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At least 595 records · Page 33

High Thermoelectric Performance in 2D Sb 2 Te 3 and Bi 2 Te 3 Nanoplate Composites Enabled by Energy Carrier Filtering and Low Thermal Conductivity

Thermoelectrics are an important class of materials with great potential in alternative energy applications. In this study, two-dimensional (2D) nanoplates of the layered chalcogenides, Sb 2 Te 3 and Bi 2 Te 3 , are synthesized and composites of the two are investigated for their thermoelectric properties. The two materials, Sb 2 Te 3 and Bi 2 Te 3 , were synthesized as hexagonal, 2D nanoplates via a colloidal polyol route. The as-synthesized Sb 2 Te 3 and Bi 2 Te 3 vary drastically from one another in their lateral and vertical dimensions as revealed by scanning electron microscopy and atomic force microscopy. The single crystalline nanoplate nature is deduced by high-resolution transmission electron microscopy and selected area electron diffraction. Nanoplates have well-defined hexagonal facets as seen in the scanning and transmission electron microscopy images. The nanoplates were consolidated as an anisotropic nanostructured pellet via spark plasma sintering. Preferred orientation observed in the powder X-ray diffraction pattern and scanning electron microscopy images of the fractured pellets confirm the anisotropic structure of the nanoplates. Thermoelectric properties in the parallel and perpendicular directions were measured, revealing strong anisotropy with a significant reduction to thermal conductivity in the perpendicular direction due to increased phonon scattering at nanoplate interfaces. All compositions, except that of the 25% Bi 2 Te 3 nanoplate composite, behave as degenerate semiconductors with increasing electrical resistivity as the temperature increases. The Seebeck coefficient is also increased dramatically in the nanocomposites, the highest reaching 210 μV/K for 15% Bi 2 Te 3 . The increase in Seebeck is attributed to energy carrier filtering at the nanoplate interfaces. Overall, these enhanced thermoelectric properties lead to a drastic increase in the thermoelectric performance in the perpendicular direction, with zT ~ 1.26, for the 15% Bi 2 Te 3 nanoplate composite at 450 K.

36 MATERIALS SCIENCE↗

Moisture-Driven Formation and Growth of Quasi-2-D Organolead Halide Perovskite Crystallites

Ruddlesden–Popper phase quasi-2-D organolead halide perovskites like n-butylammonium methylammonium lead iodide (nBA-MAPI) exhibit improved moisture stability over typical 3-D perovskite materials, making them exciting for use in a variety of applications such as photovoltaic (PV) devices. This improved stability is the result of a unique disproportionation-based degradation mechanism that protects the bulk of the nBA-MAPI from extensive damage through the formation of a protective, low-n surface layer. In addition to this surface layer, nBA-MAPI films also exhibit the dynamic growth of micrometer-scale crystallites and cracks at the surface of the film, unique and potentially important byproducts of quasi-2-D perovskite disproportionation. Here, we present a detailed study of these crystallites using several analytical techniques including photoluminescence spectroscopy (PL), confocal fluorescence microscopy (CFM), atomic force microscopy (AFM) combined with time-of-flight-secondary ion mass spectrometry (ToF-SIMS), and others in an effort to better understand the relationship between material disproportionation and crystallite growth. Our results show that the crystallites form after exposure to humid air and confirm that they are composed of low-n phases of nBA-MAPI. The crystallites are found to extend into the interior of the film and exhibit continued growth while exposed to moisture over 72 h. This growth is accompanied by both a decrease in the bulk 2-D phase and an increase in a 3-D-like phase in the surface PL spectra, indicating that the crystallites are likely a product of moisture-driven disproportionation. Importantly, similar crystallites are also observed to form within model PV devices, indicating that such processes must be accounted for when designing future devices containing materials like nBA-MAPI.

36 MATERIALS SCIENCE↗

Monitoring Volumetric Changes in Silicon Thin-Film Anodes through In Situ Optical Diffraction Microscopy

A high-resolution in situ spectroelectrochemical optical diffraction experiment has been created to understand the volume expansion/contraction process of amorphous silicon (a-Si) thin-film anodes. Electrodes consisting of 1D transmissive gratings of silicon have been produced through photolithographic methods. After glovebox assembly in a home-built Teflon cell, monitoring of the diffraction efficiency of these gratings during the lithiation/delithiation process is performed using an optical microscope equipped with a Bertrand lens. When the diffraction efficiency along with optical constants obtained from in situ spectroscopic ellipsometry is utilized, volume changes of the active materials can be deduced. Unlike transmission electron microscopy and atomic force microscopy characterization methods of observing silicon’s volume expansion, this experiment allows for real-time monitoring of the volume change at charge/discharge cycles greater than just the first few along with an experimental environment that directly mimics that of a real battery. This technique reflects promising results that provide needed insight into understanding the lithium alloying reaction and subsequent induced capacity fade during the cycling of alloying anodes in lithium-ion batteries.

