Showing papers on "Amorphous solid published in 2017"
TL;DR: In this article, Li deposition is observed and measured on a solid electrolyte in the vicinity of a metallic current collector, and an electrochemomechanical model of plating-induced Li infiltration is proposed.
Abstract: Li deposition is observed and measured on a solid electrolyte in the vicinity of a metallic current collector. Four types of ion-conducting, inorganic solid electrolytes are tested: Amorphous 70/30 mol% Li2S-P2S5, polycrystalline β-Li3PS4, and polycrystalline and single-crystalline Li6La3ZrTaO12 garnet. The nature of lithium plating depends on the proximity of the current collector to defects such as surface cracks and on the current density. Lithium plating penetrates/infiltrates at defects, but only above a critical current density. Eventually, infiltration results in a short circuit between the current collector and the Li-source (anode). These results do not depend on the electrolytes shear modulus and are thus not consistent with the Monroe–Newman model for “dendrites.” The observations suggest that Li-plating in pre-existing flaws produces crack-tip stresses which drive crack propagation, and an electrochemomechanical model of plating-induced Li infiltration is proposed. Lithium short-circuits through solid electrolytes occurs through a fundamentally different process than through liquid electrolytes. The onset of Li infiltration depends on solid-state electrolyte surface morphology, in particular the defect size and density.
665 citations
TL;DR: In this paper, a scaling behavior of moisture-induced grain degradation in polycrystalline CH3NH3PbI3 films was reported, which can be explained by the degradation along the inplane direction, which is initiated at the grain boundary.
Abstract: The stability of perovskite solar cells has shown a huge variation with respect to the film process and film morphology, while the underlining mechanism for the morphology-dependent degradation of the perovskite film has remained elusive. Herein, we report a scaling behavior of moisture-induced grain degradation in polycrystalline CH3NH3PbI3 films. The degradation rates of CH3NH3PbI3 films in moisture were shown to be sensitive to the grain sizes. The duration that was needed for different films to degrade by the same percent showed a linear relationship with the grain size, despite the fact that the films were formed by five different deposition methods. This scaling behavior can be explained by the degradation along the in-plane direction, which is initiated at the grain boundary (GB). The GBs of CH3NH3PbI3 films consist of an amorphous intergranular layer, which allows quick diffusion of moisture into the perovskite films. It was found that thermal annealing induced surface self-passivation plays a critical role in stabilizing the surfaces of thin films and single crystals by reducing the moisture-sensitive methylammonium ions at the surface. The determination of the scaling behavior of grain degradation highlights the importance of stabilizing the GBs to improve the stability of perovskite solar cells.
664 citations
TL;DR: In this paper, a Gaussian approximation potential (GAP) model was proposed for atomistic simulations of liquid and amorphous elemental carbon, based on a machine learning representation of the density-functional theory (DFT) potential energy surface.
Abstract: We introduce a Gaussian approximation potential (GAP) for atomistic simulations of liquid and amorphous elemental carbon. Based on a machine learning representation of the density-functional theory (DFT) potential-energy surface, such interatomic potentials enable materials simulations with close-to DFT accuracy but at much lower computational cost. We first determine the maximum accuracy that any finite-range potential can achieve in carbon structures; then, using a hierarchical set of two-, three-, and many-body structural descriptors, we construct a GAP model that can indeed reach the target accuracy. The potential yields accurate energetic and structural properties over a wide range of densities; it also correctly captures the structure of the liquid phases, at variance with a state-of-the-art empirical potential. Exemplary applications of the GAP model to surfaces of ``diamondlike'' tetrahedral amorphous carbon ($\mathit{ta}$-C) are presented, including an estimate of the amorphous material's surface energy and simulations of high-temperature surface reconstructions (``graphitization''). The presented interatomic potential appears to be promising for realistic and accurate simulations of nanoscale amorphous carbon structures.
465 citations
TL;DR: A novel OER electrocatalyst, namely oxygen-incorporated amorphous cobalt sulfide porous nanocubes (A-CoS4.6 O0.6 PNCs), show advantages over the benchmark RuO2 catalyst in alkaline/neutral medium and contribute synergistically to the outstanding electrocatalytic activity.
