CN1902471A - Method of spectroscopy - Google Patents

Method of spectroscopy Download PDF

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Publication number
CN1902471A
CN1902471A CNA2004800400456A CN200480040045A CN1902471A CN 1902471 A CN1902471 A CN 1902471A CN A2004800400456 A CNA2004800400456 A CN A2004800400456A CN 200480040045 A CN200480040045 A CN 200480040045A CN 1902471 A CN1902471 A CN 1902471A
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Prior art keywords
sample
excited
spectrum
vibration mode
excitation
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Chinese (zh)
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大卫·克拉格
强森·D·帕尔马
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Ip2ipo Innovations Ltd
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Imperial College Innovations Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/10Arrangements of light sources specially adapted for spectrometry or colorimetry
    • G01J3/108Arrangements of light sources specially adapted for spectrometry or colorimetry for measurement in the infrared range
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/44Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N2021/653Coherent methods [CARS]
    • G01N2021/655Stimulated Raman
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/636Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited using an arrangement of pump beam and probe beam; using the measurement of optical non-linear properties
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

A spectroscopy method and apparatus comprises an excitation source arranged to excite a vibrational mode of a sample and provide multi-dimensional spectral information by varying the excitation in a time or frequency domain. A parameter of a further excitation source or of the sample is controlled so as to provide coherence spectroscopy by ensuring that a non-resonant local oscillator field generated in the sample dominates a homodyne signal generated in the sample. As a result heterodyne detection is achieved in a manner allowing an output signal linearly dependent upon concentration providing improved sensitivity.

