Search

In this work we report strategies to nucleate bimetallic nanoparticles (NPs) made by gas phase synthesis of elements showing difficulty in homogeneous nucleation. It is shown that the nucleation assisted problem of bimetallic NP synthesis can be solved via the following pathways: (i) selecting an element which can itself nucleate and act as a nucleation center for the synthesis of bimetallic NPs; (ii) introducing H 2 or CH 4 as an impurity/trace gas to initiate nucleation during the synthesis of bimetallic NPs. The latter can solve the problem if none of the elements in a bimetallic NP can initiate nucleation. We illustrate the abovementioned strategies for the case of Mg based bimetallic NPs, which are interesting as hydrogen storage materials and exhibit both nucleation and oxidation issues even under ultra-high vacuum conditions. In particular, it is shown that adding H 2 in small proportions favors the formation of a solid solution/alloy structure even in the case of immiscible Mg and Ti, where normally phase separation occurs during synthesis. In addition, we illustrate the possibility of improving the nucleation rate, and controlling the structure and size distribution of bimetallic NPs using H 2 /CH 4 as a reactive/nucleating gas. This is shown to be associated with the dimer bond energies of the various formed species and the vapor pressures of the metals, which are key factors for NP nucleation.

Although nanostructured phase-change materials (PCMs) are considered as the building blocks of next-generation phase-change memory and other emerging optoelectronic applications, the kinetics of the crystallization, the central property in switching, remains ambiguous in the high-temperature regime. Therefore, we present here an innovative exploration of the crystallization kinetics of Ge 2 Sb 2 Te 5 (GST) nanoparticles (NPs) exploiting differential scanning calorimetry with ultrafast heating up to 40 000 K s -1 . Our results demonstrate that the non-Arrhenius thermal dependence of viscosity at high temperature becomes an Arrhenius-like behavior when the glass transition is approached, indicating a fragile-to-strong (FS) crossover in the as-deposited amorphous GST NPs. The overall crystal growth rate of the GST NPs is unraveled as well. This unique feature of the FS crossover is favorable for memory applications as it is correlated to improved data retention. Furthermore, we show that methane incorporation during NP production enhances the stability of the amorphous NP phase (and thereby data retention), while a comparable maximum crystal growth rate is still observed. These results offer deep insight into the crystallization kinetics of nanostructured GST, paving the way for designing nonvolatile memories with PCM dimensions smaller than 20 nm.

Chalcogenide-based nanostructured phase-change materials (PCMs) are considered promising building blocks for non-volatile memory due to their high write and read speeds, high data-storage density, and low power consumption. Top-down fabrication of PCM nanoparticles (NPs), however, often results in damage and deterioration of their useful properties. Gas-phase condensation based on magnetron sputtering offers an attractive and straightforward solution to continuously down-scale the PCMs into sub-lithographic sizes. Here we unprecedentedly present the size dependence of crystallization for Ge 2 Sb 2 Te 5 (GST) NPs, whose production is currently highly challenging for chemical synthesis or top-down fabrication. Both amorphous and crystalline NPs have been produced with excellent size and composition control with average diameters varying between 8 and 17 nm. The size-dependent crystallization of these NPs was carefully analyzed through in-situ heating in a transmission electron microscope, where the crystallization temperatures (T c ) decrease when the NPs become smaller. Moreover, methane incorporation has been observed as an effective method to enhance the amorphous phase stability of the NPs. This work therefore elucidates that GST NPs synthesized by gas-phase condensation with tailored properties are promising alternatives in designing phase-change memories constrained by optical lithography limitations.

Using reflection high-energy electron diffraction (RHEED), the growth onset of molecular beam epitaxy (MBE) deposited germanium telluride (GeTe) film on Si(111)-(√3 × √3)R30°-Sb surfaces is investigated, and a larger than expected in-plane lattice spacing is observed during the deposition of the first two molecular layers. High-resolution transmission electron microscopy (HRTEM) confirms that the growth proceeds via closed layers, and that those are stable after growth. The comparison of the experimental Raman spectra with theoretical calculated ones allows assessing the shift of the phonon modes for a quasi-free-standing ultra-thin GeTe layer with larger in-plane lattice spacing. The manifestation of the latter phenomenon is ascribed to the influence of the interface and the confinement of GeTe within the limited volume of material available at growth onset, either preventing the occurrence of Peierls dimerization or their ordered arrangement to occur normally.

