Time-resolved Spectroscopy Measurements Research Articles

Nonfullerene Acceptors Bearing Spiro-Substituted Bithiophene Units in Organic Solar Cells: Tuning the Frontier Molecular Orbital Distribution to Reduce Exciton Binding Energy.

The development of nonfullerene acceptors (NFAs), represented by ITIC, has contributed to improving the power conversion efficiency (PCE) of organic solar cells (OSCs). Although tuning the electronic structures to reduce the exciton binding energy (Eb) is considered to promote photocharge generation, a rational molecular design for NFAs has not been established. In this study, we designed and developed two ITIC-based NFAs bearing spiro-substituted bithiophene or biphenyl units (named SpiroT-DCI and SpiroF-DCI) to tune the frontier molecular orbital (FMO) distribution of NFAs. While the highest occupied molecular orbitals (HOMOs) of SpiroF-DCI and ITIC are delocalized in the main π-conjugated framework, the HOMO of SpiroT-DCI is distributed on the bithiophene unit. Reflecting this difference, SpiroT-DCI exhibits a smaller Eb than either SpiroF-DCI or ITIC, and exhibits greater external quantum efficiency in single-component OSCs. Furthermore, SpiroT-DCI shows improved PCEs for bulk-heterojunction OSCs with a donor of PBDB-T, compared with that of either SpiroT-DCI or ITIC. Time-resolved spectroscopy measurements show that the photo-induced intermolecular charge separation is effective even in pristine SpiroT-DCI films. This study highlights the introduction of spiro-substituted bithiophene units that are effective in tuning the FMOs of ITIC, which is desirable for reducing the Eb and improving the PCE in OSCs.

The phonon-modulated Jahn–Teller distortion of the nitrogen vacancy center in diamond

The negatively charged nitrogen vacancy (NV) center in diamond is an optically accessible material defect with a unique combination of spin and optical properties that has attracted interest in quantum-information sciences and as a design candidate for nanoscale quantum sensors. Here, we present time-resolved nonlinear optical spectroscopy measurements, conducted with ultrabroadband laser pulses, that reveal strong modulation of the excited-state by the longitudinal optical (LO) phonon of the diamond lattice. The LO phonon and its overtones geometrically distort neighboring NV centers, driving long lived (3.5 ps) excited state relaxation of coupled NV centers after the initial excitation and ultrafast (<150 fs) decay of the Jahn–Teller distortion. These observations elevate the LO phonon to an important tuning mode of the Jahn–Teller conical intersection and help resolve previous spectroscopy experiments that noted longer-lived excited-state dynamics.

Time-resolved Auger-Meitner spectroscopy of the photodissociation dynamics of CS2

Abstract The photodissociation dynamics of UV excited CS2 are investigated using time-resolved Auger-Meitner spectroscopy. Auger-Meitner decay is initiated by inner-shell ionisation with a femtosecond duration X-ray (179.9 eV) probe generated by the FERMI free electron laser. The time-delayed X-ray probe removes an electron from the S(2p) orbital leading to secondary emission of a high energy electron through Auger-Meitner decay. We monitor the electron kinetic energy of the Auger-Meitner emission as a function of pump-probe delay and observe time-dependent changes in the spectrum that correlate with the formation of bound, excited-state CS2 molecules at early times, and CS + S fragments on the picosecond timescale. The results are analysed based on a simplified kinetic scheme that provides a time constant for dissociation of approximately 1.2 ps, in agreement with previous time-resolved X-ray photoelectron spectroscopy measurements (Gabalski, et al. J. Phys. Chem. Lett. 2023, 14, 7126–7133).

Incoherent ultrafast energy transfer in phycocyanin 620 from Thermosynechococcus vulcanus revealed by polarization-controlled two dimensional electronic spectroscopy.

