CN102243175A - Surface plasma resonance light detection device based on ellipsoidal reflector light collection structure - Google Patents
Surface plasma resonance light detection device based on ellipsoidal reflector light collection structure Download PDFInfo
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Abstract
The invention discloses a surface plasma resonance light detection device based on an ellipsoidal reflector light collection structure, relating to the field of analysis equipment and overcoming the problems of frequently changed receiving angle and lower collection frequency of a detector and more complexity of a detection device. The surface plasma resonance light detection device can be used in detection analysis of SPR (Surface Plasmonic Resonance), SPR-SERS (Surface-Enhanced Raman Scattering) and SPR-SEF (Surface Enhanced Fluorescence). In the invention, a material to be detected 9, a metal film 10 and glass 11 are arranged in an ellipsoidal reflector 12 provided with a window 13. An exciting light 14 hits an interface of the glass 11 and the metal film 10 in an SPR angle, a light spot of the exciting light is positioned on a focus of the ellipsoidal reflector 12, one part of the exciting light 14 becomes reflecting light 15 and enters a receiving device 17 positioned at the other focus of the ellipsoidal reflector after being reflected by the ellipsoidal reflector 12. Because of the action of surface plasmonic resonance coupling, signal light 16 of the material to be tested 9 also enters the receiving device 17 after being reflected by the ellipsoidal reflector 12.
Description
Technical field
The present invention relates to the analytical equipment field.Be particularly related to surface plasma body resonant vibration optical detection device based on ellipsoidal reflector light collection structure.The pick-up unit that the present invention relates to can be used for the fluorescence and the Raman diffused light of check and analysis surface plasma body resonant vibration, surface plasma body resonant vibration enhancing.
Background technology
Advantages such as the fluorescence that surface plasma body resonant vibration, surface plasma body resonant vibration strengthen is modern important optical detective technologies with the Raman diffused light analysis, has highly sensitively, and selectivity is strong, and the few and method of need sample size is easy are widely used in biochemical analysis field.
Surface plasma resonance (SPR) is a kind of physical phenomenon, when incident light incides the interface of two media of different refractivity near with the SPR angle (for example glass and gold two media), can cause the resonance of metal free electron, because luminous energy that resonance has caused Electron absorption, thereby reflected light is weakened greatly in certain angle.Wherein, make the incident angle of reflected light complete obiteration be called the SPR angle.SPR changes with layer on surface of metal outside change of refractive, and the kind of change of refractive and the test substance that is combined in the metal surface is relevant with quantity.Therefore can obtain the kind and the quantity of test substance indirectly by obtaining the dynamic change at SPR angle.The common structure of surface plasma resonance has Otto, two kinds of Kretschmann, and wherein the Kretschmann structure applications is the most extensive.
Along with the intensification that the surface plasma resonance phenomenon is understood, simultaneously also for overcome conventional fluorescence and Raman scattering signal light intensity a little less than, thereby cause the lower problem of signal to noise ratio (S/N ratio), by application surface plasma resonance (Surface plasmonic resonance, be called for short: SPR) strengthen fluorescence method (Surface Enhanced Fluorescence, be called for short: SEF) (Surface-enhanced Raman scattering is called for short: SERS) improve the sensitivity that detects fluorescence and Raman diffused light with strengthening the Raman scattering method.
SEF and two kinds of detection methods of SERS for being strengthened by SPR abbreviate SPR-SEF and SPR-SERS as.SPR-SEF and SPR-SERS generally can be based on Kretschmann and two kinds of structures of Reverse Kretschmann, Fig. 1 has set forth the principle of the surface plasma body resonant vibration coupling enhancing fluorescence method (SPR-SEF) of Kretschmann structure: test substance 1 places the gold or silver-colored film 2 tops of tens nanometer thickness, incident light 4 enters half-sphere mirror 3, when the angle of incident light satisfies the surface plasma resonance condition, the latent ripple that dies that incident light produces sees through metallic film 2, at the interface with the plasma resonance that excites generation, and produce the SPR evanescent wave on the border of test substance 1 and metallic film 2.Fluorescent material in the test substance 1 is excited by evanescent wave, produces the surface plasma radiation with the plasma coupling again, and fluorescence and surface plasma that the excited state attenuation is produced resonate, and at a certain coning angle θ
FThe distinguishable polarized fluorescence 6 of last generation wavelength, this intensity of fluorescence has had the raising of highly significant when more not resonating.
