CA1272616A - Spectrophotometer - Google Patents
SpectrophotometerInfo
- Publication number
- CA1272616A CA1272616A CA000503989A CA503989A CA1272616A CA 1272616 A CA1272616 A CA 1272616A CA 000503989 A CA000503989 A CA 000503989A CA 503989 A CA503989 A CA 503989A CA 1272616 A CA1272616 A CA 1272616A
- Authority
- CA
- Canada
- Prior art keywords
- light
- photodiodes
- filters
- individual
- spectral
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
- 230000003595 spectral effect Effects 0.000 claims abstract description 39
- 238000004458 analytical method Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 13
- 230000006872 improvement Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 description 22
- 238000002835 absorbance Methods 0.000 description 18
- 239000000523 sample Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 11
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 230000002452 interceptive effect Effects 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 210000002966 serum Anatomy 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- VSYMNDBTCKIDLT-UHFFFAOYSA-N [2-(carbamoyloxymethyl)-2-ethylbutyl] carbamate Chemical compound NC(=O)OCC(CC)(CC)COC(N)=O VSYMNDBTCKIDLT-UHFFFAOYSA-N 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BBBFJLBPOGFECG-VJVYQDLKSA-N calcitonin Chemical compound N([C@H](C(=O)N[C@@H](CC(C)C)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC=1NC=NC=1)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC=1C=CC(O)=CC=1)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)NCC(=O)N[C@@H](CO)C(=O)NCC(=O)N[C@@H]([C@@H](C)O)C(=O)N1[C@@H](CCC1)C(N)=O)C(C)C)C(=O)[C@@H]1CSSC[C@H](N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)O)C(=O)N1 BBBFJLBPOGFECG-VJVYQDLKSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000001429 visible spectrum 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
- G01J3/02—Details
-
- 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
- G01J3/02—Details
- G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
- G01J3/0229—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using masks, aperture plates, spatial light modulators or spatial filters, e.g. reflective filters
-
- 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
- G01J3/02—Details
- G01J3/0256—Compact construction
- G01J3/0259—Monolithic
-
- 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
- G01J3/02—Details
- G01J3/0262—Constructional arrangements for removing stray light
-
- 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
- G01J3/02—Details
- G01J3/04—Slit arrangements slit adjustment
-
- 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
- G01J3/2803—Investigating the spectrum using photoelectric array detector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02162—Coatings for devices characterised by at least one potential jump barrier or surface barrier for filtering or shielding light, e.g. multicolour filters for photodetectors
- H01L31/02164—Coatings for devices characterised by at least one potential jump barrier or surface barrier for filtering or shielding light, e.g. multicolour filters for photodetectors for shielding light, e.g. light blocking layers, cold shields for infrared detectors
-
- 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
- G01J3/2803—Investigating the spectrum using photoelectric array detector
- G01J2003/2806—Array and filter array
-
- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/07—Centrifugal type cuvettes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/064—Stray light conditioning
- G01N2201/0642—Light traps; baffles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/069—Supply of sources
- G01N2201/0696—Pulsed
Abstract
ABSTRACT OF THE DISCLOSURE
An improved spectrophotometer, especially suitable for use in centrifugal analysis instrumentation, is disclosed. The spectrophotometer is improved by including therein a detector comprising a photodiode array assembly having a photodiode array, a spectral filter assembly situated substantially parallel thereto and in the path of incident light and means for attenuating stray light which would otherwise impinge on each of the photodiodes of the array.
An improved spectrophotometer, especially suitable for use in centrifugal analysis instrumentation, is disclosed. The spectrophotometer is improved by including therein a detector comprising a photodiode array assembly having a photodiode array, a spectral filter assembly situated substantially parallel thereto and in the path of incident light and means for attenuating stray light which would otherwise impinge on each of the photodiodes of the array.
Description
1~7i~
BACKGROUND OF ~HE INVENTION
-Field of the Invention The invention relates to a spectrophotometer.
~ore particularly, it relates to an improved spectrophotometer especially useful for optical analysis of samples in a centrifugal analyz~r.
Bac~ground Art SpectrophotOmeters are well known in the art, and comprise various main components. The light source usually comprises one or two continuous-emission lamps, e.g., halogen, deuterium, mercury arc and/or xenon. Prism or grating devices are used for the dispersion. The detectors are generally photomultipliers, or silicon photodiodes. The numerous kinds of available components and the various possible structures can be combined in numerous ways to construct a spectrophotometer having desired characteristics for a particular intendPd use.
The disadvantages of known spectrophotometers are mainly due to the light source and the monochromator used. Particularly in spectrophotometers used in centrifugal analyzers, it is desirable to use a light ~ource such as a flash lamp in order to enable high speed absorbance measurements. Accordingly, although the tungsten-halogen lamp is undoubtedly the most frequently-used source for applications in the visible spectrum, it has the following well-known disadvantages:
a) very weak emission of ultraviolet light;
b) very great variation of light intensity in the useful spectrum; the intensity of light at 290 nm is about 9D0 times less than at 700 nm;
c) the proportion of interfering light is considerable, wnich means that expensive blocking filters need to be used;
d) the system for compensating variations in light intensity with wavelength must have a wide dynamic range;
,, ~7~
e) the service lif~ is relatively short;
f) the light output is relatively low;
g) the dissipated power is considerable; and h) the electric supply means for the lamp is relatively heavy and bulky.
In order to alleviate the disadvantages with the aforementioned kind of lamp, light can be obtained from lamps producing different kinds of electric (flash) discharges, e.g. xenon, mercury or argon lamps. xenon lamps have the most uniform spectrum, and their light efficiency is much greater than that of tungsten.
However, the lamps are usually supplied for higher power than 100 W, and are very difficult to cool. AlSo, the lamp supply and mounting means are very voluminous and 5 expensive.
The grating monochromator is a preferred method of continuously varying the wavelength. However, the proportion of interfering light resulting from the associated lamp and monochromator must be very low, e.g., less than 1 x 10 4, if it is desired to make measurements having a low linearity error ~e.g. lower than 1.5% up to an attenuation of 1000 times ~corresponding to an absorbance of 3)). To obtain performance of this kind, double-grating monochromators are ordinarily used, since single-grating monochromators have too high a proportion of interfering light. However, double-grating mmonochromators are expensive, bulky and take a relatively long time to align.