Description

Method of spectroscopy
The present invention relates to a kind of method of spectroscopy, particularly the multidimensional wave spectroscopy.
Known numerous method of spectroscopy is used to study the coupling of two or more secondary systems (two-level system).A kind of known method is two-dimentional nuclear magnetic spectroscopy (2D-NMR).An example of described system is at " peacekeeping two dimension NMR Wave Spectrum (Basic one-and two-dimensional NMR spectroscopy) on basis " the 2nd edition (in April, 1993) (John Wiley of Friebolin; The Sons publication) open in.Well-known NMR depends on the sympathetic of magnetic nuclear and externally-applied magnetic field.In order in the NMR wave spectrum, to launch crowded data, developed 2D-NMR.In typical 2D-NMR figure, sample is limited by first and second excitation pulses that delay time lag is opened.Owing to the sympathetic of sample room and particularly spin-spin coupling, the information that obtains from second excitation pulse is different from the information that obtains from first excitation pulse that extra dimension is provided.Fourier transform is applied to time spectrum from each excitation pulse to obtain frequency spectrum separately.Frequency spectrum is drawn to form the surface on orthogonal axis.Lip-deep peak provides relevant sample room sympathetic additional information.
2D-NMR figure can be used for measuring molecular structure and be provided for determining only, the distinctive feature (" fingerprint ") of the composition of solution.It is widely used in the molecular structure of Analysis of Complex potpourri at chemistry in biology and other subject.Yet 2D-NMR lacks sensitivity, typically 10 15-10 18Other detecting limitation of molecular level.In addition, 2D-NMR only provides limited solution in time domain.
In other known method of spectroscopy, be similar to those technology of in the 2D-NMR Wave Spectrum, using and in 2D vibration or infrared (IR) Wave Spectrum, adopt, wherein the vibration mode of atom or molecule is to be excited.A kind of such known so-called " pumping-probe " (pump-probe) technology is that people such as Woutersen is at J.Phys.Chem.B 104,11316-11320, disclosed technology in 2000 " Wave Spectrum of the two-dimension vibration of use polarization sensitive is measured the structure (Structure Determination of Trialanine in Water Using Polarization Sensitive Two-DimensionalVibrational Spectroscopy) of three alanine in water ".Further also carried out 2D-IR pumping-probe test, for example people such as Hamm is at Proc.Nat.Acad.Sci.96, disclosed in 2036,1999 " about the two-dimentional IR nonlinear wave spectroscopy (The two-dimensional IR non-linear spectroscopy of a cyclicpenta-peptide in relation to its three-dimensional structure) of five-peptide of the ring-type of its three-dimensional structure ".
According to known IR system, at first pumping pulse, the pulse of popping one's head in subsequently, final spectrogram on axle separately, provide representative about sample in the surface of the sympathetic information of vibration-vibration.Because the mathematical description of the secondary quantum regime of coupling equates that in essence therefore analysis principle and the technology of using can be used in the 2D IR Wave Spectrum equally in 2D-NMR.Yet detection sensitivity is imported the strict restriction of laser noise, and the result shows the very little variation of generation on big background signal, is particularly caused the little variation of the intensity of incident beam by the little variation of the optical density (OD) of same sample.Therefore, lower to the sensitivity of the concentration of the composition that will detect.
Another problem of Chan Shenging is when exciting with the probing wave strong point in mid infrared region in some cases, therefore can run into the problem at the execution detector of the difference in that zone.
Present technology also is not provided at the highly sensitive quality under the low concentration, or allows the full range of given complicated chemical sample and the fingerprint of real-time results, to the high interim sharpness of the timetable of molecular interactions.Particularly the multidimensional wave spectroscopy is not also implemented the situation of low concentration.
The present invention provides in the claims.
To describe embodiment of the present invention by embodiment now, the device of the method for a kind of enforcement Wave Spectrum according to the present invention will be shown with reference to Fig. 1.
In general, the method for spectroscopy that the present invention relates to depends on the exciting of vibration mode of in system atom or molecule, and for example the infrared excitation source excites.The sympathetic permission two dimension in system between the vibration or the information of multidimensional obtain by suitable mode of excitation (regimes).The present invention depends on that allowing output signal to be the linear process of heterodyning that changes with sample concentration surveys.As a result, for example compare with the autodyne probe method, can analyze lower concentration, wherein said autodyne probe method is a kind of quadratic function that depends on concentration, therefore, is very weak small-signal for low concentration.And the present invention further depends on from the heterodyne execution ground of external source or depends on the field that is produced by the local oscillator the sample, so that quadratic term in the linear term decision output signal.
With reference to Fig. 1, the device that illustrates generally includes a sample 10, contains lasing light emitter and detector 14 at the infrared band divergent-ray. Adjustable laser 12 and 18 emission wavelength/wave number separately is 3164cm -1And 2253cm -1Excitation beam, it excites one or more sample molecule structural vibrations patterns and by modulating frequency or provide variable time delay to obtain multidimensional data.Produced to provide with the output of effectively discrete input beam form or to read by the 3rd laser 16 at the fixed frequency light beam of 795nm, frequency (strictly producing as the 4th bundle) changes by the sympathetic of structure of sample 10.The signal of this detection usually at electromagnetic spectrum as visible or near infrared part at 740nm, contain photon energy and be no less than 1eV..In order to obtain multidimensional data, by the continuous beam excitation described sample of interval in time domain.Yet any suitable multidimensional wave spectroscopy technology may be utilized, for example by changing at frequency domain rather than in the input of time domain.Similarly, by obtaining any dimension in other pulse of time domain or in other frequency of frequency domain.Although show transmission plan, under suitable situation,, can adopt reflection scheme (wherein sample reflects the light beam that is detected) for example at the sample of surface deposition.