Abstract: A novel OER electrocatalyst, namely oxygen-incorporated amorphous cobalt sulfide porous nanocubes (A-CoS4.6 O0.6 PNCs), show advantages over the benchmark RuO2 catalyst in alkaline/neutral medium. Experiments combining with calculation demonstrate that the desirable O* adsorption energy, associated with the distorted CoS4.6 O0.6 octahedron structure and the oxygen doping, contribute synergistically to the outstanding electrocatalytic activity.
460 citations
TL;DR: This work proposes a mechanism, supported by constitutive modelling, in which the crystalline phase blocks the propagation of localized shear bands when under strain, and the strength of the resulting dual-phase material is a near-ideal 3.3 gigapascals—making this the strongest magnesium-alloy thin film yet achieved.
Abstract: Combining the benefits of nanocrystals with those of amorphous metallic glasses leads to a dual-phase material—comprising sub-10-nanometre-sized nanocrystalline grains embedded in amorphous glassy shells—that exhibits a strength approaching the ideal theoretical limit. Nanostructuring of crystalline metal alloys can yield high-strength materials, but these tend to soften as the strain is increased. Ge Wu et al. describe a strategy that combines the benefits of nanocrystallinity with those of single-phase amorphous metallic glasses to yield a dual-phase material—nanocrystalline grains each enclosed in an amorphous glassy shell—that exhibits strength approaching the ideal theoretical limit. They demonstrate this approach with a magnesium alloy and prepare the strongest thin films yet achieved for any magnesium alloy. The authors suggest that this material could be a promising coating for wear-resistant surfaces. It is not easy to fabricate materials that exhibit their theoretical ‘ideal’ strength. Most methods of producing stronger materials are based on controlling defects to impede the motion of dislocations, but such methods have their limitations. For example, industrial single-phase nanocrystalline alloys1,2 and single-phase metallic glasses3 can be very strong, but they typically soften at relatively low strains (less than two per cent) because of, respectively, the reverse Hall–Petch effect4 and shear-band formation. Here we describe an approach that combines the strengthening benefits of nanocrystallinity with those of amorphization to produce a dual-phase material that exhibits near-ideal strength at room temperature and without sample size effects. Our magnesium-alloy system consists of nanocrystalline cores embedded in amorphous glassy shells, and the strength of the resulting dual-phase material is a near-ideal 3.3 gigapascals—making this the strongest magnesium-alloy thin film yet achieved. We propose a mechanism, supported by constitutive modelling, in which the crystalline phase (consisting of almost-dislocation-free grains of around six nanometres in diameter) blocks the propagation of localized shear bands when under strain; moreover, within any shear bands that do appear, embedded crystalline grains divide and rotate, contributing to hardening and countering the softening effect of the shear band.
420 citations
TL;DR: Interestingly, it is found that the amorphousTiO2 shells offer superior buffering properties compared to crystalline TiO2 layers for unprecedented cycling stability, and accelerating rate calorimetry testing reveals that the TiO1 -encapsulated Si nanoparticles are safer than conventional carbon-coated Si-based anodes.
Abstract: Smart surface coatings of silicon (Si) nanoparticles are shown to be good examples for dramatically improving the cyclability of lithium-ion batteries. Most coating materials, however, face significant challenges, including a low initial Coulombic efficiency, tedious processing, and safety assessment. In this study, a facile sol–gel strategy is demonstrated to synthesize commercial Si nanoparticles encapsulated by amorphous titanium oxide (TiO2), with core–shell structures, which show greatly superior electrochemical performance and high-safety lithium storage. The amorphous TiO2 shell (≈3 nm) shows elastic behavior during lithium discharging and charging processes, maintaining high structural integrity. Interestingly, it is found that the amorphous TiO2 shells offer superior buffering properties compared to crystalline TiO2 layers for unprecedented cycling stability. Moreover, accelerating rate calorimetry testing reveals that the TiO2-encapsulated Si nanoparticles are safer than conventional carbon-coated Si-based anodes.
369 citations
TL;DR: It is shown that amorphous CP can be used as general synthesis precursors of highly complex mixed metal oxide shells and can be applied to produce ternary and quaternary metal oxide onions with tunable size and composition.