Phycocyanin 620 (PC620) is the outermost light-harvesting complex in phycobilisome of cyanobacteria, engaged in light collection and energy transfer to the core antenna, allophycocyanin. Recently, long-lived exciton-vibrational coherences have been observed in allophycocyanin, accounting for the coherent energy transfer [Zhu et al., Nat. Commun. 15, 3171 (2024)]. PC620 has a nearly identical spatial location of three α84-β84 phycocyanobilin pigment pairs to those in allophycocyanin, inferring an existence of possible coherent energy transfer pathways. However, whether PC620 undergoes coherent or incoherent energy transfer remains debated. Furthermore, accurate determination of energy transfer rates in PC620 is still necessary owing to the spectral overlap and broadening in conventional time-resolved spectroscopic measurements. In this work, the energy transfer process within PC620 was directly resolved by polarization-controlled two dimensional electronic spectroscopy (2DES) and global analysis. The results show that the energy transfer from α84 to the adjacent β84 has a lifetime constant of 400fs, from β155 to β84 of 6-8ps, and from β155 to α84 of 66ps, fully conforming to the Förster resonance energy transfer mechanism. The circular dichroism spectrum also reveals that the α84-β84 pigment pair does not form excitonic dimer, and the observed oscillatory signals are confirmed to be vibrational coherence, excluding the exciton-vibrational coupling. Nodal line slope analysis of 2DES further reveals that all the vibrational modes participate in the energy dissipation of the excited states. Our results consolidate that the ultrafast energy transfer process in PC620 is incoherent, where the twisted conformation of α84 is suggested as the main cause for preventing the formation of α84-β84 excitonic dimer in contrast to allophycocyanin.

Trivalent lanthanide sorption onto illite in the presence of carbonate: A study combining thermodynamic sorption modeling, time-resolved laser fluorescence spectroscopy, and parallel factor analysis

Formation of aqueous actinide complexes with dissolved inorganic carbon (DIC) in groundwater decreases the sorption of actinides onto clay minerals in a geological disposal environment. Hence, the effect of DIC on actinide sorption must be evaluated quantitatively. In this study, batch sorption experiments using Eu(III) and Sm(III) as the chemical analogs of trivalent actinides were performed to assess their sorption behavior onto illite in the presence of DIC. In the studied pH region between 8.4 and 11, the sorption was significantly lower in the presence of DIC, with the largest effect being observed at pH 9–10. The effect increased with increasing DIC from 10 to 50 mM. A thermodynamic sorption model (TSM) was used to evaluate the results of batch sorption experiments. The experimental results can only be predicted when ternary-surface complexes with carbonate ions are considered. Moreover, information on the chemical forms of sorbed Eu on illite was obtained via time-resolved laser fluorescence spectroscopy (TRLFS) measurements. Parallel factor analysis of TRLFS data indicated the presence of two chemical species of Eu. These chemical species exhibited pH dependence, which is consistent with that of the surface species predicted using the TSM. In the presence of DIC, the dominant chemical species showed a long fluorescence lifetime and was inferred to coordinate with carbonate ions, supporting the validity of the TSM.

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes.

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. A detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-Namido complexes using a high-spin ground-state analogue as a spectral model for the 5T2 excited state.

Charge Transfer Kinetics in Halide Perovskites: On the Constraints of Time-Resolved Spectroscopy Measurements.

Understanding photophysical processes in lead halide perovskites is an important aspect of optimizing the performance of optoelectronic devices. The determination of exact charge carrier extraction rate constants remains elusive, as there is a large and persistent discrepancy in the reported absolute values. In this review, we concentrate on experimental procedures adopted in the literature to obtain kinetic estimates of charge transfer processes and limitations imposed by the spectroscopy technique employed. Time-resolved techniques (e.g., transient absorption-reflection and time-resolved photoluminescence spectroscopy) are commonly employed to probe charge transfer at perovskite/transport layer interfaces. The variation in sample preparation and measurement conditions can produce a wide dispersion of the measured kinetic parameters. The selected time window and the kinetic fitting model employed introduce additional uncertainty. We discuss here evaluation strategies that rely on multiexponential fitting protocols (regular or stretched) and show how the dispersion in the reported values for carrier transfer rate constants can be resolved.

