CN104502323A - Transparent flexible surface enhanced Raman active substrate and preparation method thereof - Google Patents
Transparent flexible surface enhanced Raman active substrate and preparation method thereof Download PDFInfo
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- CN104502323A CN104502323A CN201410800796.9A CN201410800796A CN104502323A CN 104502323 A CN104502323 A CN 104502323A CN 201410800796 A CN201410800796 A CN 201410800796A CN 104502323 A CN104502323 A CN 104502323A
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Abstract
The invention discloses a transparent flexible surface enhanced Raman active substrate and a preparation method thereof. The preparation method of the substrate comprises the following steps: taking a transparent flexible material such as polybutylene terephthalate (PET) plastics as a substrate, performing O2 plasma etching to form a nano wire array, loading gold, silver and other precious metal nanoparticles on the nano wire surface by virtue of a coating technology, and forming a three-dimensional nanometer structure array. The transparent flexible surface enhanced Raman active substrate provided by the invention is uniform in morphology and controllable in structure and has high-density electromagnetic hot spots in three-dimensional distribution. Therefore, the substrate has high sensitivity and reproducibility. The PET plastic film is high in flexibility and high in transparency, and incident laser and Raman scattered light easily penetrate through the substrate at low loss, so that the substrate can be used for in-situ detection of to-be-detected objects. The preparation method provided by the invention is simple in process, large-area preparation is easily realized, even roll-to-roll production process is permitted, and the cost is low.
Description
Technical field
The present invention relates to a kind of transparent flexible surface reinforced Raman active substrate and preparation method thereof, especially based on the surface reinforced Raman active substrate and preparation method thereof of noble-metal-supported nano wire three-dimensional structure array.
Background technology
Surface enhanced raman spectroscopy (SERS) utilizes the surface enhanced Raman scattering effect of substrate, significantly enhance the detection sensitivity of Raman spectrum, can be provided by the mode of Non-Destructive Testing and analyze the abundant structural information of thing, be used to, in the detection of multiple trace analysis thing, in biological chemistry, environmental chemistry, biophysics and molecular biology etc., have huge application potential.The high sensitivity of SERS depends on the enhancement effect of SERS substrate, is mainly derived from the Electromagnetic enhancement of local in metal nano gap, i.e. electromagnetic hotspot.The electromagnetic intensity of focus decides the enhancer of SERS substrate, namely the average signal participating in the binding molecule of SERS strengthens, and the high density distribution of focus will increase molecule in microcell and is in the probability near focus, thus improve the sensitivity detected, also can improve the homogeneity of basal signal simultaneously.Three-dimensional nano structure array based on noble metal nano particles loaded with nano line (nanometer rods, nano wire) can obtain the electromagnetic hotspot of high density, high strength, is the effective way realizing high-performance SERS substrate.Current most of SERS substrate is all hard and lighttight, generally needs to use solvent from object to be detected surface extractions test substance, and be then added drop-wise in SERS substrate and detect, whole process is complicated and consuming time.Therefore, need a kind of highly sensitive SERS substrate directly can carrying out in situ detection at body surface of development badly, and the key realizing original position quick SERS detection is preparation that is flexible, transparent SERS substrate.
Summary of the invention
An object of the present invention is to provide the substrate of a kind of transparent flexible surface reinforced Raman active.
Two of object of the present invention is the preparation method providing a kind of surface reinforced Raman active substrate.
Three of object of the present invention is to provide a kind of non-transparent flexible substrate that uses to carry out the method for in situ detection to analysis thing.
For achieving the above object, the present invention is by the following technical solutions:
The substrate of a kind of transparent flexible surface reinforced Raman active, is characterized in that this substrate with poly terephthalic acid class plastics (PET) for substrate, passes through O
2plasma etching forms nanowire arrays, then with coating technique at nano wire area load noble metal nano particles.