U.S. Patent No. 3,810,696 discloses a spectrophotometer comprising a flash tube and an interference filter or a monochromator to produce two light beams, the first of which travels through a sample for analysis and the second of which reaches a detector which delivers a reference signal corresponding to the intensity of the second beam. U.S. Patent No. 4,241,998 ~ ~ 7~
discloses a spectrophotometer intended in particular for the optical analysis of samples in a centrifugal analyzer. The spectrophotometer comprises a flash tube, a ~stabilizing optical device for deriving a light beam - 5 having a constant spatial distribution from each flash from the flash tube, a grating monochromator for dispersing the light delivered by the stabilizing device and for delivering a beam of filtered light, an optical element for dividing the filtered beam to produce two beams, the first of which travels through a sample for analysis and the second of which reaches a detector which delivers a reference signal corresponding to the intensity of the second beam, and a second detector placed to r~ceive the beam emerging from the sample.
SUMMARY OF THE INVENTION
The present invention provides an improvement in a spectrophotometer of the type previously described, which overcomes or alleviates many of the problems with such conventional instruments. In particular, the invention provides a novel photodiode array assembly as a detector, which is espe~ially suitable for use in an optical system of a small absorbance, multi-wavelength spectrophotometer. A typical application of such a spectrophotometer is in an automated clinical analyzer, such as those commonly used in medical laboratories. ~he critical nature of medical analysis requires a detection system to determine various substances of clinical interest in biological specimens, such as blood serum, urine, spinal fluid and the like, which is capable of a high degree of sensitivity. This sensitivity is frustrated by small sample size and high absorbance levels associated with a biological sample. Accordingly, the present invention enables an increase of sensitivity at the photodiode surface, by specifically controling the components of light impacting on individual photodiodes of ~ 7~
the detector assembly, without resort to double-gratings or other relatively complex and expensive apparatus of the prior art.
In a preferred embodiment, an improved spectrophotometer of the invention comprises:
a flash lamp;
a grating monochromator for dispersing the light delivered by the flash lamp and for delivering a beam of filtered light which travels through a sample for 0 analysis; and a detector situated to receive the beam emerging from the sample. The improvement of-the invention involves the detector comprising a photodiode array ass~mbly including:
a) a plurality of individual photodiodes 5 situated in a first plane;
b) a plurality of individual spectral filters situated substantially parallel to the first plane and adjacent to the plurality of photodiodes such that light passing through each of the individual spectral filters will impinge upon only one of the individual photodiodes;
and c) means for attenuating stray light, the means being situated substantially parallel to the first plane and adjacent the plurality OI individual spectral filters ~5 such that the means is located above each of the individual photodiodes, said attenuating means being capable of determining the spectral bandpass and the central wavelength of the light impinging on the individual photodiodes.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure l is an exploded view in perspective showing components of a preferred optical detector useful in an improved spectrophotometer according to the present invention;
~7'~
~ igure 2 is a perspective view of the detector shown in Figure 1, but illustrating the detector in its fully-assembled condition;
Figure 3 is an enlarged, partial cross sectional view of the fully-assembled detector shown in Figure 2, illustrating details of construction thereof;
Figure 4 is a schematic diagram in perspective, showing the detector of Figures 1-3 and other components of an improved optical system of a spectrophotometer which incorporates the concepts of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides an improvement in a spectrophotometer which is especially suitable for use in a centrifugal clinical chemical analyzer comprising a rotor rotating at high speed, e.g., approximately 1800 rpm, and bearing small volume samples and/or reagents for analyzing such samples. Such a spectrophotometer generally will ideally have the following features:
1) ability to measure absorbance of liquid samples deposited in analysis cells while rotating the cells at approximately 1800 rpm;
BACKGROUND OF ~HE INVENTION
-Field of the Invention The invention relates to a spectrophotometer.
~ore particularly, it relates to an improved spectrophotometer especially useful for optical analysis of samples in a centrifugal analyz~r.
Bac~ground Art SpectrophotOmeters are well known in the art, and comprise various main components. The light source usually comprises one or two continuous-emission lamps, e.g., halogen, deuterium, mercury arc and/or xenon. Prism or grating devices are used for the dispersion. The detectors are generally photomultipliers, or silicon photodiodes. The numerous kinds of available components and the various possible structures can be combined in numerous ways to construct a spectrophotometer having desired characteristics for a particular intendPd use.
The disadvantages of known spectrophotometers are mainly due to the light source and the monochromator used. Particularly in spectrophotometers used in centrifugal analyzers, it is desirable to use a light ~ource such as a flash lamp in order to enable high speed absorbance measurements. Accordingly, although the tungsten-halogen lamp is undoubtedly the most frequently-used source for applications in the visible spectrum, it has the following well-known disadvantages:
a) very weak emission of ultraviolet light;
b) very great variation of light intensity in the useful spectrum; the intensity of light at 290 nm is about 9D0 times less than at 700 nm;
c) the proportion of interfering light is considerable, wnich means that expensive blocking filters need to be used;
d) the system for compensating variations in light intensity with wavelength must have a wide dynamic range;
,, ~7~
e) the service lif~ is relatively short;
f) the light output is relatively low;
g) the dissipated power is considerable; and h) the electric supply means for the lamp is relatively heavy and bulky.
In order to alleviate the disadvantages with the aforementioned kind of lamp, light can be obtained from lamps producing different kinds of electric (flash) discharges, e.g. xenon, mercury or argon lamps. xenon lamps have the most uniform spectrum, and their light efficiency is much greater than that of tungsten.
However, the lamps are usually supplied for higher power than 100 W, and are very difficult to cool. AlSo, the lamp supply and mounting means are very voluminous and 5 expensive.
The grating monochromator is a preferred method of continuously varying the wavelength. However, the proportion of interfering light resulting from the associated lamp and monochromator must be very low, e.g., less than 1 x 10 4, if it is desired to make measurements having a low linearity error ~e.g. lower than 1.5% up to an attenuation of 1000 times ~corresponding to an absorbance of 3)). To obtain performance of this kind, double-grating monochromators are ordinarily used, since single-grating monochromators have too high a proportion of interfering light. However, double-grating mmonochromators are expensive, bulky and take a relatively long time to align.
