CN102353450A - Spectral analysis method based on photon counting full spectrum direct reading - Google Patents
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Abstract
The invention provides a spectral analysis method based on photon counting full spectrum direct reading. The spectral analysis method comprises the following steps of: generating a characteristic spectrum to be observed by a sample under the action of an excitation source; making multiplex light mingled with the characteristic spectrum incident into a light splitting system through an incident optical device; chromatically dispersing the incident multiplex light into a monochromatic spectral image by the light splitting system; imaging the spectral image on a sensitive face of a photon counting imaging detector; reconstructing the spectral image by the photon counting imaging detector in a digitalized manner through position sensitive detection and photon counting; and qualitatively and quantitatively analyzing the sample by an information processing and displaying unit according to the position of each pixel in the digital spectral image and signal intensity. The spectral analysis method provided by the invention has the advantages of low detection limit, high reading precision, high data stability, large linear dynamic range and the like, and can be used for realizing full spectrum direct reading, that is to say, a plurality of substance components can be analyzed at the same time, each spectral line in a working wavelength range can be fully utilized, the working speed is high, and corresponding instruments have the characteristics of simple structure, high operating stability, low production and operating cost, convenience for upgrading and debugging, and the like.
Description
Technical field
The present invention relates to a kind of spectroscopic analysis methods of novelty, promptly a kind of " photon counting is composed direct-reading entirely " spectroscopic analysis methods based on " photon counting imaging detector ".This method preferably resolves between " composing direct-reading entirely " and " detection sensitivity ", " data stability ", " reading accuracy " and " linear dynamic range " can not both technical barriers of getting both; On the basis of realizing " composing direct-reading entirely ", " detection sensitivity ", " data stability ", " reading accuracy " and " linear dynamic range " of spectral analysis have been improved.
The technical field that the present invention relates to comprises fields such as spectroscopic analysis methods research, spectral analysis technique application and spectrometric instrument manufacturing.
Background technology
That spectral analysis technique has is highly sensitive, selectivity good, easy to operate fast, advantage such as antijamming capability is strong and accuracy is good.Divide according to the mechanism that produces characteristic spectrum, spectroscopic analysis methods can be divided into several big type of absorption spectroscopy, emission spectrometry, scattering (or Raman) spectroscopic methodology and fluorescent spectrometry etc.No matter adopt which kind of method, the basic comprising of method is roughly the same, mainly partly is made up of excitaton source, beam splitting system, detector and information processing and demonstration etc.
1) effect of excitaton source provides the energy excitation sample to produce characteristic spectrum, comprises characteristic spectrums such as absorption spectrum, emission spectrum, scattering (or Raman) spectrum and fluorescence spectrum.
2) effect of beam splitting system is that it mainly is made up of incident diaphragm, collimating mirror, chromatic dispersion beam splitter/device, object lens and outgoing diaphragm etc. the spectrum picture that is mingled with the incident complex light chromatic dispersion monochromatizing of characteristic spectrum.General chromatic dispersion beam splitter/device commonly used mainly contains several types such as prism, grating and interference device.
3) effect of detector is light signal to be converted to the electric signal (voltage/current/quantity of electric charge) that (but accompaniment signal gain process) is easy to transmission process through opto-electronic conversion.
4) information processing then is that the signal of detector output is handled and analyzed with demonstration, and analysis result is come out with the picture and text formal representation that the various people of being convenient to (or machine) understand.
According to the type of detector and the difference of signal processing mode thereof, spectroscopic analysis methods can be divided into " charge integration method " and " photon counting method " two big types again:
1) the charge integration method is that electronics or the quantity of electric charge in hole through measuring continuous storage accumulation comes inverting incident light intensity, i.e. the mode of " survey electric current ", and this also is that traditional spectral analysis technique adopts more a kind of method.Corresponding detector serves as typical case's representative with charge-coupled image sensor (CCD/Charge Coupled Device), charge injection device (CID/Charge Injection Device), photodiode (PD/Photo Diode) and avalanche photodide (APD/Avalanche Photodiode) etc.