A kind of method using the substrate of above-mentioned transparent flexible surface reinforced Raman active to carry out in situ detection, it is characterized in that the concrete steps of the method are: directly by described substrate surface and object under test surface contact, incident laser arrives substrate surface from the back side through substrate, Raman enhancement effect is produced in the cubical array of substrate surface, Raman diffused light is collected through substrate again, realizes the in situ detection to determinand.Also can adopt traditional detection mode, be dripped by test analyte solution and detect at substrate surface, incident light is incident from front, and scattered light is also collected from front.
Prepare a method for above-mentioned transparent flexible surface reinforced Raman active substrate, it is characterized in that the concrete steps of the method are:
utilize O
2plasma etching PET substrate obtains nanowire arrays;
adopt coating technique at PET nanowire arrays area load noble metal nano particles.
The concrete steps of the nano wire described in preparation are: by certain size, PET film that thickness is about 200 μm is flat in plasma chamber substrate disc, substrate disc water-cooled.Through forvacuum, then pass into high-purity O
2, flow velocity 20-100 sccm, controls cavity air pressure and is less than 10 Pa.Open radio-frequency power supply and start etching, radio-frequency power is 100-200W, etching time 5-20 min, produces nanowire arrays in pet sheet face.Nanowire arrays also can pass through O
2the thin polymer film (as polymetylmethacrylate etc.) of other transparent flexible of plasma etching obtains.
The concrete steps of above-mentioned noble metal nano particles load are: by the PET film transfer after plasma etching in plated film chamber, adopt thermal evaporation or magnetron sputtering or ion sputtering at noble metals such as PET nano wire surface deposition gold or silver, nominal thickness is 10-50 nm, noble metal on nano wire top, nano particle is formed on sidewall and bottom, forms three-dimensional structure SERS substrate.
Advantage of the present invention and effect are: the present invention compared with prior art, has the following advantages:
1) the surface reinforced Raman active substrate pattern prepared of method provided by the invention is homogeneous, and structure-controllable, can realize the high density electromagnetic hotspot of distributed in three dimensions, have high sensitivity and reappearance;
2) the present invention adopts poly terephthalic acid class plastic sheeting (PET) to be substrate, and pliability is good, and transparency is high, and incident laser and Raman diffused light are easy to pass substrate with lower loss, realize the in situ detection to determinand;
3) preparation method's technique provided by the invention is simple, is easy to realize large area preparation, even allows the production run of reel-to-reel, with low cost.
Accompanying drawing explanation
Accompanying drawing 1 is the stereoscan photograph of transparent flexible surface reinforced Raman active of the present invention substrate, and illustration is high resolution scanning electromicroscopic photograph.
Accompanying drawing 2 is concentration 1 × 10
-4the Surface enhanced raman spectroscopy that the rhodamine (R6G) of M is probe molecule, wherein curve a is the spectral line that conventional sense mode obtains, and curve b is the spectral line that in-situ detection method obtains, and illustration is the schematic diagram of two kinds of detection modes.
Embodiment
Embodiment one: the present embodiment is that substrate prepares nanowire arrays with PET, then with coating technique at nano wire area load Ag nano particle, and with 1 × 10
-4the rhodamine (R6G) of M is as probe molecule, and carry out the test of Surface enhanced raman spectroscopy, detailed process is as follows:
1) preparation of nanowire arrays: by certain size, PET film that thickness is about 200 μm is flat in plasma chamber substrate disc, substrate disc water-cooled.Through forvacuum, then pass into high-purity O
2, flow velocity 20 – 100 sccm, controls cavity air pressure and is less than 10 Pa.Open radio-frequency power supply and start etching, radio-frequency power is 100 – 200W, etching time 5 – 20 min, produces nanowire arrays in pet sheet face;
2) Ag nano particle load: by the PET film transfer after plasma etching to hot evaporation chamber, forvacuum to 10
-5pa, opens evaporation power supply, slow making alive to 18 V, and electric current about 11 A, after temperature stabilization, opens baffle plate and start evaporation, evaporation rate about 0.1 nm/s, and the nominal thickness of evaporation silver is 10 – 30 nm.As shown in Figure 1, Ag forms equally distributed nano particle in nano wire top, sidewall and bottom, forms the surface reinforced Raman active substrate of three-dimensional structure;
3) surface reinforced Raman active substrate is for analyzing the detection of thing: with 1 × 10
-4the rhodamine (R6G) of M, as probe molecule, carries out Surface Raman Spectra test to the nanowire arrays three-dimensional structure surface reinforced Raman active substrate of the Ag load of preparation.Adopt LabRAM HR laser capture microdissection Raman spectrometer, 100 times of object lens, with 514 nm laser excitations, incident power is 50 μ W.Laser is incident from the pro and con of substrate respectively.In Fig. 2, curve a is the incident Raman spectrum obtained with collection (i.e. conventional sense mode) in front, shows that substrate of the present invention has high Raman active and sensitivity; Curve b is the Raman spectrum that incident and collection (i.e. in situ detection mode) from the negative obtains, although the signal caused due to the absorption of substrate to incident light and scattered light is relatively weak, but the fingerprint peaks of R6G is clear and legible, confirm that this substrate can be used for carrying out in situ detection to determinand.