U.S. Patent No. 3,810,696 discloses a spectrophotometer comprising a flash tube and an interference filter or a monochromator to produce two light beams, the first of which travels through a sample for analysis and the second of which reaches a detector which delivers a reference signal corresponding to the intensity of the second beam. U.S. Patent No. 4,241,998 ~ ~ 7~
discloses a spectrophotometer intended in particular for the optical analysis of samples in a centrifugal analyzer. The spectrophotometer comprises a flash tube, a ~stabilizing optical device for deriving a light beam - 5 having a constant spatial distribution from each flash from the flash tube, a grating monochromator for dispersing the light delivered by the stabilizing device and for delivering a beam of filtered light, an optical element for dividing the filtered beam to produce two beams, the first of which travels through a sample for analysis and the second of which reaches a detector which delivers a reference signal corresponding to the intensity of the second beam, and a second detector placed to r~ceive the beam emerging from the sample.
SUMMARY OF THE INVENTION
The present invention provides an improvement in a spectrophotometer of the type previously described, which overcomes or alleviates many of the problems with such conventional instruments. In particular, the invention provides a novel photodiode array assembly as a detector, which is espe~ially suitable for use in an optical system of a small absorbance, multi-wavelength spectrophotometer. A typical application of such a spectrophotometer is in an automated clinical analyzer, such as those commonly used in medical laboratories. ~he critical nature of medical analysis requires a detection system to determine various substances of clinical interest in biological specimens, such as blood serum, urine, spinal fluid and the like, which is capable of a high degree of sensitivity. This sensitivity is frustrated by small sample size and high absorbance levels associated with a biological sample. Accordingly, the present invention enables an increase of sensitivity at the photodiode surface, by specifically controling the components of light impacting on individual photodiodes of ~ 7~
the detector assembly, without resort to double-gratings or other relatively complex and expensive apparatus of the prior art.
In a preferred embodiment, an improved spectrophotometer of the invention comprises:
a flash lamp;
a grating monochromator for dispersing the light delivered by the flash lamp and for delivering a beam of filtered light which travels through a sample for 0 analysis; and a detector situated to receive the beam emerging from the sample. The improvement of-the invention involves the detector comprising a photodiode array ass~mbly including:
a) a plurality of individual photodiodes 5 situated in a first plane;
b) a plurality of individual spectral filters situated substantially parallel to the first plane and adjacent to the plurality of photodiodes such that light passing through each of the individual spectral filters will impinge upon only one of the individual photodiodes;
and c) means for attenuating stray light, the means being situated substantially parallel to the first plane and adjacent the plurality OI individual spectral filters ~5 such that the means is located above each of the individual photodiodes, said attenuating means being capable of determining the spectral bandpass and the central wavelength of the light impinging on the individual photodiodes.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure l is an exploded view in perspective showing components of a preferred optical detector useful in an improved spectrophotometer according to the present invention;
~7'~
~ igure 2 is a perspective view of the detector shown in Figure 1, but illustrating the detector in its fully-assembled condition;
Figure 3 is an enlarged, partial cross sectional view of the fully-assembled detector shown in Figure 2, illustrating details of construction thereof;
Figure 4 is a schematic diagram in perspective, showing the detector of Figures 1-3 and other components of an improved optical system of a spectrophotometer which incorporates the concepts of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides an improvement in a spectrophotometer which is especially suitable for use in a centrifugal clinical chemical analyzer comprising a rotor rotating at high speed, e.g., approximately 1800 rpm, and bearing small volume samples and/or reagents for analyzing such samples. Such a spectrophotometer generally will ideally have the following features:
1) ability to measure absorbance of liquid samples deposited in analysis cells while rotating the cells at approximately 1800 rpm;
2) brief duration of measurement of multiple samples on the rotor, i.e. in less than about 350 milliseconds;
3) time available per measurement of less than about 5 microseconds;
4) measurement of small volumes of liquid samples, i.e., on the order of 200 microliters;
5) continuous selection of wavelengths, between 30 about 340 and 640 nm;
6) a bandwidth of about 8 nm;
7) a wide range of measurable absorbance, i.e., from 0.G to 3Ø
8) have a relatively small size so as, for example, to fit into a laboratory bench top, or desk top analyzer;
7~
.-- Ç -- .
7~
.-- Ç -- .
9) have no moving parts to greatly improve reliability; and
10) have a minimum number of optical elements to be aligned, thus improving manufacturability and 5 reliability.
The foregoing features are particularly important in automatic instruments in order to make up the considerable differences in absorbance between normal cases and pathological cases of samples of biological 10 material under examination - e.g., between a lypaemic serum and a normal serum. An instrument having the foregoing characteristics is described in ~o-pending Canadian Patent Applications Serial Nos. 480,653 480,654, and 480,657, filed May ~, 1985.
In addition, the centrifugal analysis instrument which is improved with the present invention enables reproducibility of measurements compatible with the requirements for enzyme reactions. This refers to the 20 reproducibility of measurements of absorbance on a single sample. This is particularly important in the case of kinetic methods. In these methods the variation in absorbance is slow, i.e. the measurements can be speeded up if reproducibility is good. In these methods also, the 25 absorbance level is sometimes quite high (1.7-2.2). Thus, reproducibility must be excellent over a wide range of absorbance, a feature achieved by the present improvements.
Als~, according to the instant invention excellent linearity between absorbance and concentration 30 over a wide range of absorbance is achieved This linearlty simplifies the use of the instrument, in that a calibration curve is not needed. Linearity is difficult to obtain at high absorbance, specially in the ultraviolet, and depends on the puritv of the 35 monochromatic light, i.e. on the proportion of interferina r'.
~ à
light, which is defined by the ratio of (a) the inten~ity of residual light emitted outside the selected spe~tral band to (b) the intensity of light inside the selected spectral band.
~urthermore, the improvements of the present invention, in order to reduce the bulk and cost of conventional spectrophotometers, utilize for the detector a photodiode array associated with conventional electronics.
The aforementioned photometri~ performance i~ a centrifugal analyzer, if it is ~o be achieved during a relatively short measuring time, creates special technical difficulties relating to the required signal/noise ratio and to obtaining a light beam having the required spectral purity for ultimate interpretation by the electronics of the instrument. Since it is ordinarily desired to make reproducible measurements with a maximum signal attenuation of about 1000 times through the sample, it is usually necessary for the signalJnoise ratio to be at least 2X10- at zero absorbance. Since the measurement time is very sbort (less than 5 microseconds~ an amplifier having a wide pass band is needed, which makes it difficult to obtain the desired signal/noise ratio since, as is known, the noise increases with the width of the amplifier pass-band. The effect of this noise is considerable compared with the effect of noise in conventional spectrophotometers, in which the influence of noise on the measured results can be reduced by integrating the measured signal over one or more seconds.