[1]Fig. 2 illustrates fluorescent material after surface plasma coupling emission is strengthened, and it no longer is the even emitting fluorescence in space towards periphery, and this moment, fluorescence had very strong directivity, and concentrate on Z axle clamp angle be θ
FThe circular cone ring on.Because the coning angle θ that different fluorescence centre wavelength is corresponding different
F, therefore if fluorescent material centre wavelength difference, coning angle θ so
FAlso different.For the comparatively complicated fluorescent material with multi-emission wavelength and wide emission spectrum, the space distribution of fluorescent emission direction is a rainbow annulus
[2]Light 5 among Fig. 1 is reflected light of exciting light, the intensity of reflected light 5 is more little, the incident angle that incident light 4 is described is more near surface plasma resonance angle (SPR Angel), therefore, people are that rotational symmetry is placed with excitation light emission device and reflection light detector with the normal of metal surface usually, seek the SPR angle by accurate and synchronous moving.θ among Fig. 1
SPIt is the SPR angle.The principle of SPR-SERS is identical with the principle of SPR-SEF, all is to improve the signal light intensity greatly by the SPR effect.In addition, SPR-SERS spectrum has certain spectrum width, and the corresponding different directions of therefore different centre wavelengths makes and collects difficulty more.
Though SPR-SERS and SPR-SEF have improved Raman diffused light/intensity of fluorescence and directivity greatly, also there are following three problems.
The first, the shooting angle of strengthened Raman diffused light and fluorescence is determined jointly by the character of its centre wavelength and metallic film 2.If test substance has changed so, the centre wavelength of its characteristic spectrum has changed, the shooting angle of Raman diffused light and fluorescence also will change thereupon, in order to obtain maximum collection efficiency, the angle of putting that checkout equipment is used to receive the detector of Raman diffused light/fluorescence just need change and adjust simultaneously, this measure of precision to checkout equipment requires very high, and because frequent mobile detector has reduced detection efficiency.When especially the fluorescence that sends for Raman light and complicated fluorophore detects, wavelength coverage is bigger, this moment no longer corresponding single coning angle, but a series of continuous coning angle, just may need to place a plurality of detectors, this has increased detection difficulty and equipment cost again.
The second, the flashlight of SPR-SERS and SPR-SEF is distributed on the ring of certain cone angle, because size is limited, detector has only been collected one section the same with detector size on the circular cone ring, thereby has lost most of Raman diffused light/fluorescence.For reaching quite good detecting effectiveness, just need take to improve excitating light strength, increase the methods such as the amount of getting of test substance, this has improved detection difficulty and cost again
The 3rd, SPR-SERS and SPR-SEF necessarily require the incident angle of exciting light as far as possible near the SPR angle, and the SPR angle is determined jointly by the character of metallic film 2 and the wavelength and the outer medium refraction index of metallic film of exciting light 4, therefore the SPR angle is also different under the different testing conditions, and recording accurately, the SPR angle of milliradian resolution is the important content that surface plasma resonance is analyzed; Traditional SPR angle detecting device such as Fig. 3, requiring excitation light emission device 7 and reflection light detector 8 is axis of symmetry with the normal of metal surface, and synchronous change angle θ, up to finding that the faintest angle of reflected light, the incident angle θ of this moment is SPR angle θ
SPThis matching requirements excitation light emission device 7 is placed and is moved with reflection light detector 8 symmetries, has increased the complicacy and the cost of detecting instrument.
The present invention is based on the surface plasma resonance optical detection device of ellipsoidal reflector as the light collection structure, can be used for OTTO, the surface plasma resonance analysis of Kretschmann structure, and based on Kretschmann and the SPR-SERS of Reverse Kretschmann structure and the detection of SPR-SEF.The present invention has overcome existing the problems referred to above of this type systematic in the past, has not only improved the flashlight collection efficiency, and simplifies and omitted the accurate angular setting structure of detector in the pick-up unit, has guaranteed precision and has reduced equipment cost.
