Time-resolved Optical Techniques Research Articles

Recombination dynamics and manybody effect of excitons in large-area monolayer MoS2 capped with (111) NiO epitaxial layer

CVD grown monolayer MoS2 films on c-sapphire substrates are vacuum annealed and capped with (111) NiO epitaxial films using pulsed laser deposition technique. Time, energy and polarization resolved optical techniques are used to understand the effect of capping on the excitonic properties of the monolayer MoS2. It has been observed that trion contribution in the photoluminescence (PL) spectra increases after the capping, suggesting an enhancement of electron concentration in the conduction band. This has been attributed to the capping driven reduction of physisorbed air molecules from the sulphur vacancy ( VS ) sites. Note that the air molecules act as passivating agents for the VS -donors. Low temperature polarization resolved PL spectroscopy and ultrafast pump and probe transient absorption spectroscopy (TAS) show an increase of the biexcitonic population in the system after the encapsulation. The TAS study further reveals longer lifetime for both A and B excitons in capped samples implying a reduction of non-radiative recombination rate of the excitons after the capping. It has also been observed that in the capped samples, K/K′ valleys are populated with trions under sufficiently high pump powers. This has been attributed to the lower non-radiative recombination rates of the high energy photoexcited carriers and the faster transfer of either electrons or holes from the high energy pockets to the K/K′ valleys. The study further reveals different many-body effects in excitons and trions.

Characterization of Triplet State of Cyanine Dyes with Two Chromophores Effect of Molecule Structure

Quantum yields (φT) and energies (ET) of the first triplet state T1 for four molecules of cyanine dyes with two chromophores (BCDs), promising photoactive compounds for various applications, for example, as photosensitizers in photodynamic therapy (PDT) and fluorescence diagnostics (FD), were studied in 1-propanol solutions by steady-state and time-resolved optical absorption techniques. BCDs differ by the structure of the central heterocycle, connecting the chromophores. The heterocycle structure is responsible for electron tunneling between chromophores, for which efficiency can be characterized by splitting of the BCD triplet energy levels. It was shown that the increase in the tunneling efficiency reduces ET values and increases φT values. This aspect is very promising for the synthesis of new effective photosensitizers based on cyanine dyes with two interacting chromophores for various applications, including photodynamic therapy.

Refraction, beam splitting and dispersion of GHz surface acoustic waves by a phononic crystal

We exploit a time-resolved ultrafast optical technique to study the propagation of point-excited surface acoustic waves on a microscopic two-dimensional phononic crystal in the form of a square lattice of holes in a silicon substrate. Constant-frequency images and the dispersion relation are extracted, and the latter measured in detail in the region around the phononic band gap. Mode conversion and refraction at the interface between the phononic crystal and surrounding non-structured silicon substrate is studied at constant frequencies. Symmetric phonon beam splitting, for example, is shown to lead to a striking Maltese-cross pattern when phonons exit a square region of phononic crystal excited near its center.

Time-Resolved Optical Spectrum Measurement of Multi-Mode Fabry-Perot Laser Diodes

Fabry-Perot (FP) laser diodes usually have multiple longitudinal modes. An optical spectrum analyzer (OSA) is able to measure the average power distribution of the mode structure but cannot detect the dynamics of mode competition which is the origin of the mode partition noise. We demonstrate a time-resolved optical spectrum measurement technique based on frequency-to-time conversion through time gating, chromatic dispersion, and real-time waveform sampling. This allows to investigate the dynamics of mode competition and correlation of relative intensity noises among different FP modes of the diode laser.

Recent Development of Ultrafast Optical Characterizations for Quantum Materials.