The problem of obtaining an adequate signal/noise ratio is made even more difficult because it is usually desired to use silicone photodiodes; the association of a photodiode with an amplifier is noisier than a photomultiplier operating at a weak signal level. This applies more particularly to wavelengths below 400 nm for measurements ~'7'~
of high absorbance value~ (A-3), since ~ilicone pho~odiode~ have a lower sensitivity than photomultipliers in this part of the spectrum.
Largely conventional analog-to-digital conversion electronic circuitry is used to convert current signals from the detector into digital information signals readable by associated microprocessor controlled circuitry.
In order to obtain the photometric characteristics described hereinbefore, the light beam supplied by the monochromator must have very high spectral purity, in order to avoid the well-known problems of nonlinearity due to interfering light and bandwidth effects. There are certain difficulties in obtaining a light beam having the spectral purity required for photometric purposes, if the cost and bulk of the spectrophotometer are to be simultaneously reduced. For these purposes, according to the invention, the proportion of interfering light is reduced to a value of approximately 1 x 10 4 at a waveleng~h of 340 nm, using a detector assembly comprising a photodiode array, a - multiwavelength spectral filter assembly between the photodiode array and the light source and means for attenuating stray light from the source prior to its impinging upon the spectral filter assembly.
Referring now to the drawings, and with particular reference to Figures 1 through 3, a preferrec photodiode array detector assembly in accordance with the invention is shown generally at 10. The assembly 10 essentially comprises a photodiode array 12, a spectral filter assembly 14 and a means to attenuate stray light 16. The spectral filter assembly 14 comprises a plurality of optical grade glass f ilters 18 which are individually chosen for their pre-selected transmittance characteristics depending on the wavelength of light it is 1~ 7~
desired to have measured by the individual photodiode~ of the array 12 which are below each of tbe filters. ~he filters 18 are assembled such that the four edges (indicated at 20) of each individual filter which are 5 normal to the array 12 are surrounded by an optically opaque, poorly light-transmissive material 12a, such as a black epoxy. The opaque material 12a effectively shields the sides of each of the optical filters 18 from light not incident to the chosen surfaces of each filter. The opaque material 12a, in this pr*ferred embodiment, also holds together the individual filters 18 in a desired planar configuration. The filter assembly 14, as shown, is mounted in a plane substantially parallel to the photodiode array 12 and in the path of incident light from a light source such that each individual one of the filters 18 is optically associated with a corresponding photodiode of the array 12. The means for attenuating stray light 16 that originates external to the spectral filter assembly 14, but which is not blocked by the opaque material shielding the side portion of each of ~he optical filters, in a preferred embodiment of the invention, comprises a mask~, of a suitable substance such as flat-black anodized metal, having a plurality of narrow slits therein which are located above the centerline of the surface area of each photodiode of the array 12. The stray light attenuating means 16 is, as shown mounted in a plane substantially parallel to that of the filter assembly 14 and overlays the surfaces of the filters 1~
thereof. The light attenuating means 16 also determines the central wavelength of light which impinges on the individual photodiodes of the array 12 by virtue of its lateral position in the focused spectrum of light. The width of slits ~2 in means 16 furthermore functions to determine, to a more or less extent, the bandpass of the spectrophotometer. The slit width of slits 22 of means 16 I,, also helps to normalize signal differences resulting from efficiency variations as a function of wavelength (e.g., caused by the source,spectrum grating efficiency, photodiode efficiency, and transmittance of filter assembly 14).
In the preferred fabrication of the detector assembly 10, the photodiode array 12, filter assembly 14 and light attenuating means 16 are mounted, as shown in Figures 1 and 2, in a suitable base 24 which includes a plurality of electrically conductive metal contacts 26 for electrical connection, when the assembly 10 is in use, to largely conventional electronic circuitry which, as well known to those skilled in the art, is capable of receiving and converting output signals produced by the photodiode array 12 in response to the intensities of light impinging thereupon. In a particular case the conversion can be, for example, to a digital readout corresponding to the absorbance of light by a constituent of a sample of biological material under analysis. The contacts ~6 are secured in the base 24, which can be made of a Ceramic, phenolic or other suitable commercially available dielectric material, in a well known manner so that they are in electrical connection with the output portion of individual ones of the photodiodes of the array 12 ~Figure 3).
As best shown in FigUre 3, the individual filters 18 are positioned in contact with the photodiodes of the array 12, and the stray light attenuating means 16 is positioned over the array 12 in contact with the filters 18, such that the slits 22 thereof create an incident light path (as shown by the arrows) through the means 16, ~he filters 18 and to the diodes of the array 12.
~owever, the opaque material 12a functions effectively to block any of the incident light, after entering a particular slit 22, from impinging upon any of the 1~7;~
The foregoing features are particularly important in automatic instruments in order to make up the considerable differences in absorbance between normal cases and pathological cases of samples of biological 10 material under examination - e.g., between a lypaemic serum and a normal serum. An instrument having the foregoing characteristics is described in ~o-pending Canadian Patent Applications Serial Nos. 480,653 480,654, and 480,657, filed May ~, 1985.
In addition, the centrifugal analysis instrument which is improved with the present invention enables reproducibility of measurements compatible with the requirements for enzyme reactions. This refers to the 20 reproducibility of measurements of absorbance on a single sample. This is particularly important in the case of kinetic methods. In these methods the variation in absorbance is slow, i.e. the measurements can be speeded up if reproducibility is good. In these methods also, the 25 absorbance level is sometimes quite high (1.7-2.2). Thus, reproducibility must be excellent over a wide range of absorbance, a feature achieved by the present improvements.
Als~, according to the instant invention excellent linearity between absorbance and concentration 30 over a wide range of absorbance is achieved This linearlty simplifies the use of the instrument, in that a calibration curve is not needed. Linearity is difficult to obtain at high absorbance, specially in the ultraviolet, and depends on the puritv of the 35 monochromatic light, i.e. on the proportion of interferina r'.
~ à
light, which is defined by the ratio of (a) the inten~ity of residual light emitted outside the selected spe~tral band to (b) the intensity of light inside the selected spectral band.
~urthermore, the improvements of the present invention, in order to reduce the bulk and cost of conventional spectrophotometers, utilize for the detector a photodiode array associated with conventional electronics.