The character of ellipsoidal reflector according to the Fermat principle in the geometrical optics, necessarily converges to another focus of ellipsoidal reflector as shown in Figure 7 after the ellipsoidal reflector reflection through any light of a focus of ellipsoidal reflector.
[1] Lv Fengting, Zheng Hairong, the room analogy, the surface strengthens the fluorescence progress. chemical progress, (2007) Vol.19No.2/3
[2]Ignacy?Gryczynski，Joanna?Malicka，Zygmunt?Gryczynski，and?Joseph?R.Lakowicz，Radiative?decay?engineering?4.Experimental?studies?of?surface?plasmon-coupled?directional?emission.Analytical?Biochemistry?324(2004)170-182
Summary of the invention
The present invention is based on the surface plasma resonance optical detection device of ellipsoidal reflector as the light collection structure, Fig. 4, Fig. 5 and Fig. 6 are the technical solution used in the present invention, wherein the technical scheme of Fig. 4 is (to be called for short: KR) structure based on Kretschmann, the technical scheme of Fig. 5 is that (be called for short: RK) structure, the technical scheme of Fig. 6 are based on the Otto structure based on Reverse Kretschmann.To be illustrated with regard to several schemes below.
Among Fig. 4, test substance 9 places metallic film 10 tops of tens nanometer thickness, and glass 11 can be that hemisphere also can be triangle.Test substance 9, metallic film 10 all places ellipsoidal reflector 12 inside with glass 11, and the side of ellipsoidal reflector 12 has window 13.Exciting light 14 with near the angle of surface plasma resonance angle (SPR Angel) through window 13 incident glass 11, get on metallic film 10 surfaces, hot spot just in time is positioned at a focus place of ellipsoidal reflector 12 on it, exciting light 14 parts become reflected light 15, enter the receiving trap 17 that is arranged in another focus place of ellipsoidal reflector through the reflection of ellipsoidal reflector 12.Because the effect of surface plasma coupling, the SERS of test substance 9 or SEF flashlight 16 also enter the receiving trap 17 at another focus place that is arranged in ellipsoidal reflector 12 through ellipsoidal reflector 12 reflections.
Among Fig. 5, test substance 18 places metallic film 19 tops of tens nanometer thickness, and glass 20 can be that hemisphere also can be isosceles triangle.Test substance 18, metallic film 19, glass 20 all places the inside of ellipsoidal reflector 21, and the napex of ellipsoidal reflector 21 has window 22.Exciting light 23 is along the major axis of ellipsoidal reflector 21, through window 22, incide in the test substance 18, its hot spot just in time is positioned at a focus place of ellipsoidal reflector, because the effect of surface plasma coupling, the SERS of test substance 9 or SEF flashlight 24 enter the receiving trap 25 at another focus place that is arranged in ellipsoidal reflector 21 through ellipsoidal reflector 21 reflections.
Among Fig. 4 and Fig. 5, because 14 dozens of exciting lights all just in time are positioned at the hot spot on the test substance 18 on the focus of ellipsoidal reflector at hot spot on the metallic film 10 and 23 dozens of exciting lights, at this moment, this focus can be regarded reflected light 15 as, flashlight 16, the eye point of flashlight 24, and receiving trap is positioned on another focus of ellipsoidal reflector, so according to the characteristics of Fermat principle and ellipsoidal reflector, reflected light 15, flashlight 16 and flashlight 24 all will enter the receiving trap 17 or 25 that is positioned at another focus place after the ellipsoidal reflector reflection.
