CN103901013A - Method and device for enhancing evanescent field-excited film Raman signal - Google Patents
Method and device for enhancing evanescent field-excited film Raman signal Download PDFInfo
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- CN103901013A CN103901013A CN201210575352.0A CN201210575352A CN103901013A CN 103901013 A CN103901013 A CN 103901013A CN 201210575352 A CN201210575352 A CN 201210575352A CN 103901013 A CN103901013 A CN 103901013A
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Abstract
The invention discloses a method and a device for enhancing an evanescent field-excited film Raman signal. The method comprises that a film to be detected is formed on the surface of a prism, incident light is emitted to the prism so that total reflection is produced at the interface between the prism and the film to be detected, a Raman signal of the film to be detected is excited by an evanescent field produced by the total reflection, and a refractive index of a covering layer on the film to be detected is improved so that the evanescent field is enhanced and the Raman signal of the film to be detected is enhanced. The method can utilize optical fibers or an optical waveguide to replace the prism and realize enhancement of the Raman signal of the film to be detected by enhancement of the evanescent field of the optical fibers or optical waveguide. The method for enhancing a Raman signal has simple processes, good repeatability, good surface selectivity, a flexible and adjustable evanescent field polarization state and easy control of a cover layer refractive index, is very suitable for detection of Raman signals of solid ultrathin films such as a monomolecular adsorption layer and a surface decorative layer.
Description
Technical field
The present invention relates to prism total reflection technology, optical waveguide technique and Raman spectroscopy, particularly a kind of Enhancement Method and device of evanescent field excitation film Raman signal.
Background technology
Raman spectroscopy is equally mainly used in studying the vibration of molecule with infrared absorption spectroscopies, but in the Raman spectrum of molecule, has comprised the relevant molecular structure more abundanter than molecule infrared absorption spectrum and the information of character.Can determine the kind of molecule by the raman scattering spectrum of research molecule, obtain the information such as symmetric property and spatial orientation thereof of molecule.
The maximum problem that Raman spectroscopy runs in application comes from its intrinsic defect---and Raman signal is extremely faint, has therefore invented the whole bag of tricks and has strengthened this faint signal.These methods comprise that electron resonance strengthens Raman spectroscopy, Surface enhanced raman spectroscopy (SERS) technology, phasmon enhancing Raman spectrum (PERS) technology and prism total reflection Raman technology (TIRR) etc.Total reflection Raman spectroscopy has a maximum point to the humidification of signal, is positioned at the critical angle of prism total reflection, but total reflection condition is now easy to be subject to the impact of external environment and is destroyed.Although therefore in the time using total reflection Raman technology, incident angle being possessed to certain surplus has sacrificed certain signal enhancing effect but can guarantee meeting of total reflection condition.The signal intensity of prism total reflection Raman scattering while being greater than critical angle incident for strengthening, the present invention adopts and regulates the method for prism surface overlayer refractive index to strengthen its evanescent field.
Optical fiber and optical waveguide utilize light certain thickness high refractive index layer and around interface total reflection between low refractive index dielectric incident light is retrained, it can long-rangely be propagated, be mainly used in the communications field.Say in essence, the optical fiber of excellent performance or optical waveguide should be able to be resisted the multiple interference from the external world, and the variation of environment response is the smaller the better to external world.But just need while being applied to sensing and fields of measurement optical fiber and optical waveguide to have higher sensitivity to measured.By just can make it take into account the requirement that passes light and sensing dual role to the design and rational of optical fiber or optical waveguide structure, become and there is highly sensitive sensing measurement element.
Utilize the evanescent field of optical fiber or optical waveguide to excite the Raman signal of film just need to be optimized design to strengthen the intensity of its surperficial evanescent field to the structure of optical fiber or optical waveguide; On the other hand, also can be by regulating optical fiber or waveguide surface overlayer refractive index further to improve the intensity of evanescent field.The present invention adopts these two kinds of methods to strengthen optical fiber and optical waveguide evanescent field, and then realizes the enhancing of film Raman signal to be measured.
Summary of the invention
For solve prism total reflection evanescent field, fiber evanescent field and optical waveguide evanescent field a little less than, the extremely faint problem of film Raman signal to be measured being excited by it, the invention provides one and utilize high index of refraction covering layer material to strengthen evanescent field, and then strengthen the method and apparatus of film Raman signal to be measured.
