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Long-lived charge separation in two-dimensional ligand-perovskite heterostructures
Rational design of heterojunctions using nanostructured materials is a useful strategy for achieving efficient interfacial charge separation in photovoltaics. Heterojunctions can be constructed between organic ligands and inorganic layer in two-dimensional (2D) perovskites, taking advantage of their highly programmable structures. We investigate electron and hole transfer at the interface between the thiophene-based semiconducting ligands and the lead halide inorganic sublattices using time-resolved photoluminescence and transient reflection spectroscopy in single 2D perovskite crystals. Here, these measurements demonstrate charge transfer time of ~ 10 ps and long-lived charge-separated state over the nanosecond timescale in 2D ligand-perovskite heterostructures. The efficient charge transfer processes with slow charge recombination suggest the potential for improving exciton dissociation and charge transport in 2D perovskite solar cells.
User's manual for GAMNAS: Geometric and Material Nonlinear Analysis of Structures
GAMNAS (Geometric and Material Nonlinear Analysis of Structures) is a two dimensional finite-element stress analysis program. Options include linear, geometric nonlinear, material nonlinear, and combined geometric and material nonlinear analysis. The theory, organization, and use of GAMNAS are described. Required input data and results for several sample problems are included.
f -Orbital based Dirac states in a two-dimensional uranium compound
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Strained bilayer WSe 2 with reduced exciton-phonon coupling
We explore excitonic absorption and emission in bilayer WSe 2 under tensile strain. We observe a redshift of 110 meV in the energy of the A exciton absorption peak (at the direct gap at the K point in the Brillouin zone) under 2.1% uniaxial tensile strain. In addition, under the same strain, the spectral linewidth of the A exciton at room temperature decreases by a factor of 2, from 70 to 36 meV. We show that this decrease is a result of suppression of phonon-mediated exciton scattering channels. This suppression is associated with the relative upshift under strain of the Q valley in the conduction band (involved in the indirect exciton emission), which is nearly degenerate with the K valley (involved in the A exciton). We analyze the strain-dependent absorption and photoluminescence spectra to determine the relative positions of these valleys and to infer intervalley scattering rates. Our model describes well the decrease and the distinct trends in the A exciton linewidth of monolayer and bilayer WSe 2 under strain. The findings show that strain can be used to tune, as well as to probe, the relative energies of band extrema and exciton scattering channels in two-dimensional semiconductors.
Structural descriptor for enhanced spin-splitting in 2D hybrid perovskites
Abstract Two-dimensional (2D) hybrid metal halide perovskites have emerged as outstanding optoelectronic materials and are potential hosts of Rashba/Dresselhaus spin-splitting for spin-selective transport and spin-orbitronics. However, a quantitative microscopic understanding of what controls the spin-splitting magnitude is generally lacking. Through crystallographic and first-principles studies on a broad array of chiral and achiral 2D perovskites, we demonstrate that a specific bond angle disparity connected with asymmetric tilting distortions of the metal halide octahedra breaks local inversion symmetry and strongly correlates with computed spin-splitting. This distortion metric can serve as a crystallographic descriptor for rapid discovery of potential candidate materials with strong spin-splitting. Our work establishes that, rather than the global space group, local inorganic layer distortions induced via appropriate organic cations provide a key design objective to achieve strong spin-splitting in perovskites. New chiral perovskites reported here couple a sizeable spin-splitting with chiral degrees of freedom and offer a unique paradigm of potential interest for spintronics.
Chemically-Controlled Stacking of Inorganic Subnets in Coordination Networks: Metal–Organic Magnetic Multilayers
Coordination networks (CNs), such as, for instance, metal–organic frameworks (MOFs), can turn into remarkable magnets, with various topologies of spin carriers and unique opportunities of cross-coupling to other functionalities. Alternatively, distinct inorganic subnetworks that are spatially segregated by organic ligands can lead to coexisting magnetic systems in a single bulk material. Here, we present a system of two CNs of general formula Mn(H 2 O) x (OOC-(C 6 H 4 ) y -COO). The compound with two water molecules and one aromatic ring (x = 2; y = 1) has a single two-dimensional magnetic subnet, while the material with x = 1.5 and y = 2 shows, additionally, another type of magnetic layer. In analogy to magnetic multilayers that are deposited by physical methods, these materials can be regarded as metal–organic magnetic multilayers (MOMMs), where the stacking of different types of magnetic layers is controlled by the choice of an organic ligand during the chemical synthesis. Lastly, this work further paves the way toward organic–inorganic nanostructures with functional magnetic properties.
Evidence for moiré excitons in van der Waals heterostructures
Recent advances in the isolation and stacking of monolayers of van der Waals materials have provided approaches for the preparation of quantum materials in the ultimate two-dimensional limit(1,2). In van der Waals heterostructures formed by stacking two monolayer semiconductors, lattice mismatch or rotational misalignment introduces an in-plane moire superlattice(3). It is widely recognized that the moire superlattice can modulate the electronic band structure of the material and lead to transport properties such as unconventional superconductivity(4) and insulating behaviour driven by correlations(5-7); however, the influence of the moire superlattice on optical properties has not been investigated experimentally. Here we report the observation of multiple interlayer exciton resonances with either positive or negative circularly polarized emission in a molybdenum diselenide/tungsten diselenide (MoSe 2 /WSe 2 ) heterobilayer with a small twist angle. We attribute these resonances to excitonic ground and excited states confined within the moire potential. This interpretation is supported by recombination dynamics and by the dependence of these interlayer exciton resonances on twist angle and temperature. These results suggest the feasibility of engineering artificial excitonic crystals using van der Waals heterostructures for nanophotonics and quantum information applications.
How Substitutional Point Defects in Two-Dimensional WS 2 Induce Charge Localization, Spin–Orbit Splitting, and Strain
Control of impurity concentrations in semiconducting materials is essential to device technology. Because of their intrinsic confinement, the properties of two-dimensional semiconductors such as transition metal dichalcogenides (TMDs) are more sensitive to defects than traditional bulk materials. The technological adoption of TMDs is dependent on the mitigation of deleterious defects and guided incorporation of functional foreign atoms. The first step toward impurity control is the identification of defects and assessment of their electronic properties. Here, we present a comprehensive study of point defects in monolayer tungsten disulfide (WS 2 ) grown by chemical vapor deposition using scanning tunneling microscopy/spectroscopy, CO-tip noncontact atomic force microscopy, Kelvin probe force spectroscopy, density functional theory, and tight-binding calculations. We observe four different substitutional defects: chromium (Cr W ) and molybdenum (Mo W ) at a tungsten site, oxygen at sulfur sites in both top and bottom layers (O S top/bottom), and two negatively charged defects (CD type I and CD type II). Their electronic fingerprints unambiguously corroborate the defect assignment and reveal the presence or absence of in-gap defect states. Cr W forms three deep unoccupied defect states, two of which arise from spin-orbit splitting. The formation of such localized trap states for Cr W differs from the Mo W case and can be explained by their different d shell energetics and local strain, which we directly measured. Utilizing a tight-binding model the electronic spectra of the isolectronic substitutions O S and Cr W are mimicked in the limit of a zero hopping term and infinite on-site energy at a S and W site, respectively. The abundant CDs are negatively charged, which leads to a significant band bending around the defect and a local increase of the contact potential difference. In addition, CD-rich domains larger than 100 nm are observed, causing a work function increase of 1.1 V. While most defects are electronically isolated, we also observed hybrid states formed between CrW dimers. Finally, the important role of charge localization, spin-orbit coupling, and strain for the formation of deep defect states observed at substitutional defects in WS 2 as reported here will guide future efforts of targeted defect engineering and doping of TMDs.
Widespread Negative Longitudinal Piezoelectric Responses in Ferroelectric Crystals with Layered Structures
In this study, we investigate the underlying mechanisms of the universal negative piezoelectricity in low-dimensional layered materials by carrying out first-principles calculations. Two-dimensional layered ferroelectric CuInP 2 S 6 is analyzed in detail as a typical example, but the theory can be applied to any other low-dimensional layered piezoelectrics. Consistent with the theory proposed in [Phys. Rev. Lett. 119, 207601 (2017), the anomalous negative piezoelectricity in CuInP 2 S 6 also results from its negative clamped-ion term, which cannot be compensated by the positive internal-strain part. Here, we focus on a more general rule by proposing that having a negative clamped-ion term should be universal among piezoelectric materials, which is attributed to the “lag of Wannier center” effect. The internal-strain term, which is the change in polarization due to structural relaxation in response to strain, is mostly determined by the spatial structure and chemical bonding of the material. In a low-dimensional layered piezoelectric material such as CuInP 2 S 6 , the internal-strain term is approximately zero. This is because the internal structure of the molecular layers, which are bonded by the weak van der Waals interaction, responds little to the strain. As a result, the magnitude of the dipole, which depends strongly on the dimension and structure of the molecular layer, also has a small response with respect to strain. An equation bridging the internal strain responses in low-dimensional and three-dimensional piezoelectrics is also derived to analytically express this point. This work aims to deepen our understanding about this anomalous piezoelectric effect, especially in low-dimensional layered materials, and provide strategies for discovering materials with novel electromechanical properties.
Atomically thin two-dimensional organic-inorganic hybrid perovskites
Organic-inorganic hybrid perovskites, which have shown to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C 4 H 9 NH 3 ) 2 PbBr 4 with well-defined square shape and large size. Different from the other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials.
Theoretical study of the crystal and electronic properties of α - RuI 3
The material α-RuCl 3 , with a two-dimensional Ru honeycomb sublattice, has attracted considerable attention because it may be a realization of the Kitaev quantum spin liquid. Recently, a new honeycomb material, α-RuCl 3 , was prepared under moderately high pressure, and it is stable under ambient conditions. However, different from α-RuCl 3 , α-RuI 3 was reported to be a paramagnetic metal without long-range magnetic order down to 0.35 K. Here, the structural and electronic properties of the quasi-two-dimensional α-RuI 3 are theoretically studied. First, based on first-principles density functional theory calculations, the ABC stacking honeycomb-layer R$\bar{3}$ (No. 148) structure is found to be the most likely stacking order for α-RuI 3 along the c axis. Furthermore, both R$\bar{3}$ and P$\bar{3}$1c are dynamically stable because no imaginary frequency modes were obtained in the phononic dispersion spectrum without Hubbard U. Moreover, the different physical behavior of α-RuI 3 compared to α-RuCl 3 can be understood naturally. The strong hybridization between Ru 4d and I 5p orbitals decreases the “effective” atomic Hubbard repulsion, leading the electrons of RuI3 to be less localized than in RuCl 3 . As a consequence, the effective electronic correlation is reduced from Cl to I, leading to the metallic nature of α-RuI 3 . Based on the DFT+U (Ueff=2 eV) plus spin-orbital coupling, we obtained a spin-orbit Mott insulating behavior for α-RuCl 3 and, with the same procedure, a metallic behavior for α-RuI 3 , in good agreement with experimental results. Furthermore, when introducing large (unrealistic) U eff =6 eV, the spin-orbit Mott gap opens in α-RuI 3 as well, supporting the physical picture we are proposing. Our results provide guidance to experimentalists and theorists working on two-dimensional transition metal tri-iodide layered materials.
Anomalous orbital structure in two-dimensional titanium dichalcogenides
Generally, lattice distortions play a key role in determining the electronic ground states of materials. Although it is well known that trigonal distortions are generic to most two dimensional transition metal dichalcogenides, the impact of this structural distortion on the electronic structure and topological properties has not been understood conclusively. Here, by using a combination of polarization dependent X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) and atomic multiplet cluster calculations, we have investigated the electronic structure of titanium dichalcogenides TiX 2 (X = S, Se, Te), where the magnitude of the trigonal distortion increase monotonically from S to Se and Te. Our results reveal the presence of an anomalously large crystal field splitting. This unusual kind of crystal field splitting is likely responsible for the unconventional electronic structure of TiX 2 compounds and ultimately controls the degree of the electronic phase protection. Our findings also indicate the drawback of the distorted crystal field picture in explaining the observed electronic ground state and emphasize the key importance of trigonal symmetry, metal-ligand hybridization and electron-electron correlations in defining the electronic structures at the Fermi energy.
Correlation Between Bands Structure and Magneto-Transport Properties in n-type HgTe/CdTe Superlattice with Relatively Thin CdTe Barrier
Theoretical calculations of the electronic properties of n-type HgTe/CdTe superlattices (SLs) in the envelope function formalism have provided a reasonable agreement with the experimental data on the magneto-transport behavior. Numerical results of the band energies E(d{sub 2}), E(k{sub z}) and E(k{sub p}) in the direction of growth and in plane of the SLs predict that the system retains semiconductor characteristics for d{sub 1}/d{sub 2} = 2.69 and d{sub 2}<10 nm. For d{sub 2} = 3.2 nm the calculated effective band gap (E{sub g}({Gamma},4.2 K) = 48 meV) suggests that the material sample is a two-dimensional modulated nanostructure and a potential candidate to be used for the far infrared detection applications.
Interface- and discontinuity-aware numerical schemes for plasma 3-T radiation diffusion in two and three dimensions
A set of numerical schemes is developed for two- and three-dimensional time-dependent 3-T radiation diffusion equations in systems involving multi-materials. To resolve sub-cell structure, interface reconstruction is implemented within any cell that has more than one material. Therefore, the system of 3-T radiation diffusion equations is solved on two- and three-dimensional polyhedral meshes. The focus of the development is on the fully coupling between radiation and material, the treatment of nonlinearity in the equations, i.e., in the diffusion terms and source terms, treatment of the discontinuity across cell interfaces in material properties, the formulations for both transient and steady states, the property for large time steps, and second order accuracy in both space and time. The discontinuity of material properties between different materials is correctly treated based on the governing physics principle for general polyhedral meshes and full nonlinearity. The treatment is exact for arbitrarily strong discontinuity. The scheme is fully nonlinear for the full nonlinearity in the 3-T diffusion equations. Three temperatures are fully coupled and are updated simultaneously. The scheme is general in two and three dimensions on general polyhedral meshes. The features of the scheme are demonstrated through numerical examples for transient problems and steady states. The effects of some simplifications of numerical schemes are also shown through numerical examples, such as linearization, simple average of diffusion coefficient, and approximate treatment for the coupling between radiation and material.
Unit-cell-thick zeolitic imidazolate framework films for membrane application
Zeolitic imidazolate frameworks (ZIFs) are a subset of metal–organic frameworks with more than 200 characterized crystalline and amorphous networks made of divalent transition metal centres (for example, Zn 2+ and Co 2+ ) linked by imidazolate linkers. ZIF thin films have been intensively pursued, motivated by the desire to prepare membranes for selective gas and liquid separations. To achieve membranes with high throughput, as in ångström-scale biological channels with nanometre-scale path lengths, ZIF films with the minimum possible thickness—down to just one unit cell—are highly desired. However, the state-of-the-art methods yield membranes where ZIF films have thickness exceeding 50 nm. Here we report a crystallization method from ultradilute precursor mixtures, which exploits registry with the underlying crystalline substrate, yielding (within minutes) crystalline ZIF films with thickness down to that of a single structural building unit (2 nm). The film crystallized on graphene has a rigid aperture made of a six-membered zinc imidazolate coordination ring, enabling high-permselective H 2 separation performance. The method reported here will probably accelerate the development of two-dimensional metal–organic framework films for efficient membrane separation.
Enhancement of interlayer exchange in an ultrathin two-dimensional magnet
Following the recent isolation of monolayer CrI 3 , many more two-dimensional van der Waals magnetic materials have been isolated. Their incorporation in van der Waals heterostructures offers a new platform for spintronics, proximity magnetism and quantum spin liquids. A primary question in this field is how exfoliating crystals to the few-layer limit influences their magnetism. Studies of CrI 3 have shown a different magnetic ground state for ultrathin exfoliated films compared with the bulk, but the origin is not yet understood. Here, we use electron tunnelling through few-layer crystals of the layered antiferromagnetic insulator CrCl 3 to probe its magnetic order and find a tenfold enhancement of the interlayer exchange compared with bulk crystals. Moreover, temperature- and polarization-dependent Raman spectroscopy reveals that the crystallographic phase transition of bulk crystals does not occur in exfoliated films. This results in a different low-temperature stacking order and, we hypothesize, increased interlayer exchange. In conclusion, our study provides insight into the connection between stacking order and interlayer interactions in two-dimensional magnets, which may be relevant for correlating stacking faults and mechanical deformations with the magnetic ground states of other more exotic layered magnets such as RuCl 3 .
Probing excitonic states in suspended two-dimensional semiconductors by photocurrent spectroscopy
The optical response of semiconducting monolayer transition-metal dichalcogenides (TMDCs) is dominated by strongly bound excitons that are stable even at room temperature. However, substrate-related effects such as screening and disorder in currently available specimens mask many anticipated physical phenomena and limit device applications of TMDCs. Here, we demonstrate that that these undesirable effects are strongly suppressed in suspended devices. Extremely robust (photogain > 1,000) and fast (response time < 1 ms) photoresponse allow us to study, for the first time, the formation, binding energies, and dissociation mechanisms of excitons in TMDCs through photocurrent spectroscopy. By analyzing the spectral positions of peaks in the photocurrent and by comparing them with first-principles calculations, we obtain binding energies, band gaps and spin-orbit splitting in monolayer TMDCs. For monolayer MoS2, in particular, we obtain an extremely large binding energy for band-edge excitons, Ebind ≥ 570 meV. Along with band-edge excitons, we observe excitons associated with a van Hove singularity of rather unique nature. In conclusion, the analysis of the source-drain voltage dependence of photocurrent spectra reveals exciton dissociation and photoconversion mechanisms in TMDCs.