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At least 397 records · Page 22

Composite Nature of Layered Hybrid Perovskites: Assessment on Quantum and Dielectric Confinements and Band Alignment

Layered hybrid organic–inorganic perovskites (HOPs) have re-emerged as potential technological solutions for next-generation photovoltaic and optoelectronic applications. Their two-dimensional (2D) nature confers them a significant flexibility and results in the appearance of quantum and dielectric confinements. Such confinements are at the origin of their fascinating properties, and understanding them from a fundamental level is of paramount importance for optimization. Here, we provide an in-depth investigation of band alignments of 2D HOP allowing access to carriers’ confinement potentials. 2D HOPs are conceptualized as composite materials in which pseudoinorganic and -organic components are defined. In this way, computational modeling of band alignments becomes affordable using first-principles methods. First, we show that the composite approach is suitable to study the position-dependent dielectric profiles and enables clear differentiation of the respective contributions of inorganic and organic components. Then we apply the composite approach to a variety of 2D HOPs, assessing the impact on the confinement potentials of well and barrier thickness, of the nature of the inorganic well, and of structural transitions. Using the deduced potentials, we further discuss the limitations of the effective mass approximation, scrutinizing the electronic properties of this family of composite materials. Our simulations demonstrate type-I dominant band alignment in 2D HOPs. Finally, we outline design principles on band alignment toward achieving specific optoelectronic properties. Furthermore, we present alternative theoretical methods to inspect the properties of 2D hybrid perovskites and expect that the composite approach will be applicable to other classes of layered materials.

36 MATERIALS SCIENCE↗

Quasiparticle Level Alignment for Photocatalytic Interfaces

Electronic level alignment at the interface between an adsorbed molecular layer and a semiconducting substrate determines the activity and efficiency of many photocatalytic materials. Standard density functional theory (DFT)-based methods have proven unable to provide a quantitative description of this level alignment. This requires a proper treatment of the anisotropic screening, necessitating the use of quasiparticle (QP) techniques. However, the computational complexity of QP algorithms has meant a quantitative description of interfacial levels has remained elusive. We provide a systematic study of a prototypical interface, bare and methanol-covered rutile TiO2(110) surfaces, to determine the type of many-body theory required to obtain an accurate description of the level alignment. This is accomplished via a direct comparison with metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), and two-photon photoemission (2PP) spectroscopy. We consider GGA DFT, hybrid DFT, and G0W0, scQPGW1, scQPGW0, and scQPGW QP calculations. Our results demonstrate that G0W0, or our recently introduced scQPGW1 approach, are required to obtain the correct alignment of both the highest occupied and lowest unoccupied interfacial molecular levels (HOMO/LUMO). These calculations set a new standard in the interpretation of electronic structure probe experiments of complex organic molecule/semiconductor interfaces.

Environmental Molecular Sciences Laboratory↗

Self-Assembly of Atomically Aligned Nanoparticle Superlattices from Pt–Fe 3 O 4 Heterodimer Nanoparticles

Multicomponent nanoparticle superlattices (SLs) promise the integration of nanoparticles (NPs) with remarkable electronic, magnetic, and optical properties into a single structure. Here, we demonstrate that heterodimers consisting of two conjoined NPs can self-assemble into novel multicomponent SLs with a high degree of alignment between the atomic lattices of individual NPs, which has been theorized to lead to a wide variety of remarkable properties. Specifically, by using simulations and experiments, we show that heterodimers composed of larger Fe 3 O 4 domains decorated with a Pt domain at one vertex can self-assemble into an SL with long-range atomic alignment between the Fe 3 O 4 domains of different NPs across the SL. The SLs show an unanticipated decreased coercivity relative to nonassembled NPs. In situ scattering of the self-assembly reveals a two-stage mechanism of self-assembly: translational ordering between NPs develops before atomic alignment. Here our experiments and simulation indicate that atomic alignment requires selective epitaxial growth of the smaller domain during heterodimer synthesis and specific size ratios of the heterodimer domains as opposed to specific chemical composition. This composition independence makes the self-assembly principles elucidated here applicable to the future preparation of multicomponent materials with fine structural control.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Molecular Electronic Level Alignment at Weakly Coupled Organic Film/Metal Interfaces

