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.

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.

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.

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.

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.

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.

CO2 Photoreduction on Metal Oxide Surface Is Driven by Transient Capture of Hot Electrons: Ab Initio Quantum Dynamics Simulation.

The most critical bottleneck in CO2 photoreduction lies in the activation of CO2 to form an anion radical, CO2•-, or other intermediates by the photoexcited electrons, because CO2 has a high-energy lowest unoccupied molecular orbital (LUMO). Taking rutile TiO2(110) as a prototypical surface, we use time-dependent ab initio nonadiabatic molecular dynamics simulations to reveal that the excitation of bending and antisymmetric stretching vibrations of CO2 can sufficiently stabilize the CO2 LUMO below the conduction band minimum, allowing it to trap photoexcited hot electrons and get reduced. Such vibrational excitations occur by formation of a transient CO2•- adsorbed in an oxygen vacancy. CO2 can trap the hot electrons for nearly 100 fs and dissociate to form CO within 30-40 fs after the trapping. We propose that the activation of the CO2 bending and antisymmetric stretching vibrations driven by hot electrons applies to other CO2 reduction photocatalysts and can be realized by different techniques and material design.

Interfacial Hydrogen-Bonding Dynamics in Surface-Facilitated Dehydrogenation of Water on TiO2(110).

Molecular-level understanding of the dehydrogenation of interfacial water molecules on metal oxides and their interactive nature relies on the ability to track the motion of light and small hydrogen atoms, which is known to be difficult. Here, we report precise measurements of the surface-facilitated water dehydrogenation process at terminal Ti sites of TiO2(110) using scanning tunneling microscopy. Our measured hydrogen-bond dynamics of H2O and D2O reveal that the vibrational and electronic excitations dominate the sequential transfer of two H (D) atoms from a H2O (D2O) molecule to adjacent surface oxygen sites, manifesting the active participation of the oxide surface in the dehydrogenation processes. Our results show that, at the stoichiometric Ti5c sites, individual H2O molecules are energetically less stable than the dissociative form, where a barrier is expected to be as small as approximately 70-120 meV on the basis of our experimental and theoretical results. Moreover, our results reveal that interfacial hydrogen bonds can effectively assist H atom transfer and exchange across the surface. The revealed quantitative hydrogen-bond dynamics provide a new atomistic mechanism for water interactions on metal oxides in general.

Dynamics of Single-Molecule Dissociation by Selective Excitation of Molecular Phonons.

Breaking bonds selectively in molecules is vital in many chemistry reactions and custom nanoscale device fabrications. The scanning tunneling microscope (STM) has proved to be an ideal tool to initiate and view bond-selective chemistry at the single-molecule level, offering opportunities for the further study of the dynamics in single molecules on metal surfaces. We demonstrate H─HS and H─S bond breaking on Au(111) induced by tunneling electrons using low-temperature STM. An experimental study combined with theoretical calculations shows that the dissociation pathway is facilitated by vibrational excitations. Furthermore, the dissociation probabilities of the two different dissociation processes are bias dependent due to different inelastic-tunneling probabilities, and they are also closely linked to the lifetime of inelastic-tunneling electrons. Combined with time-dependent ab initio nonadiabatic molecular dynamics simulations, the dynamics of the injected electron and the phonon-excitation-induced molecule dissociation can be understood at the atomic scale, demonstrating the potential application of STM for the investigation of excited-state dynamics of single molecules on surfaces.

Delocalized Impurity Phonon Induced Electron-Hole Recombination in Doped Semiconductors.

Semiconductor doping is often proposed as an effective route to improving the solar energy conversion efficiency by engineering the band gap; however, it may also introduce electron-hole (e-h) recombination centers, where the determining element for e-h recombination is still unclear. Taking doped TiO2 as a prototype system and by using time domain ab initio nonadiabatic molecular dynamics, we find that the localization of impurity-phonon modes (IPMs) is the key parameter to determine the e-h recombination time scale. Noncompensated charge doping introduces delocalized impurity-phonon modes that induce ultrafast e-h recombination within several picoseconds. However, the recombination can be largely suppressed using charge-compensated light-mass dopants due to the localization of their IPMs. For different doping systems, the e-h recombination time is shown to depend exponentially on the IPM localization. We propose that the observation that delocalized IPMs can induce fast e-h recombination is broadly applicable and can be used in the design and synthesis of functional semiconductors with optimal dopant control.

Phonon-Assisted Ultrafast Charge Transfer at van der Waals Heterostructure Interface.

The van der Waals (vdW) interfaces of two-dimensional (2D) semiconductor are central to new device concepts and emerging technologies in light-electricity transduction where the efficient charge separation is a key factor. Contrary to general expectation, efficient electron-hole separation can occur in vertically stacked transition-metal dichalcogenide heterostructure bilayers through ultrafast charge transfer between the neighboring layers despite their weak vdW bonding. In this report, we show by ab initio nonadiabatic molecular dynamics calculations, that instead of direct tunneling, the ultrafast interlayer hole transfer is strongly promoted by an adiabatic mechanism through phonon excitation occurring on 20 fs, which is in good agreement with the experiment. The atomic level picture of the phonon-assisted ultrafast mechanism revealed in our study is valuable both for the fundamental understanding of ultrafast charge carrier dynamics at vdW heterointerfaces as well as for the design of novel quasi-2D devices for optoelectronic and photovoltaic applications.

Ultrafast Dynamics of Photongenerated Holes at a CH3OH/TiO2 Rutile Interface.

Photogenerated charge carrier dynamics near molecule/TiO2 interfaces are important for the photocatalytic and photovoltaic processes. To understand this fundamental aspect, we performed a time-domain ab initio nonadiabatic molecular dynamics study of the photogenerated hole dynamics at the CH3OH/rutile TiO2(110) interface. We studied the forward and reverse hole transfer between TiO2 and CH3OH as well as the hole energy relaxation to the valence band maximum. First, we show that the hole-trapping ability of CH3OH depends strongly on the adsorption structure. Only when the CH3OH is deprotonated to form chemisorbed CH3O will ∼15% of the hole be trapped by the molecule. Second, we find that strong fluctuations of the HOMO energies of the adsorbed molecules induced by electron-phonon coupling provide additional channels, which accelerate the hole energy relaxation. Third, we demonstrate that the charge transfer and energy relaxation processes depend significantly on temperature. When the temperature decreases from 100 to 30 K, the forward hole transfer and energy relaxation processes are strongly suppressed because of the reduction of phonon occupation. These results indicate that the molecule/TiO2 energy level alignment, thermal excitation of a phonon, and electron-phonon coupling are the key factors that determine the photogenerated hole dynamics. Our studies provide valuable insights into the photogenerated charge and energy transfer dynamics at molecule/semiconductor interfaces.

Nonnuclear nearly free electron conduction channels induced by doping charge in nanotube-molecular sheet composites.

Nearly free electron (NFE) states with density maxima in nonnuclear (NN) voids may have remarkable electron transport properties ranging from suppressed electron-phonon interaction to Wigner crystallization. Such NFE states, however, usually exist near the vacuum level, which makes them unsuitable for transport. Through first principles calculations on nanocomposites consisting of carbon nanotube (CNT) arrays sandwiched between boron nitride (BN) sheets, we describe a stratagem for stabilizing the NN-NFE states to below the Fermi level. By doping the CNTs with negative charge, we establish Coulomb barriers at CNTs walls that, together with the insulating BN sheets, define the transverse potentials of one-dimensional (1D) transport channels, which support the NN-NFE states.

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.

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.

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.

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.

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.