2) the photon counting rule is to regard optical radiation as be made up of single one by one photon photon stream, comes inverting incident light intensity through the counting (being step-by-step counting) to photon.The used detector of tradition serves as typical case's representative with photomultiplier (PMT/Photomultiplier Tube).
What deserves to be mentioned is: PMT can work in " charge integration " pattern equally.What the tradition spectral analysis technique mostly adopted is this mode, is just using PMT as a simple high-gain, highly sensitive charge integrator.
Compare with the charge integration method, photon counting method has the following advantages:
1) high signal to noise ratio (S/N ratio) and extremely low ground unrest
Because what photon counting method adopted is the step-by-step counting mode,, pulse height will not count when being lower than certain threshold value, therefore can filter out most noise, have very high signal to noise ratio (S/N ratio).
The ground unrest of photon counting method is mainly derived from the dark counts of detector.The dark counts that works in the detector under the photon counting mode is very little, usually less than 1count/scm
2So photon counting method has extremely low ground unrest.
2) high detection sensitivity and extremely low radiation flux lower limit
Because photon counting method may detect single photon, so its detection sensitivity is very high, corresponding radiation flux lower limit is also very low, can reach 10 usually
-18W/cm
2Even it is lower.
3) leakage current influence and good anti-drift
Because what photon counting method adopted is the step-by-step counting mode; Therefore its biggest advantage is exactly not receive the leakage current or the influence of dark current; Have good anti-drift, avoided the difficult problem of many puzzlement data stability such as dark current of zero point drift and the gain drift and the detector of amplifier in the charge integration method.
4) extremely wide dynamic range
Because the radiation flux lower limit of photon counting method is very low, and its radiation flux upper limit only is subject to the maximum count rate (usually 10
5-10
6Between the Hz), so the non-constant width of its dynamic range, can reach 10 usually
4-10
5About.
Usually, the quality of estimating a kind of spectroscopic analysis methods (or a spectrometric instrument) mainly is to see its " detection limit ", " data stability " (repeatable accuracy), " reading accuracy " and technical indicators such as " linear dynamic ranges ".Through above-mentioned comparative analysis, be not difficult to find out and adopt photon counting method to carry out spectral analysis that These parameters can both be increased dramatically:
1) because the sensitivity of photon counting method is very high, even may detect single photon, so " detection limit " of photon counting method is lower, can carry out trace (or ultratrace) analysis.
2) because the signal to noise ratio (S/N ratio) of photon counting method is very high, may detect very faint line strength and change, it is higher therefore to adopt photon counting method to carry out the reading accuracy of quantitative test.
3) because photon counting method does not receive the detector leakage current or the influence of dark current, have good anti-drift, so the data stability of photon counting method is higher, just repeatable accuracy is higher.
4) because therefore the non-constant width of dynamic range of photon counting method adopts photon counting method to carry out spectral analysis, can greatly improve the linear dynamic range of quantitative test.
In addition, because photon counting method need not detector is freezed, therefore can reduce the production run cost of spectrometric instrument accordingly.
According to whether Wavelength scanning mechanism being set, spectroscopic analysis methods can be divided into " scanning method " and " composing the direct-reading method entirely " two kinds again:
1) scanning method need be provided with the mode detecting light spectrum Density Distribution of Wavelength scanning mechanism with scanning, and this also is that traditional spectral analysis technique adopts more a kind of method.Corresponding detector serves as typical case's representative with PD, APD, PMT and other " point (or direction) " detector etc.
2) compose the direct-reading method entirely and claim imaging method again, but it need not Wavelength scanning mechanism just distribution of direct detection spectral concentration or spectrum picture.Corresponding detector serves as typical case's representative with CCD, CID, PD array and other " face battle array (or linear array) " detector.
The cost of stepper motor and optical system is the exponential relationship growth with its measure of precision in the Wavelength scanning mechanism, and Wavelength scanning mechanism is more accurate, and its operation stability is poor more.So with respect to scanning method; The benefit that adopts full spectrum direct-reading method to carry out spectral analysis is: can analyze multiple material composition simultaneously; Can make full use of each the bar spectral line in the operating wavelength range; Operating rate is fast, and corresponding apparatus structure is simple, operation stability is high, the production run cost is relatively low and the upgrading adjustment is convenient.