According to an aspect of the present invention, a kind of intensifier of evanescent field excitation film Raman signal is proposed, this device comprises: prism, film to be measured, overlayer and Raman scattering light collecting device, wherein said film-shaped to be measured is formed in prism one bottom surface, overlayer is placed in film to be measured top, incident laser is injected the interface between prism and film to be measured after prism total reflection is occurred, follow total reflection to produce evanescent field in same interface, this evanescent field penetrates film to be measured and enters overlayer, and then excites film Raman signal to be measured; Strengthen the evanescent field in film to be measured by increasing overlayer refractive index, and then strengthen film Raman signal to be measured, the Raman signal of this enhancing imports Raman spectrometer analysis into after being collected by Raman scattering light collecting device.
According to a further aspect in the invention, a kind of intensifier of fiber evanescent field excitation film Raman signal is proposed, this device comprises: optical fiber, film to be measured, overlayer and Raman scattering light collecting device, the wherein covering between attenuate or removal optical fiber partial zones, film-shaped to be measured is formed between this fiber region, overlayer is placed in film to be measured top, utilize end face coupling scheme that incident laser is coupled into optical fiber, follow light to produce evanescent field in the propagation of fiber core layer at optical fiber surface, this evanescent field penetrates film to be measured and enters overlayer, and then excite film Raman signal to be measured, strengthen the evanescent field intensity in film to be measured by increasing overlayer refractive index, and then strengthening film Raman signal to be measured, the Raman signal of this enhancing is imported into Raman spectrometer analysis by Raman scattering light collecting device along film normal direction to be measured or from optical fiber one end face is collected.
According to a further aspect of the present invention, a kind of intensifier of optical waveguide evanescent field excitation film Raman signal is proposed, this device comprises: optical waveguide, film to be measured, overlayer, and Raman scattering light collecting device, wherein said film-shaped to be measured is formed in light guide surface, overlayer is placed in film to be measured top, utilize end face coupling scheme or grating coupling scheme or prism-coupled mode that incident laser is coupled into optical waveguide and form guided wave, follow the propagation of guided wave to produce evanescent field in light guide surface, this evanescent field penetrates film to be measured and enters overlayer, and then excite film Raman signal to be measured, strengthen the evanescent field intensity in film to be measured by increasing overlayer refractive index, and then strengthening film Raman signal to be measured, the Raman signal of this enhancing is imported into Raman spectrometer analysis by Raman scattering light collecting device along film normal direction to be measured or from optical waveguide one end face is collected.
In accordance with a further aspect of the present invention, a kind of Enhancement Method of evanescent field excitation film Raman signal has been proposed, wherein the method utilizes high-index material to cover film to be measured, in order to strengthen the evanescent field of film to be measured inside, and then strengthens the film Raman signal to be measured by evanescent field excitation.
Can find out from technique scheme, the Enhancement Method of evanescent field excitation surface film Raman signal of the present invention has following beneficial effect:
1, compare the electron resonance extensively adopting at present and strengthen Raman spectroscopy, Surface enhanced raman spectroscopy (SERS) technology, phasmon enhancing Raman spectrum (PERS) technology, it is low, simple to operate that the method that the present invention proposes has cost, be easy to control versatility and the advantage such as reproducible.
2, compared with the method for traditional use body beam excitation Raman signal, the method surface selectivity that the present invention proposes is good, and longitudinal frame is high, be very suitable for surveying monomolecular adsorption layer, the Raman signal of the solid ultrathin membranes such as finishing coat.
3, compared with the method for traditional use body beam excitation Raman signal, the method that the present invention proposes is not vulnerable to body and disturbs mutually, allows the dynamic process of in-situ test surface reaction.
4, compared with the method for traditional use body beam excitation Raman signal, the method that the present invention proposes can flexible evanescent field polarization state, is easy to realize the enhancing of Raman signal in various polarization situations and detection (unpolarized, TE, TM, circular polarization etc.).Therefore the present invention is particularly useful for the detection of Raman depolarization rate, the active detection of Raman light of film molecule etc. of film.
