Unifying the order and disorder dynamics in photoexcited VO2.

Photoinduced phase transition (PIPT) is always treated as a coherent process, but ultrafast disordering in PIPT is observed in recent experiments. Utilizing the real-time time-dependent density functional theory method, here we track the motion of individual vanadium (V) ions during PIPT in VO2 and uncover that their coherent or disordered dynamics can be manipulated by tuning the laser fluence. We find that the photoexcited holes generate a force on each V-V dimer to drive their collective coherent motion, in competing with the thermal-induced vibrations. If the laser fluence is so weak that the photoexcited hole density is too low to drive the phase transition alone, the PIPT is a disordered process due to the interference of thermal phonons. We also reveal that the photoexcited holes populated by the V-V dimerized bonding states will become saturated if the laser fluence is too strong, limiting the timescale of photoinduced phase transition.

Origin of Immediate Damping of Coherent Oscillations in Photoinduced Charge-Density-Wave Transition.

In stark contrast to the conventional charge density wave (CDW) materials, the one-dimensional CDW on the In/Si(111) surface exhibits immediate damping of the CDW oscillation during the photoinduced phase transition. Here, we successfully reproduce the experimental observation of the photoinduced CDW transition on the In/Si(111) surface by performing real-time time-dependent density functional theory (rt-TDDFT) simulations. We show that photoexcitation promotes valence electrons from the Si substrate to the empty surface bands composed primarily of the covalent p-p bonding states of the long In-In bonds. Such photoexcitation generates interatomic forces to shorten the long In-In bonds and thus drives the structural transition. After the structural transition, these surface bands undergo a switch among different In-In bonds, causing a rotation of the interatomic forces by about π/6 and thus quickly damping the oscillations in feature CDW modes. These findings provide a deeper understanding of photoinduced phase transitions.

Rapid Transition of the Hole Rashba Effect from Strong Field Dependence to Saturation in Semiconductor Nanowires.

The electric field manipulation of the Rashba spin-orbit coupling effects provides a route to electrically control spins, constituting the foundation of the field of semiconductor spintronics. In general, the strength of the Rashba effects depends linearly on the applied electric field and is significant only for heavy-atom materials with large intrinsic spin-orbit interaction under high electric fields. Here, we illustrate in 1D semiconductor nanowires an anomalous field dependence of the hole (but not electron) Rashba effect (HRE). (i) At low fields, the strength of the HRE exhibits a steep increase with the field so that even low fields can be used for device switching. (ii) At higher fields, the HRE undergoes a rapid transition to saturation with a giant strength even for light-atom materials such as Si (exceeding 100 meV Å). (iii) The nanowire-size dependence of the saturation HRE is rather weak for light-atom Si, so size fluctuations would have a limited effect; this is a key requirement for scalability of Rashba-field-based spintronic devices. These three features offer Si nanowires as a promising platform for the realization of scalable complementary metal-oxide-semiconductor compatible spintronic devices.

Revealing the Origin of Fast Electron Transfer in TiO2-Based Dye-Sensitized Solar Cells.

In dye-sensitized solar cells (DSCs), the electron transfer from photoexcited dye molecules to semiconductor substrates remains a major bottleneck. Replacing TiO2 with ZnO is expected to enhance the efficiency of DSCs, owing to the latter possesses a much larger electron mobility, but similar bandgap and band positions as TiO2 remain. However, the record efficiency of ZnO-based DSCs is only 7% compared with 13% of TiO2-based DSCs due to the even slower electron-transfer rate in ZnO-based DSCs, which becomes a long-standing puzzle. Here, we computationally investigate the electron transfer from the dye molecule into ZnO and TiO2, respectively, by performing the first-principles calculations within the frame of the Marcus theory. The predicted electron-transfer rate in the TiO2-based DSC is about 1.15 × 10(9) s(-1), a factor of 15 faster than that of the ZnO-based DSC, which is in good agreement with experimental data. We find that the much larger density of states of the TiO2 compared with ZnO near the conduction band edge is the dominant factor, which is responsible for the faster electron-transfer rate in TiO2-based DSCs. These denser states provide additional efficient channels for the electron transfer. We also provide design principles to boost the efficiency of DSCs through surface engineering of high mobility photoanode semiconductors.

