WO2014208349A1 - Dispositif de mesure optique et procédé de mesure optique - Google Patents

Dispositif de mesure optique et procédé de mesure optique Download PDF

Info

Publication number
WO2014208349A1
WO2014208349A1 PCT/JP2014/065587 JP2014065587W WO2014208349A1 WO 2014208349 A1 WO2014208349 A1 WO 2014208349A1 JP 2014065587 W JP2014065587 W JP 2014065587W WO 2014208349 A1 WO2014208349 A1 WO 2014208349A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
signal
probe
sample
optical
Prior art date
Application number
PCT/JP2014/065587
Other languages
English (en)
Japanese (ja)
Inventor
孝嘉 小林
啓介 瀬戸
Original Assignee
国立大学法人電気通信大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人電気通信大学 filed Critical 国立大学法人電気通信大学
Priority to JP2015523971A priority Critical patent/JPWO2014208349A1/ja
Publication of WO2014208349A1 publication Critical patent/WO2014208349A1/fr

Links

Images

Classifications

    • 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
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0208Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using focussing or collimating elements, e.g. lenses or mirrors; performing aberration correction
    • 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
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/021Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using plane or convex mirrors, parallel phase plates, or particular reflectors
    • 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
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0218Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using optical fibers
    • 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
    • G01J3/08Beam switching arrangements
    • 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

