Pump-probe Transient Absorption Research Articles

Photoinduced carrier transfer dynamics in a monolayer MoS2/PbS quantum dots heterostructure

Two-dimensional molybdenum disulfide (MoS2) has been proven to be a candidate in photodetectors, and MoS2/lead sulfide (PbS) quantum dots (QDs) heterostructure has been used to expand the optical response wavelength of MoS2. Time-resolved pump-probe transient absorption measurements are performed to clarify the carrier transfer dynamics in the MoS2/PbS heterostructure. By comparing the carrier dynamics in MoS2 and MoS2/PbS under different pump wavelengths, we found that the excited electrons in PbS QDs can transfer rapidly (<100 fs) to MoS2, inducing its optical response in the near-infrared region, although the pump light energy is lower than the bandgap of MoS2. Besides, interfacial excitons can be formed in the heterostructure, prolonging the lifetime of the excited carriers, which could be beneficial for the extraction of the carriers in devices.

Ultrabroadband Near-Infrared Transient Absorption Spectrometer with Simultaneous 900-2350 nm Detection.

In this work, we detail an ultrafast pump-probe transient absorption (TA) spectrometer capable of probing the near-infrared (NIR) spectral region from 900 to 2350 nm simultaneously. Two key advances were required to overcome previous spectral window limitations, which typically result from constrained supercontinuum ranges (e.g., 1700 nm) and/or InGaAs detector line rates, especially those with >1700 nm range. First, we generated a broadband NIR supercontinuum using the 1980 nm idler beam of an optical parametric amplifier and implement a unique spectral filtering scheme to balance the detected spectrum. Second, we used a prism-based spectrometer system equipped with high speed InGaAs cameras having ∼2500 nm sensitivity cutoffs. To the best knowledge of the authors, such an extended probe range was previously inaccessible because the combination of two optical geometries either using different supercontinuum crystal materials for generating the NIR and shortwave infrared (SWIR) regions, or using differing pump wavelengths, were required. Finally, we demonstrate the performance and capabilities of the ultrabroadband TA spectroscopy system by presenting data showing ultrafast charge photogeneration in a polymer : fullerene blend thin-film and comparing the results to the literature with a complete agreement.

Transient-absorption spectroscopy of dendrimers via nonadiabatic excited-state dynamics simulations.

The efficiency of light-harvesting and energy transfer in multi-chromophore ensembles underpins natural photosynthesis. Dendrimers are highly branched synthetic multi-chromophoric conjugated supra-molecules that mimic these natural processes. After photoexcitation, their repeated units participate in a number of intramolecular electronic energy relaxation and redistribution pathways that ultimately funnel to a sink. Here, a model four-branched dendrimer with a pyrene core is theoretically studied using nonadiabatic molecular dynamics simulations. We evaluate excited-state photoinduced dynamics of the dendrimer, and demonstrate on-the-fly simulations of its transient absorption pump-probe (TA-PP) spectra. We show how the evolutions of the simulated TA-PP spectra monitor in real time photoinduced energy relaxation and redistribution, and provide a detailed microscopic picture of the relevant energy-transfer pathways. To the best of our knowledge, this is the first of this kind of on-the-fly atomistic simulation of TA-PP signals reported for a large molecular system.

Deciphering intersystem crossing and energy transfer mechanisms in a nonacoordinated ternary europium(iii) complex: a combined spectroscopic and theoretical study.

A monochromatic red emitting nonacoordinate organoeuropium complex with the formula [Eu(hfaa)3(Ph-TerPyr)] (Eu-1) incorporating hexafluoroacetylacetone (hfaa) primary ligands and a tridentate 4'-phenyl-2,2':6',2''-terpyridine (Ph-TerPyr) ancillary ligand has been synthesized. The complex was characterized by analytical and spectroscopic methods, and its structure was established by single crystal X-ray diffraction (SC-XRD) analysis at low temperature, which explicitly confirms that the coordination sphere is composed of a EuO6N3 core. Under the UV excitation, Eu-1 displayed typical red emission in solution with a long-excited state lifetime (τ obs = 1048.06 ± 9.39 μs) with a good photoluminescence quantum yield (Q L Eu = 41.14%). We have utilized pump-probe ultrafast transient absorption spectroscopy in tandem with the time-dependent density functional theory (TD-DFT) and the Lanthanide Luminescence Software Package (LUMPAC) to explore the intricate photophysical event that occurs in the vicinity of the ligands of Eu-1 sensitized photoluminescence (PL).

