Zero-dimensional environmentally friendly carbon quantum dots(CQDs)combined with two-di-mensional materials have a wide range of applications in optoelec-tronic devices.We combined steady-state and transient absorp-ti...Zero-dimensional environmentally friendly carbon quantum dots(CQDs)combined with two-di-mensional materials have a wide range of applications in optoelec-tronic devices.We combined steady-state and transient absorp-tion spectroscopies to study the energy transfer dynamics between CQDs and molybdenum disulfide(MoS_(2)).Transient absorption plots showed photoinduced absorption and stimulated emission features,which involved the intrinsic and defect states of CQDs.Adding MoS_(2)to CQDs solution,the lowest unoccupied molecular orbital of CQDs transferred energy to MoS_(2),which quenched the intrinsic emission at 390 nm.With addition of MoS_(2),CQD-MoS_(2)composites quenched defect emission at 490 nm and upward absorption,which originated from another energy transfer from the defect state.Two energy transfer paths between CQDs and MoS_(2)were efficiently manipulated by changing the concentration of MoS_(2),which laid a foundation for improving device performance.展开更多
Using the fully propagated time-dependent Hartree–Fock method, we identify that both the dynamic core polarization and multiorbital contributions are important in the attosecond transient absorption of CO molecules.T...Using the fully propagated time-dependent Hartree–Fock method, we identify that both the dynamic core polarization and multiorbital contributions are important in the attosecond transient absorption of CO molecules.The dynamics of core electrons effectively modifies the behaviors of electrons in the highest occupied molecular orbital, resulting in the modulation of intensity and position of the absorption peaks. Depending on the alignment angles, different inner orbitals are identified to contribute, and even dominate the total absorption spectra. As a result, multi-electron fingerprints are encoded in the absorption spectra, which shed light on future applications of attosecond transient absorption in complex systems.展开更多
Photoinduced electron transfer processes between fullerenes (C60 / C70) and N, N, N, N tetra - ( p-methylphenyl ) - 4, 4 diamino - 1, 1- diphenyl ether ( TPDAE ) have been studied by nanosecond laser flash photolysis....Photoinduced electron transfer processes between fullerenes (C60 / C70) and N, N, N, N tetra - ( p-methylphenyl ) - 4, 4 diamino - 1, 1- diphenyl ether ( TPDAE ) have been studied by nanosecond laser flash photolysis. Quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C60 / C70 ) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes ( C60 / C70 ) and radical cations of TPDAE appear.展开更多
Ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy measures the time- and frequencydependent light losses after light–matter interactions. In the linear region, the matter response to an XUV light ...Ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy measures the time- and frequencydependent light losses after light–matter interactions. In the linear region, the matter response to an XUV light field is usually determined by the complex refractive index ̃n. The absorption signal is directly related to the imaginary part of ̃n, namely, the absorption index. The real part of ̃n refers to the real refractive index, which describes the chromatic dispersion of an optical material. However, the real refractive index information is usually not available in conventional absorption experiments. Here, we investigate the refractive index line shape in ultrafast XUV transient absorption spectroscopy by using a scheme that the XUV pulse traverses the target gas jet off-center. The jet has a density gradient in the direction perpendicular to the gas injection direction, which induces deflection on the XUV radiation. Our experimental and theoretical results show that the shape of the frequency-dependent XUV deflection spectra reproduces the refractive index line profile. A typical dispersive refractive index line shape is measured for a single-peak absorption;an additional shoulder structure appears for a doublet absorption.Moreover, the refractive index line shape is controlled by introducing a later-arrived near-infrared pulse to modify the phase of the XUV free induction decay, resulting in different XUV deflection spectra. The results promote our understanding of matter-induced absorption and deflection in ultrafast XUV spectroscopy.展开更多
Attosecond transient absorption(ATA)has been developed as an all-optical technique for probing electron dynamics in matter.Here we present a scheme that can modify the laserinduced state and the corresponding ATA spec...Attosecond transient absorption(ATA)has been developed as an all-optical technique for probing electron dynamics in matter.Here we present a scheme that can modify the laserinduced state and the corresponding ATA spectrum via excitation by a pair of XUV attosecond pulses and by a time-delayed mid-infrared(MIR)laser probe.Different from the scheme of the electronic excitation by a single XUV attosecond pulse,the application of a pair of XUV pulses provides extra degrees of freedom,such as the time delay and the intensity ratio between two XUV pulses,which make it possible to adjust the pump process,resulting in the modification of the ATA spectrum.We show that by varying the time delay between the two XUV pulses,the population of the dark state and the ATA spectrum of the laser-induced state have periodic modulations.We also demonstrate that the peak of the ATA spectrum of the laser-induced state appears at a fixed time delay between the XUV pair and the MIR laser when the intensity ratio is large,and it changes with the time delay when the intensity ratio is small,which can be related to either one of two peaks in the population of the dark state.展开更多
