CN109374550A - Super-resolution spectrograph spectrum calibration method based on optical transmission spectra - Google Patents

Super-resolution spectrograph spectrum calibration method based on optical transmission spectra Download PDF

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CN109374550A
CN109374550A CN201811366179.7A CN201811366179A CN109374550A CN 109374550 A CN109374550 A CN 109374550A CN 201811366179 A CN201811366179 A CN 201811366179A CN 109374550 A CN109374550 A CN 109374550A
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spectrum
absorption cell
optical transmission
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transmission spectra
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李志伟
施海亮
罗海燕
陈迪虎
金伟
熊伟
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Hefei Institutes of Physical Science of CAS
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/27Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • G01N21/274Calibration, base line adjustment, drift correction

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Abstract

The super-resolution spectrograph spectrum calibration method based on optical transmission spectra that the invention discloses a kind of, pass through vacuum respectively using no background stable and uniform radiation source and has the absorption cell of object gas, absorbance spectrum and vacuum background spectrum are distinguished using super-resolution spectrometer, and the ratio between the two obtains actual measurement optical transmission spectra;It is long by absorption cell temperature, gas pressure and journey, theoretical optical transmission spectra is calculated in conjunction with Hitran database;The peak valley spectrum point and corresponding wavelength (wave number) value of the positioning of optical transmission spectra precision are obtained using Gauss curve fitting, spectral calibration coefficient is obtained by least square fitting, theoretical peak valley wavelength (wave number) value uncertainty, Gauss curve fitting uncertainty and least square fitting uncertainty are synthesized to obtain spectral calibration precision.Actual measurement is carried out using the present invention, has obtained spectral calibration coefficient and spectral calibration uncertainty.