Electronic level alignment at interfaces of molecular materials with inorganic semiconductors and metals controls many interfacial phenomena. How the intrinsic properties of the interacting systems define the electronic structure of their interface remains one of the most important problems in molecular electronics and nanotechnology that can be solved through a combination of surface science experimental techniques and theoretical modeling. In this article, we address this fundamental problem through experimental and computational studies of molecular electronic level alignment of thin films of C6F6 on noble metal surfaces. The unoccupied electronic structure of C6F6 is characterized with single molecule resolution using low-temperature scanning tunneling microscopy-based constant-current distance-voltage spectroscopy. The experiments are performed on several noble metal surfaces with different work functions and distinct surface-normal projected band structures. In parallel, the electronic structures of the quantum wells (QWs) formed by the lowest unoccupied molecular orbital state of the C6F6 monolayer and multilayer films and their alignment with respect to the vacuum level of the metallic substrates are calculated by solving the Schrödinger equation for a semiempirical one-dimensional (1D) potential of the combined system using input from density functional theory. Our analysis shows that the level alignment for C6F6 molecules bound through weak van der Waals interactions to noble metal surfaces is primarily defined by the image potential of metal, the electron affinity of the molecule, and the molecule surface distance. We expect the same factors to determine the interfacial electronic structure for a broad range of molecule/metal interfaces.

Environmental Molecular Sciences Laboratory↗

Alignment switching in 3D-printed smectic liquid crystal elastomers

Extrusion-based additive manufacturing has emerged as a powerful platform for designing shape-morphing materials through controlled orientation. However, existing approaches primarily rely on a single mode of flow-induced alignment, limiting orientation programmability. Herein, we present a direct-ink-writing approach for smectic liquid crystal elastics that exploits two distinct alignment modes within a single ink. The smectic ink exhibits shear- and temperature-dependent orientation switching, enabling molecular alignment either perpendicular or parallel to the print direction. Combined rheological, X-ray, and molecular dynamics analyses reveal that this alignment inversion arises from the preservation or collapse of smectic layers under flow. This reversible switching encodes both contractile and elongational actuation within individual filaments, greatly expanding the design freedom of printed liquid crystal elastomers. We demonstrate 2D and 3D structures with diverse programmed shape transformations, highlighting the potential of this platform for adaptive soft actuators and architected functional materials.

Lee, Jin Hyeong [Pusan National University, Busan,↗

Extreme Magneto-transport of Bulk Carbon Nanotubes in Sorted Electronic Concentrations and Aligned High Performance Fiber

We explored high-field (60 T) magneto-resistance (MR) with two carbon nanotube (CNT) material classes: (1) unaligned single-wall CNTs (SWCNT) films with controlled metallic SWCNT concentrations and doping degree and (2) CNT fiber with aligned, long-length microstructure. All unaligned SWCNT films showed localized hopping transport where high-field MR saturation definitively supports spin polarization instead of a more prevalent wave function shrinking mechanism. Nitric acid exposure induced an insulator to metal transition and reduced the positive MR component. Aligned CNT fiber, already on the metal side of the insulator to metal transition, had positive MR without saturation and was assigned to classical MR involving electronic mobility. Subtracting high-field fits from the aligned fiber’s MR yielded an unconfounded negative MR, which was assigned to weak localization. It is concluded that fluctuation induced tunnelling, an extrinsic transport model accounting for most of the aligned fiber’s room temperature resistance, appears to lack MR field dependence.