Small-molecule organic solar cell is a category of clean energy potential device since charge transfers between donor and acceptor.The morphologies,co-assembly behavior,interaction sites,and charge transfer of BTID-nF...Small-molecule organic solar cell is a category of clean energy potential device since charge transfers between donor and acceptor.The morphologies,co-assembly behavior,interaction sites,and charge transfer of BTID-nF(n=1,2)/PC71BM donor-acceptor system in the active layer of organic solar cell have been studied employing scanning tunneling microscopy(STM),scanning tunneling spectroscopy(STS),density functional theory(DFT)calculations,and transient absorption(TA)spectroscopy.The results show that BTID-1F and BTID-2F form bright strip structures,whereas BTID-nF(n=1,2)/PC71BM form ridge-like structures with each complex composed of one BTID-nF(n=1,2)molecule and four PC71BM molecules which adsorbed around the BTID-nF(n=1,2)molecule by S···πinteraction.With the assistance of S···πinteraction between BTID-nF(n=1,2)and PC71BM,BTID-nF(n=1,2)/PC71BM co-assembled ridge-like structures are more stable than the BTID-nF(n=1,2)ridge structures.To investigate the charge transfer of BTID-nF(n=1,2)/PC71BM system,STS measurements,DFT calculation,and TA spectroscopy are further performed.The results show that charge transfer occurs in BTID-nF(n=1,2)/PC71BM system with the electron transferring from BTID-nF(n=1,2)molecules to PC71BM.展开更多
A bulk heterojunction in organic solar cells is where charge separation and recombination occur.Molecular orientation at the interface is one of the key factors that dictate solar cell efficiency.Although X-ray scatte...A bulk heterojunction in organic solar cells is where charge separation and recombination occur.Molecular orientation at the interface is one of the key factors that dictate solar cell efficiency.Although X-ray scattering-based methods can determine donor/acceptor domain orientations between an anisotropic phase and an isotropic fullerene-based phase,the rise of nonfullerene solar cells presents a new challenge in delineating local molecular directions at the interface between two anisotropic donor/acceptor domains.Here,we determine interfacial molecular orientations of three high-efficiency small molecule solar cells(ZR1:Y6,B1:BO-4 Cl,and BTR:BO-4 Cl)using polarization-selective transient absorption spectroscopy.The polarization anisotropy of charge separation dynamics indicates an angle of~90°between ZR1 and Y6 molecules at the interface,an angle close to 0°between B1 and BO-4 Cl,and random orientations between BTR and BO-4 Cl.These observations provide complementary information to X-ray scattering measurements and highlight polarization-selective transient absorption spectroscopy as a tool to probe interfacial structure and dynamics of key photophysical steps in energy conversion.展开更多
Over the past decade the integration of ultrafast spectroscopy with nanoscience has greatly propelled the development of nanoscience, as the key information gleaned from the mechanistic studies with the assistance of ...Over the past decade the integration of ultrafast spectroscopy with nanoscience has greatly propelled the development of nanoscience, as the key information gleaned from the mechanistic studies with the assistance of ultrafast spectroscopy enables a deeper understanding of the structure–function interplay and various interactions involved in the nanosystems.This mini-review presents an overview of the recent advances achieved in our ultrafast spectroscopy laboratory that address the ultrafast dynamics and related mechanisms in several representative nanomaterial complex systems by means of femtosecond time-resolved transient absorption spectroscopy. We attempt to convey instructive, consistent information regarding the important processes, pathways, dynamics, and interactions involved in the nanomaterial complex systems,most of which exhibit excellent performance in photocatalysis.展开更多
Nanoparticles with non-spherical shapes are now being widely used for various photonic applications.We observe experimentally that the magnitude as well as the time dependence of the transient absorption of a colloid ...Nanoparticles with non-spherical shapes are now being widely used for various photonic applications.We observe experimentally that the magnitude as well as the time dependence of the transient absorption of a colloid of silver nanoplatelets depends on the relative polarization of the pump and probe pulses.There have been a few reports about the dependence of the transient signal magnitude on polarization,but little information is available on its temporal dependence.Using a theoretical model,we show that this observed behavior arises from the fact that the energy absorption by a non-spherical nanoparticle depends on,among other factors,the nanoparticle orientation with respect to the pump and probe polarization directions.It is essential to consider this when estimating nanoparticle characteristics such as carrier thermalization time,carrier–phonon scattering time,and complex polarizability from transient absorption measurements.展开更多
In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a q...In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a quantum yield of 0.67,much higher than that of systems with other metal complexes of rnesoporphyrin dimethyl ester.Neither EDTA nor MV^(2+) quenches the stationary fluorescence of SnP,implying that the reaction does not take place at the singlet state.With flash photolysis we obtain the T-T absorption spectrum of SnP(λ_(max)-440 nm).By following the decay of this absorption,the triplet life time of SnP is estimated to be 41 μs.The life time is related to the concentration of either MV^(2+) or EDTA.Good linear relationships are obtained by plotting τ_0/τ vs.the concentration of MV^(2+) or EDTA(Stern-Volmer plot),from which we determine the quenching constants:k_q(MV^(2+))=5.5×10~7 mol^(-7) s^(-1);kq(EDTA)=2.7×10~7 mol^(-1),s^(-1).The data suggests that upon photolysis of the above ternary system,both oxidative quenching and reductive quenching of the triplet state of the sensitizer are occurring.From the measured phosphorescence spectrum(λ_(max) 704nm)and the ground state redox potentials (E_(1/2)^(red)~-0.84V,E_(1/2)^(ox)~ Ag/AgCl,KCl(sat.)),we obtain the redox potential of triplet SnP to be E (P^+/P)~-0.33 V, E(P/P-)~+0.92 V.Matching this data with the redox potential of MV^(2+) and EDTA,we establish the fact that during the photolysis of the SnP/MV^(2+)/EDTA ternary system,both oxidative and reductive quenching are thermodynamically favorable processes.This is also the reason why the SnP sensitized reaction is much more efficient relative to other mesoporphyrin derivatives.展开更多
