CN212693587U - A femtosecond time-resolved absorption spectroscopy detection system - Google Patents
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- CN212693587U CN212693587U CN202020822363.4U CN202020822363U CN212693587U CN 212693587 U CN212693587 U CN 212693587U CN 202020822363 U CN202020822363 U CN 202020822363U CN 212693587 U CN212693587 U CN 212693587U
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Abstract
本实用新型公开了一种飞秒时间分辨吸收光谱探测系统，其中，激光脉冲光源发射的飞秒脉冲光经第一分束片分束，其中一束作为泵浦光，其经第一倍频BBO晶体后产生倍频脉冲光，然后经第一透镜聚焦后传输至被测样品的表面；另一束再经第二分束片分成第一、二分束光，第一分束光经第二倍频BBO晶体产生倍频脉冲光，经过第一反射镜、第二透镜和第一带孔平面镜后传输至第三倍频BBO晶体，第二分束光经超连续白光产生组件产生超连续白光，然后穿过第一带孔平面镜后传输至第三倍频BBO晶体，并与倍频脉冲光重叠从而产生放大的白光，再经第三分束片分束，一束进入探测器，另一束作为探测光和参考光，被光谱仪收集。本实用新型可以提高系统光谱信号的探测灵敏度。
The utility model discloses a femtosecond time-resolved absorption spectrum detection system, wherein the femtosecond pulse light emitted by a laser pulse light source is divided into beams by a first beam splitting plate, and one beam is used as a pump light, which is subjected to a first frequency doubling. The BBO crystal generates frequency-doubling pulsed light, which is then focused by the first lens and transmitted to the surface of the tested sample; the other beam is divided into the first and second sub-beams by the second beam splitter, and the first sub-beam is passed through the second beam splitter. The frequency-doubling BBO crystal generates frequency-doubling pulse light, which is transmitted to the third frequency-doubling BBO crystal after passing through the first reflecting mirror, the second lens and the first apertured plane mirror. , and then pass through the first apertured plane mirror and transmit to the third frequency-doubling BBO crystal, and overlap with the frequency-doubling pulse light to generate amplified white light, which is then split by the third beam splitter, one beam enters the detector, and the other beam enters the detector. The beams are used as probe light and reference light and are collected by the spectrometer. The utility model can improve the detection sensitivity of the spectral signal of the system.
Description
Technical Field
The utility model relates to a spectral measurement technical field, in particular to femto second time resolution absorption spectrum detection system.
Background
The femtosecond time-resolved absorption spectrum is a pumping-detection technology, and the principle is that one beam of light is used as pumping light to excite a sample, particles in a ground state are pumped to an excited state, then the other beam of light is used as detection light, and the change of the particle number on an energy level of the excited state along with time is detected. The technology is widely applied to scientific research in chemical, physical, material, biological and other fields.
The signal-to-noise ratio of the spectrum signal is a key technical index of the femtosecond time resolution spectrum technology, and directly influences the application range of the technology. Taking a polymer solar cell as an example, the femtosecond time-resolved absorption spectroscopy technology is an important means for researching the photoelectric conversion mechanism of the polymer solar cell. Under the actual working condition of the solar cell (1sun condition), the exciton annihilation effect is negligible, but at higher excitation light density, the exciton annihilation is easy to occur, so that the research result of the time-resolved spectrum cannot reflect the physical process of the solar cell under the actual working condition. Therefore, in the experimental process, the excitation light density needs to be reduced as much as possible, but the reduction of the excitation light density simultaneously reduces the signal intensity of the time-resolved spectrum, which requires a higher detection sensitivity of the femtosecond time-resolved absorption spectroscopy system. In addition, studies in many fields such as biology and photochemistry have high requirements for sensitivity of the technique.
