Time-resolved Optical Spectroscopy Research Articles

Hot-phonon effects in photo-excited wide-bandgap semiconductors

Carrier and lattice relaxation after optical excitation is simulated for the prototypical wide-bandgap semiconductors CuI and ZnO. Transient temperature dynamics of electrons, holes as well as longitudinal-optic (LO), transverse-optic (TO) and acoustic phonons are distinguished. Carrier-LO-phonon interaction constitutes the dominant energy-loss channel as expected for polar semiconductors and hot-phonon effects are observed for strong optical excitation. Our results support the findings of recent time-resolved optical spectroscopy experiments.

Hot Carrier Transfer in a Graphene/PtSe2 Heterostructure Tuned by a Substrate-Introduced Effective Electric Field

The van der Waals heterojunction involving graphene (Gr) with transition metal dichalcogenides (TMDs) is regarded as a promising structure for its outstanding performance in optoelectronic response. The electron-hole thermalization has been deemed to be the main reason for the subband gap excitation charge transfer from Gr to TMDs. However, the role of the intricate interlayer interaction of Gr and TMDs still requires intensive investigation. Here, we have investigated the photocarrier dynamics in a five-layer PtSe2/Gr heterojunction by using time-resolved optical pump and terahertz probe spectroscopy. Interestingly, after photoexcitation, electron transfer from PtSe2 to Gr has been demonstrated successfully in the PtSe2/Gr/substrate heterojunction; by contrast, no observable charge transfer occurs in the Gr/PtSe2/substrate heterostructure. The prominent difference for the different stacking sequences between Gr and PtSe2 can be ascribed to the effective electric field introduced by the fused silica substrate. A physical picture accounting for the effective electric field introduced by the substrate has been proposed to interpret the charge transfer process in the TMD/Gr heterostructure. More importantly, the electric field induced by the substrate plays a dominant role in controlling the charge transfer pathway in the TMDs/Gr heterojunction. This study not only sheds light on the substrate engineering of the van der Waals heterojunction but also provides new insight into the layer interaction dynamics in the Gr/TMD heterojunction.

Time resolved speckle contrast optical spectroscopy at quasi-null source-detector separation for non-invasive measurement of microvascular blood flow.

Time (or path length) resolved speckle contrast optical spectroscopy (TD-SCOS) at quasi-null (2.85 mm) source-detector separation was developed and demonstrated. The method was illustrated by in vivo studies on the forearm muscle of an adult subject. The results have shown that selecting longer photon path lengths results in higher hyperemic blood flow change and a faster return to baseline by a factor of two after arterial cuff occlusion when compared to SCOS without time resolution. This indicates higher sensitivity to the deeper muscle tissue. In the long run, this approach may allow the use of simpler and cheaper detector arrays compared to time resolved diffuse correlation spectroscopy that are based on readily available technologies. Hence, TD-SCOS may increase the performance and decrease cost of devices for continuous non-invasive, deep tissue blood flow monitoring.

PH-dependence of signaling-state formation in Drosophila cryptochrome

Cryptochromes, FAD-dependent blue light photoreceptors, undergo a series of electron transfer reactions after light excitation. Time-resolved optical spectroscopy was employed to investigate the pH dependence of all light-dependent reactions in the cryptochrome from fruit flies. Signal state formation experiments on a time scale of seconds were found to be strongly pH dependent, and formation of both anionic and neutral FAD radicals could be detected, with reaction rates increasing by a factor of ~2.5 from basic to neutral pH values. Additionally, the influence of the amino acid His378 was investigated in further detail: Two protein variants, DmCry H378A and H378Q, showed significantly reduced rate constants for signal state formation, which again differed at neutral and alkaline pH values. Hence, His378 was identified as an amino acid responsible for the pronounced pH dependence; however, this amino acid can be excluded as a proton donor for the protonation of the anionic FAD radical. Other conserved amino acids appear to alter the overall polarity of the binding pocket and thus to be responsible for the pronounced pH dependence. Furthermore, the influence of pH and other experimental parameters, such as temperature, glycerol or ferricyanide concentrations, on the intermediately formed FAD–tryptophan radical pair was explored, which deprotonates on a microsecond time scale with a clear pH dependence, and subsequently recombines within milliseconds. Surprisingly, the latter reaction showed no pH dependence; potential reasons are discussed. All results are reviewed in terms of the photoreceptor and potential magnetoreceptor functions of Drosophila cryptochrome.