Two dimethylamino-carbaldehyde derivatives with different π-bridge lengths were prepared, and their transient optical properties and photophysical mechanisms were investigated by transient absorption spectroscopy and...Two dimethylamino-carbaldehyde derivatives with different π-bridge lengths were prepared, and their transient optical properties and photophysical mechanisms were investigated by transient absorption spectroscopy and Z-scan measurements. Owing to the difference in molecular structures, the two compounds exhibit different populations of locally excited states and, therefore, they also produce different transient absorption spectra. After photoexcitation, both molecular materials exhibit a wide excited state absorption band from 450 nm to 1000 nm. Meanwhile, the excited state lifetimes are dramatically different, 2 ns and 100 ps, for the two molecules. A figure of merit greater than 2 at the wavelength of1000 nm is obtained. The results show that modulating the population of the locally excited states in this type of molecule can be a promising approach for obtaining optical switching and solar cell materials.展开更多
Antimony trisulfide(Sb_(2)S_(3)) solar cells suffer from large open circuit voltage deficits due to their intrinsic defects which limit the power conversion efficiency.Thus,it is important to elucidate these defects’...Antimony trisulfide(Sb_(2)S_(3)) solar cells suffer from large open circuit voltage deficits due to their intrinsic defects which limit the power conversion efficiency.Thus,it is important to elucidate these defects’ origin and defects at the interface.Here,we discover that sulfide radical defects have a significant impact on the performance of Sb_(2)S_(3)solar cells.Moreover,it has been illustrated that these defects at the CdS/Sb_(2)S_(3)interface can be reduced by optimizing the deposition process.A trap distribution model is used to quantify the defect density at the CdS/Sb_(2)S_(3)interface.It shows that the interface defects can be reduced by24% by improving the deposition process.This work reveals the importance of interface defects and guides the future optimization of Sb_(2)S_(3)solar cells.展开更多
The degradation characteristic of 4-bromdiphenyl ether (BDE-4) was investigated in different solutions.The study indicates that the process of direct degradation of this compound is dependent upon the bromine and th...The degradation characteristic of 4-bromdiphenyl ether (BDE-4) was investigated in different solutions.The study indicates that the process of direct degradation of this compound is dependent upon the bromine and the ether bond connected to diphenyl by electron beam.laser flash photolysis was employed to determine the degradation of each species (cationic,neutral,and anionic).From these data,intermediate products of BDE-4 degradation were shown for direct irradiationdegradation.The neutral radical was formed during the photolysis of these compounds.For all the compounds,diphenyl ether and hydroxybiphenyl were observed as common products.Reaction of the BDE-4 under electron beam was debromide.The debromide rate of BDE-4 at pH=5.5 is somewhat lower than that of BDE-4 at pH=10.0.The decomposition rate for BDE-4 is 99.8% at pH=10.0 on the dose of 14 kGy.BDE-4 from its radical could provide bromine ion into water and the cation radical of BDE-4 formed quickly recombine with hydrogen radical and formed phenyl ether.展开更多
Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years,the influence of temperature and the type of the employed ho...Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years,the influence of temperature and the type of the employed hole transport layer(HTL)on the charge carrier dynamics and recombination processes in perovskite photovoltaic devices is still largely unexplored.In particular,significant knowledge is missing on how these crucial parameters for radiative and non-radiative recombinations,as well as for efficient charge extraction vary among different perovskite crystalline phases that are induced by temperature variation.Herein,we perform micro photoluminescence(pPL)and ultrafast time resolved transient absorption spectroscopy(TAS)in Glass/Perovskite and two dierent Glass/ITO/HTL/Perovskite configurations at temperatures below room temperature,in order to probe the charge carrier dynamics of different perovskite crystalline phases,while considering also the effect of the employed HTL polymer.Namely,CH_(3)NH_(3)Pbb films were deposited on Glass,PEDOT:PSS and PTAA polymers,and the developed Glass/CH_(3)NH_(3)PbI_(3)and Glass/ITO/HTL/CH_(3)NH_(3)PbI_(3)architectures were studied from 85 K up to 215 K in order to explore the charge extraction dynamics of the CH_(3)NH_(3)PbI_(3)orthorhombic and tetragonal crystalline phases.It is observed an unusual blueshift of the bandgap with temperature and the dual emission at temperature below of 100 K and also,that the charge carrier dynamics,as expressed by hole injection times and free carrier recombination rates,are strongly depended on the actual pervoskite crystal phase,as well as,from the selected hole transport material.展开更多