Core-shell structured Fe nanoparticles (NPs) produced by high pressure magnetron sputtering gas condensation were studied using transmission electron microscopy (TEM) techniques, electron diffraction, electron energy-loss spectroscopy (EELS), tomographic reconstruction, and Wulff shape construction analysis. The core-shell structure, which is composed of an Fe core surrounded by a maghemite (γ-Fe2O3) and/or magnetite (Fe3O4) shell, was confirmed by fast Fourier transform (FFT) analysis combined with EELS. It was found that the particle size and shape strongly depend on the gas environment. Moreover, extensive analysis showed that NPs with a size between 10-20 nm possess a truncated cubic morphology, which is confined by the 6 {100} planes that are truncated by the 12 {110} planes at different degrees. For NPs larger than 20 nm, the rhombic dodecahedron defined by the 12 {110} planes is the predominant crystal shape, while truncated rhombic dodecahedrons, as well as non-truncated and truncated cubic NPs, were also observed. The NPs without truncation showed a characteristic inward relaxation indicating that besides thermodynamics kinetics also plays a crucial role during particle growth.

The technological success of phase-change materials in the field of data storage and functional systems stems from their distinctive electronic and structural peculiarities on the nanoscale. Recently, superlattice structures have been demonstrated to dramatically improve the optical and electrical performances of these chalcogenide based phase-change materials. In this perspective, unravelling the atomistic structure that originates the improvements in switching time and switching energy is paramount in order to design nanoscale structures with even enhanced functional properties. This study reveals a high- resolution atomistic insight of the [GeTe/Sb2Te3] interfacial structure by means of Extended X-Ray Absorption Fine Structure spectroscopy and Transmission Electron Microscopy. Based on our results we propose a consistent novel structure for this kind of chalcogenide superlattices.

In the past years, halide capping became one of the most promising strategies to passivate the surface of colloidal quantum dots (CQDs) in thin films to be used for electronic and optoelectronic device fabrication. This is due to the convenient processing, strong n-type characteristics, and ambient stability of the devices. Here, we investigate the effect of three counterions (ammonium, methylammonium, and tetrabutylammonium) in iodide salts used for treating CQD thin films and shed light on the mechanism of the ligand exchange. We obtain two- and three-dimensional square-packed PbS CQD superlattices with epitaxial merging of nearest neighbor CQDs as a direct outcome of the ligand-exchange reaction and show that the order in the layer can be controlled by the nature of the counterion. Furthermore, we demonstrate that the acidity of the environment plays an important role in the substitution of the carboxylates by iodide ions at the surface of lead chalcogenide quantum dots. Tetrabutylammonium iodide shows lower reactivity compared to methylammonium and ammonium iodide due to the nonacidity of the cation, which eventually leads to higher order but also poorer carrier transport due to incomplete removal of the pristine ligands in the QD thin film. Finally, we show that single-step blade-coating and immersion in a ligand exchange solution such as the one containing methylammonium iodide can be used to fabricate well performing bottom-gate/bottom-contact PbS CQD field effect transistors with record subthreshold swing.

GeTe-Sb2Te3 superlattices are nanostructured phase-change materials which are under intense investigation for non-volatile memory applications. They show superior properties compared to their bulk counterparts and significant efforts exist to explain the atomistic nature of their functionality. The present work sheds new light on the interface formation between GeTe and Sb2Te3, contradicting previously proposed models in the literature. For this purpose [GeTe(1 nm)-Sb2Te3(3 nm)]15 superlattices were grown on passivated Si(111) at 230 °C using molecular beam epitaxy and they have been characterized particularly with cross-sectional HAADF scanning transmission electron microscopy. Contrary to the previously proposed models, it is found that the ground state of the film actually consists of van der Waals bonded layers (i.e. a van der Waals heterostructure) of Sb2Te3 and rhombohedral GeSbTe. Moreover, it is shown by annealing the film at 400 °C, which reconfigures the superlattice into bulk rhombohedral GeSbTe, that this van der Waals layer is thermodynamically favored. These results are explained in terms of the bonding dimensionality of GeTe and Sb2Te3 and the strong tendency of these materials to intermix. The findings debate the previously proposed switching mechanisms of superlattice phase-change materials and give new insights in their possible memory application.

