Time-resolved Optical Measurements Research Articles

Time-resolved optical absorption measurements of calcium fluoride crystals

This paper examines time-resolved optical absorption measurements in a CaF2 crystal. It is shown that defects with a concentration of about 1017 cm−3 are introduced into the sample within about 10−8 s. The decay curves of defects created by a nanosecond electron pulse in CaF2 were measured in the temperature range from 300 to 700 K. It is found that decay curves are decomposed into three bimolecular decay stages. The totality of the obtained experimental data can be consistently explained within the framework of the assumption of thermal disorder of the fluorite anionic sublattice. The result of electron-hole recombination is the formation of fairly “simple” defect structures in the CaF2 crystal.

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.

Spin wavepackets in the Kagome ferromagnet Fe3Sn2: Propagation and precursors

The propagation of spin waves in magnetically ordered systems has emerged as a potential means to shuttle quantum information over large distances. Conventionally, the arrival time of a spin wavepacket at a distance, d, is assumed to be determined by its group velocity, vg. Here, we report time-resolved optical measurements of wavepacket propagation in the Kagome ferromagnet Fe3Sn2 that demonstrate the arrival of spin information at times significantly less than d/vg. We show that this spin wave "precursor" originates from the interaction of light with the unusual spectrum of magnetostatic modes in Fe3Sn2. Related effects may have far-reaching consequences toward realizing long-range, ultrafast spin wave transport in both ferromagnetic and antiferromagnetic systems.

Optical Saturation Produces Spurious Evidence for Photoinduced Superconductivity in K_{3}C_{60}.

We discuss a systematic error in time-resolved optical conductivity measurements that becomes important at high pump intensities. We show that common optical nonlinearities can distort the photoconductivity depth profile, and by extension distort the photoconductivity spectrum. We show evidence that this distortion is present in existing measurements on K_{3}C_{60}, and describe how it may create the appearance of photoinduced superconductivity where none exists. Similar errors may emerge in other pump-probe spectroscopy measurements, and we discuss how to correct for them.

Effect of Air Exposure on Electron-Beam-Induced Degradation of Perovskite Films.

Organic-inorganic halide perovskites are interesting candidates for solar cell and optoelectronic applications owing to their advantageous properties such as a tunable band gap, low material cost, and high charge carrier mobilities. Despite making significant progress, concerns about material stability continue to impede the commercialization of perovskite-based technology. In this article, we investigate the impact of environmental parameters on the alteration of structural properties of MAPbI3 (CH3NH3PbI3) thin films using microscopy techniques. These characterizations are performed on MAPbI3 thin films exposed to air, nitrogen, and vacuum environments, the latter being possible by using dedicated air-free transfer setups, after their fabrication into a nitrogen-filled glovebox. We observed that even less than 3 min of air exposure increases the sensitivity to electron beam deterioration and modifies the structural transformation pathway as compared to MAPbI3 thin films which are not exposed to air. Similarly, the time evolution of the optical responses and the defect formation of both air-exposed and non-air-exposed MAPbI3 thin films are measured by time-resolved photoluminescence. The formation of defects in the air-exposed MAPbI3 thin films is first observed by optical techniques at longer timescales, while structural modifications are observed by transmission electron microscopy (TEM) measurements and supported by X-ray photoelectron spectroscopy (XPS) measurements. Based on the complementarity of TEM, XPS, and time-resolved optical measurements, we propose two different degradation mechanism pathways for air-exposed and non-air-exposed MAPbI3 thin films. We find that when exposed to air, the crystalline structure of MAPbI3 shows gradual evolution from its initial tetragonal MAPbI3 structure to PbI2 through three different stages. No significant structural changes over time from the initial structure are observed for the MAPbI3 thin films which are not exposed to air.

Interface Engineering Modulated Valley Polarization in MoS2/hBN Heterostructure

Layered transition metal dichalcogenides (TMDs) provide a favorable research platform for the advancement of spintronics and valleytronics because of their unique spin-valley coupling effect, which is attributed to the absence of inversion symmetry coupled with the presence of time-reversal symmetry. To maneuver the valley pseudospin efficiently is of great importance for the fabrication of conceptual devices in microelectronics. Here, we propose a straightforward way to modulate valley pseudospin with interface engineering. An underlying negative correlation between the quantum yield of photoluminescence and the degree of valley polarization was discovered. Enhanced luminous intensities were observed in the MoS2/hBN heterostructure but with a low value of valley polarization, which was in stark contrast to those observed in the MoS2/SiO2 heterostructure. Based on the steady-state and time-resolved optical measurements, we reveal the correlation between exciton lifetime, luminous efficiency, and valley polarization. Our results emphasize the significance of interface engineering for tailoring valley pseudospin in two-dimensional systems and probably advance the progression of the conceptual devices based on TMDs in spintronics and valleytronics.