Definitions

  • the present invention relates to an optical measurement device and an optical measurement method with low noise and high sensitivity.
  • An optical measurement is performed in which a sample is irradiated with a light beam and the state of a substance or biomolecule is measured without contact. Depending on the object to be measured, the obtained signal strength is very small and may be buried in noise.
  • lock-in detection method for detecting a minute signal buried in noise.
  • a product of a trigonometric function of a set frequency (lock-in frequency) and a signal is taken, and after converting the signal of that frequency to a low frequency, a signal component is taken out by a low-pass filter.
  • lock-in detection effectively works as a narrow-band bandpass filter.
  • noise observed at a frequency different from the lock-in frequency is removed, and a signal in the vicinity of the lock-in frequency is detected, thereby improving the signal / noise ratio.
  • the bandwidth can be narrowed and noise can be removed more effectively.
  • the lock-in detection method is applied to detection of low intensity probe light and detection of minute modulation applied to the probe light.
  • This modulation may be applied directly to the probe light source or may be induced by a stimulus applied to the sample.
  • noise observed near the lock-in frequency cannot be removed in principle.
  • the time constant is increased in order to reduce the bandwidth and improve the signal-to-noise ratio by the integration effect, there is a problem that the response to changes in the signal is delayed and high-speed detection cannot be performed.
  • a dual beam method is known as a method for canceling long-time scale fluctuations included in probe light using lock-in detection.
  • light from a light source is divided into probe light used for measuring the sample and reference light that does not pass through the sample, and is modulated at different frequencies.
  • the probe light after passing through the sample and the reference light are superimposed and incident on the same detector.
  • the signal from the detector is obtained by separately obtaining the signal of the probe light and the reference light by lock-in detection at each modulation frequency, and taking the ratio.
  • balance detection method as a method for removing noise observed at the same frequency as the detection included in the probe light (see, for example, Patent Document 1 and Non-Patent Documents 1 and 2).
  • the balance detection method light from a light source is divided into probe light and reference light. After the probe light is incident on a sample, each light is detected by two detectors and the difference is obtained. Since the noise is included in the probe light and the reference light in phase, the noise observed at the same frequency can be removed by taking the difference.
  • the known balance detection method has some drawbacks.
  • Non-Patent Document 3 A method of detecting a minute signal over multiple wavelengths by detecting white probe light transmitted through a sample with a multi-channel lock-in amplifier and observing a Raman spectrum is known (for example, Non-Patent Document 3). reference).
  • the frequency at which noise is observed is different between the reference light and the probe light, and noise that fluctuates at high speed near the lock-in frequency cannot be removed. Further, in the balance detection method using two detectors, it is difficult to perform calibration and characteristic adjustment between two optical paths and two detection systems.
  • an object of the present invention is to provide an optical measurement technique and configuration capable of detecting a signal with low noise and high sensitivity using a single detector.
  • a new balanced circuit is used to efficiently remove noise near the observation frequency and detect a desired signal with low intensity with high sensitivity.
  • the optical measuring device is: A light source; A first optical element that splits light from the light source into probe light and reference light; A first path for guiding the probe light to the sample; A second path of the reference light in which an optical path length is adjusted so as to give a relative delay between the reference light and the probe light on a time axis; A detector that outputs the detection signal by detecting the probe light that irradiates the sample, and the reference light, the optical path length of which has been adjusted, with a common detection element; Among the detection signals, a signal derived from the probe light and a signal derived from the reference light are balanced by applying opposite signs to the signal derived from the probe light and the signal derived from the reference light, respectively. A balancer that outputs the difference between the two as the measurement result of the sample.
  • “equilibrium” means to balance the absolute value of the signal intensity derived from the probe light and the signal intensity derived from the reference light.
  • an optical measurement method is provided.
  • the optical measurement method is Split the light from the light source into probe light and reference light, Irradiate the sample with the probe light, Giving a relative delay between the reference light and the probe light on the time axis; Detecting the probe light irradiated on the sample and the reference light given the delay with the same detection element, Among the detected signals, the signal derived from the probe light and the signal derived from the reference light are balanced by applying opposite signs to the signal derived from the probe light, and the signal derived from the probe light A difference between signals derived from the reference light is acquired as a measurement result of the sample.
  • FIG. 16 is a diagram illustrating an application example of the optical measurement device of FIG. 15 to guided Raman measurement. It is a figure which shows the effect of the noise cancellation using the reference light delayed by 1/4 period of intensity modulation light, and the effect of feedback control. It is a schematic diagram of the sample used by measurement. It is a figure which shows the effect of the induced Raman measurement to which the method of embodiment is applied. It is a figure which shows the effect of the feedback control of embodiment.
  • FIG. 1 is a schematic configuration diagram of an optical measurement apparatus 10A according to the first embodiment.
  • the optical measurement apparatus 10 ⁇ / b> A includes a light source 11, optical elements 12 and 15, a detector 18, a transimpedance amplifier (TIA) 31, and a balancer 30.
  • the light source 11 is a pulse light source that emits single-wavelength pulse light
  • the optical elements 12 and 15 are polarization beam splitters.
  • Probe pulse light L P that has passed through the polarizing beam splitter 12 passes through the sample 20 along the path P1, and is incident on the polarization beam splitter 15.
  • the polarization beam splitter 15, and the probe pulse light L P passed through the path P1, the reference pulse light L R passing through the path P2 is incident on the detector 18 are superimposed spatially.
  • Path P2 of the reference pulse light L R is about half of the delay of the pulse period is set to a length given.
  • the reference pulse light LR is incident on the polarization beam splitter 15 with a phase delayed by 180 ° with respect to the pulse repetition period.
  • the reference pulse light LR is a probe on the time axis. appearing in between pulses intermediate position of the pulse light L P.
  • the pulse repetition frequency of the light source 11 is 76 MHz.
  • the probe pulse light L P transmitted through the sample such as molecular vibrations of the sample, and information I minute strength.
  • Reference pulse light L R and the detected probe pulse light L P by the detector 18 is input balancer (the balance circuit) 30.
  • An electric pulse synchronized with the pulsed light L is input to the balancer 30 and is used for canceling noise.
  • the balancer 30 outputs the information I after the noise is canceled.
  • FIG. 2 shows a configuration example of the balancer 30.
  • the balancer 30 receives a pulse signal (including a probe pulse signal and a reference pulse signal) detected by the detector 18 and converted into a voltage by the TIA, and an electric pulse synchronized with the pulsed light.
  • a pulse signal including a probe pulse signal and a reference pulse signal
  • the balancer 30 includes a bandpass filter 32, a phase adjuster 33, a comparator 34, a multiplier 38, and an averaging circuit 41.
  • the balancer 30 may optionally include a bias power source 36, a capacitor 35, a resistor 37, an active low pass filter 42, and an active high pass filter 43.
  • the current output from the detector 18 such as a photodiode is converted into a voltage signal of an appropriate level by the TIA 31 and input to the multiplier 38.
  • This voltage signal includes a probe pulse component and a reference pulse component.
  • the electric pulse signal synchronized with the pulse light from the pulse light source 11 is converted into a 76 MHz sine wave synchronized with the pulse light by the 76 MHz band pass filter 32 and the phase adjuster 33, for example.
  • This sine wave is further converted into a square wave (rectangular wave) by the comparator 34, and square waves of +1 and ⁇ 1 are input to the multiplier 38.
  • the bias power source 36, the capacitor 35, and the resistor 37 are used when a bias is applied to the square wave generated by the comparator 34.
  • the capacitor 35 and the resistor 37 decouple the bias voltage B generated by the bias power source 36 and the square wave.
  • the intensity of the horizontal polarization component (probe pulse light L P ) and the vertical polarization component (reference pulse light L R ). are equal, it is not necessary to apply a bias. As will be described later in the embodiments, it is effective to adjust the signal intensity ratio between the probe light and the reference light by applying a bias when using multi-wavelength detection light.
  • a multiplier 38 multiplies the probe pulse signal and the reference pulse signal by a square wave.
  • the probe pulse signal is multiplied by 1 ((1 + B) times when a bias voltage is applied), and the reference pulse signal is multiplied by -1 ((-1 + B) times when a bias voltage is applied) and output from the multiplier 38. .
  • the probe pulse signal and the reference pulse signal whose signs are reversed are averaged by the averaging circuit 41 and canceled out.
  • the averaging circuit 41 is a passive low-pass filter 41 composed of, for example, a capacitor and a resistor, and outputs a difference by averaging the probe pulse signal and the reference pulse signal that have opposite signs.
  • the output signal is the information component I derived from the sample after the noise is canceled out.
  • the output Vout of the averaging circuit 41 is expressed as follows.
  • Vout (probe pulse signal) ⁇ 1 + (reference pulse signal) ⁇ ( ⁇ 1)