The photoelectric detector (such as CCD, photodiode) is an important component of femtosecond time-resolved spectrum device, and is used for detecting the change of the optical signal detected by the system. When the detection light intensity is small, the noise of the photoelectric detector can interfere the detection light signal, and becomes an important factor influencing the sensitivity of the femtosecond time-resolved absorption spectrum signal. At present, the femtosecond pulse light is used for exciting a nonlinear medium (such as ultrapure water, sapphire and the like) to generate super-continuous white light, which is a main mode for generating femtosecond time-resolved absorption spectrum detection light, but a white light signal generated by the mode is often weak, and becomes an important reason for limiting the sensitivity of the mode. Therefore, how to improve the intensity of the detection optical signal and further improve the sensitivity of the femtosecond time-resolved absorption spectrum is a technical problem which is urgently needed to be solved at present.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to overcome prior art's shortcoming and not enough, provide a femto second time resolution absorption spectrum detection system, this system can produce the detecting light of high strength, broadband to improve detecting light intensity, and then improve the detectivity of signal.
The purpose of the utility model is realized through the following technical scheme: a femtosecond time-resolved absorption spectrum detection system for detecting the variation process of the excited state particle number of a detected sample along with time, the system comprises: a laser pulse light source (1), a first beam splitter (2), a first frequency doubling BBO crystal (4), a first lens (9), a second beam splitter (15), a second frequency doubling BBO crystal (16), a first reflector (17), a second lens (18), a super-continuous white light generating assembly, a first perforated plane mirror (25), a third frequency doubling BBO crystal (26), a third beam splitter (28), a detector (40) and a spectrometer (41), wherein,
the laser pulse light source (1) is used for emitting femtosecond pulse light, the first beam splitter (2) and the second beam splitter (15) are sequentially arranged along a femtosecond pulse light transmission path emitted by the laser pulse light source (1), the femtosecond pulse light is divided into two beams of femtosecond pulse light after passing through the first beam splitter (2), one beam of the femtosecond pulse light is used as pump light, and the other beam of the femtosecond pulse light is divided into first beam splitter light and second beam splitter light through the second beam splitter (15);
the first frequency doubling BBO crystal (4), the first lens (9) and the tested sample are sequentially arranged along a pumping light transmission path, the femtosecond pulse light split by the first beam splitting sheet (2) generates frequency doubling pulse light after passing through the first frequency doubling BBO crystal (4) and is used as pumping light, and the pumping light is focused by the first lens (9) and then is transmitted to the surface of the tested sample;
a second frequency doubling BBO crystal (16), a first reflector (17) and a second lens (18) are arranged on the transmission path of the first split beam, a super-continuous white light generating assembly is arranged on the transmission path of the second split beam, and a first band-hole plane mirror (25) and a third frequency doubling BBO crystal (26) are simultaneously positioned on the transmission paths of the first split beam and the second split beam; the first split beam generates frequency doubling pulse light through a second frequency doubling BBO crystal (16), and the frequency doubling pulse light is transmitted to a third frequency doubling BBO crystal (26) after being reflected by a first reflector (17), focused by a second lens (18) and reflected by a first plane mirror (25) with a hole; the second split beam generates the supercontinuum light through the supercontinuum light generating assembly, the supercontinuum light passes through the first plane mirror (25) with holes and then is transmitted to the third frequency doubling BBO crystal (26), and the supercontinuum light and the frequency doubling pulse light generated by the second frequency doubling BBO crystal (16) are overlapped at the third frequency doubling BBO crystal (26) and generate amplified white light;
the third beam splitter (28) is located on a transmission path of the amplified white light, the amplified white light is collimated by the fifth lens (27), then transmitted to the third beam splitter (28), and is split into two beams by the third beam splitter (28), one beam enters the detector (40), and the other beam is used as detection light and reference light and is collected by the spectrometer (41).
Preferably, the super-continuum white light generating assembly comprises a continuum attenuating plate (20), an iris diaphragm (21), a third lens (22), a sapphire plate (23) and a fourth lens (24), wherein the continuum attenuating plate (20), the iris diaphragm (21), the third lens (22), the sapphire plate (23) and the fourth lens (24) are sequentially arranged along a transmission path of the second split beam.
