CN102928397B - Holographic Tip-Enhanced Raman Spectroscopy instrument optical system - Google Patents

Holographic Tip-Enhanced Raman Spectroscopy instrument optical system Download PDF

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CN102928397B
CN102928397B CN201210439788.7A CN201210439788A CN102928397B CN 102928397 B CN102928397 B CN 102928397B CN 201210439788 A CN201210439788 A CN 201210439788A CN 102928397 B CN102928397 B CN 102928397B
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filter sheet
lens
edge filter
laser
amici prism
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CN102928397A (en
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王翔
任斌
张向苏
任雪畅
炉庆洪
刘守
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Xiamen University
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Xiamen University
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Abstract

Holographic Tip-Enhanced Raman Spectroscopy instrument optical system, relates to Raman spectrometer.Be provided with laser instrument, Amici prism group, edge filter sheet, high na value lens, sample stage and Raman signal and gather lens, the excitation beam that the beam of laser bundle that described Amici prism group is used for being sent by laser instrument is divided into two bundles to run parallel, described Amici prism group is provided with block prism and triangular prism, described edge filter sheet is located at Amici prism group front, two bundle laser is incident in Raman signal with 45° angle and gathers lens; The two bundle excitation beams that described high na value lens are used for edge filter sheet to reflect converge at a tip end focus point; Described Raman signal gathers lens and is used for the Raman signal of collection to be transported to spectrometer and detecting device carries out light splitting and detection.System is simple, easy to operate.In actual applications, can design for different detected object and just putting and be inverted two kinds of patterns.