  • the output of the averaging circuit 41 is further output through an active low-pass filter 42 having a cutoff frequency of 10 kHz using an operational amplifier and an active high-pass filter 43 having a cut-on frequency of 400 Hz.
  • the combination of the active filters 42 and 43 functions as a band pass filter with a gain of 100 times.
  • the optical measuring device 10A shown in FIGS. 1 and 2 has the following characteristics. (a) dividing the pulsed light generated at the same time from the same light source 11 by dividing the reference pulse light L R and the probe pulse light L P, contained in the reference pulse light L R and the probe pulse light L P The nature of noise is the same. (b) detection system because of the same probe pulse light L P and the reference pulse light L R, the frequency characteristics of the detection system are identical. Therefore, noise can be canceled including the frequency at which the signal is observed. The use of (c) a square wave, even if the timing of the reference pulse light L R and the probe pulse light L P is slightly deviated from one period of 2 minutes of repetitive pulses, the maximum equilibrium is obtained. That is, the degree of cancellation is not sensitive to the optical path difference, and the optical system can be easily adjusted.
  • FIG. 3 is a flowchart of the optical measurement method of the first embodiment. Irradiating the pulse light (S101), it divides the pulsed light to the reference pulse light L R and the probe pulse light L P (S102). The probe pulse light L P is incident on the sample to measure the sample (S103). The reference pulsed light L R giving half of the delay of the pulse period (S104), spatially overlap the reference pulse light and probe pulse light (S105). The superimposed optical signal is detected and converted into an electrical signal (S106).
  • FIG. 4 is a schematic configuration diagram of the optical measurement apparatus 10B of the second embodiment.
  • the optical measuring device 10B splits the light from the light source 11 into probe pulse light and reference pulse light to give a delay to the reference pulse light, and the probe pulse signal detected by the same detector 18 in the balancer 30. It is the same as the optical measurement apparatus 10A of the first embodiment in that a reference pulse signal is input and an electric pulse synchronized with pulse light is input.
  • Optical measuring device 10B is arranged a polarization beam splitter 15 in front of the sample 20, and that the combined probe pulse light L P and the reference pulse light L R is incident on the sample 20, the probe pulse from the stimulation unit (not shown) in that the stimulus S to synchronize with light L P is applied to the sample 20, different from the optical measuring device 10A of the first embodiment.
  • the sample is optically non-uniform and the transmittance of the sample changes during imaging.
  • the optical path of the probe pulse light L P and the reference pulse light L R from the specimen 20 to the detector 18 is different from the intensity ratio of the reference pulse light L R and the probe pulse light L P is changed during measurement, a possibility that the equilibrium is broken There is.
  • FIG. 5 is a flowchart of the optical measurement method of the second embodiment. Irradiating the pulse light (S201), it divides the pulsed light to the reference pulse light L R and the probe pulse light L P (S202).
  • the reference pulsed light L R giving half of the delay of the pulse period (S204), spatially overlap the reference pulse light L R and the probe pulse light L P (S205).
  • With the superimposed pulsed light incident on the specimen providing a synchronized stimulus probe pulse light L P to the sample (S206).
  • S207 measuring the sample under the influence of the stimulus
  • the pulsed light transmitted through the sample is detected and converted into an electric signal (S208).
  • FIG. 6 is a schematic configuration diagram of an optical measuring device 50 according to the third embodiment.
  • balanced detection is applied to multi-channel lock-in detection in which multiple signals are locked in in parallel.
  • the optical measuring device 50 corresponds to a white light source 51, optical elements 52 and 55, a spectroscope 58, a plurality of detectors 18-1 to 18-n (hereinafter collectively referred to as “detector 18” as appropriate), and each detector. Includes TIAs 31-1 to 31-n (referred to collectively as “TIA31” where appropriate), a plurality of balancers 30-1 to 30-n (referred to as “balancer 30” as appropriate), and a multi-channel lock-in amplifier 59. .
  • the optical element 52 is a polarization beam splitter as in the first and second embodiments.
  • the detector 18 is, for example, an avalanche photodiode (APD).
  • the white light source 51 generates white pulse light including a plurality of continuous wavelengths using, for example, a pulse laser having a pulse repetition frequency of 76 MHz and a photonic crystal fiber (PCF).
  • the center wavelength of the pulse laser is, for example, 800 nm.
  • FIG. 7 shows a spectrum of white pulse light emitted from the white light source 51.
  • the white pulse light has an intensity from 575 nm to 780 nm.
  • the white pulse light and probe pulse light L P at the polarization beam splitter 52 is split into the reference pulse light L R.
  • Light component reflected by the polarizing beam splitter 52, as the reference pulsed light L R, is incident on the polarization beam splitter 55 via the mirror 53 and 54.
  • the optical path length of the reference pulse light L R is set to a length delayed a half period (phase 180 °) relative to the pulse repetition period of the white light source 51.
  • the pump pulse light L S is branched from the light emitted from the pulse laser used in the white light source 51, for example, and is intensity-modulated by a chopper (not shown). Pump pulse light L S is synchronized with the probe pulse light L P, but the reference pulse light L R of phase 180 °.
  • the probe pulse light L P , the reference pulse light L R , and the pump pulse light L S are incident on the sample 20.
  • molecular vibrations according to the wavelength are generated and scattering occurs.
  • the influence of the scattering intensity of the probe pulse light L P to synchronize the pump pulse light L S is modulated.
  • the reference pulse light L R of different pump pulse light L S and the timing is not affected.
  • the pump pulse light L S is removed by short-pass filter SPF, Puroparusu light L P having received the reference pulse light L R and the intensity modulation, via the lens 57 and the optical fiber 61 Spectroscopy Guided to instrument 58.
  • Spectrometer 58 disperses reference pulse light L R and the probe pulse light L P, respectively. The separated light of each wavelength is detected by detectors 18-1 to 18-n. The detection result is input to the corresponding balancers 30-1 to 30-n.
  • Each of the balancers 30-1 to 30-n has the configuration shown in FIG. 2, and receives the voltage signal of the TIA 31 and an electric pulse synchronized with the white pulse light.
  • the ⁇ 1 logic at each balancer 30 probe pulse light L P and the reference pulse light L R is canceled, only the portion which receives the intensity modulation is extracted as a sample information by scattering.
  • the output of each balancer 30 is lock-in detected by the multi-channel lock-in amplifier 59 at the modulation frequency of the pump pulse light.
  • the measurement speed is remarkably increased compared with a method of obtaining a spectrum by normal one-channel lock-in detection.
  • the multi-channel lock-in amplifier 59 is, for example, a 128-channel lock-in amplifier, measurement can be performed at a speed 128 times that of normal one-channel lock-in detection.
  • White light usually has high noise, but by using the balancers 30-1 to 30-n, noise can be canceled at each wavelength and minute information can be detected with high sensitivity and high speed.
  • the pulse light generated from the same light source at the same time is divided into probe pulse light and reference pulse light, which are included in the probe pulse light and reference pulse light. Noise becomes the same, and the effect of balanced detection is maximized.
  • the single spectroscope 58 can split the light into each wavelength. .
  • each of the balancers 30 can adjust ⁇ 1 logic (sign-inverted square wave) by applying a bias (see FIG. 2), it is particularly effective for sample measurement using white light.
  • the bias level is B
  • the signal output Vout obtained by each balancer 30 for each wavelength is expressed as follows.
  • Vout (probe pulse signal) ⁇ (1 + B) + (reference pulse signal) ⁇ ( ⁇ 1 + B)
  • optical splitting is required in which the intensity of the probe pulse light and the reference pulse light are the same at all wavelengths. This is difficult to achieve at 52.
  • the signal intensity of the probe pulse light and the reference pulse light can be corrected evenly by applying an appropriate bias by the balancer 30 at the subsequent stage. Therefore, the maximum balance can be obtained at all wavelengths.
  • ⁇ Fourth embodiment> 8 and 9 are schematic configuration diagrams of the optical measurement apparatus 100 according to the fourth embodiment.
  • the equilibrium detection and multi-channel lock-in detection of the third embodiment are applied to a guided Raman microscope.
  • a stimulated Raman scattering method as a method for observing a Raman scattering spectrum and intensity reflecting molecular vibration information.
  • a sample is irradiated with synchronized pulse laser beams of at least two wavelengths having different wavelengths.
  • the difference in wavelength corresponds to the energy of molecular vibration
  • the intensity of light having a short wavelength decreases and the intensity of light having a long wavelength increases.
  • a decrease in the intensity of light having a short wavelength is referred to as induced Raman loss
  • an increase in the intensity of light having a long wavelength is referred to as induced Raman gain. Since molecular vibration differs depending on the substance, qualitative analysis can be performed using stimulated Raman scattering.
  • the probe pulse light detected for each wavelength is subjected to multichannel lock-in detection, so that the stimulated Raman scattering intensity at each wavelength is obtained, and the sample is made relatively to the incident light. Sweep to obtain an image by stimulated Raman scattering spectrum.
  • the optical measurement apparatus 100 includes a white light source 110, polarization beam splitters 119 and 122, a stage 127 that drives the sample 20 relative to the light pulse, and a measurement system that measures light from the sample 20. 150.
  • the white light source 110 includes a pulse laser light source 101 and a photonic crystal fiber (PCF) 116.
  • the pulse laser light source 101 is composed of, for example, a titanium sapphire pulse laser.
  • the titanium sapphire pulse laser outputs pulse light at a center wavelength of 800 nm, a pulse width of 2.5 ps, a pulse repetition frequency of 76 MHz, and an average output of 450 mW by a passive mode-locking operation using titanium sapphire as a gain medium, and is synchronized with the pulse light.
