First-Principles Studies of the Electronic and Optical Properties of Zinc Titanium Nitride: The Role of Cation Disorder
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36 MATERIALS SCIENCE↗
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Results for “disordered materials”
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Fluctuation-induced odd-frequency spin-triplet pairing in a disordered electron liquid
Here we consider a two-dimensional disordered conductor in the regime when the superconducting phase is destroyed by the magnetic field. We analyze a combination of fluctuations of different origin which results in an effective interaction amplitude suitable for a spontaneous s-wave odd-frequency pairing instability. We observe that the end point of the superconductivity is a quantum critical point separating the conventional superconducting phase from a state with the odd-frequency spin-triplet pairing instability. We speculate that this could shed light on a rather mysterious insulating state observed in strongly disordered superconducting films in a broad region of the magnetic fields.
36 MATERIALS SCIENCE↗
Coherent quantum transport in disordered systems: A unified polaron treatment of hopping and band-like transport
Quantum transport in disordered systems is studied using a polaron-based master equation. The polaron approach is capable of bridging the results from the coherent band-like transport regime governed by the Redfield equation to incoherent hopping transport in the classical regime. A non-monotonic dependence of the diffusion coefficient is observed both as a function of temperature and system-phonon coupling strength. In the band-like transport regime, the diffusion coefficient is shown to be linearly proportional to the system-phonon coupling strength and vanishes at zero coupling due to Anderson localization. In the opposite classical hopping regime, we correctly recover the dynamics described by the Fermi’s Golden Rule and establish that the scaling of the diffusion coefficient depends on the phonon bath relaxation time. In both the hopping and band-like transport regimes, it is demonstrated that at low temperature, the zero-point fluctuations of the bath lead to non-zero transport rates and hence a finite diffusion constant. Application to rubrene and other organic semiconductor materials shows a good agreement with experimental mobility data.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Ni/Li Disordering in Layered Transition Metal Oxide: Electrochemical Impact, Origin, and Control
Lithium-ion batteries (LIBs) not only power most of today’s hybrid electric vehicles (HEV) and electric vehicles (EV) but also are considered as a very promising system for grid-level storage. Large-scale applications for LIBs require substantial improvement in energy density, cost, and lifetime. Layered Li(NixMnyCoz)O2 (NMC, x+y+z=1) materials from solid-solution approaches to LiMO2 (M = Ni, Mn, Co, etc) are the most promising candidates for their high reversible capacity, better environmental compatibility, and lower cost compared with the traditional LiCoO2. In order to further boost Li storage capacity, a great deal of attention has been directed toward developing Ni-rich NMCs. However, structural disorder as a result of Ni/Li exchange in octahedral sites becomes a critical issue when Ni content increases to high values, as it leads to a detrimental effect on Li diffusivity, cycling stability, first-cycle efficiency, and overall electrode performance. Increasing efforts have been dedicated to improving the electrochemical performance of NMC materials via reduction of cationic mixing. Therefore, it is important to summarize this research field and provide in-depth insight into impact of Ni/Li disorder on electrochemical characteristics in layered NMC materials and its origin to accelerate the future development of NMC materials with high performance. In this Account, we start by analyzing the impact of Ni/Li disorder on electrochemical characteristics in layered NMC materials. The antisite Ni in the Li layer can limit the rate performance by impeding the Li-ion transport. It will also degrade the cycling stability by inducing the anisotropic stress in the bulk structure. Nevertheless, the antisite Ni-ions don’t always bring drawbacks to the electrochemical performance, some studies including our works found that it can improve the thermal stability and the cycling structure stability of Ni-rich NMC materials. We next discussed the driving forces and the kinetic advantages accounting for the Ni/Li exchange and summarized that the steric effect of cation size and the magnetic interactions between TM cations are the two main driving forces to promote the Ni/Li exchange during synthesis procedure and the electrochemical cycling, and the low energy barrier of Ni2+ migration from the 3a site in TM layer to 3b site in Li layer further provides the kinetic advantage. Based on above understandings, we reviewed the progress made to control the Ni/Li disorder and summarized three main ways: (i) suppressing the driving force from the steric effect by ion exchange; (ii) tuning the magnetic interaction by cationic substitution; (iii) kinetic controlling of Ni migration. Finally, our brief outlooks on the future development of controlling the Ni/Li disorder in NMC materials are provided. It is believed that this Account will provide significant understanding and inspirations toward developing high-performance NMC materials with controlled Ni/Li disorder.