25 ENERGY STORAGE↗

Silica Nanoparticle-Induced Structural Reorganizations in Pulmonary Surfactant Films: What Monolayer Compression Isotherms Do Not Say

The interaction of nanoparticles (NPs) with pulmonary surfactant is important for understanding the potential adverse effects of inhaled engineered and incidental nanomaterials. The effects of a low concentration (0.001 wt %) of charged, hydrophilic silica NPs of hydrodynamic diameter of ~20 nm on the phase behavior and lateral structure of lipid-only and naturally derived surfactant monolayers were investigated at the air/water interface using surface pressure–area isotherms and Brewster angle microscopy, respectively. Atomic force microscopy was used to image the morphology of films transferred onto mica substrate with nanometer resolution. We show herein that the silica NPs can significantly alter the condensed domain size and shape even in the absence of apparent differences in the monolayer compression isotherms. The cationic particles notably induce structural and morphological progressions in a binary model containing anionic phosphoglycerol that are similar to those observed for the natural surfactant film that contains cationic proteins. These findings specifically highlight the impact of the NP charge on the phase transformations in pulmonary surfactant, with implications for the engineering of nanomaterials for commercial use and bioapplications.

membrane organization↗

Two-Step Thermoresponsive Ultrafiltration Membranes from Polymerization of Lyotropic Liquid Crystals

Here, in this study, we present the fabrication of a two-step thermoresponsive ultrafiltration (UF) membrane through polymerization of a lyotropic liquid crystal (LLC). A mixture of commercially available Pluronic F 127 block copolymer, water (containing ammonium persulfate as the initiator), and polymerizable oil (n-butyl acrylate/ethylene glycol dimethacrylate) is used to create an LLC with a lamellar structure, as characterized by cross-polarized light microscopy and atomic force microscopy. Differential scanning calorimetry is employed to evaluate the thermoresponsive behavior of the polymerized LLC (polyLLC). Two-step thermoresponsiveness (~35 and ~50 °C) of the polyLLC is observed due to the lower critical solution temperature (LCST) of F 127 and melting of the crystalline structure of the polyethylene oxide (PEO) chains of the F 127 surfactant. In the next step, the obtained mesophase is cast on a nonwoven polyester support sheet followed by thermal polymerization. The hydration capacity, water flux, water flux recovery after fouling, and molecular weight cutoff (MWCO) of the obtained membrane are evaluated at different temperatures to examine its thermoresponsiveness. The experimental results reveal that the UF membrane has a reversible thermoresponsive behavior at the LCST and PEO melting of polyLLC. Additionally, the cleaning efficiency of the fouled membrane can be enhanced by using its thermoresponsive behavior, resulting in an extended lifetime of the product. Furthermore, the MWCO of the membrane can be altered with temperature due to the pore size change with temperature stimulus.

36 MATERIALS SCIENCE↗

Solution-Based Synthesis of Crystalline Silicon from Liquid Silane through Laser and Chemical Annealing

We report a solution process for the synthesis of crystalline silicon from the liquid silane precursor cyclohexasilane (Si 6 H 12 ). Polysilane films were crystallized through thermal and laser annealing, with plasma hydrogenation at atmospheric pressure generating further structural changes in the films. The evolution from amorphous to microcrystalline is characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy and impedance spectroscopy. A four-decade enhancement in the electrical conductivity is attributed to a disorder-order transition in a bonded Si network. Lastly, our results demonstrate a potentially attractive approach that employs a solution process coupled with ambient post-processing to produce crystalline silicon thin films.

36 MATERIALS SCIENCE↗

Three-dimensional structural dynamics of DNA origami Bennett linkages using individual-particle electron tomography

Scaffolded DNA origami has proven to be a powerful and efficient technique to fabricate functional nanomachines by programming the folding of a single-stranded DNA template strand into three-dimensional (3D) nanostructures, designed to be precisely motion-controlled. Although two-dimensional (2D) imaging of DNA nanomachines using transmission electron microscopy and atomic force microscopy suggested these nanomachines are dynamic in 3D, geometric analysis based on 2D imaging was insufficient to uncover the exact motion in 3D. In this paper, we use the individual-particle electron tomography method and reconstruct 129 density maps from 129 individual DNA origami Bennett linkage mechanisms at ~6-14 nm resolution. The statistical analyses of these conformations lead to understanding the 3D structural dynamics of Bennett linkage mechanisms. Moreover, our effort provides experimental verification of a theoretical kinematics model of DNA origami, which can be used as feedback to improve the design and control of motion via optimized DNA sequences and routing.