Description

Super-resolution spectrograph spectrum calibration method based on optical transmission spectra
Technical field
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra that the present invention relates to a kind of, belongs to spectral calibration skill Art field.
Background technique
Spectral calibration is exactly by the abscissa serial number of spectrometer measurement numerical value pass corresponding with input wavelength (or wave number) foundation System.Spectral measurement is the wavelength and strength relationship for characterizing object to be measured, and the accuracy of wavelength is directly related with intensity measurements, Therefore spectrometer is firstly the need of progress spectral calibration.
Common spectrum calibration method has monochromator method and standard spectral method, and spectral calibration requires the wavelength of light source uncertain It spends that small, stability is good, has multiple spectral lines within the scope of instrument spectral and be uniformly distributed, breadth of spectrum line is differentiated much smaller than instrument spectral Rate, and the intensity of spectral line meets the requirement of instrument signal to noise ratio.For super-resolution spectral instrument, the energy of monochromator at present And breadth of spectrum line is not able to satisfy above-mentioned requirements, usually uses spectral line lamp or tunable laser, passes through multiple known incoming waves The method that long and corresponding output spectrum point is fitted obtains corresponding wave number.But either spectral line lamp or laser, light What source issued is all several or single feature spectral line, larger with instrument measured spectra (continuous spectrum) property difference.And spectral line lamp Existing characteristics line is few and is unevenly distributed, and influence of the laser vulnerable to factors such as noise, vibration, temperature in environment causes Reality output wavelength has differences with setting output wavelength, causes spectral calibration coefficient inaccurate, finally influences spectrum quantification The precision of measurement.
It is interacted during radiative transfer with gas molecule, by the original light radiation of process changes such as absorbing, scattering, Wherein absorption spectrum is one of the most effective technology for obtaining Atmospheric components information.Absorption wave of the variety classes molecule to light radiation Long different, absorption intensity is temperature dependent with gas concentration.Gas molecules sorb spectrum has a fixed characteristic frequency, environment because Plain (temperature, pressure, concentration etc.) a small range variation only will cause the variation of absorption peak line width and depth, and the center of absorption peak Position is constant, by control measuring state, reasonably selects spectrometer measurement gas, is penetrated by high-precision Radiance transfer calculation Rate spectrum can be used as the high-precision standard source of spectral calibration.
Summary of the invention
For the deficiency of existing super-resolution spectrometer spectrum calibration method, the invention proposes one kind to be based on transmitance light The super-resolution spectrograph spectrum calibration method of spectrum, this method are suitable for laboratory super-resolution spectrometer spectral calibration, while excellent It can be used for super-resolution spectrometer star glazing spectrum calibration after changing robot scaling equipment.
The technical solution adopted by the invention is as follows:
Super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the method steps are as follows:
(1) temperature and pressure measuring instrumentss in integrating sphere are opened, integrating sphere nitrogen circulating system and Water-cooling circulating system are opened System opens tungsten halogen lamp radiation source, and to temperature and pressure in ball, stable, nitrogen gas concn is greater than 99% or more, formed steady and continuous without Background radiation source;
(2) absorption cell control temperature setting is T, opens absorption cell vacuum evacuation device after setting temperature is reached in pond, will inhale Vacuum degree is evacuated in receives pond better than 10-4pa;
(3) integrating sphere forms uniform Lambertion area source after issuing the even light of radiation source, enters behind the vacuum absorption pond of Cheng Changwei L Super-resolution spectrometer is penetrated, temperature T stable and uniform in absorption cell, radiation source is full of spectrometer aperture, visual field;
(4) super-resolution spectrometer collection N width data, initial data averagely denoise, and bias light is obtained after error correction Compose B0
(5) absorption cell is filled with a certain amount of object gas, reads pressure P in absorption cell by high-precision pressure measuring instrumentss, Keep absorption cell temperature T constant;
(6) super-resolution spectrometer collection N width data, initial data averagely denoise, and obtain after error correction and absorb light Compose B1
(7) by object gas absorption spectrum B1With vacuum measurement background spectrum B0The ratio between obtain be measurement optical transmission spectra τ1
(8) according to the long L of absorption cell journey, temperature T and pressure P, in conjunction with Hitran database gas absorption cross-section parameter, meter Calculate the theoretical transmission spectrum τ under the state0