Corrole-Substituted Fluorescent Heme Proteins.

Although fluorescent proteins have been utilized for a variety of biological applications, they have several optical limitations, namely weak red and near-infrared emission and exceptionally broad (>200 nm) emission profiles. The photophysical properties of fluorescent proteins can be enhanced through the incorporation of novel cofactors with the desired properties into a stable protein scaffold. To this end, a fluorescent phosphorus corrole that is structurally similar to the native heme cofactor is incorporated into two exceptionally stable heme proteins: H-NOX from Caldanaerobacter subterraneus and heme acquisition system protein A (HasA) from Pseudomonas aeruginosa. These yellow-orange emitting protein conjugates are examined by steady-state and time-resolved optical spectroscopy. The HasA conjugate exhibits enhanced fluorescence, whereas emission from the H-NOX conjugate is quenched relative to the free corrole. Despite the low fluorescence quantum yields, these corrole-substituted proteins exhibit more intense fluorescence in a narrower spectral profile than traditional fluorescent proteins that emit in the same spectral window. This study demonstrates that fluorescent corrole complexes are readily incorporated into heme proteins and provides an inroad for the development of novel fluorescent proteins.

Fluence-dependent dynamics of localized excited species in monolayer versus bulk MoS2

Transition-metal dichalcogenides are characterized by a layered lattice structure, facilitating the fabrication of two-dimensional crystals. Concerning their electronic properties, these monolayers differ fundamentally from the bulk material, exhibiting direct band gaps and significantly higher exciton binding energies. Hence, to shed light on how the crystal thickness influences the relevant excited states and in particular their dynamics, we performed time-resolved optical pump-probe spectroscopy on monolayer and bulk samples of molybdenum disulfide ($\mathrm{Mo}{\mathrm{S}}_{2}$) for a broad range of excitation fluences. The observed transient spectra result from photoinduced shifts in the band structure. Here, we find evidence for a localized nature of the excited species as opposed to the common model of band-gap renormalization. At high excitation densities, strong collisional broadening of the shifted absorption occurs. Within the first picosecond after excitation, the free carriers thermalize, while in the monolayer, additionally, electrons and holes pair to form excitons. On longer time scales up to several nanoseconds, the excited populations decay. In the bulk sample, the corresponding signal reduction could be described in terms of a defect-assisted Auger recombination of electrons and holes. For monolayer $\mathrm{Mo}{\mathrm{S}}_{2}$, in contrast, two-dimensional diffusion leads to recombination of the excitons at defect sites.

Microsecond Photoluminescence and Photoreactivity of a Metal-Centered Excited State in a Hexacarbene-Co(III) Complex.

The photofunctionality of the cobalt–hexacarbene complex [Co(III)(PhB(MeIm)3)2]+ (PhB(MeIm)3 = tris(3-methylimidazolin-2-ylidene)(phenyl)borate) has been investigated by time-resolved optical spectroscopy. The complex displays a weak (Φ ∼ 10–4) but remarkably long-lived (τ ∼ 1 μs) orange photoluminescence at 690 nm in solution at room temperature following excitation with wavelengths shorter than 350 nm. The strongly red-shifted emission is assigned from the spectroscopic evidence and quantum chemical calculations as a rare case of luminescence from a metal-centered state in a 3d6 complex. Singlet oxygen quenching supports the assignment of the emitting state as a triplet metal-centered state and underlines its capability of driving excitation energy transfer processes.