Claims (5)
1. a transparent flexible surface reinforced Raman active substrate, is characterized in that this substrate with poly terephthalic acid class plastics (PET) for substrate, passes through O
2plasma etching forms nanowire arrays, then with coating technique at nano wire area load noble metal nano particles.
2. the method using the transparent flexible surface reinforced Raman active substrate described in claim 1 to carry out in situ detection, it is characterized in that described detection concrete steps are: directly by described substrate surface and object under test surface contact, incident laser arrives substrate surface from the back side through substrate, Raman enhancement effect is produced in the cubical array of substrate surface, Raman diffused light is collected through substrate again, realizes the in situ detection to determinand; Also can adopt traditional detection mode, be dripped by test analyte solution and detect at substrate surface, incident light is incident from front, and scattered light is also collected from front.
3. prepare a method for transparent flexible surface reinforced Raman active according to claim 1 substrate, it is characterized in that the concrete steps of the method are:
utilize O
2plasma etching PET substrate obtains nanowire arrays;
adopt coating technique at nanowire arrays area load Ag nano particle.
4. method according to claim 3, is characterized in that the concrete steps of nano wire described in preparing are: by certain size, PET film that thickness is about 200 μm is flat in plasma chamber substrate disc, substrate disc water-cooled; Through forvacuum, then pass into high-purity O
2, flow velocity 20-100 sccm, controls cavity air pressure and is less than 10 Pa; Open radio-frequency power supply and start etching, radio-frequency power is 100-200W, etching time 5-20 min, produces nanowire arrays in pet sheet face; Nanowire arrays also can pass through O
2the thin polymer film (as polymetylmethacrylate etc.) of other transparent flexible of plasma etching obtains.
5. according to method according to claim 3, it is characterized in that the concrete steps of described noble metal nano particles load are: by the PET film transfer after plasma etching in plated film chamber, adopt thermal evaporation or magnetron sputtering or ion sputtering at noble metals such as PET nano wire surface deposition gold or silver, nominal thickness is 10-30 nm, noble metal on nano wire top, nano particle is formed on sidewall and bottom, forms the surface reinforced Raman active substrate of three-dimensional structure.
