Vertical Dipole Dominates Charge Carrier Lifetime in Monolayer Janus MoSSe.

Two-dimensional semiconductor materials with vertical dipoles are promising photocatalysts as vertical dipoles not only promote the electron-hole separation but also enhance the carrier redox ability. However, the influence of vertical dipoles on carrier recombination in such materials, especially the competing relationship between vertical dipoles and band gaps, is not yet clear. Herein, first-principles calculations and nonadiabatic molecular dynamics simulations were combined to clarify the influence of band gap and vertical dipole on the carrier lifetime in Janus MoSSe monolayer. By comparing with the results of MoS2 and MoSe2 as well as exploring the carrier lifetime of MoSSe under strain regulation, it has been demonstrated that the vertical dipole, rather than the band gap, is the dominant factor affecting the carrier lifetime. Strikingly, a linear relationship between the carrier lifetime and vertical dipole is revealed. These findings have important implications for the design of high-performance photocatalysts and optoelectronic devices.

Real-Time Ab Initio Investigation on Hot Electron Relaxation Dynamics in Silicon.

The relaxation of hot electrons in semiconductors is pivotal for both energy harvesting processes and optoelectronics. Utilizing a self-developed non-adiabatic molecular dynamics simulation approach in the momentum space (NAMD_k), we have examined the dynamics of hot electrons in silicon. Whether excited from the Γ or L point, the relaxation dynamics exhibit two distinct stages. Initially, within 100 fs, electrons scatter with phonons throughout the Brillouin zone. Subsequently, over a few picoseconds, they further relax toward the conduction band minimum as a whole. This picture of hot electron relaxation is highly consistent with the quasi-equilibrium hot electron ensemble (HEE) concept. Throughout the hot electron relaxation process, energy transfer to phonons is efficient, leading to time-dependent phonon excitation, which is thoroughly analyzed. This investigation provides a novel perspective on hot electron relaxation in silicon, which holds substantive implications for the realm of photovoltaic and optoelectronic device applications.

Ultrafast many-body bright-dark exciton transition in anatase TiO2.

The momentum-forbidden dark excitons can have a pivotal role in quantum information processing, Bose-Einstein condensation, and light-energy harvesting. Anatase TiO2 with an indirect band gap is a prototypical platform to study bright to momentum-forbidden dark exciton transition. Here, we examine, by GW plus the real-time Bethe-Salpeter equation combined with the nonadiabatic molecular dynamics (GW + rtBSE-NAMD), the many-body transition that occurs within 100 fs from the optically excited bright to the strongly bound momentum-forbidden dark excitons in anatase TiO2. Comparing with the single-particle picture in which the exciton transition is considered to occur through electron-phonon scattering, within the GW + rtBSE-NAMD framework, the many-body electron-hole Coulomb interaction activates additional exciton relaxation channels to notably accelerate the exciton transition in competition with other radiative and nonradiative processes. The existence of dark excitons and ultrafast bright-dark exciton transitions sheds insights into applications of anatase TiO2 in optoelectronic devices and light-energy harvesting as well as the formation process of dark excitons in semiconductors.

Ab initio real-time quantum dynamics of charge carriers in momentum space.

Application of the non-adiabatic molecular dynamics (NAMD) approach is limited to studying carrier dynamics in the momentum space, as a supercell is required to sample the phonon excitation and electron-phonon (e-ph) interaction at different momenta in a molecular dynamics simulation. Here we develop an ab initio approach for the real-time charge carrier quantum dynamics in the momentum space (NAMD_k) by directly introducing e-ph coupling into the Hamiltonian based on the harmonic approximation. The NAMD_k approach maintains the zero-point energy and includes memory effects of carrier dynamics. The application of NAMD_k to the hot carrier dynamics in graphene reveals the phonon-specific relaxation mechanism. An energy threshold of 0.2 eV-defined by two optical phonon modes-separates the hot electron relaxation into fast and slow regions with lifetimes of pico- and nanoseconds, respectively. The NAMD_k approach provides an effective tool to understand real-time carrier dynamics in the momentum space for different materials.

Ultrafast charge transfer coupled to quantum proton motion at molecule/metal oxide interface.

