon chip, spin-coated thin film
Sample.
Solution concentration：2mg/ml
Rotary rpm：4000 rpm
Solid substrate：Except the monocrystalline silicon piece of oxide layer
2）Obtained film sample is placed in vacuum drying chamber, kept in a vacuum at least 12 hours, to remove residual
Organic solvent；Then film thickness is measured with ellipsometer.
3) in the mixed solvent that macromolecule mixed film is put into butanone/acetone/water is annealed, and volume ratio is 7/3/15, system
The macromolecule surface that standby nanostructured is evenly distributed.
4）In the substrate of nanostructured, one layer of silverskin of sputtering obtains wide area surface enhancing Raman scattering substrate.Enhancing
The factor reaches 2.5 × 107 。
Claims (1)
1. a kind of wide area surface strengthens the preparation method of Raman scattering substrate, it is characterised in that：With polystyrene and poly- methyl
Methyl acrylate mixed film to prepare particle diameter is in the in the mixed solvent wetting removal that butanone/acetone/water volume ratio is 7/3/15
78 nanometers, spacing is 80 nanometers, equally distributed high molecular nanometer structure, using high molecular nanometer structure as substrate, by vertical
Sputter 30 nano-silver layers and prepare the wide spectrum surface enhanced Raman scattering substrate that area reaches 3.5cm × 3.5cm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109856116A (en) * | 2019-02-28 | 2019-06-07 | 吉林大学 | A kind of classifying nano cone array and preparation method thereof using the chemical reaction of Surface enhanced Raman scattering in-situ monitoring |
| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
| CN111426676A (en) * | 2020-04-21 | 2020-07-17 | 东华大学 | Surface enhanced Raman scattering substrate based on metal nanometer bowl and preparation method thereof |
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| US20150049332A1 (en) * | 2013-07-30 | 2015-02-19 | The Curators Of The University Of Missouri | Gold nanoisland arrays |
| KR20170008045A (en) * | 2015-07-13 | 2017-01-23 | 한국과학기술원 | metal nano islands forming method for surface enhanced Raman spectroscopy using repeated dewetting |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150049332A1 (en) * | 2013-07-30 | 2015-02-19 | The Curators Of The University Of Missouri | Gold nanoisland arrays |
| KR20170008045A (en) * | 2015-07-13 | 2017-01-23 | 한국과학기술원 | metal nano islands forming method for surface enhanced Raman spectroscopy using repeated dewetting |
Non-Patent Citations (2)
| Title |
|---|
| A. M. HIGGINS，R. A. L. JONES: "Anisotropic spinodal dewetting as a route to self-assembly of patterned surfaces", 《NATURE》 * |
| 彭娟，崔亮等: "高分子表面有序微结构的构筑与调控", 《科学通报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
| CN109856116A (en) * | 2019-02-28 | 2019-06-07 | 吉林大学 | A kind of classifying nano cone array and preparation method thereof using the chemical reaction of Surface enhanced Raman scattering in-situ monitoring |
| CN109856116B (en) * | 2019-02-28 | 2021-06-29 | 吉林大学 | Hierarchical nanocone array for in-situ monitoring of chemical reaction by using surface enhanced Raman scattering and preparation method thereof |
| CN111426676A (en) * | 2020-04-21 | 2020-07-17 | 东华大学 | Surface enhanced Raman scattering substrate based on metal nanometer bowl and preparation method thereof |
| CN111426676B (en) * | 2020-04-21 | 2022-03-25 | 东华大学 | Surface enhanced Raman scattering substrate based on metal nanometer bowl and preparation method thereof |
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