CN205898685U - Disposable surface reinforcing raman spectroscopy chip - Google Patents
Disposable surface reinforcing raman spectroscopy chip Download PDFInfo
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- CN205898685U CN205898685U CN201420536225.4U CN201420536225U CN205898685U CN 205898685 U CN205898685 U CN 205898685U CN 201420536225 U CN201420536225 U CN 201420536225U CN 205898685 U CN205898685 U CN 205898685U
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- layer
- disposable
- raman
- chip
- raman spectroscopy
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- 238000001069 Raman spectroscopy Methods 0.000 title abstract description 23
- 230000003014 reinforcing effect Effects 0.000 title abstract 3
- 230000000694 effects Effects 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 35
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 20
- 238000001237 Raman spectrum Methods 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims 2
- 238000012360 testing method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000003623 enhancer Substances 0.000 description 5
- 230000010354 integration Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The disclosed disposable surface reinforcing raman spectroscopy chip of this practicality is the sheet structure, and including bottom, intermediate level and superficial layer, the bottom is insulation substrate, and the intermediate level is conducting layer, the coating film layer of superficial layer for having surface reinforcing raman spectroscopy effect. The disclosed superficial layer nanostructured of this practicality has a great roughness great specific surface promptly, the await measuring molecule of event more than can load more, and signal enhancement has certain effect to the raman. And the cost of manufacture is low, has price advantage, but disposable, promptly with throwing promptly to reduce interference and used repeatedly's pollution problem, need not after the test to carry out cleaning treatment, convenient to use to the surface.
Description
Technical field
The utility model is related to Raman spectrum detection field, more particularly, to a kind of disposable surface-enhanced Raman light
Spectrum (surface enhanced raman scattering, sers) chip.
Background technology
Normal Raman spectrum is relatively low due to detection sensitivity, generally more difficult for trace molecules detection.At present, have and much grind
Study carefully and focus on the various substrates with SERS effect of exploitation, mainly have and processed using redox reaction effect
Roughened metal surface afterwards；With means such as physical vapor deposition, sputterings, metal nanoparticle is deposited on the unlike material such as glass surface
Substrate；The metal-sol of spherical, bar-shaped, core shell structure etc.；By monodispersed gold or silver nano-grain by certain mode
It is self-assembled to the mfon (van duyne seminar of Northwestern Univ USA) that inert substrate forms array；Photonic crystal substrate etc..
From the point of view of traditional electro-deposition with erosion theory, hydrogen ion issues raw reduction reaction in higher negative voltage and produces
Raw hydrogen will be unfavorable for the generation of the metal coating of densification.But when hydrogen ion is issued in higher negative voltage with precious metal ion
Porous pattern can be formed during raw codeposition.And porous pattern can increase the specific surface area of plated film, thus it is special to produce some
Catalytic performance.Using this principle, existing nickel porous, copper, selenium, silver, palladium, lead etc. are reported.But being applied to electricity its porous property more
Catalytic field, and be not applied in SERS.In addition, this porous electrode is applied to surface-enhanced Raman light
In spectrum, some technical barriers need to be solved.The selection of such as base material, the control of reaction condition and the control of ambient interferences are asked
Topic.
Utility model content
The purpose of the utility model patent is to provide a kind of disposable SERS chip, cost
Low, can single use, instant throwing, can be used for small-sized Raman signal detection instrument.
A kind of disposable SERS chip that the utility model provides, structure in the form of sheets, including
Bottom, intermediate layer and superficial layer, bottom is insulated substrate, and intermediate layer is conductive layer, and superficial layer is to have surface-enhanced Raman light
The film plating layer of spectrum effect.
In order to increase the specific surface area of plated surface film layer, strengthen Raman detection signal, there is SERS effect
The film plating layer answered has porous pattern.Optimum state is plated surface film layer is in porous nano dendritic structure.
Conductive layer can be directly using conductive material or can be the conductive layer being formed by serigraphy or can be vacuum evaporation shape
The conductive layer becoming or the conductive layer of sputtering formation.Conductive layer can produce the metal of SERS effect using having
Material.Gold, silver, copper are to be typically considered the base material that can obtain higher enhancer, and the order of three kinds of metals is silver > gold
> copper.The metal material that therefore conductive layer is adopted can be gold, silver, copper.