Determination of the refractive-index change in the excited state based on transient absorption microscopy

Photoinduced excited-state carriers can affect both the absorption coefficient and refractive index of materials and influence the performance of photoelectric devices. Femtosecond time-resolved pump–probe transient absorption (TA) spectroscopy is usually used to detect carrier dynamics and excited-state absorption coefficients; however, measurements of transient refractive-index change are still difficult. We propose a method for determining the excited-state refractive-index change using TA microscopy. In TA measurements, a Fabry–Pérot cavity formed by the front and back surfaces of the sample could lead to interference of the probe light. As the wavelength of standing waves in the Fabry–Pérot cavity is closely related to the refractive index, the carrier-induced excited-state refractive-index change was obtained by comparing the transmission probe spectra between the ground and excited states. The proposed method was used to study the dynamics of excited-state refractive-index change in a perovskite film.

Ultrafast optical characteristics of Mn-doped CdS quantum dots

Cadmium sulfide (CdS) quantum dots (QDs) doped with different concentrations of manganese (Mn = 0, 1, 3, 5, and 7 %) are synthesized via thermolysis of diselenocarbamato complexes of cadmium in the trioctylphosphine oxide (TOPO). The QDs show quantum size effects in the optical spectra and exhibit band-edge emission. The TEM images revealed that the QDs are spherical within the range of 3 to 5 nm. The nonlinear optical studies and optical limiting characteristics are studied. From open and closed aperture data, the nonlinear absorption coefficient (β) and refractive indices (n2) values are found to be in the range of 4–16 x10-9 cm2/w and 8-14x10-15 cm2/w. The cross relaxations and energy transfer mechanism of quantum dots are studied using the transient absorption pump–probe experiment.

Ab Initio Study of Charge Separation Dynamics and Pump-Probe Spectroscopy in the P3HT/PCBM Blend.

We develop a bottom-up computational method for excited-state dynamics and time-resolved spectroscopy signals in molecular aggregates, on the basis of ab initio excited-state calculations. As an application, we consider the charge separation dynamics and pump-probe spectroscopy in the amorphous P3HT/PCBM blend. To simulate quantum dynamics and time-resolved spectroscopy, the model Hamiltonian for single-excitation and double-excitation manifolds was derived on the basis of fragment-based excited-state calculations within the GW approximation and the Bethe-Salpeter equation. After elucidating the energetics of the electron-hole separation and examining linear absorption spectrum, we investigated the quantum dynamics of exciton and charge carriers in comparison with the pump-probe transient absorption spectra. In particular, we introduced the pump-probe excited-state absorption (ESA) anisotropy as a spectroscopic signature of charge carrier dynamics after exciton dissociation. We found that the charge separation dynamics can be probed by the pump-probe ESA anisotropy dynamics after charge-transfer excitations. The present study provides the fundamental information for understanding the experimental spectroscopy signals, by elucidating the relationship between the excited states, the exciton and charge carrier dynamics, and time-resolved spectroscopy.

Dual Emission Bands of a 2D Perovskite Single Crystal with Charge Transfer State Characteristics.

Several hybrid halide 2D-perovskite species emit light with an emergent and controversial broadband emission Stokes-shifted down from the narrow band emission. This paper uncovers the sub- and above-bandgap emission and absorption characteristics of PEA2PbI4 prepared with gap states introduced during single crystal growth. Here, gap states led to coexistent intrinsic and heterostructured electronic frameworks that are selectively accessible with ultraviolet (UV) and infrared (IR) light, respectively, resulting in the phenomenon of photoluminescence (PL) switching from narrowband green to broadband red. Electron-energy dependent cathodoluminescence shows a relative increase in the broadband red PL intensity as the electron penetration depth increases from 30 nm to 2 μm, confirming the heterostructured framework is formed in the bulk of the crystal. Excitation-emission power slope of 2.5 and up-conversion pump transient absorption (TA) spectra suggest that the IR up-conversion excitation with red photoluminescence, peaked at 655 nm, is a multiphoton process occurring in the heterostructured framework through a nonlinear optical response. The energetic pathways toward the dual emission bands are revealed by pump-probe transient absorption spectroscopy, showing energetically broad gap states with high sensitivity to an IR pump are upconverted and subsequently quickly relax from high to low energy levels within 4 ps. Furthermore, the up-conversion red PL demonstrates a linear polarization with magnetic field effects, thus affirming that the band-like heterostructured framework is crystallographically aligned with characteristics of spatially extended charge-transfer states.