An imaging method has been developed based on charge collection in a scanning electron microscope (SEM) that allows discrimination between the amorphous and crystalline states of Phase-change Random Access Memory (PRAM) line cells. During imaging, the cells are electrically connected and can be switched between the states and the resistance can be measured. This allows for electrical characterization of the line cells in-situ in the SEM. Details on sample and measurement system requirements are provided which turned out to be crucial for the successful development of this method. Results show that the amorphous or crystalline state of the line cells can be readily discerned, but the spatial resolution is relatively poor. Nevertheless, it is still possible to estimate the length of the amorphous mark, and also for the first time, we could directly observe the shift of the amorphous mark from one side of the line cell to the other side when the polarity of the applied (50 ns) RESET pulse was reversed.

Here we report the extraordinary thermal stability of Mg rich bimetallic nanoparticles (NPs), which is important for hydrogen storage technology. The enhanced NP stability is accomplished because of two critical improvements: (i) no void development within NPs (nanoscale Kirkendall effect) during their formation and (ii) suppressed Mg evaporation and NP hollowing during Mg hydrogenation at elevated temperature. The mechanism leading to the improved thermal stability of Mg-based bimetallic NPs is shown to be due to MgH2 hydride formation before evaporation can take place. These findings were tested for various compositions of Mg with Ni, Cu, and Ti, which are interesting combinations of materials for hydrogen storage systems. To achieve this we first demonstrate the synthesis mechanism of Mg-Ni and Mg-Cu NPs, which is well controlled at the single particle level, in order to accomplish multi-shell, alloy and intermetallic structures of interest for hydrogen storage tests. Aberration corrected transmission electron microscopy was carried out to unravel the detailed atomic structure and composition of the bimetallic NPs after production, processing, and hydrogenation. Finally, a simple and effective methodology is proposed for tuning the composition of the Mg-based bimetallic NPs based on the temperature-dependent nucleation behavior of NPs in the gas-phase.

We report the rational design and synthesis of DAB poly(propylene imine) dendrimer (DAB) intercalated graphite oxide (GO) hybrids with tailorable interlayer distances. The amine groups originating from the intercalated dendrimer molecules cross-link adjacent GO sheets and strongly favour CO2 adsorption under wet flue gas conditions.

Colloidal nanocrystals electronic energy levels are determined by strong size-dependent quantum confinement. Understanding the configuration of the energy levels of nanocrystal superlattices is vital in order to use them in heterostructures with other materials. A powerful method is reported to determine the energy levels of PbS nanocrystal assemblies by combining the utilization of electric-double-layer-gated transistors and advanced ab-initio theory., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The reversible amorphous-crystalline phase change in a chalcogenide material, specifically the Se1-xTex alloy, has been investigated for the first time using ultrafast differential scanning calorimetry. Heating rates and cooling rates up to 5000 K/s were used. Repeated reversible amorphous-crystalline phase switching was achieved by consecutively melting, melt-quenching, and recrystallizing upon heating. Using a well-conditioned method, the composition of a single sample was allowed to shift slowly from 15 at. %Te to 60 at. %Te, eliminating sample-to-sample variability from the measurements. Using Energy Dispersive X-ray Spectroscopy composition analysis, the onset of melting for different Te-concentrations was confirmed to coincide with the literature solidus line, validating the use of the onset of melting Tm as a composition indicator. The glass transition Tg and crystallization temperature Tc could be determined accurately, allowing the construction of extended phase diagrams. It was found that Tm and Tg increase (but Tg/Tm decrease slightly) with increasing Te-concentration. Contrarily, the Tc decreases substantially, indicating that the amorphous phase becomes progressively unfavorable. This coincides well with the observation that the critical quench rate to prevent crystallization increases about three orders of magnitude with increasing Te concentration. Due to the employment of a large range of heating rates, non-Arrhenius behavior was detected, indicating that the undercooled liquid SeTe is a fragile liquid. The activation energy of crystallization was found to increase 0.5-0.6 eV when the Te concentration increases from 15 to 30 at. % Te, but it ceases to increase when approaching 50 at. % Te.