Boosting Excited-State Energy Transfer by Anchoring Dipole Orientation in Binary Thermally Activated Delayed Fluorescence/J-Aggregate Assemblies.

Förster resonance energy transfer (FRET) has been widely applied in fluorescence imaging, sensing and so on, while developing useful strategy of boosting FRET efficiency becomes a key issue that limits the application. Except optimizing spectral properties, promoting orientation factor (κ2) has been well discussed but rarely utilized for boosting FRET. Herein, we constructed binary nano-assembling of two thermally activated delayed fluorescence (TADF) emitters (2CzPN and DMAC-DPS) with J-type aggregate of cyanine dye (C8S4) as doping films by taking advantage of their electrostatic interactions. Time-resolved spectroscopic measurements indicated that 2CzPN/Cy-J films exhibit an order of magnitude higher kFRET than DMAC-DPS/Cy-J films. Further quantitative analysing on kFRET and kDET indicated higher orientation factor (κ2) in 2CzPN/Cy-J films play a key role for achieving fast kFRET, which was subsequently confirmed by anisotropic measurements. Corresponding DFT/TDDFT calculation revealed strong "two-point" electrostatic anchoring in 2CzPN/Cy-J films that is responsible for highly orientated transitions. We provide a new strategy for boosting FRET in nano-assemblies, which might be inspired for designing FRET-based devices of sensing, imaging and information encryption.

Enhancing Carrier Transport in 2D/3D Perovskite Heterostructures through Organic Cation Fluorination.

The interfacial 2D/3D perovskite heterostructures have attracted extensive attention due to their unique ability to combine the high stability of 2D perovskites with the remarkable efficiency of 3D perovskites. However, the carrier transport mechanism within the 2D/3D perovskite heterostructures remains unclear. In this study, the carrier transport dynamics in 2D/3D perovskite heterostructures through a variety of time-resolved spectroscopic measurements is systematically investigated. Time-resolved photoluminescence results reveal nanosecond hole transfer from the 3D to 2D perovskites, with enhanced efficiency through the introduction of fluorine atoms on the phenethylammonium (PEA) cation. Transient absorption measurements unveil the ultrafast picosecond electron and energy transfer from 2D to 3D perovskites. Furthermore, it is demonstrated that the positioning of fluorination on the PEA cations effectively regulates the efficiency of charge and energy transfer within the heterostructures. These insightful findings shed light on the underlying carrier transport mechanism and underscore the critical role of cation fluorination in optimizing carrier transport within 2D/3D perovskite heterostructure-based devices.

Spatiotemporal dispersion compensation for a 200-THz noncollinear optical parametric amplifier.

A noncollinear optical parametric amplifier (NOPA) can produce few-cycle femtosecond laser pulses that are ideally suited for time-resolved optical spectroscopy measurements. However, the nonlinear-optical process giving rise to ultrabroadband pulses is susceptible to spatiotemporal dispersion problems. Here, we detail refinements, including chirped-pulse amplification (CPA) and pulse-front matching (PFM), that minimize spatiotemporal dispersion and thereby improve the properties of ultrabroadband pulses produced by a NOPA. The description includes a rationale behind the choices of optical and optomechanical components, as well as assessment protocols. We demonstrate these techniques using a 1kHz, second-harmonic Ti:sapphire pump configuration, which produces ∼5-fs duration pulses that span from about 500 to 800nm with a bandwidth of about 200THz. To demonstrate the utility of the CPA-PFM-NOPA, we measure vibrational quantum beats in the transient-absorption spectrum of methylene blue, a dye molecule that serves as a reference standard.

