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 Laser Control of Antiferromagnetic-Ferrimagnetic Switching in Two-Dimensional Ferromagnetic Semiconductor Heterostructures.

Realizing ultrafast control of magnetization switching is of crucial importance for information processing and recording technology. Here, we explore the laser-induced spin electron excitation and relaxation dynamics processes of CrCl3/CrBr3 heterostructures with antiparallel (AP) and parallel (P) systems. Although an ultrafast demagnetization of CrCl3 and CrBr3 layers occurs in both AP and P systems, the overall magnetic order of the heterostructure remains unchanged due to the laser-induced equivalent interlayer spin electron excitation. More crucially, the interlayer magnetic order switches from antiferromagnetic (AFM) to ferrimagnetic (FiM) in the AP system once the laser pulse disappears. The microscopic mechanism underpinning this magnetization switching is dominated by the asymmetrical interlayer charge transfer combined with a spin-flip, which breaks the interlayer AFM symmetry and ultimately results in an inequivalent shift in the moment between two FM layers. Our study opens up a new idea for ultrafast laser control of magnetization switching in two-dimensional opto-spintronic devices.

Strongly anisotropic ultrafast dynamic behavior of GaTe dominated by the tilted and flat bands.

The anisotropic transport properties of gallium telluride (GaTe) have been reported by several experiments, giving rise to many debates recently. The anisotropic electronic band structure of GaTe shows the extreme difference between the flat band and tilted band in two distinct directions,Γ¯-X¯andΓ¯-Y¯, and which we called as the mixed flat-tilted band (MFTB). Focusing on such two directions, the relaxation of photo-generated carriers has been studied using the non-adiabatic molecular dynamics (NAMD) method to investigate the anisotropic behavior of ultrafast dynamics. The results show that the relaxation lifetime is different in flat band direction and tilted band direction, which is evidence for the existence of anisotropic behavior of the ultrafast dynamic, and such anisotropic behavior comes from the different intensities of electron-phonon coupling of the flat band and tilted band. Furthermore, the ultrafast dynamic behavior is found to be affected strongly by spin-orbit coupling (SOC) and such anisotropic behavior of the ultrafast dynamic can be reversed by SOC. The tunable anisotropic ultrafast dynamic behavior of GaTe is expected to be detected in ultrafast spectroscopy experiments and it may provide a tunable application in nanodevice design. The results may also provide a reference for the investigation of MFTB 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.

Enhanced Electron Transfer and Spin Flip through Spin-Orbital Couplings in Organic/Inorganic Heterojunctions: A Nonadiabatic Surface Hopping Simulation.

The circumstances of transferred electrons across organic/inorganic interfaces have attracted intensive interest because of the distinctive electronic structure properties of those two components. Leveraging ab initio nonadiabatic molecular dynamics methods in conjunction with spin dynamics induced by spin-orbital couplings (SOCs), this study reports two competitive channels during photoinduced dynamical processes in the prototypical ZnPc/monolayer MoS2 heterojunction. Interestingly, the electron-transfer and relaxation processes occur simultaneously because of the enhancement of electron-phonon couplings and expansion of dynamical pathways by SOCs, suggesting that the electron-transfer rate and relaxation processes can be tuned by SOCs, hence yielding the performance promotion of photovoltaic and photocatalytic devices. Additionally, approximately half of the transferred electrons flip their spin within 1.6 ps because of strong SOCs in MoS2, achieving great agreement with experimental measurements. This investigation provides instructive perspectives for designing novel devices and applications based on organic/inorganic heterojunctions, demonstrating the importance of spin dynamics simulations in exploring sophisticated photoinduced processes in materials.

Ultrafast self-trapping of photoexcited carriers sets the upper limit on antimony trisulfide photovoltaic devices.

Antimony trisulfide (Sb2S3) is considered to be a promising photovoltaic material; however, the performance is yet to be satisfactory. Poor power conversion efficiency and large open circuit voltage loss have been usually ascribed to interface and bulk extrinsic defects By performing a spectroscopy study on Sb2S3 polycrystalline films and single crystal, we show commonly existed characteristics including redshifted photoluminescence with 0.6 eV Stokes shift, and a few picosecond carrier trapping without saturation at carrier density as high as approximately 1020 cm-3. These features, together with polarized trap emission from Sb2S3 single crystal, strongly suggest that photoexcited carriers in Sb2S3 are intrinsically self-trapped by lattice deformation, instead of by extrinsic defects. The proposed self-trapping explains spectroscopic results and rationalizes the large open circuit voltage loss and near-unity carrier collection efficiency in Sb2S3 thin film solar cells. Self-trapping sets the upper limit on maximum open circuit voltage (approximately 0.8 V) and thus power conversion efficiency (approximately 16 %) for Sb2S3 solar cells.