WO1991003714A1 - A spectrometric method and a spectrometer - Google Patents
A spectrometric method and a spectrometer Download PDFInfo
- Publication number
- WO1991003714A1 WO1991003714A1 PCT/FI1990/000202 FI9000202W WO9103714A1 WO 1991003714 A1 WO1991003714 A1 WO 1991003714A1 FI 9000202 W FI9000202 W FI 9000202W WO 9103714 A1 WO9103714 A1 WO 9103714A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- optical
- intensity
- spectrometer
- analyzed
- signals
- Prior art date
Links
- 238000004611 spectroscopical analysis Methods 0.000 title claims abstract description 8
- 230000003287 optical effect Effects 0.000 claims abstract description 26
- 230000005855 radiation Effects 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 10
- 238000010276 construction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 241000331231 Amorphocerini gen. n. 1 DAD-2008 Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- G01J2003/2853—Averaging successive scans or readings
-
- 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
- G01J3/30—Measuring the intensity of spectral lines directly on the spectrum itself
- G01J3/36—Investigating two or more bands of a spectrum by separate detectors
Definitions
- the invention relates to a spectrometric method and a spectrometer for analyzing optical radiation by causing dispersion of an optical beam and detecting the intensity of one or more discrete wavelengths of the dispersed optical radiation.
- the spectrum of light passed through a material and reflected or scattered from it provides informa- tion on the chemical and physical structure of the material.
- the spectral analysis starting from the ultraviolet region far into the infrared region of light, is usually carried out by a spectrometer by means of which light is collected from an object, polarized and then dispersed into the spectrum of its wavelength components by means of a prism or grating, for instance.
- a light intensity detector is thereby subjected to monochromatic radiation the wavelength of which depends on the position of the grating or prism with respect to the incoming beam of light and the detector.
- the intensities of the different wavelength com ⁇ ponents of light can be measured.
- an alternative solution is to use the Michelson inter ⁇ ferometer and the acousto-optical crystal. Both of them are used widely but the available constructions are expensive and liable to disturbances; on the other hand, they require less space than the echano- optical construction described above.
- the spectrum of optical radiation is determined by measuring separ ⁇ ately the intensity of each discrete wavelength.
- alternative methods have been developed in which the measuring spectrum to be used is divided into several (N) discrete portions and a mask is dis ⁇ posed between the radiation source and the detector.
- the mask shields off spectrum portions with N different combinations.
- the sum of the remaining radiation components is detected and the intensities of individual spectrum portions as well as the final spectrum are calculated by the inverse Hadamard transform from the detection results obtained with the N different combinations.
- a N-fold improvement is achieved in the signal-to-noise ratio.
- This kind of multiplexing is also advantageous in that the intens ⁇ ity of the light impinging on the detector is greater than in conventional methods, which further helps to improve the signal-to-noise ratio of the detection.
- the mask required by the Hadamard transform has been formed by a mechanically displace- able shield, which is difficult to construct for rapid measurements and for measurements to be per- formed under difficult conditions.
- the Hadamard transform and its application in spectrometers are described, e.g., in Hadamard Transform Optics , M. Harvit, N.J.A., Sloane, Academic Press, New York, 1979, p. 1-47.
- Liquid crystal masks or other electrically con- trolled masks completely avoiding mechanically moving parts are disclosed in U.S. Patent 4,615,619 and in Multiplex Advantage in Hadamard Transform Spectro- metry Utilizing Solid-State Encoding Masks with Uni- form. Bistable Optical Transmission Defects, D.C. Tilotta et al., Applied Optics, 1 October 1987, Vol. 26, No. 19, p. 4285-4292.
- a drawback of the liquid crystal mask is, how ⁇ ever, the limited spectral transmittance range (usually a wavelength below 1 ⁇ m, poor contrast and slowness particularly at low temperatures).
- the object of the present invention is to pro ⁇ vide a novel spectrometric method and a spectrometer in which the sensitivity and the signal-to-noise ratio can be improved by various mathematical trans- forms with a construction simpler and more ad ⁇ vantageous than previously.
- the present invention applies the Hadamard transform or some other suitable mathematical trans ⁇ form by causing the dispersion of the radiation to be analyzed by a diffraction prism or grating or some other technique in such a way that the wavelength components of the dispersed radiation fall on pre- determined N detector elements in a detector array, and each detector element in the array produces an electric signal proportional to the intensity of the radiation which strikes it.