Anisotropic Time-Resolved Dynamics of Crystal Growth Induced by a Single Laser Pulse Nucleation

Nucleation and growth of crystallites are induced by the shockwave of a single laser nanosecond pulse in highly supersaturated solutions of potassium nitrate (saltpeter). The kinetics of the turbidity resulting from the light scattering by the growing crystals is observed by time-resolved optical spectroscopy. With an optical path of 10 mm, we first focused on the early part of the growth under various conditions, but it is limited by the detection system to a few percent of the total growth. Remarkably, in this domain and for all supersaturated concentrations studied, the turbidity increases proportionally with time. This zero-order process with an accretion rate constant (k = 4.7 × 107 L mol–1 s–1) implies that the nuclei and growing crystals’ concentration remain constant. This concentration is determined from the final diameter of crystals that are observed to have a bipyramidal shape by transmission electron microscopy (TEM). Moreover, the number of accretion sites per crystal must be constant in this time range and they are identified as the apexes. In complement, the kinetics detected with shorter optical paths permits us to observe larger parts of the total growth (up to 35% with 1 mm of optical path). In this case, after the linear part, the turbidity increase is markedly accelerated, indicating that the number of accretion sites per crystal increases rapidly with the crystal size and that the edges and facet sites also fix the molecules. The complete analysis by a homogeneous kinetics model of the signals obtained under various conditions concludes to an anisotropic growth of the crystals with another accretion rate constant (k′ = 100 L mol–1 s–1) that is much lower on these edges and facet sites than on the apexes. However, this contribution becomes predominant only when the crystals develop to a larger size.

Terahertz probe of nonequilibrium carrier dynamics and ultrafast photocurrents in the topological insulator Sb2Te3

In this study, we report the ultrafast excitation and dynamics of the carrier and photocurrent in a 3D typical topological insulator Sb2Te3. We utilize time-resolved optical pump-THz probe spectroscopy to explore the nonequilibrium carrier dynamics of Sb2Te3. The electron system undergoes an ultrafast relaxation and releases through intra-band and inter-band scattering. Additionally, THz emission spectroscopy is employed to investigate the different ultrafast photocurrents in Sb2Te3 through tuning the polarization of excitation pulses and rotating the sample's azimuthal angle. We distinguish the different ultrafast photocurrents driven by the linear photogalvanic effect, circular photogalvanic effect, and thermoelectric effect. Our results potentially enable an all-optical modulation of THz emission without any external bias field, which could play an important role in the development of topological insulator-based high-speed THz optoelectronic and opto-spintronic devices.

Photophysical properties of N719 and Z907 dyes, benchmark sensitizers for dye-sensitized solar cells, at room and low temperature.

Two benchmark sensitizers used for dye-sensitized solar cells, ruthenium polypyridyl N719 and Z907 dyes were investigated with spectroscopic methods as steady-state absorption, time-gated phosphorescence and femto-/nanosecond time-resolved transient absorption at room temperature and at 160 K. Aim of this study was to perform comprehensive photophysical study of dye excited singlet and triplet metal-to-ligand charge transfer (MLCT) states including states lifetimes, dependency on temperature and dye concentration and obtain detailed information on the excitation decay pathway. Transient absorption and phosphorescence decay data provided a clearer picture of the dynamics of the excited MLCT states. Based on data analysis, the excitation decay pathway consists of rapid intersystem crossing to the triplet MLCT state that undergoes state solvation and vibrational relaxation. It was demonstrated that the lifetime of the fully relaxed triplet MLCT is also strongly dependent on dye concentration for both molecules, providing a viable explanation for a large inconsistency seen in previous studies.

Two-photon absorption enhancement for organic acceptor molecules with QD antennas.