Understanding how the nuclear quantum effects (NQEs) in the hydrogen bond (H-bond) network influence the photoexcited charge transfer at semiconductor/molecule interface is a challenging problem. By combining two kinds of emerging molecular dynamics methods at the ab initio level, the path integral-based molecular dynamics and time-dependent nonadiabatic molecular dynamics, and choosing CH3OH/TiO2 as a prototypical system to study, we find that the quantum proton motion in the H-bond network is strongly coupled with the ultrafast photoexcited charge dynamics at the interface. The hole trapping ability of the adsorbed methanol molecule is notably enhanced by the NQEs, and thus, it behaves as a hole scavenger on titanium dioxide. The critical role of the H-bond network is confirmed by in situ scanning tunneling microscope measurements with ultraviolet light illumination. It is concluded the quantum proton motion in the H-bond network plays a critical role in influencing the energy conversion efficiency based on photoexcitation.

High Photoreactivity on a Reconstructed Anatase TiO2(001) Surface Predicted by Ab Initio Nonadiabatic Molecular Dynamics.

Anatase TiO2(001) surface with (4 × 1) reconstruction is proposed to be a highly active catalytic surface. In this work, using time-domain ab initio nonadiabatic molecular dynamics, we reveal that the ridge structure formed by anatase(001) surface reconstruction is the photoreactive site for hole migration and trapping. Moreover, the ridge structure is destroyed by low-coverage CH3OH adsorption, leading to the suppression of its high photoreactivity. However, when the CH3OH coverage is increased and intermolecular hydrogen bonds (H-bonds) form, the ridge structure and its high photoreactivity are restored. Furthermore, the hole trapping dynamics is strongly coherent with intermolecular proton transfer in structures with intermolecular H-bonds. Our study proves that anatase TiO2(001)-(4 × 1) is a highly photoreactive surface where the ridge is the photoreactive site for hole trapping, which is coherent with the proton transfer process.

Effects of oxygen vacancies on the photoexcited carrier lifetime in rutile TiO2.

The photoexcited carrier lifetime in semiconductors plays a crucial role in solar energy conversion processes. The defects or impurities in semiconductors are usually proposed to introduce electron-hole (e-h) recombination centers and consequently reduce the photoexcited carrier lifetime. In this report, we investigate the effects of oxygen vacancies (OV) on the carrier lifetime in rutile TiO2, which has important applications in photocatalysis and photovoltaics. It is found that an OV introduces two excess electrons which form two defect states in the band gap. The lower state is localized on one Ti atom and behaves as a small polaron, and the higher one is a hybrid state contributed by three Ti atoms around the OV. Both the polaron and hybrid states exhibit strong electron-phonon (e-ph) coupling and their charge distributions become more and more delocalized when the temperature increases from 100 to 700 K. Such strong e-ph coupling and charge delocalization enhance the nonadibatic coupling between the electronic states along the hole relaxation path, where the defect states behave as intermediate states, leading to a distinct acceleration of e-h recombination. Our study provides valuable insights to understand the role of defects on photoexcited carrier lifetime in semiconductors.

Excited electron and spin dynamics in topological insulator: A perspective from ab initio non-adiabatic molecular dynamics.

We perform an ab initio non-adiabatic molecular dynamics simulation to investigate the non-equilibrium spin and electron dynamics in a prototypical topological insulator (TI) Bi2Se3. Different from the ground state, we reveal that backscattering can happen in an oscillating manner between time-reversal pair topological surface states (TSSs) in the non-equilibrium dynamics. Analysis shows the phonon excitation induces orbital composition change by electron-phonon interaction, which further stimulates spin canting through spin-orbit coupling. The spin canting of time-reversal pair TSSs leads to the non-zero non-adiabatic coupling between them and then issues in backscattering. Both the spin canting and backscattering result in ultrafast spin relaxation with a timescale around 100 fs. This study provides critical insights into the non-equilibrium electron and spin dynamics in TI at the ab initio level and paves a way for the design of ultrafast spintronic materials.

Time- and momentum-resolved image-potential states of 2H-MoS2 surface.

Rydberg-like image potential states (IPSs) form special series surface states on metal and semiconducting surfaces. Here, using time-resolved and momentum-resolved multi-photon photoemission (mPPE), we measured the energy positions, band dispersion, and carrier lifetimes of IPSs at the 2H-MoS2 surface. The energy minima of the IPSs (n = 1 and 2) were located at 0.77 and 0.21 eV below the vacuum level. In addition, the effective masses of these two IPSs are close to the rest mass of the free electron, clearly showing nearly-free-electron character. These properties suggest a good screening effect in the MoS2 parallel to the surface. The multi-photon resonances between the valence band and IPS (n = 1) are observed, showing a k‖-momentum-dependent behavior. Our time-resolved mPPE measurements show that the lifetime of photoexcited electrons in the IPS (n = 1) is about 33 fs.

Ultrafast Ferroelectric Ordering on the Surface of a Topological Semimetal MoTe2.