59 BASIC BIOLOGICAL SCIENCES↗

Extending the low-temperature operation of sodium metal batteries combining linear and cyclic ether-based electrolyte solutions

Nonaqueous sodium-based batteries are ideal candidates for the next generation of electrochemical energy storage devices. However, despite the promising performance at ambient temperature, their low-temperature (e.g., < 0 °C) operation is detrimentally affected by the increase in the electrolyte resistance and solid electrolyte interphase (SEI) instability. Here, to circumvent these issues, we propose specific electrolyte formulations comprising linear and cyclic ether-based solvents and sodium trifluoromethanesulfonate salt that are thermally stable down to –150 °C and enable the formation of a stable SEI at low temperatures. When tested in the Na||Na coin cell configuration, the low-temperature electrolytes enable long-term cycling down to –80 °C. Via ex situ physicochemical (e.g., X-ray photoelectron spectroscopy, cryogenic transmission electron microscopy and atomic force microscopy) electrode measurements and density functional theory calculations, we investigate the mechanisms responsible for efficient low-temperature electrochemical performance. We also report the assembly and testing between –20 °C and –60 °C of full Na||Na 3 V 2 (PO 4 ) 3 coin cells. The cell tested at –40 °C shows an initial discharge capacity of 68 mAh g –1 with a capacity retention of approximately 94% after 100 cycles at 22 mA g –1 .

25 ENERGY STORAGE↗

How nanoscale surface steps promote ice growth on feldspar: microscopy observation of morphology-enhanced condensation and freezing

Ice in the atmosphere affects Earth's radiative properties and initiates most precipitation. Growing ice often requires a solid surface, either to catalyze freezing of supercooled cloud droplets or to serve as a substrate for ice deposited from water vapor. There is evidence that this surface is typically provided by airborne mineral dust; but how chemistry, structure and morphology interrelate to determine the ice-nucleating ability of mineral surfaces remains elusive. Here, we combine optical microscopy with atomic force microscopy to explore the mechanisms of initial ice growth on alkali feldspar, a mineral proposed to dominate ice nucleation in Earth's atmosphere. When cold air becomes supersaturated with respect to water, we discovered that ice rapidly spreads along steps of a feldspar surface. By measuring how ice propagation depends on surface-step height we establish a scenario where supercooled liquid water condenses at steps without having to overcome a nucleation barrier, and subsequently freezes quickly. Finally, our results imply that steps, which are common even on macroscopically flat feldspar surfaces, can accelerate water condensation followed by freezing, thus promoting glaciation and dehydration of mixed-phase clouds.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Atomic layer deposition of lithium zirconium oxides for the improved performance of lithium-ion batteries

Recently there has been increasing interest to develop lithium-containing films as solid-state electrolytes or surface coatings for lithium-ion batteries (LIBs) and related systems. Here, in this study, we for the first time investigated the thin film growth of lithium zirconium oxides (Li x Zr y O or LZOs) through combining two individual atomic layer deposition (ALD) processes of ZrO 2 and LiOH, i.e., sub-ALD of ZrO 2 and LiOH. We revealed that the hygroscopic nature of the LiOH component has a big impact on the growth of LZOs. We found that an increased temperature to 225 °C was more effective than an elongated purge to mitigate the adverse effects of physisorbed H 2 O. We further discovered that, during the resultant LZO super-ALD processes, the growth of sub-ALD LiOH has been promoted while the growth of sub-ALD ZrO 2 has been inhibited. In this study, a suite of instruments has been applied to characterize the LZO super-ALD processes and the resultant LZO films, including in situ quartz crystal microbalance (QCM), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), atomic force microscopy (AFM), synchrotron-based X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Furthermore, we applied the resulting LZO films over LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) cathodes in LIBs and demonstrated that the LZO coating films could evidently improve the lithium-ion insertion and extraction rates of the NMC622 electrodes up to 3.4 and 2.6 times, respectively. The LZO-coated NMC622 cathodes exhibited much better performance than the uncoated NMC622 ones.