Introduction through the above-mentioned background technology is not difficult to find out:
1) adopt simple " charge integration method " to carry out spectral analysis (for example detector adopts CCD or CID or PD etc.); Though can reach the purpose of " composing direct-reading entirely "; Corresponding but " detection sensitivity " and " data stability " can be severely limited, and " reading accuracy " and " linear dynamic range " also can receive certain influence.
2) adopt simple " photon counting method " to carry out spectral analysis (for example detector adopts PMT) with the mode of scanning; Though corresponding " detection sensitivity " and " data stability " can be increased dramatically; " reading accuracy " and " linear dynamic range " also can obtain certain optimization; But can't realize " composing direct-reading entirely ", can't have many advantages of " composing the direct-reading method entirely ".
In sum; If adopt a kind of detector that can either " photon counting " can " compose direct-reading entirely " again; I.e. " photon counting imaging detector "; Just can on the basis of " composing direct-reading entirely ", significantly improve " detection sensitivity ", " data stability ", " reading accuracy " and " linear dynamic range " of corresponding light spectral analysis method.
Summary of the invention
The objective of the invention is also can compose the spectroscopic analysis methods of direct-reading entirely for design high sensitivity, high data stability, high scale precision, big linear dynamic range; Comprise absorption spectroscopy, emission spectrometry, scattering (or Raman) spectroscopic methodology, fluorescent spectrometry and general spectroscopic analysis methods etc.; A kind of technical thought and scheme of novelty are provided, promptly a kind of " photon counting is composed direct-reading entirely " spectroscopic analysis methods based on " photon counting imaging detector ".This method preferably resolves traditional spectroscopic analysis methods can not both technical barriers of getting both between " composing direct-reading entirely " and " detection sensitivity ", " data stability ", " reading accuracy " and " linear dynamic range "; On the basis of realizing " composing direct-reading entirely ", improved " detection sensitivity ", " data stability ", " reading accuracy " and " linear dynamic range " of spectroscopic analysis methods.
Technical scheme of the present invention: a kind of " photon counting is composed direct-reading entirely " spectroscopic analysis methods, include but not limited to following steps,
S100. under the effect of excitaton source 1, produce characteristic spectrum to be observed after sample pre-service premenstruum (premenstrua);
S200. the complex light that is mingled with characteristic spectrum incides beam splitting system 2 through beam incident optical device;
S300. beam splitting system 2 is with the spectrum picture of the complex light chromatic dispersion monochromatizing of incident;
S400. spectrum picture images on the sensitive area of photon counting imaging detector 3 through the outgoing optical devices;
S500. photon counting imaging detector 3 is through " the quick detection in position " and " photon counting ", with digitized mode reconstruct spectrum picture;
S600. information processing and display unit 4 carry out qualitative and quantitative analysis according to the position and the signal intensity of each pixel in the digital spectrum image to sample.
Further, described photon counting imaging detector 3 mainly partly is made up of optics input window, photocathode, MCP, position-sensitive anode, electronics sensing circuit and DC high-voltage power supply etc.
Further, above-mentioned steps S500, the principle of work of promptly said photon counting imaging detector 3 and flow process, more specifically do,
S510. spectrum picture can be regarded the photon stream of being made up of the single photon of Different Plane position one by one as in spatial and temporal scope, and each photon in the photon stream bombards the photocathode at diverse location place through optics input window order successively;
S520. under certain quantum efficiency, photocathode is single photoelectron through external photoeffect with single photon conversion;
S530. single photoelectron bombards microchannel plate (MCP/Microchannel Plate) straight under the effect of quickening bias field, after the MCP multiplication, form an electronics cloud cluster;
S540. the electronics cloud cluster is getted over the quick anode and collected by position-sensitive anode that puts in place under the effect of quickening bias field;
S550. the quantity of electric charge collected according to each metallic conductor on the position-sensitive anode of electronics sensing circuit or electronics cloud cluster moment of arriving each metallic conductor timing point; Centroid position to the electronics cloud cluster is decoded, but this centroid position just inverting be the incoming position of single photon;
S560. just on corresponding position, once counting after accomplishing the position decoding of single photon;
S570. at certain image integration in the time, through to " position decoding " of a large amount of photons and " photon counting " on diverse location, i.e. circulation step S510-S560, just restructural spectrum picture repeatedly.
