Embodiment
With reference to Fig. 1; The spectrophotometer 1 of prior art generally includes a light source cell 101 that complex light is provided; One produces the control module 104 that 103, one said measurement results of foundation of measuring unit that 102, one of monochromatic monochromators produce measurement result produce said displacement according to displacement; Usually adopt deuterium lamp and tungsten lamp complex light to be provided in the light source cell 101 as light source; Can certainly adopt other habitual light source, dispersion element is all arranged in the monochromator 102 usually, dispersion element adopts grating more; Usually adopt the just profound gauge mechanism of direct motor drive to make the dispersion element rotation in the monochromator 102, also can adopt impulse motor and reducing gear to drive to locate the monochromatic light of a certain wavelength to locate the monochromatic light of a certain wavelength.Described displacement can be the leading screw amount of feeding of said sine gauge mechanism, also can be the amount of spin of said impulse motor and reducing gear.Displacement in the preferred embodiments of the present invention adopts the leading screw amount of feeding of sine gauge mechanism.Measuring unit 103 generally includes the sample chamber, in the wavelength calibration process of prior art, has no material in the sample chamber.Control module is according to the leading screw amount of feeding of the measurement result control sine gauge mechanism of said measuring unit.
With reference to Fig. 2, be the flow chart illustration of the operation steps 2 of all band wavelength calibration method, comprise the steps:
S21 add have a plurality of characteristic peaks standard substance as sample,
S22 obtains the measurement result of standard substance,
S23 sets the pairing displacement of monochromatic wavelength between these two peak values according to pairing monochromatic wavelength of two adjacent characteristic peaks and displacement in the said measurement result.
Wherein, step S21 joins the standard substance with a plurality of characteristic peaks in the sample chamber of said measuring unit 103, and this preferred embodiment selects for use holmium glass as standard substance.
The measurement result that S22 obtains standard substance is meant that the mode through scanning obtains a plurality of characteristic peaks of holmium glass; The mode of said scanning is meant the monochromatic while that different wave length constantly is provided for said measuring unit at said monochromator 102; Control module 104 constantly detects the energy value of exporting after the opto-electronic conversion in the measuring unit 103; Whenever detect an energy minimum point and just note, the characteristic peaks of the just corresponding standard substance of each said energy minimum point this moment.Obtaining a plurality of characteristic peaks thus is respectively λ
2:37.9nm, λ
3:536.6nm, λ
4:460.0nm, λ
5:453.6nm, λ
6:446.1nm, λ
7:418.6nm, λ
8:361.0nm, λ
9:287.7nm and λ
10:241.5nm.Control module 104 detects characteristic peak λ simultaneously successively
2,λ
3,λ
4,λ
5,λ
6,λ
7,λ
8,λ
9And λ
10,Corresponding respectively leading screw amount of feeding S
2, S
3, S
4, S
5, S
6, S
7, S
8, S
9And S
10The described leading screw amount of feeding is based on the leading screw amount of feeding at zero point, and the zero point among the present invention is at hall position.Utilize formula (2) to calculate the wavelength calibration COEFFICIENT K again
2, K
3, K
4, K
5, K
6, K
7, K
8And K
9
As illustrating, also can be through analyzing a plurality of characteristic peaks that holmium glass obtains holmium glass in advance.
Calculate above-mentioned wavelength calibration COEFFICIENT K
2, K
3, K
4, K
5, K
6, K
7, K
8And K
9, can be respectively to wavelength coverage at λ
2λ
3Between, λ
3λ
4Between, λ
4λ
5Between, λ
5λ
6Between, λ
6λ
7Between, λ
7λ
8Between, λ
8λ
9Between and λ
9λ
10Between wavelength carry out segmentation and proofread and correct.Because the wavelength coverage of complex light is 190nm to 900nm in the system of present embodiment; In order to make correction more accurate; Segmentation is more careful; Also comprise in the wavelength coverage of utilizing said complex light; Pairing wavelength of monochromatic inherent feature peak value and displacement, and edge peak value pairing wavelength and the displacement adjacent with said inherent feature peak value in a plurality of characteristic peaks of standard substance are set the pairing displacement of monochromatic wavelength between the corresponding monochromatic light of corresponding monochromatic light of said inherent feature peak value and said edge peak value.Specifically be exactly the inherent feature peak value λ that scans the deuterium lamp light source
1:656.1nm, and λ
1Corresponding leading screw amount of feeding S
1, between 656.1nm and 637.9nm, just can utilize formula (2) to calculate correction coefficient K like this to the wavelength of this wavelength period
1
The correction coefficient of the wavelength period of wavelength between 656.1nm and 900nm adopts the correction coefficient of the wavelength period section the most adjacent with it, i.e. wavelength calibration COEFFICIENT K between 656.1nm and the 637.9nm
1
As illustrating; For the wavelength calibration that makes the wavelength period between 656.1nm and the 900nm more accurate; Can adopt the way of the corresponding leading screw amount of feeding of characteristic peaks and the characteristic peaks of scanning praseodymium neodymium glass; Wavelength between 656.1nm and the 900nm is carried out careful segmentation again, utilize formula (2) to calculate corresponding correction coefficient to every section and more fine proofread and correct.
