US3697180A - Apparatus for automatically recording the hedepolarization ratios of raman bands - Google Patents

Apparatus for automatically recording the hedepolarization ratios of raman bands Download PDF

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Publication number
US3697180A
US3697180A US95700A US3697180DA US3697180A US 3697180 A US3697180 A US 3697180A US 95700 A US95700 A US 95700A US 3697180D A US3697180D A US 3697180DA US 3697180 A US3697180 A US 3697180A
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Prior art keywords
light
rays
raman
sample
polarized
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Expired - Lifetime
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US95700A
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English (en)
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Hajime Mori
Mamoru Irizuki
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Jeol Ltd
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Jeol Ltd
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Priority claimed from JP9852769A external-priority patent/JPS5146434B1/ja
Priority claimed from JP1738370A external-priority patent/JPS5114913B1/ja
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/21—Polarisation-affecting properties
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J4/00—Measuring polarisation of light

Definitions

  • Ru (X) represents the intensity of the rays of Raman light scattered from a sample as a result of illuminating the sample with a ray of incident lightpolarized perpendicular to a plane
  • Rh (X) represents the intensity of the rays of Raman light scattered from the sample by illuminating the sample with a ray of incident light polarized parallel to the said plane.
  • a Raman spectrum is first observed by illuminating the sample with an incident ray of light polarized parallel to aplane and then again observed by illuminating the sample with an incident ray of light polarized perpendicular to the said plane.
  • the depolarization ratios are then calculated by comparing two intensities of the same line in the two spectra. This method, to say the least, is quite troublesome, not to mention the margin of error involved due to the fluctuation of the incident light intensity, plus, of course, the human element.
  • the two rays of Raman light are then alternately applied to a monochromator where they are dispersed according to wavelength and detected by a detecting means such as a photomultiplier. That is to say, two electrical signals based on the two different rays of incident light are alternately detected by the detecting means.
  • the signals are then amplified and-their ratio is automatically calculated by a division circuit and recorded by a recorder. This procedure is continuously repeated so that the ratio of each set of signals is continuously and automatically recorded by the recorder.
  • the depolarization ratios are obtained by a single scanning of the monochromator, thereby shortening the ratio measuring time. Further, since the sample is illuminated alternately, the two Raman spectra are observed under identical condi- "tions, thus ensuring precise measurement of the depolarization ratios.
  • FIG. 1 shows one embodiment of the invention in which the light path between the light source and the sample is bifurcated.
  • FIG. 4 shows another embodiment of this invention.
  • FIG. 8 shows the sector used in the embodiment shown in FIG. 7.
  • FIG. 9 shows yet another embodiment of this invention in which the sector is inserted in the optical path between the sample and the monochromator.
  • FIG. 11 shows one more embodiment of this invention.
  • a coherent ray of light polarized parallel to a reference plane, preferably the horizontal plane, is produced by a laser 1.
  • the optical path of the coherent ray of light is changed by a sector 2 which takes the form of a fan-shaped reflector as shown in FIG. 2.
  • the said sector is mounted on a shaft 3 rotated by a motor 4.
  • Also mounted on the said shaft is a chopper 5 and a gear 6, the said gear 6 being meshed to gear 7, on a shaft 8 of which a second sector 9, identical in form to the sector 2, is mounted. Accordingly, the rotation of the sector 9 is synchronized with the rotation of the sector 2.
  • the light deflected by the sector 2 is reflected by a mirror 10 so as to follow Path B, the said light being polarized perpendicular to the plane by a half-wave plate 11 and directed to Path C by a mirror 12 and the sector 9.
  • two light rays, one polarized parallel to the plane and the other polarized perpendicular to the plane illuminate the sample 13 alternately, and in so doing, excite the said sample causing a scattering of Raman light rays.
  • the light rays scattered from the sample are then directed to a scanning monochromator 14 where they are dispersed according to wave length. Once dispersed, the rays are converted into electrical signals by a photomultiplier l5 and amplified by an amplifier 16.
  • the amplified signals are then fed into gate circuits l7 and 18.
  • light emanating from a light source 19 is detected by a phototransistor 20 and applied to the respective gate circuits via a waveforming circuit 21 as gate signals.
  • the chopper 5, shown in FIG. 3, located between the light source 19 and the phototransistor 20, is synchronized so as to pass light when the sample 13 is illuminated by incident light polarized parallel to the plane and to intercept light when the sample 13 is illuminated by incident light polarized perpendicular to the plane.
  • the gate circuit 17 is opened when the sample is illuminated by incident light polarized parallel to the plane, enabling signals based on Raman light rays generated by parallel incident light to pass through the said gate circuit and into filter 22 where they are smoothed.