Accompanying drawing explanation
Fig. 1 is prism total reflection evanescent field excitation film Raman signal intensifier structural drawing according to an embodiment of the invention;
Fig. 2 is fiber evanescent field excitation film Raman signal intensifier structural drawing according to an embodiment of the invention;
Fig. 3 is optical waveguide evanescent field excitation film Raman signal intensifier structural drawing according to an embodiment of the invention;
Fig. 4 is the optical waveguide evanescent field excitation film Raman signal intensifier structural drawing according to further embodiment of this invention;
Fig. 5 A and 5B be record based on Fig. 4 shown device be deposited on the enhancing Raman spectrum of the CuPc ultrathin membrane of light guide surface by vacuum vapour deposition.
[main element symbol description]
1-liquid tank, wherein, 1a-liquid tank inlet, 1b-liquid tank liquid outlet;
2-prism coupler;
3-optical fiber;
4-optical waveguide, wherein, 4a-high index of refraction gradient film;
5-film to be measured, wherein, 5a-phthalocyanine copper film to be measured;
6-overlayer;
7-Raman scattering light collecting device;
8-optical fiber or optical waveguide support
9-photodetector.
10a-inputs couple prism, and 10b-exports couple prism.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in further detail.
The Enhancement Method of evanescent field excitation film Raman signal of the present invention utilizes high-index material to cover film to be measured, in order to strengthen the evanescent field of film to be measured inside, thereby strengthens the film Raman signal to be measured by evanescent field excitation.
A kind of intensifier of prism total reflection evanescent field excitation film Raman signal has been proposed according to one embodiment of present invention.The structural drawing of this device of Fig. 1, with reference to Fig. 1, this device comprises: liquid tank 1 (overlayer 6 installs additional while being liquid), prism 2, film to be measured 5, overlayer 6, prism bracket (not shown) and Raman scattering light collecting device 7 etc.Described film to be measured 5 is formed at prism 2 one bottom surfaces, overlayer 6 is placed in film to be measured 5 tops, incident laser is injected the interface between prism 2 and film to be measured 5 after prism 2 total reflection is occurred, follow total reflection to produce evanescent field in same interface, this evanescent field penetrates film 5 to be measured and enters overlayer 6, and then excite film 5 Raman signals to be measured, by utilizing high-index material to strengthen the evanescent field in film 5 to be measured as overlayer 6, and then strengthen film 5 Raman signals to be measured, the Raman signal of this enhancing imports Raman spectrometer analysis into after being collected by Raman scattering light collecting device 7.
Wherein prism 2 is Dove prism, and this is in order to reduce prism thickness to meet the requirement of large-numerical aperture lens focus distance in Raman scattering light collecting device 7.In concrete enforcement, the shape that also can take other to prism 2 is to meet the requirement of Raman scattering light collecting device 7 focusings.As shown in Figure 1, incident laser is at prism 2 surface excitation evanescent fields, this evanescent field and then excite the film to be measured 5 that is formed at prism 2 surfaces to produce Raman signal, the Raman scattering light collecting device 7 being positioned in prism side or reflected light direction is collected and it is sent into Raman spectrometer analysis by optical fiber this signal.After prism 2 surface dielectrics become overlayer 6 from air, the evanescent field on prism 2 surfaces is enhanced, and therefore the Raman signal of film 5 to be measured is enhanced.
A kind of intensifier of fiber evanescent field excitation film Raman signal has been proposed according to another embodiment of the present invention.Fig. 2 is the structural drawing of this device.With reference to Fig. 2, this device comprises: optical fiber 3, film to be measured 5, overlayer 6, liquid tank 1 (overlayer 6 installs additional while being liquid) (not shown), structure of fiber_optic 8 and Raman scattering light collecting device 7 etc.Before film 5 to be measured is formed at optical fiber 3 surfaces, first attenuate or remove the fibre cladding between film to be measured 5 areal coverage, makes evanescent field penetrate optical fiber 3 surfaces; Or after the fibre cladding of removing between film to be measured 5 areal coverage, further these interval optical fiber 3 sandwich layers of attenuate, make the evanescent field that appears optical fiber 3 surfaces obtain enhancing.Then, film 5 to be measured is formed between this fiber region, overlayer 6 is placed in film to be measured 5 tops, utilize end face coupling scheme that incident laser is coupled into optical fiber 3, follow light to produce evanescent field in the propagation of optical fiber 3 sandwich layers on optical fiber 3 surfaces, this evanescent field penetrates film 5 to be measured and enters overlayer 6, and then excites film 5 Raman signals to be measured; Strengthen the evanescent field intensity in film 5 to be measured by increasing overlayer 6 refractive indexes, and then strengthening film 5 Raman signals to be measured, the Raman signal of this enhancing is imported into Raman spectrometer analysis by Raman scattering light collecting device 7 along film 5 normal directions to be measured or from optical fiber 3 one end faces are collected.