Description

Holographic Tip-Enhanced Raman Spectroscopy instrument optical system
Technical field
The present invention relates to Raman spectrometer, especially relate to holographic Tip-Enhanced Raman Spectroscopy instrument optical system.
Background technology
No matter normal Raman spectrum or Surface enhanced raman spectroscopy, its spatial resolution all cannot break through optical diffraction limit, thus there is great limitation to the object of research.
It is found that in recent years, adopt " Tip-Enhanced Raman Spectroscopy technology " tens nanometers can be reached to the spatial resolution of the breakthrough optical diffraction limit of several Nano grade and monomolecular detection sensitivity.Under normal pressure and air conditions, Tip-Enhanced Raman Spectroscopy technology (hereinafter referred to as TERS) is at present uniquely can in the surface and interface optical characterisation technology of several nanometer to tens nanoscale sampling chemical analysis information.Therefore, no matter commercial Application, or basic scientific research all has very large demand to " Tip-Enhanced Raman Spectroscopy instrument ", is the study hotspot in current Raman spectrum field to the development of TERS instrument, Application and Development.Optical system is the main of TERS is also important ingredient.
The basic functional principle of TERS is: utilize scanning probe microscopy that gold or silver-colored needle point are approached substrate, under the laser of suitable wavelength and polarization irradiates, tip end produces due to surface plasmon resonance effect the electromagnetic field strengthened, and is therefore positioned at the Raman signal of sample below needle point and is enhanced.TERS has high sensitivity and spatial resolution, and can obtain pattern and the chemical information of sample surfaces simultaneously.Only need the laser power adopting milliwatt level, therefore paid attention to widely.
At present, more international renowned companies, as NTMDT, Renishaw and Nanonics are proposed business-like TERS instrument.The independent intellectual property rightization of TERS instrument is also seen in application, as US Patent No. 2002/0154301, and patent US2010/0245816; Chinese patent CN101082585A and the acquired Chinese patent 201110354369.9 of applicant.
A common feature of above TERS instrument is its optical system is substantially all be based upon on the basis of Confocal laser endomicroscopy.This makes instrumentation difficulty large, and cost is high.The high-caliber research work delivered in the world is up to now substantially all that the instrument developed voluntarily in laboratory obtains, and rarely has and obtains high-caliber achievement in research at commercial TERS instrument.
Summary of the invention
The object of the present invention is to provide holographic Tip-Enhanced Raman Spectroscopy instrument optical system.
The present invention is provided with:
A laser instrument, described laser instrument is used for the Raman signal of excited sample, as system excitation source;
An Amici prism group, the excitation beam that the beam of laser bundle that described Amici prism group is used for being sent by laser instrument is divided into two bundles to run parallel, described Amici prism group is provided with block prism and triangular prism, and described Amici prism is mounted on laser instrument front;
An edge filter sheet, the excitation beam that two bundles that described edge filter sheet is used for reflection beam splitting prism composition run parallel, and in Raman collection light path the exciting and the noise such as sample light, Rayleigh scattering of filtering reflection, described edge filter sheet is located at Amici prism group front, two bundle laser is incident in Raman signal with 45° angle and gathers lens;
High na value lens, the two bundle excitation beams that described high na value lens are used for edge filter sheet to reflect converge at a tip end focus point;
A sample stage, described sample stage is for placing testing sample;
Raman signal gathers lens, and described Raman signal gathers lens and is used for the Raman signal of collection to be transported to spectrometer and detecting device carries out light splitting and detection.
Described laser instrument can adopt LD laser instrument or gas laser etc.
Described edge filter sheet can adopt long pass filter sheet or notch filter sheet etc.
The present invention has following outstanding advantages:
1, the laser beam of the outgoing light beam that becomes two bundles to run parallel by prism component, two light beams realize assembling through high-NA camera lens.Obviously, this is a kind of new holographic register system.This system is simple, easy to operate.In actual applications, can design for different detected object and just putting and be inverted two kinds of patterns.
2, the exciting when avoiding needle point and spot coupling due to needle tip bracket (semi-girder of the such as afm tip) reflection to exciting light Gauss center of twin-beam, drastically increase the launching efficiency of laser, and reduce and reflect the ground unrest caused thus, thus effectively improve Raman spectral collection and signal transacting.
3, compact optical system is conducive to TERS instrument miniaturization and practical.Above feature makes the present invention and patent US2002/0154301, US2010/0245816, CN101082585A compare to have unique superior and innovate.
4, the present invention is different from the product reported at present, and the present invention adopts twin-beam focusing system, so claim holographic TERS optical system.Relative to the TERS instrument system reported at present facilitate easy-to-use, important application can be obtained in actual production, research.
Accompanying drawing explanation
Fig. 1 is the structural representation of positively fixed type optical system of the present invention.
Fig. 2 is the structural representation of inversion type optical system of the present invention.
In fig 1 and 2, be respectively labeled as: 1 is laser instrument, 2 is block prisms, and 3 is triangular prisms, 4 is edge filter sheets, and 5 is high na value lens, and 6 is needle points, and 7 is sample stage, 8 is that Raman signal gathers lens, and 9 is raman spectroscopic systems, and 10 is focused light enlarged drawings in tip end.
Embodiment
Provide the structural representation of positively fixed type optical system of the present invention see Fig. 1 and 2, Fig. 1, Fig. 2 provides the structural representation of inversion type optical system of the present invention.
The embodiment of the present invention is provided with:
A laser instrument 1, described laser instrument 1 for the Raman signal of excited sample, as system excitation source;
An Amici prism group, the excitation beam that the beam of laser bundle that described Amici prism group is used for being sent by laser instrument is divided into two bundles to run parallel, described Amici prism group is provided with block prism 2 and triangular prism 3, and described Amici prism is mounted on laser instrument 1 front;
An edge filter sheet 4, the excitation beam that two bundles that described edge filter sheet 4 forms for reflection beam splitting prism run parallel, and in Raman collection light path the exciting and the noise such as sample light, Rayleigh scattering of filtering reflection, described edge filter sheet 4 is located at Amici prism group front, two bundle laser is incident in Raman signal with 45° angle and gathers lens 8;
High na value lens 5, described high na value lens 5 converge at a needle point 6 end focus point for the two bundle excitation beams reflected by edge filter sheet 4;
A sample stage 7, described sample stage 7 is for placing testing sample;
A Raman signal gathers lens 8, and described Raman signal gathers lens 8 and comprises spectrometer and detecting device for the Raman signal of collection is transported to raman spectroscopic system 9() carry out light splitting and detection.
Described laser instrument 1 can adopt LD laser instrument or gas laser etc.
Described edge filter sheet 4 can adopt long pass filter sheet or notch filter sheet etc.
In FIG, adopt positively fixed type structure, namely testing sample is opaque, and needle point 6 inserts from two light beams angle, and light beam converging focal point drops on needle point 6 end.
In fig. 2, adopt inversion type structure, namely testing sample is the transparent body, and needle point 6 end is positioned at twin-beam converging focal point.