  • FIG. 4 shows another embodiment of this invention in which the same optical system as described in the aforedescribed embodiment is used for obtaining the two incident light rays polarized parallel and perpendicular to the plane.
  • the sectors 30 and 31 are different as shown in FIG. 5.
  • Sections 32 of the sectors for example, take the form of fan-shaped mirrors and sections 33 serve to absorb the light emanating from the laser 1.
  • FIG. 6A shows the train of light signals illuminated onto the sample 13.
  • the period th represents the period in which the incident light polarized parallel to the plane illuminated the sample 13
  • period tu represents the period in which the incident light polarized perpendicular to the plane illuminates the said sample
  • period tc represents the period in which the sample is not illuminated at all.
  • Raman light rays scattered from the sample are dispersed according to wavelength by a monochromator 34.
  • one circuit produces and records the Raman spectrum.
  • Another circuit (interconnected) produces and records the depolarization ratio.
  • the rays are converted into pulse signals, having frequencies proportional to the intensities of the said rays, by a photomultiplier 35.
  • the pulse signals are then amplified by pre-and main-amplifiers 36 and 37.
  • Low amplitude noise, such as dark current, in the said pulse signals is removed by discriminator 38, the output of which is fed into a gate circuit 39 into which gate signals are also fed.
  • the gate signals are based on the light generated by lamp 119.
  • the light generated by the said lamp is detected by a phototransistor and converted into an electrical signal. Again, during the period tu and the subsequent period to, the light generated by lamp 19 is intercepted by a chopper 5.
  • the signals detected by the phototransistor 20 are amplified by an AC amplifier 40 and wave formed by a Schmitt circuit 41.
  • the output of the Schmitt circuit 41 is then fed into a gate signal forming circuit 42 in which the phases and the level of the signals are regulated. Thence, the pulsed signals enter the gate circuit 39 which is opened during the period th and the subsequent period to.
  • the intensity of the Raman signals passed through the said gate circuit is counted by a photoncounter 43 and the Raman spectrum is recorded by 2-pen recorder 44.
  • the monomultivibrator pulses output is fed into a pulse controller 46 where the pulse widths and heights are controlled.
  • the controlled pulses are then fed into a filter 47 and smoothed.
  • the voltage E of the smoothed signal is expressed as follows:
  • the said output signals are amplified by an AC amplifier 48 where the DC component Edc is removed by a coupling condenser, so as to produce voltages E, E and E,, as shown in FIG. 6D.
  • the said voltages are expressed algebraically as follows:
  • FIG. 6F shows the output signal of the synchronizing rectifier 52
  • FIG. 6G shows the rectified output after being smoothed by filter 54.
  • the output voltage E of the said filter is expressed as follows:
  • sections 74 and 75 represent polarizers in which the- Raman light rays polarized parallel and perpendicular to the plane respectively pass. Sections 76 serve to intercept the passageof light. Thus, the two Raman light rays enter the monochromator alternately.
  • the depolarization ratios are measured by the electrical units used in the prior described embodiments.
  • the gate signal is produced by chopper 77, mounted fixedly on the periphery of the sector and thereby rotating in unison with the said sector, a light source 78 and a phototransistor 79.
  • An apparatus for automatically recording the Raman Spectrum and the depolarization ratios of Raman bands of a sample comprising:
  • C. means for alternately illuminating said sample with said two incident rays of light
  • G an analyzing circuit for providing a signal indicative of the ratio of the intermittent electrical signals resulting from the two differently polarized rays of light
  • H means for recording the output signals of said detecting means and said analyzing circuit simultaneously.
  • said light source comprises a laser providing a plane polarized monochromatic output.
  • An apparatus for automatically recording the Raman Spectrum and the depolarization ratios of Raman bands of a sample comprising:
  • C. means for alternately illuminating said sample with said two incident rays of light
  • an analyzing circuit for providing a signal indicative of the ratio of the intermittent electrical signals supplied thereto comprising:
  • circuit means for comparing the signal voltage of the Raman light resulting from the parallel polarized incident rays of light to a reference voltage
  • a control circuit and a circuit means for feeding back the differential voltage observed in the comparing circuit to control the intensity of both electrical signals maintaining the signal based on the parallel polarized incident rays of light constant; i circuit means for producing a signal being the difference between the signal voltage of the Raman light resulting from the perpendicular polarized incident rays of light, said signal being indicative of the depolarization ratios; and,
  • H means for recording the depolarization ratios and the output signal of the detecting means simultaneously.
  • C. means for alternately illuminating said sample with said two incident rays of light
  • G means for producing a differential signal of said electrical signals
  • H means for attenuating the intensity of the incident light polarized parallel to the plane according to said differential signal so as to equalize the intensities of the two Raman light rays;