Transient tuning of material properties by light usually requires intense laser fields in the nonlinear excitation regime. Here, we report ultrafast ferroelectric ordering on the surface of a paraelectric topological semimetal 1T'-MoTe2 in the linear excitation regime, with the order parameter directly proportional to the excitation intensity. The ferroelectric ordering, driven by a transient electric field created by electrons trapped ångstroms away from the surface in the image potential state (IPS), is evidenced in two-photon photoemission spectroscopy showing the energy relaxation rate proportional to IPS electron density, but with negligible change in the free-electron-like parallel dispersion. First-principles calculations reveal an improper ferroelectric ordering associated with an anharmonic interlayer shearing mode. Our findings demonstrate an ultrafast charge-based pathway for creating transient polarization orders.

Bidirectional and reversible tuning of the interlayer spacing of two-dimensional materials.

Interlayer spacing is expected to influence the properties of multilayer two-dimensional (2D) materials. However, the ability to non-destructively regulate the interlayer spacing bidirectionally and reversibly is challenging. Here we report the preparation of 2D materials with tunable interlayer spacing by introducing active sites (Ce ions) in 2D materials to capture and immobilize Pt single atoms. The strong chemical interaction between active sites and Pt atoms contributes to the intercalation behavior of Pt atoms in the interlayer of 2D materials and further promotes the formation of chemical bonding between Pt atom and host materials. Taking cerium-embedded molybdenum disulfide (MoS2) as an example, intercalation of Pt atoms enables interlayer distance tuning via an electrochemical protocol, leading to interlayer spacing reversible and linear compression and expansion from 6.546 ± 0.039 Å to 5.792 ± 0.038 Å (~11 %). The electronic property evolution with the interlayer spacing variation is demonstrated by the photoluminescence (PL) spectra, delivering that the well-defined barrier between the multilayer and monolayer layered materials can be artificially designed.

Strong Modulation of Band Gap, Carrier Mobility and Lifetime in Two-Dimensional Black Phosphorene through Acoustic Phonon Excitation.

Black phosphorene (BP) has been attracting intense attention due to its high charge mobility and potential applications in electronic, optical and optoelectronic devices. We demonstrate by ab initio molecular dynamics and nonadiabatic quantum dynamics simulations that the excitation of out-of-plane acoustic phonon (ZA) provides strong modulation of the band gap, carrier lifetime and carrier mobility in BP. A 1% tensile strain can significantly enhance ZA mode excitation at room temperature, distinctly reducing the band gap, carrier mobility, and lifetime. These electronic properties can be tuned easily by influencing the excitation amplitude of the ZA mode. Unique to the family of two-dimensional materials, the ZA mode plays an essential role in controlling the electronic properties of BP. The results of our study provide valuable guidelines for design of functional nanodevices based on 2D BP.

Dynamic sampling iterative phase retrieval for holographic data storage.

A dynamic sampling iterative phase retrieval method, which dynamically samples the Fourier intensity distribution of the reconstruction beam captured by the detector, is proposed to shorten the iterative number and decrease the phase error rate of phase retrieval in the phase-modulated holographic data storage. By the dynamic sampling method, that keeping relatively low frequency component of Fourier intensity spectrum at the beginning of iteration and gradually releasing more high frequency component at the subsequent iterations, we shortened the iterative number by 2 times and decreased the phase error rate to some extent because our method provided a better convergent path to the phase retrieval. We also believe the thought of our method can be used in more image retrieval fields.

Real-time GW-BSE investigations on spin-valley exciton dynamics in monolayer transition metal dichalcogenide.

We develop an ab initio nonadiabatic molecular dynamics (NAMD) method based on GW plus real-time Bethe-Salpeter equation (GW + rtBSE-NAMD) for the spin-resolved exciton dynamics. From investigations on MoS2, we provide a comprehensive picture of spin-valley exciton dynamics where the electron-phonon (e-ph) scattering, spin-orbit interaction (SOI), and electron-hole (e-h) interactions come into play collectively. In particular, we provide a direct evidence that e-h exchange interaction plays a dominant role in the fast valley depolarization within a few picoseconds, which is in excellent agreement with experiments. Moreover, there are bright-to-dark exciton transitions induced by e-ph scattering and SOI. Our study proves that e-h many-body effects are essential to understand the spin-valley exciton dynamics in transition metal dichalcogenides and the newly developed GW + rtBSE-NAMD method provides a powerful tool for exciton dynamics in extended systems with time, space, momentum, energy, and spin resolution.

Dynamics of Photoexcited Small Polarons in Transition-Metal Oxides.