Zheng, Jiaxin↗
Imaging Valley Excitons in a 2D Semiconductor with Scanning Tunneling Microscope-Induced Luminescence
Valley excitons dominate the optoelectronic response of transition-metal dichalcogenides and are drastically affected by structural and environmental inhomogeneities localized in these materials. Critical to understanding and controlling these nanoscale excitonic changes is the ability to correlate the imaging of excitonic states with crystalline structures on the atomic scale. Here, in this study, we apply scanning tunneling microscope-induced luminescence microscopy to image valley excitons in a semiconducting transition-metal dichalcogenide monolayer decoupled by a 10 nanometer-thick hexagonal-boron-nitride flake incorporated in a lateral homojunction on an Au electrode surface. This design enables the observation of chiral excitonic emission arising from neutral and charged valley excitons of the monolayer semiconductor at ambipolar voltages with a quantum efficiency up to similar to ~10 -5 photon/electron. The measured light helicity demonstrates considerable circular polarization dependent on the sample voltage, reaching as much as 40%. The real-space luminescence imaging maps$-$at subnanometer resolution$-$of the valley excitons reveal striking spatial variations associated with localized inhomogeneities, including surface impurities and possibly nanoscale dielectric and/or potential disorders in the monolayer. Our study introduces a promising format for 2D materials to explore and tailor their optoelectronic processes at the atomic scale.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Theory of thermal properties of magnetic materials with unknown entropy
Theoretical approaches to study thermal properties of magnetic materials typically require accurate models of magnetic interactions in order to define the entropy. Here we introduce a complementary approach for examining thermal properties in magnetic systems where an accepted model for such interactions does not exist. In place of a specific model for magnetic interactions, the approach integrates measurements of temperature dependent magnetization of the studied material into a first principles computational scheme. The approach calculates system pressure from thermally disordered microstates that properly incorporate vibrational and spin subsystems at each temperature as well as the coupling between these subsystems. We apply the approach to calculate phonon modes and to investigate the anomalously low thermal expansion of the classical Invar alloy, Fe 0.65 Ni 0.35 . Here, the calculated phonon dispersions for Invar are in excellent agreement with measured data. The Invar thermal expansion is shown to remain small between 50 K and room temperature, consistent with the experimentally observed low thermal expansion value in this same temperature range. This anomalously small thermal expansion is directly connected to a small positive contribution from lattice thermal disorder that is nearly canceled by a large negative magnetic disorder contribution. By contrast, calculations for bcc Fe show a much larger thermal expansion, consistent with experiment, which is dominated by a large contribution from lattice thermal disorder that is reduced only slightly by a small negative contribution from that of magnetism. These findings give insights into the unusual nature of magnetism and spin-lattice coupling in Invar and Fe. In addition, they give promising preliminary support to the presented new methodology as a complementary way to investigate thermal properties of magnetic materials. The success achieved on Invar and Fe motivates future testing of the approach on other magnetic materials.
36 MATERIALS SCIENCE↗
Probing disorder in isometric pyrochlore and related complex oxides
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nuclear (including radiation effects), materials a↗
Superheating suppresses structural disorder in layered BiI3 semiconductors grown by the Bridgman method
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Johns, Paul M.↗
Fast Li-Ion Conductivity in Superadamantanoid Lithium Thioborate Halides
Lithium thioborates are promising fast Li-ion conducting materials, with similar properties to their lithium thiophosphate counterparts that have enabled the development of solid-state Li-ion batteries. By comparison, thioborates have scarcely been developed, however, offering new space for materials discovery. In this work, we report a new class of lithium thioborate halides that adopt a so-called supertetrahedral adamantanoid structure that houses mobile lithium ions and halide anions within interconnected 3D structural channels. Investigation of the structure using single-crystal XRD, neutron powder diffraction, and neutron PDF reveals significant lithium and halide anion disorder. The phases are non-stoichiometric, adopting slightly varying halide contents within the materials. These new superadamantanoid materials exhibit high ionic conductivities up to 1.4 mS cm -1 , which can be effectively tuned by the polarizability of the halide anion within the channels.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Multi-principal elemental intermetallic nanoparticles synthesized via a disorder-to-order transition
Nanoscale multi-principal element intermetallics (MPEIs) may provide a broad and tunable compositional space of active, high–surface area materials with potential applications such as catalysis and magnetics. However, MPEI nanoparticles are challenging to fabricate because of the tendency of the particles to grow/agglomerate or phase-separated during annealing. Here, we demonstrate a disorder-to-order phase transition approach that enables the synthesis of ultrasmall (4 to 5 nm) and stable MPEI nanoparticles (up to eight elements). We apply just 5 min of Joule heating to promote the phase transition of the nanoparticles into L1 0 intermetallic structure, which is then preserved by rapidly cooling. This disorder-to-order transition results in phase-stable nanoscale MPEIs with compositions (e.g., PtPdAuFeCoNiCuSn), which have not been previously attained by traditional synthetic methods. This synthesis strategy offers a new paradigm for developing previously unexplored MPEI nanoparticles by accessing a nanoscale-size regime and novel compositions with potentially broad applications.