Among Fig. 6,26 is the metallic film of tens nanometer thickness, and 27 is air layer or other media, and glass 28 can be that hemisphere also can be isosceles triangle.The difference of Otto structure and Kretschmann structure is in the Otto structure glass and metallic film by enough near, but directly contact, and in the Kretschmann structure, metallic film be directly be deposited on after evaporating on glass.Metallic film 26, glass 28 all in ellipsoidal reflector 33, have window 29 on the ellipsoidal reflector 33.Total reflection takes place after in window 29 is got to glass 28 in exciting light 30, the position that total reflection takes place just in time is positioned on the focus of ellipsoidal reflector, and reflected light 31 enters the detector 32 that is positioned at ellipsoidal reflector 33 another focus places after ellipsoidal reflector 33 reflections.The Otto structure is used for surface plasma resonance more at present and detects, and is not used in Raman light and fluorescence analysis that surface plasma resonance strengthens.
Description of drawings
Fig. 1 is the SPR-SEF principle schematic
[3]
Fig. 2 is a SPR-SEF flashlight distribution schematic diagram
[3]
Fig. 3 is that traditional SPR detects principle schematic
[3]
Fig. 4 is based on KR structure SPR, SPR-SERS and the SPR-SEF device synoptic diagram of ellipsoidal reflector
Fig. 5 is based on RK structure SPR, SPR-SERS and the SPR-SEF device synoptic diagram of ellipsoidal reflector
Fig. 6 is based on the Otto structure SPR pick-up unit synoptic diagram of ellipsoidal reflector
Fig. 7 is the ellipsoidal reflector principle schematic
[3]Joseph?R.Lakowicz，Radiative?decay?engineering?3.Surface?plasmon-coupled?directional?emission，Analytical?Biochemistry?324(2004)153-169
Embodiment
Below in conjunction with the instructions synoptic diagram the present invention is described in detail.
As shown in Figure 4, the embodiment based on the device of ellipsoidal reflector light collection structure is:
The kind of the character of the wavelength of exciting light 14 and metallic film 10 and test substance 9 and quantity have determined surface plasma resonance angle (SPR Angel) jointly, the design is by detecting under the different incidence angles degree, and the intensity of reflected light 15 is determined the surface plasma resonance angle.Specifically, change the incident angle of exciting light 14, the intensity of reflected light 15 will change, since the centre wavelength of fluorescence with excite light wavelength and inequality, and of paramount importance part is the spectral line of excitation wavelength both sides in the raman scattering spectrum, be Stokes line and anti-stockes line, the intensity that therefore only need read exciting light wave band in the detector 17 is promptly known the intensity of reflected light 15.The intensity of reflected light 15 hour illustrates the most effective of SPR, and the incident angle of exciting light 14 is surface plasma resonance angle (SPR Angle).The present invention only need change the incident angle of exciting light 14, and need not the acceptance angle of synchronous change receiving trap as conventional apparatus, greatly reduces the mechanical complexity and the cost of pick-up unit.
After recording the surface plasma resonance angle, exciting light 14 incides on the metallic film 10 with the surface plasma resonance angle, its hot spot just in time is positioned on the focus of ellipsoidal reflector 12, this moment reflected light 15 intensity minimums, what therefore receiving trap 17 was received mainly is flashlight 16, can obtain corresponding SPR-SERS or SPR-SEF spectrum after the analysis.Here the design's receiving trap 17 positions need not along with the change of the characteristic wavelength of Raman diffused light or fluorescence and change as can be seen, as long as select the ellipsoidal reflector 12 of suitable parameters for use, just the characteristic spectrum of the SERS of various test substances, different wave length or SEF all can be reflexed to the fixing receiving trap 17 on another focus that is arranged in ellipsoidal reflector.Adopt this mode, the flashlight of collecting is the flashlight on the whole coning angle annulus, be not the part signal light of only collecting as on the coning angle annulus on the conventional apparatus, so collection efficiency improves greatly.During identical sensitivity, detect required sample size and excite light intensity also to decrease.Device of the present invention is also succinct than conventional apparatus, and is stable.
Implementation method in implementation method in the accompanying drawing 5 and the accompanying drawing 4 is similar.Different is that test substance 18 is gradually lost ripple to excite, but the light 23 that is excited directly excites, and is in the test substance of excited state and the plasma coupling that the metal surface produces, and at the SERS resonance angle place generation flashlight corresponding with the emission wavelength of SEF.Therefore this scheme need not to find out specific surface plasma body resonant vibration angle and can detect test substance, has also reduced the interference of exciting light to flashlight.