Origin of the Distinct Diffusion Behaviors of Cu and Ag in Covalent and Ionic Semiconductors.

It is well known that Cu diffuses faster than Ag in covalent semiconductors such as Si, which has prevented the replacement of Ag by Cu as a contact material in Si solar cells for reducing the cost. Surprisingly, in more ionic materials such as CdTe, Ag diffuses faster than Cu despite that it is larger than Cu, which has prevented the replacement of Cu by Ag in CdTe solar cells to improve the performance. But, so far, the mechanisms behind these distinct diffusion behaviors of Cu and Ag in covalent and ionic semiconductors have not been addressed. Here we reveal the underlying mechanisms by combining the first-principles calculations and group theory analysis. We find that the symmetry controlled s-d coupling plays a critical role in determining the diffusion behaviors. The s-d coupling is absent in pure covalent semiconductors but increases with the ionicity of the zinc blende semiconductors, and is larger for Cu than for Ag, owing to its higher d orbital energy. In conjunction with Coulomb interaction and strain energy, the s-d coupling is able to explain all the diffusion behaviors from Cu to Ag and from covalent to ionic hosts. This in-depth understanding enables us to engineer the diffusion of impurities in various semiconductors.

Tuning the optical, magnetic, and electrical properties of ReSe2 by nanoscale strain engineering.

Creating materials with ultimate control over their physical properties is vital for a wide range of applications. From a traditional materials design perspective, this task often requires precise control over the atomic composition and structure. However, owing to their mechanical properties, low-dimensional layered materials can actually withstand a significant amount of strain and thus sustain elastic deformations before fracture. This, in return, presents a unique technique for tuning their physical properties by "strain engineering". Here, we find that local strain induced on ReSe2, a new member of the transition metal dichalcogenides family, greatly changes its magnetic, optical, and electrical properties. Local strain induced by generation of wrinkle (1) modulates the optical gap as evidenced by red-shifted photoluminescence peak, (2) enhances light emission, (3) induces magnetism, and (4) modulates the electrical properties. The results not only allow us to create materials with vastly different properties at the nanoscale, but also enable a wide range of applications based on 2D materials, including strain sensors, stretchable electrodes, flexible field-effect transistors, artificial-muscle actuators, solar cells, and other spintronic, electromechanical, piezoelectric, photonic devices.

Tunable Polarity Behavior and Self-Driven Photoswitching in p-WSe2/n-WS2 Heterojunctions.

Van der Waals (vdW) p-n heterojunctions consisting of various 2D layer compounds are fascinating new artificial materials that can possess novel physics and functionalities enabling the next-generation of electronics and optoelectronics devices. Here, it is reported that the WSe2/WS2 p-n heterojunctions perform novel electrical transport properties such as distinct rectifying, ambipolar, and hysteresis characteristics. Intriguingly, the novel tunable polarity transition along a route of n-"anti-bipolar"-p-ambipolar is observed in the WSe2/WS2 heterojunctions owing to the successive work of conducting channels of junctions, p-WSe2 and n-WS2 on the electrical transport of the whole systems. The type-II band alignment obtained from first principle calculations and built-in potential in this vdW heterojunction can also facilitate the efficient electron-hole separation, thus enabling the significant photovoltaic effect and a much enhanced self-driven photoswitching response in this system.

Efficient real-time time-dependent density functional theory method and its application to a collision of an ion with a 2D material.

We have developed an efficient real-time time-dependent density functional theory (TDDFT) method that can increase the effective time step from <1 as in traditional methods to 0.1-0.5 fs. With this algorithm, the TDDFT simulation can have comparable speed to the Born-Oppenheimer (BO) ab initio molecular dynamics (MD). As an application, we simulated the process of an energetic Cl particle colliding onto a monolayer of MoSe(2). Our simulations show a significant energy transfer from the kinetic energy of the Cl particle to the electronic energy of MoSe(2), and the result of TDDFT is very different from that of BO-MD simulations.

