The Crystal Structure of Al4SiC4 Revisited.

Al4SiC4 is a ternary wide-band-gap semiconductor with a high strength-to-weight ratio and excellent oxidation resistance. It consists of slabs of Al4C3 separated by SiC layers with the space group of P63mc. The space group allows Si to occupy two different 2a Wykoff sites, with previous studies reporting that Si occupies only one of the two sites, giving it an ordered structure. Another hitherto unexplored possibility is that Si can be randomly distributed on both 2a sites. In this work, we revisit the published ordered crystal structure using experimental methods and density functional theory (DFT). Al4SiC4 was synthesized by high-temperature sintering at 1800 °C from a powder mixture of Al4C3 and SiC. Neutron diffraction confirmed that Al4SiC4 crystallized with the space group of P63mc, with diffraction patterns that could be fitted to both the ordered and the disordered structures. Scanning transmission electron microscopy, however, provided clear evidence supporting the latter, with DFT calculations further confirming that it is 0.16 eV lower in energy per Al4SiC4 formula unit than the former. TEM analysis revealed Al vacancies in some of the atomic layers that can introduce p-type doping and direct band gaps of 0.7 and 1.2 eV, agreeing with our optical measurements. Finally, we propose that although the calculated formation energy of the Al vacancies is high, the vacancies are stabilized by entropy effects at the high synthesis temperature. This indicates that the cooling procedure after high-temperature synthesis can be important in determining the vacancy content and the electronic properties of Al4SiC4.

From Insulator to Superconductor: A Series of Pressure-Driven Transitions in Quasi-One-Dimensional TiS3 Nanoribbons.

Transition metal trichalcogenides (TMTCs) offer remarkable opportunities for tuning electronic states through modifications in chemical composition, temperature, and pressure. Despite considerable interest in TMTCs, there remain significant knowledge gaps concerning the evolution of their electronic properties under compression. In this study, we employ experimental and theoretical approaches to comprehensively explore the high-pressure behavior of the electronic properties of TiS3, a quasi-one-dimensional (Q1D) semiconductor, across various temperature ranges. Through high-pressure electrical resistance and magnetic measurements at elevated pressures, we uncover a distinctive sequence of phase transitions within TiS3, encompassing a transformation from an insulating state at ambient pressure to the emergence of an incipient superconducting state above 70 GPa. Our findings provide compelling evidence that superconductivity at low temperatures of ∼2.9 K is a fundamental characteristic of TiS3, shedding new light on the intriguing high-pressure electronic properties of TiS3 and underscoring the broader implications of our discoveries for TMTCs in general.

Two-dimensional heavy fermions in the van der Waals metal CeSiI.

Heavy-fermion metals are prototype systems for observing emergent quantum phases driven by electronic interactions1-6. A long-standing aspiration is the dimensional reduction of these materials to exert control over their quantum phases7-11, which remains a significant challenge because traditional intermetallic heavy-fermion compounds have three-dimensional atomic and electronic structures. Here we report comprehensive thermodynamic and spectroscopic evidence of an antiferromagnetically ordered heavy-fermion ground state in CeSiI, an intermetallic comprising two-dimensional (2D) metallic sheets held together by weak interlayer van der Waals (vdW) interactions. Owing to its vdW nature, CeSiI has a quasi-2D electronic structure, and we can control its physical dimension through exfoliation. The emergence of coherent hybridization of f and conduction electrons at low temperature is supported by the temperature evolution of angle-resolved photoemission and scanning tunnelling spectra near the Fermi level and by heat capacity measurements. Electrical transport measurements on few-layer flakes reveal heavy-fermion behaviour and magnetic order down to the ultra-thin regime. Our work establishes CeSiI and related materials as a unique platform for studying dimensionally confined heavy fermions in bulk crystals and employing 2D device fabrication techniques and vdW heterostructures12 to manipulate the interplay between Kondo screening, magnetic order and proximity effects.

Robustness of Trion State in Gated Monolayer MoSe2 under Pressure.

Quasiparticles consisting of correlated electron(s) and hole(s), such as excitons and trions, play important roles in the optical phenomena of van der Waals semiconductors and serve as unique platforms for studies of many-body physics. Herein, we report a gate-tunable exciton-to-trion transition in pressurized monolayer MoSe2, in which the electronic band structures are modulated continuously within a diamond anvil cell. The emission energies of both the exciton and trion undergo large blueshifts over 90 meV with increasing pressure. Surprisingly, the trion binding energy remains constant at 30 meV, regardless of the applied pressure. Combining ab initio density functional theory calculations and quantum Monte Carlo simulations, we find that the remarkable robustness of the trion binding energy originates from the spatially diffused nature of the trion wave function and the weak correlation between its constituent electron-hole pairs. Our findings shed light on the optical properties of correlated excitonic quasiparticles in low-dimensional materials.