As illustrating; Said standard substance can also be holmium solution or praseodymium neodymium glass; And other have the material of a plurality of characteristic peaks, and general wavelength adopts holmium glass or holmium solution as standard substance when 656.1nm is following; Wavelength adopts the praseodymium neodymium glass as standard substance when 656.1nm is above.
The correction coefficient of the wavelength period of wavelength between 190nm and 241.5nm adopts the correction coefficient of the wavelength period section the most adjacent with it, i.e. wavelength calibration COEFFICIENT K between 241.5nm and the 287.7nm
9
Utilize formula that the wavelength calibration COEFFICIENT K proofreaies and correct monochromatic wavelength λ shown in formula (4),
Wherein, S
λBe the leading screw amount of feeding that obtains after proofreading and correct, d is the grating constant of grating, and n is the order of diffraction time, and φ is the half the of angle between incident light and the diffraction light of grating, and L is the sinusoidal arm lengths of sine gauge, k
λBe the correction coefficient of monochromatic wavelength λ place wavelength period, λ
Λ _ MaxBe higher value in two boundary wave long values of monochromatic wavelength λ place wavelength period, S
Λ _ MaxBe the screw mandrel amount of feeding of higher value in two boundary wave long values of monochromatic wavelength λ place wavelength period.
For example, desiring to make the light of 254nm to arrive the sample chamber, specifically is to accomplish like this:
Judge 254nm in (287.7,241.5) wavelength period, the correction coefficient of this wavelength period is K
9, bigger wavelength is 287.7.
Calculate the amount of feeding of screw mandrel according to formula (4)
Screw mandrel amount of feeding driving pulse motor according to formula (4) calculates makes the monochromatic wavelength of outgoing reach 254nm exactly, accomplishes the wavelength calibration process.
As illustrating, utilize the wavelength calibration COEFFICIENT K also can adopt formula (5) to the formula that monochromatic wavelength λ proofreaies and correct.
Wherein, d is the grating constant of grating, and n is the order of diffraction time, and φ is the half the of angle between incident light and the diffraction light of grating; L is the sinusoidal arm lengths of sine gauge, and N is the wavelength period sum of monochromatic wavelength λ to 656.1nm, and for example, 254nm has passed through to 656.1nm: [656.1; 637.9), [637.9,536.6), [536.6,460.0), [460.0,453.6), [453.6; 446.1), [446.1,418.6), [418.6,361.0), [361.0,287.7) and [287.7; 241.5) totally 9 wavelength period, N=9 so, k
iBe the correction coefficient of emergent light wavelength X apart from the wavelength period of the required process of 656.1nm, wherein, λ
iBe less boundary value in two boundary values, λ
I-1It is bigger boundary value in two boundary values.λ when comprising the wavelength period of λ
iValue is λ.
As illustrating, utilize the wavelength calibration COEFFICIENT K also can adopt formula (6) to the formula that monochromatic wavelength λ proofreaies and correct.
Wherein, d is the grating constant of grating, and n is the order of diffraction time, and φ is the half the of angle between incident light and the diffraction light of grating, and L is the sinusoidal arm lengths of sine gauge, k
λBe the correction coefficient of emergent light wavelength X place wavelength period, λ
Λ _ MaxBe higher value in two boundary wave long values of emergent light wavelength X place wavelength period, T
Λ _ MaxBe the screw mandrel amount of feeding and the S of higher value in two boundary wave long values of emergent light wavelength X place wavelength period
1Difference.