The SPR that only is applicable in the accompanying drawing 6 detects, it is also different that the incident angle difference of exciting light 30, detector 32 record intensity, when detector 32 records intensity hour, the incident angle of corresponding exciting light is the SPR angle, and infers the feature that to be adsorbed on the biomolecule on the metallic film 26 thus.
Claims (6)
1. surface plasma body resonant vibration optical detection device based on ellipsoidal reflector light collection structure.
2. the surface plasma body resonant vibration optical detection device based on ellipsoidal reflector light collection structure described in the claim 1 comprises: respectively based on all designs of Kretschmann structure, Reverse Kretschmann structure and Otto structure.
3. the surface plasma body resonant vibration optical detection device based on ellipsoidal reflector light collection structure based on the Kretschmann structure comprises described in the claim 2: a side has the ellipsoidal reflector of incidence window, be fixed on test substance, metallic film, glass on the focus in the ellipsoidal reflector, and be fixed on detector or light conduction device on another focus of ellipsoidal reflector.This structure can be used for SPR, SPR-SEF, SPR-SERS check and analysis.
4. the surface plasma body resonant vibration optical detection device based on ellipsoidal reflector light collection structure based on Reverse Kretschmann structure comprises described in the claim 2: an ellipsoidal reflector that has incidence window in the ellipsoidal mirror bottom, be fixed on test substance, metallic film, glass on the focus in the ellipsoidal reflector, and be fixed on detector or light conduction device on another focus of ellipsoidal reflector.This structure can be used for SPR-SEF, the SPR-SERS check and analysis.
5. the structure of Otto described in the claim 2 comprises for the surface plasma body resonant vibration optical detection device based on ellipsoidal reflector light collection structure on basis: a side has the ellipsoidal reflector of incidence window, be fixed on the metallic film on the focus in the ellipsoidal reflector, glass, and be fixed on detector or light conduction device on another focus of ellipsoidal reflector.This structure can be used for SPR and detects.
6. claim 1,2,3,4, the effect of ellipsoidal reflector described in 5 be, various flashlights reflections by surface plasma body resonant vibration strengthen after that test substance on the focus of ellipsoidal reflector sends and guiding with being positioned at be positioned at ellipsoidal reflector another focus on shaping, filtering light path and detector.
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Cited By (8)
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| CN102590147A (en) * | 2012-02-01 | 2012-07-18 | 中国科学院化学研究所 | Surface plasma resonance system capable of adjusting sensitivity and dynamic range and detection method thereof |
| CN104412099A (en) * | 2012-06-29 | 2015-03-11 | 精工爱普生株式会社 | Substance detection device and wristwatch type body fat burning measurement device |
| CN104792763A (en) * | 2014-09-11 | 2015-07-22 | 上海鉴谱光电科技有限公司 | Raman scattering excitation method and device |
| CN106546533A (en) * | 2015-09-20 | 2017-03-29 | 简佩蓉 | A kind of use full aperture angle parabolic lens collects the equipment of Surface Enhanced Raman Scattering Spectrum |
| CN107831142A (en) * | 2017-12-07 | 2018-03-23 | 黄保坤 | Light scattering confocal excitation collection system |
| CN109475037A (en) * | 2018-12-14 | 2019-03-15 | 华中科技大学 | A kind of plasma active enhancing method and generating device |
| CN112285065A (en) * | 2020-11-26 | 2021-01-29 | 深圳瀚光科技有限公司 | SPR sensor based on double elliptical reflectors and application |
| CN113406047A (en) * | 2021-05-20 | 2021-09-17 | 杭州电子科技大学 | Fluorescence detection sensing device based on cavity enhanced surface plasma resonance |
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| CN112285065A (en) * | 2020-11-26 | 2021-01-29 | 深圳瀚光科技有限公司 | SPR sensor based on double elliptical reflectors and application |
| CN113406047A (en) * | 2021-05-20 | 2021-09-17 | 杭州电子科技大学 | Fluorescence detection sensing device based on cavity enhanced surface plasma resonance |
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Application publication date: 20111116 |