Further, above-mentioned steps S540, the physical process that the quick anode of ascending the throne is collected the electronics cloud cluster; More specifically do; The electronics cloud cluster can directly be getted over the quick anode that puts in place under the effect of quickening bias field, or gets over earlier to semiconductor layer, is sensed position-sensitive anode through electric charge induction then.
Further; Between sample and the beam splitting system 2, between beam splitting system 2 and the photon counting imaging detector 3 and in the beam splitting system 2, corresponding incident and outgoing optical devices can be set to realize optical functions such as optical alignment, focusing, break-in, beam split, dim light, filtering, elimination parasitic light and diaphragm limit light according to practical application request.
Further; Corresponding Wavelength scanning mechanism can be set moving beam splitting system 2 or photon counting imaging detector 3 again or other optical element according to practical application request, thereby read the spectrum picture of beam splitting system 2 outputs with segmentation or subregional mode according to preset span lengths.
Further, described excitaton source 1 provide energy in sample with generation characteristic spectrum to be observed, mode such as mode of excitation comprises that optical excitation, electricity excite, thermal excitation and other radiation excitation; Described characteristic spectrum comprises spectrum such as absorption spectrum, emission spectrum, scattering (or Raman) spectrum and fluorescence spectrum.
Further, described beam splitting system 2 is with the spectrum picture of the incident complex light chromatic dispersion monochromatizing that is mingled with characteristic spectrum, comprises one dimension spectrogram and two-dimentional spectrogram; Corresponding chromatic dispersion light-splitting method can adopt single index method, diffraction approach and interferometric method, or the crossed dispersion method that forms of above-mentioned three kinds of method combination in any.
Effect of the present invention:
1. because the integrated advantage of " photon counting method ", so advantage such as this spectroscopic analysis methods has detection limit low (highly sensitive), reading accuracy is high, data stability is high (repeatable accuracy is high) and linear dynamic range is big.
2. because the integrated advantage of " composing the direct-reading method entirely ", so this spectroscopic analysis methods has advantages such as can analyzing multiple material composition simultaneously, can make full use of that the fast and corresponding apparatus structure of each bar spectral line, operating rate in the operating wavelength range is simple, operation stability is high, production run cost, upgrading adjustment are convenient.
Description of drawings
For the technical scheme in the clearer explanation embodiment of the invention, the accompanying drawing of required use is done simple the introduction in will describing embodiment below.Conspicuous, the accompanying drawing in describing below only is some embodiments of the present invention.
Fig. 1 is " photon counting is composed direct-reading entirely " spectroscopic analysis methods basic procedure block diagram;
Fig. 2 is direct playback mode " photon counting imaging detector " basic structure synoptic diagram;
Fig. 3 is electric charge induction playback mode " photon counting imaging detector " basic structure synoptic diagram;
Fig. 4 is the crossed dispersion light-dividing device synoptic diagram of being made up of biprism;
Fig. 5 is the crossed dispersion light-dividing device synoptic diagram of being made up of prism and echelle grating;
Fig. 6 is dissimilar position-sensitive anode basic structure synoptic diagram.
The drawing reference numeral explanation:
The 1-excitaton source; The 2-beam splitting system; 3-photon counting imaging detector; 4-information processing and display unit.
Embodiment
Embodiment one:
As shown in Figure 1, a kind of " photon counting is composed direct-reading entirely " spectroscopic analysis methods specifically includes but not limited to following steps:
S100. under the effect of excitaton source 1, produce characteristic spectrum to be observed after sample pre-service premenstruum (premenstrua).