The advent of intense ultrashort optical pulses spanning a frequency range from terahertz to the visible has opened a new era in the experimental investigation and manipulation of quantum materials. The generation of strong optical field in an ultrashort time scale enables the steering of quantum materials nonadiabatically, inducing novel phenomenon or creating new phases which may not have an equilibrium counterpart. Ultrafast time-resolved optical techniques have provided rich information and played an important role in characterization of the nonequilibrium and nonlinear properties of solid systems. Here, some of the recent progress of ultrafast optical techniques and their applications to the detection and manipulation of physical properties in selected quantum materials are reviewed. Specifically, the new development in the detection of the Higgs mode and photoinduced nonequilibrium response in the study of superconductors by time-resolved terahertz spectroscopy are discussed.

Rare earth effect on laser produced plasma dynamics during pulsed laser deposition of doped cobalt ferrite

The addition of rare earth elements the ferrites can lead to significant changes in structural, magnetic and electric properties of bulk materials and also of thin films deposited by pulsed laser deposition. The present study relies on the analysis of the laser induced plasma of three sets of cobalt ferrite targets doped with various concentrations of RE elements (Dy, Gd, Yb) and proposes a correlation of the derived results with structural investigations of the films obtained during the same experiment. ICCD imaging and space-and time-resolved optical emission spectroscopy techniques were used to obtain information on the dynamics and excitation temperatures of various species found in the laser produced plasmas (LPP). Initial investigations on the global behavior of the LPP revealed that the addition of RE reduced the drift velocities of the formed plasma structures, the lowest ones being observed for the targets doped with the heaviest RE (Yb). Space-and time-resolved spectroscopy measurements applied for all main elements (Fe, Co and RE - both neutral and ionic species) showed a complex dynamic system, with decreased/increased kinetic energies for neutrals/ions at high dopant concentrations, suggesting a possible re-sputtering effect at the films surface. The individual excitation temperatures of the main elements derived from Boltzmann plots increased as the RE content was augmented via radiative collision events due to their larger diameters compared with Co, Fe or O. The spatial distribution of electron temperature can be explained by the charge separation occurring with the addition of RE in the investigated systems.

(Invited) Ultrafast Charge Recombination and Localisation in Transition Metal Oxides with Extended Visible Light Absorption

The development of materials with high activity for photocatalytic water splitting is a central challenge for the production of renewable hydrogen using sunlight. Owing to advantages such as low cost, elemental abundance, and chemical stability, transition metal oxides (TMOs) are some of the most widely used materials for this purpose. The most efficient systems developed to date reach solar-to-hydrogen conversion efficiencies (STH) of around 1%1 and are based on wide bandgap TMOs such as SrTiO3.2 Because such wide bandgap materials often absorb UV light only, TMOs with extended visible light absorption are key to bridge the activity gap towards the target for commercial applications,3 often considered to be 10% STH.While large research efforts have been devoted to TMOs with smaller bandgaps, efficiencies for such materials have typically remained relatively far from their theoretical limit. For example, Fe2O3 is one of the most studied TMOs in the field of solar fuel production, but it has so far reached only 1/3 of its theoretical maximum activity for water oxidation,4 raising the question of limitations of more fundamental nature.In this talk, I will discuss the links between ultrafast charge recombination and polaron formation in TMOs – two of the main processes considered to impose efficiency limitations. Firstly, Fe2O3, Cr2O3, and Co3O4, which have absorption onsets of around 2.1 eV, 1.9 eV, and 1.6 eV, respectively, are studied using time-resolved optical spectroscopic techniques to probe their excited state dynamics on a timescale of femtoseconds to seconds following light absorption. I will demonstrate how common photophysical features and dynamics suggest a shared pathway for the recombination and localisation of photogenerated charges in these materials, but with different branching ratios. Secondly, a comparison to wide bandgap metal oxides reveals a different relative importance of these recombination and localisation pathways compared to TMOs with smaller bandgaps. Taken together, a more general photophysical model emerges, providing insights into the performance limiting factors in TMOs, including those with extended visible light absorption.