Preferably, the sample to be measured is placed in an optical sample cell (11) with temperature and magnetic field regulation functions.
Preferably, the system also comprises a second reflector (29), an optical delay line (30), a diaphragm (31), a mechanical switch (38) and a fourth beam-splitting piece (33),
the second reflection mirror (29), the optical delay line (30), the stop (31), the mechanical switch (38) and the fourth beam splitting plate (33) are sequentially arranged on a transmission path of the beam of light as the detection light and the reference light, and the beam of light passes through the optical delay line (30), the stop (31), the mechanical switch (38) and the fourth beam splitting plate (33) after being reflected by the second reflection mirror (29) and is divided into the detection light and the reference light at the fourth beam splitting plate (33).
Furthermore, a sixth lens (37) and a second perforated plane mirror (10) are further arranged on a detection light transmission path of the system behind the fourth beam splitter (33), and after being focused by the sixth lens (37), the detection light is transmitted to the surface of the sample to be measured after being reflected by the second perforated plane mirror (10) and finally collected by a spectrometer (41).
Furthermore, the second perforated plane mirror (10) is also positioned on the light propagation path behind the first lens (9), and the pump light focused by the first lens (9) passes through the second perforated plane mirror (10), is transmitted to the surface of the measured sample, and is finally collected in the spectrometer (41).
Furthermore, a seventh lens (12), a third plane mirror (13) with holes and an eighth lens (14) are arranged on a light propagation path between the sample and the spectrometer, and the probe light and the pump light focused by the first lens (9) pass through the seventh lens (12), the third plane mirror (13) with holes and the eighth lens (14) in sequence after passing through the surface of the sample to be detected and finally enter the spectrometer (41);
the system is also provided with a ninth lens (34), a light filter (35) and a third reflector (36) on a light propagation path between the fourth beam splitter (33) and the third perforated plane mirror (13), and reference light sequentially passes through the ninth lens (34), the light filter (35) and the third reflector (36), is reflected by the third perforated plane mirror (13), and is focused to a spectrometer (41) through an eighth lens (14).
Preferably, the system is further provided with a chopper (39) between the first beam splitter (2) and the first frequency doubling BBO crystal (4).
Preferably, the laser pulse light source (1) is a femtosecond laser; the detector (40) is a photodiode; the detector of the spectrometer (41) adopts a diode array; the mechanical switch (38) is a shutter.
Preferably, the sample to be tested includes, but is not limited to, a polymer solar cell film.
The utility model discloses for prior art have following advantage and effect:
(1) the utility model discloses femto second time resolution absorption spectrum detection system adopts non-collineation optical parameter amplification technique, enlargies the super continuous white light that produces through nonlinear medium, produces the probe light of high strength, broadband, can improve probe light intensity from this, and then improves the detection sensitivity of signal.
(2) The utility model discloses used first lens and sixth lens to pump light and survey light respectively before incidenting to being surveyed the sample and focused, the lens focus that utilizes different focuses can effectively adjust the overlapping of two bundles of light in being surveyed sample department.
(3) The utility model discloses at the overlapping position department of light, used foraminiferous level crossing, contained angle when can furthest reducing pump light and detecting light incident to the sample of being surveyed has improved the overlapping range of pump and detecting light in the sample of being surveyed department.
(4) The utility model discloses use diode array to replace high sensitive CCD as the detector of spectrum appearance, can survey in real time to the strong detection light signal of this system, effectively improved the problem that the saturation easily appears in the CCD detector under high strength detection light.
(5) The utility model discloses the sample to be surveyed is placed in the sample cell in controllable temperature, magnetic field, can conveniently carry out real-time detection to the time-resolved absorption spectrum signal of sample under the different temperatures, improves the flexibility and the increase detection range of surveying.