36 MATERIALS SCIENCE↗

DNCON2_Inter: predicting interchain contacts for homodimeric and homomultimeric protein complexes using multiple sequence alignments of monomers and deep learning

Deep learning methods that achieved great success in predicting intrachain residue-residue contacts have been applied to predict interchain contacts between proteins. However, these methods require multiple sequence alignments (MSAs) of a pair of interacting proteins (dimers) as input, which are often difficult to obtain because there are not many known protein complexes available to generate MSAs of sufficient depth for a pair of proteins. In recognizing that multiple sequence alignments of a monomer that forms homomultimers contain the co-evolutionary signals of both intrachain and interchain residue pairs in contact, we applied DNCON2 (a deep learning-based protein intrachain residue-residue contact predictor) to predict both intrachain and interchain contacts for homomultimers using multiple sequence alignment (MSA) and other co-evolutionary features of a single monomer followed by discrimination of interchain and intrachain contacts according to the tertiary structure of the monomer. We name this tool DNCON2_Inter. Allowing true-positive predictions within two residue shifts, the best average precision was obtained for the Top-L/10 predictions of 22.9% for homodimers and 17.0% for higher-order homomultimers. In some instances, especially where interchain contact densities are high, DNCON2_Inter predicted interchain contacts with 100% precision. We also developed Con_Complex, a complex structure reconstruction tool that uses predicted contacts to produce the structure of the complex. Using Con_Complex, we show that the predicted contacts can be used to accurately construct the structure of some complexes. Our experiment demonstrates that monomeric multiple sequence alignments can be used with deep learning to predict interchain contacts of homomeric proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Fabrication and 3D tomographic characterization of nanowire arrays and meshes with tunable dimensions from shear-aligned block copolymers

We demonstrate a scalable method to create metallic nanowire arrays and meshes over square-centimeter-areas with tunable sub-100 nm dimensions and geometries using the shear alignment of block copolymers. We use the block copolymer poly(styrene)- b -poly(2-vinyl pyridine) (PS–P2VP) since the P2VP block complexes with metal salts like Na 2 PtCl 4 , thereby enabling us to directly pattern nanoscale platinum features. We investigate what shear alignment processing parameters are necessary to attain high quality and well-ordered nanowire arrays and quantify how the block copolymer's molecular weight affects the resulting Pt nanowires’ dimensions and defect densities. Through systematic studies of processing parameters and scanning transmission electron microscopy (STEM) tomography, we determine that the equivalent of 2–3 monolayers of PS–P2VP are required to produce a single layer of well-aligned nanowires. The resulting nanowires’ widths and heights can be tuned between 11–27 nm and 9–50 nm, respectively, and have periodicites varying between 37 and 63 nm, depending on the choice of block copolymer molecular weight. We observe that the height-to-width ratio of the nanowires also increases with molecular weight, reaching a value of almost 2 with the largest dimensions fabricated. As a result, we demonstrate that an additional layer of Pt nanowires can be orthogonally aligned on top of and without disturbing an underlying layer, thereby enabling the fabrication of Pt nanowire meshes with tunable sub-100 nm dimensions and geometries over a cm 2 -area.

36 MATERIALS SCIENCE↗

Design of a self-aligned, wide temperature range (300 mK-300 K) atomic force microscope/magnetic force microscope with 10 nm magnetic force microscope resolution

We describe the design of a wide temperature range (300 mK-300 K) atomic force microscope/magnetic force microscope with a self-aligned fibre-cantilever mechanism. An alignment chip with alignment groves and a special mechanical design are used to eliminate tedious and time consuming fibre-cantilever alignment procedure for the entire temperature range. A low noise, Michelson fibre interferometer was integrated into the system for measuring deflection of the cantilever. The spectral noise density of the system was measured to be ~12 fm/√Hz at 4.2 K at 3 mW incident optical power. Abrikosov vortices in BSCCO(2212) single crystal sample and a high density hard disk sample were imaged at 10 nm resolution to demonstrate the performance of the system.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Characterization of reactively sputtered c-axis aligned nanocrystalline InGaZnO{sub 4}