Utilize the computing method of formula (6), can effectively avoid the spectrophotometer back null position of starting shooting again to change and make correction calculation the problem of deviation occur.
Once more with reference to Fig. 1, when the method according to the preferred embodiment of the present invention obtains correction coefficient K
1, K
2, K
3, K
4, K
5, K
6, K
7, K
8And K
9, control module 104 is with said correction coefficient K
1, K
2, K
3, K
4, K
5, K
6, K
7, K
8And K
9Storage; Put into sample with taking out in the sample chamber of standard substance from measuring unit 103 this moment, and the measuring process of beginning spectrophotometer 1: light source cell 101 provides complex light for spectrophotometer 1; Monochromator 102 provides monochromatic light with certain wavelength for said measuring unit 103; The monochromatic wavelength that said measuring unit 103 needs depends on the testing requirement of user to sample, and after testing requirement was confirmed, the monochromatic wavelength that said measuring unit 103 needs had just been confirmed; After monochromatic wavelength is confirmed; Said control module 104 is according to the correction coefficient of said monochromatic wavelength, said storage, and the invention described above preferred embodiment formula (4) or formula (5) or formula 6 calculate the screw mandrel amount of feeding to said monochromatic wavelength, and controls said monochromator 102 according to the said leading screw amount of feeding said monochromatic light is provided.
Spectrophotometer 1 is in measuring process, and light source cell 101 adopts the combination of deuterium lamp and tungsten lamp, and for spectrophotometer 1 provides system required complex light, short wavelength's light is provided by deuterium lamp, and long wavelength's light is provided by tungsten lamp.Monochromator 102 converts complex light into monochromatic light.Sample is deposited in sample chamber in the measuring unit 103; When monochromatic light passed through the sample chamber, part was absorbed, and part is by transmission; Measuring unit 103 light signal that transmitted light is entrained converts electric signal into and amplifies the digital signal that converts quantification into, is used for the analysis to sample.Control module 104 is responsible for the control of system, can and obtain analytical parameters with said digital signal storage forwarding, and can control the feeding of pulse motor rotating drive screw mandrel, and the control leading screw amount of feeding is with the monochromatic light of a certain wave band of accurate output.
With reference to Fig. 3; It is the flow chart illustration of the operation steps 3 of control method preferred embodiment of the present invention; This flow chart illustration is intended to explain spectrophotometer in measuring process, and control module specifically comprises the steps: for the control procedure that the monochromatic light of accurately exporting a certain wave band carries out
Step S31, monochromatic wavelength set value of foundation, from a plurality of wavelength segmentations, the selected wavelength segmentation that is complementary with said monochromatic wavelength set value;
Step S32, the said wavelength segmentation of foundation are confirmed and the corresponding correction coefficient of said wavelength segmentation and an initial displacement amount;
Step S33, the said correction coefficient of foundation and said initial displacement amount are set one and are used to produce said monochromatic displacement.
The monochromatic light that with the wavelength is 254nm is example, at first confirms the wavelength period that is complementary with wavelength 254nm to be (287.7,241.5) wavelength period, and according to aforementioned, the correction coefficient of confirming this wavelength period is K
9, the initial displacement amount is the pairing displacement of wavelength 287.7nm.With said correction coefficient K
9Computing formula of foundation calculates a displacement, just can draw with the pairing displacement addition of wavelength 287.7nm to be used to produce the amount of feeding that wavelength is the monochromatic screw mandrel of 254nm.
Among the step S33, add the long-pending of the above correction coefficient and a unit wavelength shift amount, set the said said monochromatic displacement that is used to produce according to said initial displacement amount.This step further illustrates with said correction coefficient K
9Computing formula of foundation calculates the computing method of a displacement, specifically with reference to the computing method in the formula (4).Wherein, unit wavelength shift amount refers to:
Wherein, d is the grating constant of grating, and n is the order of diffraction time, and φ is the half the of angle between incident light and the diffraction light of grating, and L is the sinusoidal arm lengths of sine gauge, and N is the wavelength period at emergent light wavelength X place, λ
Λ _ MaxIt is higher value in two boundary wave long values of emergent light wavelength X place wavelength period.
