IN SITU STEM STUDY OF METAL OXIDES NANOWIRES FOR NANOELECTRONICS AND ENERGY STORAGE SYSTEMS

Interesting structures and properties of transition metal oxides have been characterized by many techniques and used for various device applications. However, simultaneous correlation between the physical and structural properties of these materials has not been widely investigated. In this work, we will use aberration-corrected scanning transmission electron microscopy to study theses materials in atomic level. Different in situ TEM techniques were performed to test the functionality of materials. The double tilt liquid nitrogen-cooling holder was used for thermal testing and scanning tunneling microscopy (STM) stage holder was used to perform electrical testing on individual nanowires

Thermoelectric properties of large-scale Zn \u3c inf\u3e 3 P \u3c inf\u3e 2 nanowire assemblies

Gram quantities of both unfunctionalized and 1,4-benzenedithiol (BDT) functionalized zinc phosphide (Zn3P2) nanowire powders, synthesized using direct reaction of zinc and phosphorus, were hot-pressed into highly dense pellets (≥98% of the theoretical density) for the determination of their thermoelectric performance. It was deduced that mechanical flexibility of the nanowires is essential for consolidating them in randomly oriented fashion into dense pellets, without making any major changes to their morphologies. Electrical and thermal transport measurements indicated that the enhanced thermoelectric performance expected of individual Zn3P 2 nanowires is still retained within large-scale nanowire assemblies. A maximum reduction of 28% in the thermal conductivity of Zn3P 2 resulted from nanostructuring. Use of nanowire morphology also led to enhanced electrical conductivity in Zn3P2. Interface engineering of the nanowires in the pellets, accomplished by hot-pressing BDT functionalized nanowires, resulted in an increase on both the Seebeck coefficient and the electrical conductivity of the nanowire pellets. It is believed that filtering of low energy carriers resulting from the variation of the chemical compositions at the nanowire interfaces is responsible for this phenomenon. Overall, this study indicated that mechanical properties of the nanowires along with the chemical compositions of their surfaces play a hitherto unknown, but vital, role in realizing highly efficient bulk thermoelectric modules based on nanowires. © 2014 IOP Publishing Ltd

Multi-Step Crystallization of Barium Carbonate: Rapid Interconversion of Amorphous and Crystalline Precursors.

The direct observation of amorphous barium carbonate (ABC), which transforms into a previously unknown barium carbonate hydrate (herewith named gortatowskite) within a few hundred milliseconds of formation, is described. In situ X-ray scattering, cryo-, and low-dose electron microscopy were used to capture the transformation of nanoparticulate ABC into gortatowskite crystals, highly anisotropic sheets that are up to 1 μm in width, yet only about 10 nm in thickness. Recrystallization of gortatowskite to witherite starts within 30 seconds. We describe a bulk synthesis and report a first assessment of the composition, vibrational spectra, and structure of gortatowskite. Our findings indicate that transient amorphous and crystalline precursors can play a role in aqueous precipitation pathways that may often be overlooked owing to their extremely short lifetimes and small dimensions. However, such transient precursors may be integral to the formation of more stable phases

Multi-Step Crystallization of Barium Carbonate: Rapid Interconversion of Amorphous and Crystalline Precursors.

The direct observation of amorphous barium carbonate (ABC), which transforms into a previously unknown barium carbonate hydrate (herewith named gortatowskite) within a few hundred milliseconds of formation, is described. In situ X-ray scattering, cryo-, and low-dose electron microscopy were used to capture the transformation of nanoparticulate ABC into gortatowskite crystals, highly anisotropic sheets that are up to 1 μm in width, yet only about 10 nm in thickness. Recrystallization of gortatowskite to witherite starts within 30 seconds. We describe a bulk synthesis and report a first assessment of the composition, vibrational spectra, and structure of gortatowskite. Our findings indicate that transient amorphous and crystalline precursors can play a role in aqueous precipitation pathways that may often be overlooked owing to their extremely short lifetimes and small dimensions. However, such transient precursors may be integral to the formation of more stable phases

Direct characterization of the Li intercalation mechanism into α-V \u3c inf\u3e 2 O \u3c inf\u3e 5 nanowires using in-situ transmission electron microscopy

© 2017 Author(s). The Li-V2O5 system has been well studied electrochemically, but there is a lack of systematic in-situ studies involving direct investigations of the structural changes that accompany the lithiation process. The open-cell battery setup inside a transmission electron microscope is ideal for studying the reaction pathway of intercalation of Li+ into nanowire cathodes. In this work, we utilize in-situ transmission electron microscopy to study the Li-V2O5 system. More specifically, we employ electron beam diffraction and electron energy-loss spectroscopy (EELS) in an open-cell battery setup to examine the phase changes within α-V2O5 nanowire cathodes upon in-situ lithiation. Our results suggest that the pristine α-V2O5 nanowire forms a Li oxide shell which then acts as a solid state electrolyte to conduct Li+ ions, and the bulk of the V2O5 nanowire undergoes transformation to the γ-Li2V2O5 phase

Stabilizing metastable tetragonal HfO \u3c inf\u3e 2 using a non-hydrolytic solution-phase route: Ligand exchange as a means of controlling particle size

This journal is © 2016 The Royal Society of Chemistry. There has been intense interest in stabilizing the tetragonal phase of HfO2 since it is predicted to outperform the thermodynamically stable lower-symmetry monoclinic phase for almost every application where HfO2 has found use by dint of its higher dielectric constant, bandgap, and hardness. However, the monoclinic phase is much more thermodynamically stable and the tetragonal phase of HfO2 is generally accessible only at temperatures above 1720 °C. Classical models comparing the competing influences of bulk free energy and specific surface energy predict that the tetragonal phase of HfO2 ought to be stable at ultra-small dimensions below 4 nm; however, these size regimes have been difficult to access in the absence of synthetic methods that yield well-defined and monodisperse nanocrystals with precise control over size. In this work, we have developed a modified non-hydrolytic condensation method to precisely control the size of HfO2 nanocrystals with low concentrations of dopants by suppressing the kinetics of particle growth by cross-condensation with less-reactive precursors. This synthetic method enables us to stabilize tetragonal HfO2 while evaluating ideas for critical size at which surface energy considerations surpass the bulk free energy stabilization. The phase assignment has been verified by atomic resolution high angle annular dark field images acquired for individual nanocrystals

Direct evidence of M \u3c inf\u3e 2 phase during the monoclinic-tetragonal (rutile) phase transition of W-doped VO \u3c inf\u3e 2 nanowires

© 2017 Author(s). Identifying different phases of VO2 during the metal−insulator phase transition is critical for device application due to the difference of electrical, mechanical and magnetic properties of phases. However, most studies so far were carried out using microprobe analyses, which lack the spatial resolution needed to identify nanoscale phases and changes. Taking advantage of in situ low temperature aberration-corrected scanning transmission electron microscopy, we observed the existence of M2 phase alongside M1 and R phase in the W-doped nanowires close to transition temperature. The localized stress caused by adding W in the structure results in the stabilization of nanosize grains of M2 phase in structure along with M1 and R phases. The observation of the metastable M2 phase even for unclamped nanowires suggests the possibility of finely modulating the phase diagram of VO2 through a combination of finite size and doping

Energy-driven surface evolution in beta-MnO \u3c inf\u3e 2 structures

© 2018, Tsinghua University Press and Springer-Verlag GmbH Germany. Exposed crystal facets directly affect the electrochemical/catalytic performance of MnO2 materials during their applications in supercapacitors, rechargeable batteries, and fuel cells. Currently, the facet-controlled synthesis of MnO2 is facing serious challenges due to the lack of an in-depth understanding of their surface evolution mechanisms. Here, combining aberration-corrected scanning transmission electron microscopy (STEM) and high-resolution TEM, we revealed a mutual energy-driven mechanism between beta-MnO2 nanowires and microstructures that dominated the evolution of the lateral facets in both structures. The evolution of the lateral surfaces followed the elimination of the {100} facets and increased the occupancy of {110} facets with the increase in hydrothermal retention time. Both self-growth and oriented attachment along their {100} facets were observed as two different ways to reduce the surface energies of the beta-MnO2 structures. High-density screw dislocations with the 1/2 \u3c 100\u3e Burgers vector were generated consequently. The observed surface evolution phenomenon offers guidance for the facet-controlled growth of beta-MnO2 materials with high performances for its application in metal-air batteries, fuel cells, supercapacitors, etc