Optically controlled single-valley exciton doublet states with tunable internal spin structures and spin magnetization generation.

Manipulating quantum states through light-matter interactions has been actively pursued in two-dimensional materials research. Significant progress has been made toward the optical control of the valley degrees of freedom in semiconducting monolayer transition-metal dichalcogenides, based on doubly degenerate excitons from their two distinct valleys in reciprocal space. Here, we introduce a type of optically controllable doubly degenerate exciton states that come from a single valley, dubbed as single-valley exciton doublet (SVXD) states. They are unique in that their constituent holes originate from the same valence band, making possible the direct optical control of the spin structure of the excited constituent electrons. Combining ab initio GW plus Bethe-Salpeter equation (GW-BSE) calculations and a theoretical analysis method, we demonstrate such SVXD in substrate-supported monolayer bismuthene-which has been successfully grown using molecular beam epitaxy. In each of the two distinct valleys in the Brillouin zone, strong spin-orbit coupling and [Formula: see text] symmetry lead to a pair of degenerate 1s exciton states (the SVXD states) with opposite spin configurations. Any coherent linear combinations of the SVXD in a single valley can be excited by light with a specific polarization, enabling full manipulation of their internal spin configurations. In particular, a controllable net spin magnetization can be generated through light excitation. Our findings open routes to control quantum degrees of freedom, paving the way for applications in spintronics and quantum information science.

Tuneable 2D surface Bismuth incorporation on InAs nanosheets.

The chemical bonding at the interface between compound semiconductors and metals is central in determining electronic and optical properties. In this study, new opportunities for controlling this are presented for nanostructures. We investigate Bi adsorption on 2D wurtzite InAs (112̄0) nanosheets and find that temperature-controlled Bi incorporation in either anionic- or cationic-like bonding is possible in the easily accesible range between room temperature and 400 °C. This separation could not be achieved for ordinary zinc blende InAs(110) surfaces. As the crystal structures of the two surfaces have identical nearest neighbour configurations, this indicates that overall geometric differences can significantly alter the adsorption and incorporation. Ab initio theoretical modelling confirms observed adsorption results, but indicate that both the formation energies as well as kinetic barriers contributes to the observed temperature dependent behaviour. Further, we find that the Bi adsorption rate can differ by at least 2.5 times between the two InAs surfaces while being negligible for standard Si substrates under similar deposition conditions. This, in combination with the observed interface control, provides an excellent opportunity for tuneable Bi integration on 2D InAs nanostructures on standard Si substrates.

A 2D Bismuth-Induced Honeycomb Surface Structure on GaAs(111).

Two-dimensional (2D) topological insulators have fascinating physical properties which are promising for applications within spintronics. In order to realize spintronic devices working at room temperature, materials with a large nontrivial gap are needed. Bismuthene, a 2D layer of Bi atoms in a honeycomb structure, has recently attracted strong attention because of its record-large nontrivial gap, which is due to the strong spin-orbit coupling of Bi and the unusually strong interaction of the Bi atoms with the surface atoms of the substrate underneath. It would be a significant step forward to be able to form 2D materials with properties such as bismuthene on semiconductors such as GaAs, which has a band gap size relevant for electronics and a direct band gap for optical applications. Here, we present the successful formation of a 2D Bi honeycomb structure on GaAs, which fulfills these conditions. Bi atoms have been incorporated into a clean GaAs(111) surface, with As termination, based on Bi deposition under optimized growth conditions. Low-temperature scanning tunneling microscopy and spectroscopy (LT-STM/S) demonstrates a well-ordered large-scale honeycomb structure, consisting of Bi atoms in a √3 × âˆš3 30° reconstruction on GaAs(111). X-ray photoelectron spectroscopy shows that the Bi atoms of the honeycomb structure only bond to the underlying As atoms. This is supported by calculations based on density functional theory that confirm the honeycomb structure with a large Bi-As binding energy and predict Bi-induced electronic bands within the GaAs band gap that open up a gap of nontrivial topological nature. STS results support the existence of Bi-induced states within the GaAs band gap. The GaAs:Bi honeycomb layer found here has a similar structure as previously published bismuthene on SiC or on Ag, though with a significantly larger lattice constant and only weak Bi-Bi bonding. It can therefore be considered as an extreme case of bismuthene, which is fundamentally interesting. Furthermore, it has the same exciting electronic properties, opening a large nontrivial gap, which is the requirement for room-temperature spintronic applications, and it is directly integrated in GaAs, a direct band gap semiconductor with a large range of (opto)electronic devices.