Impact of the Anthryl Linking Mode on the Photophysics and Excited-State Dynamics of Re(I) Complexes [ReCl(CO)3(4'-An-terpy-κ2N)

Rhenium(I) complexes with 2,2′:6′,2″-terpyridines (terpy) substituted with 9-anthryl (1) and 2-anthryl (2) were synthesized, and the impact of the anthryl linking mode on the ground- and excited-state properties of resulting complexes [ReCl(CO)3(4′-An-terpy-κ2N)] (An—anthryl) was investigated using a combination of steady-state and time-resolved optical techniques accompanied by theoretical calculations. Different attachment positions of anthracene modify the overlap between the molecular orbitals and thus the electronic coupling of the anthracene and {ReCl(CO)3(terpy-κ2N)} chromophores. Following the femtosecond transient absorption, the lowest triplet excited state of both complexes was found to be localized on the anthracene chromophore. The striking difference between 1 and 2 concerns the triplet-state formation dynamics. A more planar geometry of 2-anthryl-terpy (2), and thus better electronic communication between the anthracene and {ReCl(CO)3(terpy-κ2N)} chromophores, facilitates the formation of the 3An triplet state. In steady-state photoluminescence spectra, the population ratio of 3MLCT and 3An was found to be dependent not only on the anthryl linking mode but also on solvent polarity and excitation wavelengths. In dimethyl sulfoxide (DMSO), compounds 1 and 2 excited with λexc > 410 nm show both 3MLCT and 3An emissions, which are rarely observed. Additionally, the abilities of the designed complexes for 1O2 generation and light emission under the external voltage were preliminary examined.

On the Deposition Process of Ceramic Layer Thin Films for Low-Carbon Steel Pipe Protection.

Ceramic thin films with variable thicknesses have been used in many applications. In order to protect the petroleum transportation pipes against the harmful H2S action, two ceramic materials as thin layers are proposed. In this article, pulsed laser deposition (PLD) of ceramic layers by in situ time-resolved optical techniques is investigated. Two ceramic materials were used as targets and real-time monitoring of the PLD process was realized via ICCD fast camera imaging and optical emission spectroscopy. The space–time displacement of the ceramic emissions was analyzed in order to determine the plasma structure and respective kinetic energies. Spectral-resolved investigation allowed the determination of plasma species individual velocities (in the first case: 43 km/s for C ionic species, 11 km/s for Si, from 25 to 5 km/s for atomic species; in the second case: 32 km/s for C ionic species, 11 km/s for W species, and 15 and 53 km/s for neutral species). SEM and AFM techniques were implemented to analyze the resulting ceramic layers showing homogeneous surfaces with characteristic material droplets. The ablation crater also reveals selective ablation during the deposition process. EDX results show that Al/Si is retained in the thin films similar to the target composition.

Novel Cu(I)-5-nitropyridine-2-thiol Cluster with NIR Emission: Structural and Photophysical Characterization.

A novel Cu(I) cluster compound has been synthesized by reacting CuI with the 2,2′-dithiobis(5-nitropyridine) ligand under solvothermal conditions. During the reaction, the original ligand breaks into the 5-nitropyridine-2-thiolate moiety, which acts as the coordinating ligand with both N- and S-sites, leading to a distorted octahedral Cu6S6 cluster. The structure has been determined by single-crystal X-ray diffraction and FT-IR analysis, and the photophysical properties have been determined in the solid state by means of steady-state and time-resolved optical techniques. The cluster presents a near-infrared emission showing an unusual temperature dependence: when passing from 77 to 298 K, a blue-shift of the emission band is observed, associated with a decrease in its intensity. Time-dependent-density functional theory calculations suggest that the observed behavior can be ascribed to a complex interplay of excited states, basically in the triplet manifold.

Time-resolved vibrational-pump visible-probe spectroscopy for thermal conductivity measurement of metal-halide perovskites.