The photophysics of an inorganic/organic hybrid system was studied by time-resolved optical spectroscopy, focusing on the goal of increasing the two-photon efficiency of photoresponsive systems. The hybrid system consists of CdS/ZnS core/shell quantum dots (QDs) as energy donor and coumarin derivatives as energy acceptor molecules. The spectral overlap of QD emission and coumarin 343 absorption promotes a Förster resonance energy tranfer (FRET) mechanism leading to a FRET efficiency up to nearly 90%. Additionally, time-correlated single photon counting showed a faster fluorescence decay while acceptor molecules were attached to the QD surface. Femtosecond transient absorption measurements demonstrated an ultrafast FRET reaction. Importantly, FRET was observed also after two-photon excitation of the QDs indicating that the chosen QDs can act as two-photon antennas.

Structure and excited-state dynamics of dimeric copper(i) photosensitizers investigated by time-resolved X-ray and optical transient absorption spectroscopy.

Time-resolved X-ray (tr-XAS) and optical transient absorption (OTA) spectroscopy in the picosecond time scale coupled with Density Functional theory (DFT) and X-ray absorption near-edge structure (XANES) calculations are applied to study three homoleptic Cu(i) dimeric chromophores with ethyl and longer propyl spacers, denoted as [Cu2(mphenet)2]Cl2 (C1), [Cu2(mphenet)2](ClO4)2 (C2) and [Cu2(mphenpr)2](ClO4)2 (C3) (where mphenet = 1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane and mphenpr = 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane). Tr-XAS analysis after light illumination at ∼ 100 ps illustrate the formation of a flattened triplet excited state in all 3 complexes. Optical transient absorption (OTA) analysis for C1 monitored in water and C2 and C3 measured in acetonitrile reveals distinct excited-state lifetimes of 169 ps, 670 ps and 1600 ps respectively. These differences are associated to changes in the solvent (comparing C1 and C2) and the flexibility of the ligand to adapt after Cu flattening upon excitation (C2 and C3). Our results are important for the improved structural dynamics of these types of Cu-based dimeric compounds, and can guide the integration of these chromophores into more complex solar energy conversion schemes.

Time-Resolved Optical Emission Spectroscopy Reveals Nonequilibrium Conditions for CO2 Splitting in Atmospheric Plasma Sustained with Ultrafast Microwave Pulsation

Among the pool of Power-to-X technologies, plasmas show high potential for the efficient use of intermittent renewable energies. High efficiencies of CO$_{2}$ conversion have been reported while using microwave plasmas at vacuum conditions which are, however, not suitable for CO$_{2}$ mitigation at industrial scales. Here we show that ultrafast pulsation of microwaves allow significant improvements of energy efficiencies during CO$_{2}$ splitting at atmospheric pressure as compared to continuous wave operation of the microwave source. Moreover, by the interrogation of the plasma with time-resolved optical emission spectroscopy we can, for the first time, observe the evolution of the vibrational and rotational temperatures and define a time window where nonequilibrium can be expected at the beginning of the pulse of an atmospheric CO$_{2}$ microwave plasma. In spite of the evidence of nonequilibrium in our system, thermal mechanism appears to dominate the CO$_{2}$ dissociation. It is shown that a fine control of the energy deposition in the plasma is possible with ultrafast pulsation of the microwave energy supply.

Ultrafast dynamics in the high-symmetry and in the charge density wave phase of 2H−NbSe2