Wherein optical fiber 3 used can be side polishing fiber, D type optical fiber, double-tapered fiber or go cladded-fiber one of them, what Fig. 2 represented is fiber optic component used is side polishing fiber situation; Wherein Raman scattering light collecting device 7 used can use round lens combination to carry out the collection of single-point Raman signal, also can utilize cylindrical lens and round lens combination to collect with the effect of line integral and further strengthen Raman signal the Raman signal in Shang compare Chang path, the guided wave direction of propagation.As shown in Figure 2, follow light to produce evanescent field in the propagation of optical fiber 3 sandwich layers on optical fiber 3 surfaces, this evanescent field penetrates the film to be measured 5 that is positioned at side polishing fiber 3 surfaces, and then exciting the Raman signal of film 5 to be measured, the Raman scattering light collecting device 7 being positioned in side polishing fiber 3 sides or end face emergent light direction is collected and it is sent into Raman spectrometer analysis by optical fiber this Raman signal.After side polishing fiber 3 surface dielectrics become overlayer 6 from air, the evanescent field on side polishing fiber 3 surfaces is enhanced, and therefore the Raman signal of film 5 to be measured is enhanced.
A kind of intensifier of optical waveguide evanescent field excitation film Raman signal has also been proposed according to another embodiment of the present invention.Fig. 3 is the structural drawing of this device, and with reference to Fig. 3, this device comprises: optical waveguide 4, film to be measured 5, overlayer 6, liquid tank 1 (overlayer 6 installs additional while being liquid), optical waveguide support 8 and Raman scattering light collecting device 7 etc.Described film to be measured 5 is formed at optical waveguide 4 surfaces, overlayer 6 is placed in film to be measured 5 tops, utilize end face coupling scheme or grating coupling scheme or prism-coupled mode that incident laser is coupled into optical waveguide 4 and form guided wave, follow the propagation of guided wave to produce evanescent field on optical waveguide 4 surfaces, this evanescent field penetrates film 5 to be measured and enters overlayer 6, and then excites film 5 Raman signals to be measured; Strengthen the evanescent field intensity in film 5 to be measured by increasing overlayer 6 refractive indexes, and then strengthening film 5 Raman signals to be measured, the Raman signal of this enhancing is imported into Raman spectrometer analysis by Raman scattering light collecting device 7 along film 5 normal directions to be measured or from optical waveguide 4 one end faces are collected.
Wherein optical waveguide 4 used can be two-dimensional waveguide, three-dimensional waveguide etc.; Wherein Raman scattering light collecting device 7 used can use round lens combination to carry out the collection of single-point Raman signal, also can utilize cylindrical lens and round lens combination to collect with the effect of line integral and further strengthen Raman signal the Raman signal in Shang compare Chang path, the guided wave direction of propagation.As shown in Figure 3, described film 5 to be measured is directly formed at optical waveguide 4 surfaces, or before film 5 to be measured is formed at optical waveguide 4 surfaces, first at optical waveguide 4 surface deposition one deck high index of refraction gradient films, for strengthening the evanescent field that appears light guide surface.Incident laser is coupled into optical waveguide 4 through end face coupling scheme or prism-coupled mode or grating coupling scheme, become guided wave, produce evanescent field along guided wave travel path on optical waveguide 4 surfaces, this evanescent field penetrates the film to be measured 5 that is positioned at optical waveguide 4 surfaces, and then exciting the Raman signal of film 5 to be measured, the Raman scattering light collecting device 7 being positioned in optical waveguide 4 sides or end face emergent light direction is collected and it is sent into Raman spectrometer analysis by optical fiber this signal.After optical waveguide 4 surfaces are covered by high index of refraction gradient film 4a, the evanescent field that enters film 5 to be measured obtains and strengthens, and therefore the Raman signal of film 5 to be measured is enhanced.The Raman signal of this enhancing passes to Raman spectrometer analysis after being collected by Raman scattering light collecting device 7.