S200. the complex light that is mingled with characteristic spectrum incides beam splitting system 2 through beam incident optical device;
S300. beam splitting system 2 is with the spectrum picture of the complex light chromatic dispersion monochromatizing of incident;
S400. spectrum picture images on the sensitive area of photon counting imaging detector 3 through the outgoing optical devices;
S500. photon counting imaging detector 3 is through " the quick detection in position " and " photon counting ", with digitized mode reconstruct spectrum picture;
S600. information processing and display unit 4 carry out qualitative and quantitative analysis according to the position and the signal intensity of each pixel in the digital spectrum image to sample.
Above-mentioned photon counting imaging detector 3 mainly partly is made up of optics input window, photocathode, MCP, semiconductor layer (optional), position-sensitive anode, electronics sensing circuit and DC high-voltage power supply etc., like Fig. 2, shown in Figure 3.
Above-mentioned steps S500, i.e. the principle of work of photon counting imaging detector 3 and flow process more specifically are:
S510. spectrum picture can be regarded the photon stream of being made up of the single photon of Different Plane position one by one as in spatial and temporal scope, and each photon in the photon stream bombards the photocathode at diverse location place through optics input window order successively;
S520. under certain quantum efficiency, photocathode is single photoelectron through external photoeffect with single photon conversion;
S530. single photoelectron bombards MCP straight under the effect of quickening bias field, after the MCP multiplication, form an electronics cloud cluster;
S540. the electronics cloud cluster is getted over the quick anode and collected by position-sensitive anode that puts in place under the effect of quickening bias field;
S550. the quantity of electric charge collected according to each metallic conductor on the position-sensitive anode of electronics sensing circuit or electronics cloud cluster moment of arriving each metallic conductor timing point; Centroid position to the electronics cloud cluster is decoded, but this centroid position just inverting be the incoming position of single photon;
S560. just on corresponding position, once counting after accomplishing the position decoding of single photon;
S570. at certain image integration in the time, through to " position decoding " of a large amount of photons and " photon counting " on diverse location, i.e. circulation step S510-S560, just restructural spectrum picture repeatedly.
Above-mentioned steps S540; The quick anode of ascending the throne is collected the physical process of electronics cloud cluster; More specifically be: the electronics cloud cluster can directly be getted over the quick anode (as shown in Figure 2) that puts in place under the effect of quickening bias field; Or get over earlier to semiconductor layer, sensed position-sensitive anode (as shown in Figure 3) through electric charge induction then.
Embodiment two:
For spontaneous radiation and testing sample is light source, can not need excitaton source 1, can dispense this step of S100, and all the other steps are identical with S200-S600.The spectroscopic analysis methods that this embodiment is corresponding can be used for the analyzing and researching spectral characteristic of superweak luminescence phenomenon and general light source.
Embodiment three:
Per sample with excitaton source 1 the different of the mechanism that produces characteristic spectrum that interact; Promptly produce the difference of the mechanism of characteristic spectrum according to step S100; All the other step S200-S600 remain unchanged, and can derive methods such as " photon counting is composed direct-reading entirely " absorption spectroscopy, " photon counting is composed direct-reading entirely " emission spectrometry, " photon counting is composed direct-reading entirely " scattering (or Raman) spectroscopic methodology and " photon counting is composed direct-reading entirely " fluorescent spectrometry accordingly.This embodiment explains that the present invention can be used for the analysis of spectrum such as absorption spectrum, emission spectrum, scattering (or Raman) spectrum and fluorescence spectrum.
Embodiment four:
The chromatic dispersion beam splitter of beam splitting system 2; Be chromatic dispersion light-splitting method and the principle of step S300; Both can adopt single refracting prisms, diffraction grating or interferometer; The crossed dispersion light-dividing device (like Fig. 4, shown in Figure 5) that also can adopt above-mentioned three kinds of chromatic dispersion beam splitter combination in any to form, corresponding spectrogram both can be the one dimension spectrogram, also can be two-dimentional spectrogram.This embodiment explanation; Under the prerequisite that step S100, S200, S400-S600 remain unchanged; Step S300 only need adopt corresponding chromatic dispersion light-splitting method and principle; Just can make the present invention be used for the one dimension or the analysis of two-dimentional spectrogram, comprise refraction spectrogram, diffraction spectrogram, interference spectrogram and the mixed type spectrogram etc. that intersects.