- the optical multiplexing used in the prior art is replaced with the multiplexing of the outputs of the detector elements by connecting them electrically together in N different combinations to form N sum signals, respectively.
- sum signals correspond to an electric signal produced by a single detector from an optical sum signal in optical multiplexing.
- Each sum signal is sampled and after N sum signals have been measured, the intensities of individual wave lengths are calculated by an inverse algorithm corresponding to the summing operation, and the spectrum of the optical radiation to be analyzed is determined.
- an advantageous spectrometer providing high sensitivity, high resolution and wavelength accuracy without any mechanical or electric mask and avoiding the restrictions set by the above-mentioned liquid crystal shields on wavelength, speed and temperature.
- the device can be fitted in a very small space with a low power consumption and without moving parts so that it is suitable for use under difficult conditions and is portable.
- the number N of the dis ⁇ crete wavelengths to be detected simultaneously is notably greater than in a conventional mask tech ⁇ nique, even several thousands, that is, a greater im ⁇ provement is achieved in the signal-to-noise ratio when the transform method is used.
- Figure 1 illustrates schematically the basic principle of the spectrometer of the present inven ⁇ tion
- Figures 2 and 4 are examples of transform mat ⁇ rices to be used in connection with the invention.
- Figure 3 shows a circuit diagram of a detecting and multiplexing circuitry of the invention.
- FIG. 1 illustrating the general operation of the spectrometer of the invention will now be referred to.
- a beam of light to be analyzed impinges on an optical means, in this particular case a grating G which refracts different wavelengths into different refracting angles ⁇ - j _ ... B n , thus causing the dispersion of the beam of light L to be analyzed into different wavelength components, of which each N wavelength component l ... l n strikes a detector element D ⁇ ... O ⁇ assigned to it in an array of de ⁇ tector elements positioned in the refraction plane of the beam of light. Each detector element produces an output signal proportional to the intensity of the wavelength component which has struck it.
- each output signal can be connected selectively to the input of a common amplifier Al.
- the switches SWl ... SWN are controlled in an order determined by an applied mathematical transform, such as the Hadamard trans ⁇ form, one after another into N different combinations of closed and opened switches. These combinations produce N successive sum signals formed by the dif ⁇ ferent output . signals in the input of the amplifier Al and amplified in its output. Digital samples are extracted from the output signal of the amplifier Al by means of an analog-to-digital converter ADC.
- the digital samples are applied to a computer 2 which calculates, by the inverse Hadamard transform from the N sum signals obtained with the different switch combinations, the intensity of each discrete wave- length 1- ⁇ •••l n to ⁇ e analyzed and therethrough the spectrum of the optical radiation to be analyzed and displays it as such graphically or numerically or directly as a calibrated material concentration or in some other suitable manner by means of a printer 3, for instance.
- the computer 2 that determines which way of transform and transform mat ⁇ rix is used as well as the positions of the switches SWl ... SWN, the connection between the computer 2 and the switches is indicated with a broken line 4.
- the photodetectors are photodiodes, but they can alternatively be any detectors capable of producing a signal proportional to the intensity or energy of the light impinging on them, such as photoresistors, pyrometric elements, etc. Accordingly, the operation of the detectors may be based on photoelectricity or photoconductivity, and the measurements may utilize combination of signals proportional to the sums of resistances, voltages or currents.
- the reflection grating G causing the dispersion of the optical beam to be analyzed may be replaced with any optical device capable of causing dispersion. In place of reflected refracted light it is thereby possible to measure the intensity of the different wavelengths of refracted light passed through such a device.
- FIG. 2 shows a cyclic Simplex matrix suited for use in the above-described con- nection.
- Each position in a horizontal row of the matrix corresponds to one switching means, whereby the positions indicated "1" signify a closed switch and the positions indicated "0" signify an open switch.
- This kind of Simplex matrix control is easily realizable by a shift register provided with a parallel output.
- the computer controlling the measuring operation applies the first row of the matrix in series form to the shift register. There ⁇ after the code passes cyclically through the shift register in such a way that the last bit emerging from the shift register is returned to the beginning of the shift register.
- the signal-to-noise ratio obtained by this kind of Simplex matrix is /N times better as compared with individual measurements carried out by N detectors.
- Figure 3 shows the circuit according to the preferred embodiment of the invention to realize the system of Figure 1.