The reaction mechanism of 3 chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3 chlorophenol aqueous solutions have been saturated with air or N 2 previously. Under alkaline condi...The reaction mechanism of 3 chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3 chlorophenol aqueous solutions have been saturated with air or N 2 previously. Under alkaline condition, the reaction of OH radical with 3 chlorophenol produces 3 chlorinated phenoxyl radical, with the absorption peaks at 400 nm and 417 nm. Under neutral condition, the reaction of OH radical with 3 chlorophenol produces OH adduct with the maximal absorption at about 340 nm. And in acid solution, the reaction of H with 3 chlorophenol produces H adduct with the maximal absorption at about 320 nm. 3 chlorophenol is compared with 4 and 2 chlorophenols from the free radical pathways. The results show that the positions of chlorine on the aromatic ring strongly influence the dehalogenation and degradation process.展开更多
This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy tog...This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques. Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties. Reductive electron-transfer with transfer rate faster than 10^11 s^-1 is found. This PET process is also consolidated by femtosecond transient absorption spectra.展开更多
As one of the biological endogenous pigments,biliverdin(BV)and its dimethyl ester(BVE)have extremely weak uorescence in solution with quantum yield less than 0.01%.However,the situation reverses with the addition of z...As one of the biological endogenous pigments,biliverdin(BV)and its dimethyl ester(BVE)have extremely weak uorescence in solution with quantum yield less than 0.01%.However,the situation reverses with the addition of zinc ions.The strength for uorescence of BVE-Zn^2+ complex is greatly enhanced and uorescence quantum yield can increase to5%.Herein,we studied ultrafast excited state dynamics of BVE-Zn^2+ complex in ethanol,npropanol,and DMSO solutions in order to reveal the mechanism of uorescence quantum yield enhancement.The results show that BVE can form a stable coordination complex with zinc with 1:1 stoichiometry in solution.BVE is structurally and energetically more stable in the complex.Using picosecond time-resolve uorescence and femtosecond transient absorption spectroscopy,we show that smaller non-radiative rate constant of BVE-Zn^2+ complex in DMSO is the key to increasing its uorescence quantum yield and the excited state decay mechanism is also revealed.These results provide valuable information about the uorescence property change after BVE binding to metal ions and may provide a guidance for the study of phytochromes or other uorescence proteins in which BV/BVE acts as chromophores.展开更多
Cuprous oxide(Cu_(2)O)has attracted plenty of attention for potential nonlinear photonic applications due to its superior third-order nonlinear optical property such as two-photon absorption.In this paper,we investiga...Cuprous oxide(Cu_(2)O)has attracted plenty of attention for potential nonlinear photonic applications due to its superior third-order nonlinear optical property such as two-photon absorption.In this paper,we investigated the two-photon excitation induced carrier dynamics of a Cu_(2)O thin film prepared by radio-frequency magnetron sputtering,using the femtosecond transient absorption experiments.Biexponential dynamics including an ultrafast carrier scattering(<1 ps)followed by a carrier recombination(>50 ps)were observed.The time constant of carrier scattering under two-photon excitation is larger than that under one-photon excitation,due to the different transition selection rules and smaller absorption coefficient of the two-photon excitation.展开更多
One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance...One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance. In this research,we carried out a detailed study on electron transfer process at the interface of nanowire CH_(3) NH_(3) PbI_(3)(N-MAPbI_(3))/Phenyl C61 butyric acid methyl-ester synonym(PCBM), as well as the interface of compact CH_(3) NH_(3) PbI_(3)(C-MAPbI_(3))/PCBM by transient absorption spectroscopy. By comparing the carrier recombination dynamics of N-MAPbI_(3), N-MAPbI_(3)/PCBM,C-MAPbI_(3), and C-MAPbI_(3)/PCBM from picosecond(ps) to hundred nanosecond(ns) time scale, it is demonstrated that electron transfer at N-MAPbI_(3)/PCBM interface is less efficient than that at C-MAPbI_(3)/PCBM interface. In addition, electron transfer efficiency at C-MAPbI_(3)/PCBM interface was found to be excitation density-dependent, and it reduces with photo-generation carrier concentration increasing in a range from 1.0 × 1018 cm^(-3)–4.0 × 1018 cm^(-3). Hot electron transfer,which leads to acceleration of electron transfer between the interfaces, was also visualized as carrier concentration increases from 1.0 × 10^(18) cm^(-3)–2.2 × 10^(18) cm^(-3).展开更多
The excited-state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzoxazole dye in different solvents is investigated using ultrafast femtosecond transient absorption spectroscopy combined with quantum chemical...The excited-state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzoxazole dye in different solvents is investigated using ultrafast femtosecond transient absorption spectroscopy combined with quantum chemical calculations.Conformational conversion from the syn-enol configuration to the keto configuration is proposed as the mechanism of excited-state intramolecular proton transfer.The duration of excited-state intramolecular proton transfer is measured to range from 50 fs to 200 fs in different solvents.This time is strongly dependent on the calculated energy gap between the N-S;and T-S;structures in the S;state.Along the proton transfer reaction coordinate,the vibrational relaxation process on the S;state potential surface is observed.The duration of the vibrational relaxation process is determined to be from8.7 ps to 35 ps dependent on the excess vibrational energy.展开更多
基金supported by the National Natural Science Foundation of China(No.61805134 and No.11974229)Applied Basic Research Program in Shanxi Province,China(No.201801D221016 and No.202103021223254)+2 种基金Scientific and Technological Innovation Pro-grams of Higher Education Institutions in Shanxi(No.2020L0235 and No.2021L257)Linfen Key Re-search and Development Program(No.2028)Graduate Innovation Project in Shanxi Province(No.2022Y498).