Drawings
Fig. 1 is a schematic diagram of the femtosecond time-resolved absorption spectrum detection system of the present invention.
Wherein, 1-a laser pulse light source, 2-a first beam splitting sheet, 3-a fourth reflector, 4-a first frequency doubling BBO crystal, 5-a fifth reflector, 6-a sixth reflector, 7-a seventh reflector, 8-an eighth reflector, 9-a first lens, 10-a second perforated plane mirror, 11-an optical sample cell, 12-a seventh lens, 13-a third perforated plane mirror, 14-an eighth lens, 15-a second beam splitting sheet, 16-a second frequency doubling BBO crystal, 17-a first reflector, 18-a second lens, 19-a ninth reflector, 20-a continuous attenuation sheet, 21-an iris diaphragm, 22-a third lens, 23-a sapphire sheet, 24-a fourth lens, 25-a first perforated plane mirror, 26-a third frequency doubling BBO crystal, 27-a fifth lens, 28-a third beam splitter, 29-a second reflector, 30-an optical delay line, 31-a diaphragm, 32-a tenth reflector, 33-a fourth beam splitter, 34-a ninth lens, 35-a light filter, 36-a third reflector, 37-a sixth lens, 38-a mechanical switch, 39-a chopper, 40-a detector and 41-a spectrometer.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the present invention is not limited thereto.
Example 1
The embodiment discloses a femtosecond time-resolved absorption spectrum detection system, which is used for detecting the time-dependent change process of the excited state particle number of a detected sample, and as shown in fig. 1, the system comprises: the device comprises a laser pulse light source 1, a first beam splitting sheet 2, a first frequency doubling BBO crystal 4, a first lens 9, a second beam splitting sheet 15, a second frequency doubling BBO crystal 16, a first reflector 17, a second lens 18, a super-continuous white light generation assembly, a first perforated plane mirror 25, a third frequency doubling BBO crystal 26, a third beam splitting sheet 28, a detector 40 and a spectrometer 41. The sample to be tested in this embodiment includes, but is not limited to, a polymer solar cell film.
The laser pulse light source 1 is a femtosecond laser and can be used for emitting 800nm femtosecond pulse light. The first beam splitting sheet 2 and the second beam splitting sheet 15 are sequentially arranged along a femtosecond pulse light transmission path emitted by the laser pulse light source 1, the femtosecond pulse light is divided into two beams of femtosecond pulse light after passing through the first beam splitting sheet 2, one beam of femtosecond pulse light is used as pump light, and the other beam of femtosecond pulse light is divided into the first beam splitting light and the second beam splitting light through the second beam splitting sheet 15.
The first frequency doubling BBO crystal (barium metaborate crystal) 4, the first lens 9 and the sample to be measured are sequentially arranged along the pump light transmission path, and the first lens 9 is a long focusing lens. The femtosecond pulse light split by the first beam splitting sheet (2) generates frequency doubling pulse light (400nm) after passing through the first frequency doubling BBO crystal 4 and is used as pump light, and the pump light is transmitted to the surface of a detected sample after being focused by the first lens 9.
In this embodiment, a second perforated plane mirror 10 may be further disposed on the light propagation path after the first lens 9, and the pump light focused by the first lens 9 passes through the second perforated plane mirror 10, then is transmitted to the surface of the sample to be measured, and finally is collected in the spectrometer 41.
In addition, a chopper 39 may be further disposed between the first beam splitter 2 and the first frequency doubling BBO crystal 4, so that the femtosecond pulsed light split by the first beam splitter 2 passes through the chopper first and then reaches the first frequency doubling BBO crystal 4, and the chopper may be used to control the presence or absence of the pump light.
The tested sample is placed in an optical sample cell 11 with the temperature and magnetic field adjusting function, and the time-resolved absorption spectrum signals of the sample at different temperatures can be conveniently detected by the system in real time by utilizing the temperature adjusting function.