Crystallinity and texturing of RF sputtered c-axis aligned crystal InGaZnO{sub 4} (CAAC IGZO) thin films were quantified using X-ray diffraction techniques. Above 190 °C, nanocrystalline films with an X-ray peak at 2θ = 30° (009 planes) developed with increasing c-axis normal texturing up to 310 °C. Under optimal conditions (310 °C, 10% O{sub 2}), films exhibited a c-axis texture full-width half-maximum of 20°. Cross-sectional high-resolution transmission electron microscopy confirmed these results, showing alignment variation of ±9° over a 15 × 15 nm field of view and indicating formation of much larger aligned domains than previously reported. At higher deposition temperatures, c-axis alignment was gradually lost as polycrystalline films developed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of TiO{sub 2} thickness on nanocomposited aligned ZnO nanorod/TiO{sub 2} for dye-sensitized solar cells

The TiO{sub 2} films were deposited on glass substrate at different thicknesses with different deposition frequencies (1, 2, 3 and 4 times) using spin coating technique and their structural properties were investigated. Subsequently, the nanocomposited aligned ZnO nanorods and TiO{sub 2} were formed by deposited the TiO{sub 2} on top of aligned ZnO Nanorod on ITO-coated glass at different thicknesses using the same method of TiO{sub 2} deposited on glass substrate. The nanocomposited aligned ZnO nanorod/TiO{sub 2} were coated with different thicknesses of 900µm, 1815µm, 2710µm, 3620µm and ZnO without TiO{sub 2}. The dye-sensitized solar cells were fabricated from the nanocomposited aligned ZnO nanorod/TiO{sub 2} with thickness of 900µm, 1815µm, 2710µm and 3620µm and ZnO without TiO{sub 2} and their photovoltaic properties of the DSSCs were investigated. From the solar simulator measurement the solar energy conversion efficiency (η) of 2.543% under AM 1.5 was obtained for the ZnO nanorod/TiO{sub 2} photoanode-2710µm Dye-Sensitized solar cell.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. Here, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by construction captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, the both the level alignment and work function changes. This approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.

36 MATERIALS SCIENCE↗

Vapor-to-glass preparation of biaxially aligned organic semiconductors

Physical vapor deposition (PVD) provides a route to prepare highly stable and anisotropic organic glasses that are utilized in multi-layer structures such as organic light-emitting devices. While previous work has demonstrated that anisotropic glasses with uniaxial symmetry can be prepared by PVD, here, we prepare biaxially aligned glasses in which molecular orientation has a preferred in-plane direction. With the collective effect of the surface equilibration mechanism and template growth on an aligned substrate, macroscopic biaxial alignment is achieved in depositions as much as 180 K below the clearing point TLC−iso (and 50 K below the glass transition temperature Tg) with single-component disk-like (phenanthroperylene ester) and rod-like (itraconazole) mesogens. The preparation of biaxially aligned organic semiconductors adds a new dimension of structural control for vapor-deposited glasses and may enable polarized emission and in-plane control of charge mobility.

Chemistry↗

EXTENDED NEUTRAL HYDROGEN IN THE ALIGNED SHELL GALAXIES Arp 230 AND MCG -5-7-1: FORMATION OF DISKS IN MERGING GALAXIES?