Attosecond magnetization dynamics in non-magnetic materials driven by intense femtosecond lasers

Irradiating solids with ultrashort laser pulses is known to initiate femtosecond timescale magnetization dynamics. However, sub-femtosecond spin dynamics have not yet been observed or predicted. Here, we explore ultrafast light-driven spin dynamics in a highly nonresonant strong-field regime. Through state-of-the-art ab initio calculations, we predict that a nonmagnetic material can transiently transform into a magnetic one via dynamical extremely nonlinear spin-flipping processes, which occur on attosecond timescales and are mediated by cascaded multi-photon and spin–orbit interactions. These are nonperturbative nonresonant analogs to the inverse Faraday effect, allowing the magnetization to evolve in very high harmonics of the laser frequency (e.g. here up to the 42nd, oscillating at ~100 attoseconds), and providing control over the speed of magnetization by tuning the laser power and wavelength. Remarkably, we show that even for linearly polarized driving, where one does not intuitively expect the onset of an induced magnetization, the magnetization transiently oscillates as the system interacts with light. This response is enabled by transverse light-driven currents in the solid, and typically occurs on timescales of ~500 attoseconds (with the slower femtosecond response suppressed). An experimental setup capable of measuring these dynamics through pump–probe transient absorption spectroscopy is simulated. Our results pave the way for attosecond regimes of manipulation of magnetism.

Accurate Relativistic Real-Time Time-Dependent Density Functional Theory for Valence and Core Attosecond Transient Absorption Spectroscopy

First principles theoretical modeling of out-of-equilibrium processes observed in attosecond pump-probe transient absorption spectroscopy (TAS) triggering pure electron dynamics remains a challenging task, especially for heavy elements and/or core excitations containing fingerprints of scalar and spin-orbit relativistic effects. To address this, we formulate a methodology for simulating TAS within the relativistic real-time, time-dependent density functional theory (RT-TDDFT) framework, for both the valence and core energy regimes. Especially for TAS, full four-component (4c) RT simulations are feasible but computationally demanding. Therefore, in addition to the 4c approach, we also introduce the atomic mean-field exact two-component (amfX2C) Hamiltonian accounting for one- and two-electron picture-change corrections within RT-TDDFT. amfX2C preserves the accuracy of the parent 4c method at a fraction of its computational cost. Finally, we apply the methodology to study valence and near-L2,3-edge TAS processes of experimentally relevant systems and provide additional physical insights using relativistic nonequilibrium response theory.

Physical mechanisms on FRET and ICT for efficient Y6:PM6 as bulk heterojunction active layers.

Organic solar cells (OSCs) have emerged as a promising new energy technology because of their advantages of efficient light harvesting, comprehensive material sources, and flexible and translucent devices. In this study, fluorescence resonance energy transfer (FRET) and intermolecular charge transfer (ICT) in the donor-acceptor system for efficient OSCs of the Y6:PM6 heterostructure are investigated with ultrafast pump-probe transient absorption spectroscopy, time-resolved fluorescence spectroscopy, steady absorption, and fluorescence spectroscopy, which is significantly supported by theoretical results. The physical mechanisms of FRET and ICT in the donor-acceptor system for efficient OSCs of the Y6:PM6 heterostructure are investigated theoretically and experimentally. FRET can decrease the recombination of electron-hole in the donor's fluorescence and enhance the acceptor's fluorescence. Our study contributes to a better understanding of FRET and ICT and provides valuable references for the rational design of FRET- and ICT-based OSCs.

Unveiling Ultrafast Carrier Extraction in Highly Efficient 2D/3D Bilayer Perovskite Solar Cells

The development of multidimensional heterostructure (2D/3D) lead halide perovskites has emerged as an effective approach to enhancing the efficiency and long-term stability of perovskite solar cells (PSCs). However, a fundamental understanding of the working mechanisms, such as carrier extraction, and carrier transfer dynamics in the multidimensional perovskites heterostructures remains elusive. Here, we observe the ultrafast carrier extraction in highly efficient 2D/3D bilayer PSCs (power conversion efficiency of 21.12%) via femtosecond time-resolved pump–probe transient absorption spectroscopy (TAS). Notably, the formation of quasi-equilibrium states resulting in a subband absorption feature with an ultrafast lifetime of 440 fs was observed, and this feature is found only in 2D/3D perovskite heterostructure. The short-lived feature gives rise to the local electric-field-induced electroabsorption, resulting in an enhanced power conversion efficiency in 2D/3D PSCs. These findings can help comprehend the advanced working mechanism of highly efficient solar cells and other 2D/3D bilayer perovskite-based optoelectronic devices.

Degradation of CdS Yellow and Orange Pigments: A Preventive Characterization of the Process through Pump-Probe, Reflectance, X-ray Diffraction, and Raman Spectroscopy.