Electronic structural Moiré pattern effects on MoS2/MoSe2 2D heterostructures.

The structural and electronic properties of MoS2/MoSe2 bilayers are calculated using first-principles methods. It is found that the interlayer van der Waals interaction is not strong enough to form a lattice-matched coherent heterostructure. Instead, a nanometer-scale Moiré pattern structure will be formed. By analyzing the electronic structures of different stacking configurations, we predict that the valence-band maximum (VBM) state will come from the Γ point due to interlayer electronic coupling. This is confirmed by a direct calculation of a Moiré pattern supercell containing 6630 atoms using the linear scaling three-dimensional fragment method. The VBM state is found to be strongly localized, while the conduction band minimum (CBM) state is only weakly localized, and it comes from the MoS2 layer at the K point. We predict such wave function localization can be a general feature for many two-dimensional (2D) van der Waals heterostructures and can have major impacts on the carrier mobility and other electronic and optical properties.

Direct bandgap emission from strain-doped germanium.

Germanium (Ge) is an attractive material for Silicon (Si) compatible optoelectronics, but the nature of its indirect bandgap renders it an inefficient light emitter. Drawing inspiration from the significant expansion of Ge volume upon lithiation as a Lithium (Li) ion battery anode, here, we propose incorporating Li atoms into the Ge to cause lattice expansion to achieve the desired tensile strain for a transition from an indirect to a direct bandgap. Our first-principles calculations show that a minimal amount of 3 at.% Li can convert Ge from an indirect to a direct bandgap to possess a dipole transition matrix element comparable to that of typical direct bandgap semiconductors. To enhance compatibility with Si Complementary-Metal-Oxide-Semiconductors (CMOS) technology, we additionally suggest implanting noble gas atoms instead of Li atoms. We also demonstrate the tunability of the direct-bandgap emission wavelength through the manipulation of dopant concentration, enabling coverage of the mid-infrared to far-infrared spectrum. This Ge-based light-emitting approach presents exciting prospects for surpassing the physical limitations of Si technology in the field of photonics and calls for experimental proof-of-concept studies.

Dynamical Symmetry-Reduction-Induced Giant Anharmonicity in IV-VI Compounds: Role of Cation Lone-Pair s Electrons.

The low thermal conductivity of group IV-VI semiconductors is often attributed to the soft phonons and giant anharmonicity observed in these materials. However, there is still no broad consensus on the fundamental origin of this giant anharmonic effect. Utilizing first-principles calculations and group symmetry analysis, we find that the cation lone-pairs s electrons in IV-VI materials cause a significant coupling between occupied cation s orbitals and unoccupied cation p orbitals due to the symmetry reduction when atoms vibrate away from their equilibrium positions under heating. This leads to an electronic energy gain, consequently flattening the potential energy surface and causing soft phonons and strong anharmonic effects. Our findings provide an intrinsic understanding of the low thermal conductivity in IV-VI compounds by connecting the anharmonicity with the dynamical electronic structures, and can also be extended to a large family of hybrid systems with lone-pair electrons, for promising thermoelectric applications and predictive designs.

The seeds and homogeneous nucleation of photoinduced nonthermal melting in semiconductors due to self-amplified local dynamic instability.

Laser-induced nonthermal melting in semiconductors has been studied over the past four decades, but the underlying mechanism is still under debate. Here, by using an advanced real-time time-dependent density functional theory simulation, we reveal that the photoexcitation-induced ultrafast nonthermal melting in silicon occurs via homogeneous nucleation with random seeds originating from a self-amplified local dynamic instability. Because of this local dynamic instability, any initial small random thermal displacements of atoms can be amplified by a charge transfer of photoexcited carriers, which, in turn, creates a local self-trapping center for the excited carriers and yields the random nucleation seeds. Because a sufficient amount of photoexcited hot carriers must be cooled down to band edges before participating in the self-amplification of local lattice distortions, the time needed for hot carrier cooling is the response for the longer melting time scales at shorter laser wavelengths. This finding provides fresh insights into photoinduced ultrafast nonthermal melting.