25 ENERGY STORAGE↗
Relaxation mechanisms in a disordered system with Poisson-level statistics
Here we discuss the interplay between many-body localization and spin symmetry. To this end, we study the time evolution of several observables in the anisotropic t- j model. Like the Hubbard chain, the studied model contains charge and spin degrees of freedom, yet it has smaller Hilbert space and thus allows for numerical studies of larger systems. We compare the field disorder that breaks the $\mathbb{Z}_2$ spin symmetry and a potential disorder that preserves the latter symmetry. In the former case, sufficiently strong disorder leads to localization of all studied observables, at least for the studied system sizes. However, in the case of symmetry-preserving disorder, we observe that odd operators under the $\mathbb{Z}_2$ spin transformation relax towards the equilibrium value at relatively short timescales that grow only polynomially with the disorder strength. On the other hand, the dynamics of even operators and the level statistics within each symmetry sector are consistent with localization. Our results indicate that localization exists within each symmetry sector for symmetry-preserving disorder. Odd operators' apparent relaxation is due to their time evolution between distinct symmetry sectors.
36 MATERIALS SCIENCE↗
Benchmarking Guanidinium Organosulfonate Hydrogen-Bonded Frameworks for Structure Determination of Encapsulated Guests
Single crystal X-ray diffraction (SCXRD) is arguably the most definitive method for molecular structure determination, but it is often challenged by compounds that are liquids or oils at room temperature or do not form crystals adequate for analysis. Our laboratory previously reported a simple, cost-effective, single-step crystallization method based on guanidinium organosulfonate (GS) hydrogen bonded frameworks for structure determination of a wide range of encapsulated guest molecules, including assignment of the absolute configuration of chiral centers. Herein, we expand on those results and report a head-to-head comparison of the GS method with adamantoid “molecular chaperones”, which have been reported to be useful hosts for structure determination. Inclusion compounds limited to only two GS hosts are characterized by low R1 values and Flack parameters, infrequent disorder of the host and guest, and manageable disorder when it does exist. The structures of some target molecules that were not included or resolved using the adamantoid chaperones were successfully included and resolved by the GS hosts, and vice versa. Of the 32 guests attempted by the GS method, 31 inclusion compounds afforded successful guest structure solutions, a 97% success rate. The GS hosts and adamantoid chaperones are complementary with respect to guest inclusion, arguing that both should be employed in the arsenal of methods for structure determination. Furthermore, the low cost of organosulfonate host components promises an accessible route to molecular structure determination for a wide range of users.