Among the step S31, said a plurality of wavelength segmentations comprise the corresponding wavelength segmentation of wavelength with any two adjacent feature peaks of holmium solution.The characteristic peaks of holmium solution is respectively 637.9nm, 536.6nm, 460.0nm, 453.6nm, 446.1nm, 418.6nm, 361.0nm, 287.7nm and 241.5nm.Therefore a plurality of wavelength segmentations comprise (637.9,536.6), (536.6,460.0), (460.0,453.6), (453.6,446.1), (446.1,418.6), (418.6,361.0), (361.0,287.7) and (287.7,241.5) 8 segmentations.Select for use the characteristic peaks of holmium solution to carry out segmentation; Mainly be because the stability of characteristics of holmium solution; And when the light source that the most often adopts in the spectrophotometer is deuterium lamp and tungsten lamp; Monochromatic wavelength coverage is between 190nm to 900nm, and the characteristic peaks of holmium solution is between the 190nm to 900nm just, can be with wavelength coverage in the even segmentation of the wavelength between the 190nm to 900nm.
As illustrating, also can adopt the characteristic peaks of holmium glass to carry out segmentation.
Among the step S31; Said a plurality of wavelength segmentation comprises a corresponding wavelength segmentation of wavelength with said monochromatic wavelength lower limit and said holmium solution first characteristic peak, and the pairing correction coefficient of this wavelength segmentation is identical with the pairing calibration factor of wavelength of two characteristic peaks that wavelength is the shortest of said holmium solution.Be in a plurality of wavelength segmentations, comprise (190,241.5) this segmentation, and the correction coefficient of (190,241.5) segmentation is identical with the correction coefficient of (287.7,241.5) segmentation.
As illustrating,, in practical operation, also can (190,241.5) and (287.7,241.5) be merged one section (190,287.7) because the correction coefficient of (190,241.5) segmentation is identical with the correction coefficient of (287.7,241.5) segmentation.
Among the step S31; Said a plurality of wavelength segmentation comprises the corresponding first wavelength segmentation of wavelength with the highest wavelength characteristic peak of intrinsic peak of deuterium lamp and said holmium solution; With the corresponding second wavelength segmentation of the wavelength at said monochromatic wavelength higher limit and the intrinsic peak of said deuterium lamp, the said first wavelength segmentation is identical with the pairing correction coefficient of the second wavelength segmentation.Be that a plurality of wavelength segmentations comprise (656.1,637.9) segmentation and (900,656.1) segmentation, and the correction coefficient of (656.1,637.9) segmentation is identical with the correction coefficient of (900,656.1) segmentation.
Said a plurality of wavelength segmentation comprises the corresponding wavelength segmentation of wavelength with any two adjacent feature peaks of praseodymium neodymium glass.Promptly the correction coefficient of (900,656.1) segmentation can not adopt the correction coefficient of (656.1,637.9) segmentation yet; But with the characteristic peaks of praseodymium neodymium glass with the wavelength segmentation once more between (900,656.1), and calculate the correction coefficient of each segmentation successively; (900; 656.1) between adopt with the same method of the present invention and carry out proofreading and correct carefully, make the spectrophotometric monochromator monochromatic light of output wavelength scope between (900,656.1) more exactly.
With reference to Fig. 4, be the structure key diagram of the spectrophotometer 4 of control system preferred embodiment of the present invention, this structure key diagram is on the basis of Fig. 1, to further specifying of control module 104, specifically comprises:
Search device 401 for one, be used for according to a monochromatic wavelength set value, from a plurality of wavelength segmentations, the selected wavelength segmentation that is complementary with said monochromatic wavelength set value;
A locating device 402 is used for confirming and the corresponding correction coefficient of said wavelength segmentation and an initial displacement amount according to said wavelength segmentation;
A calculation element 403 is used for setting one and being used to produce said monochromatic displacement according to described correction coefficient and said initial displacement amount.
The monochromatic light that with the wavelength is 254nm is example, at first confirms the wavelength period that is complementary with wavelength 254nm to be (287.7,241.5) wavelength period, and according to aforementioned, the correction coefficient of confirming this wavelength period is K
9, the initial displacement amount is the pairing displacement of wavelength 287.7nm.With said correction coefficient K
9Computing formula of foundation calculates a displacement, just can draw with the pairing displacement addition of wavelength 287.7nm to be used to produce the amount of feeding that wavelength is the monochromatic screw mandrel of 254nm.