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104730062A (en) * | 2015-04-16 | 2015-06-24 | 苏州大学 | Transparent flexible surface-enhanced Roman spectroscopy substrate (SERS) and preparation method and application thereof |
| CN104849259A (en) * | 2015-06-05 | 2015-08-19 | 中物院成都科学技术发展中心 | Preparation method of flexible surface enhanced Raman substrate |
| CN105129724A (en) * | 2015-08-11 | 2015-12-09 | 中国科学院电子学研究所 | Manufacturing method of surface-enhanced Raman scattering (SERS) substrate |
| CN105548141A (en) * | 2016-01-22 | 2016-05-04 | 中国科学院城市环境研究所 | Method for online monitoring of pollutants in water |
| CN105675579A (en) * | 2016-01-15 | 2016-06-15 | 中国科学院合肥物质科学研究院 | Silver cubic nanoparticle-polyethylene flexible transparent film as well as preparation method and application thereof |
| CN106884146A (en) * | 2017-01-17 | 2017-06-23 | 大连民族大学 | A kind of micro-content organism remains highly sensitive surface-enhanced Raman detection substrate and preparation and application |
| CN107290331A (en) * | 2017-06-08 | 2017-10-24 | 北京航空航天大学 | A kind of hydrophobicity composite high-molecular film is used for the method for Raman detection |
| CN108226130A (en) * | 2017-12-28 | 2018-06-29 | 浙江大学 | For the soft light Meta Materials laminated film and method of nitrite detection |
| CN108760714A (en) * | 2018-03-05 | 2018-11-06 | 华南理工大学 | The method that noble metal quenching fluorescence is used in Raman spectrum |
| CN109470675A (en) * | 2017-09-08 | 2019-03-15 | 清华大学 | The preparation method of molecular vehicle |
| CN109470677A (en) * | 2017-09-08 | 2019-03-15 | 清华大学 | Molecular detector arrangement |
| CN109470678A (en) * | 2017-09-08 | 2019-03-15 | 清华大学 | The method of Molecular Detection |
| CN109490277A (en) * | 2018-11-08 | 2019-03-19 | 莆田学院 | A kind of surface plasma body resonant vibration fexible film and preparation method thereof |
| CN110082341A (en) * | 2019-05-30 | 2019-08-02 | 合肥工业大学 | SERS substrate preparation based on nanosphere etching and its application in explosive TNT detection |
| CN110314830A (en) * | 2019-07-09 | 2019-10-11 | 山东大学 | Flexible surface based on single layer ordered nano array of particles enhances Raman scattering substrate |
| CN110320198A (en) * | 2019-07-05 | 2019-10-11 | 重庆大学 | A kind of array SERS substrate of integrated convex lens and preparation method thereof |
| CN110426385A (en) * | 2019-08-14 | 2019-11-08 | 山东师范大学 | A kind of flexible surface enhancing Raman substrate and preparation method and application |
| CN110658173A (en) * | 2018-06-28 | 2020-01-07 | 宁波山功新材料科技有限公司 | Recyclable flexible surface enhanced Raman substrate and preparation method thereof |
| CN111024674A (en) * | 2019-11-08 | 2020-04-17 | 南通大学 | Manufacturing method of novel pure flexible three-dimensional PDMS surface Raman enhanced substrate |
| CN111122633A (en) * | 2019-12-25 | 2020-05-08 | 同济大学 | Method for identifying solid surface nano plastic particles in situ based on scanning electron microscope-Raman technology |
| CN111366571A (en) * | 2020-03-12 | 2020-07-03 | 华东师范大学 | CsPbBr 3-Au-based flexible photoinduced enhanced Raman sensor and preparation and application thereof |
| CN113419400A (en) * | 2021-05-31 | 2021-09-21 | 西安电子科技大学 | Plasma flexible transparent film based on nanoimprint lithography and preparation method thereof |
| CN114199854A (en) * | 2021-12-15 | 2022-03-18 | 曲阜师范大学 | Preparation method of SERS substrate constructed by flexible transparent cone ordered array |
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Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104730062A (en) * | 2015-04-16 | 2015-06-24 | 苏州大学 | Transparent flexible surface-enhanced Roman spectroscopy substrate (SERS) and preparation method and application thereof |
| CN104849259A (en) * | 2015-06-05 | 2015-08-19 | 中物院成都科学技术发展中心 | Preparation method of flexible surface enhanced Raman substrate |
| CN104849259B (en) * | 2015-06-05 | 2018-02-23 | 中物院成都科学技术发展中心 | A kind of preparation method of flexible surface enhancing Raman substrate |