- the computer 2 controlling the measuring applies the Hadamard matrix one row at a time through a parallel bus 34 in e.g. binary form to a decoder 31 which again converts the applied data into the original matrix row, in which the state of each position appears as the "0" or "1" state of the corresponding output of the decoder 31.
- Each output in the decoder 31 is connected to one input in a corresponding AND gate 32 when a trigger signal TRIG is applied to another input in the gate 32.
- the output of each gate 32 is applied to a cor ⁇ responding memory element 33 having both an inverting and a noninverting output.
- a reset signal RESET is applied to the reset input of each memory element 33.
- the noninverting input of each memory element 33 con ⁇ trols a corresponding switch transistor Qll ... Q1N connected between the cathode of the corresponding detector diode Dl and the noninverting input of the amplifier Al.
- the inverting output of each memory element 33 is connected to a corresponding switch transistor Q21 ... Q2N connected between the cathode of the corresponding detector diode Dl ... DN and the inverting input of the amplifier Al.
- the anodes of the detector diodes Dl ... DN are connected to a low potential, such as earth.
- the output signals of the decoder 31 set the memory elements 33 through the AND gates 32 to a "0" or "1" state in accordance with the first matrix row of the Hadamard transform when the trigger signal TRIG is in the state "1".
- the outputs of the memory elements 33 control the corresponding switch transistor pairs Qll ... QN and Q21 ... Q2N in such way that the photo diode Dl ... DN corresponding to the memory element 33 is connected to the noninvert ⁇ ing input of the differential amplifier when the non- inverting output of the memory element is 1, and equivalently, to the inverting input of the amplifier Al when the inverting output of the memory element 33 is in the state "1".
- a charging voltage load is simultaneously applied to the inputs of the amplifier Al through the transistors Q3 and Q4, respectively, and thus also to the cathodes of the photodiodes Dl ... DN, whereby the junction capacitances of the diodes are charged in the reverse direction.
- the control signal LOAD-CMD of the transistors Q3 and Q4 is removed, the charging voltage loa(j is removed and the diodes remain connected to the inputs of the amplifier Al in accordance with the respective matrix row.
- DN is discharged by a leakage current proportional to the intensity of light striking the diode, whereby a voltage propor ⁇ tional to the difference between the total inten- sities of light entering the diode groups connected to the inputs of the differential amplifier Al is obtained from the output of the differential amplifier Al after a selected measuring period.
- This voltage is sampled, and the sample is digitized and stored in the memory of the computer 2.
- the memory elements 33 are then reset to zero by the signal RESET and a new Hadamard matrix row is applied through the decoder 31 to the memory elements 33, whereafter the above-mentioned charging and measuring operations are removed. The same is repeated until all N horizontal rows of the Hadamard matrix are gone through and the corresponding measuring data are stored in the memory of the computer.
- the intensities of individual wavelength regions are then determined by the inverse Hadamard transform and the results are shown in suitable form.
- This measuring method in which two detector assemblies are compared with each other, provides a /N-fold improvement in the signal- to-noise ratio as compared with separate measurings carried out by N elements. In the preferred embodi ⁇ ment of the invention, 1024 elements are used, so the obtained improvement is 32-fold.
- Figure 5 shows an 8-row matrix Hg suited for the above-mentioned connection.
- the elements indicated “1” signify diodes to be connected to the noninverting input of the amplifier Al
- the elements indicated “-1” signify diodes to be con ⁇ nected to the inverting input.
- the state "0" corresponds to the element "-1" of the matrix H g .