Numerical study of disorder on the orbital magnetization in two dimensions.

The modern theory of orbital magnetization (OM) was developed by using Wannier function method, which has a formalism similar with the Berry phase. In this manuscript, we perform a numerical study on the fate of the OM under disorder, by using this method on the Haldane model in two dimensions, which can be tuned between a normal insulator or a Chern insulator at half filling. The effects of increasing disorder on OM for both cases are simulated. Energy renormalization shifts are observed in the weak disorder regime and topologically trivial case, which was predicted by a self-consistent T-matrix approximation. Besides this, two other phenomena can be seen. One is the localization trend of the band orbital magnetization. The other is the remarkable contribution from topological chiral states arising from nonzero Chern number or large value of integrated Berry curvature. If the fermi energy is fixed at the gap center of the clean system, there is an enhancement of |M| at the intermediate disorder, for both cases of normal and Chern insulators, which can be attributed to the disorder induced topological metal state before localization.

Uncovering and tailoring hidden Rashba spin-orbit splitting in centrosymmetric crystals.

Hidden Rashba and Dresselhaus spin splittings in centrosymmetric crystals with subunits/sectors having non-centrosymmetric symmetries (the R-2 and D-2 effects) have been predicted theoretically and then observed experimentally, but the microscopic mechanism remains unclear. Here we demonstrate that the spin splitting in the R-2 effect is enforced by specific symmetries, such as non-symmorphic symmetry in the present example, which ensures that the pertinent spin wavefunctions segregate spatially on just one of the two inversion-partner sectors and thus avoid compensation. We further show that the effective Hamiltonian for the conventional Rashba (R-1) effect is also applicable for the R-2 effect, but applying a symmetry-breaking electric field to a R-2 compound produces a different spin-splitting pattern than applying a field to a trivial, non-R-2, centrosymmetric compound. This finding establishes a common fundamental source for the R-1 effect and the R-2 effect, both originating from local sector symmetries rather than from the global crystal symmetry per se.

Barrier tunneling of the loop-nodal semimetal in the hyperhoneycomb lattice.

We theoretically investigate the barrier tunneling in the 3D model of the hyperhoneycomb lattice, which is a nodal-line semimetal with a Dirac loop at zero energy. In the presence of a rectangular potential, the scattering amplitudes for different injecting states around the nodal loop are calculated, by using analytical treatments of the effective model, as well as numerical simulations of the tight binding model. In the low energy regime, states with remarkable transmissions are only concentrated in a small range around the loop plane. When the momentum of the injecting electron is coplanar with the nodal loop, nearly perfect transmissions can occur for a large range of injecting azimuthal angles if the potential is not high. For higher potential energies, the transmission shows a resonant oscillation with the potential, but still with peaks being perfect transmissions that do not decay with the potential width. These strikingly robust transports of the loop-nodal semimetal can be approximately explained by a momentum dependent Dirac Hamiltonian.

Route towards Localization for Quantum Anomalous Hall Systems with Chern Number 2.

The quantum anomalous Hall system with Chern number 2 can be destroyed by sufficiently strong disorder. During its process towards localization, it was found that the electronic states will be directly localized to an Anderson insulator (with Chern number 0), without an intermediate Hall plateau with Chern number 1. Here we investigate the topological origin of this phenomenon, by calculating the band structures and Chern numbers for disordered supercells. We find that on the route towards localization, there exists a hidden state with Chern number 1, but it is too short and too fluctuating to be practically observable. This intermediate state cannot be stabilized even after some "smart design" of the model and this should be a universal phenomena for insulators with high Chern numbers. By performing numerical scaling of conductances, we also plot the renormalization group flows for this transition, with Chern number 1 state as an unstable fixed point. This is distinct from known results, and can be tested by experiments and further theoretical analysis.

Electric-Field Tunable Band Offsets in Black Phosphorus and MoS2 van der Waals p-n Heterostructure.