Embodiment five:
The formal name used at school of " photon counting imaging detector 3 " is claimed " anode detector " or " multianode detector " again, and other title form comprises " photon counting imaging sensor ", " single photon counting imaging detector ", " single photon imaging detector " " and " particle counting imaging detector " etc.During concrete the application; The photon counting imaging detector 3 that can adopt variety classes, dissimilar and different size to be to satisfy actual application demand, for example wavelength coverage, detection sensitivity, spatial resolution, image fault degree, effective application demands such as imaging area, maximum count rate and integrated level.
1] according to using the wavelength coverage, the optics input window material can be selected devitrified glass, quartz glass and magnesium fluoride glass etc. for use.
2] according to using the wavelength coverage, photocathode can be selected CsI, CsTe, S20, S25, Au for use or have the semiconductor photocathode etc. of negative electron affinity (NEA).The inner surface that photocathode can be plated in the optics input window to be to constitute the photocathode of transmission-type, also can directly be plated on the madial wall of first MCP input end to constitute reflective photocathode.In addition, middle extreme ultraviolet, extreme ultraviolet and even the X ray higher for energy can not need photocathode, can directly accomplish opto-electronic conversion and electron multiplication dual-use function by MCP, and at this moment the optics input window material can be selected titanium, aluminium or beryllium etc. for use.
The MCP that 3] can adopt 2,3 or even greater number is to realize the electron multiplication function.2 MCP adopt the cascade of " V " type, and its electron gain can reach 10
6-10
73 MCP adopt " Z " type to pile up, and its gain can reach 10
7-10
8The MCP that is used for " photon counting " works in " saturated gain " pattern usually.
4] position-sensitive anode is by several or numerously have geometry in particular or the metallic conductor that puts in order constitutes; Metallic conductor is produced on the dielectric substrate usually, and material can be selected good conductors such as copper, aluminium or gold for use; Dielectric substrate can be selected quartz glass, aluminium oxide ceramics or other insulating material for use.Structure type includes but not limited to multianode micro channel array (MAMA/Multi-Anode Microchannel Array), spline shape anode (WSA/Wedge and Strip Anodes), vernier anode (Vernier Anode), delay line (Delay-line), crossbanding (Cross Strip) and resistor-type anode (Resistive Anode) etc., and is as shown in Figure 6.
5] semiconductor layer adopts high-purity polycrystalline germanium or other semiconductor material usually, and the hundreds of approximately nanometers of thickness are about square resistance 100M Ω; Semiconductor layer is produced on the dielectric substrate usually, and several millimeters of substrate thickness are convenient to and valve material or the devitrified glass of copper sealing-in, aluminium oxide ceramics or other seal, sealing materials but backing material adopts usually.
6] usually optics input window, photocathode, MCP and position-sensitive anode are packaged into a vacuum device, and have high direct voltage input interface and signal output interface; Or optics input window, photocathode, MCP and semiconductor layer be packaged into a vacuum device, position-sensitive anode is then read the electronics cloud cluster that semiconductor layer is collected from the vacuum device outside with the electric charge induction mode.
7] the electronics sensing circuit mainly by charge-sensitive preamplifier, Gauss's shaping mainly put, data acquisition and processing module etc. constitute.
The effect of charge-sensitive preamplifier is to realize electric charge-voltage or electric charge-current conversion.When electron gain is big, can dispense charge-sensitive preamplifier in the electronics sensing circuit.
The main effect of putting of Gauss's shaping is that pulse signals is carried out accurate Gauss's shaping to improve signal to noise ratio (S/N ratio), its essence is a low-pass filter circuit.
Data acquisition and processing module can adopt " data collecting card+microprocessor " or " analog to digital conversion+PLD or field programmable gate array+digital signal processor " again or other pattern.
8] DC high-voltage power supply is that MCP provides quiescent operation voltage with each acceleration bias field.
This embodiment explanation; According to practical application request; The present invention can adopt the photon counting imaging detector 3 of variety classes, dissimilar and different size, can derive multiple " photon counting is composed direct-reading entirely " spectroscopic analysis methods based on different " photon counting imaging detector 3 " thus.