文摘Zero-dimensional environmentally friendly carbon quantum dots(CQDs)combined with two-di-mensional materials have a wide range of applications in optoelec-tronic devices.We combined steady-state and transient absorp-tion spectroscopies to study the energy transfer dynamics between CQDs and molybdenum disulfide(MoS_(2)).Transient absorption plots showed photoinduced absorption and stimulated emission features,which involved the intrinsic and defect states of CQDs.Adding MoS_(2)to CQDs solution,the lowest unoccupied molecular orbital of CQDs transferred energy to MoS_(2),which quenched the intrinsic emission at 390 nm.With addition of MoS_(2),CQD-MoS_(2)composites quenched defect emission at 490 nm and upward absorption,which originated from another energy transfer from the defect state.Two energy transfer paths between CQDs and MoS_(2)were efficiently manipulated by changing the concentration of MoS_(2),which laid a foundation for improving device performance.
基金Supported by the National Basic Research Program of China under Grant No 2013CB922203the National Natural Science Foundation of China under Grant No 11374366+1 种基金the Innovation Foundation of National University of Defense Technology under Grant No B110204the Hunan Provincial Innovation Foundation for Postgraduate under Grant No CX2011B010
文摘Using the fully propagated time-dependent Hartree–Fock method, we identify that both the dynamic core polarization and multiorbital contributions are important in the attosecond transient absorption of CO molecules.The dynamics of core electrons effectively modifies the behaviors of electrons in the highest occupied molecular orbital, resulting in the modulation of intensity and position of the absorption peaks. Depending on the alignment angles, different inner orbitals are identified to contribute, and even dominate the total absorption spectra. As a result, multi-electron fingerprints are encoded in the absorption spectra, which shed light on future applications of attosecond transient absorption in complex systems.
文摘Photoinduced electron transfer processes between fullerenes (C60 / C70) and N, N, N, N tetra - ( p-methylphenyl ) - 4, 4 diamino - 1, 1- diphenyl ether ( TPDAE ) have been studied by nanosecond laser flash photolysis. Quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C60 / C70 ) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes ( C60 / C70 ) and radical cations of TPDAE appear.
基金support of the Joint Centre for Extreme Photonics.Funding:This work is supported by the start-up grant of ShanghaiTech University,Double First-Class Initiative Fund of ShanghaiTech University,Shanghai Rising-Star Program(22QA1406200)National Natural Science Foundation of China(12274297,92250303)+7 种基金Shanghai Science and Technology Program(21511105000)NSERC Discovery Grant program(RGPIN-327147-2012)by the U.S.Army Research Office through Award W911NF-14-1-0383Part of this research used Beamline 03U of the Shanghai Synchrotron Radiation Facilitysupported by the ME2 project under contract no.11227902the National Natural Science Foundation of China.Y.F.and C.J.are supported by the National Natural Science Foundation of China(12274230,91950102,and 11834004)Funding of NJUST(TSXK2022D005)H.X.is supported by the National Natural Science Foundation of China(12074063 and 12264003)。
文摘Ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy measures the time- and frequencydependent light losses after light–matter interactions. In the linear region, the matter response to an XUV light field is usually determined by the complex refractive index ̃n. The absorption signal is directly related to the imaginary part of ̃n, namely, the absorption index. The real part of ̃n refers to the real refractive index, which describes the chromatic dispersion of an optical material. However, the real refractive index information is usually not available in conventional absorption experiments. Here, we investigate the refractive index line shape in ultrafast XUV transient absorption spectroscopy by using a scheme that the XUV pulse traverses the target gas jet off-center. The jet has a density gradient in the direction perpendicular to the gas injection direction, which induces deflection on the XUV radiation. Our experimental and theoretical results show that the shape of the frequency-dependent XUV deflection spectra reproduces the refractive index line profile. A typical dispersive refractive index line shape is measured for a single-peak absorption;an additional shoulder structure appears for a doublet absorption.Moreover, the refractive index line shape is controlled by introducing a later-arrived near-infrared pulse to modify the phase of the XUV free induction decay, resulting in different XUV deflection spectra. The results promote our understanding of matter-induced absorption and deflection in ultrafast XUV spectroscopy.
基金supported by the National Natural Science Foundation of China(Grant Nos.91950102 and 11834004)the Natural Science Foundation of Jiangsu Province(Grant No.BK20220925)the Funding of Nanjing University of Science and Technology(NJUST)(Grant No.TSXK2022D005)
文摘Attosecond transient absorption(ATA)has been developed as an all-optical technique for probing electron dynamics in matter.Here we present a scheme that can modify the laserinduced state and the corresponding ATA spectrum via excitation by a pair of XUV attosecond pulses and by a time-delayed mid-infrared(MIR)laser probe.Different from the scheme of the electronic excitation by a single XUV attosecond pulse,the application of a pair of XUV pulses provides extra degrees of freedom,such as the time delay and the intensity ratio between two XUV pulses,which make it possible to adjust the pump process,resulting in the modification of the ATA spectrum.We show that by varying the time delay between the two XUV pulses,the population of the dark state and the ATA spectrum of the laser-induced state have periodic modulations.We also demonstrate that the peak of the ATA spectrum of the laser-induced state appears at a fixed time delay between the XUV pair and the MIR laser when the intensity ratio is large,and it changes with the time delay when the intensity ratio is small,which can be related to either one of two peaks in the population of the dark state.
基金the National Basic Research Program of China(Nos.2017YFA0205000 and 2016YFA0200700)the National Natural Science Foundation of China(Nos.21773041,21972031,21301092,and 20962002)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000).
