CN104515764A - Raman surface-enhanced sensor based on photocatalysis principles - Google Patents
Raman surface-enhanced sensor based on photocatalysis principles Download PDFInfo
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- CN104515764A CN104515764A CN201310467449.4A CN201310467449A CN104515764A CN 104515764 A CN104515764 A CN 104515764A CN 201310467449 A CN201310467449 A CN 201310467449A CN 104515764 A CN104515764 A CN 104515764A
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Abstract
The invention provides a Raman surface-enhanced sensor based on photocatalysis principles during normal usage. Compared with a general Raman surface-enhanced sensor, the Raman surface-enhanced sensor in the present invention allows a micro amount of target molecules to be detected in a liquid sample to be adsorbed and to gather on the surface of the sensor by utilizing photocatalysis technology. The degree of infiltration between the liquid sample and the surface of the sensor is improved, and the Raman surface-enhanced effect is enhanced.
Description
Art
Patent of the present invention relates to the structure that a kind of Raman surface strengthens sensor.Wherein have employed photocatalysis principle, improve the enhancing effect that Raman surface strengthens sensor.
Background technology
Utilize Raman surface enhancement effect can carry out the measurement of trace materials molecular spectrum, it has the potentiality of Single Molecule Detection, and therefore the field such as analyzed chemistry, life science, physics is paid attention to.And the sensor with Raman surface enhancement effect obtains researchist's close attention equally.The colloid adopting the nano particle of the precious metal such as gold or silver to form or the metallic film of nanostructured, under the exciting of laser, the surface plasmon polariton produced in surface of metal particles produces the main cause that Raman surface strengthens effect.There is multiple patent (as publication number: CN101057132A, CN1878875, CN1930475) to be used for describing Raman and strengthen substrate and the substrate using method as sensor.As a kind of sensor, Raman strengthens substrate and the raman spectral signal of micro substance molecule in the liquid be placed on it (solution can be water or other solvent), solid sample can be amplified, thus realizes the measurement of trace materials qualitative, quantitative.But do not infiltrate (such as aqueous solution) because Raman strengthens between the particle of the metal Nano structure of substrate surface and fluid sample, can measurement sensistivity be affected.
It is the surface effect utilizing nano metal material that Raman surface strengthens sensor, on enhancing substrate surface (or in the very near scope in distance surface, this distance general is less than 100nm) Raman spectrum of material molecule, because in fluid sample, measurement of species molecular conecentration is very low, little by the molecular weight on adsorption or distance surface, if there is the nonwettable problem of sample solution again, even if Raman surface strengthens sensor itself and strengthens effect very well, Raman surface also will be caused to strengthen sensor cannot normally play a role.
How being enriched on enhancing sensor surface by molecule to be measured for the trace in fluid sample, overcoming simultaneously or weaken the not Infiltrating between fluid sample and sensor surface, is the problem that this patent solves.
Summary of the invention
A kind of Raman surface of patented invention of the present invention strengthens sensor, and make use of photocatalysis principle when measurement.Compare common Raman surface and strengthen sensor, this sensor is owing to employing photocatalysis technology, the nano-metal particle of micro-target molecule and sensor surface in fluid sample can be caused to produce adsorb, realize target molecule is in the enrichment on metal nanoparticle surface, also can improve the infiltration degree between fluid sample and sensor surface simultaneously, improve Raman surface and strengthen effect.
The technical scheme of patent of the present invention is:
Patent of the present invention proposes the light-catalysed principle of a kind of employing, improves the sensor construction that Raman surface strengthens effect.At Quartz glass surfaces, sputter coating mode or spin coating titania nanoparticles material is adopted to hang solution, form the titanium deoxid film with nanostructured, and on film, adopt the mode of sputter coating or spin coating nano-silver colloid, prepare one deck nano silver film.
When measurement, drip the measurement sample (being generally aqueous solution) of tapping body at sensor surface, and side uses Raman microscope on a sensor, utilizes the mode of backward scattering to carry out raman spectroscopy measurement.Wavelength is adopted to be less than the ultraviolet light of 380nm, titanium deoxid film is irradiated below quartz glass substrate, utilize the Honda-Fijishima effect of titanic oxide material, the internal electron of titanium dioxide semiconductor material is made to enter conduction band from valence band transition, and hole is left in material, under electric field force effect, hole and electronics lay respectively at the surface of titania nanoparticles material, these surface charges and hole, redox reaction can be there is with sample (being generally aqueous solution), namely famous Honda-Fijishima effect, and due to the existence of nano-Ag particles, electronics likely can be imported into metallic particles, partial reduction reaction can occur in surface of metal particles, thus, part in liquid is surperficial in Argent grain with the ionic adsorption of positive electricity, by metal surface plasma polariton resonance principle, obtain Raman enhanced spectrum signal.
In the above process, make use of Honda-Fijishima effect, at TiO
2granular material surface produces electric charge, and conduct on silver metal (or metal) particle, make metallic particles charged, adsorption effect is produced by electric field, the distance of the polarity that furthered sample molecule (or charged sample ions) and metallic particles, and make it to be adsorbed in surface of metal particles, form enrichment effect; Also improve the infiltration degree of aqueous sample and sensor surface simultaneously, improve Raman and strengthen effect.But some redox reaction also can affect Raman Measurement data unit, as peak position moves, spectral shape changes etc., and these needs are distinguished and certification in actual use.