Claims (3)

1. holographic Tip-Enhanced Raman Spectroscopy instrument optical system, is characterized in that being provided with:
A laser instrument, described laser instrument is used for the Raman signal of excited sample, as system excitation source;
An Amici prism group, the excitation beam that the beam of laser bundle that described Amici prism group is used for being sent by laser instrument is divided into two bundles to run parallel, described Amici prism group is provided with block prism and triangular prism, and described Amici prism is mounted on laser instrument front;
An edge filter sheet, the excitation beam that two bundles that described edge filter sheet is used for the formation of reflection beam splitting prism group run parallel, and in Raman collection light path filtering reflection excite and sample light, Rayleigh scattering light, described edge filter sheet is located at Amici prism group front, the angle that edge filter sheet and two restraints the excitation beam run parallel is 45 °, and the excitation beam that two bundles through edge filter sheet run parallel is normally incident in high na value lens;
High na value lens, the two bundle excitation beams that described high na value lens are used for edge filter sheet to reflect converge at a tip end focus point;
A sample stage, described sample stage is for placing testing sample;
Raman signal gathers lens, and described Raman signal gathers lens and is used for the Raman signal of collection to be transported to spectrometer and detecting device carries out light splitting and detection.
2. holographic Tip-Enhanced Raman Spectroscopy instrument optical system as claimed in claim 1, is characterized in that described laser instrument adopts LD laser instrument or gas laser.
3. holographic Tip-Enhanced Raman Spectroscopy instrument optical system as claimed in claim 1, is characterized in that described edge filter sheet adopts long pass filter sheet or notch filter sheet.
CN201210439788.7A 2012-11-07 2012-11-07 Holographic Tip-Enhanced Raman Spectroscopy instrument optical system Active CN102928397B (en)

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CN103743720B (en) * 2014-01-20 2016-03-16 厦门大学 A kind of confocal Raman microscopy with angle resoluting ability
CN103743721B (en) * 2014-01-20 2015-10-14 厦门大学 Phasmon strengthens Raman spectrum dynamic detection system
CN103852461B (en) * 2014-03-28 2016-01-20 厦门大学 A kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy
CN105067587A (en) * 2015-08-17 2015-11-18 苏州优谱德精密仪器科技有限公司 Enhanced Raman spectroscopy system
CN105067588A (en) * 2015-08-17 2015-11-18 苏州优谱德精密仪器科技有限公司 Novel enhanced Raman spectroscopy system
CN105510296B (en) * 2015-12-29 2018-08-31 北京华泰诺安探测技术有限公司 The portable fluorescence Raman spectrum detection system that disappears
CN106323470B (en) * 2016-08-04 2019-01-15 北京华泰诺安探测技术有限公司 The Polarization Modulation Raman probe and optical spectrum detecting method of use space output laser

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CN101082585A (en) * 2007-07-19 2007-12-05 清华大学 Reflexion type near-field Raman spectrometer instrument head
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Publication number Priority date Publication date Assignee Title
US3817634A (en) * 1971-03-10 1974-06-18 Nat Res Dev Testing of optically active substances by polarized radiation
US5510894A (en) * 1988-12-22 1996-04-23 Renishaw Plc Spectroscopic apparatus and methods
US5864397A (en) * 1997-09-15 1999-01-26 Lockheed Martin Energy Research Corporation Surface-enhanced raman medical probes and system for disease diagnosis and drug testing
DE102004061728A1 (en) * 2004-12-17 2006-06-29 Technische Universität Dresden Surface-resolved determination of Raman scattering and spectral separation uses objective to produce point-resolved image of scattering from specimen which is fed to interferometer, after which it passes to focal plane array detector
CN101082585A (en) * 2007-07-19 2007-12-05 清华大学 Reflexion type near-field Raman spectrometer instrument head
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