文摘Small-molecule organic solar cell is a category of clean energy potential device since charge transfers between donor and acceptor.The morphologies,co-assembly behavior,interaction sites,and charge transfer of BTID-nF(n=1,2)/PC71BM donor-acceptor system in the active layer of organic solar cell have been studied employing scanning tunneling microscopy(STM),scanning tunneling spectroscopy(STS),density functional theory(DFT)calculations,and transient absorption(TA)spectroscopy.The results show that BTID-1F and BTID-2F form bright strip structures,whereas BTID-nF(n=1,2)/PC71BM form ridge-like structures with each complex composed of one BTID-nF(n=1,2)molecule and four PC71BM molecules which adsorbed around the BTID-nF(n=1,2)molecule by S···πinteraction.With the assistance of S···πinteraction between BTID-nF(n=1,2)and PC71BM,BTID-nF(n=1,2)/PC71BM co-assembled ridge-like structures are more stable than the BTID-nF(n=1,2)ridge structures.To investigate the charge transfer of BTID-nF(n=1,2)/PC71BM system,STS measurements,DFT calculation,and TA spectroscopy are further performed.The results show that charge transfer occurs in BTID-nF(n=1,2)/PC71BM system with the electron transferring from BTID-nF(n=1,2)molecules to PC71BM.
基金financially supported from National Key R&D Program of China(2016YFA0200700)the National Natural Science Foundation of China(22071207,21721001,21805230,51873217,21734008,51773047,52073068)。
文摘A bulk heterojunction in organic solar cells is where charge separation and recombination occur.Molecular orientation at the interface is one of the key factors that dictate solar cell efficiency.Although X-ray scattering-based methods can determine donor/acceptor domain orientations between an anisotropic phase and an isotropic fullerene-based phase,the rise of nonfullerene solar cells presents a new challenge in delineating local molecular directions at the interface between two anisotropic donor/acceptor domains.Here,we determine interfacial molecular orientations of three high-efficiency small molecule solar cells(ZR1:Y6,B1:BO-4 Cl,and BTR:BO-4 Cl)using polarization-selective transient absorption spectroscopy.The polarization anisotropy of charge separation dynamics indicates an angle of~90°between ZR1 and Y6 molecules at the interface,an angle close to 0°between B1 and BO-4 Cl,and random orientations between BTR and BO-4 Cl.These observations provide complementary information to X-ray scattering measurements and highlight polarization-selective transient absorption spectroscopy as a tool to probe interfacial structure and dynamics of key photophysical steps in energy conversion.
基金support from the National Natural Science Foundation of China (21573211 and 21421063)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB01020200)the Fundamental Research Funds for the Central Universities of China (WK2340000063)
文摘Over the past decade the integration of ultrafast spectroscopy with nanoscience has greatly propelled the development of nanoscience, as the key information gleaned from the mechanistic studies with the assistance of ultrafast spectroscopy enables a deeper understanding of the structure–function interplay and various interactions involved in the nanosystems.This mini-review presents an overview of the recent advances achieved in our ultrafast spectroscopy laboratory that address the ultrafast dynamics and related mechanisms in several representative nanomaterial complex systems by means of femtosecond time-resolved transient absorption spectroscopy. We attempt to convey instructive, consistent information regarding the important processes, pathways, dynamics, and interactions involved in the nanomaterial complex systems,most of which exhibit excellent performance in photocatalysis.
文摘Nanoparticles with non-spherical shapes are now being widely used for various photonic applications.We observe experimentally that the magnitude as well as the time dependence of the transient absorption of a colloid of silver nanoplatelets depends on the relative polarization of the pump and probe pulses.There have been a few reports about the dependence of the transient signal magnitude on polarization,but little information is available on its temporal dependence.Using a theoretical model,we show that this observed behavior arises from the fact that the energy absorption by a non-spherical nanoparticle depends on,among other factors,the nanoparticle orientation with respect to the pump and probe polarization directions.It is essential to consider this when estimating nanoparticle characteristics such as carrier thermalization time,carrier–phonon scattering time,and complex polarizability from transient absorption measurements.