We investigate carrier and collective mode dynamics in 2H-NbSe$_2$ using time-resolved optical pump-probe spectroscopy and compare the results with first-principle calculations. Broadband ultrafast reflectivity studies of 2H-NbSe$_2$ in a wide temperature interval covering the normal, charge density wave (CDW) and superconducting phase were performed. Spectral features observed in the transient reflectivity experiment were associated with specific optical transitions obtained from band structure calculations. Displacive excitation of coherent phonons showed CDW-associated coherent oscillations of the soft phonon mode across the whole spectral range. Temperature evolution of this coherent phonon mode in the low-excitation linear regime shows softening of the mode down to the CDW transition temperature T$_{CDW}$ with subsequent hardening below T$_{CDW}$. The global fit of the broadband probe data reveals four different relaxation times associated with characteristic electron-electron, electron-phonon and phonon-phonon relaxation processes. From first principle calculations of electron-phonon coupling we associate the few picosecond electron-phonon relaxation time $\tau_2$ with a specific group of phonons with frequencies around 20 meV. On the other hand, the anomalously long relaxation time of $\tau_3$~100 ps is associated with anharmonicity-driven phonon-phonon scattering. All relaxation processes result from anomalies near the second order CDW phase transition that are reflected in the temperature dependencies of the characteristic relaxation times and amplitudes of optical densities. At highest fluences we observe electronic melting of the CDW and disappearance of the mode hardening below T$_{CDW}$.

Emission dynamics of conjugated oligomer (BECV-DHF)/quantum dot perovskite [formula omitted] composites in solutions

In this paper, we performed steady-state spectroscopy and time-resolved optical spectroscopy (TRS) of conjugated oligomer 1,4-bis(9-ethyl-3-carbazo-vinylene)-9,9-dihexyl-fluorene (BECV-DHF)/perovskite quantum dot (PQD) (CsPbBr3) (LUMAR)] composites in solution. Furthermore, we investigated the lasing properties of the composites under nanosecond laser pumping. PQDs were dissolved in various solvents. These solutions were blended to form composite solutions with various weight ratios. The transmission, absorption, fluorescence, and band gap of BECV-DHF and PQDs were measured for various solvents and concentrations. Toluene was found to be the best solvent for blending PQDs and BECV-DHF. The absorption and fluorescence spectra of the blends showed the superposition of features of both materials. TEM analysis showed that the BECV-DHF and PQDs were separated by a distance of 9.75 Å. The calculated Förster radius between the BECV-DHF and PQDs was found to be approximately 50 Å – 60 Å. The presence of PQDs in the BECV-DHF solution reduces the lifetime of the excited states of BECV-DHF, and the fluorescence intensity of the PQDs precedes the fluorescence intensity of the BECV-DHF; hence, the underlying mechanism was Förster-type resonant energy transfer (FRET). The spectrally narrow peaks of PQDs and the BECV-DHF/PQDs were obtained at 523 nm using optical cavity. The spectral narrowing of the full width at half maximum (FWHM) was improved from 15 nm to 8.36 nm compared to BECV-DHF/PQDs with pure PQDs. This strategy of obtaining a short-chain stable laser material via the addition of conjugated oligomer could potentially facilitate the development of efficient optoelectronic devices.

Long-lived and disorder-free charge transfer states enable endothermic charge separation in efficient non-fullerene organic solar cells

Organic solar cells based on non-fullerene acceptors can show high charge generation yields despite near-zero donor–acceptor energy offsets to drive charge separation and overcome the mutual Coulomb attraction between electron and hole. Here, we use time-resolved optical spectroscopy to show that free charges in these systems are generated by thermally activated dissociation of interfacial charge-transfer states that occurs over hundreds of picoseconds at room temperature, three orders of magnitude slower than comparable fullerene-based systems. Upon free electron–hole encounters at later times, both charge-transfer states and emissive excitons are regenerated, thus setting up an equilibrium between excitons, charge-transfer states and free charges. Our results suggest that the formation of long-lived and disorder-free charge-transfer states in these systems enables them to operate closely to quasi-thermodynamic conditions with no requirement for energy offsets to drive interfacial charge separation and achieve suppressed non-radiative recombination.