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.

Light-induced Weyl semiconductor-to-metal transition mediated by Peierls instability

Elemental tellurium is a strongly spin-orbit coupled Peierls-distorted semiconductor whose band structure features topologically protected Weyl nodes. Using time-dependent density functional theory calculations, we show that impulsive optical excitation can be used to transiently control the amplitude of the Peierls distortion, realizing a mechanism to switch tellurium between three states: Weyl semiconductor, Weyl metal and non-Weyl metal. Further, we present experimental evidence of this inverse-Peierls distortion using time-resolved optical second harmonic generation measurements. These results provide a pathway to multifunctional ultrafast Weyl devices and introduce Peierls systems as viable hosts of light-induced topological transitions.

Dynamical criticality of spin-shear coupling in van der Waals antiferromagnets

The interplay between a multitude of electronic, spin, and lattice degrees of freedom underlies the complex phase diagrams of quantum materials. Layer stacking in van der Waals (vdW) heterostructures is responsible for exotic electronic and magnetic properties, which inspires stacking control of two-dimensional magnetism. Beyond the interplay between stacking order and interlayer magnetism, we discover a spin-shear coupling mechanism in which a subtle shear of the atomic layers can have a profound effect on the intralayer magnetic order in a family of vdW antiferromagnets. Using time-resolved X-ray diffraction and optical linear dichroism measurements, interlayer shear is identified as the primary structural degree of freedom that couples with magnetic order. The recovery times of both shear and magnetic order upon optical excitation diverge at the magnetic ordering temperature with the same critical exponent. The time-dependent Ginzburg-Landau theory shows that this concurrent critical slowing down arises from a linear coupling of the interlayer shear to the magnetic order, which is dictated by the broken mirror symmetry intrinsic to the monoclinic stacking. Our results highlight the importance of interlayer shear in ultrafast control of magnetic order via spin-mechanical coupling.

Low-Frequency Oscillations in Optical Measurements of Metal-Nanoparticle Vibrations.

Time-resolved optical measurements of vibrating metal nanoparticles have been used extensively to probe the ultrafast mechanical properties of the nanoparticles and of the surrounding liquid, but nearly all investigations so far have been limited to the linear regime. Here, we report the observation of a low-frequency oscillating signal in transient-absorption measurements of nanoparticles with octahedral gold cores and cubic silver shells; the signal appears at the difference of two mechanical vibrational frequencies in the particles, suggesting a nonlinear mixing process. We tentatively attribute this proposed mixing to a nonlinear coupling between a vibrational mode of the nanoparticle and its optical-frequency plasmon resonance. The optimization of this nonlinear transduction may enable high-efficiency opto-mechanical frequency mixing in the GHz-THz frequency regime.

Optical spectroscopy and ultrafast pump-probe study of a quasi-one-dimensional charge density wave in CuTe

CuTe is a two-dimensional (2D) layered material; yet it forms a quasi-one-dimensional (quasi-1D) charge-density-wave (CDW) along the $a$ axis in the $ab$ plane at high transition temperature ${T}_{\mathrm{CDW}}=335\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. However, the anisotropic properties of CuTe remain to be explored. Here, we performed combined transport, polarized infrared reflectivity, and ultrafast pump-probe spectroscopy studies to investigate the underlying CDW physics of CuTe. Polarized optical measurements clearly revealed that an energy gap gradually forms along the $a$ axis upon cooling, while optical evidence of a gap signature is absent along the $b$ axis, suggesting pronounced electronic anisotropy in this quasi-2D material. Time-resolved optical reflectivity measurements revealed that the amplitude and relaxation time of photoexcited quasiparticles change dramatically across the CDW phase transition. Performing fast Fourier transformation of the oscillation signals arising from collective excitations, we identify the 1.65-THz mode as the CDW amplitude mode, whose energy softens gradually at elevated temperatures. Consequently, we provide further evidence for the formation of completely anisotropic CDW order in CuTe, which is quite rare in quasi-2D materials.