文摘In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a quantum yield of 0.67,much higher than that of systems with other metal complexes of rnesoporphyrin dimethyl ester.Neither EDTA nor MV^(2+) quenches the stationary fluorescence of SnP,implying that the reaction does not take place at the singlet state.With flash photolysis we obtain the T-T absorption spectrum of SnP(λ_(max)-440 nm).By following the decay of this absorption,the triplet life time of SnP is estimated to be 41 μs.The life time is related to the concentration of either MV^(2+) or EDTA.Good linear relationships are obtained by plotting τ_0/τ vs.the concentration of MV^(2+) or EDTA(Stern-Volmer plot),from which we determine the quenching constants:k_q(MV^(2+))=5.5×10~7 mol^(-7) s^(-1);kq(EDTA)=2.7×10~7 mol^(-1),s^(-1).The data suggests that upon photolysis of the above ternary system,both oxidative quenching and reductive quenching of the triplet state of the sensitizer are occurring.From the measured phosphorescence spectrum(λ_(max) 704nm)and the ground state redox potentials (E_(1/2)^(red)~-0.84V,E_(1/2)^(ox)~ Ag/AgCl,KCl(sat.)),we obtain the redox potential of triplet SnP to be E (P^+/P)~-0.33 V, E(P/P-)~+0.92 V.Matching this data with the redox potential of MV^(2+) and EDTA,we establish the fact that during the photolysis of the SnP/MV^(2+)/EDTA ternary system,both oxidative and reductive quenching are thermodynamically favorable processes.This is also the reason why the SnP sensitized reaction is much more efficient relative to other mesoporphyrin derivatives.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.U1630103 and 11704273)Natural Science Foundation of Jiangsu Province,China(Grant No.BK20170375)Natural Science Foundation of the Higher Education Institutions of Jiangsu Province,China(Grant No.17KJB140021)
文摘Two dimethylamino-carbaldehyde derivatives with different π-bridge lengths were prepared, and their transient optical properties and photophysical mechanisms were investigated by transient absorption spectroscopy and Z-scan measurements. Owing to the difference in molecular structures, the two compounds exhibit different populations of locally excited states and, therefore, they also produce different transient absorption spectra. After photoexcitation, both molecular materials exhibit a wide excited state absorption band from 450 nm to 1000 nm. Meanwhile, the excited state lifetimes are dramatically different, 2 ns and 100 ps, for the two molecules. A figure of merit greater than 2 at the wavelength of1000 nm is obtained. The results show that modulating the population of the locally excited states in this type of molecule can be a promising approach for obtaining optical switching and solar cell materials.
基金support from the National Key R&D Program of China(2019YFE0120300)the National Natural Science Foundation of China(NSFC,11904266,62204174 and 91850207)the Fundamental Research Funds for the Central Universities(2042021kf0202 and 2042021kf0069)。
文摘Antimony trisulfide(Sb_(2)S_(3)) solar cells suffer from large open circuit voltage deficits due to their intrinsic defects which limit the power conversion efficiency.Thus,it is important to elucidate these defects’ origin and defects at the interface.Here,we discover that sulfide radical defects have a significant impact on the performance of Sb_(2)S_(3)solar cells.Moreover,it has been illustrated that these defects at the CdS/Sb_(2)S_(3)interface can be reduced by optimizing the deposition process.A trap distribution model is used to quantify the defect density at the CdS/Sb_(2)S_(3)interface.It shows that the interface defects can be reduced by24% by improving the deposition process.This work reveals the importance of interface defects and guides the future optimization of Sb_(2)S_(3)solar cells.
基金supported by the National Natural Science Foundation of China (Grant Nos.40830744,40973072)the National Key Technology Research and Development Program in the 11th Five Year Plan of China (Grant Nos. 2008BAC32B03,2009BAA24B04)the Shanghai leading Academic Discipline Project (Grant No.S30109)
文摘The degradation characteristic of 4-bromdiphenyl ether (BDE-4) was investigated in different solutions.The study indicates that the process of direct degradation of this compound is dependent upon the bromine and the ether bond connected to diphenyl by electron beam.laser flash photolysis was employed to determine the degradation of each species (cationic,neutral,and anionic).From these data,intermediate products of BDE-4 degradation were shown for direct irradiationdegradation.The neutral radical was formed during the photolysis of these compounds.For all the compounds,diphenyl ether and hydroxybiphenyl were observed as common products.Reaction of the BDE-4 under electron beam was debromide.The debromide rate of BDE-4 at pH=5.5 is somewhat lower than that of BDE-4 at pH=10.0.The decomposition rate for BDE-4 is 99.8% at pH=10.0 on the dose of 14 kGy.BDE-4 from its radical could provide bromine ion into water and the cation radical of BDE-4 formed quickly recombine with hydrogen radical and formed phenyl ether.
文摘Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years,the influence of temperature and the type of the employed hole transport layer(HTL)on the charge carrier dynamics and recombination processes in perovskite photovoltaic devices is still largely unexplored.In particular,significant knowledge is missing on how these crucial parameters for radiative and non-radiative recombinations,as well as for efficient charge extraction vary among different perovskite crystalline phases that are induced by temperature variation.Herein,we perform micro photoluminescence(pPL)and ultrafast time resolved transient absorption spectroscopy(TAS)in Glass/Perovskite and two dierent Glass/ITO/HTL/Perovskite configurations at temperatures below room temperature,in order to probe the charge carrier dynamics of different perovskite crystalline phases,while considering also the effect of the employed HTL polymer.Namely,CH_(3)NH_(3)Pbb films were deposited on Glass,PEDOT:PSS and PTAA polymers,and the developed Glass/CH_(3)NH_(3)PbI_(3)and Glass/ITO/HTL/CH_(3)NH_(3)PbI_(3)architectures were studied from 85 K up to 215 K in order to explore the charge extraction dynamics of the CH_(3)NH_(3)PbI_(3)orthorhombic and tetragonal crystalline phases.It is observed an unusual blueshift of the bandgap with temperature and the dual emission at temperature below of 100 K and also,that the charge carrier dynamics,as expressed by hole injection times and free carrier recombination rates,are strongly depended on the actual pervoskite crystal phase,as well as,from the selected hole transport material.