The second frequency doubling BBO crystal 16, the first reflector 17 and the second lens 18 are arranged on the transmission path of the first split beam, the supercontinuum light generating assembly is arranged on the transmission path of the second split beam, and the first holey plane mirror 25 and the third frequency doubling BBO crystal 26 are simultaneously positioned on the transmission paths of the first split beam and the second split beam. The first mirror 17 is placed on a one-dimensional translation stage (see the notation below the first mirror 17 in fig. 1) that allows a small range of movement in the front and back directions.
The first split beam of light generates 400nm frequency doubling pulse light through a second frequency doubling BBO crystal 16, and the frequency doubling pulse light can be used as pump light for amplifying the super-continuous white light, and is transmitted to a third frequency doubling BBO crystal 26 after being reflected by a first reflector 17, focused by a second lens 18 and reflected by a first plane mirror 25 with holes; the second split beam passes through the super-continuous white light generating assembly, the super-continuous white light is generated by the super-continuous white light generating assembly, the super-continuous white light passes through the first plane mirror 25 with holes and then is transmitted to the third frequency doubling BBO crystal 26, and the super-continuous white light and the frequency doubling pulse light generated by the second frequency doubling BBO crystal 16 are overlapped at the third frequency doubling BBO crystal 26 to generate amplified white light. The third frequency doubling BBO crystal 26 is placed on a two-dimensional translation stage (see the symbol below the third frequency doubling BBO crystal 26 in fig. 1), and can realize small-range movement in the front, rear, left and right directions.
The super-continuous white light generation assembly comprises a continuous attenuation sheet 20, an iris diaphragm 21, a third lens 22, a sapphire sheet 23 and a fourth lens 24, wherein the continuous attenuation sheet 20, the iris diaphragm 21, the third lens 22, the sapphire sheet 23 and the fourth lens 24 are sequentially arranged along a transmission path of second split light. The third lens 22 and the fourth lens 24 are placed on a one-dimensional translation stage, respectively (see the symbols below the third lens 22 and the fourth lens 24 in fig. 1), and a small range of movement in the front and rear directions can be achieved.
The third beam splitter 28 is located on the transmission path of the amplified white light, and the amplified white light is split into two beams by the third beam splitter 28, and one beam enters the detector 40, which can be used to detect the intensity fluctuation of the white light signal. In the present embodiment, the detector 40 is a photodiode.
In this embodiment, a fifth lens 27 is further disposed on the light propagation path between the third frequency doubling BBO crystal 26 and the third beam splitter 28, and the fifth lens 27 can collimate the amplified white light.
The other beam is collected by the spectrometer 41 as probe light and reference light. Specifically, the system is further provided with a second reflector 29, an optical delay line 30, an aperture 31, a mechanical switch 38 and a fourth beam splitting plate 33 in sequence on the propagation path of the beam of light, the beam of light is reflected to the optical delay line 30 through the second reflector 29, then passes through the aperture 31, the quality of amplified white light is selected through the aperture 31, and then passes through the mechanical switch 38 to the fourth beam splitting plate 33, the beam of light is split into detection light and reference light at the fourth beam splitting plate 33. In the present embodiment, the mechanical switch 38 is a shutter.
The optical delay line 30 is used to adjust the time delay difference between the pump light and the probe light, thereby detecting the spectral signal of the sample at different time delay differences. The amplified white light is used as the detection light, so that the detection light intensity can be improved, and the detection sensitivity of signals can be further improved.
The system is also provided with a sixth lens 37 on the detection light transmission path behind the fourth beam splitter 33, and the second perforated plane mirror 10 is also positioned on the path, and the detection light is focused by the sixth lens 37, then transmitted to the surface of the measured sample after being reflected by the second perforated plane mirror 10.
The second plane mirror 10 with holes can reduce the included angle of the pump light and the probe light when the pump light and the probe light are incident to the tested sample to the maximum extent, and the overlapping range of the pump light and the probe light at the tested sample is enlarged.