A Review: Principles and Applications of High-Pressure In Situ Time-Resolved Transient Absorption Spectroscopy

Time-resolved transient absorption (TA) spectroscopy measurement technology provides detailed information into the ultrafast dynamics by tracking the transitions and deactivation processes of the excited-state carriers, which holds vast potential for investigating processes related to the luminescence and nonradiative recombination of materials. Pressure is considered a potent tool for tuning the carrier dynamic behaviors. The combination of high-pressure experimental technology and time-resolved TA spectroscopy measurement technology enables researchers to reveal the inherent relation between the structure and optical properties of materials, which is crucial for optimizing material performance and applications in the field of optoelectronics. In this review, the principles and the theoretical foundations of high-pressure time-resolved TA spectroscopy measurement technology will be introduced, and the research advancements in ultrafast dynamics processes of materials under high pressure will be summarized and discussed. In addition, we will expound on the future prospects of time-resolved TA spectroscopy measurement technology to detect the ultrafast dynamic behaviors of materials and complexes under the coregulation of temperature and pressure.

Ultrafast photochemical processes in 1,2-dichloroethene measured with a universal XUV probe.

The presence of two chlorine atoms in 1,2-dichloroethene allows for isomerization around the double bond. This isomerization can lead to rich photochemistry. We present a time-resolved pump-probe photoelectron spectroscopy measurement on both the cis- and trans- isomers of 1,2-dichloroethene. A universal XUV probe of 22.3 eV is used allowing observation of photoelectrons formed anywhere on the potential energy surface, even from the ground-state or dissociation products. Following excitation with a 200 nm pump both ultrafast excited state dynamics and product formation are observed within the time resolution of the experiment. Excited state population begins to return to the ground state on an ultrafast time scale (<70 fs) and population of products channels is observed on the same timescale. With the aid of ab initio calculations it is found that population transfer from the excited state is facilitated by vibrational modes involving C-C-H bends.

Modulation of carrier conduction in CsPbBr3 perovskite quantum dots with band-aligned electron and hole acceptors.

The lead halide perovskites have emerged as promising materials with intriguing photo-physical properties and have immense potential for photovoltaic applications. A comprehensive study on the kinetics of charge carrier (electron/hole) generation and transfer across the interface is key to realizing their future scope for efficient device engineering. Herein, we investigate the interfacial charge transfer (CT) dynamics in cesium lead halide (CsPbBr3) perovskite quantum dots (PQDs) with energetically favorable electron acceptors, anthraquinone (AQ) and p-benzoquinone (BQ), and hole acceptors such as pyrene and 4-(dimethylamino)pyridine (DMAP). With various steady-state and time-resolved spectroscopic and microscopic measurements, a faster electron transfer rate is estimated for CsPbBr3 PQDs with BQ compared to that of AQ, while a superior hole transfer for DMAP is divulged compared to pyrene. In concurrence with the spectroscopic measurements, conducting atomic force microscopic studies across the electrode-PQD-electrode junction reveals an increment in the conductance of the PQD in the presence of both the electron and hole acceptors. The variation of the density of states calculation in the presence of the hole acceptors offers strong support and validation for faster CT efficiency. The above findings suggest that a careful selection of simple yet efficient molecular arrangements can facilitate rapid carrier transfer, which can be designed as auxiliary layers for smooth CT and help in the engineering of cost-effective photovoltaic devices.

Near-surface magma flow instability drives cyclic lava fountaining at Fagradalsfjall, Iceland

Lava fountains are a common manifestation of basaltic volcanism. While magma degassing plays a clear key role in their generation, the controls on their duration and intermittency are only partially understood, not least due to the challenges of measuring the most abundant gases, H2O and CO2. The 2021 Fagradalsfjall eruption in Iceland included a six-week episode of uncommonly periodic lava fountaining, featuring ~ 100–400 m high fountains lasting a few minutes followed by repose intervals of comparable duration. Exceptional conditions on 5 May 2021 permitted close-range (~300 m), highly time-resolved (every ~ 2 s) spectroscopic measurement of emitted gases during 16 fountain-repose cycles. The observed proportions of major and minor gas molecular species (including H2O, CO2, SO2, HCl, HF and CO) reveal a stage of CO2 degassing in the upper crust during magma ascent, followed by further gas-liquid separation at very shallow depths (~100 m). We explain the pulsatory lava fountaining as the result of pressure cycles within a shallow magma-filled cavity. The degassing at Fagradalsfjall and our explanatory model throw light on the wide spectrum of terrestrial lava fountaining and the subsurface cavities associated with basaltic vents.