Understanding thermal transport at the microscale to the nanoscale is crucially important for a wide range of technologies ranging from device thermal management and protection systems to thermal-energy regulation and harvesting. In the past decades, non-contact optical methods, such as time-domain and frequency-domain thermoreflectance, have emerged as extremely powerful and versatile thermal metrological techniques for the measurement of material thermal conductivities. Here, we report the measurement of thermal conductivity of thin films of CH3NH3PbI3 (MAPbI3), a prototypical metal-halide perovskite, by developing a time-resolved optical technique called vibrational-pump visible-probe (VPVP) spectroscopy. The VPVP technique relies on the direct thermal excitation of MAPbI3 by femtosecond mid-infrared optical pump pulses that are wavelength-tuned to a vibrational mode of the material, after which the time dependent optical transmittance across the visible range is probed in the ns to the μs time window using a broadband pulsed laser. Using the VPVP method, we determine the thermal conductivities of MAPbI3 thin films deposited on different substrates. The transducer-free VPVP method reported here is expected to permit spectrally resolving and spatiotemporally imaging of the dynamic lattice temperature variations in organic, polymeric, and hybrid organic-inorganic semiconductors.

Nonthermal Transport of Energy Driven by Photoexcited Carriers in Switchable Solid States of GeTe

Phase change alloys have seen widespread use from rewritable optical discs to the present day interest in their use in emerging neuromorphic computing architectures. In spite of this enormous commercial interest, the physics of carriers in these materials is still not fully understood. Here, we describe the time and space dependence of the coupling between photoexcited carriers and the lattice in both the amorphous and crystalline states of one phase change material, GeTe. We study this using a time-resolved optical technique called picosecond acoustic method to investigate the \textit{in situ} thermally assisted amorphous to crystalline phase transformation in GeTe. Our work reveals a clear evolution of the electron-phonon coupling during the phase transformation as the spectra of photoexcited acoustic phonons in the amorphous ($a$-GeTe) and crystalline ($\alpha$-GeTe) phases are different. In particular and surprisingly, our analysis of the photoinduced acoustic pulse duration in crystalline GeTe suggests that a part of the energy deposited during the photoexcitation process takes place over a distance that clearly exceeds that defined by the pump light skin depth. In the opposite, the lattice photoexcitation process remains localized within that skin depth in the amorphous state. We then demonstrate that this is due to supersonic diffusion of photoexcited electron-hole plasma in the crystalline state. Consequently these findings prove the existence of a non-thermal transport of energy which is much faster than lattice heat diffusion.

A time-domain phase diagram of metastable states in a charge ordered quantum material

Metastable self-organized electronic states in quantum materials are of fundamental importance, displaying emergent dynamical properties that may be used in new generations of sensors and memory devices. Such states are typically formed through phase transitions under non-equilibrium conditions and the final state is reached through processes that span a large range of timescales. Conventionally, phase diagrams of materials are thought of as static, without temporal evolution. However, many functional properties of materials arise as a result of complex temporal changes in the material occurring on different timescales. Hitherto, such properties were not considered within the context of a temporally-evolving phase diagram, even though, under non-equilibrium conditions, different phases typically evolve on different timescales. Here, by using time-resolved optical techniques and femtosecond-pulse-excited scanning tunneling microscopy (STM), we track the evolution of the metastable states in a material that has been of wide recent interest, the quasi-two-dimensional dichalcogenide 1T-TaS2. We map out its temporal phase diagram using the photon density and temperature as control parameters on timescales ranging from 10−12 to 103 s. The introduction of a time-domain axis in the phase diagram enables us to follow the evolution of metastable emergent states created by different phase transition mechanisms on different timescales, thus enabling comparison with theoretical predictions of the phase diagram, and opening the way to understanding of the complex ordering processes in metastable materials.

Back to the Future: Genetically Encoded Fluorescent Proteins as Inert Tracers of the Intracellular Environment.