Abstract: Metal-organic frameworks (MOFs) or coordination polymers (CPs) have been used as precursors for synthesis of materials. Unlike crystalline MOF, amorphous CP is nonspecific to metal cation species, therefore its composition can be tuned easily. Here, it is shown that amorphous CP can be used as general synthesis precursors of highly complex mixed metal oxide shells. As a proof of concept, NiCo coordination polymer spheres are first synthesized and subsequently transformed into seven-layered NiCo oxide onions by rapid thermal oxidation. This approach is very versatile and can be applied to produce ternary and quaternary metal oxide onions with tunable size and composition. The NiCo oxide onions exhibit exceptional charge storage capability in aqueous electrolyte with high specific capacitance (≈1900 F g-1 at 2 A g-1 ), good rate capability, and ultrahigh cycling stability (93.6% retention over 20 000 cycles). A hybrid supercapacitor against graphene/multishelled mesoporous carbon sphere shows a high energy density of 52.6 Wh kg-1 at a power density of 1604 W kg-1 (based on active materials weight), as well as remarkable cycling stability.
344 citations
TL;DR: The results demonstrated that both robust metallic Ni interface layers and amorphous NiS can be utilized as electron cocatalysts to markedly boost the visible-light H2 evolution over g-C3N4 semiconductor.
Abstract: The construction of exceptionally robust and high-quality semiconductor–cocatalyst heterojunctions remains a grand challenge toward highly efficient and durable solar-to-fuel conversion. Herein, novel graphitic carbon nitride (g-C3N4) nanosheets decorated with multifunctional metallic Ni interface layers and amorphous NiS cocatalysts were fabricated via a facile three-step process: the loading of Ni(OH)2 nanosheets, high-temperature H2 reduction, and further deposition of amorphous NiS nanosheets. The results demonstrated that both robust metallic Ni interface layers and amorphous NiS can be utilized as electron cocatalysts to markedly boost the visible-light H2 evolution over g-C3N4 semiconductor. The optimized g-C3N4-based photocatalyst containing 0.5 wt % Ni and 1.0 wt % NiS presented the highest hydrogen evolution of 515 μmol g–1 h–1, which was about 2.8 and 4.6 times as much as those obtained on binary g-C3N4-1.0%NiS and g-C3N4-0.5%Ni, respectively. Apparently, the metallic Ni interface layers play m...
304 citations
TL;DR: An approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting is reported, which have superior kinetics for hydrogen- and oxygen-evolution.
Abstract: Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm−2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec−1. Moreover, we achieve 10 mA cm−2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2. Electrocatalysts based on earth-abundant elements have emerged as promising candidates to replace noble metal materials. Here, the authors develop porous hybrid nanostructures combining amorphous Ni-Co complexes with 1T phase MoS2for enhanced electrocatalytic activity for overall water splitting.
281 citations
TL;DR: In this paper, the authors used in situ electron microscopy to show how gold and silver nanocrystals nucleate from supersaturated aqueous solutions in three distinct steps: spinodal decomposition into solute-rich and solutepoor liquid phases, nucleation of amorphous nanoclusters within the metal-rich liquid phase, followed by crystallization of these amomorphous clusters.
Abstract: The nucleation and growth of solids from solutions impacts many natural processes and is fundamental to applications in materials engineering and medicine. For a crystalline solid, the nucleus is a nanoscale cluster of ordered atoms that forms through mechanisms still poorly understood. In particular, it is unclear whether a nucleus forms spontaneously from solution via a single- or multiple-step process. Here, using in situ electron microscopy, we show how gold and silver nanocrystals nucleate from supersaturated aqueous solutions in three distinct steps: spinodal decomposition into solute-rich and solute-poor liquid phases, nucleation of amorphous nanoclusters within the metal-rich liquid phase, followed by crystallization of these amorphous clusters. Our ab initio calculations on gold nucleation suggest that these steps might be associated with strong gold-gold atom coupling and water-mediated metastable gold complexes. The understanding of intermediate steps in nuclei formation has important implications for the formation and growth of both crystalline and amorphous materials.
277 citations
TL;DR: Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)-electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nanoscale while minimizing beam damage during imaging.
Abstract: Lithium metal has been considered the "holy grail" anode material for rechargeable batteries despite the fact that its dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanying solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and mesostructures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)-electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nanoscale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation-dominated EDLi (5 min at 0.5 mA cm-2) is amorphous, while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials but also yield crucial structural information on the EDLi evolution with and without electrolyte additives.