Nonequilibrium warm dense matter investigated with laser-plasma-based XANES down to the femtosecond.

The use of laser-plasma-based x-ray sources is discussed, with a view to carrying out time-resolved x-ray absorption spectroscopy measurements, down to the femtosecond timescale. A review of recent experiments performed by our team is presented. They concern the study of the nonequilibrium transition of metals from solid to the warm dense regime, which imposes specific constraints (the sample being destroyed after each shot). Particular attention is paid to the description of experimental devices and methodologies. Two main types of x-ray sources are compared, respectively, based on the emission of a hot plasma, and on the betatron radiation from relativistic electrons accelerated by laser.

A comprehensive analysis of charge transfer effects on donor-pyrene (bridge)-acceptor systems using different substituents.

The alternant polycyclic aromatic hydrocarbon pyrene has photophysical properties that can be tuned with different donor and acceptor substituents. Recently, a D (donor)-Pyrene (bridge)-A (acceptor) system, DPA, with the electron donor N,N-dimethylaniline (DMA), and the electron acceptor trifluoromethylphenyl (TFM), was investigated by means of time-resolved spectroscopic measurements (J. Phys. Chem. Lett. 2021, 12, 2226-2231). DPA shows great promise for potential applications in organic electronic devices. In this work, we used the ab initio second-order algebraic diagrammatic construction method ADC(2) to investigate the excited-state properties of a series of analogous DPA systems, including the originally synthesized DPAs. The additionally investigated substituents were amino, fluorine, and methoxy as donors and nitrile and nitro groups as acceptors. The focus of this work was on characterizing the lowest excited singlet states regarding charge transfer (CT) and local excitation (LE) characters. For the DMA-pyrene-TFM system, the ADC(2) calculations show two initial electronic states relevant for interpreting the photodynamics. The bright S1 state is locally excited within the pyrene moiety, and an S2 state is localized ~0.5 eV above S1 and characterized as a donor to pyrene CT state. HOMO and LUMO energies were employed to assess the efficiency of the DPA compounds for organic photovoltaics (OPVs). HOMO-LUMO and optical gaps were used to estimate power conversion and light-harvesting efficiencies for practical applications in organic solar cells. Considering the systems using smaller D/A substituents, compounds with the strong acceptor NO2 substituent group show enhanced CT and promising properties for use in OPVs. Some of the other compounds with small substituents are also found to be competitive in this regard.

Insights into the Semiconductor SERS Activity: The Impact of the Defect-Induced Energy Band Offset and Electron Lifetime Change.

The significant boost in surface-enhanced Raman scattering (SERS) by the chemical enhancement of semiconducting oxides is a pivotal finding. It offers a prospective path toward high uniformity and low-cost SERS substrates. However, a detailed understanding of factors that influence the charge transfer process is still insufficient. Herein, we reveal the important role of defect-induced band offset and electron lifetime change in SERS evolution observed in a MoO3 oxide semiconductor. By modulating the density of oxygen vacancy defects using ultraviolet (UV) light irradiation, SERS is found to be improved with irradiation time in the first place, but such improvement later deteriorates for prolonged irradiation even if more defects are generated. Insights into the observed SERS evolution are provided by ultraviolet photoelectron spectroscopy and femtosecond time-resolved transient absorption spectroscopy measurements. Results reveal that (1) a suitable offset between the energy band of the substrate and the orbitals of molecules is facilitated by a certain defect density and (2) defect states with relatively long electron lifetime are essential to achieve optimal SERS performance.