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
US95700A 1969-12-08 1970-12-07 Apparatus for automatically recording the hedepolarization ratios of raman bands Expired - Lifetime US3697180A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9852769A JPS5146434B1 (enExample) 1969-12-08 1969-12-08
JP1738370A JPS5114913B1 (enExample) 1970-02-28 1970-02-28

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FR (1) FR2072238A5 (enExample)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3807862A (en) * 1972-12-18 1974-04-30 Sybron Corp Raman spectroscopy in the presence of fluorescence
US3817634A (en) * 1971-03-10 1974-06-18 Nat Res Dev Testing of optically active substances by polarized radiation
DE2650994A1 (de) * 1975-11-07 1977-05-18 Stefan Ridderstedt Vorrichtung zur abschliessbaren halterung eines gegenstands an einer stationaeren aufbewahrungsstelle
US4672196A (en) * 1984-02-02 1987-06-09 Canino Lawrence S Method and apparatus for measuring properties of thin materials using polarized light
US5139334A (en) * 1990-09-17 1992-08-18 Boston Advanced Technologies, Inc. Hydrocarbon analysis based on low resolution raman spectral analysis
US6124928A (en) * 1997-03-07 2000-09-26 Kaiser Optical Systems, Inc. Methods and apparatus for obtaining a selectively polarized induced emission
CN105974397A (zh) * 2016-07-12 2016-09-28 南京信息工程大学 基于琼斯矩阵的偏振激光雷达标定方法及偏振激光雷达

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4586819A (en) * 1982-07-09 1986-05-06 Hitachi, Ltd. Laser Raman microprobe

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414354A (en) * 1964-10-28 1968-12-03 Perkin Elmer Corp Raman spectrometers
US3572938A (en) * 1969-02-18 1971-03-30 Us Navy Polarimeter

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414354A (en) * 1964-10-28 1968-12-03 Perkin Elmer Corp Raman spectrometers
US3572938A (en) * 1969-02-18 1971-03-30 Us Navy Polarimeter

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Claasen et al. Applied Spectroscopy, Vol. 23, No. 1 Jan. Feb. 1969, pages 8 12. *
Hawes et al., Analytical Chemistry, Vol. 38, No. 13, Dec. 1966 pages 1842 1847. *
Murphy et al., The Journal of Chemical Physic, Vol. 47, No. 5, Sept. 1, 1967, pp. 1836 1839. *

Cited By (8)

* Cited by examiner, † Cited by third party
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
US3807862A (en) * 1972-12-18 1974-04-30 Sybron Corp Raman spectroscopy in the presence of fluorescence
DE2650994A1 (de) * 1975-11-07 1977-05-18 Stefan Ridderstedt Vorrichtung zur abschliessbaren halterung eines gegenstands an einer stationaeren aufbewahrungsstelle
US4672196A (en) * 1984-02-02 1987-06-09 Canino Lawrence S Method and apparatus for measuring properties of thin materials using polarized light
US5139334A (en) * 1990-09-17 1992-08-18 Boston Advanced Technologies, Inc. Hydrocarbon analysis based on low resolution raman spectral analysis
US6124928A (en) * 1997-03-07 2000-09-26 Kaiser Optical Systems, Inc. Methods and apparatus for obtaining a selectively polarized induced emission
CN105974397A (zh) * 2016-07-12 2016-09-28 南京信息工程大学 基于琼斯矩阵的偏振激光雷达标定方法及偏振激光雷达
CN105974397B (zh) * 2016-07-12 2018-06-19 南京信息工程大学 基于琼斯矩阵的偏振激光雷达标定方法及偏振激光雷达

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DE2060409A1 (de) 1971-06-16
FR2072238A5 (enExample) 1971-09-24

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