(9) in the apparent absorption peak of regional choice peak valley feature of the left, center, right of spectral region three, theoretical penetrate is obtained Peak valley wavelength or wave number the spectrum point corresponding with actual measurement transmitance of rate spectrum, peak valley wavelength or wave number are carried out with corresponding spectrum point Fitting obtains spectral calibration coefficient;
(10) spectral calibration uncertainty is calculated.
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the theory The calculation method of optical transmission spectra are as follows:
Theoretical transmission spectrum is quantitatively calculated according to Beer-Lambert, and the radiation energy that integrating sphere issues is through absorption cell Theoretical transmission after interior gas effect are as follows: τ0=exp (- α cL), wherein α (cm2/ mol) it is gas absorption cross-section, c (mol/cm3) For target gas levels, L (cm) is absorption cell effective length;α(cm2/ mol) Hitran database is come from, according in absorption cell Temperature T and pressure P, the associated ideal equation of gas state calculate gas concentration in absorption cellWherein T0=273.16K For standard state temperature, P0=101333Pa is standard state pressure, n0=2.67 × 1019mol/cm3For standard state gas point Subnumber density.
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the absorption Peak valley wavelength or wave number value and spectrum point Peak Search Method are as follows:
Actual measurement optical transmission spectra and theoretical transmission spectrum can be accurately positioned peak valley point using Gauss curve fitting, obtain Wavelength or wave number value and spectrum point after taking fitting, improve spectral calibration precision;Gauss curve fitting formula are as follows:
Wherein A is Gaussian function normalization coefficient, X0It is quasi- for theoretical transmission spectrum and actual measurement optical transmission spectra peak valley point Wavelength or wave number or spectrum point, σ after conjunction determine the width of Gaussian function.
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the spectrum Calibration coefficient approximating method are as follows:
It surveys optical transmission spectra point and theory of correspondences optical transmission spectra peak valley wavelength or wave numerical fitting uses least square Method, fitting formula are as follows:
P (x)=p1xn+p2xn-1+…+pnx+pn+1
Wherein n is the fitting order of selection, pn(n=1,2 ... n, n+1) is fitting coefficient.
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the spectrum Calibrate uncertainty calculation method are as follows:
Spectral calibration uncertainty σ includes the uncertainty σ of theoretical transmission spectrum peak valley wavelength or wave number value1, peak-seeking Error σ2, return calculate error σ3,
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the integrating sphere Nitrogen circulating system and water-cooling circulating system respectively include the nitrogen cylinder being connected with integrating sphere and discharge pipe, water cooling unit and circulation Pipeline, the circulation line of water-cooling circulating system are arranged in tungsten halogen lamp lamp holder bottom, for tungsten halogen lamp fever source heat-dissipating, avoid sealing The excessively high damage light source of temperature in ball;Certain flow nitrogen continual rinsing is maintained using nitrogen circulating system in integrating sphere, avoids sky The influence that gas (steam, oxygen etc.) measures optical transmission spectra is absorbed in gas.
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the tungsten halogen lamp It is distributed in integrating sphere, is correspondingly arranged on light barrier by each tungsten halogen lamp, avoid the radiant light of tungsten halogen lamp direct using light barrier It is emitted integrating sphere mouth, guarantees that the radiation of ball mouth has good lambert's property.
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the integrating sphere Interior temperature, pressure, nitrogen gas concn are utilized respectively thermometer in integrating sphere, pressure gauge in integrating sphere, nitrogen gas concn prison in integrating sphere Survey table real-time monitoring.
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the absorption cell Vacuum evacuation device includes the aspiration pump being connected to absorption cell, it is ensured that can be extracted into higher vacuum in absorption cell and obtain high-precision Background spectrum;Absorption cell is connected to under test gas gas cylinder and monitors absorption cell flow of aerating air by flowmeter;Temperature in absorption cell, Pressure is utilized respectively thermometer in absorption cell, pressure gauge real-time monitoring in absorption cell.
The super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the absorption cell For the sealing absorption cell with certain length, wherein absorption cell two sides are sealed using plated film window, guarantee optical transmission spectra measurement Wave band has good through characteristic;Absorption cell pipeline outer-layer sealing ring passes through external oil temperature regulating device around heat conductive circulation oil Realize the different temperatures control of absorption cell, the external oil temperature regulating device uses temperature controller and circulation line.
The invention has the characteristics that and good result:
(1) present invention measures vacuum background spectrum and object gas absorption spectrum using same covering device respectively, the two it Optical transmission spectra is surveyed than calculating, eliminating measuring device influences optical transmission spectra baseline;
(2) spectrum calibration method of the present invention can be not only used for the spectral calibration of laboratory super-resolution spectrometer, simultaneously This method can be by using sun fraunhofer line or other known stable spectral line as with reference to for spaceborne super-resolution spectrum The in-orbit spectral calibration of instrument.
Detailed description of the invention
Fig. 1 is optical transmission spectra measuring device structural schematic diagram.
Fig. 2 is theoretical transmission spectrum and the absorption peak for choosing calculating spectral calibration coefficient.
Fig. 3 is spectral calibration Coefficient Fitting curve.
Specific embodiment
There can be optimal understanding to the present invention according to following detailed description and in conjunction with attached drawing.
Embodiment
Super-resolution spectrograph spectrum calibration method based on optical transmission spectra, first measures optical transmission spectra, then to spectrum into Row calibration.
One, optical transmission spectra is measured
Optical transmission spectra is measured using attached device shown in FIG. 1, optical transmission spectra measuring device includes nitrogen cylinder and discharge Pipeline 1, integrating sphere 2, nitrogen gas concn monitors table 3, water cooling unit and circulation line 4, aspiration pump 5, absorption cell 6, temperature control in integrating sphere Instrument and circulation line 7, under test gas gas cylinder 8, flowmeter 9, super-resolution spectrometer 10, tungsten halogen lamp and light barrier 11, integrating sphere Interior thermometer 12, pressure gauge 13 in integrating sphere, thermometer 14 in absorption cell, pressure gauge 15 in absorption cell.
Optical transmission spectra measures implementation method the following steps are included: opening in integrating sphere pressure in thermometer 12 and integrating sphere Table 13 is absorbed by steam, oxygen in air in nitrogen cylinder and 1 continual rinsing of discharge pipe elimination ball etc. and is done to radiation source It disturbs, and monitors 3 real-time measurement of table with nitrogen gas concn in integrating sphere, opening water cooling unit and circulation line 4 prevents temperature in ball sealer It is excessively high, it is formed in integrating sphere mouth without back after the even light of the integrated ball 2 of light issued using the tungsten halogen lamp in tungsten halogen lamp and light barrier 11 Scape uniform Lambertion area source, tungsten halogen lamp are distributed in integrating sphere, light barrier are correspondingly arranged on by each tungsten halogen lamp, using light barrier It avoids the radiant light of tungsten halogen lamp from being directly emitted integrating sphere mouth, guarantees that the radiation of ball mouth has good lambert's property;It is right to open aspiration pump 5 Absorption cell 6 is vacuumized, and is opened absorption cell temperature controller and circulation line 7 for absorption cell 6 and is maintained at set temperature, works as absorption cell Air pump is stablized and closed when reaching vacuum level requirements to pressure gauge 15 in interior thermometer 14 and absorption cell, opens super-resolution spectrometer 10 measurement background spectrums.It opens under test gas gas cylinder 8 and is filled with object gas into absorption cell, inflation speed is controlled by flowmeter 9 Degree closes under test gas gas cylinder 8 when observing in absorption cell pressure expression to predetermined pressure, opens super-resolution spectrometer 10 and measure Absorption spectrum;The ratio between absorption spectrum and vacuum background spectrum are optical transmission spectra.
Two, spectrum is calibrated
Steps are as follows for super-resolution spectrometer spectral calibration coefficient method:
(1) theoretical transmission spectrum calculates
Theoretical optical transmission spectra, the long L=of the effective journey of absorption cell are calculated by taking the parameter of laboratory installation actual absorption pond as an example 500cm.An atmospheric pressure CO is inflated in absorption cell2, temperature 20 degree of temperature of holding, according toCalculate gas in absorption cell Bulk concentration c=2.49mol/cm3, inquiry Hitran database acquisition CO2Gas absorption cross-section α (cm2/ mol), according to formula τ0 =exp (- α cL) calculates theoretical CO2Gas 1568-1583nm optical transmission spectra is as shown in Figure 2.
(2) spectral calibration coefficient calculates
With lab space heterodyne spectrometer (resolution ratio σ=0.27cm-1) measurement optical transmission spectra, space heterodyne spectrograph It is linear relationship between incident wave number and spectrum point (fringe frequency), Choice Theory peak valley wave number is as shown in Figure 2.It is quasi- using Gauss The peak valley spectrum point and corresponding wavelength (wave number) value for obtaining the positioning of optical transmission spectra precision are closed, least square linear fit result is such as Shown in Fig. 3, obtained spectral calibration equation is
σ=- 0.0113i+6393.40593
Wherein spectrum coordinate points i=0~8191.The wherein uncertainty σ of theoretical transmission spectrum peak valley wave number value1= 0.000005cm-1, peak-seeking error σ2=0.005cm-1, return calculate error σ3=0.008cm-1, final synthetic spectrum calibration is not Degree of certainty σ=0.009cm-1