The absorbance of the sample to be measured is calculated by the following formula:
wherein, IprobeIs the white light spectrum measured when the mechanical switch 38 is on and the chopper 39 is in the light blocking state; i isdarkIs the dark noise measured when both the mechanical switch 38 and the chopper 39 are in the light blocking state; i ispumpIs the spectrum measured when the mechanical switch 38 is off and the chopper 39 is in the on state; i ispump+probeIs the spectrum of white light measured when mechanical switch 38 and chopper 39 are both on.
In this embodiment, the spectrometer 41 uses a diode array as a detector, and compared with a high-sensitivity CCD, the diode array can detect a strong detection light signal of the system in real time, so that the problem that the CCD detector is easily saturated under high-intensity detection light is effectively improved.
In addition, the system also provides a seventh lens 12, a third perforated flat mirror 13 and an eighth lens 14 in the light propagation path between the sample and the spectrometer. The seventh lens 12 is a long focusing lens.
After passing through the surface of the sample to be measured, the pump light focused by the first lens 9 is collimated by the seventh lens 12, passes through the third plane mirror 13 with holes, and is focused to the spectrometer 41 by the eighth lens 14, and the whole propagation path of the pump light forms a pump light path. Similarly, after passing through the surface of the sample to be detected, the detection light is collimated by the seventh lens 12, passes through the third perforated plane mirror 13, and is focused to the spectrometer 41 by the eighth lens 14, and the whole propagation path of the detection light constitutes a detection light path.
The system also provides a ninth lens 34, a filter 35 and a third mirror 36 in the light path between the fourth beam splitter 33 and the third apertured flat mirror 13. The reference light sequentially passes through the ninth lens 34, the filter 35 and the third reflector 36, is reflected by the third perforated plane mirror 13, and is focused to the spectrometer 41 through the eighth lens 14, and the whole propagation path of the reference light forms a reference light path. The lines between the elements in fig. 1 represent the light propagation paths between the elements.
In this embodiment, the setting positions and the number of the reflectors may be determined according to actual needs, and the reflectors may be used to change the directions of the pump light, the probe light, and the reference light, so as to adjust the light propagation path, thereby flexibly setting the positions and angles of the elements of the system and adjusting the total occupied area of the system.
For example, in order to control the same optical path length that the pump light and the probe light pass when reaching the sample surface, a mirror group composed of four mirrors, namely a fifth mirror 5, a sixth mirror 6, a seventh mirror 7, and an eighth mirror 8, is disposed between the first frequency doubling BBO crystal 4 and the first lens 9, and the frequency doubling pulse light generated by the first frequency doubling BBO crystal 4 passes through the fifth mirror 5, the sixth mirror 6, the seventh mirror 7, and the eighth mirror 8 in sequence, and then reaches the first lens 9 for focusing.
For a more reasonable layout of system components, a fourth mirror 3 is disposed on the light propagation path between the first beam splitter 2 and the second beam splitter 15, and the two beams of light split by the first beam splitter 2 are propagated in parallel by reflection of the fourth mirror 3.
A ninth reflecting mirror 19 is disposed between the second beam splitter 15 and the continuous attenuation sheet 20, the second split beam split by the second beam splitter 15 can be reflected to the continuous attenuation sheet 20 by the ninth reflecting mirror 19, and the reflected pulse light and the first split beam propagate in parallel.
The tenth mirror 32 is disposed between the mechanical switch 38 and the fourth beam splitting plate 33, and the pulse light passing through the mechanical switch 38 may reach the tenth mirror 32 first, and then be reflected by the tenth mirror 32 to the fourth beam splitting plate 33.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be equivalent replacement modes, and all are included in the scope of the present invention.
Claims (10)
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| CN115128113B (en) * | 2022-06-21 | 2024-07-30 | 上海科技大学 | Self-reference X-ray free electron laser pulse arrival time diagnosis device |
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