Softening of the optical phonon by reduced interatomic bonding strength without depolarization.

Softening of the transverse optical (TO) phonon, which could trigger ferroelectric phase transition, can usually be achieved by enhancing the long-range Coulomb interaction over the short-range bonding force1, for example, by increasing the Born effective charges2. However, it suffers from depolarization effects3,4 as the induced ferroelectricity is suppressed on size reduction of the host materials towards high-density nanoscale electronics. Here, we present an alternative route to drive the TO phonon softening by showing that the abnormal soft TO phonon in rocksalt-structured ultrawide-bandgap BeO (ref. 5) is mainly induced by a substantial reduction in the short-range bonding interaction due to the Be-O bond stretching caused by an electron cloud-overlap-induced Coulomb repulsion between two adjacent oxygen ions that are arranged octahedrally around an extremely small Be ion. We further demonstrate the emergence of robust ferroelectricity in strain-induced perovskite BaZrO3 and ultrathin HfO2 and ZrO2 films6,7 grown epitaxially on lattice-mismatched SiO2/Si substrate arising from the softening of the TO phonon driven by a reduction in the short-range bonding strength of biaxial strain-induced stretching bonds. These findings shed light on developing a unified theory for ferroelectricity enhancement in ultrathin films free from depolarization fields by tailoring chemical bonds using ionic radius differences, strains, doping and lattice distortions.

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.

Enhanced light emission of germanium light-emitting-diode on 150 mm germanium-on-insulator (GOI).

Germanium-on-insulator (GOI) has emerged as a novel platform for Ge-based electronic and photonic applications. Discrete photonic devices, such as waveguides, photodetectors, modulators, and optical pumping lasers, have been successfully demonstrated on this platform. However, there is almost no report on the electrically injected Ge light source on the GOI platform. In this study, we present the first fabrication of vertical Ge p-i-n light-emitting diodes (LEDs) on a 150 mm GOI substrate. The high-quality Ge LED on a 150-mm diameter GOI substrate was fabricated via direct wafer bonding followed by ion implantations. As a tensile strain of 0.19% has been introduced during the GOI fabrication process resulting from the thermal mismatch, the LED devices exhibit a dominant direct bandgap transition peak near 0.785 eV (∼1580 nm) at room temperature. In sharp contrast to conventional III-V LEDs, we found that the electroluminescence (EL)/photoluminescence (PL) spectra show enhanced intensities as the temperature is raised from 300 to 450 K as a consequence of the higher occupation of the direct bandgap. The maximum enhancement in EL intensity is a factor of 140% near 1635 nm due to the improved optical confinement offered by the bottom insulator layer. This work potentially broadens the GOI's functional variety for applications in near-infrared sensing, electronics, and photonics.

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.

Revealing angular momentum transfer channels and timescales in the ultrafast demagnetization process of ferromagnetic semiconductors.

Ultrafast control of magnetic order by light provides a promising realization for spintronic devices beyond Moore's Law and has stimulated intense research interest in recent years. Yet, despite 2 decades of debates, the key question of how the spin angular momentum flows on the femtosecond timescale remains open. The lack of direct first-principle methods and pictures for such process exacerbates the issue. Here, we unravel the laser-induced demagnetization mechanism of ferromagnetic semiconductor GaMnAs, using an efficient time-dependent density functional theory approach that enables the direct real-time snapshot of the demagnetization process. Our results show a clear spin-transfer trajectory from the localized Mn-d electrons to itinerant carriers within 20 fs, illustrating the dominant role of [Formula: see text] interaction. We find that the total spin of localized electrons and itinerant carriers is not conserved in the presence of spin-orbit coupling (SOC). Immediately after laser excitation, a growing percentage of spin-angular momentum is quickly transferred to the electron orbital via SOC in about 1 ps, then slowly to the lattice via electron-phonon coupling in a few picoseconds, responsible for the 2-stage process observed experimentally. The spin-relaxation time via SOC is about 300 fs for itinerant carriers and about 700 fs for Mn-d electrons. These results provide a quantum-mechanical microscopic picture for the long-standing questions regarding the channels and timescales of spin transfer, as well as the roles of different interactions underlying the GaMnAs demagnetization process.

The Pentagonal Nature of Self-Assembled Silicon Chains and Magic Clusters on Ag(110).

The atomic structures of self-assembled silicon nanoribbons and magic clusters on Ag(110) substrate have been studied by high-resolution noncontact atomic force microscopy (nc-AFM) and tip-enhanced Raman spectroscopy (TERS). Pentagon-ring structures in Si nanoribbons and clusters have been directly visualized. Moreover, the vibrational fingerprints of individual Si nanoribbon and cluster retrieved by subnanometer resolution TERS confirm the pentagonal nature of both Si nanoribbons and clusters. This work demonstrates that Si pentagon can be an important element in building silicon nanostructures, which may find important applications for future nanoelectronic devices based on silicon.