The aforementioned photometri~ performance i~ a centrifugal analyzer, if it is ~o be achieved during a relatively short measuring time, creates special technical difficulties relating to the required signal/noise ratio and to obtaining a light beam having the required spectral purity for ultimate interpretation by the electronics of the instrument. Since it is ordinarily desired to make reproducible measurements with a maximum signal attenuation of about 1000 times through the sample, it is usually necessary for the signalJnoise ratio to be at least 2X10- at zero absorbance. Since the measurement time is very sbort (less than 5 microseconds~ an amplifier having a wide pass band is needed, which makes it difficult to obtain the desired signal/noise ratio since, as is known, the noise increases with the width of the amplifier pass-band. The effect of this noise is considerable compared with the effect of noise in conventional spectrophotometers, in which the influence of noise on the measured results can be reduced by integrating the measured signal over one or more seconds.
The problem of obtaining an adequate signal/noise ratio is made even more difficult because it is usually desired to use silicone photodiodes; the association of a photodiode with an amplifier is noisier than a photomultiplier operating at a weak signal level. This applies more particularly to wavelengths below 400 nm for measurements ~'7'~
of high absorbance value~ (A-3), since ~ilicone pho~odiode~ have a lower sensitivity than photomultipliers in this part of the spectrum.
Largely conventional analog-to-digital conversion electronic circuitry is used to convert current signals from the detector into digital information signals readable by associated microprocessor controlled circuitry.
In order to obtain the photometric characteristics described hereinbefore, the light beam supplied by the monochromator must have very high spectral purity, in order to avoid the well-known problems of nonlinearity due to interfering light and bandwidth effects. There are certain difficulties in obtaining a light beam having the spectral purity required for photometric purposes, if the cost and bulk of the spectrophotometer are to be simultaneously reduced. For these purposes, according to the invention, the proportion of interfering light is reduced to a value of approximately 1 x 10 4 at a waveleng~h of 340 nm, using a detector assembly comprising a photodiode array, a - multiwavelength spectral filter assembly between the photodiode array and the light source and means for attenuating stray light from the source prior to its impinging upon the spectral filter assembly.
Referring now to the drawings, and with particular reference to Figures 1 through 3, a preferrec photodiode array detector assembly in accordance with the invention is shown generally at 10. The assembly 10 essentially comprises a photodiode array 12, a spectral filter assembly 14 and a means to attenuate stray light 16. The spectral filter assembly 14 comprises a plurality of optical grade glass f ilters 18 which are individually chosen for their pre-selected transmittance characteristics depending on the wavelength of light it is 1~ 7~
desired to have measured by the individual photodiode~ of the array 12 which are below each of tbe filters. ~he filters 18 are assembled such that the four edges (indicated at 20) of each individual filter which are 5 normal to the array 12 are surrounded by an optically opaque, poorly light-transmissive material 12a, such as a black epoxy. The opaque material 12a effectively shields the sides of each of the optical filters 18 from light not incident to the chosen surfaces of each filter. The opaque material 12a, in this pr*ferred embodiment, also holds together the individual filters 18 in a desired planar configuration. The filter assembly 14, as shown, is mounted in a plane substantially parallel to the photodiode array 12 and in the path of incident light from a light source such that each individual one of the filters 18 is optically associated with a corresponding photodiode of the array 12. The means for attenuating stray light 16 that originates external to the spectral filter assembly 14, but which is not blocked by the opaque material shielding the side portion of each of ~he optical filters, in a preferred embodiment of the invention, comprises a mask~, of a suitable substance such as flat-black anodized metal, having a plurality of narrow slits therein which are located above the centerline of the surface area of each photodiode of the array 12. The stray light attenuating means 16 is, as shown mounted in a plane substantially parallel to that of the filter assembly 14 and overlays the surfaces of the filters 1~
thereof. The light attenuating means 16 also determines the central wavelength of light which impinges on the individual photodiodes of the array 12 by virtue of its lateral position in the focused spectrum of light. The width of slits ~2 in means 16 furthermore functions to determine, to a more or less extent, the bandpass of the spectrophotometer. The slit width of slits 22 of means 16 I,, also helps to normalize signal differences resulting from efficiency variations as a function of wavelength (e.g., caused by the source,spectrum grating efficiency, photodiode efficiency, and transmittance of filter assembly 14).
In the preferred fabrication of the detector assembly 10, the photodiode array 12, filter assembly 14 and light attenuating means 16 are mounted, as shown in Figures 1 and 2, in a suitable base 24 which includes a plurality of electrically conductive metal contacts 26 for electrical connection, when the assembly 10 is in use, to largely conventional electronic circuitry which, as well known to those skilled in the art, is capable of receiving and converting output signals produced by the photodiode array 12 in response to the intensities of light impinging thereupon. In a particular case the conversion can be, for example, to a digital readout corresponding to the absorbance of light by a constituent of a sample of biological material under analysis. The contacts ~6 are secured in the base 24, which can be made of a Ceramic, phenolic or other suitable commercially available dielectric material, in a well known manner so that they are in electrical connection with the output portion of individual ones of the photodiodes of the array 12 ~Figure 3).
As best shown in FigUre 3, the individual filters 18 are positioned in contact with the photodiodes of the array 12, and the stray light attenuating means 16 is positioned over the array 12 in contact with the filters 18, such that the slits 22 thereof create an incident light path (as shown by the arrows) through the means 16, ~he filters 18 and to the diodes of the array 12.
~owever, the opaque material 12a functions effectively to block any of the incident light, after entering a particular slit 22, from impinging upon any of the 1~7;~
- 11 photodiodes of the array 12 which are not intentionally positioned directly beneath that slit. Such a preferred construction in accordance with the invention has been found experimentally to reduce ~cross talk~, or the effect of such incident light impinging upon an unintended photodiode, to a value of less than about 60 ppm.
Referring now to Figure 4 of the drawings, a preferred embodiment of an improved optical system of a spectrophotometer of the type aforedescribed, which incorporates the concepts of the present invention, is indicated generally at 28. The system 28, it is to be appreciated, is of largely conventional design except for the inclusion of the detector assembly 10. Furthermore, it is to be appreciated that the system 28 can be incorporated into a conventional optical housing, but preferably is enclosed in a cast aluminum housing machined such that a first surface of ~he concave diffraction grating is located at a critical distance from both the entrance slit of the housing, through which light emerging from the sample passes, and the detector assembly. This configuration enables manufacturing ease as well as tight optical focusing. In addition, all machining of th~
casting is done from the same end to improve tolerances.
The system 28 comprises the detector assembly 10, z concave halographic grating 30 ~Instruments, S.A. Inc.
