A kind of integration type femtosecond time resolution fluorescence lifetime measurement spectrometer
Technical field
The present invention relates to time resolved spectroscopy measuring instruments, particularly relate to a kind of integration type femtosecond time resolution fluorescence longevity
Measure spectrum instrument is ordered, this spectrometer excites sample using a branch of femtosecond laser, then to excite using another beam femtosecond laser
The sample stimulated radiation of state so that the fluorescence volume of sample free radiation is reduced, and spectral detection system is by all samples being collected into
Fluorescence is integrated, and compares the Fluorescence integral intensity for having stimulated radiation and during without stimulated radiation, obtains fluorescence lifetime letter
Number point coordinates time-delay technique, realizes the fluorescence lifetime for measuring femtosecond time resolution, invention increases fluorescence lifetime measurements
Detection sensitivity.
Background technology
Time resolution pumping-detection technology [volumes such as ultrafast laser spectral principle and technical foundation, Weng Yuxiang, Chen Hailong,
, Chemical Industry Press in 2013], also known as pump probe double-pulsed technology [time resolved spectroscopy basis, Guo's plinth, 2012
Year, Higher Education Publishing House], it has a wide range of applications in the numerous areas of modern science, as photophysical process, photochemistry are anti-
Should, Biochemical processes, light-catalyzed reaction, energy and charge transfer process, Characterization of Nano-materials etc..Fluorescence lifetime measurement is in life
The analysis of object fluorescence probe, Solar use, fluorescent molecular optical physics spectrochemical property, substance excitation state dynamics research etc.
There are many applications;Femtosecond time resolution spectral instrument of the present invention equally applies pumping-detection technology.Han Ke profits et al.
[Chinese Patent Application No.:201310392018.6] establish femtosecond time resolution transient absorption and the two-in-one spectrum of fluorescence deficit
Two kinds of pumping-detection technologies are attached in a spectrometer, extend the application of femtosecond time resolution spectral instrument by instrument.
The current more common main having time correlated single photon counter of fluorescence lifetime measurement instrument, streak camera, femtosecond
Time-resolved fluorescence upconversion emission instrument, femtosecond time resolution Fluorescence depletion spectroscopy instrument etc..Single Photon Counting device
Temporal resolution highest is also at tens picoseconds;The temporal resolution of streak camera reaches as high as picosecond, but price is very
It is expensive;The temporal resolution of femtosecond time resolution fluorescence upconversion emission instrument is limited by upper conversion crystal, and general ratio is used
Femto-second laser pulse width it is twice big;The temporal resolution of femtosecond time resolution Fluorescence depletion spectroscopy instrument is very high, still
It often only measures a wavelength of fluorescence when measuring fluorescence, in terms of reducing its fluorescence lifetime measurement in hypofluorescence substance
Using.
Invention content
It is an object of the invention to obtain a kind of integration type femtosecond time resolution fluorescence lifetime measurement spectrometer, should have very
Good temporal resolution will also have good fluorescence intensity detection limit.
To achieve these goals, the technical solution adopted by the present invention is:
Integration type femtosecond time resolution fluorescence lifetime measurement spectrometer, including detection and pumping laser light path system, sample
Fluorescent collecting system and spectral detection system;
All components are all placed on optical flat;
Femtosecond laser detects light beam, and the sample in sample cell is in spatially cross-coincidence with femtosecond laser pump beam;
Femtosecond laser detection light beam spatially intersects, and have certain intervals in time with femtosecond laser pump beam,
This time interval is adjusted by time delay device;
Femtosecond laser detection light beam is after being adjusted by time delay device, by delayer back mirror and sample cell
Front mirror realizes space crossed overlap on sample cell with femtosecond laser pump beam;
Fluorescent acquisition system is after the fluorescence that sample is radiated is collected by phosphor collection mirror, to be reflected by fluorescent reflection mirror
Onto fluorescent foci mirror, focused on fiber entrance by fluorescent foci mirror, sub-ray spectrometer is then imported by optical fiber;
Spectral measurement system be fluorescence after sub-ray spectrometer is divided, multi-color spectrum is formed on the detector, on detector
Multi-color spectrum integrated to obtain fluorescence integrated signal by computer;
After optical chopper operation, no femtosecond laser detection light beam will be obtained on computers and has femtosecond laser to detect light
Two fluorescence integrated signals of beam, the difference of the two fluorescence integrated signals is exactly fluorescence lifetime signaling point;
Fluorescence lifetime signaling point is depicted as delay time curve on computers, just obtains the integration type femtosecond of sample
Time-resolved fluorescence life curve.
Optical flat material be duralumin or stainless steel, dimensions:Long is about 120cm, and wide about 60cm, thickness are about
1cm;
The phosphor collection mirror and fluorescent foci mirror can be but not limited to lens, paraboloidal mirror, spherical mirror;
The sample cell is the cuvette that light path is 1mm or 2mm or 10mm;
The optical chopper, triggering frequency signal are set in 20Hz from femto-second laser, chopping frequency
To between 1000Hz;
The detector can be but not limited to photodiode array, charge coupled cell.
Description of the drawings
Fig. 1 is the integration type femtosecond time resolution fluorescence lifetime measurement spectrometer architecture schematic diagram of the present invention.