The structural and electronic properties of black phosphorus/MoS2 (BP/MoS2) van der Waals (vdW) heterostructure are investigated by first-principles calculations. It is demonstrated that the BP/MoS2 bilayer is a type-II p-n vdW heterostructure, and thus the lowest energy electron-hole pairs are spatially separated. The band gap of BP/MoS2 can be significantly modulated by external electric field, and a transition from semiconductor to metal is observed. It gets further support from the band edges of BP and MoS2 in BP/MoS2 bilayer, which show linear variations with E⊥. BP/MoS2 bilayer also exhibits modulation of its band offsets and band alignment by E⊥, resulting in different spatial distribution of the lowest energy electron-hole pairs. Our theoretical results may inspire much interest in experimental research of BP/MoS2 vdW heterostructures and would open a new avenue for application of the heterostructures in future nano- and optoelectronics.

Sulfur vacancy activated field effect transistors based on ReS2 nanosheets.

Rhenium disulphide (ReS2) is a recently discovered new member of the transition metal dichalcogenides. Most impressively, it exhibits a direct bandgap from bulk to monolayer. However, the growth of ReS2 nanosheets (NSs) still remains a challenge and in turn their applications are unexplored. In this study, we successfully synthesized high-quality ReS2 NSs via chemical vapor deposition. A high-performance field effect transistor of ReS2 NSs with an on/off ratio of ∼10(5) was demonstrated. Through both electrical transport measurements at varying temperatures (80 K-360 K) and first-principles calculations, we find sulfur vacancies, which exist intrinsically in ReS2 NSs and significantly affect the performance of the ReS2 FET device. Furthermore, we demonstrated that sulfur vacancies can efficiently adsorb and recognize oxidizing (O2) and reducing (NH3) gases, which electronically interact with ReS2 only at defect sites. Our findings provide experimental groundwork for the synthesis of new transition metal dichalocogenides, supply guidelines for understanding the physical nature of ReS2 FETs, and offer a new route toward tailoring their electrical properties by defect engineering in the future.

Highly sensitive and fast phototransistor based on large size CVD-grown SnS2 nanosheets.

A facile and fruitful CVD method is reported for the first time, to synthesize high-quality hexagonal SnS2 nanosheets on carbon cloth via in situ sulfurization of SnO2. Moreover, highly sensitive phototransistors based on SnS2 with an on/off ratio surpassing 10(6) under ambient conditions and a rising time as short as 22 ms under vacuum are fabricated, which are superior than most phototransistors based on LMDs. Electrical transport measurements at varied temperatures together with theoretical calculations verify that sulfur vacancies generated by the growth process would induce a defect level near the bottom of the conduction band, which significantly affects the performance of the SnS2 device. These findings may open up a new pathway for the synthesis of LMDs, shed light on the effects of defects on devices and expand the building blocks for high performance optoelectronic devices.

The optical phonon resonance scattering with spin-conserving and spin-flip processes between Landau levels in graphene.

In the frame of Huang-Rhys's lattice relaxation model, we theoretically investigate the electron relaxation assisted by optical phonon resonance scattering among Landau levels with spin-conserving and spin-flip processes in graphene. We not only consider the longitudinal optical (LO) phonon scattering, but also the surface optical (SO) phonon scattering induced by the polar substrate under the graphene. The relaxation rate displays a Gaussian distribution by considering the effect of lattice relaxation that arises from the electron-deformation potential acoustic phonon interaction. We find that the relaxation rate of the spin-conserving process is three orders of magnitude larger than that of the spin-flip process for the same phonon mode. Moreover, the discrepancy of relaxation rates between the SO and LO phonon scattering is at two orders of magnitude for the same process. The opposite temperature dependence of the relaxation rates are also obtained in the resonance energy regime in the present model. In addition, the influences of the strength of Rashba spin-orbital coupling, the dielectric constant of different polar substrates and the distance between the graphene and substrate on the relaxation rates are also discussed quantitatively for the SO phonon scattering. The obtained results could be useful for the graphene-based applications on the mid-infrared and terahertz modulation and spintronic devices.