Intralayer charge-transfer moiré excitons in van der Waals superlattices.

Moiré patterns of transition metal dichalcogenide heterobilayers have proved to be an ideal platform on which to host unusual correlated electronic phases, emerging magnetism and correlated exciton physics. Whereas the existence of new moiré excitonic states is established1-4 through optical measurements, the microscopic nature of these states is still poorly understood, often relying on empirically fit models. Here, combining large-scale first-principles GW (where G and W denote the one-particle Green's function and the screened Coulomb interaction, respectively) plus Bethe-Salpeter calculations and micro-reflection spectroscopy, we identify the nature of the exciton resonances in WSe2/WS2 moiré superlattices, discovering a rich set of moiré excitons that cannot be captured by prevailing continuum models. Our calculations show moiré excitons with distinct characters, including modulated Wannier excitons and previously unidentified intralayer charge-transfer excitons. Signatures of these distinct excitonic characters are confirmed experimentally by the unique carrier-density and magnetic-field dependences of different moiré exciton resonances. Our study highlights the highly non-trivial exciton states that can emerge in transition metal dichalcogenide moiré superlattices, and suggests new ways of tuning many-body physics in moiré systems by engineering excited-states with specific spatial characters.

Unconventional excitonic states with phonon sidebands in layered silicon diphosphide.

Complex correlated states emerging from many-body interactions between quasiparticles (electrons, excitons and phonons) are at the core of condensed matter physics and material science. In low-dimensional materials, quantum confinement affects the electronic, and subsequently, optical properties for these correlated states. Here, by combining photoluminescence, optical reflection measurements and ab initio theoretical calculations, we demonstrate an unconventional excitonic state and its bound phonon sideband in layered silicon diphosphide (SiP2), where the bound electron-hole pair is composed of electrons confined within one-dimensional phosphorus-phosphorus chains and holes extended in two-dimensional SiP2 layers. The excitonic state and emergent phonon sideband show linear dichroism and large energy redshifts with increasing temperature. Our ab initio many-body calculations confirm that the observed phonon sideband results from the correlated interaction between excitons and optical phonons. With these results, we propose layered SiP2 as a platform for the study of excitonic physics and many-particle effects.

Intervalley Excitonic Hybridization, Optical Selection Rules, and Imperfect Circular Dichroism in Monolayer h-BN.

We perform first-principles GW plus Bethe-Salpeter equation calculations to investigate the photophysics of monolayer hexagonal boron nitride (h-BN), revealing excitons with novel k-space characteristics. The excitonic states forming the first and third peaks in its absorption spectrum are s-like, but those of the second peak are notably p-like, a first finding of strong co-occurrence of bright s-like and bright p-like states in an intrinsic 2D material. Moreover, even though the k-space wave function of these excitonic states are centered at the K and K^{'} valleys as in monolayer transition metal dichalcogenides, the k-space envelope functions of the basis excitons at one valley have significant extents to the basin of the other valley. As a consequence, the optical response of monolayer h-BN exhibits a lack of circular dichroism, as well as a coupling that induces an intervalley mixing between s- and p-like states.

Narrow-band high-lying excitons with negative-mass electrons in monolayer WSe2.

Monolayer transition-metal dichalcogenides (TMDCs) show a wealth of exciton physics. Here, we report the existence of a new excitonic species, the high-lying exciton (HX), in single-layer WSe2 with an energy of ~3.4 eV, almost twice the band-edge A-exciton energy, with a linewidth as narrow as 5.8 meV. The HX is populated through momentum-selective optical excitation in the K-valleys and is identified in upconverted photoluminescence (UPL) in the UV spectral region. Strong electron-phonon coupling results in a cascaded phonon progression with equidistant peaks in the luminescence spectrum, resolvable to ninth order. Ab initio GW-BSE calculations with full electron-hole correlations explain HX formation and unmask the admixture of upper conduction-band states to this complex many-body excitation. These calculations suggest that the HX is comprised of electrons of negative mass. The coincidence of such high-lying excitonic species at around twice the energy of band-edge excitons rationalizes the excitonic quantum-interference phenomenon recently discovered in optical second-harmonic generation (SHG) and explains the efficient Auger-like annihilation of band-edge excitons.

