Optical-phonon mediated exciton energy relaxation with highly preserved spin states Optical-phonon mediated exciton energy relaxation with highly preserved spin states in a single quantum dot
H. Kumano, H. Kobayashi, S. Ekuni, Y. Hayashi, M. Jo, H. Sasakura, S. Adachi, S. Muto, I. Suemune
High degree of preservation of spin states during energy relaxation processes mediated by optical phonons is demonstrated in a single quantum dot. Optical-phonon resonance and relevant suppression of spin relaxation are clearly identified as dip structures in photoluminescence excitation spectra probed by the positive trion emission. The absence of continuum states makes this observation possible under the cross-circularly polarized detection with respect to a circularly polarized pumping. Consequently, distinguishably high degree of circular polarization up to ~0.85 is achieved without applying external magnetic field at the optical-phonon resonance. Rate equation analysis reveals that the spin-flip probability during energy relaxation is restricted to less than 7.5%. It is also indicated that the spin flip time of the positive trion ground state is extended by more than 3 times compared with that of neutral exciton ground state. This corresponds to the spin flip time longer than 11 ns for the positive trion ground state. The influence of nuclear polarization to the present measurements is also discussed.
Perovskites have been the focus of attention due to their multitude of outstanding optoelectronic properties and structural versatility. Two-dimensional halide perovskite such as (C_6H_5C_2H_4NH_3)_2PbI_4, or simply PEPI, forms natural multiple quantum wells with enhanced light-matter interactions, making them attractive systems for further investigation. This work reports tunable splitting of exciton modes in PEPI resulting from strong light-matter interactions, manifested as multiple dips (modes) in the reflection spectra. While the origin of the redder mode is well understood, that for the …
Efficient energy transport is highly desirable for organic semiconductor (OSC) devices such as photovoltaics, photodetectors, and photocatalytic systems. However, photo-generated excitons in OSC films mostly occupy highly localized states over their lifetime. Energy transport is hence thought to be mainly mediated by the site-to-site hopping of localized excitons, limiting exciton diffusion coefficients to below ~10^{-2} cm^2/s with corresponding diffusion lengths below ~50 nm. Here, using ultrafast optical microscopy combined with non-adiabatic molecular dynamics simulations, we present evide…
Free electrons or holes can mediate the nonradiative recombination of excitons in carbon nanotubes. Kinematic constraints arising from the quasi one-dimensional nature of excitons and charge carriers lead to a thermal activation barrier for the process. However, a model calculation suggests that the rate for recombination mediated by a free electron is the same order of magnitude as that of two-exciton recombination. Small amounts of doping may contribute to the short exciton lifetimes and low quantum yields observed in carbon nanotubes.
Exciton Coherence in CsPbBr3 Nanocrystals is Bounded by Phonon-Mediated Bright-Triplet Relaxation
Massachusetts Institute of Technology（麻省理工学院）；Center for Hybrid Organic Inorganic Semiconductors for Energy（有机无机半导体混合能源中心）；National Laboratory of the Rockies（落基山国家实验室）；U.S. Naval Research Laboratory（美国海军研究实验室）；Lund University（隆德大学）
Moiré potentials in two-dimensional materials have been proven to be of fundamental importance to fully understand the electronic structure of van der Waals heterostructures, from superconductivity to correlated excitonic states. However, understanding how the moiré phonons, so-called phasons, affect the properties of the system still remains an uncharted territory. In this work, we demonstrate how phasons are integral to properly describing and understanding low-temperature interlayer exciton diffusion in WS2/WSe2 heterostructure. We perform photoluminescence (PL) spectroscopy to understand h…
Second harmonic generation (SHG) is a non-linear optical process, where two photons coherently combine into one photon of twice their energy. Efficient SHG occurs for crystals with broken inversion symmetry, such as transition metal dichalcogenide monolayers. Here we show tuning of non-linear optical processes in an inversion symmetric crystal. This tunability is based on the unique properties of bilayer MoS2, that shows strong optical oscillator strength for the intra- but also inter-layer exciton resonances. As we tune the SHG signal onto these resonances by varying the laser energy, the SHG…