The dynamics of photoexcited polarons in transition-metal oxides (TMOs), including their formation, migration, and quenching, plays an important role in photocatalysis and photovoltaics. Taking rutile TiO2 as a prototypical system, we use ab initio nonadiabatic molecular dynamics simulation to investigate the dynamics of small polarons induced by photoexcitation at different temperatures. The photoexcited electron is trapped by the distortion of the surrounding lattice and forms a small polaron within tens of femtoseconds. Polaron migration among Ti atoms is strongly correlated with quenching through an electron-hole (e-h) recombination process. At low temperature, the polaron is localized on a single Ti atom and polaron quenching occurs within several nanoseconds. At increased temperature, as under solar cell operating conditions, thermal phonon excitation stimulates the hopping and delocalization of polarons, which induces fast polaron quenching through the e-h recombination within 200 ps. Our study proves that e-h recombination centers can be formed by photoexcited polarons, which provides new insights to understand the efficiency bottleneck of photocatalysis and photovoltaics in TMOs.

Improved phase retrieval in holographic data storage based on a designed iterative embedded data.

Embedded data are used to retrieve phases quicker with high accuracy in phase-modulated holographic data storage (HDS). We propose a method to design an embedded data distribution using iterations to enhance the intensity of the high-frequency signal in the Fourier spectrum. The proposed method increases the antinoise performance and signal-to-noise ratio (SNR) of the Fourier spectrum distribution, realizing a more efficient phase retrieval. Experiments indicate that the bit error rate (BER) of this method can be reduced by a factor of one after 10 iterations.

Accurate Computation of Nonadiabatic Coupling with Projector Augmented-Wave Pseudopotentials.

Synergy of nonadiabatic molecular dynamics with real-time time-dependent density functional theory has led to significant progress in modeling excited-state dynamics in nanoscale and condensed matter systems over the past decade. Nonadiabatic coupling (NAC) is the central quantity in such simulations, and its accurate and efficient evaluation is an enduring challenge in time-dependent Kohn-Sham theory, particularly in conjunction with planewave basis sets and projector augmented-wave (PAW) pseudopotentials because of the complexity of the PAW "all-electron" wave function. We report a method for rigorous evaluation of the NAC with PAW wave functions and demonstrate an efficient approximation to the rigorous NAC that gives comparable accuracy. As a validation, we intensely examine the NAC matrix elements calculated using both pseudo- and all-electron wave functions under the PAW formalism in six representative systems. The approximate NAC obtained with pseudowave functions is close to the exact all-electron NAC, with the largest deviations observed when subshell d-electrons are involved in the transitions. The developed approach provides a rigorous and convenient methodology for the numerical computation of NAC in the Kohn-Sham theory framework.

Interlayer Polarization Explains Slow Charge Recombination in Two-Dimensional Halide Perovskites by Nonadiabatic Molecular Dynamics Simulation.

Two-dimensional (2D) perovskites for applications in photovoltaics and optoelectronics are attracting a great deal of research interest. The nonradiative electron-hole (e-h) recombination is the major efficiency loss channel. Herein, we report a study of the thickness dependence of the e-h recombination dynamics in diamine-based 2D perovskite via ab initio NAMD. For multilayer structures, due to the emergence of spontaneous interlayer electric polarization, which is induced by the collective and correlated reorientation of methylammonium molecules, the electron and hole at the band edges are localized in different inorganic layers, suppressing the e-h recombination. Furthermore, a broad range of phonon excitation also inspired rapid pure dephasing related to the microscopic origin for longer recombination times. The combination of the two effects leads to the observation of a prolonged carrier lifetime in multilayer 2D perovskites, which is essential to understanding the nonradiative e-h recombination mechanism in such materials.

Tuning the Carrier Lifetime in Black Phosphorene through Family Atom Doping.

It is highly desirable to control the carrier lifetime in two-dimensional (2D) materials to suit the needs of various device functionalities. In this work, by ab initio nonadiabatic molecular dynamics simulation, we find the single atom doping from phosphorus family elements can sufficiently tune the carrier lifetime in black phosphorene (BP). Instead of forming electron-hole (e-h) recombination centers, the e-h recombination is suppressed by doping compared with the pristine BP. Moreover, it is found the carrier lifetime has a strong correlation with the mass of the doping atoms. A doping atom with larger mass leads to a longer lifetime. With the heaviest family element Bi doping, the carrier lifetime increases from 0.29 to 5.34 ns. This trend can be understood from the reduction of the nuclear velocity due to the heavy doping atom. We propose this conclusion can be extended to other monoelemental 2D semiconductors, which provides important guidance for the future design of functional nanodevices.