In Situ Pseudopotentials for Electronic Structure Theory.

We present a general method of constructing in situ pseodopotentials from first-principles, all-electron, and full-potential electronic structure calculations of a solid. The method is applied to bcc Na, at low-temperature equilibrium volume. The essential steps of the method involve (i) calculating an all-electron Kohn-Sham eigenstate, (ii) replacing the oscillating part of the wave function (inside the muffin-tin spheres) of this state, with a smooth function, (iii) representing the smooth wave function in a Fourier series, and (iv) inverting the Kohn-Sham equation, to extract the pseudopotential that produces the state generated in steps i-iii. It is shown that an in situ pseudopotential can reproduce an all-electron full-potential eigenvalue up to the sixth significant digit. A comparison of the all-electron theory, in situ pseudopotential theory, and the standard nonlocal pseudopotential theory demonstrates good agreement, e.g., in the energy dispersion of the 3s band state of bcc Na.

Valley-dependent exciton fine structure and Autler-Townes doublets from Berry phases in monolayer MoSe2.

The Berry phase of Bloch states can have profound effects on electron dynamics1-3 and lead to novel transport phenomena, such as the anomalous Hall effect and the valley Hall effect4-6. Recently, it was predicted that the Berry phase effect can also modify the exciton states in transition metal dichalcogenide monolayers, and lift the energy degeneracy of exciton states with opposite angular momentum through an effective valley-orbital coupling1,7-11. Here, we report the observation and control of the Berry phase-induced splitting of the 2p exciton states in monolayer molybdenum diselenide (MoSe2) using the intraexciton optical Stark spectroscopy. We observe the time-reversal-symmetric analogue of the orbital Zeeman effect resulting from the valley-dependent Berry phase, which leads to energy difference of +14 (-14) meV between the 2p+ and 2p- exciton states in the K (K') valley, consistent with the ordering from our ab initio GW-Bethe-Salpeter equation results. In addition, we show that the light-matter coupling between intraexciton states is remarkably strong, leading to a prominent valley-dependent Autler-Townes doublet under resonant driving. Our study opens up pathways to coherently manipulate the quantum states and excitonic excitation with infrared radiation in two-dimensional semiconductors.

Ab initio study of hot electrons in GaAs.

Hot carrier dynamics critically impacts the performance of electronic, optoelectronic, photovoltaic, and plasmonic devices. Hot carriers lose energy over nanometer lengths and picosecond timescales and thus are challenging to study experimentally, whereas calculations of hot carrier dynamics are cumbersome and dominated by empirical approaches. In this work, we present ab initio calculations of hot electrons in gallium arsenide (GaAs) using density functional theory and many-body perturbation theory. Our computed electron-phonon relaxation times at the onset of the Γ, L, and X valleys are in excellent agreement with ultrafast optical experiments and show that the ultrafast (tens of femtoseconds) hot electron decay times observed experimentally arise from electron-phonon scattering. This result is an important advance to resolve a controversy on hot electron cooling in GaAs. We further find that, contrary to common notions, all optical and acoustic modes contribute substantially to electron-phonon scattering, with a dominant contribution from transverse acoustic modes. This work provides definitive microscopic insight into hot electrons in GaAs and enables accurate ab initio computation of hot carriers in advanced materials.

Direct observation of lithium-ion transport under an electrical field in LixCoO2 nanograins.

The past decades have witnessed the development of many technologies based on nanoionics, especially lithium-ion batteries (LIBs). Now there is an urgent need for developing LIBs with good high-rate capability and high power. LIBs with nanostructured electrodes show great potentials for achieving such goals. However, the nature of Li-ion transport behaviors within the nanostructured electrodes is not well clarified yet. Here, Li-ion transport behaviors in Li(x)CoO(2) nanograins are investigated by employing conductive atomic force microscopy (C-AFM) technique to study the local Li-ion diffusion induced conductance change behaviors with a spatial resolution of ~10 nm. It is found that grain boundary has a low Li-ion diffusion energy barrier and provides a fast Li-ion diffusion pathway, which is also confirmed by our first principles calculation. This information provides important guidelines for designing high performance LIBs from a point view of optimizing the electrode material microstructures and the development of nanoionics.