  • a pulse electric signal is output.
  • the output light of the pulse laser light source 101 is guided to the beam splitter 104 via the isolator 103.
  • the isolator 103 blocks the return light from the subsequent optical element to the pulse laser light source 101 and stabilizes the operation of the pulse laser light source 101.
  • the beam splitter (BS) 104 splits the pulsed light output from the pulse laser light source 101, reflects 40%, and transmits 60%.
  • the pulsed light transmitted through the BS 104 is guided to the half-wave plate 114 through a concave lens 112 having a focal length of 60 mm and a convex lens 113 having a focal length of 120 mm.
  • the lenses 112 and 113 adjust the beam diameter so as to fill the pupil plane of the objective lens 115.
  • the plane of polarization is adjusted by rotating the half-wave plate 114 around the optical axis.
  • the pulsed light whose polarization plane has been adjusted enters a microscope objective lens 115 having a magnification of 40 and a numerical aperture of 0.65.
  • the pulsed light collected by the objective lens 115 is introduced into a polarization-maintaining PCF 116 having a length of 30 cm.
  • the PCF 116 is made of silica, and the cross section has a structure in which regularly arranged voids surround the core. A region having a void has a refractive index substantially smaller than that of the core and functions as a cladding.
  • the difference in refractive index between the core and the clad is large, the incident light is confined in a narrow space region, the energy density of the incident light is increased, and a large nonlinear optical effect is obtained. Due to this large nonlinear effect, the wavelength of the incident light is converted into white light having an intensity in a wide range of wavelengths by the power of the pulse laser 101. If the direction of the polarization plane of the incident light is appropriate due to the polarization maintaining function of the PCF 116, linearly polarized light is output.
  • the white light generated by the PCF 116 is collimated by the microscope objective lens 117 having a magnification of 40 and a numerical aperture of 0.65. At this time, the direction of the polarization plane of white light is adjusted by rotating the PCF 116.
  • the collimated white pulse light L becomes the output of the white light source 110.
  • White pulse light L is split into the reference pulse light L R and the probe pulse light L P by the polarization beam splitter (PBS) 119.
  • Reference pulse light L R is the pulsed laser light source 101 pulse repetition minute delayed half cycle with respect to the period, i.e. after a long optical path in phase is delayed 180 ° min, enters the PBS122, spatial and probe pulse light L P Is superimposed on.
  • the PBSs 119 and 122 both transmit horizontally polarized light and reflect vertically polarized light. When polarized light whose plane of polarization is inclined by 45 ° is incident on PBS 119, the intensity of transmitted horizontal polarized light and reflected vertical polarized light are substantially equal.
  • PBS122 transmits the probe pulse light L P is a horizontally polarized light, by reference pulsed light L R is vertically polarized light is reflected, the reference pulse light L R and the probe pulse light L P is overlapped with a high throughput .
  • Reference pulse light L R and the probe pulse light L P passes through the short-pass interference filter 111.
  • the short-path interference filter 111 blocks white light having a wavelength component of 780 nm or more and superimposes the modulated pump pulse light L S on the same axis.
  • the intensity of the 40% pulse light reflected by the BS 104 is modulated (on / off) by the optical chopper 105 and used as the pump pulse light L S.
  • the pump pulse light L S passes through a convex lens 107 having a focal length of 170 mm and a concave lens 108 having a focal length of 150 mm. Lenses 107 and 108, the beam diameter of the pumping pulse light L S equal to the beam diameter of the white pulse light L.
  • the pump pulse light L S is guided to the delay stage 109.
  • Delay stage 109 includes two mirrors M1, M2 in parallel to slide by a micrometer (not shown), synchronized with the probe pulse light L P by adjusting the optical path length of the pump pulse light L S.
  • the power of the pump pulse light L S is adjusted by the neutral density filter 106.
  • the signal-to-noise ratio increases as the power of the pump pulse light L S increases, but the large power causes the sample 20 to be destroyed. Therefore, the neutral density filter 106 is used to adjust the power of the pump pulse light L S to a level that does not destroy the sample 20 while maintaining a large signal-to-noise ratio.
  • Pump pulse light L S is on a short-pass interference filter 111, it is superimposed on the probe pulse light L P and the reference pulse light L R.
  • the short path interference filter 111 functions as a mirror for 800 nm light.
  • Pump pulse light L S and the probe pulse light L P is the timing matches, stimulated Raman signal is obtained as the intensity modulation of the probe pulse light L P.
  • the reference pulse light L R do not interact since the pump pulse light L S and timing is deviated.
  • the probe pulse light L P superimposed, the reference pulse light L R, and the pump pulse light L S is transmitted through the convex lens 124 of the concave lens 123 and the focal length 200mm focal length 100 mm.
  • the lenses 123 and 124 expand the beam diameter of the combined light so as to fill the pupil plane of the objective lens 126 at the subsequent stage.
  • the combined light passes through the beam splitter 125 having a reflectance of 8% and a transmittance of 92%, and then enters the objective lens 126.
  • the beam condensed by the objective lens 126 irradiates the sample 20 fixed to the stage 127.
  • the stage 127 is, for example, a piezo-driven stage, and sweeps the sample 20 with respect to incident light during measurement.
  • the beam reflected by the beam splitter 125 passes through the neutral density filter 129 and then forms an image on the CCD camera 131 by the imaging lens 130.
  • the neutral density filter 129 adjusts the intensity of the image formed on the CCD camera 131.
  • the light transmitted through the sample 20 is collimated by the condenser lens 132.
  • the collimated light is guided to the short pass filter 133, and the pump pulse light L S among the light included in the collimated light is blocked.
  • Collimated light pumping pulse light L S is removed is condensed by the convex lens 134 of focal length 100 mm, it is input to the measurement system 150 via a multimode optical fiber 135.
  • FIG. 9 shows a connection relationship between units of the optical measurement apparatus 100 with the measurement system 150 as the center.
  • Optical signal obtained by the stimulated Raman microscope 160 (including a reference pulse light L R and the probe pulse light L P) is introduced into the spectrometer 136 by the multi-mode optical fiber 135.
  • the spectroscope 136 the light from the multimode optical fiber 135 is irradiated onto the diffraction grating (not shown) in parallel by a collimating mirror (not shown), and the light dispersed by the diffraction grating is bundled by the camera mirror (not shown).
  • An image is formed on the end face of the fiber 137.
  • the spectroscope 136 has a focal length of 300 mm and a diffraction grating engraving density of 1200 g / mm.
  • the bundle fiber 137 is a bundle of 16 vertical fibers and 128 horizontal optical fibers, and divides the split light beam into 128. Every 16 bundle fibers 137 are bundled into one optical fiber 138.
  • the APD 139 has a function (action) for amplifying a weak detection signal by itself by avalanche breakdown.
  • the probe pulse signal and the reference pulse signal detected by each APD 139 and converted into a voltage by the TIA 141 are input to the corresponding balancer 140.
  • Each balancer 140 has the same configuration as the balancer 30 of FIG.
  • the balancer 140 multiplies the probe pulse signal and the reference pulse signal by a square wave whose bias is adjusted, and the signs of the probe pulse signal and the reference pulse signal are opposite to each other.
  • the probe pulse signal with the opposite sign and the reference pulse signal are added by a low-pass filter (see FIG. 2), and a difference is obtained.
  • Signal output from the balanced device 140, the reference pulse light L S and the probe pulse light L P is canceled each other, it is placed only information representing the effect of stimulated Raman scattering.
  • the timing at which the probe pulse signal and the reference pulse signal are reversed is controlled by an electric pulse signal synchronized with the pulse laser beam supplied from the pulse laser light source 101.
  • the signals output from each of the balancers 140-1 to 140-n are connected to the input of the multi-channel lock-in amplifier 142.
  • the multi-channel lock-in amplifier 142 is formed by connecting four 32-channel lock-in amplifiers to 128 channels, for example.
  • the optical measurement apparatus 100 includes a chopper controller 144, a piezo stage controller 148, and a computer 146 as a control system.
  • a reference signal for detecting lock-in is supplied from the chopper controller 144 to the multi-channel lock-in amplifier 142.
  • the chopper controller 144 controls power supply to the optical chopper 105 (see FIG. 8). Further, upon receiving a signal of the rotation speed of the optical chopper 105, the rotation speed is feedback-controlled.
  • the computer 146 controls the multi-channel lock-in amplifier 142, collects data from the multi-channel lock-in amplifier 142, and outputs a control signal to the piezo stage controller 148.
  • the piezo stage controller 148 receives a control signal from the computer 146 and controls an actuator (not shown) of the piezo stage 127. While the output signal from the multi-channel lock-in amplifier 142 is collected by the computer 146, the sample 20 is swept by the piezo stage 127 to obtain a stimulated Raman spectrum at each measurement point.
  • the multi-channel lock-in amplifier 142 and the piezo stage 127 are controlled by software installed in the computer 146.
  • FIG. 10 is a stimulated Raman loss image obtained by the optical measurement apparatus 100.
  • FIG. 10A shows an image obtained by summing the signals of the 40th to 50th channels
  • FIG. 10B shows an image obtained by summing the signals of the 55th to 65th channels.
  • the sample 20 a film prepared by dissolving polystyrene (PS) and polymethyl methacrylate (PMMA) in toluene at a weight ratio of 1: 1, and dropping the solution on a slide glass and drying it was used.
  • the lock-in detection time constant is 1000 ms
  • the pixel size is 0.5 ⁇ 0.5 ⁇ m
  • the image size is 20 ⁇ 20 ⁇ m. The lighter the shade, the higher the signal intensity, and the darker, the smaller the signal intensity.