Investigation of Thermally Activated Delayed Fluorescence in Donor–Acceptor Organic Emitters with Time-Resolved Absorption Spectroscopy

In this contribution, we utilize multiple time-resolved and nonlinear optical measurements and quantum chemical simulations to investigate the excited-state dynamics of organic chromophores with thermally activated delayed fluorescent (TADF) characteristics. We are most interested in probing the influence of a phenylene linker on the photophysical properties of emitters composed of carbazole-based donors linked to either a phthalonitrile (PN) or diphenyltriazine (Trz) acceptor. The PN-acceptor compounds display a near double-fluorescence quantum yield (ΦF) enhancement in oxygen-free conditions. The fluorescent lifetime measurements indicate that the Trz-acceptor compounds are more efficient fluorescence emitters and quickly go from a delocalized to localized state. They also reveal that only the PN-acceptor compounds display a long-lived emissive lifetime component associated with TADF activity. Analysis of the nanosecond transient absorption spectra and kinetics reveals long-lived excited-state absorption (ESA) bands associated with triplet states for the PN-acceptor compounds. No ESA bands were observed for the Trz-acceptor compounds, despite observing a quantum yield enhancement for the Trz-acceptor compounds after oxygen purging. From the transient absorption measurements, it was determined that the PN-acceptor compounds have reverse intersystem crossing rates (krISC) that are able to compete with other triplet decay pathways. From quantum chemical calculations, it is proposed that inclusion of the phenylene linker prevents sufficient highest occupied molecular orbital/lowest unoccupied molecular orbital separation and suppresses TADF activity and that directly linking multiple donors to the acceptor will aid in achieving TADF activity.

Boosting quantum yields in two-dimensional semiconductors via proximal metal plates

Monolayer transition metal dichalcogenides (1L-TMDs) have tremendous potential as atomically thin, direct bandgap semiconductors that can be used as convenient building blocks for quantum photonic devices. However, the short exciton lifetime due to the defect traps and the strong exciton-exciton interaction in TMDs has significantly limited the efficiency of exciton emission from this class of materials. Here, we show that exciton-exciton interaction in 1L-WS2 can be effectively screened using an ultra-flat Au film substrate separated by multilayers of hexagonal boron nitride. Under this geometry, induced dipolar exciton-exciton interaction becomes quadrupole-quadrupole interaction because of effective image dipoles formed within the metal. The suppressed exciton-exciton interaction leads to a significantly improved quantum yield by an order of magnitude, which is also accompanied by a reduction in the exciton-exciton annihilation (EEA) rate, as confirmed by time-resolved optical measurements. A theoretical model accounting for the screening of the dipole-dipole interaction is in a good agreement with the dependence of EEA on exciton densities. Our results suggest that fundamental EEA processes in the TMD can be engineered through proximal metallic screening, which represents a practical approach towards high-efficiency 2D light emitters.

Hydrogen peroxide disproportionation: time-resolved optical measurements of spectra, scattering and imaging combined with correlation analysis and simulations

We study how time-dependent optical measurements of spectra, scattering, and imaging can be used to add to the understanding of heterogeneous reactions, compared to work performed using tools developed for homogeneous reactions. Using hydrogen peroxide disproportionation by potassium permanganate as a model reaction, we measure the entire spectrum over reaction time, enabling a clear and useful correlation analysis and assignment of chemical species in heterogeneous conditions. We measure time-dependent dynamic light scattering to study oxygen nanobubble product formation kinetics and equilibrium. We perform macroscopic video-rate reaction imaging and information-theoretic analysis to characterize reaction and transport contributions to the observed signal. To illustrate the differences arising from measuring sample subsets vs the entire system, we integrate stochastic and macroscopic numerical simulations of reaction-diffusion to study homogeneous and heterogeneous reaction conditions. We hope the tools presented here may help understanding other chemical reactions in similar conditions.

Photo-Thermal Switching of Individual Plasmonically Activated Spin Crossover Nanoparticle Imaged by Ultrafast Transmission Electron Microscopy.