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Spectrometry And Color Measurement (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI894184 | 1989-09-05 | ||
FI894184A FI82863C (sv) | 1989-09-05 | 1989-09-05 | Spektrometriskt förfarande och spektrometer |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991003714A1 true WO1991003714A1 (en) | 1991-03-21 |
Family
ID=8528943
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI1990/000202 WO1991003714A1 (en) | 1989-09-05 | 1990-08-27 | A spectrometric method and a spectrometer |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU6273890A (sv) |
FI (1) | FI82863C (sv) |
WO (1) | WO1991003714A1 (sv) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0567994A1 (en) * | 1992-04-28 | 1993-11-03 | Nec Corporation | Spectral band variable type radiometer |
US5323424A (en) * | 1991-03-29 | 1994-06-21 | U.S. Philips Corporation | Multistage decoder |
WO2000006979A1 (en) * | 1998-07-31 | 2000-02-10 | The Research Foundation Of State University Of New York | Sensors for detection and spectroscopy |
EP0911620A3 (de) * | 1997-09-12 | 2000-04-19 | Perkin Elmer Bodenseewerk Zweigniederlassung der Berthold GmbH & Co. KG | Detektoreinrichtung zur Verwendung in der Atomabsorptionsspektroskopie |
AU2003203962B2 (en) * | 1997-09-12 | 2005-09-15 | Perkin Elmer Bodenseewerk Zweigniederlassung Der Berthold Gmbh & Co. Kg | Detector device to be used in the atomic absorption spectroscopy |
WO2007121593A1 (en) * | 2006-04-26 | 2007-11-01 | Abb Research Ltd | Method for measurement and determination of concentration within a mixed medium |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4007989A (en) * | 1975-09-29 | 1977-02-15 | International Business Machines Corporation | Hadamard filter design |
US4242695A (en) * | 1978-01-27 | 1980-12-30 | Hitachi, Ltd. | Low dark current photo-semiconductor device |
US4318615A (en) * | 1978-04-10 | 1982-03-09 | Hisayuki Sagusa | Automatic rate analyzing method |
US4557601A (en) * | 1981-09-24 | 1985-12-10 | Hitachi, Ltd. | Elimination of ghost component in flow injection analysis method |
-
1989
- 1989-09-05 FI FI894184A patent/FI82863C/sv not_active IP Right Cessation
-
1990
- 1990-08-27 AU AU62738/90A patent/AU6273890A/en not_active Abandoned
- 1990-08-27 WO PCT/FI1990/000202 patent/WO1991003714A1/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4007989A (en) * | 1975-09-29 | 1977-02-15 | International Business Machines Corporation | Hadamard filter design |
US4242695A (en) * | 1978-01-27 | 1980-12-30 | Hitachi, Ltd. | Low dark current photo-semiconductor device |
US4318615A (en) * | 1978-04-10 | 1982-03-09 | Hisayuki Sagusa | Automatic rate analyzing method |
US4557601A (en) * | 1981-09-24 | 1985-12-10 | Hitachi, Ltd. | Elimination of ghost component in flow injection analysis method |
Non-Patent Citations (2)
Title |
---|
DERWENT'S ABSTRACT, No. A86 81C C/04; & SU,A,661 263, publ. week 8004. * |
PATENT ABSTRACTS OF JAPAN, Vol. 7, No. 146, P206; & JP,A,58 058 423, 07-04-1983, TOKYO SHIBAURA DENKI K.K. * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5323424A (en) * | 1991-03-29 | 1994-06-21 | U.S. Philips Corporation | Multistage decoder |
EP0567994A1 (en) * | 1992-04-28 | 1993-11-03 | Nec Corporation | Spectral band variable type radiometer |
EP0911620A3 (de) * | 1997-09-12 | 2000-04-19 | Perkin Elmer Bodenseewerk Zweigniederlassung der Berthold GmbH & Co. KG | Detektoreinrichtung zur Verwendung in der Atomabsorptionsspektroskopie |
US6229604B1 (en) * | 1997-09-12 | 2001-05-08 | Bodenseewerk Perkin-Elmer Gmbh | Detector device to be used in atomic absorption spectroscopy |
AU2003203962B2 (en) * | 1997-09-12 | 2005-09-15 | Perkin Elmer Bodenseewerk Zweigniederlassung Der Berthold Gmbh & Co. Kg | Detector device to be used in the atomic absorption spectroscopy |
WO2000006979A1 (en) * | 1998-07-31 | 2000-02-10 | The Research Foundation Of State University Of New York | Sensors for detection and spectroscopy |
US6038023A (en) * | 1998-07-31 | 2000-03-14 | The Research Foundation Of State University Of New York | Sensors for detection and spectroscopy |
WO2007121593A1 (en) * | 2006-04-26 | 2007-11-01 | Abb Research Ltd | Method for measurement and determination of concentration within a mixed medium |
Also Published As
Publication number | Publication date |
---|---|
FI82863C (sv) | 1991-04-25 |
FI82863B (fi) | 1991-01-15 |
FI894184A0 (fi) | 1989-09-05 |
AU6273890A (en) | 1991-04-08 |
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