As part of an ongoing study of the neutral hydrogen (H I) morphology and kinematics of 'shell' elliptical galaxies, we present Very Large Array observations of two shell galaxies with aligned shells, Arp 230 and MCG -5-7-1. Our data provide the first H I images of Arp 230 and deeper images of MCG -5-7-1 than previously reported. Optical images of Arp 230 reveal a bright, aligned, interleaved shell system, making it an ideal candidate for 'phase-wrapped' shell formation following a radial encounter with a smaller companion. The fainter, non-interleaved shells of MCG -5-7-1 do not clearly favor a particular formation scenario. The H I we detect in both galaxies extends to nearly the same projected distance as the optical shells. In Arp 230 this gas appears to be anti-correlated with the aligned shells, consistent with our expectations for phase-wrapped shells produced in a radial encounter. In MCG -5-7-1, we observe gas associated with the shells making a 'spatial wrapping' or looping scenario more plausible. Although the extended gas component in both galaxies is unevenly distributed, the gas kinematics are surprisingly regular, looking almost like complete disks in rotation. We use the H I kinematics and optical data to determine mass-to-light ratios M/L{sub B} of 2.4{sup +3.0}{sub -0.5} (at 13.5 kpc, 4.5 R{sub e} ) for Arp 230 and M/L{sub B} of 30 {+-} 7 (at 40 kpc, 7 R{sub e} ) in MCG -5-7-1. In both systems we find that this ratio changes as a function of radius, indicating the presence of a dark halo. By comparing orbital and precession timescales, we conclude that the potentials are slightly flattened. We infer a 5%-10% flattening for Arp 230 and less flattening in the case of MCG -5-7-1. Finally, we present images of the H I associated with the inner disk or (polar) ring of each galaxy and discuss possible explanations for their different present-day star formation rates. We detect total H I masses of 1.1 Multiplication-Sign 10{sup 9} M{sub Sun} in Arp 230 and 3.7 Multiplication-Sign 10{sup 9} M{sub Sun} in MCG -5-7-1. Both systems have H I masses, scale sizes, and regular kinematics similar to those of non-aligned shell galaxies we have previously studied (Cen A and NGC 2865). Furthermore, we (re-)emphasize in this paper that shell galaxies such as MCG -5-7-1, along with previously studied galaxies NGC 5128 (Cen A) and NGC 2865, are unique in that they provide evidence of recent accretion with gas and collisionless stars showing clear association, though the displacement suggests the presence of significant gas-dynamical interaction.

79 ASTRONOMY AND ASTROPHYSICS↗

Alignments of the galaxies in and around the Virgo cluster with the local velocity shear

Observational evidence is presented for the alignment between the cosmic sheet and the principal axis of the velocity shear field at the position of the Virgo cluster. The galaxies in and around the Virgo cluster from the Extended Virgo Cluster Catalog that was recently constructed by Kim et al. are used to determine the direction of the local sheet. The peculiar velocity field reconstructed from the Sloan Digital Sky Survey Data Release 7 is analyzed to estimate the local velocity shear tensor at the Virgo center. Showing first that the minor principal axis of the local velocity shear tensor is almost parallel to the direction of the line of sight, we detect a clear signal of alignment between the positions of the Virgo satellites and the intermediate principal axis of the local velocity shear projected onto the plane of the sky. Furthermore, the dwarf satellites are found to appear more strongly aligned than their normal counterparts, which is interpreted as an indication of the following. (1) The normal satellites and the dwarf satellites fall in the Virgo cluster preferentially along the local filament and the local sheet, respectively. (2) The local filament is aligned with the minor principal axis of the local velocity shear while the local sheet is parallel to the plane spanned by the minor and intermediate principal axes. Our result is consistent with the recent numerical claim that the velocity shear is a good tracer of the cosmic web.

79 ASTRONOMY AND ASTROPHYSICS↗

A steady-state alignment front in an accretion disk subjected to Lense–Thirring torques

Using only physical mechanisms, i.e., 3D magnetohydrodynamics (MHD) with no phenomenological viscosity, we have simulated the dynamics of a moderately thin accretion disk subject to torques whose radial scaling mimics those produced by lowest-order post-Newtonian gravitomagnetism. In this simulation, we have shown how, in the presence of MHD turbulence, a time-steady transition can be achieved between an inner disk region aligned with the equatorial plane of the central mass’s spin and an outer region orbiting in a different plane. The position of the equilibrium orientation transition is determined by a balance between gravitomagnetic torque and warp-induced inward mixing of misaligned angular momentum from the outer disk. If the mixing is interpreted in terms of diffusive transport, the implied diffusion coefficient is ≃(0.6–0.8)c{sub s}{sup 2}/Ω for sound speed c{sub s} and orbital frequency Ω. This calibration permits estimation of the orientation transition’s equilibrium location given the central mass, its spin parameter, and the disk’s surface density and scaleheight profiles. However, the alignment front overshoots before settling into an equilibrium, signaling that a diffusive model does not fully represent the time-dependent properties of alignment fronts under these conditions. Because the precessional torque on the disk at the alignment front is always comparable to the rate at which misaligned angular momentum is brought inward to the front by warp-driven radial motions, no break forms between the inner and outer portions of the disk in our simulation. Our results also raise questions about the applicability to MHD warped disks of the traditional distinction between “bending wave” and “diffusive” regimes.