Metuchen, New Jersey), an optical transmission sli~ 32, an emission lens 34, a container 36, such as a glass or plastic ampule or cuvette, for containing a sample liquid or chemical 38 to be analyzed in the spectrophotometer, z source lens 40 and a light source 42. The lenses 3~ and 40 are of optical quality ground glass and are of a type conventionally used in spectrophotometric instrumentation, and are commercially available from Melles Griot. The light source 42 is a xenon lamp for producing light pulses lasting approximately 2.3microseconds which is considerably
Referring now to Figure 4 of the drawings, a preferred embodiment of an improved optical system of a spectrophotometer of the type aforedescribed, which incorporates the concepts of the present invention, is indicated generally at 28. The system 28, it is to be appreciated, is of largely conventional design except for the inclusion of the detector assembly 10. Furthermore, it is to be appreciated that the system 28 can be incorporated into a conventional optical housing, but preferably is enclosed in a cast aluminum housing machined such that a first surface of ~he concave diffraction grating is located at a critical distance from both the entrance slit of the housing, through which light emerging from the sample passes, and the detector assembly. This configuration enables manufacturing ease as well as tight optical focusing. In addition, all machining of th~
casting is done from the same end to improve tolerances.
The system 28 comprises the detector assembly 10, z concave halographic grating 30 ~Instruments, S.A. Inc.
Metuchen, New Jersey), an optical transmission sli~ 32, an emission lens 34, a container 36, such as a glass or plastic ampule or cuvette, for containing a sample liquid or chemical 38 to be analyzed in the spectrophotometer, z source lens 40 and a light source 42. The lenses 3~ and 40 are of optical quality ground glass and are of a type conventionally used in spectrophotometric instrumentation, and are commercially available from Melles Griot. The light source 42 is a xenon lamp for producing light pulses lasting approximately 2.3microseconds which is considerably
- 12 -less than the time spent by a sample in the axis of the light beam in the case of a rapid rotary analyzer e.g.
with a rotor rotating at 1800 rpm. The xenon lamp is of the bulb type and has a power of about 7 W. If the energy released per flash is 0.3 joules for 2.3 microseconds, the mean power emltted during these 2.3 microseconds is equivalent to that from a 130 kW continuous xenon lamp.
Clearly, there is a gain in light level and consequently in the signal/noise ratio by using a pulsed lamp like light source 42. However, as described herein, the detector assembly 10 is constructed such that these, and the other difficulties of conventional spectrophotometers previously described, are overcome or minimized, in accordance with the concepts of the invention.
In use of the detector assembly 10 in the optical system 28, light emitted from the source 42 is focused by the lens 40 through the container 36 containing the sample 38. As well known to those skilled in the art, certain constituents of the sample 38 will absorb certain wavelengths of the light emitted from the source 42, and other wavelengths will be emitted therefrom and impinge upon the lens 34. The lens 34 functions to focus such emitted wavelength of light through the slit 32 and onto the grating 30. The grating 30, in turn, disperses and reflects the light from the slit 32 which impinges thereupon to the detector assembly 10, where the intensities of light are detected and converted into electrical signals indicative of the presence andfor amount of constituents present in the sample 38, as previously described.
The components of the detector assembly 10 can be selected as fo~lows. Preferred for use as the filters 18 are those commercially available from Hoya Optical Company. For example, the filters which have been selected for use in an especially preferred embodiment of ~`7~
with a rotor rotating at 1800 rpm. The xenon lamp is of the bulb type and has a power of about 7 W. If the energy released per flash is 0.3 joules for 2.3 microseconds, the mean power emltted during these 2.3 microseconds is equivalent to that from a 130 kW continuous xenon lamp.
Clearly, there is a gain in light level and consequently in the signal/noise ratio by using a pulsed lamp like light source 42. However, as described herein, the detector assembly 10 is constructed such that these, and the other difficulties of conventional spectrophotometers previously described, are overcome or minimized, in accordance with the concepts of the invention.
In use of the detector assembly 10 in the optical system 28, light emitted from the source 42 is focused by the lens 40 through the container 36 containing the sample 38. As well known to those skilled in the art, certain constituents of the sample 38 will absorb certain wavelengths of the light emitted from the source 42, and other wavelengths will be emitted therefrom and impinge upon the lens 34. The lens 34 functions to focus such emitted wavelength of light through the slit 32 and onto the grating 30. The grating 30, in turn, disperses and reflects the light from the slit 32 which impinges thereupon to the detector assembly 10, where the intensities of light are detected and converted into electrical signals indicative of the presence andfor amount of constituents present in the sample 38, as previously described.
The components of the detector assembly 10 can be selected as fo~lows. Preferred for use as the filters 18 are those commercially available from Hoya Optical Company. For example, the filters which have been selected for use in an especially preferred embodiment of ~`7~
- 13 -thc invention are commercially designated V-340, ~-44C, Y-50, Y-52 and 0-56. These filters have well known optical transmission and absorbance properties.
Alternatively, optical improvements can be made over the aforedescribed. If narrow band interference filters, such as those available from Microcoating Laboratories, are used in place of the previously-described ~cutoff~ filters;
however these filters result in additional cost. The filters are, prefera~ly, cut to a size of about 4mm length X
0.8 mm width x 0.8 mm height, and thereafter several of such filters having the capability of passing different wavelengths therethrough (depending on which wavelengths are ultimately desired to impinge upon the individual ones of the photodiodes with which the filter assembly is to be used) are assembled together in a linear array as previously described.
The optically opaque material utilized between the filters can be, for example, a black epoxy commercially available from Epoxy Technology, Inc., Billerica, MA, under the name EP0-TEK 320*. This material is described by the manufacturer as a two-component, room temperature curing, black epoxy, a 0.0005 inch thick film of which will transmit less than 0.0001~ of light over a wavelength range of 300 angstroms to 1 micron. Full details of the method of use of such material to form the filter array of the invention are available from the foregoing manufacturer.
The photodiode array 12 can be any suitable commercially available array designed for use in, e.g.
spectrophotometric optical systems. Especially advantageous for use in the present invention are the multi-element silicon detectors manufactured by Hamamatsu Corporati~n, Midlesex, NJ.