Over the past decades, the discovery and development of genetically encoded fluorescent proteins (FPs) has brought a revolution into our ability to study biologic phenomena directly within living matter. First, FPs enabled fluorescence-labeling of a variety of molecules of interest to study their localization, interactions and dynamic behavior at various scales—from cells to whole organisms/animals. Then, rationally engineered FP-based sensors facilitated the measurement of physicochemical parameters of living matter—especially at the intracellular level, such as ion concentration, temperature, viscosity, pressure, etc. In addition, FPs were exploited as inert tracers of the intracellular environment in which they are expressed. This oft-neglected role is made possible by two distinctive features of FPs: (i) the quite null, unspecific interactions of their characteristic β-barrel structure with the molecular components of the cellular environment; and (ii) their compatibility with the use of time-resolved fluorescence-based optical microscopy techniques. This review seeks to highlight the potential of such unique combinations of properties and report on the most significative and original applications (and related advancements of knowledge) produced to date. It is envisioned that the use of FPs as inert tracers of living matter structural organization holds a potential for several lines of further development in the next future, discussed in the last section of the review, which in turn can lead to new breakthroughs in bioimaging.

Influence of heating effect in Thomson scattering diagnosis of laser-produced plasmas in air

A state diagnosis of laser-produced plasma in air generated by a 1064 nm pulse laser was investigated by the Thomson scattering (TS) method. The evolutions of the electron temperature and electron density were obtained as a function of the time delay which ranged from 300–3200 ns. The heating effect produced by the 532 nm probe beam with different energies on the air plasma at different interaction times was further studied using a time-resolved optical emission spectroscopy technique. The influence of the probe beam on the electron density was found to be negligible, whereas its influence on electron temperature is evident. In addition, the heating effect of the probe beam on the plasma strongly depends on the energy of the probe beam, and gradually weakens with increasing time delay. Our results are helpful for further understanding the TS method and its application in plasma diagnostics.

Improvement of the timing properties of Ce-doped oxyorthosilicate LYSO scintillating crystals

The aim of this work has been to improve the time resolution of radiation detectors for future high-energy physics experiments and medical imaging applications. Ce-doped oxyorthosilicate Lu2SiO5:Ce (LSO) and mixed oxyorthosilicate Lu1.6Y0.4SiO5:Ce (LYSO) have been investigated as prospective scintillators for such high-time-resolution applications. A differential optical absorption technique with sub-picosecond time resolution upon selective excitation of Ce3+ ions to different excited states has been adopted to study carrier dynamics in these scintillators, and coincidence time resolution measured using 511 keV γ-quanta has been exploited to test their timing properties. A delay in population of the emitting level of Ce3+ has been observed, and is interpreted in terms of electron trapping, which is more pronounced in mixed yttrium-containing LYSO crystals due to composition fluctuations. It is shown that the delay, which affects the luminescence response time, can be eliminated by co-doping of LYSO:Ce with calcium at concentrations as low as 5 ppm. The faster kinetics of electron transfer correlates with a better coincidence time resolution. Thermalization and spatial distribution of non-equilibrium carriers has been studied theoretically to link the results obtained by the time-resolved differential optical absorption technique with the behavior of the non-equilibrium carriers generated by irradiation.

A time-domain view of charge carriers in semiconductor nanocrystal solids.

The movement of charge carriers within semiconductor nanocrystal solids is fundamental to the operation of nanocrystal devices, including solar cells, LEDs, lasers, photodetectors, and thermoelectric modules. In this perspective, we explain how recent advances in the measurement and simulation of charge carrier dynamics in nanocrystal solids have led to a more complete picture of mesoscale interactions. Specifically, we show how time-resolved optical spectroscopy and transient photocurrent techniques can be used to track both equilibrium and non-equilibrium dynamics in nanocrystal solids. We discuss the central role of energetic disorder, the impact of trap states, and how these critical parameters are influenced by chemical modification of the nanocrystal surface. Finally, we close with a forward-looking assessment of emerging nanocrystal systems, including anisotropic nanocrystals, such as nanoplatelets, and colloidal lead halide perovskites.