Above-mentioned preferred embodiment of the present invention and the institute's application technology principle of being merely, any technician who is familiar with the present technique field is in the technical scope that the present invention discloses, and the variation that can expect easily or replacement all should be encompassed in protection scope of the present invention.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the instructions just explains principle of the present invention; The present invention also has various changes and modifications under the prerequisite that does not break away from spirit and scope of the invention, and these variations and improvement all fall in the scope of requirement protection of the present invention.
Claims (8)
1. one kind " photon counting is composed direct-reading entirely " spectroscopic analysis methods is characterized in that: include but not limited to following steps,
S100. under the effect of excitaton source (1), produce characteristic spectrum to be observed after sample pre-service premenstruum (premenstrua);
S200. the complex light that is mingled with characteristic spectrum incides beam splitting system (2) through beam incident optical device;
S300. beam splitting system (2) is with the spectrum picture of the complex light chromatic dispersion monochromatizing of incident;
S400. spectrum picture images on the sensitive area of photon counting imaging detector (3) through the outgoing optical devices;
S500. photon counting imaging detector (3) is through " the quick detection in position " and " photon counting ", with digitized mode reconstruct spectrum picture;
S600. information processing and display unit (4) carry out qualitative and quantitative analysis according to the position and the signal intensity of each pixel in the digital spectrum image to sample.
2. spectroscopic analysis methods according to claim 1 is characterized in that: above-mentioned steps S500, and the principle of work and the flow process of promptly said photon counting imaging detector (3), more specifically do,
S510. spectrum picture can be regarded the photon stream of being made up of the single photon of Different Plane position one by one as in spatial and temporal scope, and each photon in the photon stream bombards the photocathode at diverse location place through optics input window order successively;
S520. under certain quantum efficiency, photocathode is single photoelectron through external photoeffect with single photon conversion;
S530. single photoelectron bombards microchannel plate (MCP/Microchannel Plate) straight under the effect of quickening bias field, after the MCP multiplication, form an electronics cloud cluster;
S540. the electronics cloud cluster is getted over the quick anode and collected by position-sensitive anode that puts in place under the effect of quickening bias field;
S550. the quantity of electric charge collected according to each metallic conductor on the position-sensitive anode of electronics sensing circuit or electronics cloud cluster moment of arriving each metallic conductor timing point; Centroid position to the electronics cloud cluster is decoded, but this centroid position just inverting be the incoming position of single photon;
S560. just on corresponding position, once counting after accomplishing the position decoding of single photon;
S570. at certain image integration in the time, through to " position decoding " of a large amount of photons and " photon counting " on diverse location, i.e. circulation step S510-S560, just restructural spectrum picture repeatedly.
3. spectroscopic analysis methods according to claim 2; It is characterized in that: above-mentioned steps S540; The quick anode of ascending the throne is collected the physical process of electronics cloud cluster, more specifically does, the electronics cloud cluster can directly be getted over the quick anode that puts in place under the effect of quickening bias field; Or get over earlier to semiconductor layer, sensed position-sensitive anode through electric charge induction then.
4. spectroscopic analysis methods according to claim 1; It is characterized in that: between sample and the beam splitting system (2), between beam splitting system (2) and the photon counting imaging detector (3) and in the beam splitting system (2); According to practical application request corresponding incident or outgoing optical devices are set, to realize optical alignment, focusing, break-in, beam split, dim light, filtering, elimination parasitic light and diaphragm limit light.
5. spectroscopic analysis methods according to claim 1; It is characterized in that: corresponding Wavelength scanning mechanism can be set moving beam splitting system (2) or photon counting imaging detector (3) again or other optical element according to practical application request, thereby read the spectrum picture of beam splitting system (2) output with segmentation or subregional mode according to preset span lengths.
6. spectroscopic analysis methods according to claim 1; It is characterized in that: described excitaton source (1) provide energy in sample with generation characteristic spectrum to be observed, mode of excitation comprises that optical excitation, electricity excite, thermal excitation and other radiation excitation mode; Described characteristic spectrum comprises absorption spectrum, emission spectrum, scattering (or Raman) spectrum and fluorescence spectrum.