TL;DR: In this article, amorphous cobalt-iron hydroxide (CoFeH) nanosheets are synthesized by facile electrodeposition as an efficient catalyst for both electrochemical and PEC water oxidation.
Abstract: Finding efficient electrocatalysts for oxygen evolution reaction (OER) that can be effectively integrated with semiconductors is significantly challenging for solar-driven photo-electrochemical (PEC) water splitting. Herein, amorphous cobalt–iron hydroxide (CoFeH) nanosheets are synthesized by facile electrodeposition as an efficient catalyst for both electrochemical and PEC water oxidation. As a result of the high electrochemically active surface area and the amorphous nature, the optimized amorphous CoFeH nanosheets exhibit superior OER catalytic activity in alkaline environment with a small overpotential (280 mV) to achieve significant oxygen evolution (j = 10 mA cm−2) and a low Tafel slope (28 mV dec−1). Furthermore, CoFeH nanosheets are simply integrated with BiVO4 semiconductor to construct CoFeH/BiVO4 photoanodes that exhibit a significantly enhanced photocurrent density of 2.48 mA cm−2 (at 1.23 V vs reversible hydrogen electrode (RHE)) and a much lower onset potential of 0.23 V (vs RHE) for PEC-OER. Careful electrochemical and optical studies reveal that the improved OER kinetics and high-quality interface at the CoFeH/BiVO4 junction, as well as the excellent optical transparency of CoFeH nanosheets, contribute to the high PEC performance. This study establishes amorphous CoFeH nanosheets as a highly competitive candidate for electrochemical and PEC water oxidation and provides general guidelines for designing efficient PEC systems.
TL;DR: A general three-stage synthesis strategy is described to produce a family of hybrid materials comprising amorphous bimetallic oxide nanoparticles anchored on N-doped reduced graphene oxide with simultaneous control of nanoparticle elemental composition, size, and crystallinity.
Abstract: Metal oxides of earth-abundant elements are promising electrocatalysts to overcome the sluggish oxygen evolution and oxygen reduction reaction (OER/ORR) in many electrochemical energy-conversion devices. However, it is difficult to control their catalytic activity precisely. Here, a general three-stage synthesis strategy is described to produce a family of hybrid materials comprising amorphous bimetallic oxide nanoparticles anchored on N-doped reduced graphene oxide with simultaneous control of nanoparticle elemental composition, size, and crystallinity. Amorphous Fe0.5 Co0.5 Ox is obtained from Prussian blue analog nanocrystals, showing excellent OER activity with a Tafel slope of 30.1 mV dec-1 and an overpotential of 257 mV for 10 mA cm-2 and superior ORR activity with a large limiting current density of -5.25 mA cm-2 at 0.6 V. A fabricated Zn-air battery delivers a specific capacity of 756 mA h gZn-1 (corresponding to an energy density of 904 W h kgZn-1 ), a peak power density of 86 mW cm-2 and can be cycled over 120 h at 10 mA cm-2 . Other two amorphous bimetallic, Ni0.4 Fe0.6 Ox and Ni0.33 Co0.67 Ox , are also produced to demonstrate the general applicability of this method for synthesizing binary metal oxides with controllable structures as electrocatalysts for energy conversion.
TL;DR: An extremely large-scale vibrational mode analysis of a model amorphous solid finds that the scaling law predicted by the mean-field theory is violated at low frequency, and in the continuum limit, the vibrational modes converge to a mixture of phonon modes that follow the Debye law and soft localized modes that following another universal non-Debye scaling law.
Abstract: The low-frequency vibrational and low-temperature thermal properties of amorphous solids are markedly different from those of crystalline solids. This situation is counterintuitive because all solid materials are expected to behave as a homogeneous elastic body in the continuum limit, in which vibrational modes are phonons that follow the Debye law. A number of phenomenological explanations for this situation have been proposed, which assume elastic heterogeneities, soft localized vibrations, and so on. Microscopic mean-field theories have recently been developed to predict the universal non-Debye scaling law. Considering these theoretical arguments, it is absolutely necessary to directly observe the nature of the low-frequency vibrations of amorphous solids and determine the laws that such vibrations obey. Herein, we perform an extremely large-scale vibrational mode analysis of a model amorphous solid. We find that the scaling law predicted by the mean-field theory is violated at low frequency, and in the continuum limit, the vibrational modes converge to a mixture of phonon modes that follow the Debye law and soft localized modes that follow another universal non-Debye scaling law.