  • the signals of the 40th to 50th channels in FIG. 10 (A) mainly show the contribution of PS.
  • the signals of the 55th to 65th channels in FIG. 10B mainly show the contribution of PMMA.
  • the images in FIGS. 10A and 10B are created from the same data obtained by one imaging. 10A and 10B show different contrasts, and it is possible to analyze that the concentration ratio of PS and PMMA varies depending on the position in the film.
  • FIG. 11 is a diagram showing induced Raman spectra at different pixel positions.
  • Each spectrum is a spectrum in which the spectrum of PS and the spectrum of PMMA overlap, but the intensity ratio of the Raman band derived from PS and the Raman band derived from PMMA is different.
  • the solid line has a large intensity ratio of the PS-derived Raman band, and the broken line has a large intensity ratio of the PMMA-derived Raman band.
  • FIG. 12 is a diagram showing the effect of the present invention.
  • the light from the same light source is divided into the probe pulse light and the reference pulse light, the reference pulse light is delayed by half the pulse repetition period of the light source, and the probe pulse light transmitted through the sample.
  • the reference pulse light to which the delay is given is detected simultaneously, the sign of the signal of the probe light or the reference light is inverted by multiplication with ⁇ 1 logic by the balancer 30, and the balance process is performed by the bias.
  • noise can be reduced and a desired signal can be obtained with high sensitivity.
  • the balance 30 is connected to the lock-in amplifier, the signal intensity obtained by directly chopping only the probe pulse light (left column), and the signal obtained by simultaneously chopping the probe pulse light and the reference pulse light. Intensity is shown (right column).
  • the intensity in the case of only the probe pulse light is 7.31 ⁇ 10 ⁇ 1 V, whereas it becomes 3.01 ⁇ 10 ⁇ 3 V when the reference pulse light and the probe pulse light are incident simultaneously.
  • the signal intensity after equilibrium is reduced to 1/243 compared to the case of probe pulse light alone. This means that noise included in the probe pulse light is also detected as 1/243.
  • the stimulus and the pump pulse light are synchronized only with the probe pulse light. Intensity modulation by stimulation or induced Raman effect occurs only in the probe pulse light, and does not occur in the reference pulse light. By taking the difference between the probe pulse light and the reference pulse light by the balancer 30, only the influence of the stimulus S and the induced Raman signal can be detected with high sensitivity.
  • the pulsed light from the light source is divided into the probe light and the reference light, and the reference light is delayed by a half cycle of the pulse repetition, and then the optical signal is transmitted by the common photodetector. The detected signal was multiplied by a square wave of ⁇ 1 to cancel the noise.
  • a sine wave is used for the balancing process for noise cancellation.
  • the detected signal is multiplied by a synchronization signal that is synchronized with the light from the light source and phase-adjusted.
  • the phase of the synchronization signal By adjusting the phase of the synchronization signal, the difference between the detection signal of the probe light and the detection signal of the reference light is minimized (equilibrium) to cancel the optical noise, and only the desired signal component is extracted.
  • FIG. 13 is a schematic diagram of an optical measurement apparatus 200 according to the fifth embodiment.
  • Periodic intensity modulation is given to the light from the light source 201 by the intensity modulator 202 driven by the synchronization signal source 207.
  • Light given intensity-modulated is divided into reference light L R and the probe light L P to be used in the sample measured by the beam splitter 203.
  • the reference light L R is given a delay corresponding to a quarter period of intensity modulation by an additional optical path after the beam splitter 203. Delay provided to the reference light L R, since the reference light L R and the probe light L P need be distinguished, not be a quarter period strictly intensity modulation may be in the vicinity thereof.
  • the probe light L P and the reference light L R are overlapped using the beam splitter 206 and are incident on the sample 210.
  • the probe light L P and the reference light L R after passing through the sample 210 are converted into an electric signal by the common light detection element 211 and amplified to an appropriate size by the preamplifier 212.
  • the detection signal of the probe light L P is A cos (wt)
  • the detection signal of the reference light L R is B sin (wt).
  • A is an amount proportional to the intensity of the probe light L P
  • B is an amount proportional to the intensity of the reference light L R
  • w is an angular frequency of the synchronization signal.
  • the optical noise is represented by fluctuations of A and B, but the probe light L P and the reference light L R divide the light at the same time, and therefore fluctuate in proportion to each other.
  • the ratio of A and B is determined by the characteristics of the optical element and is constant.
  • the electrical signal detected by the light detection element 211 is A cos (wt) + B sin (wt) It is expressed as This detection signal is input to the balancer 230 after amplification.
  • the balancer 230 includes a multiplier 231, a phase shifter 232, and a low pass filter 233.
  • the output of the preamplifier 212 is connected to the input of the multiplier 231.
  • the phase of the synchronization signal output from the synchronization signal source 207 is adjusted by the phase shifter 232, and is input to the multiplier 231 and multiplied by the detected signal.
  • the synchronization signal input to the multiplier 231 is represented by C cos (wt + f) It expresses.
  • f is the phase of the synchronization signal and is adjusted by the phase shifter 232. Therefore, the output from the multiplier 231 is (1/2) AC ⁇ cos (2wt + f) + cos f ⁇ + (1/2) BC ⁇ sin (2wt + f) – sin f ⁇ It becomes.
  • This signal is input to the low pass filter 233, and only the low frequency component is output.
  • the output signal of the balancer 230 is proportional to A cos f – B sin f. That is, when the phase f is appropriately selected, it can be seen that the difference between the detection signal of the probe light L P and the detection signal of the reference light L R is output.
  • the output of the balancer 230 becomes zero.
  • f is tan -1 (A / B) + 2np (n is an integer). That is, even when the ratio of A and B is not equal due to the characteristics of the optical element, the output of the balancer 230 can be made zero by adjusting f, and can be balanced. This adjustment can cancel the optical noise even when the ratio of A and B varies.
  • a periodic stimulus is given to the sample 210 by the stimulus source 208 driven by the synchronization signal source 207.
  • the phase of the stimulus is controlled to be in phase with the probe light L P so that only the probe light L P is subjected to intensity modulation induced by the stimulus. Since the effect of the stimulus modulates only the intensity A of the probe light L P , the low-pass filter 233 outputs only the signal induced by the stimulus in which the optical noise has been canceled.
  • FIG. 14 is a schematic configuration diagram of an optical measuring device 300 which is a modification of the fifth embodiment.
  • a spectroscope 311 is inserted immediately before the light detection element 211, and a resonator 312 that resonates with intensity modulation of the light source is inserted immediately after the light detection element 211.
  • the configuration, arrangement, and functions of the other components are the same as those in FIG.
  • the configuration of FIG. 13 can make the intensity ratio of the detection signal of the probe light and the reference light constant even if the detection signal does not contain a DC component.
  • the resonator 312 can be used (a DC component is not included in the signal from the resonator).
  • the resonator 312 does not include a load resistance that causes thermal noise, the thermal noise (electrical noise) is eliminated, and only a specific frequency component of the light detection signal is extracted and supplied to the balancer 230. It is possible to prevent mixing of frequencies that are not related to measurement, such as external noise, and to improve the signal to noise ratio.
  • FIG. 15 is a schematic diagram of an optical measurement apparatus 400 according to the sixth embodiment. Also in FIG. 15, the spectroscope 311 is disposed immediately before the light detection element 211, and the resonator 312 is disposed immediately after.
  • the reference light L R that does not pass through the sample 210 and the probe light L P that passes through the sample 210 are spatially overlapped and detected by a single light detection element 211, and a detection signal is input to the balancer 430. Further, the sample is irradiated with pump light (stimulation), the intensity of the pump light is modulated by the frequency of the reference signal, and the output of the balancer 430 is detected by lock-in at the frequency of the reference signal.
  • phase shifter 232 feedback control of the phase shifter 232 is performed based on a DC component included in the output of the multiplier 231.
  • the balancer 430 includes a multiplier 231, a first low-pass filter 433, a second low-pass filter 434, an integrator 435, and a phase shifter 232.
  • the second low-pass filter 434 extracts a DC component from the output signal of the multiplier 231, and the phase shifter 232 is driven by the integrated signal.
  • the output of the reference signal source 451 is input to the intensity modulator 452 and the lock-in detector 450.
  • the stimulation signal from the stimulation source 208 is synchronized with the probe light L P , is subjected to intensity modulation by the intensity modulator 452, and then enters the sample 210.
  • the frequency of the reference signal is set sufficiently higher than the frequency of the state change of the sample 210 due to imaging or the like.
  • the cutoff frequency of the first low-pass filter 233 is set to be larger than the frequency of the reference signal.
  • the cutoff frequency of the integrator 435 is set smaller than the frequency of the reference signal and larger than the frequency of the state change of the sample 210.
  • the magnitude relationship of each frequency is (Intensity modulation frequency of light source)> (cutoff frequency of first low-pass filter 433) > (Reference signal frequency)> (Integrator 435 cutoff frequency)> (Sample state change frequency) It becomes.
  • the cut-off frequency of the first low-pass filter 433 is higher than the frequency of the reference signal (that is, the stimulus signal) and higher than the frequency of the state change of the sample 210, information on the state change induced by the stimulus of the sample 210 is included.