36 MATERIALS SCIENCE↗
In situ X-ray powder diffraction studies of the synthesis of graphene oxide and formation of reduced graphene oxide
Graphene oxide (GO) and reduced graphene oxide (rGO) are important materials in a wide range of fields. The modified Hummers methods, for synthesizing GO, and subsequent thermal reduction to rGO, are often employed for production of rGO. However, the mechanism behinds these syntheses methods are still unclear. We present an in situ X-ray diffraction study of the synthesis of GO and thermal reduction of GO. The X-ray diffraction revealed that the Hummers method includes an intercalation state and finally formation of additional crystalline material. The formation of GO is observed during both the intercalation and the crystallization stage. During thermal reduction of GO three stages were observed: GO, a disordered stage, and the rGO stage. The appearance of these stages depends on the heating ramp. The aim of this study is to provide deeper insight into the chemical and physical processes during the syntheses. - Graphical abstract: In situ X-ray diffraction results for of the modified Hummers synthesis and the thermal reduction of graphene oxide, revealing three stages for both syntheses as well as new GO diffraction peaks and unidentified crystalline material for the Hummers synthesis and a disordered stage for the thermal reduction of graphene oxide. Display Omitted - Highlights: • Hummers synthesis consists of three stages: dissolution, intercalation and crystal. • GO is produced early on during the synthesis and display new diffraction peaks. • An unidentified triclinic phase is observed for the Hummers synthesis. • Thermal reduction of GO display three stages: GO, a disordered stage and rGO. • In situ XRD indicate reformation of rGO even for fast heated thermal reduction.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
General 2.5 power law of metallic glasses
Metallic glass (MG) is an important new category of materials, but very few rigorous laws are currently known for defining its “disordered” structure. Recently we found that under compression, the volume ( V ) of an MG changes precisely to the 2.5 power of its principal diffraction peak position (1/ q 1 ). In the present study, we find that this 2.5 power law holds even through the first-order polyamorphic transition of a Ce 68 Al 10 Cu 20 Co 2 MG. This transition is, in effect, the equivalent of a continuous “composition” change of 4 f -localized “big Ce” to 4 f -itinerant “small Ce,” indicating the 2.5 power law is general for tuning with composition. The exactness and universality imply that the 2.5 power law may be a general rule defining the structure of MGs.
36 MATERIALS SCIENCE↗
The Effect Of Electronic Energy Loss On Irradiation-induced Grain Growth In Nanocrystalline Oxides
Grain growth of nanocrystalline materials is generally thermally activated, but can also be driven by irradiation at much lower temperature. In nanocrystalline ceria and zirconia, energetic ions deposit their energy to both atomic nuclei and electrons. Our experimental results have shown that irradiationinduced grain growth is dependent on the total energy deposited, where electronic energy loss and elastic collisions between atomic nuclei both contribute to the production of disorder and grain growth. Our atomistic simulations reveal that a high density of disorder near grain boundaries leads to locally rapid grain movement. The additive effect from both electronic excitation and atomic collision cascades on grain growth demonstrated in this work opens up new possibilities for controlling grain sizes to improve functionality of nanocrystalline materials.
Environmental Molecular Sciences Laboratory↗
Molecule@MOF: A New Class of Opto-electronic Materials.
Metal organic frameworks (MOFs) are extended, nanoporous crystalline compounds consisting of metal ions interconnected by organic ligands. Their synthetic versatility suggest a disruptive class of opto - electronic materials with a high degree of electrical tunability and without the property - degrading disorder of organic conductors. In this project we determined the factors controlling charge and energy transport in MOFs and evaluated their potential for thermoelectric energy conversion. Two strategies for a chieving electronic conductivity in MOFs were explored: 1) using redox active 'guest' molecules introduced into the pores to dope the framework via charge - transfer coupling (Guest@MOF), 2) metal organic graphene analogs (MOGs) with dispersive band structur es arising from strong electronic overlap between the MOG metal ions and its coordinating linker groups. Inkjet deposition methods were developed to facilitate integration of the guest@MOF and MOG materials into practical devices.
36 MATERIALS SCIENCE↗
Vibrational relaxation dynamics in layered perovskite quantum wells
Significance Halide perovskites, especially layered perovskites, offer a number of advantages to creating bright and efficient light-emitting devices and other optoelectronic applications. The organic–inorganic hybrid layered perovskite features complex lattice dynamics due to the ionic character of the crystal and the softness arising from noncovalent bonds between molecular moieties and the inorganic network. Especially, the packing geometry of the organic barriers leads to a structural deformation of inorganic octahedral, which strongly affects the properties that are crucial for device applications. In this work, we use high-resolution resonant impulsive stimulated Raman spectroscopy of a variety of ligand substitutions in layered perovskites. We find the composition of organic ligands can substantially change the dephasing rate of optical phonons and their temperature dependence, due to varying degrees of anharmonicity in the lattice and dynamic structural disorder.
36 MATERIALS SCIENCE↗