Exclusive triplet electron transfer leading to long-lived radical ion-pair formation in an electron rich platinum porphyrin covalently linked to fullerene dyad.

The formation of a high-energy, long-lived radical ion-pair by electron transfer exclusively from the triplet excited state, is demonstrated in a newly synthesized platinum porphyrin-fullerene dyad, in which the porphyrin ring is modified with three electron rich triphenylamine entities. The spin selectivity of the electron transfer leading to the formation of the radical ion-pair is demonstrated using time-resolved optical and EPR spectroscopic techniques.

Enforcing Extended Porphyrin J-Aggregate Stacking in Covalent Organic Frameworks.

The potential of covalent organic frameworks (COFs) for realizing porous, crystalline networks with tailored combinations of functional building blocks has attracted considerable scientific interest in the fields of gas storage, photocatalysis, and optoelectronics. Porphyrins are widely studied in biology and chemistry and constitute promising building blocks in the field of electroactive materials, but they reveal challenges regarding crystalline packing when introduced into COF structures due to their nonplanar configuration and strong electrostatic interactions between the heterocyclic porphyrin centers. A series of porphyrin-containing imine-linked COFs with linear bridges derived from terephthalaldehyde, 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, 4,4′-biphenyldicarboxaldehyde and thieno[3,2-b]thiophene-2,5-dicarboxaldehyde, were synthesized, and their structural and optical properties were examined. By combining X-ray diffraction analysis with density-functional theory (DFT) calculations on multiple length scales, we were able to elucidate the crystal structure of the newly synthesized porphyrin-based COF containing thieno[3,2-b]thiophene-2,5-dicarboxaldehyde as linear bridge. Upon COF crystallization, the porphyrin nodes lose their 4-fold rotational symmetry, leading to the formation of extended slipped J-aggregate stacks. Steady-state and time-resolved optical spectroscopy techniques confirm the realization of the first porphyrin J-aggregates on a > 50 nm length scale with strongly red-shifted Q-bands and increased absorption strength. Using the COF as a structural template, we were thus able to force the porphyrins into a covalently embedded J-aggregate arrangement. This approach could be transferred to other chromophores; hence, these COFs are promising model systems for applications in photocatalysis and solar light harvesting, as well as for potential applications in medicine and biology.

OH* Chemiluminescence Imaging of the Combustion Products From a Methane-Fueled Rotating Detonation Engine

Pressure gain combustion (PGC) has been conceived to convert fuel's chemical energy into thermal energy and mechanical energy, thereby reducing the entropy production in the process. Recent research has shown that the rotating detonation combustor (RDC) can provide excellent specific thrust, specific impulse, and pressure gain within a small volume through rapid energy release by continuous detonation in the circumferential direction. The RDC as a PGC system for power generating gas turbines in combined cycle power plants could provide significant efficiency gains. However, few past studies have employed fuels that are relevant to power generation turbines, since RDC research has focused mainly on propulsion applications. In this study, we present experimental results from RDC operated on methane and oxygen-enriched air to represent reactants used in land-based power generation. The RDC is operated at a high pressure by placing a back-pressure plate downstream of the annular combustor. Past studies have focused mainly on probe measurements inside the combustor, and thus, little information is known about the nature of the products exiting the RDC. In particular, it is unknown if chemical reactions persist outside the RDC annulus, especially if methane is used as the fuel. In this study, we apply two time-resolved optical techniques to simultaneously image the RDC products at framing rate of 30 kHz: (1) direct visual-imaging to identify the overall size and extent of the plume, and (2) OH* chemiluminescence imaging to detect the reaction zones if any. Results show dynamic features of the combustion products that are consistent with the probe measurements inside the rotating detonation engine (RDE). Moreover, presence of OH* in the products suggests that the oblique shock wave and reactions persist downstream of the detonation zone in the RDC.