Fig. 4 is the device schematic diagram that the Enhancement Method of evanescent field excitation film Raman signal of the present invention is applied to optical waveguide.As shown in Figure 4, this device comprises: input couple prism 10a, output couple prism 10b, optical waveguide 4, high index of refraction gradient film 4a, liquid tank 1 (overlayer 6 installs additional while being liquid), phthalocyanine copper film 5a to be measured, optical waveguide support 8 and Raman scattering light collecting device 7 etc.Incident laser is coupled into chip of light waveguide 4 by input couple prism 10a becomes guided wave, produce evanescent field along guided wave travel path on optical waveguide 4 surfaces, this evanescent field is enhanced between high index of refraction gradient film 4a areal coverage, and then exciting the Raman signal of the phthalocyanine copper film 5a to be measured that is positioned at high index of refraction gradient film 4a surface, the Raman scattering light collecting device 7 that is positioned at optical waveguide 4 another sides is collected and it is sent into Raman spectrometer analysis by optical fiber this signal.Guided wave enters photodetector 9 at the other end of optical waveguide 4 by output couple prism 1b coupling output, by photodetector 9, its intensity is carried out to record.Pass into high refractive index liquid 6 in liquid tank 1 after, the evanescent field on optical waveguide 4 surfaces is enhanced again, and therefore the Raman signal of phthalocyanine copper film 5a to be measured is also strengthened again.
Covering layer material is liquid, comprising: water, aqueous solution, organic solvent, organic solution etc.Above-mentioned high refractive index liquid covering layer material need meet the following conditions: (1) this liquid covers after film 5 to be measured, and structure and the character of film 5 to be measured are constant, still keep its integrality; (2) this liquid covers after film 5 to be measured, and structure and the character of prism, optical fiber or optical waveguide that film to be measured 5 belows contact are with it constant, still keep its integrality; (3) this liquid covers after film 5 to be measured, and before covering, the prism total reflection of excitation or optical fiber guided mode or Optical Waveguides are not destroyed by this liquid; (4) this liquid does not have strong absorption to used light source light; (5) this liquid does not have Raman signal in interested film Raman signal SPECTRAL REGION to be measured.
Covering layer material can also be solid film, and this solid film need meet the following conditions: (1) this solid film covers after film 5 to be measured, and structure and the character of film 5 to be measured are constant, still keep its integrality; (2) this solid film covers after film 5 to be measured, and structure and the character of prism, optical fiber or optical waveguide that film to be measured 5 belows contact are with it constant, still keep its integrality; (3) this solid film covers after film 5 to be measured, and before covering, the prism total reflection of excitation or optical fiber guided mode or Optical Waveguides are not destroyed by this solid film; (4) this solid film does not have strong absorption to used light source light; (5) this solid film does not have Raman signal in interested film Raman signal SPECTRAL REGION to be measured.
In the intensifier of evanescent field excitation film Raman signal of the present invention, adjustable incident light polarization direction, the evanescent field that makes to constrain in film to be measured becomes transverse electric wave or transverse magnetic wave, then increase film to be measured top overlayer refractive index, be used for strengthening the inner polarization evanescent field of film to be measured, thereby strengthen the film polarization Raman signal to be measured by this polarization evanescent field excitation.
In the intensifier of evanescent field excitation film Raman signal of the present invention, described film Raman signal to be measured is collected and enters Raman spectrometer and survey along film normal direction to be measured; Or along the prism total reflection light direction of propagation, film Raman signal to be measured is collected and entered Raman spectrometer and survey; Or from optical fiber one end face, film Raman signal to be measured is collected and entered Raman spectrometer and survey; Or from optical waveguide one end face, film Raman signal to be measured is collected and entered Raman spectrometer and survey.
The present invention also proposes a kind of Enhancement Method of evanescent field excitation film Raman signal, and the method utilizes high-index material to cover film 5 to be measured, in order to strengthen the evanescent field of film to be measured 5 inside, and then strengthens the film Raman signal to be measured by evanescent field excitation.
In one embodiment, above-mentioned film-shaped to be measured is formed in prism one surface, and evanescent field results from the interface between prism and film to be measured by prism total reflection.
In another embodiment, above-mentioned film-shaped to be measured is formed in optical fiber surface, before film-shaped to be measured is formed in optical fiber surface, first attenuate or remove the fibre cladding between film to be measured areal coverage, makes the evanescent field of following guided wave to produce in the propagation of fiber core layer penetrate film 5 to be measured; Or after the fibre cladding of removing between film to be measured areal coverage, further this interval fiber core layer of attenuate, makes to follow the evanescent field that guided wave produces in the propagation of fiber core layer to obtain enhancing.