In order to obtain the improved sensitivity of the present invention, the parameter of modifier is surveyed to realize process of heterodyning.This can be undertaken by the process of heterodyning excitaton source that an outside is provided, and for example contains another excitation laser or broadband laser source (not shown) or passes through suitably modulation excitation laser 12 or 20.
In any case, concerning the skilled reader, will understand from following discussion or know under variety of way that system is variable or modulation.The reader of wherein said this area can discuss based on this, and the test by routine can realize the purpose of being correlated with.
By definition, comprise that all method of spectroscopy of the present invention all launch a kind of signal, its intensity can be as giving a definition:
I=(E LO) 2+(E HO) 2+(E LO×E HO)cosφ (1)
Here, E HOBe the homodyne signal of sample, can be considered to total electric field by the sample composition emission that is detected.E LOBe " local oscillator ", that is, have a fixed phase difference φ with the field that imposes on the same frequency of detector.In the homodyne of standard is surveyed, there is not local oscillator field, intensity is homodyne E simply HO 2, its concentration with chemical system to be studied is secondary and changes.In process of heterodyning is surveyed, a local oscillator is set in addition and makes its time and space consistent with detector.By doing like this, and any suitable technique that the reader by this area is familiar with is removed (E LO) 2, this cross-term is used to determine equation.General knowledge by local oscillator strength knows that it is linear that output field is on concentration.
With typical one dimension wave spectrum such as absorption spectra, the method that fourier-transform infrared (FTIR) spectrum etc. adapts is compared, and can understand the basic Physical Mechanism of the exploitation according to the present invention best.Described one-dimensional wave spectroscopy depends on induction and/or measures the overall status variation.Different with described " population spectroscopies ", the present invention includes " coherence spectroscopy ".
In quantum mechanical picture, photon contains two with molecular state and separates but relevant bisection.In fact what change overall (for example, " being excited into the electronics of first excited state ") sympatheticly relates to two sympathetic with the incident field, separately as the state of discussing respectively half.By relatively, relevant with known to the single sympathetic generation of incident field, two molecular staties quantum mechanics completely overlap.This system and two states between the correlated frequency of different-energy vibrate back and forth.This vibration is with distinctive frequency (for example, top E HO) launch one successively.Now clear why homodyne cause one with the quadratic function relation that is detected photon.Yet for as second sympathetic, field of the present invention is introduced into the outside (or in sample) of sample, has linear function on the concentration: the field of each sample molecule adds a field that produces photon detection from external field.Therefore we define two types Wave Spectrum, utilize relevant (coherence spectroscopy) and utilize overall (population spectroscopies).Coherence spectroscopy need be complementary as the direct result of condition-energy and power conservation-to determine the outbound course to light beam.For one group single, discrete input wavelength is determined only outbound course (angle).
As a result, the inventive method provides a kind of astonishing level of sensitivity, under the situation of the signal field that produces in sample, and depends on the such fact in heterodyne execution ground that automatically has correct facies relationship.
As for implementing the mode that process of heterodyning is surveyed therein, as mentioned above, perhaps by changing sample parameters or obtaining by the external field generator.
For the sample that sample for example provides in solution, local oscillator field will be present in the sample/solvent naturally with the form of the non--resonant contribution of intrinsic generation.It is bigger that-resonant contribution non-by guaranteeing (said 10 times) significantly and partly distributed than resonance or the homodyne of signal, E LOAnd cross-term (cross terms) is used for governing equation formula (1), and we can think fully that signal is a process of heterodyning.Equally, signal is linear on concentration, and reaches before the detection limit, can clearly obtain lower concentration far away.And by changing the type of solvent, the concentration of solvent or volume, or the different-thickness of sampling receptacle can be controlled the relative size that local oscillator distributes, and allow to check large-scale concentration.
In the another kind of mode, can control the correlation parameter of sample by the fluorescent absorption molecule that adds appropriate amount, the Electron absorption of described fluorescent absorption molecule is the resonance with visible light beam.This absorption causes radiation and as the polarization of the molecule of local oscillator field.This is a kind of useful especially method, because can accurately control the concentration of local oscillator molecules.Under the sort of situation, additional excitation source provides the polarization that needs.
Under interior-sample situation, as those local oscillator field (E that produces inherently or inherently LO) 2Can remove by determining and deduct specific local oscillated signal.This local oscillated signal can obtain in calibration steps.