Fig. 2 is the integration type femtosecond time resolution fluorescence of a concentration of 1mmol/L PBBO dyestuff ethanol solutions in embodiment 1
Lifetime measurement curve.
Fig. 3 is the integration type femtosecond time resolution of a concentration of 0.1mmol/L OX750 dyestuff ethanol solutions in embodiment 2
Fluorescence lifetime measurement curve.(a) the spectrum evolution curve that OX750 solution fluorescences spectrum changes over time;(b) it is glimmering at 660nm
Curve (blue filled box) that luminous intensity changes with delay time and by total fluorescence after fluorescence intensity integration at all wavelengths
The curve (red short side frame) that intensity changes with delay time.
Specific embodiment
Attached drawing is please referred to, Fig. 1 is the structural diagram of the present invention.The integration type femtosecond time resolution fluorescence lifetime of the present invention
Optical flat length described in measure spectrum instrument is about 120cm, and wide about 60cm, there are two light inlet, the first light inlet 2 is femtosecond
Laser acquisition beam inlet, for stimulated radiation sample;Second light inlet 3 is femtosecond laser pump beam entrance, for exciting
Sample.
All components are all placed on optical flat 1, and femtosecond laser detection light beam 2 is with femtosecond laser pump beam 3 in sample
In spatially cross-coincidence where sample in product pond 4, femtosecond laser detection light beam 2 is after being adjusted by time delay device 5,
By delayer back mirror 6 and sample cell front mirror 7, pumped where the sample in sample cell 4 with femtosecond laser
Light beam 3 is in spatially cross-coincidence;
Femtosecond laser is submitted where detecting the sample of light beam 2 and femtosecond laser pump beam 3 in sample cell 4 in space
Fork overlaps and has specified time interval, this time interval is adjusted by time delay device 5;
Fluorescent acquisition system is after the fluorescence that sample is radiated is collected by phosphor collection mirror 8, by fluorescent reflection mirror 9 instead
It is mapped on fluorescent foci mirror 10, is focused on 11 entrance of optical fiber by fluorescent foci mirror 10, light splitting is then imported by optical fiber
Spectrometer 12;
Spectral measurement system is fluorescence after the light splitting of sub-ray spectrometer 12, and multi-color spectrum is formed on detector 13, is detected
Multi-color spectrum on device 13 carries out Integral Processing by computer 14 and obtains fluorescence integrated signal;
It, will be obtaining no femtosecond laser detection light beam on computers and have femtosecond laser spy after optical chopper 15 is run
Two fluorescence integrated signals of light beam are surveyed, the difference of the two fluorescence integrated signals is exactly fluorescence lifetime signaling point;
Fluorescence lifetime signaling point is depicted as delay time to curve on computer 14 and is fitted, just obtains sample
Integration type femtosecond time resolution fluorescence lifetime.
Phosphor collection mirror 8 and fluorescent foci mirror 10 can be but not limited to lens, paraboloidal mirror or spherical mirror;
Sample cell 4 is the cuvette that light path is 1mm or 2mm or 10mm;
Optical chopper 15, triggering frequency signal are set in 20Hz extremely from femto-second laser, chopping frequency
Between 1000Hz;
Detector 13 can be but not limited to photodiode array or charge coupled cell.
Embodiment 1
Integration type femtosecond is being measured for integration type femtosecond time resolution fluorescence lifetime measurement spectrometer of the present invention
The time resolution in performance during the time-resolved fluorescence service life is investigated, molten using the PBBO dyestuff ethyl alcohol of 1m mol/L
Liquid is test specimen, measures integration type femtosecond time resolution fluorescence lifetime signal.The absorption spectrum peak value of PBBO is attached in 320nm
Closely, only when 490nm pump beams and 800nm detection light beam two light pulses on room and time all in sample cell
When being overlapped at sample, the fluorescence of PBBO can be just inspired, it is hereby achieved that integration type femtosecond time resolution fluorescence lifetime measurement
The time resolution receptance function of spectrometer.The Instrument response function obtained in the present embodiment uses Gaussian function fitting, obtains
Standard variance is 0.104 picosecond, and full width at half maximum is 0.246 picosecond.Experimental data figure is shown in attached drawing 2.
Embodiment 2
Sex-limited energy is detected for the invention integration type femtosecond time resolution fluorescence lifetime measurement spectrometer fluorescence intensity
Investigation, use the 0.1m mol/L ethanol solutions of OX750 dyestuffs as sample;Pump light is 490nm, 1.5mW;Detecting light is
800nm, 1mW.The integration type femtosecond time resolution fluorescence lifetime measurement spectrum of sample is measured, experimental data is shown in attached drawing 3.It is wherein left
Figure (a) is the evolution curve that the OX750 fluorescence spectrums measured change with delay time;Right figure (b) is including glimmering not to OX750
Photopeak does the fluorescence intensity of 660nm unicast strong points that integrates with the attenuation curve (blue filled box) of delay time and right
The integrated fluorescence intensities that OX750 fluorescence peaks obtain after integrating with delay time attenuation curve (red short side frame).It can see
Go out, before the noise of curve is significantly less than integration after integration.This is one and represents the curve that OX750 fluorescence signals generate.