Cadmium yellow degradation afflicts numerous paintings realized between the XIXth and XXth centuries. The degradation process and its kinetics is not completely understood. It consists of chalking, lightening, flaking, spalling, and, in its most deteriorated cases, the formation of a crust over the original yellow paint. In order to improve the comprehension of the process, mock-up samples of CdS in yellow and orange tonalities were studied by means of structural analysis and optical characterization, with the principal techniques used in the field of cultural heritage. Mock ups were artificially degraded with heat treatment and UV exposure. Relevant colorimetric variation appears in CIE Lab coordinates from reflectance spectra. XRD, SEM-EDS, and Raman spectroscopy revealed the formation of cadmium sulfate, whilst time-resolved photoluminescence and pump–probe transient absorption spectroscopy suggest the formation of a defective phase, compatible with Cd vacancies and the formation of both CdO and CdSO4 superficial clusters.

Ultrafast Studies of ZrTe3 by Transient Absorption Spectrometer.

Two-dimensional (2D) tri-TMDCs carrier dynamics provide a platform for studying excitons through Ultrafast Pump-Probe Transient Absorption Spectroscopy. Here we studied the ZrTe3 nanosheets (NTs) exciton dynamics by transient absorption (TA) spectrometer. We observed different carrier dynamics in the ZrTe3 NTs sample at different pump powers and with many wavelengths in the transient absorption spectrometer. The shorter life decay constant is associated with electron-phonon relaxation. Similarly, the longer-life decay constant represents the long live process that is associated with charge separation. The interactions between carrier-phonons at nanoscale materials can be changed by phonons quantum confinements. The hot carrier lifetime determined the strength of carrier phonon interactions. The value of fast decay in the conduction band is due to carrier relaxation or the carrier gets trapped due to surface states or localized defects. The value of slow decay is due to the recombination of surface state and localized defects processes. The lifetime declines for long wavelengths as size decreases. Whereas, during short wavelength-independent decay, carrier characteristics have been observed. TA spectroscopy is employed to investigate insight information of the carrier’s dynamical processes such as carrier lifetime, cooling dynamics, carrier diffusion, and carrier excitations. The absorption enhanced along excitons density with the increase of pump power, which caused a greater number of carriers in the excited state than in the ground state. The TA signals consist of trap carriers and (electron-hole) constituents, which can be increased by TA changes that rely on photoexcitation and carrier properties.

Photocycle of point defects in highly- and weakly-germanium doped silica revealed by transient absorption measurements with femtosecond tunable pump

We report pump-probe transient absorption measurements addressing the photocycle of the Germanium lone pair center (GLPC) point defect with an unprecedented time resolution. The GLPC is a model point defect with a simple and well-understood electronic structure, highly relevant for several applications. Therefore, a full explanation of its photocycle is fundamental to understand the relaxation mechanisms of such molecular-like systems in solid state. The experiment, carried out exciting the sample resonantly with the ultraviolet (UV) GLPC absorption band peaked at 5.1 eV, gave us the possibility to follow the defect excitation-relaxation dynamics from the femto-picosecond to the nanosecond timescale in the UV–visible range. Moreover, the transient absorption signal was studied as a function of the excitation photon energy and comparative experiments were conducted on highly- and weakly-germanium doped silica glasses. The results offer a comprehensive picture of the relaxation dynamics of GLPC and allow observing the interplay between electronic transitions localized on the defect and those related to bandgap transitions, providing a clear evidence that the role of dopant high concentration is not negligible in the earliest dynamics.

Acoustic Vibration Modes of Gold–Silver Core–Shell Nanoparticles

Bimetallic Au/Ag core–shell cuboid nanoparticles (NPs) exhibit a complex plasmonic response dominated by a dipolar longitudinal mode and higher-order transverse modes in the near-UV, which may be exploited for a range of applications. In this paper, we take advantage of the strong signature of these modes in the NP ultrafast transient optical response, measured by pump-probe transient absorption (TA) spectroscopy, to explore the NP vibrational landscape. The fast Fourier transform analysis of the TA dynamics reveals specific vibration modes in the frequency range 15–150 GHz, further studied by numerical simulations based on the finite element method. While bare Au nanorods exhibit extensional and breathing modes, the bimetallic NPs undergo more complex motions, involving the displacement of facets, edges and corners. The amplitude and frequency of these modes are shown to depend on the Ag shell thickness, as the silver load modifies the NP aspect ratio and mass. Moreover, the contributions of the vibrational modes to the experimental TA spectra are shown to vary with the probe laser wavelength at which the signal is monitored. Using the combined simulations of the NP elastic and optical properties, we elucidate this influence by analyzing the effect of the mechanisms involved in the acousto-plasmonic coupling.