In an embodiment again, above-mentioned film 5 to be measured is directly formed at optical waveguide 4 surfaces, follows the propagation of guided wave in optical waveguide 4 and the evanescent field that produces penetrates film 5 to be measured; Or before film 5 to be measured is formed at optical waveguide 4 surfaces, first at optical waveguide 4 surface deposition one deck high index of refraction gradient films, make to follow the propagation of guided wave in optical waveguide 4 and the evanescent field that produces on optical waveguide 4 surfaces obtains and strengthens.
Wherein, film 5 to be measured is the one in unimolecular layer, simple grain sublayer, polymolecular layer, multiparticle layer, and these film thicknesses are less, is enough to make evanescent field penetrate film and interact with top overlayer.
Wherein, described covering layer material is liquid, for example, be water, aqueous solution, organic solvent or organic solution, and these liquid possess following characteristic:
(1) this liquid covers after film to be measured, and structure and the character of film to be measured are constant, still keep its integrality;
(2) this liquid covers after film to be measured, and structure and the character of prism, optical fiber or optical waveguide that film to be measured below contacts are with it constant, still keep its integrality;
(3) this liquid covers after film to be measured, and before covering, the prism total reflection of excitation or optical fiber guided mode or Optical Waveguides are not destroyed by this liquid;
(4) this liquid does not have strong absorption to used light source light;
(5) this liquid does not have Raman signal in interested film Raman signal SPECTRAL REGION to be measured.
Covering layer material can be also solid film, possesses following characteristic:
(1) this solid film covers after film 5 to be measured, and structure and the character of film 5 to be measured are constant, still keep its integrality;
(2) this solid film covers after film 5 to be measured, and structure and the character of prism, optical fiber or optical waveguide that film to be measured below contacts are with it constant, still keep its integrality;
(3) this solid film covers after film 5 to be measured, and before covering, the prism total reflection of excitation or optical fiber guided mode or Optical Waveguides are not destroyed by this solid film;
(4) this solid film does not have strong absorption to used light source light;
(5) this solid film does not have Raman signal in interested film Raman signal SPECTRAL REGION to be measured.
In the method for the invention, adjustable incident light polarization direction, the evanescent field that makes to constrain in film to be measured becomes transverse electric wave or transverse magnetic wave, then increase film to be measured top overlayer refractive index, be used for strengthening the inner polarization evanescent field of film to be measured, thereby strengthen the film polarization Raman signal to be measured by this polarization evanescent field excitation.
Wherein, described film Raman signal to be measured is collected and enters Raman spectrometer and survey along film normal direction to be measured; Or along the prism total reflection light direction of propagation, film Raman signal to be measured is collected and entered Raman spectrometer and survey; Or from optical fiber one end face, film Raman signal to be measured is collected and entered Raman spectrometer and survey; Or from optical waveguide one end face, film Raman signal to be measured is collected and entered Raman spectrometer and survey.
Fig. 5 A and 5B are the Raman signals that utilizes the phthalocyanine copper film that the intensifier of optical waveguide evanescent field excitation film Raman signal of the present invention records.These experimental datas have fully proved to adopt high refractive index liquid can effectively improve the Raman signal by the phthalocyanine copper film 5a to be measured of the surperficial evanescent field excitation of optical waveguide 4 as overlayer 6.The Raman signal that can find out the phthalocyanine copper film 5a to be measured of optical waveguide 4 surface vacuum evaporations from Fig. 5 A is obviously strengthened in the NaCl of high index of refraction solution (massfraction is 2%), there is very large quantitative change in some spectral strengths, some spectrum peak presents the qualitative change of growing out of nothing.From Fig. 5 B, can obviously find out the regulating and controlling effect of NaCl solution refractive index (with solution concentration positive correlation) to phthalocyanine copper film 5a Raman signal intensity to be measured: NaCl solution refractive index is larger, and the enhancing of Raman signal is more remarkable.This embodiment has proved method of the present invention validity in practice.
It should be noted that, in accompanying drawing or instructions description, similar or identical part is all used identical figure number.Indicate for convenient, in accompanying drawing, the size of each several part is not proportional with full-size(d).Moreover the element or the implementation that do not illustrate in accompanying drawing or describe, be the form known to person of ordinary skill in the field.In addition, although the demonstration of the parameter that comprises particular value can be provided herein, should be appreciated that, parameter is without definitely equaling corresponding value, but can in acceptable error margin or design constraint, be similar to corresponding value.