TL;DR: In this article, amorphous gallium oxide thin films were deposited by radio frequency (RF) magnetron sputtering, and the metal-semiconductor-metal (MSM) PD was fabricated and compared with a β-Ga2O3 film prepared side-by-side as the control sample.
Abstract: Recently, Ga2O3-based, solar-blind photodetectors (PDs) have been extensively studied for various commercial and military applications. However, to date, studies have focused only on the crystalline phases, especially β-Ga2O3, and the crystalline quality must be carefully controlled because of its strong impact on device characteristics. Based on previous reports, amorphous-semiconductor-based PDs can also be expected to exhibit excellent photodetection characteristics. In this work, amorphous gallium oxide thin films were deposited by radio frequency (RF) magnetron sputtering, and the metal–semiconductor–metal (MSM) PD was fabricated and compared with a β-Ga2O3 film prepared side-by-side as the control sample. The as-sputtered film possessed a high density of defects, including structural disorders, oxygen vacancies, and likely, dangling bonds, resulting in record-high responsivity (70.26 A/W) for a thin-film-type gallium oxide PD due to a high internal gain and the contribution of extrinsic transitions ...
TL;DR: In this paper, a modern, improved definition of glass is proposed, which states that glass is a nonequilibrium, non-crystalline state of matter that appears solid on a short time scale but continuously relaxes towards the liquid state.
Abstract: The objective of this communication is to clarify the meanings of solid and liquid, to dwell on the ultimate fate of glass in the limit of infinitely long time, and to propose a modern, improved definition of glass. We review the four characteristic states of matter related to vitrification: the stable equilibrium liquid (L), the metastable supercooled liquid (SCL), the unstable nonequilibrium glass (G), and the stable crystal (C). We also discuss some relevant terms and phenomena, including glass transition, crystallization, non-crystalline, amorphous, solid, and frozen. We review several previously published definitions of glass and finally propose an improved definition in two alternative forms. The first improved definition is: “Glass is a nonequilibrium , non-crystalline state of matter that appears solid on a short time scale but continuously relaxes towards the liquid state.” This is an intuitive description for the general public and young students. An alternative, more detailed definition to be understood and used by advanced students, researchers, and professors is: “Glass is a nonequilibrium , non-crystalline condensed state of matter that exhibits a glass transition. The structure of glasses is similar to that of their parent supercooled liquids (SCL) , and they spontaneously relax toward the SCL state. Their ultimate fate , in the limit of infinite time, is to crystallize.” This definition is for experts who understand the meaning of glass transition.
TL;DR: In this paper, a solution to the fabrication of amorphous Ga2O3 solar-blind photodetectors on rigid and flexible substrates at room temperature is reported.
Abstract: A solution to the fabrication of amorphous Ga2O3 solar-blind photodetectors on rigid and flexible substrates at room temperature is reported. A robust improvement in the response speed is achieved by delicately controlling the oxygen flux in the reactive radio frequency magnetron sputtering process. Temporal response measurements show that the detector on quartz has a fast decay time of 19.1 µs and a responsivity of 0.19 A W−1 as well, which are even better than those single crystal Ga2O3 counterparts prepared at high temperatures. X-ray photoelectron spectroscopy and current–voltage tests suggest that the reduced oxygen vacancy concentration and the increased Schottky barrier height jointly contribute to the faster response speed. Amorphous Ga2O3 solar-blind photodetector is further constructed on polyethylene naphthalate substrate. The flexible devices demonstrate similar photoresponse behavior as the rigid ones, and no significant degradation of the device performance is observed in bending states and fatigue tests. The results reveal the importance of finely tuned oxygen processing gas in promoting the device performance and the applicability of room-temperature synthesized amorphous Ga2O3 in fabrication of flexible solar-blind photodetectors.
TL;DR: In this paper, a conformal, ultrathin, amorphous TiO2 film deposited by low-temperature atomic layer deposition (ALD) on top of b-Si can simultaneously address both charge recombination and low electrochemical stability.