In other method, can adopt traditional optical heterodyne method, wherein local oscillator field produces in the outside of sample, and is directly incident on the detector with sample field.The generation of described local oscillator is for example passed through usually, and the continuum in having the suitable liquid or solid of part visible light beam produces.Under the sort of situation, the special parameter of control external signal so that relevant in above-mentioned equation (1), preponderate, compare with traditional optical heterodyne law system, wherein linear distribution such as above-mentioned to carry out detailed discussion very wide.Remove (E LO) 2, can use the confinement detector to realize that simply in this detector, the mechanical wheel that will have slit is incorporated into excitation beam at (" isolating switch ").The repetition frequency that slit blocks light beam (reference frequency) is delivered to the confinement detector, and this confinement detector is that frequency filter-it is measured the whole network signal from detector and is extracted in the signal content that reference frequency takes place basically.If this reference frequency is different from the repetition frequency of the light beam that produces local oscillator signals, the network signal composition proprietary to local oscillator will reduce.Like this, E LO 2Item disappears, E HO 2Item can be ignored, and cross-term is linear on concentration.
In another embodiment, at people such as Muller " Imaging the Thermodynamic State of LipidMembranes with Multiplex CARS Spectroscopy " J.Phys.Chem.B.106, " frequency multiplexing technique " type of describing among the 3715-3723 is by realizing in infrared use wideband pulse, by the infrared transistion of hypervelocity pulse generation with while excited sample and the spectra part around it.By the input angle of suitable selection light beam, can obtain only direction corresponding to incoming frequency.As a result, output signal is the taper ray that contains the polishing wax information of having living space; In the case, detector 14 can be the 2D detector array, catches the spectral information that is encoded into space dimensionality as charge-coupled device (CCD).In case obtain improved resolutions of spectra once more, except space dimensionality, additional dimension postponed by the burst length or by the frequency change that goes through in the above introduce with provide other, the spectral information that produces of detailed relevant sample completely.The process of heterodyning of covering frequence wave band is obtained by " continuum generation ", and wherein, many local oscillator frequencies produce in sample, and for example the external excitation by white light is to provide the heterodyne field sympathetic with broadband excitation.
In specific implementations of the present invention, utilize the geometrics (that is, not being listed in the three beams of laser 12,16,18 on same plane) and the broadband excitation bundle (input wavelength exists with single bundle on a large scale) of known conduct " block post in advance ".In this way, produce an output angle scope, for the only outbound course of given combination results of the discrete wavelength of the standard that in two infrared beams, exists.Therefore, spectral information is launched into the output beam of spatial character, and detector array catches in a chance (shot) effectively, and this chance can be set up by using narrow wave band excitation beam and point-to-point modulation.
Other, in the selectable embodiment, do not use process of heterodyning, ultraviolet or as seen excite excitation electron resonance, this resonance produces the fluorescence that is caused by the transition between the electron energy level successively.This is the combination of direct infrared excitation type discussed above.Under the sort of situation, do not need additional " reading " signal from laser 16.Import modulation infrared and ultraviolet light beam and change time delay and produce multidimensional data in the mode of describing in detail above once more, but based on population spectroscopies.
The present invention's enforcement that can be widely used, particularly wherein using the variable frequency or the time delay of two or more light, the multidimensional optics Wave Spectrum of measuring vibrations/vibronic coupling directly or indirectly is to be suitable for studying that molecule is confirmed and/or any field of structure.This technology is effective especially when hanging down molecular conecentration.For example the present invention has improved the level of sensitivity of low-concentration detection, so that in suitable frequency range of choice, can study gas phase and surface-deposited samples with permission affirmation as the composition in the protein solution and their concentration in complex mixture.
Those skilled in the art can recognize and can adopt any suitable special composition and technology to implement the present invention.Typically, at least a infrared laser source and at least a ultraviolet that other can be modulated, the visible or infrared laser source modulated can be adopted, any suitable laser or in fact any other suitable excitaton source can be used.As the situation of two infrared excitation light beams discussing with reference to Fig. 1 under, can add other fixed frequency light beam and can adopt any suitable source once more.Similarly, sample and solvent can be any suitable type, and the composition of wherein controlling it to be being modulated into system as above described in detail, and with any suitable phase, comprise that gas phase and liquid phase/solution are mutually.Can adopt any suitable detector, for example other known detector in CCD or the 2D IR Wave Spectrum technology.
The scope of excitation wavelength is infrared usually as mentioned above, but can for the suitable wavelength of any needs to excite structural vibrations pattern to be analyzed.Although above-mentioned discussion relates to two-dimension analysis basically, the appropriate variation of the parameter that can excite by input is introduced any dimension, frequency for example, time delay/pulse number, or any other suitable parameters.