| CN105129724A (en) * | 2015-08-11 | 2015-12-09 | 中国科学院电子学研究所 | Manufacturing method of surface-enhanced Raman scattering (SERS) substrate |
| CN105675579A (en) * | 2016-01-15 | 2016-06-15 | 中国科学院合肥物质科学研究院 | Silver cubic nanoparticle-polyethylene flexible transparent film as well as preparation method and application thereof |
| CN105675579B (en) * | 2016-01-15 | 2018-05-29 | 中国科学院合肥物质科学研究院 | Silver-colored cubic nanometer particle-polyethylene flexible transparent film and its preparation method and application |
| CN105548141A (en) * | 2016-01-22 | 2016-05-04 | 中国科学院城市环境研究所 | Method for online monitoring of pollutants in water |
| CN106884146B (en) * | 2017-01-17 | 2019-01-11 | 大连民族大学 | A kind of highly sensitive surface-enhanced Raman of micro-content organism residual detects substrate and preparation and application |
| CN106884146A (en) * | 2017-01-17 | 2017-06-23 | 大连民族大学 | A kind of micro-content organism remains highly sensitive surface-enhanced Raman detection substrate and preparation and application |
| CN107290331A (en) * | 2017-06-08 | 2017-10-24 | 北京航空航天大学 | A kind of hydrophobicity composite high-molecular film is used for the method for Raman detection |
| CN109470678A (en) * | 2017-09-08 | 2019-03-15 | 清华大学 | The method of Molecular Detection |
| CN109470675A (en) * | 2017-09-08 | 2019-03-15 | 清华大学 | The preparation method of molecular vehicle |
| CN109470677A (en) * | 2017-09-08 | 2019-03-15 | 清华大学 | Molecular detector arrangement |
| CN109470675B (en) * | 2017-09-08 | 2024-04-02 | 清华大学 | Preparation method of molecular carrier |
| CN108226130A (en) * | 2017-12-28 | 2018-06-29 | 浙江大学 | For the soft light Meta Materials laminated film and method of nitrite detection |
| CN108760714A (en) * | 2018-03-05 | 2018-11-06 | 华南理工大学 | The method that noble metal quenching fluorescence is used in Raman spectrum |
| CN110658173A (en) * | 2018-06-28 | 2020-01-07 | 宁波山功新材料科技有限公司 | Recyclable flexible surface enhanced Raman substrate and preparation method thereof |
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| CN109490277B (en) * | 2018-11-08 | 2021-12-07 | 莆田学院 | Surface plasma resonance flexible film and preparation method thereof |
| CN110082341B (en) * | 2019-05-30 | 2021-09-28 | 合肥工业大学 | Preparation of SERS substrate based on nanosphere etching and application of SERS substrate in explosive TNT detection |
| CN110082341A (en) * | 2019-05-30 | 2019-08-02 | 合肥工业大学 | SERS substrate preparation based on nanosphere etching and its application in explosive TNT detection |
| CN110320198A (en) * | 2019-07-05 | 2019-10-11 | 重庆大学 | A kind of array SERS substrate of integrated convex lens and preparation method thereof |
| CN110314830A (en) * | 2019-07-09 | 2019-10-11 | 山东大学 | Flexible surface based on single layer ordered nano array of particles enhances Raman scattering substrate |
| CN110426385A (en) * | 2019-08-14 | 2019-11-08 | 山东师范大学 | A kind of flexible surface enhancing Raman substrate and preparation method and application |
| CN111024674A (en) * | 2019-11-08 | 2020-04-17 | 南通大学 | Manufacturing method of novel pure flexible three-dimensional PDMS surface Raman enhanced substrate |
| CN111122633A (en) * | 2019-12-25 | 2020-05-08 | 同济大学 | Method for identifying solid surface nano plastic particles in situ based on scanning electron microscope-Raman technology |
| CN111366571A (en) * | 2020-03-12 | 2020-07-03 | 华东师范大学 | CsPbBr 3-Au-based flexible photoinduced enhanced Raman sensor and preparation and application thereof |
| CN113419400A (en) * | 2021-05-31 | 2021-09-21 | 西安电子科技大学 | Plasma flexible transparent film based on nanoimprint lithography and preparation method thereof |
| CN114199854A (en) * | 2021-12-15 | 2022-03-18 | 曲阜师范大学 | Preparation method of SERS substrate constructed by flexible transparent cone ordered array |
| CN114199854B (en) * | 2021-12-15 | 2024-01-12 | 曲阜师范大学 | Preparation method of SERS substrate constructed by flexible transparent cone ordered array |
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Application publication date: 20150408 |