Confined Concrete in Fiber-Reinforced Polymer Partially Wrapped Square Columns: Axial Compressive Behavior and Strain Distributions by a Particle Image Velocimetry Sensing Technique.

Strengthening existing reinforced concrete (RC) columns using a partial wrapping strengthening technique (PWST) by fiber-reinforced polymer (FRP) strips has been widely implemented. However, compared with the confinement mechanism of confined concrete in columns strengthened with the FRP full wrapping strengthening technique (FWST), the confinement mechanism of confined concrete in FRP partially wrapped columns is less understood. This paper presents the results of an experimental investigation into the behavior of confined concrete in FRP partially wrapped square columns under axial compression. The effects of FRP strip width and thickness on stress⁻strain behavior were thoroughly investigated. The novel particle image velocimetry (PIV) non-contact strain sensing technique was adopted to measure the strain in the specimens. Results show that the axial strains as well as the hoop strains are generally larger at the mid-plane of adjacent FRP strips than those at the mid-plane of each FRP strip, and considerable variation in hoop strains along the height of the specimens was observed. Comparisons between the experimental results and predictions by existing design-oriented stress⁻strain models were carried out to examine the accuracy of the models. A new design-oriented stress⁻strain model is proposed for confined concrete in FRP partially wrapped square columns and the comparisons between laboratory results and predictions from the proposed model show that the proposed model is superior to the existing models.

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.

Strong Absorption Enhancement in Si Nanorods.

We report two orders of magnitude stronger absorption in silicon nanorods relative to bulk in a wide energy range. The local field enhancement and dipole matrix element contributions were disentangled experimentally by single-dot absorption measurements on differently shaped particles as a function of excitation polarization and photon energy. Both factors substantially contribute to the observed effect as supported by simulations of the light-matter interaction and atomistic calculations of the transition matrix elements. The results indicate strong shape dependence of the quasidirect transitions in silicon nanocrystals, suggesting nanostructure shape engineering as an efficient tool for overcoming limitations of indirect band gap materials in optoelectronic applications, such as solar cells.

Quasi-Direct Optical Transitions in Silicon Nanocrystals with Intensity Exceeding the Bulk.

Comparison of the measured absolute absorption cross section on a per Si atom basis of plasma-synthesized Si nanocrystals (NCs) with the absorption of bulk crystalline Si shows that while near the band edge the NC absorption is weaker than the bulk, yet above ∼ 2.2 eV the NC absorbs up to 5 times more than the bulk. Using atomistic screened pseudopotential calculations we show that this enhancement arises from interface-induced scattering that enhances the quasi-direct, zero-phonon transitions by mixing direct Γ-like wave function character into the indirect X-like conduction band states, as well as from space confinement that broadens the distribution of wave functions in k-space. The absorption enhancement factor increases exponentially with decreasing NC size and is correlated with the exponentially increasing direct Γ-like wave function character mixed into the NC conduction states. This observation and its theoretical understanding could lead to engineering of Si and other indirect band gap NC materials for optical and optoelectronic applications.

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.

Reinterpretation of the expected electronic density of states of semiconductor nanowires.

One-dimensional semiconductor nanowires hold the promise for various optoelectronic applications since they combine the advantages of quantized in-plane energy levels (as in zero-dimensional quantum dots) with a continuous energy spectrum along the growth direction (as in three-dimensional bulk materials). This dual characteristic is reflected in the density of states (DOS), which is thus the key quantity describing the electronic structures of nanowires, central to the analysis of electronic transport and spectroscopy. By comparing the DOS derived from the widely used "standard model", the effective mass approximation (EMA) in single parabolic band mode, with that from direct atomistic pseudopotential theory calculations for GaAs and InAs nanowires, we uncover significant qualitative and quantitative shortcomings of the standard description. In the EMA description the nanowire DOS is rendered as a series of sharply rising peaks having slowly decaying tails, with characteristic peak height and spacing, all being classifiable in the language of atomic orbital momenta 1S, 1P, 1D, etc. Herein we find in the thinner nanowires that the picture changes significantly in that not only does the profile of each DOS peak lose its pronounced asymmetry, with significant changes in peak width, height, and spacing, but also the origin of the high-energy peaks changes fundamentally: below some critical diameter, the region of atomic orbital momentum classified states is occupied by a new set of DOS peaks folded-in from other non-Γ-valleys. We describe explicitly how distinct physical effects beyond the conventional EMA model contribute to these realistic DOS features. These results represent a significant step toward understanding the intriguing electronic structure of nanowires reflecting the coexistence of discrete and continuum states. Experimental examinations of the predicted novel DOS features are called for.