We report for the first time the intercalation of low-molecular-weight hyperbranched polyethyleneimine (PEI) into graphite oxide (GO) for the facile, bulk synthesis of novel graphene-based hybrid (GO-PEI) materials exhibiting tailored interlayer galleries. The size of the intercalant as well as the loading in GO were systematically investigated to determine their contribution to the basal spacing of the resulting materials. Powder X-ray diffraction measurements demonstrated the generation of constrained hybrid systems along the c axis that exhibit considerably increased interlayer distances compared with the starting, pristine GO. The results of X-ray photoelectron and FTIR studies are consistent with a "grafting-to" process of the intercalated PEI with the oxygen functional groups present along the GO framework. Furthermore, it was found that a great number of the nitrogen-containing groups in PEI still remain available within the newly formed, confined micro-environment of intercalated GO galleries. The increased surface area of the GO-PEI hybrids in conjunction with the remaining available active groups of intercalated PEI render the synthesised hybrids very attractive candidates as nanostructured adsorbents., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Sb2Te3 films are used for studying the epitaxial registry between two-dimensionally bonded (2D) materials and three-dimensional bonded (3D) substrates. In contrast to the growth of 3D materials, it is found that the formation of coincidence lattices between Sb2Te3 and Si(111) depends on the geometry and dangling bonds of the reconstructed substrate surface. Furthermore, we show that the epitaxial registry can be influenced by controlling the Si(111) surface reconstruction and confirm the results for ultrathin films.

The determination of the dynamic spring constant (kd) of atomic force microscopy cantilevers is of crucial importance for converting cantilever deflection to accurate force data. Indeed, the non-destructive, fast, and accurate measurement method of the cantilever dynamic spring constant by Sader et al. [Rev. Sci. Instrum. 83, 103705 (2012)] is confirmed here for plane geometry but surface modified cantilevers. It is found that the measured spring constants (keff, the dynamic one kd), and the calculated (kd,1) are in good agreement within less than 10% error.

Nowadays bimetallic nanoparticles (NPs) have emerged as key materials for important modern applications in nanoplasmonics, catalysis, biodiagnostics, and nanomagnetics. Consequently the control of bimetallic structural motifs with specific shapes provides increasing functionality and selectivity for related applications. However, producing bimetallic NPs with well controlled structural motifs still remains a formidable challenge. Hence, we present here a general methodology for gas phase synthesis of bimetallic NPs with distinctively different structural motifs ranging at a single particle level from a fully mixed alloy to core-shell, to onion (multi-shell), and finally to a Janus/dumbbell, with the same overall particle composition. These concepts are illustrated for Mo-Cu NPs, where the precise control of the bimetallic NPs with various degrees of chemical ordering, including different shapes from spherical to cube, is achieved by tailoring the energy and thermal environment that the NPs experience during their production. The initial state of NP growth, either in the liquid or in the solid state phase, has important implications for the different structural motifs and shapes of synthesized NPs. Finally we demonstrate that we are able to tune the alloying regime, for the otherwise bulk immiscible Mo-Cu, by achieving an increase of the critical size, below which alloying occurs, closely up to an order of magnitude. It is discovered that the critical size of the NP alloy is not only affected by controlled tuning of the alloying temperature but also by the particle shape.

High temperature annealing of gas phase synthesized Mg nanoparticles surrounded by an MgO shell leads to formation of hollow MgO nanoshells due to the evaporation assisted Kirkendall effect. Under electron beam exposure in TEM, the (220) MgO facets reduce their high surface energy by forming cube facets, which is followed by nanoshell size reduction and collapse within a few minutes. However, in ambient conditions the nanoshells remain stable for significant periods of time and further degrade by becoming filled with carbon while lossing any MgO identity. Finally, in moderate low vacuum they remained stable for months indicating promise for applications.

A computer-controlled procedure is outlined here that first determines the position of the amorphous-crystalline interface in an image. Subsequently, from a time series of these images, the velocity of the crystal growth front is quantified. The procedure presented here can be useful for a wide range of applications, and we apply the new approach to determine growth rates in a so-called fast-growth-type phase-change material. The growth rate (without nucleation) of this material is of interest for comparison with identical material used in phase-change random access memory cells. Crystal growth rates in the amorphous phase-change layers have been measured at various temperatures using in situ heating in a transmission electron microscope. Doped SbTe films (20 nm thick) were deposited on silicon nitride membranes, and samples with and without silicon oxide capping layer were studied. The activation energy for growth was found to be 3.0 eV. The samples without capping layer exhibit a nucleation rate that is an order of magnitude higher than the samples with a silicon oxide capping layer. This difference can be attributed to the partial oxidation of the phase-change layer in air. However, the growth rates of the samples with and without capping are quite comparable.