The beneficial effect of patent of the present invention it is possible to realize sample molecule in the enrichment strengthening substrate sensor surface, improves detection sensitivity; The non-infiltration problem improved or eliminate fluid sample and strengthen between substrate sensor, improves the effect of surface enhanced.
Accompanying drawing 1 is multilayer Raman surface enhancing sensor construction simplified schematic diagram
In accompanying drawing 1,1 quartz glass substrate 2TiO
2nanometer particle film layer 3 nano-metal particle thin layer 4 micro objective 5 sample 6 ultraviolet illumination
Shown in accompanying drawing 1, the mode on quartz glass substrate 1 surface by sputter coating, or by spin coating TiO
2the mode of nano granule suspension, forms one deck TiO
2nanometer particle film layer 2.In the above again by splash-proofing sputtering metal (gold, silver) film, or the mode of spin coating metal nanoparticle colloid (gold size, elargol), form one deck nano-metal particle film, form complete Raman surface and strengthen sensor.When measuring use, fluid sample 5 is placed on sensor surface, and top 4 is Raman microscope object lens, and adopt ultraviolet light (wavelength is less than 380nm) to irradiate below quartz glass, quartz glass layer irradiates TiO
2thin layer, produce photocatalytic effect, sample molecule can produce enrichment in surface of metal particles, improves the infiltration degree between fluid sample and substrate simultaneously, improves surface enhanced effect.
Claims (4)
1. one kind utilizes the Raman surface of photocatalysis principle to strengthen sensor.Quartz glass substrate surface prepares one deck TiO
2nanometer particle film layer, prepares one deck nano-metal particle film thereon, forms complete Raman surface and strengthens sensor.When measuring use, adopt ultraviolet light (wavelength is less than 380nm) to irradiate below quartz glass, penetrate quartz glass layer and irradiate TiO
2film, produce photocatalytic effect, sample molecule can produce enrichment in surface of metal particles, improves the infiltration degree between fluid sample and substrate simultaneously, improves surface enhanced effect.
2. according to the TiO that claim 1 is narrated
2nanometer particle film, by the mode of sputter coating, or can pass through spin coating TiO
2the mode of nano granule suspension, forms one deck TiO
2nanometer particle film layer.Film thickness scope is from 10 nanometers to 100 micron.
3. according to claim 1 and 2, at TiO
2on film, can by splash-proofing sputtering metal (material is gold, silver) film, or the mode of spin coating metal nanoparticle colloid (gold size, elargol), form one deck nano-metal particle film, form complete Raman surface and strengthen sensor.
4. according to claim 1,2, and described in 3, when sensor measurement uses, fluid sample is placed on sensor surface, adopts ultraviolet light (wavelength is less than 380nm) to irradiate below quartz glass, penetrates quartz glass and expose to TiO
2thin layer, produce photocatalytic effect, sample molecule can produce enrichment in surface of metal particles, improves the infiltration degree between fluid sample and substrate simultaneously, improves surface enhanced effect.
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Cited By (5)
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CN106053427A (en) * | 2016-05-23 | 2016-10-26 | 中国科学院生态环境研究中心 | Heavy metal hexavalent chromium detection method |
CN106226285A (en) * | 2016-10-07 | 2016-12-14 | 复旦大学 | A kind of gold be core dopamine be " Raman quiet zone " substrate of shell and its preparation method and application |
CN106248648A (en) * | 2016-07-10 | 2016-12-21 | 复旦大学 | Gold is " Raman quiet zone " substrate that core silver is shell and preparation method and application |
CN111289493A (en) * | 2020-03-27 | 2020-06-16 | 电子科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
CN111489897A (en) * | 2019-01-25 | 2020-08-04 | 清华大学 | Photocatalytic structure and preparation method thereof |
-
2013
- 2013-10-08 CN CN201310467449.4A patent/CN104515764A/en active Pending
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106053427A (en) * | 2016-05-23 | 2016-10-26 | 中国科学院生态环境研究中心 | Heavy metal hexavalent chromium detection method |
CN106248648A (en) * | 2016-07-10 | 2016-12-21 | 复旦大学 | Gold is " Raman quiet zone " substrate that core silver is shell and preparation method and application |
CN106248648B (en) * | 2016-07-10 | 2019-10-15 | 复旦大学 | Gold is " Raman quiet zone " substrate and the preparation method and application thereof that core silver is shell |
CN106226285A (en) * | 2016-10-07 | 2016-12-14 | 复旦大学 | A kind of gold be core dopamine be " Raman quiet zone " substrate of shell and its preparation method and application |
CN106226285B (en) * | 2016-10-07 | 2019-10-15 | 复旦大学 | A kind of Jin Weihe dopamine is " Raman quiet zone " substrate and its preparation method and application of shell |
CN111489897A (en) * | 2019-01-25 | 2020-08-04 | 清华大学 | Photocatalytic structure and preparation method thereof |
CN111489897B (en) * | 2019-01-25 | 2022-06-21 | 清华大学 | Photocatalytic structure and preparation method thereof |
CN111289493A (en) * | 2020-03-27 | 2020-06-16 | 电子科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
CN111289493B (en) * | 2020-03-27 | 2021-08-06 | 电子科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
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Application publication date: 20150415 |