Calculations combining first-principles electron-phonon ($e$-ph) interactions with the Boltzmann equation enable studies of ultrafast carrier and phonon dynamics. However, in materials with weak Coulomb screening, electrons and holes form bound excitons and their scattering processes become correlated, posing additional challenges for modeling nonequilibrium physics. Here we show calculations of ultrafast exciton dynamics and related time-domain spectroscopies using $ab~initio$ exciton-phonon (ex-ph) interactions together with an excitonic Boltzmann equation. Starting from the nonequilibrium e…
In this paper, starting from a quantum master equation, we discuss the interaction between two negatively charged Nitrogen-vacancy color centers in diamond via exciton-polaritons propagating in a two-dimensional transition metal dichalcogenide layer in close proximity to a diamond crystal. We focus on the optical 1.945 eV transition and model the Nitrogen-vacancy color centers as two-level (artificial) atoms. We find that the interaction parameters and the energy levels renormalization constants are extremely sensitive to the distance of the Nitrogen-vacancy centers to the transition metal dic…
Atomically thin semiconductors such as monolayer MoS2 and WS2 exhibit nonlinear exciton-exciton annihilation at notably low excitation densities (below ~10 excitons/um2 in MoS2). Here, we show that the density threshold at which annihilation occurs can be tuned by changing the underlying substrate. When the supporting substrate is changed from SiO2 to Al2O3 or SrTiO3, the rate constant for second-order exciton-exciton annihilation, k_XX [cm2/s], is reduced by one or two orders of magnitude, respectively. Using transient photoluminescence microscopy, we measure the effective room-temperature ex…
Moire-Engineered Excitonic Landscape and Phonon-Mediated Recombination in Twisted WSe2 Bilayers
Indian Institute of Technology Mandi（印度技术学院曼迪分校）；CSIR-National Physical Laboratory（印度科学工业研究理事会国家物理实验室）；Academy of Scientific and Innovative Research (AcSIR)（科学与创新研究学院）；Indian Institute of Science（印度科学学院）；National Institute of Material Science（国家物质科学研究所）
Understanding the origin of electron-phonon coupling in lead-halide perovskites (LHP) is key to interpreting and leveraging their optical and electronic properties. Here we perform femtosecond-resolved, optical-pump, electron-diffraction-probe measurements to quantify the lattice reorganization occurring as a result of photoexcitation in LHP nanocrystals. Photoexcitation is found to drive a reduction in lead-halide octahedra tilts and distortions in the lattice, a result of deformation potential coupling to low energy optical phonons. Our results indicate particularly strong coupling in FAPbBr…
Systems supporting exciton-polaritons represent solid-state optical platforms with a strong built-in optical nonlinearity provided by exciton-exciton interactions. In conventional semiconductors with hydrogen-like excitons the nonlinearity rate demonstrates the inverse scaling with the binding energy. This makes excitons stable at room temperatures weakly interacting, which obviously limits the possibilities of practical applications of the corresponding materials for nonlinear photonics. We demonstrate experimentally and theoretically, that these limitations can be substantially softened in h…
The possibility of creating heterostructure of two-dimensional (2D) materials has emerged as a viable route towards realizing novel optoelectronic devices. However, the low light absorption due to their small absorption cross section, limits their realistic application. While light-matter interaction mediated by strong exciton-plasmon coupling has been demonstrated to improve absorbance and spontaneous emission in a coupled TMDC and metallic nanostructures, the fabrication of tunable broadband phototransistor with high quantum yield is still a challenging task. By synthesizing Ag nanoparticles…
Using wide spectral range in situ spectroscopic ellipsometry with systematic ultra high vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS$_2$ isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A ($1.92$ eV) and B ($2.02$ eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure…
We present evidence of a drastic renormalization of the optical conductivity of graphene on SrTiO$_3$ resulting in almost full transparency in the ultraviolet region. These findings are attributed to resonant excitonic effects further supported by \emph{ab initio} Bethe-Salpeter equation and density functional theory calculations. The ($π$,$π$*)-orbitals of graphene and Ti-3\textit{d} $t_{2g}$ orbitals of SrTiO$_3$ are strongly hybridized and the interactions of electron-hole states residing in those orbitals play dominant role in the graphene optical conductivity. These interactions are prese…