Abstract: Black silicon (b-Si) is a surface-nanostructured Si with extremely efficient light absorption capability and is therefore of interest for solar energy conversion. However, intense charge recombination and low electrochemical stability limit the use of b-Si in photoelectrochemical solar-fuel production. Here we report that a conformal, ultrathin, amorphous TiO2 film deposited by low-temperature atomic layer deposition (ALD) on top of b-Si can simultaneously address both of these issues. Combined with a Co(OH)2 thin film as the oxygen evolution catalyst, this b-Si/TiO2/Co(OH)2 heterostructured photoanode was able to produce a saturated photocurrent density of 32.3 mA cm−2 at an external potential of 1.48 V versus reversible reference electrode (RHE) in 1 M NaOH electrolyte. The enhanced photocurrent relative to planar Si and unprotected b-Si photoelectrodes was attributed to the enhanced charge separation efficiency as a result of the effective passivation of defective sites on the b-Si surface. The 8-nm ALD TiO2 layer extends the operational lifetime of b-Si from less than half an hour to four hours. Nanostructured black silicon can be used as a photoelectrode for solar-driven water splitting, but its high surface area can increase charge recombination and accelerate corrosion. Here the authors show that a thin, conformal film of TiO2 can increase both the photocurrent and the stability of black silicon.
TL;DR: A solid-state supercapacitor based on amorphous MnO2@MWCNT fibers exhibits improved energy density, superior rate capability, exceptional cycling stability, and excellent flexibility.
Abstract: Solid-state fiber-based supercapacitors have been considered promising energy storage devices for wearable electronics due to their lightweight and amenability to be woven into textiles. Efforts have been made to fabricate a high performance fiber electrode by depositing pseudocapacitive materials on the outer surface of carbonaceous fiber, for example, crystalline manganese oxide/multiwalled carbon nanotubes (MnO2/MWCNTs). However, a key challenge remaining is to achieve high specific capacitance and energy density without compromising the high rate capability and cycling stability. In addition, amorphous MnO2 is actually preferred due to its disordered structure and has been proven to exhibit superior electrochemical performance over the crystalline one. Herein, by incorporating amorphous MnO2 onto a well-aligned MWCNT sheet followed by twisting, we design an amorphous MnO2@MWCNT fiber, in which amorphous MnO2 nanoparticles are distributed in MWCNT fiber uniformly. The proposed structure gives the amorp...
TL;DR: Through extensive computer simulations for a wide range of system sizes, it is demonstrated that cyclically deformed model glasses exhibit a sharply defined yielding transition with characteristics that are independent of preparation history.
Abstract: Amorphous solids are ubiquitous among natural and man-made materials. Often used as structural materials for their attractive mechanical properties, their utility depends critically on their response to applied stresses. Processes underlying such mechanical response, and in particular the yielding behaviour of amorphous solids, are not satisfactorily understood. Although studied extensively, observed yielding behaviour can be gradual and depend significantly on conditions of study, making it difficult to convincingly validate existing theoretical descriptions of a sharp yielding transition. Here we employ oscillatory deformation as a reliable probe of the yielding transition. Through extensive computer simulations for a wide range of system sizes, we demonstrate that cyclically deformed model glasses exhibit a sharply defined yielding transition with characteristics that are independent of preparation history. In contrast to prevailing expectations, the statistics of avalanches reveals no signature of the impending transition, but exhibit dramatic, qualitative, changes in character across the transition. The onset of yielding can be difficult to define unambiguously for amorphous materials. Here the authors undertake computer simulations of model glasses of varying system sizes and show that, under oscillatory shear, they exhibit a sharp transition independent of preparation history.
TL;DR: This work demonstrates the first molecular-level conversion pathway of NO oxidation over a novel SrO-clusters@amorphous carbon nitride (SCO-ACN) photocatalyst, which is synthesized via copyrolysis of urea and SrCO3, and presents a novel in situ DRIFTS-based strategy to explore the photocatalytic reaction pathway.