Spin crossover (SCO) is a promising switching phenomenon when implemented in electronic devices as molecules, thin films or nanoparticles. Among the properties modulated along this phenomenon, optically induced mechanical changes are of tremendous importance as they can work as fast light-induced mechanical switches or allow to investigate and control microstructural strains and fatigability. The development of characterization techniques probing nanoscopic behavior with high spatio-temporal resolution allows to trigger and visualize such mechanical changes of individual nanoscopic objects. Here, ultrafast transmission electron microscopy (UTEM) is used to precisely probe the length changes of individual switchable nanoparticles induced thermally by nanosecond laser pulses. This allows revealing of the mechanisms of spin switching, leading to the macroscopic expansion of SCO materials. This study is conducted on individual pure SCO nanoparticles and SCO nanoparticles encapsulating gold nanorods that serve for plasmonic heating under laser pulses. Length changes are compared with time-resolved optical measurements performed on an assembly of these particles.

A new internally heated diamond anvil cell system for time-resolved optical and X-ray measurements

A new internally heated diamond anvil cell system for time-resolved optical and X-ray measurements

Electron temperature measurements with a hairpin resonator probe in a pulsed low pressure capacitively coupled plasma

Electron temperature is measured from time resolved hairpin resonator probe measurements in a pulsed capacitively coupled argon plasma at 400 mTorr. Effective collision frequency is related to the electron energy distribution via the effective conductivity and closes a system of equations that allow electron temperature to be determined. Results generally show good agreement with expected behavior and unfiltered time-resolved optical emission measurements.

Conserved residue PsaB-Trp673 is essential for high-efficiency electron transfer between the phylloquinones and the iron-sulfur clusters in Photosystem I.

Despite the high level of symmetry between the PsaA and PsaB polypeptides in Photosystem I, some amino acids pairs are strikingly different, such as PsaA-Gly693 and PsaB-Trp673, which are located near a cluster of 11 water molecules between the A1A and A1B quinones and the FX iron-sulfur cluster. In this work, we changed PsaB-Trp673 to PsaB-Phe673 in Synechocystis sp. PCC 6803. The variant contains ~ 85% of wild-type (WT) levels of Photosystem I but is unable to grow photoautotrophically. Both time-resolved and steady-state optical measurements show that in the PsaB-W673F variant less than 50% of the electrons reach the terminal iron-sulfur clusters FA and FB; the majority of the electrons recombine from A1A- and A1B-. However, in those reaction centers which pass electrons forward the transfer is heterogeneous: a minor population shows electron transfer rates from A1A- and A1B- to FX slightly slower than that of the WT, whereas a major population shows forward electron transfer rates to FX slowed to the ~ 10 µs time range. Competition between relatively similar forward and backward rates of electron transfer from the quinones to the FX cluster account for the relatively low yield of long-lived charge separation in the PsaB-W673F variant. A higher water content and its increased mobility observed in MD simulations in the interquinone cavity of the PsaB-W673F variant shifts the pK of PsaB-Asp575 and allows its deprotonation in situ. The heterogeneity found may be rooted in protonation state of PsaB-Asp575, which controls whether electron transfer can proceed beyond the phylloquinone cofactors.

Ultrafast Spin Dynamics of Electrochemically Grown Heusler Alloy Films

The electrochemical growth of Heusler alloy film with good morphological quality and crystalline order using single-crystalline substrate is demonstrated. Static magneto optical Kerr effect studies are employed to reveal the surface magnetization reversal of the films. An understanding of the intrinsic nature of the magnetization dynamics in this class of electrochemically grown materials is presented using time-resolved magneto optical Kerr effect measurements, under femtosecond laser excitation. Excitation laser fluence dependence study reveals the ultrafast demagnetization time, fast remagnetization time, and magnetic damping parameter as well as their correlation. © 2021 American Chemical Society. All rights reserved.

Highly Spherical Nanoparticles Probe Gigahertz Viscoelastic Flows of Simple Liquids Without the No-Slip Condition.

Simple liquids are conventionally described by Newtonian fluid mechanics, based on the assumption that relaxation processes in the flow occur much faster than the rate at which the fluid is driven. Nanoscale solids, however, have characteristic mechanical response times on the picosecond scale, which are comparable to mechanical relaxation times in simple liquids; as a result, viscoelastic effects in the liquid must be considered. These effects have been observed using time-resolved optical measurements of vibrating nanoparticles, but interpretation has often been complicated by finite velocity slip at the liquid-solid interface. Here, we use highly spherical gold nanoparticles to drive flows that are theoretically modeled without the use of the no-slip boundary condition at the particle surface. We obtain excellent agreement with this analytical theory that considers both the compression and shear relaxation properties of the liquid.