Tunable optical nonlinearities of MWCNTs with core-satellite ZnS-Au structure

In order to modulate the nonlinear optical (NLO) properties of multi walled carbon nanotubes (MWCNTs) and make them applicable to ultrafast nonlinear optical devices, we fabricated a core satellite ZnS-Au nanostructure on the surface of MWCNTs via the solvothermal method. The structure and morphology of the MWCNTs-Au-ZnS product were characterized by means of the XRD, SEM and XPS, which showed that the ZnS-Au nanoassemblies were combined along with the MWCNTs through C S covalent bond and partial ionic bond. The optical nonlinearities of the MWCNTs-Au-ZnS system were investigated using the Z-scan technique under the excitation of 532 nm ps laser pulses and kinetically analyzed using the pump-probe transient absorption spectroscopy. The results showed that the saturation absorption (SA) coefficient and the third-order nonlinear susceptibility of the MWCNTs-Au-ZnS system were adjustable with the variation of the core-satellite structure. The intensity of the saturation absorption was tuned downward below that of the pure MWCNTs, while the susceptibility of the system was tuned upward above that of the pure MWCNTs, which were attributed to the combined action of two-photon absorption of ZnS, charge transfer in the system, trap states provided by Au and charge delocalization varying with the size. These tunable nonlinearities will expand the applications of the MWCNTs-Au-ZnS system in photonic devices. • Core-satellite structure of ZnS-Au is fabricated on the surface of MWCNTs via a solvothermal method. • The core-satellite structure is connected with MWCNTs via covalent bond and partial ionic bond. • The nonlinear absorption and refraction of the MWCNTs-Au-ZnS are tuned by changing the core-satellite structures.

Ultrafast Internal Conversion Dynamics through the on-the-Fly Simulation of Transient Absorption Pump-Probe Spectra with Different Electronic Structure Methods.

An on-the-fly surface-hopping simulation protocol is developed for the evaluation of transient absorption (TA) pump-probe (PP) signals of molecular systems exhibiting internal conversion to the electronic ground state. We study the nonadiabatic dynamics of azomethane and the associating TA PP spectra at three levels of the electronic-structure theory, OM2/MRCI, SA-CASSCF, and XMS-CASPT2. The impact of these methods on the population dynamics and time-resolved TA PP signals is substantially different. This difference is attributed to the strong non-Condon effects that must be taken into account for the proper understanding and interpretation of time-resolved TA PP signals of nonadiabatic polyatomic systems. This shows that the combination of the dynamical and spectral simulations definitely provides more accurate and detailed information on the microscopic mechanisms of photophysical and photochemical processes. Hence the simulation of time-resolved spectroscopic signals provides another important dimension to examine the accuracy of quantum chemistry methods.

XUV-Initiated Dissociation Dynamics of Molecular Oxygen (O2)

We performed a time-resolved spectroscopy experiment on the dissociation of oxygen molecules after the interaction with intense extreme-ultraviolet (XUV) light from the free-electron laser in Hamburg at Deutsches Elektronen-Synchrotron. Using an XUV-pump/XUV-probe transient-absorption geometry with a split-and-delay unit, we observe the onset of electronic transitions in the O2+ cation near 50 eV photon energy, marking the end of the progression from a molecule to two isolated atoms. We observe two different time scales of 290 ± 53 and 180 ± 76 fs for the emergence of different ionic transitions, indicating different dissociation pathways taken by the departing oxygen atoms. With regard to the emerging opportunities of tuning the central frequencies of pump and probe pulses and of increasing the probe–pulse bandwidth, future pump–probe transient-absorption experiments are expected to provide a detailed view of the coupled nuclear and electronic dynamics during molecular dissociation.

Photophysics of Ag and Au alloys of M25(SR)18 clusters.

Superatom clusters, Au25(SR)18, and the silver analogand alloys of the two metals have been extensively investigated for their structure, stability, photoluminescence, and electronic properties. One can readily tune the physicochemical properties by varying the ratio of Au/Ag or the thiol ligand to attain desired properties, such as enhanced emission, increased stability, and catalytic activity. Herein, excitation emission matrix spectroscopy and pump-probe transient absorption spectroscopy are used to show that the excited state dynamics of Au25(SR)18, Ag25(SR)18, and their alloys differ significantly despite having similar structures. State-resolved excited state behavior that is well documented for gold clusters is largely affected by the metal composition, becoming less pronounced for silver analogs, resulting in diversity in terms of their excited state energy and relaxation dynamics and resultant photophysical properties, such as emission.