79 ASTRONOMY AND ASTROPHYSICS↗

Separating intrinsic alignment and galaxy-galaxy lensing

The coherent physical alignment of galaxies is an important systematic for gravitational lensing studies as well as a probe of the physical mechanisms involved in galaxy formation and evolution. We develop a formalism for treating this intrinsic alignment (IA) in the context of galaxy-galaxy lensing and present an improved method for measuring IA contamination, which can arise when sources physically associated with the lens are placed behind the lens due to photometric redshift scatter. We apply the technique to recent Sloan Digital Sky Survey (SDSS) measurements of Luminous Red Galaxy lenses and typical ( ∼ L{sub *}) source galaxies with photometric redshifts selected from the SDSS imaging data. Compared to previous measurements, this method has the advantage of being fully self-consistent in its treatment of the IA and lensing signals, solving for the two simultaneously. We find an IA signal consistent with zero, placing tight constraints on both the magnitude of the IA effect and its potential contamination to the lensing signal. While these constraints depend on source selection and redshift quality, the method can be applied to any measurement that uses photometric redshifts. We obtain a model-independent upper-limit of roughly 10% IA contamination for projected separations of r{sub p} ≈ 0.1–10 h{sup −1}Mpc. With more stringent photo-z cuts and reasonable assumptions about the physics of intrinsic alignments, this upper limit is reduced to 1–2%. These limits are well below the statistical error of the current lensing measurements. Our results suggest that IA will not present intractable challenges to the next generation of galaxy-galaxy lensing experiments, and the methods presented here should continue to aid in our understanding of alignment processes and in the removal of IA from the lensing signal.

79 ASTRONOMY AND ASTROPHYSICS↗

Polarization-shape alignment of IllustrisTNG star-forming galaxies

In star-forming disk galaxies, the radio continuum emission (1–10GHz) powered by star formation has an integrated polarization direction imperfectly aligned with the apparent disk minor axis. This polarization-shape alignment effect was previously observed in a small sample of local spirals. If this is prevalent for disk galaxies out to cosmological redshifts, novel measurements of cosmic birefringence and cosmic shear will be enabled by leveraging radio continuum surveys such as the Square Kilometre Array synergized with galaxy shape measurements. We calculate the polarization-shape misalignment angle for star-forming galaxies in the IllustrisTNG50 simulation at 0 < z < 2, assuming that additional polarized radio emission from an active galactic nucleus is negligible in at least a sizable fraction of the star-forming galaxies. The alignment found for z = 0 is consistent with local spiral data, but significantly deteriorates as redshift increases. Moreover, it degrades toward lower frequencies due to internal Faraday depolarization. Thanks to cosmic redshifting, observing higher-z galaxies at a fixed frequency greatly mitigates degradation due to reduced Faraday depolarization at the source-frame frequency. We present analytic fits to the non-Gaussian misalignment angle distribution, and evaluate Fisher information per galaxy for measuring a polarization rotation angle induced by cosmic birefringence. For observation at 4.8 GHz, the effective root-mean-square misalignment angle σα,eff is 18°, 23° and 33° at z = 0, 1 and 2, respectively. Analyzing N independent galaxies reduces the uncertainty on an isotropic cosmic birefringence signal to σ α,eff /√(N), providing competitive sensitivity once large samples are available. As accurate observation-driven models are not yet available for cosmological galaxy samples, our results motivate pilot observations to empirically characterize polarization-shape alignment, and can facilitate forecasts of cosmology and fundamental physics applications that exploit this effect.

axions↗