Claims (10)

1. the super-resolution spectrograph spectrum calibration method based on optical transmission spectra, which is characterized in that the method steps are as follows:
(1) temperature and pressure measuring instrumentss in integrating sphere are opened, integrating sphere nitrogen circulating system and water-cooling circulating system is opened, beats Tungsten halogen lamp radiation source is opened, stable, nitrogen gas concn is greater than 99% or more to temperature and pressure in ball, forms steady and continuous without background spoke Penetrate source;
(2) absorption cell control temperature setting is T, absorption cell vacuum evacuation device is opened after setting temperature is reached in pond, by absorption cell Vacuum degree is inside evacuated to better than 10-4pa;
(3) integrating sphere forms uniform Lambertion area source after issuing the even light of radiation source, incident super behind the vacuum absorption pond of Cheng Changwei L Resolution spectrometer, temperature T stable and uniform in absorption cell, radiation source are full of spectrometer aperture, visual field;
(4) super-resolution spectrometer collection N width data, initial data averagely denoise, and background spectrum B is obtained after error correction0
(5) absorption cell is filled with a certain amount of object gas, reads pressure P in absorption cell by high-precision pressure measuring instrumentss, keeps Absorption cell temperature T is constant;
(6) super-resolution spectrometer collection N width data, initial data averagely denoise, and absorption spectrum B is obtained after error correction1
(7) by object gas absorption spectrum B1With vacuum measurement background spectrum B0The ratio between obtain be measurement optical transmission spectra τ1
(8) according to the long L of absorption cell journey, temperature T and pressure P, in conjunction with Hitran database gas absorption cross-section parameter, calculating should Theoretical transmission spectrum τ under state0
(9) in the apparent absorption peak of regional choice peak valley feature of the left, center, right of spectral region three, theoretical transmission light is obtained Peak valley wavelength or wave number the spectrum point corresponding with actual measurement transmitance of spectrum, intend peak valley wavelength or wave number with corresponding spectrum point It closes, obtains spectral calibration coefficient;
(10) spectral calibration uncertainty is calculated.
2. the super-resolution spectrograph spectrum calibration method according to claim 1 based on optical transmission spectra, which is characterized in that The calculation method of the theoretical transmission spectrum are as follows:
Theoretical transmission spectrum is quantitatively calculated according to Beer-Lambert, the radiation energy that integrating sphere issues gas in absorption cell Theoretical transmission after body effect are as follows: τ0=exp (- α cL), wherein α (cm2/ mol) it is gas absorption cross-section, c (mol/cm3) it is mesh Standard gas bulk concentration, L (cm) are absorption cell effective length;α(cm2/ mol) Hitran database is come from, according to temperature T in absorption cell With pressure P, the associated ideal equation of gas state calculates gas concentration in absorption cellWherein T0=273.16K is mark Quasi- state temperature, P0=101333Pa is standard state pressure, n0=2.67 × 1019mol/cm3For standard state gas molecula number Density.
3. the super-resolution spectrograph spectrum calibration method according to claim 2 based on optical transmission spectra, which is characterized in that The absorption peak valley wavelength or wave number value and spectrum point Peak Search Method are as follows:
Actual measurement optical transmission spectra and theoretical transmission spectrum can be accurately positioned peak valley point using Gauss curve fitting, obtain quasi- Wavelength or wave number value and spectrum point after conjunction improve spectral calibration precision;Gauss curve fitting formula are as follows:
Wherein A is Gaussian function normalization coefficient, X0After theoretical transmission spectrum and actual measurement optical transmission spectra peak valley point fitting Wavelength or wave number or spectrum point, σ determine the width of Gaussian function.
4. the super-resolution spectrograph spectrum calibration method according to claim 3 based on optical transmission spectra, which is characterized in that The spectral calibration Coefficient Fitting Methods are as follows:
It surveys optical transmission spectra point and theory of correspondences optical transmission spectra peak valley wavelength or wave numerical fitting uses least square method, intend Close formula are as follows:
P (x)=p1xn+p2xn-1+…+pnx+pn+1
Wherein n is the fitting order of selection, pn(n=1,2 ... n, n+1) is fitting coefficient.
5. the super-resolution spectrograph spectrum calibration method according to claim 4 based on optical transmission spectra, which is characterized in that The spectral calibration uncertainty calculation method are as follows:
Spectral calibration uncertainty σ includes the uncertainty σ of theoretical transmission spectrum peak valley wavelength or wave number value1, peak-seeking error σ2, return calculate error σ3,
6. the super-resolution spectrograph spectrum calibration method according to claim 1 based on optical transmission spectra, which is characterized in that The integrating sphere nitrogen circulating system and water-cooling circulating system respectively include the nitrogen cylinder being connected with integrating sphere and discharge pipe, water Cold and circulation line, the circulation line of water-cooling circulating system are arranged in tungsten halogen lamp lamp holder bottom.
7. the super-resolution spectrograph spectrum calibration method according to claim 1 based on optical transmission spectra, which is characterized in that The tungsten halogen lamp is distributed in integrating sphere, is correspondingly arranged on light barrier by each tungsten halogen lamp.
8. the super-resolution spectrograph spectrum calibration method according to claim 1 based on optical transmission spectra, which is characterized in that Temperature, pressure, nitrogen gas concn are utilized respectively thermometer in integrating sphere, pressure gauge in integrating sphere, in integrating sphere in the integrating sphere Nitrogen gas concn monitors table real-time monitoring.
9. the super-resolution spectrograph spectrum calibration method according to claim 1 based on optical transmission spectra, which is characterized in that The absorption cell vacuum evacuation device includes the aspiration pump being connected to absorption cell;Absorption cell is connected to and passes through under test gas gas cylinder Flowmeter monitors absorption cell flow of aerating air;Temperature, pressure are utilized respectively thermometer in absorption cell, pressure in absorption cell in absorption cell Table real-time monitoring.
10. the super-resolution spectrograph spectrum calibration method according to claim 1 based on optical transmission spectra, feature exist In the absorption cell is the sealing absorption cell with certain length, and wherein absorption cell two sides are sealed using plated film window;Absorption cell Pipeline outer-layer sealing ring realizes that the different temperatures of absorption cell controls around heat conductive circulation oil, by external oil temperature regulating device, described External oil temperature regulating device uses temperature controller and circulation line.
CN201811366179.7A 2018-11-16 2018-11-16 Super-resolution spectrograph spectrum calibration method based on optical transmission spectra Pending CN109374550A (en)

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