Abstract: This work demonstrates the first molecular-level conversion pathway of NO oxidation over a novel SrO-clusters@amorphous carbon nitride (SCO-ACN) photocatalyst, which is synthesized via copyrolysis of urea and SrCO3. The inclusion of SrCO3 is crucial in the formation of the amorphous carbon nitride (ACN) and SrO clusters by attacking the intralayer hydrogen bonds at the edge sites of graphitic carbon nitride (CN). The amorphous nature of ACN can promote the transportation, migration, and transformation of charge carriers on SCO-ACN. And the SrO clusters are identified as the newly formed active centers to facilitate the activation of NO via the formation of Sr-NOδ(+), which essentially promotes the conversion of NO to the final products. The combined effects of the amorphous structure and SrO clusters impart outstanding photocatalytic NO removal efficiency to the SCO-ACN under visible-light irradiation. To reveal the photocatalytic mechanism, the adsorption and photocatalytic oxidation of NO over CN and SC...
TL;DR: Recent progress in understanding highly stable glasses prepared by physical vapor deposition is described and perspective on further research directions for the field is provided.
Abstract: This article describes recent progress in understanding highly stable glasses prepared by physical vapor deposition and provides perspective on further research directions for the field. For a given molecule, vapor-deposited glasses can have higher density and lower enthalpy than any glass that can be prepared by the more traditional route of cooling a liquid, and such glasses also exhibit greatly enhanced kinetic stability. Because vapor-deposited glasses can approach the bottom of the amorphous part of the potential energy landscape, they provide insights into the properties expected for the “ideal glass.” Connections between vapor-deposited glasses, liquid-cooled glasses, and deeply supercooled liquids are explored. The generality of stable glass formation for organic molecules is discussed along with the prospects for stable glasses of other types of materials.
TL;DR: In this article, the properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied using Solution Sequential Processing (SqP) to introduce 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) into poly(3-hexylthiophene-2,5-diyl) (P3HT).
Abstract: The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied Solution sequential processing (SqP) was used to introduce 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) into poly(3-hexylthiophene-2,5-diyl) (P3HT) while preserving the pristine polymer's degree of crystallinity X-ray data suggest that F4TCNQ anions reside primarily in the amorphous regions of the film as well as in the P3HT lamellae between the side chains, but do not π-stack within the polymer crystallites Optical spectroscopy shows that the polaron absorption redshifts with increasing polymer crystallinity and increases in cross section Theoretical modeling suggests that the polaron spectrum is inhomogeneously broadened by the presence of the anions, which reside on average 6–8 A from the polymer backbone Electrical measurements show that the conductivity of P3HT films doped by F4TCNQ via SqP can be improved by increasing the polymer crystallinity AC magnetic field Hall measurements show that the increased conductivity results from improved mobility of the carriers with increasing crystallinity, reaching over 01 cm2 V−1 s−1 in the most crystalline P3HT samples Temperature-dependent conductivity measurements show that polaron mobility in SqP-doped P3HT is still dominated by hopping transport, but that more crystalline samples are on the edge of a transition to diffusive transport at room temperature
TL;DR: In this article, the morphological, structural, chemical, and electrical characterization of WS2 thin films sensors were reported by drop casting a commercial solution of dispersed few-layer WS2 flakes on Si3N4 interdigitated substrates and annealing the films in air at 150°C, 250°C and 350°C.
Abstract: We report on the fabrication and on the morphological, structural, chemical and the electrical characterization of WS2 thin films sensors prepared by drop casting a commercial solution of dispersed few-layers WS2 flakes on Si3N4 interdigitated substrates and annealing the films in air at 150 °C, 250 °C and 350 °C. Thermal stability of WS2 in air at different annealing temperatures has been investigated by X-ray photoemission spectroscopy, scanning electron microscopy, X-ray diffraction and by simultaneous thermal analysis techniques. We found that WS2 is not stable in air and partially oxidizes to amorphous WO3 in the annealing temperature range 25 °C–150 °C. The oxidation of WS2 in air at 250 °C and 350 °C yields a composite crystalline WS2/WO3 hierarchical structure characterized by the presence of surface oxygen and sulphur vacancies. The contribution of each phase of the WS2/WO3 composite to the overall chemoresistive gas response utilizing H2 (1–10 ppm), NH3 (1–10 ppm) and NO2 (40 ppb–1 ppm) gases in dry air carrier is presented and discussed. WS2/WO3 composite films show excellent gas sensing properties to reducing (H2, NH3) as respect to oxidizing (NO2) gases at 150 °C operating temperature. In this work we found low detection limits of 1 ppm H2, 1 ppm NH3 and 100 ppm NO2 in dry air carrier, among the smallest so far ever reported for transition metal dichalcogenides. Furthermore, the sensor doesn’t show any cross sensitivity effects to both H2 and NH3 when exposed to water vapor. Outstanding reproducibility responses, by exposing the 150 °C annealed film to dynamic and cumulative gas pulses where obtained utilizing H2 gas.