  • the signal passes through the first low-pass filter 433 and is obtained as the output of the balancer 430. By detecting lock-in of this output at the frequency of the reference signal, a signal induced by stimulation can be obtained.
  • the output from the integrator 435 includes almost no signal induced by the stimulus. However, since it is higher than the frequency of the state change of the sample 210, information on the state change of the sample is included. That is, the signal from the integrator 435 does not include a change in the intensity A of the probe light L P induced by the stimulus, but A and B (intensities of the reference light L R) that change due to a change in the state of the sample 210 and other disturbances. ) Difference information is included. Based on the output signal of the integrator 435, the phase shifter 232 is feedback controlled so that the difference between A and B becomes zero.
  • the slow feedback control does not negate until the signal changes of the stimulation by the state change, the detection signal intensity of the reference light L R and the probe light L P The ratio can be made constant. As a result, it is possible to observe the state change of the sample based on the signal induced by the stimulus while canceling the optical noise.
  • the sample 210 is irradiated with both the probe light L P and the reference light L R in order to prevent a change in the ratio of A and B due to a change in the state of the sample 210.
  • the sixth embodiment (FIG. 16), is corrected by feedback control of the change in the ratio of a and B according to the state change of the sample 210, it is not necessary to irradiate the reference light L R on the sample 210.
  • FIG. 16 shows an example in which the configuration of the sixth embodiment is applied to stimulated Raman measurement.
  • a pulse laser is used as the light source 501.
  • the pulse repetition frequency is 76.3 MHz, and the optical path length corresponding to a quarter period is about 1 m.
  • the pulsed light is split by a beam splitter 505, and one light component is used as a stimulus source called pump light L S.
  • the intensity of the pump (pulse) light L S is modulated by the chopper 552 and irradiated onto the sample 210.
  • the pump light L S is adjusted by an appropriate optical path so that the sample 210 is irradiated simultaneously with the probe light (pulse light) L P.
  • the other pulse light component is incident on a photonic crystal fiber (PCF) 502.
  • the PCF 502 converts the monochromatic pulse laser into white pulse light.
  • the white pulse light passes through the polarizer 503 and is then divided into the probe light L P and the reference light L R by the polarization beam splitter 504.
  • the polarizer 503 is inserted to fix and adjust the polarization direction of white light.
  • the split ratio of the beam splitter 504 changes depending on the polarization direction of incident light, if the polarization direction fluctuates for each pulse, the ratio of A to B fluctuates for each pulse, and optical noise cannot be canceled. Therefore, the polarization direction is fixed by the polarizer 503 immediately before the beam splitter 504 in order to suppress the variation in the division ratio for each pulse.
  • the polarization beam splitter 504 transmits horizontally polarized light and reflects vertically polarized light. For example, if the polarization direction of the polarizer 503 is 45 °, the split ratio of the probe light L P and the reference light L R is 1: 1.
  • the probe light L P is incident on the sample 210, and information on molecular vibration is placed as intensity modulation by the induced Raman effect of the pump light L S and the probe light L P.
  • the reference light L R is spatially overlapped with the probe light L P on the polarization beam splitter 507 after being given a delay corresponding to a quarter period of pulse repetition by an additional optical path.
  • the polarization beam splitters 504 and 507 are used for dividing and superposing white light, since the probe light L P is horizontal polarization, it passes through the polarization beam splitters 504 and 507 with high transmittance. Since the reference light L R is vertically polarized light, it is reflected with a high reflectance. Therefore, the optical loss can be suppressed smaller than that of a normal beam splitter.
  • the probe light L P and the reference light L R are spectrally separated by the common spectrometer 311, and an appropriate wavelength is introduced into the common light detection element 211.
  • an appropriate wavelength is introduced into the common light detection element 211.
  • FIG. 16 for the sake of illustration, only a single light detection element 211 is depicted. However, if a plurality of light detection elements 211 are prepared for each wavelength (see FIG. 9), a spectrum obtained by simultaneous multi-wavelength measurement can be obtained. it can.
  • Figure 17 shows the effect (feedback control of the balancer 430) of optical noise canceling effect and feedback of the probe light L P measured in the system of FIG. 16.
  • the horizontal axis is obtained by standardizing the difference between the intensity A of the probe light L P and the intensity B of the reference light L R with A, and represents an optical balance shift.
  • the vertical axis is a signal obtained by normalizing the signal obtained without chopping light with A, and represents the noise in terms of modulation factor. Without noise, the signal strength is zero when there is no signal and no modulation is applied. It is due to optical noise that the signal is observed even though it is not chopped or subjected to stimulation-induced modulation.
  • Asterisk indicates the measurement result when only probe light is detected without noise cancellation. Square marks indicate measurement results when noise cancellation is performed by the balancer 430 but feedback control is not performed. Circles indicate measurement results when noise cancellation and feedback control are performed by the balancer 430.
  • the frequency of the reference signal was 4.5 kHz
  • the cutoff frequency of the first low-pass filter 433 was 10 kHz
  • the cutoff frequency of the integrator 435 and the second low-pass filter 435 was 1 kHz.
  • the sample 210 was not inserted, and the intensity ratio between the probe light L P and the reference light L R was adjusted by the angle of the polarizer 503.
  • the intensity A of the probe light L P can be obtained.
  • the intensity B of the reference light L R is obtained.
  • the star in the figure is a signal obtained by blocking the reference light without passing through the sample 210, and indicates the optical noise of the probe light L P. Modulation translated at about 1.5 ⁇ 10 -4 (Hz) - 1/2 of the optical noise is observed.
  • the lower limit of the noise is determined by the thermal noise of resistors in the circuit, noise due to active elements, and shot noise of photocurrent. The signal-to-noise ratio due to these noises is improved by increasing the incident light intensity of the light source 201.
  • the feedback function is used, and even when the intensity ratio between the probe light and the reference light is broken, the optical noise is sufficiently canceled. Disabling the feedback function increases optical noise as the intensity ratio collapses (squares), but enabling the feedback function compensates for changes in the intensity ratio even if the intensity ratio of A and B collapses. , The optical noise is canceled out to the maximum.
  • 18 to 20 show the measurement results when the optical measurements of the fifth and sixth embodiments are applied to a multi-wavelength simultaneous measurement guided Raman microscope.
  • 18A is a top view of the sample 600 used, and
  • FIG. 18B is a side view.
  • PS polystyrene
  • PVA polyvinyl alcohol
  • the solid line in FIG. 19A indicates the spontaneous Raman spectrum of polystyrene (PS), and the broken line indicates the spontaneous Raman spectrum of PVA.
  • PS has a Raman band with a peak at 3054 cm ⁇ 1 and PVA has a Raman band with a peak at 2914 cm ⁇ 1 .
  • the wave number difference between the pump light and the probe light is set near 3050 cm ⁇ 1
  • a signal mainly derived from PS is obtained
  • the wave number difference is set near 2915 cm ⁇ 1
  • a signal mainly derived from PVA is obtained.
  • FIG. 19B and FIG. 19C show imaging results when noise cancellation is performed and feedback is not performed, respectively.
  • the signal intensity is smaller as the color is black, and the signal intensity is greater as the color is white.
  • FIG. 19B shows an image obtained at a wavelength of probe light resonating with a Raman band of 3050 cm ⁇ 1 , and a strong signal is obtained in a disk shape where the PS sphere 602 exists.
  • FIG. 19B shows an image obtained at a wavelength of probe light resonating with a Raman band of 3050 cm ⁇ 1 , and a strong signal is obtained in a disk shape where the PS sphere 602 exists.
  • 19C is an image obtained at the wavelength of the probe light resonating with the 2915 cm ⁇ 1 Raman band, and the signal intensity of the portion where the PS sphere 602 does not exist is almost uniformly strong. Since the PVA 601 is excluded where the PS sphere 602 exists, the signal intensity decreases in a disk shape.
  • FIG. 19D shows an imaging result when the noise cancellation of the embodiment is not performed. Since the reference light is blocked at a wavelength that resonates with the Raman band of 3050 cm ⁇ 1 , the optical noise of the probe light is not canceled out. In this case, the signal is buried in the optical noise of the probe light, and an image of the PS sphere 602 cannot be obtained. Further, although not shown in the figure, the same applies to a wavelength resonating with a Raman band of 2915 cm ⁇ 1 . In the embodiment, it is understood that optical noise cancellation is achieved at the same multi-wavelength while passing through the spectroscope by performing the balancing process using the reference light.
  • FIGS. 19 (e) and 19 (f) show imaging results when feedback control is performed in addition to noise cancellation.
  • FIG. 19 (e) is an image obtained with the wavelength of the probe light resonating with the Raman band of 3050 cm ⁇ 1
  • FIG. 19 (f) is obtained with the wavelength of the probe light resonating with the Raman band of 2915 cm ⁇ 1 . It is an image. The same contrast as in FIGS. 19B and 19C is obtained.
  • the optical balance is automatically adjusted and the optical noise is canceled out.
  • the principle that the stimulus by the pump light is observed by appropriately setting the feedback response so that the signal induced by the stimulus is not canceled by the feedback is demonstrated.
  • This figure shows the effect that the collapse of the ratio between the intensity A of the probe light and the intensity B of the reference light being measured is automatically corrected by feedback control.
  • FIG. 20A shows a case where no feedback is applied, and the signal intensity is increased due to stimulated Raman scattering in the region where the polystyrene (PS) sphere 602 exists.
  • PS polystyrene