Strong coupling of excitonic resonances with a cavity gives rise to exciton-polaritons which possess a modified energy landscape compared to the uncoupled emitter. However, due to the femtosecond lifetime of the so-called bright polariton states and transient changes of the cavity reflectivity under excitation, it is challenging to directly measure the polariton excited state dynamics. Here, near-infrared pump-probe spectroscopy is used to investigate the ultrafast dynamics of exciton-polaritons based on strongly-coupled (6,5) single-walled carbon nanotubes in metal-clad microcavities. We pres…
Semiconductor heterostructures provide a powerful platform for the engineering of excitons. Here we report the excitonic properties of two-dimensional (2D) heterostructures that consist of monolayer MoS2 and WS2 stacked epitaxially or non-epitaxially in the vertical direction. We find similarly efficient interlayer relaxation and transition of excitons in both the epitaxial and nonepitaxial heterostructures. This is manifested by a two orders of magnitude decrease in the photoluminescence and the appearance of an extra absorption peak at low energy region. The MoS2/WS2 heterostructures show we…
Ultrafast dynamics of excitons in black phosphorus
Université de Lorraine（洛林大学）；CNRS（法国国家科学研究中心）；IJL（界面与层状材料研究所）；University of Fribourg（弗里堡大学）；Paul Scherrer Institute（保罗谢勒研究所）；TU Wien（维也纳工业大学）；University of Geneva（日内瓦大学）
The energy spectra and wavefunctions of bound excitons in important two-dimensional (2D) graphene derivatives, i.e., graphyne and graphane, are found to be strongly modified by quantum confinement, making them qualitatively different from the usual Rydberg series. However, their parity and optical selection rules are preserved. Thus a one-parameter modified hydrogenic model is applied to quantitatively explain the ab initio exciton spectra, and allows one to extrapolate the electron-hole binding energy from optical spectroscopies of 2D semiconductors without costly simulations. Meanwhile, our …
We consider the resonant energy transfer from a two-dimensional Wannier exciton (donor) to a Frenkel exciton of a molecular crystal overlayer (acceptor) when the active medias are separated by a metallic layer, possibly an electrode. We characterize the effect of the surface plasmon on this process. Using realistic values of material parameters, we show that it is possible to change the transfer rate within typically a factor of 5 (up to 44 according to geometrical configuration). We then take into account the quenching of the organic luminescence due to the proximity with the metal. This latt…
The mechanisms underlying coherent and thermally activated singlet exciton fission in pi-stacked acene crystals are clarified based on quantum dynamics simulations parameterized against a highly correlated description of the electronic excitations and their couplings to intramolecular and intermolecular vibrations. In TIPS-pentacene crystals, the relative longitudinal shift of the molecular backbones yields large electronic couplings of the triplet exciton pair with both the singlet exciton and charge transfer (CT) states. CT-mediated superexchange and direct pathways are found to contribute s…
Monolayer transition metal dichalcogenides are a promising platform to investigate many-body interactions of excitonic complexes. In monolayer tungsten diselenide, the ground-state exciton is dark (spin-indirect), and the valley degeneracy allows low-energy dark momentum-indirect excitons to form. Interactions between the dark exciton species and the optically accessible bright exciton (X) are likely to play significant roles in determining the optical properties of X at high power, as well as limiting the ultimate exciton densities that can be achieved, yet so far little is known about these …
We use Boltzmann transport equation (BE) to study time evolution of a photo-excited state in a nanoparticle including phonon-mediated exciton relaxation and the multiple exciton generation (MEG) processes, such as exciton-to-biexciton multiplication and biexciton-to-exciton recombination. BE collision integrals are computed using Kadanoff-Baym-Keldysh many-body perturbation theory (MBPT) based on density functional theory (DFT) simulations, including exciton effects. We compute internal quantum efficiency (QE), which is the number of excitons generated from an absorbed photon in the course of …