Claims (13)

1, a kind of method of spectroscopy, it has the controllable parameter of at least a excitaton source parameter and sample parameters, comprise that the control controllable parameter is to produce local oscillator field in described a large amount of samples, domination is from the homodyne signal of described sample, excites the vibration mode of described sample and obtains to be excited the spectrum of sample.
2, method as claimed in claim 1, wherein said sample are excited to obtain the spectrum of bidimensional at least.
3, method as claimed in claim 2, wherein sample excitation changes at least a time domain and frequency domain, to obtain the spectrum of bidimensional at least.
4, the method for each claim as described above, wherein said controllable parameter is a sample parameters.
5, method as claimed in claim 4, wherein said sample parameters changes by add absorbefacient molecule in described sample.
6, the method for each claim as described above, wherein said controllable parameter comprises the frequency of at least a external excitation source beam, mutually or amplitude.
7, a kind of method of spectroscopy comprises the vibration mode of excited sample, the electronic pattern of excited sample and the step of measuring samples change in fluorescence, wherein excites described sample to obtain the spectrum of bidimensional at least.
8, a kind of method of spectroscopy comprises the vibration mode of excited sample, the spectra part around the use excitation beam excited vibrational pattern, produces the broadband local oscillator field by the broadband excitation source in described sample, and the analysable output bundle of space exploration.
9, a kind of Wave Spectrum device, comprise an excitaton source with the vibration mode of excited sample, and one excitaton source in described a large amount of samples, to produce local oscillator field, arrange the homodyne signal of described sample, excite the vibration mode of described sample and obtain to be excited the spectrum of sample.
10, a kind of Wave Spectrum device, comprise an excitaton source with the vibration mode of excited sample, with one in described a large amount of samples, to produce the sample of local oscillator field, arrange the homodyne signal of described sample, excite the vibration mode of described sample and obtain to be excited the spectrum of sample.
11, a kind of Wave Spectrum device comprises one with first excitaton source of the vibration mode of excited sample and second excitaton source with the electronic pattern of excited sample, wherein excites described pattern to obtain the spectrum of bidimensional at least.
12, a kind of Wave Spectrum device, comprise an excitaton source with the vibration mode of excited sample, have detector with an excitaton source and with the spectra part around the vibration mode of excited sample, wherein excite described sample to obtain the spectrum of bidimensional at least at the probe field of the dimension at least one space.
13, a kind of as each method of claim 1-6, wherein control described parameter so that, wherein emissive porwer is by I=(E LO) 2+ (E HO) 2+ (E LO* E HO) cos φ representative, E LOBe so so that cross-term domination E HO 2
CNA2004800400456A 2003-11-07 2004-11-05 Method of spectroscopy Pending CN1902471A (en)

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GBGB0326088.2A GB0326088D0 (en) 2003-11-07 2003-11-07 Method of spectroscopy

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108896176A (en) * 2018-05-14 2018-11-27 浙江大学 A kind of Space Consistency bearing calibration of multi-optical spectrum imaging system
CN112557367A (en) * 2016-12-22 2021-03-26 波音公司 Surface sensing system and method for imaging a scanned surface of a sample by sum frequency vibration spectroscopy

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112557367A (en) * 2016-12-22 2021-03-26 波音公司 Surface sensing system and method for imaging a scanned surface of a sample by sum frequency vibration spectroscopy
CN112557367B (en) * 2016-12-22 2024-06-11 波音公司 Surface sensing system and method for imaging a scanned surface of a sample by sum frequency vibration spectroscopy
CN108896176A (en) * 2018-05-14 2018-11-27 浙江大学 A kind of Space Consistency bearing calibration of multi-optical spectrum imaging system

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EP1685370A1 (en) 2006-08-02
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