Said calculation element 403 is used for adding the long-pending of the above correction coefficient and a unit wavelength shift amount according to said initial displacement amount, sets the said said monochromatic displacement that is used to produce.Further illustrate with said correction coefficient K at this
9Computing formula of foundation calculates the computing method of a displacement, specifically with reference to the computing method in the formula (4).
Said searching in the device 401, said a plurality of wavelength segmentations comprise the corresponding wavelength segmentation of wavelength with any two adjacent feature peaks of holmium solution.The characteristic peaks of holmium solution is respectively 637.9nm, 536.6nm, 460.0nm, 453.6nm, 446.1nm, 418.6nm, 361.0nm, 287.7nm and 241.5nm.Therefore a plurality of wavelength segmentations comprise (637.9,536.6), (536.6,460.0), (460.0,453.6), (453.6,446.1), (446.1,418.6), (418.6,361.0), (361.0,287.7) and (287.7,241.5) 8 segmentations.Select for use the characteristic peaks of holmium solution to carry out segmentation; Mainly be because the stability of characteristics of holmium solution; And when the light source that the most often adopts in the spectrophotometer is deuterium lamp and tungsten lamp; Monochromatic wavelength coverage is between 190nm to 900nm, and the characteristic peaks of holmium solution is between the 190nm to 900nm just, can be with wavelength coverage in the even segmentation of the wavelength between the 190nm to 900nm.
As illustrating, also can adopt the characteristic peaks of holmium glass to carry out segmentation.
Said searching in the device 401; Said a plurality of wavelength segmentation comprises a corresponding wavelength segmentation of wavelength with said monochromatic wavelength lower limit and said holmium solution first characteristic peak, and the pairing correction coefficient of this wavelength segmentation is identical with the pairing calibration factor of wavelength of two characteristic peaks that wavelength is the shortest of said holmium solution.Be in a plurality of wavelength segmentations, comprise (190,241.5) this segmentation, and the correction coefficient of (190,241.5) segmentation is identical with the correction coefficient of (287.7,241.5) segmentation.
As illustrating,, in practical operation, also can (190,241.5) and (287.7,241.5) be merged one section (190,287.7) because the correction coefficient of (190,241.5) segmentation is identical with the correction coefficient of (287.7,241.5) segmentation.
Said searching in the device 401; Said a plurality of wavelength segmentation comprises the corresponding first wavelength segmentation of wavelength with the highest wavelength characteristic peak of intrinsic peak of deuterium lamp and said holmium solution; With the corresponding second wavelength segmentation of the wavelength at said monochromatic wavelength higher limit and the intrinsic peak of said deuterium lamp, the said first wavelength segmentation is identical with the pairing correction coefficient of the second wavelength segmentation.Be that a plurality of wavelength segmentations comprise (656.1,637.9) segmentation and (900,656.1) segmentation, and the correction coefficient of (656.1,637.9) segmentation is identical with the correction coefficient of (900,656.1) segmentation.
Said searching in the device 401, said a plurality of wavelength segmentations comprise the corresponding wavelength segmentation of wavelength with any two adjacent feature peaks of praseodymium neodymium glass.Promptly (900; 656.1) correction coefficient of segmentation can not adopt the correction coefficient of (656.1,637.9) segmentation yet, but will (900 with the characteristic peaks of praseodymium neodymium glass; 656.1) between wavelength segmentation once more; And calculate the correction coefficient of each segmentation successively, between (900,656.1), adopt and carry out proofreading and correct carefully with the same method of the present invention.
As illustrating, said control module 104 can be single-chip microcomputer, MCU, CPU or FPGA programmable gate array etc., also can be computing machine.
Spectrophotometric control method of the present invention and control system; Solved and all adopted a wavelength calibration coefficient to proofread and correct to all wavelengths and cause the inaccurate problem of wavelength calibration; The wavelength segmentation; The wavelength of each wave band all has a correction coefficient to this wave band, thereby has improved the system wavelength correction accuracy greatly.
Though described embodiment of the present invention in conjunction with accompanying drawing, those of ordinary skills can make various distortion and modification within the scope of the appended claims.