Mechanism of Complexation of Cucurbiturils with Styryl Dyes in the Presence of Sodium Cations

The complexation of styryl dyes 4-[(E)-2-(3,4-dimethoxyphenyl)]-1-ethylpyridinium perchlorate and trans-4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide with cucurbit[n]urils (CBn) (n = 6, 7) in aqueous solutions in the presence of sodium sulfate with a concentration of 0 to 1 mol/L has been studied by stationary and time-resolved optical spectroscopy, electrochemical, and quantum chemical methods. Adding the electrolyte to the solution decomposes 1 : 1 inclusion complexes with the dyes (D+ · CBn) due to competitive formation of complexes of the cavitand with sodium cations: Na+ · CBn and Na+ · CBn · Na+. Their total formation constants have been determined to be β = 2760 and 168 600 M−2 for CB7 and CB6, respectively, which agrees with the results of quantum chemical calculations. At the same time, no evidence of the presence of Na+ · CBn · D+ type complexes has been found in solutions.

Control of hot-carrier relaxation time in Au-Ag thin films through alloying.

The plasmon resonance of a structure is primarily dictated by its optical properties and geometry, which can be modified to enable hot-carrier photodetectors with superior performance. Recently, metal alloys have played a prominent role in tuning the resonance of plasmonic structures through chemical composition engineering. However, it has been unclear how alloying modifies the time dynamics of the generated hot-carriers. In this work, we elucidate the role of chemical composition on the relaxation time of hot-carriers for the archetypal AuxAg1-x thin film system. Through time-resolved optical spectroscopy measurements in the visible wavelength range, we measure composition-dependent relaxation times that vary up to 8× for constant pump fluency. Surprisingly, we find that the addition of 2% of Ag into Au films can increase the hot-carrier lifetime by approximately 35% under fixed fluence, as a result of a decrease in optical loss. Further, the relaxation time is found to be inversely proportional to the imaginary part of the permittivity. Our results indicate that alloying is a promising approach to effectively control hot-carrier relaxation time in metals.

Single Copper Atoms Enhance Photoconductivity in g-C3N4.

Graphitic carbon nitride (g-C3N4) and its doped analogues have been studied over the past decade in part due to their promising applications in heterogeneous photocatalysis; however, the effect of doping on the photoconductivity is poorly understood. Herein, we investigate Cu doped g-C3N4 (Cu-g-C3N4) and demonstrate via extended X-ray absorption fine structure that Cu+ incorporates as an individual ion. Time-resolved optical pump terahertz probe spectroscopy was utilized to measure the ultrafast photoconductivity in response to a 400 nm pump pulse and showed that the Cu+ dopant significantly enhances photoconductivity of the as-prepared powdered sample, which decays within 10 ps. Furthermore, a film preparation technique was applied that further enhanced the photoconductivity and induced a longer-lived photoconductive state with a lifetime on the order of 100 ps. This study provides valuable insight into the ultrafast photoconductivity dynamics of g-C3N4 materials, which is essential toward developing efficient g-C3N4 photocatalysts.

Trion-Mediated Förster Resonance Energy Transfer and Optical Gating Effect in WS2/hBN/MoSe2 Heterojunction.

van der Waals two-dimensional layered heterostructures have recently emerged as a platform, where the interlayer couplings give rise to interesting physics and multifunctionalities in optoelectronics. Such couplings can be rationally controlled by dielectric, separation, and stacking angles, which affect the overall charge or energy-transfer processes, and emergent potential landscape for twistronics. Herein, we report the efficient Förster resonance energy transfer (FRET) in WS2/hBN/MoSe2 heterostructure, probed by both steady-state and time-resolved optical spectroscopy. We clarified the evolution behavior of the electron-hole pairs and free electrons from the trions, that is, ∼59.9% of the electron-hole pairs could transfer into MoSe2 by FRET channels (∼38 ps) while the free electrons accumulate at the WS2/hBN interface to photogate MoSe2. This study presents a clear picture of the FRET process in two-dimensional transition-metal dichalcogenides' heterojunctions, which establishes the scientific foundation for developing the related heterojunction optoelectronic devices.