* trademark 1;~7i~
Alternatively, optical improvements can be made over the aforedescribed. If narrow band interference filters, such as those available from Microcoating Laboratories, are used in place of the previously-described ~cutoff~ filters;
however these filters result in additional cost. The filters are, prefera~ly, cut to a size of about 4mm length X
0.8 mm width x 0.8 mm height, and thereafter several of such filters having the capability of passing different wavelengths therethrough (depending on which wavelengths are ultimately desired to impinge upon the individual ones of the photodiodes with which the filter assembly is to be used) are assembled together in a linear array as previously described.
The optically opaque material utilized between the filters can be, for example, a black epoxy commercially available from Epoxy Technology, Inc., Billerica, MA, under the name EP0-TEK 320*. This material is described by the manufacturer as a two-component, room temperature curing, black epoxy, a 0.0005 inch thick film of which will transmit less than 0.0001~ of light over a wavelength range of 300 angstroms to 1 micron. Full details of the method of use of such material to form the filter array of the invention are available from the foregoing manufacturer.
The photodiode array 12 can be any suitable commercially available array designed for use in, e.g.
spectrophotometric optical systems. Especially advantageous for use in the present invention are the multi-element silicon detectors manufactured by Hamamatsu Corporati~n, Midlesex, NJ.
* trademark 1;~7i~
- 14 -In an especially preferred embodiment of the invention, it is found to be advantageous for the reduction of electronic cros~ talk inside the photodiode array itself, that a non-used photodiode be present between photodiodes which are intended for signal use.
This non-used, or ~dummy- diode must necessarily be externally electrically shorted. The use of the shorted dummy diode can reduce electronic cross talk by a factor of approximately 500. A further reduction of cross talk can be achieved by etching deep groves around the signal diodes, as described by Rim, et al., in Optical Engineering, vol. 22, NO. 5, p. 656, 1983.
The following is an example of specifications of a preferred detector array assembly which has been fabricated in accordance with the present invention. ~he example is intended to be merely illustrative of the characteristics of such a detector and to further teach how to make and use such a device, but is not to be construed as limitative of the invention in any way, the scope of which is defined solely in the appended claims.
Example PREFERRED DETECTOR ASSEMBLY
Distance ~oya Filter from ~1 Wavelength Filter No. Centerline (NM) Number -1 0.000 - 340 U-340 2 2.450 . 415 B-440 3 3.602 450 B-440 4 5.259 500 Y-50 6 7.840 577 Y-52 7 8.788 605 O-5 8 9.735 633 0-5 ~7X~
This non-used, or ~dummy- diode must necessarily be externally electrically shorted. The use of the shorted dummy diode can reduce electronic cross talk by a factor of approximately 500. A further reduction of cross talk can be achieved by etching deep groves around the signal diodes, as described by Rim, et al., in Optical Engineering, vol. 22, NO. 5, p. 656, 1983.
The following is an example of specifications of a preferred detector array assembly which has been fabricated in accordance with the present invention. ~he example is intended to be merely illustrative of the characteristics of such a detector and to further teach how to make and use such a device, but is not to be construed as limitative of the invention in any way, the scope of which is defined solely in the appended claims.
Example PREFERRED DETECTOR ASSEMBLY
Distance ~oya Filter from ~1 Wavelength Filter No. Centerline (NM) Number -1 0.000 - 340 U-340 2 2.450 . 415 B-440 3 3.602 450 B-440 4 5.259 500 Y-50 6 7.840 577 Y-52 7 8.788 605 O-5 8 9.735 633 0-5 ~7X~
- 15 -Ph sical Characteristics Y
Detector width 0.640 mm + 0.025 mm.
Detector height 4.20 mm + 0.025 mm.
No cumulative tolerances, centerline distance tolerance + 0.025 mm.
Individual filter size 0.8 mm wide x 0.8 mm thick x 3.8 mm long, + 0.1 mm.
Package: i6 pin standard dip, ceramic.
Electrical Characteristics Sensitivity: setter than 0. 3 A/W at 600 nm, 0.15 a/w at 350 nm, optimized at 340 nm.
Uniformity: + 5~ across any channel, + 10%
channel to channel on a single chip.
Rise time: l Microsecond max (330 nm to 700 nm into 50 ohms) Cross talk: 0.005% at OV bias, 5 us pulse from 330 nm to 700 nm.
Dark Current: Less than 50 pA, at 37 degrees C
(10 mV reverse Bias) Operating Temp: 20 degrees - 50 degrees C.
Noise Current: Less than 5 x 10 A
(rms)/Hl/2 at 37 degrees C.
It is to be appreciated that according to the present invention improvements can be made in a spectrophotometer for general use, e.g., one without moving mechanical parts, and has advantages resulting from the combined use of a flash lamp and the detector previously described. By definition, however, this spectrophotometer can also be used for measuring transmission or absorbance of a wide variety of samples in a given spectral range, e.g., for conventional measurements of solutions used for clinical chemical analyses, in a static or moving cell.
Detector width 0.640 mm + 0.025 mm.
Detector height 4.20 mm + 0.025 mm.
No cumulative tolerances, centerline distance tolerance + 0.025 mm.
Individual filter size 0.8 mm wide x 0.8 mm thick x 3.8 mm long, + 0.1 mm.
Package: i6 pin standard dip, ceramic.
Electrical Characteristics Sensitivity: setter than 0. 3 A/W at 600 nm, 0.15 a/w at 350 nm, optimized at 340 nm.
Uniformity: + 5~ across any channel, + 10%
channel to channel on a single chip.
Rise time: l Microsecond max (330 nm to 700 nm into 50 ohms) Cross talk: 0.005% at OV bias, 5 us pulse from 330 nm to 700 nm.
Dark Current: Less than 50 pA, at 37 degrees C
(10 mV reverse Bias) Operating Temp: 20 degrees - 50 degrees C.
Noise Current: Less than 5 x 10 A
(rms)/Hl/2 at 37 degrees C.
It is to be appreciated that according to the present invention improvements can be made in a spectrophotometer for general use, e.g., one without moving mechanical parts, and has advantages resulting from the combined use of a flash lamp and the detector previously described. By definition, however, this spectrophotometer can also be used for measuring transmission or absorbance of a wide variety of samples in a given spectral range, e.g., for conventional measurements of solutions used for clinical chemical analyses, in a static or moving cell.