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (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 Or Analysing Materials By Optical Means (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

Le problème décrit par la présente invention consiste à éliminer efficacement le bruit et à détecter un signal de très faible puissance avec un degré élevé de sensibilité. La solution de l'invention est un dispositif de mesure optique présentant une source lumineuse, un premier élément optique pour diviser la lumière provenant de la source lumineuse en lumière de sonde et en lumière de référence, un premier chemin pour guider la lumière de sonde vers l'échantillon, un deuxième chemin qui est destiné à la lumière de référence et qui présente une longueur de chemin optique qui a été ajustée pour créer un retard relatif sur l'axe du temps entre la lumière de référence et la lumière de sonde, un détecteur pour détecter la lumière de sonde, qui a irradié l'échantillon, et la lumière de référence, dont une longueur de chemin optique est ajustée, à l'aide d'un unique élément de détection commun et émettre des signaux de détection, et un dispositif d'équilibrage pour appliquer des signes opposés au signal provenant de la lumière de sonde échantillon et au signal provenant de la lumière de référence parmi les signaux de détection, pour équilibrer ceux-ci et pour émettre la différence entre le signal provenant de la lumière de sonde et le signal provenant de la lumière de référence comme résultat de mesure pour l'échantillon.
PCT/JP2014/065587 2013-06-27 2014-06-12 Dispositif de mesure optique et procédé de mesure optique WO2014208349A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015523971A JPWO2014208349A1 (ja) 2013-06-27 2014-06-12 光学測定装置及び光学測定方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013135412 2013-06-27
JP2013-135412 2013-06-27