TL;DR: Silica inks are developed, which may be 3D printed and thermally processed to produce optically transparent glass structures with sub-millimeter features in forms ranging from scaffolds to monoliths.
Abstract: Silica inks are developed, which may be 3D printed and thermally processed to produce optically transparent glass structures with sub-millimeter features in forms ranging from scaffolds to monoliths. The inks are composed of silica powder suspended in a liquid and are printed using direct ink writing. The printed structures are then dried and sintered at temperatures well below the silica melting point to form amorphous, solid, transparent glass structures. This technique enables the mold-free formation of transparent glass structures previously inaccessible using conventional glass fabrication processes.
TL;DR: In this paper, six optically transparent zinc molybdenum borotellurite glasses containing different network modifier ions (alkali, alkaline, and heavy metal oxides) were prepared by melt quenching technique.
TL;DR: It is shown that the silicon thin film electrodes with an amorphous C layer showed a remarkably improved electrochemical performance in terms of capacity retention and Coulombic efficiency.
Abstract: The next generation of lithium ion batteries (LIBs) with increased energy density for large-scale applications, such as electric mobility, and also for small electronic devices, such as microbatteries and on-chip batteries, requires advanced electrode active materials with enhanced specific and volumetric capacities. In this regard, silicon as anode material has attracted much attention due to its high specific capacity. However, the enormous volume changes during lithiation/delithiation are still a main obstacle avoiding the broad commercial use of Si-based electrodes. In this work, Si-based thin film electrodes, prepared by magnetron sputtering, are studied. Herein, we present a sophisticated surface design and electrode structure modification by amorphous carbon layers to increase the mechanical integrity and, thus, the electrochemical performance. Therefore, the influence of amorphous C thin film layers, either deposited on top (C/Si) or incorporated between the amorphous Si thin film layers (Si/C/Si)...
TL;DR: Li3PO4-coated Li electrodes have been shown to have almost insulated property with electronic conductivity of 1.4 × 10−10−10 S/cm and ionic conductivity 2.8 × 8.8−8 s/cm.
TL;DR: In this paper, the physical, thermal, structural and optical properties of Dy 3+ doped lithium alumino-borate glasses (LABD glasses) have been studied for white LED (W-LED) application.
TL;DR: The enhanced performance of Ba0.2O3−δ (BSCF) for the OER with intrinsic activity that is significantly higher than that of the benchmark IrO2 is reported, and this result was achieved via fabrication of an amorphous BSCF nanofilm on a surface-oxidized nickel substrate by magnetron sputtering.
Abstract: Perovskite oxides exhibit potential for use as electrocatalysts in the oxygen evolution reaction (OER). However, their low specific surface area is the main obstacle to realizing a high mass-specific activity that is required to be competitive against the state-of-the-art precious metal-based catalysts. We report the enhanced performance of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) for the OER with intrinsic activity that is significantly higher than that of the benchmark IrO2, and this result was achieved via fabrication of an amorphous BSCF nanofilm on a surface-oxidized nickel substrate by magnetron sputtering. The surface nickel oxide layer of the Ni substrate and the thickness of the BSCF film were further used to tune the intrinsic OER activity and stability of the BSCF catalyst by optimizing the electronic configuration of the transition metal cations in BSCF via the interaction between the nanofilm and the surface nickel oxide, which enables up to 315-fold enhanced mass-specific activity compared to the crystalline BSCF bulk phase. Moreover, the amorphous BSCF-Ni foam anode coupled with the Pt-Ni foam cathode demonstrated an attractive small overpotential of 0.34 V at 10 mA cm-2 for water electrolysis, with a BSCF loading as low as 154.8 μg cm-2.