For Raman spectrum base, gold, silver, copper are to be typically considered the base that can obtain higher enhancer
Bottom material, the order of three kinds of metals is silver > gold > copper, therefore should have certain specific aim from the selection of material.Preferably with silver
As base material.
The utility model, when implementing to use, for specific testing sample, should first analyze its molecular structure, according to Raman
Choosing rule, determines whether it has Raman active group.Secondly the resonance Raman group according to testing molecule, selects internal standard, internal standard
The addition of molecule is considered as not disturbing molecule to be determined and spectral peak wavelength location not to disturb and be advisable, to ensure the mistake of spectral strength
Difference.Finally, signal after chip surface produces SERS effect for the testing sample, the peak of analysis vibration peak are investigated
The position of Qiang Yufeng, sets up quantitation or semi-quantitative analysis method.
The utility model compared with prior art, has some superiority: (1) chip list of the present utility model surface layer is using electricity
Chemical codeposition method is obtained, and using metal ion under high polarization potential, jointly reduces with hydrogen ion, produces active
Bubble hydrogen to prepare the metal coating of profile multilayer porous as template, and it is larger that this kind of nanostructured has larger roughness
Specific surface area, therefore more testing molecules can be loaded, tool be strengthened for Raman signal and has certain effect, therefore can be used for trace
The detection of the laser Raman spectroscopy of amount molecule.(2) the utility model low manufacture cost, has price advantage.With generally make now
Other most of substrates, such as noble metal electrode etc. are reused after needing reprocessing；The utility model, can due to low cost
Single use, instant throwing, to reduce interference and reusable pollution problem, can improve reappearance and sensitive simultaneously
Degree, need not be carried out to surface after test processing, easy to use.Also can be chemically treated, and become and can be used for multiple times
Substrate.
Brief description
Accompanying drawing be the utility model single use SERS chip SEM (sem) and
Being specifically illustrating, wherein of related Raman spectrum spectrogram:
Fig. 1 is the interlayer structure schematic diagram of disposable SERS chip；
Fig. 2 is sem surface topography (a) after electro-deposition for the utility model and partial enlarged drawing (b)；
Fig. 3 be the utility model electrodeposited after, not cleaned LR laser raman spectrogram；
Fig. 4 is ag2so4The LR laser raman spectrogram of solid；
After Fig. 5 is the cleaned drying of the utility model, laser Raman spectrum on chip for the 0.01mol/l pyridine solution dropping
Figure；
Fig. 6 is that 0.01mol/l pyridine solution drips on silicon chip, and laser beats the Raman spectrogram on solution；
Fig. 7 is cyclic voltammogram on the utility model under difference sweeps speed for the 0.1mol/l naf solution；
Fig. 8 is the graph of a relation sweeping speed and electric current.
Wherein: 1, superficial layer；2nd, intermediate layer；3rd, bottom.
Specific embodiment
The described a kind of disposable SERS chip of the present embodiment preparation, as shown in figure 1, be in piece
Shape structure, including bottom 3, intermediate layer 2 and superficial layer 1, bottom 3 is insulated substrate, and intermediate layer 2 is conductive layer, and conductive layer adopts
Conductive material or become through screen printing scopiform or formed or formed by sputtering by vacuum evaporation, the metal material of employing is
Silver, superficial layer 1 is the porous nano silver dendritic structure with SERS effect.From Fig. 2 (a), electrode
Surface is rendered as porous pattern, and assumes Multi-layers distributing, and upper strata aperture is about 400 μm about, and bottom is little less than 100 μm
Hole.From Fig. 2 (b), assume nanotrees dendritic morphology.