36 MATERIALS SCIENCE↗

A microfluidic electrochemical cell for studying the corrosion of uranium dioxide (UO 2 )

We have developed a specialized microfluidic electrochemical cell that enables in situ investigation of the electrochemical corrosion of microgram quantities of redox active solids. The advantage of downscaling is the reduction of hazards, waste, expense, and greatly expanding data collection for hazardous materials, including radioactive samples. Cyclic voltammetry was used to monitor the oxidation–reduction cycle of minute quantities of micron-size uraninite (UO 2 ) particles, from the formation of hexavalent uranium (U(VI)), U 3 O 7 and reduction to UO 2+x . Reaction progress was also studied in situ with scanning electron microscopy. The electrochemical measurements matched those obtained at the bulk-scale and were consistent with ex situ characterization of the run products by X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and atomic force microscopy; thus, demonstrating the utility of the microfluidic approach for studying radioactive materials.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

The reversal of the laser-beam-induced-current contrast with varying illumination density in a Cu{sub 2}ZnSnSe{sub 4} thin-film solar cell

We apply an array of correlated spatially-resolved techniques, including μ-Raman/photoluminescence/reflectance/laser-beam-induced-current in conjunction with scanning electron microscopy and atomic force microscopy, to study the impact of the microscopic-scale thickness inhomogeneity of CdS layer in a Cu{sub 2}ZnSnSe{sub 4} thin-film solar cell. Thicker CdS regions are found to cause more light reflecting loss thus yield lower external quantum efficiencies and energy conversion efficiencies than the general area. However, these regions show much less efficiency degradation at high illumination intensity, leading to an inversion of laser-beam-induced-current contrast in the area mapping. While improving the CdS layer uniformity can boost the device performance, the finding further points out the possibility of operating thin-film photovoltaic devices based on the similar materials (such as CuInGaSe{sub 2}, CdTe, Cu{sub 2}ZnSn(S,Se){sub 4}) under a substantially higher illumination density for concentrated photovoltaic and photo-detection.

14 SOLAR ENERGY↗

Analysis of InGaN nanodots grown by droplet heteroepitaxy using grazing incidence small-angle X-ray scattering and electron microscopy

We present a detailed structural investigation of self-assembled indium gallium nitride nanodots grown on c-plane aluminum nitride templates by the droplet heteroepitaxy technique in a plasma-assisted molecular beam epitaxy reactor. Various growth parameters, including the total coverage of the metal species, relative and total metal effusion fluxes, and nitridation temperature were investigated. Analyses of in situ reflection high-energy electron diffraction patterns and comparison with simulations showed that the resulting crystal structure was a mixture of wurtzite and twinned zinc blende phases, with the zinc blende phase increasingly dominant for lower metal coverages and lower nitridation temperatures, and the wurtzite phase increasingly dominant for higher nitridation temperature. Studies by field emission scanning electron microscopy and atomic force microscopy revealed that the nanodots exhibit trimodal size distributions, with the dot morphologies of the intermediate size mode often resembling aggregations of distinct clusters. Nanodots grown at higher nitridation temperatures had larger inter-dot spacings, with hexagonal in-plane ordering observable at a sufficiently high temperature. Using grazing incidence small angle X-ray scattering, we determined the nanodots to be approximately truncated cone shaped, and extracted the mean radius, height, and inter-dot distance for each distribution. Microstructural investigations of the nanodots by cross-sectional transmission electron microscopy indicated that the majority of the dots were formed in dislocation-free regions, and confirmed that the intermediate size dots were approximately truncated cone shaped and consisted of both zinc blende and wurtzite regions. Mapping of the elemental distributions by energy dispersive X-ray spectroscopy in scanning transmission electron microscopy mode indicated highly nonuniform indium distributions within both small and intermediate size dots which are potentially indicative of indium clustering and kinetically controlled nanoscale phase separation rather than the spinodal decomposition associated with bulk diffusion. In conclusion, the observed enrichment in indium concentration towards the tops of the nanodot layers could be ascribed to the compositional pulling effect.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Microstructure and surface morphology of InAsSbBi grown by molecular beam epitaxy

The physical and chemical properties of 210 nm thick InAsSbBi layers grown by molecular beam epitaxy at temperatures between 400 and 430 °C on (100) GaSb substrates are investigated using Rutherford backscattering, X-ray diffraction, transmission electron microscopy, Nomarski optical microscopy, and atomic force microscopy. The results indicate that the layers are nearly lattice matched, coherently strained, and contain dilute Bi mole fractions. Large surface droplets with diameters on the order of 1 μm and densities on the order of 106 cm−2 are observed when the InAsSbBi growth is performed with lean As overpressures around 1%. Surface droplets are not observed when the As overpressure is increased to 4%. Small crystalline droplets with diameters on the order of 70 nm and densities on the order of 1010 cm−2 are observed between the large droplets for InAsSbBi grown at 430 °C. Analysis of one of the small droplets indicates a misoriented zinc blende crystal structure composed primarily of In, Sb, and Bi, with a lattice constant of 6.543 ± 0.038 Å. Lateral modulation in the Bi mole fraction is observed in InAsSbBi layers grown at 400 °C.

Kosireddy, R. R.↗

Tautomerism induces bending and twisting of biogenic crystals

Understanding and exploiting material flexibility through phenomena such as the bending and twisting of molecular crystals has been a subject of increased interest owing to the number of applications that benefit from these properties, such as optoelectronics, mechanophotonics, soft robotics, and smart sensors. Here, we report the growth of spontaneously bent and twisted ammonium urate crystals induced by the keto–enol tautomerism of the urate molecule. The major tautomer is native to biogenic crystals, whereas the minor tautomer functions as an effective crystal growth modifier to induce naturally bent and twisted ammonium urate crystals. We show that the degree of curvature can be tailored based on the judicious selection of growth conditions. A combination of state-of-the-art microscopy and spectroscopy techniques are used to characterize the origin of bending. Spatially resolved nano-electron diffraction and high-resolution electron microscopy of naturally bent crystals show nearly single crystallinity with local lattice deformations generated by a combination of screw and edge dislocations. These observations are consistent with photoinduced force microscopy and contact resonance atomic force microscopy, which confirmed spatially resolved changes in the intermolecular interactions and the mechanical properties throughout the cross-sectional and axial regions of bent crystals. A mechanism of bending involving the generation of regionally specific dislocations is proposed as an alternative to more commonly reported models. These findings highlight a unique characteristic of tautomeric crystals that may have broader implications for other biogenic materials.

Science & Technology - Other Topics↗

RNA nanotechnology to build a dodecahedral genome of single-stranded RNA virus

The quest for artificial RNA viral complexes with authentic structure while being non-replicative is on its way for the development of viral vaccines. RNA viruses contain capsid proteins that interact with the genome during morphogenesis. The sequence and properties of the protein and genome determine the structure of the virus. For example, the Pariacoto virus ssRNA genome assembles into a dodecahedron. Virus-inspired nanotechnology has progressed remarkably due to the unique structural and functional properties of viruses, which can inspire the design of novel nanomaterials. RNA is a programmable biopolymer able to self-assemble sophisticated 3D structures with rich functionalities. RNA dodecahedrons mimicking the Pariacoto virus quasi-icosahedral genome structures were constructed from both native and 2'-F modified RNA oligos. The RNA dodecahedron easily self-assembled using the stable pRNA three-way junction of bacteriophage phi29 as building blocks. The RNA dodecahedron cage was further characterized by cryo-electron microscopy and atomic force microscopy, confirming the spontaneous and homogenous formation of the RNA cage. The reported RNA dodecahedron cage will likely provide further studies on the mechanisms of interaction of the capsid protein with the viral genome while providing a template for further construction of the viral RNA scaffold to add capsid proteins for the assembly of the viral nucleocapsid as a model. Understanding the self-assembly and RNA folding of this RNA cage may offer new insights into the 3D organization of viral RNA genomes. Finally, the reported RNA cage also has the potential to be explored as a novel virus-inspired nanocarrier.

59 BASIC BIOLOGICAL SCIENCES↗

A MEMS lamination technology based on sequential multilayer electrodeposition

A MEMS lamination technology based on sequential multilayer electrodeposition is presented. The process comprises three main steps: (1) automated sequential electrodeposition of permalloy (Ni80Fe20) structural and copper sacrificial layers to form multilayer structures of significant total thickness; (2) fabrication of polymeric anchor structures through the thickness of the multilayer structures and (3) selective removal of copper. The resulting structure is a set of air-insulated permalloy laminations, the separation of which is sustained by insulating polymeric anchor structures. Individual laminations have precisely controllable thicknesses ranging from 500 nm to 5 mu m, and each lamination layer is electrically isolated from adjacent layers by narrow air gaps of similar scale. In addition to air, interlamination insulators based on polymers are investigated. Interlamination air gaps with very high aspect ratio (>1:100) can be filled with polyvinylalcohol and polydimethylsiloxane. The laminated structures are characterized using scanning electron microscopy and atomic force microscopy to directly examine properties such as the roughness and the thickness uniformity of the layers. In addition, the quality of the electrical insulation between the laminations is evaluated by quantifying the eddy current within the sample as a function of frequency. Fabricated laminations are comprised of uniform, smooth (surface roughness < 100 nm) layers with effective electrical insulation for all layer thicknesses and insulator approaches studied. Such highly laminated structures have potential uses ranging from energy conversion to applications where composite materials with highly anisotropic mechanical or thermal properties are required.

Kim, M↗