Fit-free analysis of fluorescence lifetime imaging data using chemometrics approach for rapid and nondestructive wood species classification

Abstract Conventional fluorescence spectroscopy has been suggested as a valuable tool for classifying wood species rapidly and non-destructively. However, because it is challenging to conduct absolute emission intensity measurements, fluorescence analysis statistics are difficult to obtain. In this study, another dimension of fluorescence, that is, fluorescence lifetime, was further evaluated to address this issue. A time-resolved fluorescence spectroscopic measurement system was first designed, mainly using a streak camera, picosecond pulsed laser at 403 nm, and a spectroscope, to collect the fluorescence time-delay (FTD) profiles and steady-state fluorescence intensity (FI) spectra simultaneously from 15 wood species. For data analysis, principal component analysis was used to “compress” the mean-centered FTD and FI spectra. Then, support vector machine classification analysis was utilized to train the wood species classification model based on their principal component scores. To avoid overfitting, ten-fold cross-validation was used to train the calibration model using 70 % of the total samples, and the remaining 30 % hold-out validation was used to test its reproducibility. The cross-validation accuracies were 100 % (5 softwoods) and 96 % (10 hardwoods), with test-validation accuracies of 96 % and 89 %.

Synthesis of plasmonic W18O49 interconnected nanowire frameworks with strong photo-enhanced hydrogen evolution reaction activity

The synthesis of high-order tungsten oxide nanowire frameworks (NWFs) is achieved using an unordinary stable molecular precursor formed by mixing tungsten hexachloride with methanol. The solvothermally obtained NWFs are well characterized with diffraction, microscopy, and nitrogen adsorption techniques. Time-resolved absorption spectroscopy and proton activity measurements reveal the stability of tungsten precursors in methanol. In butanol, the precursor decomposes rapidly into solid hydrated tungsten oxide and leads to the formation of freestanding nanowires (FNWs) after the solvothermal treatment. The NWFs show a blue shift in their characteristic plasmonic absorption wavelength when compared with FNWs. Such phenomenon is attributed to the high population of connecting nodes, which are postulated to be the plasmonic hot spots where the light-induced electromagnetic fields are amplified. The photo-deposition of palladium nanoparticles was hence selectively formed on these connecting nodes on the NWFs while showing no apparent selectivity on the FNWs. Furthermore, when applied as an electrode catalyst for the hydrogen evolution reaction, the NWFs demonstrated a much stronger photo-induced enhancement compared with the FNWs. The photo-induced effects demonstrate the advantage of plasmonic field enhancement through connected nanowires which can be obtained through a facile synthesis process.

NIR emission and up-conversion spectral studies of Er/Yb co-doped B2O3-Bi2O3-NaF-BaF2 glasses for optical amplifiers and laser applications

Er-singly and Er/Yb-codoped oxyfluoride glasses were prepared by conventional melt-quenching technique. Structural, optical, steady-state and time-resolved spectroscopy studies were performed. The down-conversion (DC) and up-conversion (UC) mechanisms in the Er3+, Yb3+ (single) and Er3+/Yb3+ (co-doped) systems were investigated under 980 nm laser excitation and the energy transfers involved in the emissions of Er3+ and Yb3+ ions were discussed. Judd-Ofelt intensity and radiative factors such as absorption cross-section (σabs) and emission cross-sections (σemi) were evaluated and an enhanced σemi was observed for the co-doped (1 mol% Er/1 mol% Yb) glasses. Gain cross-section profiles were estimated based on σabs and σemi from McCumber theory for the 4I13/2 ↔ 4I15/2 transitions. At the same time, the studied glasses also exhibited intense UC transitions from the excited states of 2H11/2, 4S3/2, and 4F9/2 to the 4I15/2 ground state of Er3+ ions and covered the strong green and red spectral regions. Time-resolved spectroscopic measurements are extended for NIR and UC emission transitions were discussed in detail.