Publications (1)

Publication Number Publication Date
WO2014208349A1 true WO2014208349A1 (fr) 2014-12-31

Family

ID=52141693

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/065587 WO2014208349A1 (fr) 2013-06-27 2014-06-12 Dispositif de mesure optique et procédé de mesure optique

Country Status (2)

Country Link
JP (1) JPWO2014208349A1 (fr)
WO (1) WO2014208349A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104764731A (zh) * 2015-04-01 2015-07-08 广西科技大学 一种拉曼光谱在线监测聚氨酯预聚物-nco含量的方法
JP2018091833A (ja) * 2016-11-29 2018-06-14 キヤノン株式会社 ノイズ低減装置およびそれを有する検出装置
WO2019145005A1 (fr) * 2018-01-23 2019-08-01 Danmarks Tekniske Universitet Appareil pour mise en œuvre d'une spectroscopie raman
JP7462655B2 (ja) 2019-01-18 2024-04-05 アーペー2エ ラマン分光法による微量のガスの検出に適した、光帰還を有する共振光学キャビティシステム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003098071A (ja) * 2001-07-19 2003-04-03 Hitachi Medical Corp 生体光計測装置
JP2004333344A (ja) * 2003-05-09 2004-11-25 Hitachi Ltd 光計測方法および装置
JP2012026830A (ja) * 2010-07-22 2012-02-09 Shimadzu Corp ガス濃度測定装置
JP2014106233A (ja) * 2012-11-27 2014-06-09 Siemens Healthcare Diagnostics Products Gmbh 透過値を確認する方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003098071A (ja) * 2001-07-19 2003-04-03 Hitachi Medical Corp 生体光計測装置
JP2004333344A (ja) * 2003-05-09 2004-11-25 Hitachi Ltd 光計測方法および装置
JP2012026830A (ja) * 2010-07-22 2012-02-09 Shimadzu Corp ガス濃度測定装置
JP2014106233A (ja) * 2012-11-27 2014-06-09 Siemens Healthcare Diagnostics Products Gmbh 透過値を確認する方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KEISUKE SETO ET AL.: "Development of a balanced detection suited to simultaneous multi- wavelength measurements with noisy white-probe- light", DAI 61 KAI JSAP SPRING MEETING KOEN YOKOSHU, 3 March 2014 (2014-03-03) *
KEISUKE SETO ET AL.: "Development of a balanced detector with biased synchronous detection and application to near shot noise limited noise cancelling of supercontinuum pulse light", REVIEW OF SCIENTIFIC INSTRUMENTS, vol. 85, no. 023702, pages 023702 - 1 - 023702-11 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104764731A (zh) * 2015-04-01 2015-07-08 广西科技大学 一种拉曼光谱在线监测聚氨酯预聚物-nco含量的方法
JP2018091833A (ja) * 2016-11-29 2018-06-14 キヤノン株式会社 ノイズ低減装置およびそれを有する検出装置
JP7000117B2 (ja) 2016-11-29 2022-01-19 キヤノン株式会社 ノイズ低減装置およびそれを有する検出装置
WO2019145005A1 (fr) * 2018-01-23 2019-08-01 Danmarks Tekniske Universitet Appareil pour mise en œuvre d'une spectroscopie raman
US11788967B2 (en) 2018-01-23 2023-10-17 Danmarks Tekniske Universitet Apparatus for carrying out Raman spectroscopy
JP7462655B2 (ja) 2019-01-18 2024-04-05 アーペー2エ ラマン分光法による微量のガスの検出に適した、光帰還を有する共振光学キャビティシステム

Also Published As

Publication number Publication date
JPWO2014208349A1 (ja) 2017-02-23

Similar Documents

Publication Publication Date Title
US7388668B2 (en) Phase sensitive heterodyne coherent anti-Stokes Raman scattering micro-spectroscopy and microscopy
JP5847821B2 (ja) コヒーレント反ストークスラマン散乱(cars)分光法における非共鳴バックグラウンド低減のための方法および装置
US9188538B2 (en) Raman microscope and Raman spectrometric measuring method
EP2522969A2 (fr) Appareil spectroscopique Raman non linéaire comprenant une fibre optique monomode pour générer le faisceau de lumière Stokes
US8804117B2 (en) Method for detecting a resonant nonlinear optical signal and device for implementing said method
US11041760B2 (en) Optical measurement device and optical measurement method
WO2014208349A1 (fr) Dispositif de mesure optique et procédé de mesure optique
EP4089400B1 (fr) Dispositif de détection de lumière et procédé de détection de lumière
KR101632269B1 (ko) 광주파수 및 강도 변조 레이저 흡수 분광 장치 및 광주파수 및 강도 변조 레이저 흡수 분광 방법
JP5051744B2 (ja) 多光子励起スペクトル及び多光子吸収スペクトル計測装置
WO2015046070A1 (fr) Dispositif et procédé de mesure optique
WO2017002535A1 (fr) Dispositif de mesure
JP2015197513A (ja) 光源装置およびそれを用いた情報取得装置
JP2004340926A (ja) 光学部品の色分散を決定するための装置および方法
WO2017090075A1 (fr) Appareil de mesure optique et procédé de mesure optique
JP2021526632A (ja) 複合マルチスペクトルラマン分光測定方法及び装置
JP2014092425A (ja) 光干渉断層撮像装置及び光干渉断層撮像方法
WO2021177195A1 (fr) Dispositif de détection de lumière et procédé de détection de lumière
JP2014126491A (ja) 情報取得システム、情報取得装置、および情報取得方法
US9013694B2 (en) System and method for measuring a wavelength-resolved state of polarization of an optical signal
JP2023524571A (ja) 周波数変調による光学活性測定

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14817719

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015523971

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14817719

Country of ref document: EP

Kind code of ref document: A1