文摘The reaction mechanism of 3 chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3 chlorophenol aqueous solutions have been saturated with air or N 2 previously. Under alkaline condition, the reaction of OH radical with 3 chlorophenol produces 3 chlorinated phenoxyl radical, with the absorption peaks at 400 nm and 417 nm. Under neutral condition, the reaction of OH radical with 3 chlorophenol produces OH adduct with the maximal absorption at about 340 nm. And in acid solution, the reaction of H with 3 chlorophenol produces H adduct with the maximal absorption at about 320 nm. 3 chlorophenol is compared with 4 and 2 chlorophenols from the free radical pathways. The results show that the positions of chlorine on the aromatic ring strongly influence the dehalogenation and degradation process.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 10504001,60878019,10821062,10934001,60677002 and 10828407)the National Basic Research Program of China (Grant Nos. 2009CB930504,2007CB307001,2006CB921601 and 2006CB806007)
文摘This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques. Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties. Reductive electron-transfer with transfer rate faster than 10^11 s^-1 is found. This PET process is also consolidated by femtosecond transient absorption spectra.
基金the National Nature Science Foundation of China(No.11674101,No.21873030 and No.91850202)。
文摘As one of the biological endogenous pigments,biliverdin(BV)and its dimethyl ester(BVE)have extremely weak uorescence in solution with quantum yield less than 0.01%.However,the situation reverses with the addition of zinc ions.The strength for uorescence of BVE-Zn^2+ complex is greatly enhanced and uorescence quantum yield can increase to5%.Herein,we studied ultrafast excited state dynamics of BVE-Zn^2+ complex in ethanol,npropanol,and DMSO solutions in order to reveal the mechanism of uorescence quantum yield enhancement.The results show that BVE can form a stable coordination complex with zinc with 1:1 stoichiometry in solution.BVE is structurally and energetically more stable in the complex.Using picosecond time-resolve uorescence and femtosecond transient absorption spectroscopy,we show that smaller non-radiative rate constant of BVE-Zn^2+ complex in DMSO is the key to increasing its uorescence quantum yield and the excited state decay mechanism is also revealed.These results provide valuable information about the uorescence property change after BVE binding to metal ions and may provide a guidance for the study of phytochromes or other uorescence proteins in which BV/BVE acts as chromophores.
基金Project supported by the National Natural Science Foundation of China(Grant No.61505178).
文摘Cuprous oxide(Cu_(2)O)has attracted plenty of attention for potential nonlinear photonic applications due to its superior third-order nonlinear optical property such as two-photon absorption.In this paper,we investigated the two-photon excitation induced carrier dynamics of a Cu_(2)O thin film prepared by radio-frequency magnetron sputtering,using the femtosecond transient absorption experiments.Biexponential dynamics including an ultrafast carrier scattering(<1 ps)followed by a carrier recombination(>50 ps)were observed.The time constant of carrier scattering under two-photon excitation is larger than that under one-photon excitation,due to the different transition selection rules and smaller absorption coefficient of the two-photon excitation.
基金supported by the National Natural Science Foundation of China (Grant Nos. 21503066 and 61904048)the Fundamental Research Project from Shenzhen Science and Technology Innovation Committee (Grant No. JCYJ20180302174021198)+2 种基金the Natural Science Foundation of Hebei ProvinceChina(Grant No. F2017201136)the Foundation of Hebei Educational Committee (Grant No. ZC2016003)。
文摘One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance. In this research,we carried out a detailed study on electron transfer process at the interface of nanowire CH_(3) NH_(3) PbI_(3)(N-MAPbI_(3))/Phenyl C61 butyric acid methyl-ester synonym(PCBM), as well as the interface of compact CH_(3) NH_(3) PbI_(3)(C-MAPbI_(3))/PCBM by transient absorption spectroscopy. By comparing the carrier recombination dynamics of N-MAPbI_(3), N-MAPbI_(3)/PCBM,C-MAPbI_(3), and C-MAPbI_(3)/PCBM from picosecond(ps) to hundred nanosecond(ns) time scale, it is demonstrated that electron transfer at N-MAPbI_(3)/PCBM interface is less efficient than that at C-MAPbI_(3)/PCBM interface. In addition, electron transfer efficiency at C-MAPbI_(3)/PCBM interface was found to be excitation density-dependent, and it reduces with photo-generation carrier concentration increasing in a range from 1.0 × 1018 cm^(-3)–4.0 × 1018 cm^(-3). Hot electron transfer,which leads to acceleration of electron transfer between the interfaces, was also visualized as carrier concentration increases from 1.0 × 10^(18) cm^(-3)–2.2 × 10^(18) cm^(-3).
基金supported by the Natural Science Foundation of Hubei Province,China(Grant No.2020CFB468)the Guiding Project of Scientific Research Plan of Department of Education of Hubei Province,China(Grant No.B2020136)+1 种基金the National Key Research and Development Program of China(Grant No.2019YFA0307700)the National Natural Science Foundation of China(Grant Nos.11974381,11674355,and 21507027)。
文摘The excited-state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzoxazole dye in different solvents is investigated using ultrafast femtosecond transient absorption spectroscopy combined with quantum chemical calculations.Conformational conversion from the syn-enol configuration to the keto configuration is proposed as the mechanism of excited-state intramolecular proton transfer.The duration of excited-state intramolecular proton transfer is measured to range from 50 fs to 200 fs in different solvents.This time is strongly dependent on the calculated energy gap between the N-S;and T-S;structures in the S;state.Along the proton transfer reaction coordinate,the vibrational relaxation process on the S;state potential surface is observed.The duration of the vibrational relaxation process is determined to be from8.7 ps to 35 ps dependent on the excess vibrational energy.