Claims (16)
1. the intensifier of an evanescent field excitation film Raman signal, this device comprises: prism (2), film to be measured (5), overlayer (6) and Raman scattering light collecting device (7), it is characterized in that, described film to be measured (5) is formed at prism (2) one bottom surfaces, overlayer (6) is placed in film to be measured (5) top, incident laser is injected the interface between prism (2) and film to be measured (5) after prism (2) total reflection is occurred, follow total reflection to produce evanescent field in same interface, this evanescent field penetrates film to be measured (5) and enters overlayer (6), and then excite film to be measured (5) Raman signal, strengthen the evanescent field in film to be measured (5) by the refractive index that increases overlayer (6), and then strengthening film to be measured (5) Raman signal, the Raman signal of this enhancing imports Raman spectrometer analysis into after being collected by Raman scattering light collecting device (7).
2. intensifier according to claim 1, is characterized in that, the Raman signal of described enhancing is collected and entered Raman spectrometer analysis by Raman scattering light collecting device (7) along film to be measured (5) normal direction; Or
Collected and enter Raman spectrometer analysis by Raman scattering light collecting device (7) along the prism total reflection light direction of propagation.
3. the intensifier of a fiber evanescent field excitation film Raman signal, this device comprises: optical fiber (3), film to be measured (5), overlayer (6) and Raman scattering light collecting device (7), it is characterized in that, covering between attenuate or removal optical fiber (3) partial zones, film to be measured (5) is formed between this fiber region, overlayer (6) is placed in film to be measured (5) top, utilize end face coupling scheme that incident laser is coupled into optical fiber (3), follow guided wave to produce evanescent field in the propagation of optical fiber (3) sandwich layer on optical fiber (3) surface, this evanescent field penetrates film to be measured (5) and enters overlayer (6), and then excite film to be measured (5) Raman signal, strengthen the evanescent field intensity in film to be measured (5) by the refractive index that increases overlayer (6), and then strengthening film to be measured (5) Raman signal, the Raman signal of this enhancing is imported into Raman spectrometer analysis by Raman scattering light collecting device (7) along film to be measured (5) normal direction or from optical fiber (3) one end faces are collected.
4. intensifier according to claim 3, is characterized in that, after the fibre cladding between film to be measured (5) areal coverage is completely removed, and further this interval fiber core layer of attenuate, and then strengthen this interval evanescent field.
5. the intensifier of an optical waveguide evanescent field excitation film Raman signal, this device comprises: optical waveguide (4), film to be measured (5), overlayer (6), and Raman scattering light collecting device (7), it is characterized in that, described film to be measured (5) is formed at optical waveguide (4) surface, overlayer (6) is placed in film to be measured (5) top, utilize end face coupling scheme or grating coupling scheme or prism-coupled mode that incident laser is coupled into optical waveguide (4) and form guided wave, follow the propagation of guided wave to produce evanescent field on optical waveguide (4) surface, this evanescent field penetrates film to be measured (5) and enters overlayer (6), and then excite film to be measured (5) Raman signal, strengthen the evanescent field intensity in film to be measured (5) by the refractive index that increases overlayer (6), and then strengthening film to be measured (5) Raman signal, the Raman signal of this enhancing is imported into Raman spectrometer analysis by Raman scattering light collecting device (7) along film to be measured (5) normal direction or from optical waveguide (4) one end faces are collected.
6. intensifier according to claim 5, it is characterized in that, before film to be measured (5) is formed at optical waveguide (4) surface, first at optical waveguide (4) surface deposition one floor height refraction gradient film (4a), for strengthening for the first time the evanescent field entering in film to be measured (5), then increase the refractive index of overlayer (6), for strengthening for the second time the evanescent field in film to be measured (5).
7. the Enhancement Method of an evanescent field excitation film Raman signal, it is characterized in that, the method utilizes high-index material to cover film to be measured (5), in order to strengthen the inner evanescent field of film to be measured (5), and then strengthen film to be measured (5) Raman signal by evanescent field excitation.
8. the Enhancement Method of evanescent field excitation film Raman signal as claimed in claim 7, wherein, described film to be measured (5) is formed at prism (2) one surfaces, and evanescent field results from interface between prism (2) and film to be measured (5) by prism total reflection.