Fig. 3 is the not cleaned Raman spectrogram of chip, as can be seen from Fig. 3, in 960cm-1There is a strong peak at place,
1176.5cm-1There is strong peak at place.Speculate that the interference existing may be ag2so4, therefore to ag2so4Solid sample is tested,
Obtain the Raman spectrogram of Fig. 4, according to spectrogram comparison it can be determined that, the main interference of chip surface is ag2so4.In order to remove table
Face ag2so4Interference, select the complex ion larger with silver ion interaction to be carried out.Fig. 5 is once purged
The chip Raman spectrogram (time of integration be 10 seconds) after dropping 0.01mol/l pyridine solution thereon again, can from Fig. 5
Arrive, 960cm-1With 1176.5cm-1Place ag2so4Interference Peaks close to disappear, positioned at 1010cm-1With 1038cm-1Two peaks are
The vibration peak of 0.01mol/l pyridine, Raman spectrogram (time of integration the is 60 seconds) phase with 12.39mol/l pyridine solution in Fig. 6
Than, intensity enhancing, illustrate that the signal on the utility model surface for the Pyridine Molecules is strengthened.Further, counted according to equation 1-1
Calculate Raman enhancer,
Wherein iprobeAdsorb the intensity in chip surface, i for Pyridine MoleculesbulkFor the intensity of pure pyridine solution, cbulk
Concentration for the pure solution of pyridine is 12.39mol/l, cprobeFor 0.01mol/l.Record 1038cm-1The intensity at place, can from Fig. 5
Obtain iprobeFor 23273.52 (time of integration is 10 seconds), i can be obtained from Fig. 6bulkFor pyridine pure solution dropping laser on silicon chip
It is 5153.13 (time of integration is 60 seconds) in the signal of liquid level of solution.Therefore through calculating enhancer ef of the present utility model
For 3.36 × 104.
Due to the utility model surface be loose structure, by calculate the electric capacity on the utility model surface for the naf solution with
Theoretical smooth silver electrode and the electric capacity (c of electrolyte interfacespec=20 × 10-6f/cm2) ratio, can get of the present utility model
Rough factor.Prepare the naf solution of 0.1mol/l, be circulated voltammetric scan in -0.5v 0v, as shown in Figure 7.Take -0.25v
The current signal at place, makees electric current and the curve sweeping speed, obtains electric current and sweep rapid-result direct ratio, and slope is 111.14 μ a s/v, such as schemes
Shown in 8.Because this geometric electrode area is 0.07065cm2,cexp=j/v=1573.14 × 10-6f/cm2, so rf=cexp/
cspec=78.66.Illustrate that the utility model has larger Rough factor, the molecule due to being adsorbed onto chip surface can be speculated
Number increases, thus enhancing detection signal.Additionally, 3.36 × 104Enhancer explanation, signal enhancing is not only due to big thick
Rugosity, makes specific surface area increase, more because nanotrees dendritic morphology has promoted the surface phasmon effect of silver and testing molecule.
To sum up, the utility model has SERS effect, can be used as SERS chip
Use, specific molecular detection can be met and require.There is in the field quick detection of Raman certain using value.
Claims (4)
1. a kind of disposable SERS chip, structure in the form of sheets, including bottom, intermediate layer and surface
Layer it is characterised in that: bottom be insulated substrate, intermediate layer be conductive layer, superficial layer be there is SERS effect
Film plating layer.
2. disposable SERS chip according to claim 1 is it is characterised in that have surface
The film plating layer strengthening Raman spectrum effect has porous pattern.
3. disposable SERS chip according to claim 2 is it is characterised in that have surface
The film plating layer strengthening Raman spectrum effect is in porous nano dendritic structure.
4. disposable SERS chip according to claim 1 is it is characterised in that conductive layer can
Directly using conductive material or can be the conductive layer being formed by serigraphy or the conductive layer that can be formed for vacuum evaporation or sputtering
The conductive layer being formed.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420536225.4U CN205898685U (en) | 2014-09-18 | 2014-09-18 | Disposable surface reinforcing raman spectroscopy chip |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420536225.4U CN205898685U (en) | 2014-09-18 | 2014-09-18 | Disposable surface reinforcing raman spectroscopy chip |
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| CN205898685U true CN205898685U (en) | 2017-01-18 |
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| CN201420536225.4U Expired - Fee Related CN205898685U (en) | 2014-09-18 | 2014-09-18 | Disposable surface reinforcing raman spectroscopy chip |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105277524A (en) * | 2014-09-18 | 2016-01-27 | 浙江工业大学 | Disposable surface-enhanced Raman spectroscopy chip and preparation method |
-
2014
- 2014-09-18 CN CN201420536225.4U patent/CN205898685U/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105277524A (en) * | 2014-09-18 | 2016-01-27 | 浙江工业大学 | Disposable surface-enhanced Raman spectroscopy chip and preparation method |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170118 Termination date: 20190918 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |