Lead-free double perovskites hold promise for stable and environmentally benign solar cells; however, they exhibit low efficiencies because defects act as charge recombination centers. Identifying trap-assisted loss mechanisms and developing defect passivation strategies constitute an urgent goal. Applying unsupervised machine learning to density functional theory and nonadiabatic molecular dynamics, we demonstrate that negatively charged Br vacancies in Cs2AgBiBr6 create deep hole traps through charge redistribution between the adjacent Ag and Bi atoms. Vacancy electrons are first accepted by Bi and then shared with Ag, as the trap transforms from shallow to deep. Subsequent charge losses are promoted by Ag and Bi motions perpendicular to rather than along the Ag–Bi axis, as can be expected. In contrast, charge recombination in pristine Cs2AgBiBr6 correlates most with displacements of Cs atoms and Br–Br–Br angles. Doping with In to replace Ag at the vacancy maintains the electrons at Bi and keeps the trap shallow.
Graphitic carbon nitride (GCN) has attracted significant attention due to its excellent performance in photocatalytic applications. Non-metal doping of GCN has been widely used to improve the efficiency of the material as a photocatalyst. Using a combination of time-domain density functional theory with nonadiabatic molecular dynamics, we study the charge carrier dynamics in oxygen and boron doped GCN systems. The reported simulations provide a detailed time-domain mechanistic description of the charge separation and recombination processes that are of fundamental importance while evaluating the photovoltaic and photocatalytic performance of the material. The appearance of smaller energy gaps due to the presence of dopant states improves the visible light absorption range of the doped systems. At the same time, the nonradiative lifetimes are shortened in the doped systems as compared to the pristine GCN. In the case of boron doped at a carbon (B–C–GCN), the charge recombination time is very long as compared to the other two doped systems owing to the smaller electron–phonon coupling strength between the valence band maximum and the trap state. The results suggest B–C–GCN as the most suitable candidate among three doped systems studied in this work for applications in photocatalysis. This work sheds light into the influence of dopants on quantum dynamics processes that govern GCN performance and, thus, guides toward building high-performance devices in photocatalysis.
Superconductor Science and Technology Supercond. Sci. Technol. 35 (2022) 035003 (15pp) https://doi.org/10.1088/1361-6668/ac455e Current-induced self-organisation of mixed superconducting states Xaver S Brems1,2, Sebastian Mühlbauer1,∗, Wilmer Y Córdoba-Camacho3, Arkady A Shanenko3,4, Alexei Vagov4,5, José Albino Aguiar3 and Robert Cubitt2,∗ 1 Heinz Maier-Leibnitz Zentrum (MLZ), Technische Universität München, Garching, 85748, Germany 2 Institut Laue-Langevin, Grenoble, 38042, France 3 Departamento de Física, Universidade Federal de Pernambuco, Recife, PE, 50740-560, Brazil 4 HSE University, Moscow, 101000, Russia 5 Institut of Theoretical Physics III, University of Bayreuth, Bayreuth, 95440, Germany E-mail: firstname.lastname@example.org and email@example.com Received 19 September 2021, revised 8 December 2021 Accepted for publication 16 December 2021 Published 20 January 2022 Abstract Small-angle neutron scattering is used in combination with transport measurements to investigate the current-induced effects on the morphology of the intermediate mixed state (IMS) domains in the intertype superconductor niobium. We report the robust self-organisation of the vortex lattice domains to elongated parallel stripes perpendicular to the applied current in a steady-state. The experimental results for the formation of the superstructure are supported by theoretical calculations, which highlight important details of the vortex matter evolution. The investigation demonstrates a mechanism of a spontaneous pattern formation that is closely related to the universal physics governing the IMS in low-κ superconductors.
MAPbBr3 (MA = CH3NH3+) doping with bismuth increases electric conductivity, charge carrier density and photostability, reduces toxicity, and expands light absorption. However, Bi doping shortens excited-state lifetimes due to formation of DY− charge recombination centers. Using nonadiabatic molecular dynamics and time−domain density functional theory, we demonstrate that the DY− center forms a deep, highly localized hole trap, which accelerates nonradiative relaxation ten-fold and is responsible for 90% of carrier losses. Hole trapping occurs by coupling between the valence band and the trap state, facilitated by the Br atoms surrounding the Bi dopant. Passivation of the DY− center with chlorines heals the local geometry distortion, eliminates the trap state, and makes the carrier lifetimes longer than even in pristine MAPbBr3. The decreased charge recombination arises from reduced nonadiabatic coupling and shortened coherence time, due to diminished electron−hole overlap around the passivated defect. Our study demonstrates accelerated nonradiative recombination in Bi-doped MAPbBr3, suggests a strategy for defect passivation and reduction of nonradiative energy losses, and provides atomistic insights into unusual defect properties of metal halide perovskites needed for rational design of high-performance perovskite solar cells and optoelectronic devices.
We made numerical calculations of the radiation-induced conductivity by computing current densities, carrier concentrations, and internal electric fields in a disordered sample biased by constant applied voltage under a pulsed or step-function irradiation in a large-signal regime. For this purpose, we used the multiple trapping model featuring an exponential trap distribution with the dispersion parameter α. Calculations of radiation-induced conductivity were done with traditional simplifications (1D-analysis, one-carrier polymer, diffusion currents neglected, and non-injecting electrodes). The nonlinear effects accompanying the large-signal radiation-induced conductivity, such as an internal field variation, the bimolecular recombination, and the charge carrier extraction by electrodes, have been consistently accounted for. Numerical analysis agrees satisfactorily with the results of previously published analytical calculations.
Recent studies have demonstrated that the band structure of a carbon nanotube (CNT) depends not only on its geometry but also on various factors such as atmosphere chemical composition and dielectric environment. Systematic studies of these effects require an efficient tool for an in situ investigation of a CNT band structure. In this work, we fabricate tunneling contacts to individual semiconducting carbon nanotubes through a thin layer of alumina and perform tunneling spectroscopy measurements. We use field-effect transistor configuration with four probe contacts (two tunnel and two ohmic) and bottom gates. Bandgap values extracted from tunneling measurements match the values estimated from the diameter value within the zone-folding approximation. We also observe the splitting of Van-Hove singularities of the density of states under an axial magnetic field.
Transcriptional pausing is crucial for the timely expression of genetic information. Biochemical methods quantify the half-life of paused RNA polymerase (RNAP) by monitoring restarting complexes across time. However, this approach may produce apparent half-lives that are longer than true pause escape rates in biological contexts where multiple consecutive pause sites are present. We show here that the 6-nitropiperonyloxymethyl (NPOM) photolabile group provides an approach to monitor transcriptional pausing in biological systems containing multiple pause sites. We validate our approach using the well-studied his pause and show that an upstream RNA sequence modulates the pause half-life. NPOM was also used to study a transcriptional region within the Escherichia coli thiC riboswitch containing multiple consecutive pause sites. We find that an RNA hairpin structure located upstream to the region affects the half-life of the 5′ most proximal pause site—but not of the 3′ pause site—in contrast to results obtained using conventional approaches not preventing asynchronous transcription. Our results show that NPOM is a powerful tool to study transcription elongation dynamics within biologically complex systems.
We propose a superconducting spin valve based on a Josephson junction with B20-family magnetic metal as a barrier material. Our analysis shows that the states of this element can be switched by reorienting the intrinsic non-collinear magnetization of the spiral magnet. This reorientation modifies long-range spin-triplet correlations and thereby strongly influences the critical Josephson current. Compared to superconducting spin valves proposed earlier, our device has the following advantages: (a) it contains only one barrier layer, which makes it easier to fabricate and control; (b) its ground state is stable, which prevents uncontrolled switching; (c) it is compatible with devices of low-T Josephson electronics. This device may switch between two logical states which exhibit two different values of critical current, or its positive and negative values. I.e. 0-π switch is achievable on a simple Josephson junction.
Photoinduced nonequilibrium processes in nanoscale materials play key roles in photovoltaic and photocatalytic applications. This review summarizes recent theoretical investigations of excited state dynamics in metal halide perovskites (MHPs), carried out using a state-of-the-art methodology combining nonadiabatic molecular dynamics with real-time time-dependent density functional theory. The simulations allow one to study evolution of charge carriers at the ab initio level and in the time-domain, in direct connection with time-resolved spectroscopy experiments. Eliminating the need for the common approximations, such as harmonic phonons, a choice of the reaction coordinate, weak electron–phonon coupling, a particular kinetic mechanism, and perturbative calculation of rate constants, we model full-dimensional quantum dynamics of electrons coupled to semiclassical vibrations. We study realistic aspects of material composition and structure and their influence on various nonequilibrium processes, including nonradiative trapping and relaxation of charge carriers, hot carrier cooling and luminescence, Auger-type charge–charge scattering, multiple excitons generation and recombination, charge and energy transfer between donor and acceptor materials, and charge recombination inside individual materials and across donor/acceptor interfaces. These phenomena are illustrated with representative materials and interfaces. Focus is placed on response to external perturbations, formation of point defects and their passivation, mixed stoichiometries, dopants, grain boundaries, and interfaces of MHPs with charge transport layers, and quantum confinement. In addition to bulk materials, perovskite quantum dots and 2D perovskites with different layer and spacer cation structures, edge passivation, and dielectric screening are discussed. The atomistic insights into excited state dynamics under realistic conditions provide the fundamental understanding needed for design of advanced solar energy and optoelectronic devices.
Based on early phenomenological ideas about the operation of superconducting single-photon detectors (SSPD or SNSPD), it was expected that materials with a lower superconducting gap should perform better in the IR range. The plausibility of this concept could be checked using two popular SSPD materials - NbN and WSi films. However, these materials differ strongly in crystallographic structure (polycrystalline B1 versus amorphous), which makes their dependence on disorder different. In our work we present a study of the single-photon response of SSPDs made from two disordered B1 structure superconductors - vanadium nitride and niobium nitride thin films. We compare the intrinsic efficiency of devices made from films with different sheet resistance values. While both materials have a polycrystalline structure and comparable diffusion coefficient values, VN films show metallic behavior over a wide range of sheet resistance, in contrast toNbNfilms with an insulator-like temperature dependence of resistivity, which may be partially due to enhanced Coulomb interaction, leading to different starting points for the normal electron density of states. The results show that even though VN devices are more promising in terms of theoretical predictions, their optimal performance was not reached due to lower values of sheet resistance.
Pressure-stabilized hydrides are a new rapidly growing class of high-temperature superconductors which is believed to be described in terms of the Bardeen–Cooper–Schrieffer theory of conventional superconductivity. Here we report synthesis of yttrium hexahydride Im3m -YH6 that was prepared in a mixture with I4/mmm-YH4 and YH7 at pressures of 165-172 GPa via laser heating above 2400 K of metallic yttrium with ammonia borane. Compressed Im3m -YH6 demonstrates superconducting transition with TC ~ 224 K at 166 GPa, much lower than theoretical predictions (> 273 K). Upper critical magnetic field Bc2(0) of this compound was found to be 116-158 T, which is 2-2.5 times greater than the calculated one. Additional current-voltage measurements show that critical current density JC may exceed 2000 A/mm2 at 0 K, which is comparable with the parameters of commercially used superconductors such as NbTi and YBCO. Superconducting density functional theory (SCDFT) and anharmonic calculations (SSCHA) point to unusually high Coulomb repulsion (µ* = 0.19-0.21) in this compound. Discovered YH6 is the first superhydride with notable signs of a deviation of superconductivity from the Bardin-Cooper-Schrieffer theory
This study investigates possibilities for extension and improvement of algorithms for generation of libration point orbits in the framework of the circular restricted three body problem. Two algorithms for orbit generation based on bisection approach using different ways for evaluation of unstable component of motion are considered. The spacecraft's state vector is periodically adjusted in such a way that unstable component of motion is neutralized and the trajectory corresponding to the corrected state vector belongs to the central manifold associated with libration point. The first algorithm uses expression for unstable component derived from linearized equations of motion. The second one is based on the procedure of reduction to central manifold, utilizing canonical coordinate transformations to nullify high order monomials in the expansion of Hamiltonian of the system in terms of Legendre polynomials. This allows expressing unstable component as one of generalized coordinates of Hamiltonian system obtained as the result of aforementioned transformation. Evaluation of these techniques proved their applicability for orbit generation. However, the second approach allows generating orbits in greater vicinity of libration point.
In this work we studied how focusing grating couplers, developed for telecommunication C-band wavelength range, can be applied in the near infrared range. In the paper we presented prospects of usage of both first and second diffraction maxima of theoretically computed diffraction grating couplers for photonic aims. The dependence of the central wavelength of the grating on the etching depth of the photonic layer, on the period and filling factor of the grating was studied. We have compared our experimental results with numerical study, performed using finite elements method of solving differential equations. The work is important for different photonic applications and introduces new prospects in application of the already fabricated devices, developed for telecommunication wavelengths. © 2021 Institute of Physics Publishing. All rights reserved.
Lead-free metal halide perovskites are environmentally friendly and have favorable electro-optical properties; however, their efficiencies are significantly below the theoretical limit. Using ab initio nonadiabatic molecular dynamics, we show that common intrinsic defects accelerate nonradiative charge recombination in CsSnI3 without creating midgap traps. This is in contrast to Pb-based perovskites, in which many defects have little influence on and even prolong carrier lifetimes. Sn-related defects, such as Sn vacancies and replacement of Sn with Cs are most detrimental, since Sn removal breaks the largest number of bonds and strongly perturbs the Sn−I lattice that supports the carriers. The defects increase the nonadiabatic electron-vibrational coupling and interact strongly with free carrier states. Point defects associated with I atoms are less detrimental, and therefore, CsSnI3 synthesis should be performed in Sn rich conditions. The study provides an atomistic rationalization of why lead-free CsSnI3 exhibits lower photovoltaic efficiency compared to some lead-based perovskites.
The injection of a long flexible rod into a two-dimensional domain yields a complex pattern commonly studied through the elasticity theory, packing analysis, and fractal geometries. 'Loop' is a one-vertex entity that naturally formed in this system. The role of the elastic features of each loop in 2D packing has not yet been discussed. In this work, we point out how the shape of a given loop in the complex structure allows estimating local deformations and forces. First, we build sets of symmetric free loops and perform compression experiments. Then, tight packing configurations are analyzed using image processing. We find that the dimensions of the loops, confined or not, obey the same dependence on the deformation. The results are consistent with a simple model based on 2D elastic theory for filaments, where the rod adopts the shape of Euler's elasticas between its contact points. The force and the stored energy are obtained from numerical integration of the analytic expressions. In an additional experiment, we obtain that the compression force for deformed loops corroborates the theoretical findings. The importance of the shape of the loop is discussed and we hope that the theoretical curves may allow statistical considerations in future investigations.
We report a study of multiphoton detection fidelity (or accuracy) for sequential photon-number resolving detectors based on micron-wide superconducting strips. It was found that an increase in the width of the superconducting strips by a factor of 5 leads to an improvement in the measurement accuracy by more than a factor of 10.
Inelastic interactions of quantum systems with the environment usually wash coherent effects out. In the case of Friedel oscillations, the presence of disorder leads to a fast decay of the oscillation amplitude. Here we show both experimentally and theoretically that in three-dimensional topological insulator Bi2Te3 there is a nesting-induced splitting of coherent scattering vectors which follows a peculiar evolution in energy. The effect becomes experimentally observable when the lifetime of quasiparticles shortens due to disorder. The amplitude of the splitting allows an evaluation of the lifetime of the electrons. A similar phenomenon should be observed in any system with a well-defined scattering vector regardless of its topological properties.
In the novel stoichiometric iron-based material RbEuFe4As4, superconductivity coexists with a peculiar longrange magnetic order of Eu 4f states. Using angle-resolved photoemission spectroscopy, we reveal a complex three-dimensional electronic structure and compare it with density functional theory calculations.Multiple superconducting gaps were measured on various sheets of the Fermi surface. High-resolution resonant photoemission spectroscopy reveals magnetic order of the Eu 4f states deep into the superconducting phase. Both the absolute values and the anisotropy of the superconducting gaps are remarkably similar to the sibling compound without Eu, indicating that Eu magnetism does not affect the pairing of electrons. A complete decoupling between Feand Eu-derived states was established from their evolution with temperature, thus unambiguously demonstrating that superconducting and a long-range magnetic orders exist independently from each other. The established electronic structure of RbEuFe4As4 opens opportunities for the future studies of the highly unorthodox electron pairing and phase competition in this family of iron-based superconductors with doping
A model of an integrated photonic device based on an O-ring resonator and loop waveguide reflector operated at telecom wavelength (1550) was developed.