7. spectroscopic analysis methods according to claim 1 is characterized in that: described beam splitting system (2) is with the spectrum picture of the incident complex light chromatic dispersion monochromatizing that is mingled with characteristic spectrum, comprises one dimension spectrogram and two-dimentional spectrogram; Corresponding chromatic dispersion light-splitting method can adopt single index method, diffraction approach and interferometric method, or the crossed dispersion method that forms of above-mentioned three kinds of method combination in any.
8. according to claim 1,2 described spectroscopic analysis methods, it is characterized in that: described photon counting imaging detector (3) mainly is made up of optics input window, photocathode, MCP, position-sensitive anode, electronics sensing circuit and DC high-voltage power supply.
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| CN102507517A (en) * | 2011-10-14 | 2012-06-20 | 深圳市世纪天源环保技术有限公司 | Photon counting full-spectrum direct reading fluorescence spectrometer |
| CN102507005A (en) * | 2011-10-14 | 2012-06-20 | 深圳市世纪天源环保技术有限公司 | Photon counting full-spectrum direct-reading emission spectrometer |
| CN104101429A (en) * | 2013-04-11 | 2014-10-15 | 刘红超 | Photoelectric sensing device |
| CN107101723A (en) * | 2017-06-13 | 2017-08-29 | 钢研纳克检测技术有限公司 | High-resolution echelle spectrometer two dimension deviation spectrum analysis and bearing calibration |
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| CN102507464A (en) * | 2011-10-14 | 2012-06-20 | 深圳市世纪天源环保技术有限公司 | Photon counting full-spectrum direct reading absorption spectrometer |
| CN102507517A (en) * | 2011-10-14 | 2012-06-20 | 深圳市世纪天源环保技术有限公司 | Photon counting full-spectrum direct reading fluorescence spectrometer |
| CN102507005A (en) * | 2011-10-14 | 2012-06-20 | 深圳市世纪天源环保技术有限公司 | Photon counting full-spectrum direct-reading emission spectrometer |
| CN102507517B (en) * | 2011-10-14 | 2013-10-30 | 深圳市世纪天源环保技术有限公司 | Photon counting full-spectrum direct reading fluorescence spectrometer |
| CN102507464B (en) * | 2011-10-14 | 2014-05-07 | 深圳市世纪天源环保技术有限公司 | Photon counting full-spectrum direct reading absorption spectrometer |
| CN104101429A (en) * | 2013-04-11 | 2014-10-15 | 刘红超 | Photoelectric sensing device |
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| CN110160470A (en) * | 2019-05-05 | 2019-08-23 | 中国科学院上海光学精密机械研究所 | The detection device and detection method of laser beam collimation |
| CN110160470B (en) * | 2019-05-05 | 2022-04-01 | 中国科学院上海光学精密机械研究所 | Device and method for detecting laser beam collimation |
| CN112197879A (en) * | 2020-09-14 | 2021-01-08 | 中国科学院西安光学精密机械研究所 | High-time-resolution single photon detection method and single photon detection system |
| CN112197879B (en) * | 2020-09-14 | 2021-10-12 | 中国科学院西安光学精密机械研究所 | High-time-resolution single photon detection method and single photon detection system |
| CN117132504A (en) * | 2023-10-20 | 2023-11-28 | 武汉怡特环保科技有限公司 | Method for removing interference based on single photon spectrum counting technology imaging |
| CN117132504B (en) * | 2023-10-20 | 2024-01-30 | 武汉怡特环保科技有限公司 | Method for removing interference based on single photon spectrum counting technology imaging |
| CN117168311A (en) * | 2023-11-02 | 2023-12-05 | 中国科学院长春光学精密机械与物理研究所 | One-dimensional relative motion measuring and detecting system |
| CN117168311B (en) * | 2023-11-02 | 2024-01-26 | 中国科学院长春光学精密机械与物理研究所 | One-dimensional relative motion measuring and monitoring system |
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