9. the Enhancement Method of evanescent field excitation film Raman signal as claimed in claim 7, wherein, described film to be measured (5) is formed at optical fiber (3) local surfaces, before film to be measured (5) is formed at optical fiber (3) local surfaces, first attenuate or remove the fibre cladding between film to be measured (5) areal coverage, makes the evanescent field of following guided wave to produce in the propagation of fiber core layer penetrate film to be measured (5); Or
After the fibre cladding of removing between film to be measured (5) areal coverage, further this interval fiber core layer of attenuate, makes to follow guided wave in the propagation of fiber core layer and the evanescent field that produces in this interval obtains and strengthens.
10. the Enhancement Method of evanescent field excitation film Raman signal as claimed in claim 7, wherein, described film to be measured (5) is directly formed at optical waveguide (4) surface, follows the propagation of guided wave in optical waveguide (4) and the evanescent field that produces penetrates film to be measured (5); Or
Before film to be measured (5) is formed at optical waveguide (4) surface, first at optical waveguide (4) surface deposition one deck high index of refraction gradient film (4a), make to follow the propagation of guided wave in optical waveguide (4) and the evanescent field that produces on optical waveguide (4) surface obtains and strengthens.
The Enhancement Method of 11. evanescent field excitation film Raman signals as described in one of as any in claim 7 to 10, wherein, described film to be measured (5) is the one in unimolecular layer, simple grain sublayer, polymolecular layer, multiparticle layer, and the thickness of film to be measured (5) is less than evanescent field penetration depth.
The Enhancement Method of 12. evanescent field excitation film Raman signals as described in one of as any in claim 7 to 10, wherein, the material of described overlayer (6) is liquid, this liquid possesses following characteristic:
(1) this liquid covers after film to be measured (5), and structure and the character of film to be measured (5) are constant, still keep its integrality;
(2) this liquid covers after film to be measured (5), structure and the character of prism (2), optical fiber (3) or optical waveguide (4) that film to be measured (5) below contacts are with it constant, still keep its integrality;
(3) this liquid covers after film to be measured (5), and before covering, the prism total reflection of excitation or optical fiber guided mode or Optical Waveguides are not destroyed by this liquid;
(4) this liquid does not have strong absorption to used light source light;
(5) this liquid does not have Raman signal in interested film Raman signal SPECTRAL REGION to be measured.
13. is according to claim 12, it is characterized in that, the material of described overlayer (6) is the one in water, aqueous solution, organic solvent, organic solution.
The Enhancement Method of 14. evanescent field excitation film Raman signals as described in one of as any in claim 7 to 11, wherein, the material of described overlayer (6) is solid film, possesses following characteristic:
(1) this solid film covers after film to be measured (5), and structure and the character of film to be measured (5) are constant, still keep its integrality;
(2) this solid film covers after film to be measured (5), structure and the character of prism (2), optical fiber (3) or optical waveguide (4) that film to be measured (5) below contacts are with it constant, still keep its integrality;
(3) this solid film covers after film to be measured (5), and before covering, the prism total reflection of excitation or optical fiber guided mode or Optical Waveguides are not destroyed by this solid film;
(4) this solid film does not have strong absorption to used light source light;
(5) this solid film does not have Raman signal in film Raman signal SPECTRAL REGION to be measured.
The Enhancement Method of 15. evanescent field excitation film Raman signals as described in one of as any in claim 7 to 10, it is characterized in that, regulate incident light polarization direction, make the evanescent field constraining in film to be measured (5) become transverse electric wave or transverse magnetic wave, then increase the refractive index of film to be measured (5) top overlayer (6), be used for strengthening the inner polarization evanescent field of film to be measured (5), thereby strengthen the polarization Raman signal by the film to be measured (5) of this polarization evanescent field excitation.
The Enhancement Method of 16. evanescent field excitation film Raman signals as described in one of as any in claim 7 to 10, wherein, described film to be measured (5) Raman signal is collected and enters Raman spectrometer and survey along film to be measured (5) normal direction; Or along the prism total reflection light direction of propagation, film to be measured (5) Raman signal is collected and entered Raman spectrometer and survey; Or from optical fiber one end face, film to be measured (5) Raman signal is collected and entered Raman spectrometer and survey; Or from optical waveguide one end face, film to be measured (5) Raman signal is collected and entered Raman spectrometer and survey.
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