A Direct Real-Time Observation of Anion Intercalation in Graphite Process and Its Fully Reversibility by SAXS/WAXS Techniques.

The process of anion intercalation in graphite and its reversibility plays a crucial role in the next generation energy-storage devices. Herein the reaction mechanism of the aluminum graphite dual ion cell by operando X-ray scattering from small angles to wide angles is investigated. The staging behavior of the graphite intercalation compound (GIC) formation, its phase transitions, and its reversible process are observed for the first time by directly measuring the repeated intercalation distance, along with the microporosity of the cathode graphite. The investigation demonstrates complete reversibility of the electrochemical intercalation process, alongside nano- and micro-structural reorganization of natural graphite induced by intercalation. This work represents a new insight into thermodynamic aspects taking place during intermediate phase transitions in the GIC formation.

Direct Observation of the Xenon Physisorption Process in Mesopores by Combining In Situ Anomalous Small-Angle X-ray Scattering and X-ray Absorption Spectroscopy.

The morphology and structural changes of confined matter are still far from being understood. This report deals with the development of a novel in situ method based on the combination of anomalous small-angle X-ray scattering (ASAXS) and X-ray absorption near edge structure (XANES) spectroscopy to directly probe the evolution of the xenon adsorbate phase in mesoporous silicon during gas adsorption at 165 K. The interface area and size evolution of the confined xenon phase were determined via ASAXS demonstrating that filling and emptying the pores follow two distinct mechanisms. The mass density of the confined xenon was found to decrease prior to pore emptying. XANES analyses showed that Xe exists in two different states when confined in mesopores. This combination of methods provides a smart new tool for the study of nanoconfined matter for catalysis, gas, and energy storage applications.

Crystallinity and Size Control of Colloidal Germanium Nanoparticles from Organogermanium Halide Reagents.

Germanium (Ge) nanoparticles are gaining increasing interest due to their properties that arise in the quantum confinement regime, such as the development of the band structure with changing size. While promising materials, significant challenges still exist related to the development of synthetic schemes allowing for good control over size and morphology in a single step. Herein, we investigate a synthetic method that combines sulfur and primary amines to promote the reduction of organometallic Ge(IV) precursors to form Ge nanoparticles at relatively low temperatures (300 °C). We propose a reaction mechanism and examine the effects of solvents, sulfur concentration, and organogermanium halide precursors. Hydrosulfuric acid (H2S) produced in situ acts as the primary reducing species, and we were able to increase the particle size more than 2-fold by tuning both the reaction time and quantity of sulfur added during the synthesis. We found that we are able to control the crystalline or amorphous nature of the resulting nanoparticles by choosing different solvents and propose a mechanism for this interaction. The reaction mechanism presented provides insight into how one can control the resulting particle size, crystallinity, and reaction kinetics. While we demonstrated the synthesis of Ge nanoparticles, this method can potentially be extended to other members of the group IV family.

Sample cartridge with built-in miniature molecule evaporator for in-situ measurement with a photoemission electron microscope.

We present a new sample holder that is compatible with Photoemission Electron Microscopes (PEEMs) and contains a molecule evaporator. With the integrated low cost evaporator, a local and controlled material deposition in clean ultra-high vacuum conditions can be achieved minimizing the contamination of the analysis chamber. Different molecule systems can easily be studied by exchanging the sample holder. This opens up new possibilities for in-situ investigation of thin film growth by means of spectromicroscopy and element-selective imaging at the nanometer scale. As an example of the performances of the setup, we present a study of the hybrid inorganic/organic system (HIOS) consisting of the organic acceptor molecule 2,2'-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (F6TCNNQ) and ZnO, which is of great interest for novel HIOS-based optoelectronic devices. Here, the ZnO surface work function modification by F6TCNNQ adsorption is investigated in-situ in a spatially resolved manner. In addition, we employ PEEM to selectively probe the chemical state of F6TCNNQ molecules in contact with ZnO (in the first monolayer) and those molecules located in multilayers (in 3D islands).

Controlling Morphology in Polycrystalline Films by Nucleation and Growth from Metastable Nanocrystals.

Solution processing of polycrystalline compound semiconductor thin film using nanocrystals as a precursor is considered one of the most promising and economically viable routes for future large-area manufacturing. However, in polycrystalline compound semiconductor films such as Cu2ZnSnS4 (CZTS), grain size, and the respective grain boundaries play a key role in dictating the optoelectronic properties. Various strategies have been employed previously in tailoring the grain size and boundaries (such as ligand exchange) but most require postdeposition thermal annealing at high temperature in the presence of grain growth directing agents (selenium or sulfur vapor with/without Na, K, etc.) to enlarge the grains through sintering. Here, we show a different strategy of controlling grain size by tuning the kinetics of nucleation and the subsequent grain growth in CZTS nanocrystal thin films during a crystalline phase transition. We demonstrate that the activation energy for the phase transition can be varied by utilizing different shapes (spherical and nanorod) of nanocrystals with similar size, composition, and surface chemistry leading to different densities of nucleation sites and, thereby, different grain sizes in the films. Additionally, exchanging the native organic ligands for inorganic surface ligands changes the activation energy for the phase change and substantially changes the grain growth dynamics, while also compositionally modifying the resulting film. This combined approach of using nucleation and growth dynamics and surface chemistry enables us to tune the grain size of polycrystalline CZTS films and customize their electronic properties by compositional engineering.

Size-dependent polar ordering in colloidal GeTe nanocrystals.

The question of the nature and stability of polar ordering in nanoscale ferroelectrics is examined with colloidal nanocrystals of germanium telluride (GeTe). We provide atomic-scale evidence for room-temperature polar ordering in individual nanocrystals using aberration-corrected transmission electron microscopy and demonstrate a reversible, size-dependent polar-nonpolar phase transition of displacive character in nanocrystal ensembles. A substantial linear component of the distortion is observed, which is in contrast with theoretical reports predicting a toroidal state.

Observation of the role of subcritical nuclei in crystallization of a glassy solid.

Phase transformation generally begins with nucleation, in which a small aggregate of atoms organizes into a different structural symmetry. The thermodynamic driving forces and kinetic rates have been predicted by classical nucleation theory, but observation of nanometer-scale nuclei has not been possible, except on exposed surfaces. We used a statistical technique called fluctuation transmission electron microscopy to detect nuclei embedded in a glassy solid, and we used a laser pump-probe technique to determine the role of these nuclei in crystallization. This study provides a convincing proof of the time- and temperature-dependent development of nuclei, information that will play a critical role in the development of advanced materials for phase-change memories.

Evidence for electronic gap-driven metal-semiconductor transition in phase-change materials.

Phase-change materials are functionally important materials that can be thermally interconverted between metallic (crystalline) and semiconducting (amorphous) phases on a very short time scale. Although the interconversion appears to involve a change in local atomic coordination numbers, the electronic basis for this process is still unclear. Here, we demonstrate that in a nearly vacancy-free binary GeSb system where we can drive the phase change both thermally and, as we discover, by pressure, the transformation into the amorphous phase is electronic in origin. Correlations between conductivity, total system energy, and local atomic coordination revealed by experiments and long time ab initio simulations show that the structural reorganization into the amorphous state is driven by opening of an energy gap in the electronic density of states. The electronic driving force behind the phase change has the potential to change the interconversion paradigm in this material class.

Solution-phase deposition and nanopatterning of GeSbSe phase-change materials.

Chalcogenide films with reversible amorphous-crystalline phase transitions have been commercialized as optically rewritable data-storage media, and intensive effort is now focused on integrating them into electrically addressed non-volatile memory devices (phase-change random-access memory or PCRAM). Although optical data storage is accomplished by laser-induced heating of continuous films, electronic memory requires integration of discrete nanoscale phase-change material features with read/write electronics. Currently, phase-change films are most commonly deposited by sputter deposition, and patterned by conventional lithography. Metal chalcogenide films for transistor applications have recently been deposited by a low-temperature, solution-phase route. Here, we extend this methodology to prepare thin films and nanostructures of GeSbSe phase-change materials. We report the ready tuneability of phase-change properties in GeSbSe films through composition variation achieved by combining novel precursors in solution. Rapid, submicrosecond phase switching is observed by laser-pulse annealing. We also demonstrate that prepatterned holes can be filled to fabricate phase-change nanostructures from hundreds down to tens of nanometres in size, offering enhanced flexibility in fabricating PCRAM devices with reduced current requirements.

Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles.

High-temperature solution phase reaction of iron(III) acetylacetonate, Fe(acac)(3), with 1,2-hexadecanediol in the presence of oleic acid and oleylamine leads to monodisperse magnetite (Fe(3)O(4)) nanoparticles. Similarly, reaction of Fe(acac)(3) and Co(acac)(2) or Mn(acac)(2) with the same diol results in monodisperse CoFe(2)O(4) or MnFe(2)O(4) nanoparticles. Particle diameter can be tuned from 3 to 20 nm by varying reaction conditions or by seed-mediated growth. The as-synthesized iron oxide nanoparticles have a cubic spinel structure as characterized by HRTEM, SAED, and XRD. Further, Fe(3)O(4) can be oxidized to Fe(2)O(3), as evidenced by XRD, NEXAFS spectroscopy, and SQUID magnetometry. The hydrophobic nanoparticles can be transformed into hydrophilic ones by adding bipolar surfactants, and aqueous nanoparticle dispersion is readily made. These iron oxide nanoparticles and their dispersions in various media have great potential in magnetic nanodevice and biomagnetic applications.