Improved quantum dot stacking for intermediate band solar cells using strain compensation.

We use thin tensile-strained AlAs layers to manage compressive strain in stacked layers of InAs/AlAsSb quantum dots (QDs). The AlAs layers allow us to reduce residual strain in the QD stacks, suppressing strain-related defects. AlAs layers 2.4 monolayers thick are sufficient to balance the strain in the structures studied, in agreement with theory. Strain balancing improves material quality and helps increase QD uniformity by preventing strain accumulation and ensuring that each layer of InAs experiences the same strain. Stacks of 30 layers of strain-balanced QDs exhibit carrier lifetimes as long as 9.7 ns. QD uniformity is further enhanced by vertical ABAB… ordering of the dots in successive layers. Strain compensated InAs/AlAsSb QD stacks show great promise for intermediate band solar cell applications.

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.

Genomic design of strong direct-gap optical transition in Si/Ge core/multishell nanowires.

Finding a Si-based material with strong optical activity at the band-edge remains a challenge despite decades of research. The interest lies in combining optical and electronic functions on the same wafer, while retaining the extraordinary know-how developed for Si. However, Si is an indirect-gap material. The conservation of crystal momentum mandates that optical activity at the band-edge includes a phonon, on top of an electron-hole pair, and hence photon absorption and emission remain fairly unlikely events requiring optically rather thick samples. A promising avenue to convert Si-based materials to a strong light-absorber/emitter is to combine the effects on the band-structure of both nanostructuring and alloying. The number of possible configurations, however, shows a combinatorial explosion. Furthermore, whereas it is possible to readily identify the configurations that are formally direct in the momentum space (due to band-folding) yet do not have a dipole-allowed transition at threshold, the problem becomes not just calculation of band structure but also calculation of absorption strength. Using a combination of a genetic algorithm and a semiempirical pseudopotential Hamiltonian for describing the electronic structures, we have explored hundreds of thousands of possible coaxial core/multishell Si/Ge nanowires with the orientation of [001], [110], and [111], discovering some "magic sequences" of core followed by specific Si/Ge multishells, which can offer both a direct bandgap and a strong oscillator strength. The search has revealed a few simple design principles: (i) the Ge core is superior to the Si core in producing strong bandgap transition; (ii) [001] and [110] orientations have direct bandgap, whereas the [111] orientation does not; (iii) multishell nanowires can allow for greater optical activity by as much as an order of magnitude over plain nanowires; (iv) the main motif of the winning configurations giving direct allowed transitions involves rather thin Si shell embedded within wide Ge shells. We discuss the physical origin of the enhanced optical activity, as well as the effect of possible experimental structural imperfections on optical activity in our candidate core/multishell nanowires.

Light-induced ultrafast spin transport in multilayer metallic films originates from sp-d spin exchange coupling.

Ultrafast interaction between the femtosecond laser pulse and the magnetic metal provides an efficient way to manipulate the magnetic states of matter. Numerous experimental advancements have been made on multilayer metallic films in the last two decades. However, the underlying physics remains unclear. Here, relying on an efficient ab initio spin dynamics simulation algorithm, we revealed the physics that can unify the progress in different experiments. We found that light-induced ultrafast spin transport in multilayer metallic films originates from the sp-d spin-exchange interaction, which can induce an ultrafast, large, and pure spin current from ferromagnetic metal to nonmagnetic metal without charge carrier transport. The resulting trends of spin demagnetization and spin flow are consistent with most experiments. It can explain a variety of ultrafast light-spin manipulation experiments with different systems and different pump-probe technologies, covering a wide range of work in this field.

Genetic-algorithm discovery of a direct-gap and optically allowed superstructure from indirect-gap Si and Ge semiconductors.

Combining two indirect-gap materials-with different electronic and optical gaps-to create a direct gap material represents an ongoing theoretical challenge with potentially rewarding practical implications, such as optoelectronics integration on a single wafer. We provide an unexpected solution to this classic problem, by spatially melding two indirect-gap materials (Si and Ge) into one strongly dipole-allowed direct-gap material. We leverage a combination of genetic algorithms with a pseudopotential Hamiltonian to search through the astronomic number of variants of Si(n)/Ge(m)/…/Si(p)/Ge(q) superstructures grown on (001) Si(1-x)Ge(x). The search reveals a robust configurational motif-SiGe(2)Si(2)Ge(2)SiGe(n) on (001) Si(x)Ge(1-x) substrate (x≤0.4) presenting a direct and dipole-allowed gap resulting from an enhanced Γ-X coupling at the band edges.

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.