Claims (12)
1. In a spectrophotometer comprising:
(a) a flash lamp;
(b) a grating monochromator for receiving a beam of light delivered by the flash lamp and which has passed through a sample for analysis; and (c) a detector situated to receive the beam of light reflected by said grating monochromator;
the improvement wherein the detector comprises;
a photodiode array assembly including:
a plurality of individual photodiodes situated in a first plane;
a plurality of individual spectral filters situated substantially parallel to said first plane and adjacent said plurality of photodiodes such that light passing through each of said individual adjacent spectral filters will impinge upon only one of said individual photodiodes; and means for attenuating stray light, said means being situated substantially parallel to said first plane and adjacent to said plurality of individual spectral filters such that said means is located above each of said individual photodiodes.
(a) a flash lamp;
(b) a grating monochromator for receiving a beam of light delivered by the flash lamp and which has passed through a sample for analysis; and (c) a detector situated to receive the beam of light reflected by said grating monochromator;
the improvement wherein the detector comprises;
a photodiode array assembly including:
a plurality of individual photodiodes situated in a first plane;
a plurality of individual spectral filters situated substantially parallel to said first plane and adjacent said plurality of photodiodes such that light passing through each of said individual adjacent spectral filters will impinge upon only one of said individual photodiodes; and means for attenuating stray light, said means being situated substantially parallel to said first plane and adjacent to said plurality of individual spectral filters such that said means is located above each of said individual photodiodes.
2. A spectrophotometer according to claim 1, wherein an optically opaque material surrounds each of said spectral filters, whereby components of light are allowed to pass through one of said spectral filters to one of said individual photodiodes but said components of light are blocked, after entering said one of said filters, from passing through any other one of said filters to any other of said photodiodes.
3. A spectrophotometer according to claim 1, wherein a substantial portion of said photodiodes are separated one from the other by an externally electrically grounded photodiode to reduce electrical crosstalk.
4. A spectrophotometer according to claim 3, wherein an optically opaque material surrounds each of said spectral filters, whereby components of light are allowed to pass through one of said spectral filters to one of said individual photodiodes but said components of light are blocked, after entering said one of said filters, from passing through any other one of said filters.
5. A method for producing a photodiode array assembly comprising the steps of:
(a) selecting a photodiode array having a plurality of individual photodiodes, each of said individual photodiodes having a preselected response to one or more wavelengths of light;
(b) selecting a spectral filter array having a plurality of individual spectral filters such that each of said individual spectral filters transmits one or more preselected wavelengths of light; and (c) mounting said spectral filter array in a plane parallel to said photodiode array such that each of said individual spectral filters is adjacent to one of said individual photodiodes; whereby light passing through one of said individual spectral filters in said spectral filter array will impact on only one of said individual photodiodes in said photodiode array.
(a) selecting a photodiode array having a plurality of individual photodiodes, each of said individual photodiodes having a preselected response to one or more wavelengths of light;
(b) selecting a spectral filter array having a plurality of individual spectral filters such that each of said individual spectral filters transmits one or more preselected wavelengths of light; and (c) mounting said spectral filter array in a plane parallel to said photodiode array such that each of said individual spectral filters is adjacent to one of said individual photodiodes; whereby light passing through one of said individual spectral filters in said spectral filter array will impact on only one of said individual photodiodes in said photodiode array.
6. A method according to claim 5, further comprising separating a substantial portion of said photodiodes one from the other with an externally electrically grounded photodiode to reduce electrical crosstalk.
7. A method according to claim 5, further comprising separating each of said spectral filters one from another by a thin film of an optically opaque material.
8. A method according to claim 5, 6 or 7 further comprising mounting a means for attenuating stray light adjacent and substantially parallel to said spectral filter array, so that light entering said attenuating means is directed through one of said spectral filters to one of said photodiodes.
9. A photodiode array assembly comprising:
a photodiode array comprising a plurality of photodiodes situated in a first plane;
a spectral filter situated substantially parallel to said first plane and adjacent said photodiode array such that light passing through said spectral filter impacts on said photodiode array; and means for attenuating stray light, said means being situated substantially parallel to said first plane and adjacent said spectral filter, such that said means is located substantially over each of said photodiodes;
whereby light entering said stray light attenuating means is directed through said spectral filters to each of said photodiodes.
a photodiode array comprising a plurality of photodiodes situated in a first plane;
a spectral filter situated substantially parallel to said first plane and adjacent said photodiode array such that light passing through said spectral filter impacts on said photodiode array; and means for attenuating stray light, said means being situated substantially parallel to said first plane and adjacent said spectral filter, such that said means is located substantially over each of said photodiodes;
whereby light entering said stray light attenuating means is directed through said spectral filters to each of said photodiodes.
10. A photodiode array assembly according to claim 9, wherein a substantial portion of said photodiodes are separated one from the other by an externally electrically grounded photodiode to reduce electrical crosstalk.
11. A photodiode array assembly according to claim 9, wherein said spectral filter comprises an array of individual filters and wherein an optically opaque material surrounds each of said spectral filters, whereby components of light are allowed to pass through one of said spectral filters to one of said photodiodes but said components of light are blocked, after entering said one of said filters, from passing through any other one of said filters to any other of said photodiodes.
12. A photodiode array assembly according to claim 11, wherein a substantial portion of said photodiodes are separated on from the other by an externally electrically grounded photodiode to reduce electrical crosstalk.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US71431285A | 1985-03-21 | 1985-03-21 | |
US714,312 | 1985-03-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1272616A true CA1272616A (en) | 1990-08-14 |
Family
ID=24869531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000503989A Expired - Fee Related CA1272616A (en) | 1985-03-21 | 1986-03-13 | Spectrophotometer |
Country Status (5)
Country | Link |
---|---|
US (1) | US4687329A (en) |
EP (1) | EP0195339B1 (en) |
JP (1) | JPS61251724A (en) |
CA (1) | CA1272616A (en) |
DE (1) | DE3686184T2 (en) |
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-
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- 1986-03-10 EP EP86103160A patent/EP0195339B1/en not_active Expired - Lifetime
- 1986-03-10 DE DE8686103160T patent/DE3686184T2/en not_active Expired - Fee Related
- 1986-03-13 CA CA000503989A patent/CA1272616A/en not_active Expired - Fee Related
- 1986-03-20 JP JP61061078A patent/JPS61251724A/en active Pending
- 1986-12-12 US US06/941,247 patent/US4687329A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS61251724A (en) | 1986-11-08 |
DE3686184D1 (en) | 1992-09-03 |
DE3686184T2 (en) | 1993-02-25 |
EP0195339A2 (en) | 1986-09-24 |
US4687329A (en) | 1987-08-18 |
EP0195339A3 (en) | 1989-05-03 |
EP0195339B1 (en) | 1992-07-29 |
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