TbMnO(3) films have been grown under compressive strain on (001)-oriented SrTiO(3) crystals. They have an orthorhombic structure and display the (001) orientation. With increasing thickness, the structure evolves from a more symmetric (tetragonal) to a less symmetric (bulk-like orthorhombic) structure, while keeping constant the in-plane compression, thereby leaving the out-of-plane lattice spacing unchanged. The domain microstructure of the films is also revealed, showing an increasing number of orthorhombic domains as the thickness is decreased: we directly observe ferroelastic domains as narrow as 4 nm. The high density of domain walls may explain the induced ferromagnetism observed in the films, while both the decreased anisotropy and the small size of the domains could account for the absence of a ferroelectric spin spiral phase.

As a tribute to the scientific work of Professor Gareth Thomas in the field of structure-property relationships this paper delineates a new possibility of Lorentz transmission electron microscopy (LTEM) to study the magnetic properties of soft magnetic films. We show that in contrast to the traditional point of view, not only does the direction of the magnetization vector in nano-crystalline films make a correlated small-angle wiggling, but also the magnitude of the magnetization modulus fluctuates. This fluctuation produces a rapid modulation in the LTEM image. A novel analysis of the ripple structure in nano-crystalline Fe-Zr-N film corresponds to an amplitude of the transversal component of the magnetization deltaMy of 23 mT and a longitudinal fluctuation of the magnetization of the order of deltaMx = 30 mT. The nano-crystalline (Fe99Zr1)1-xNx films have been prepared by DC magnetron reactive sputtering with a thickness between 50 and 1000 nm. The grain size decreased monotonically with N content from typically 100 nm in the case of N-free films to less than 10 nm for films containing 8 at%. The specimens were examined with a JEOL 2010F 200 kV transmission electron microscope equipped with a post column energy filter (GIF 2000 Gatan Imaging Filter). For holography, the microscope is mounted with a biprism (JEOL biprism with a 0.6 microm diameter platinum wire).

Three-dimensional atom-probe (3DAP) microscopy has been applied to the study of segregation at ceramic/metal (C/M) interfaces. In this article, results on the MgO/Cu(X) (where X = Ag or Sb) systems are summarized. Nanometer-size MgO precipitates with atomically clean and atomically sharp interfaces were prepared in these systems by internal oxidation. Segregation of the ternary component (Ag or Sb) at the MgO/Cu heterophase interface was enhanced by extended low-temperature anneals. Magnesia precipitates in the 3DAP reconstructions were delineated as isoconcentration surfaces, and segregation of each ternary component at the C/M interfaces was analyzed with the proximity histogram method developed at Northwestern University. This method allows the direct extraction of the Gibbsian interfacial excess of solute at the C/M interfaces from the experimental data. A value of (3.2+/-2.0) x 10(17)m(-2) at 500 degrees C is obtained for the segregation of Ag at a MgO/Cu(Ag) interface, while a value of (2.9+/-0.9) x 10(18) m(-2) at 500 degrees C is obtained for the segregation of Sb at a MgO/Cu(Sb) interface. The larger Gibbsian excess for Sb segregation at this ceramic/metal heterophase interface is most likely due to the so-called pdeltaV effect.

This article aims to make a connection between the microstructures of various nanostructured alloys and giant magnetoresistive (GMR) properties. The GMR behavior of nanoclusters embedded in a nonmagnetic matrix differs considerably from an alloy with the content of a magnetic phase above the percolation threshold; that is to say, an increase of GMR effect upon going from 300 to 10 K for the former and a decrease of the GMR effect for the latter. The following materials systems were examined with high-resolution transmission electron microscopy and magnetoelectrical resistance measurements: magnetic Co and CoFe nanoclusters in a Au matrix, NiFe clusters in a Cu matrix, and NiFe/Cu spinodal decomposition waves with interconnection of the magnetic phase. After annealing (> or = 300 degrees C), Co particles in Au become semi- or incoherent, whereas under other conditions and in all other systems, the interfaces remain coherent. This state of coherency at the interface between magnetic particles and a nonmagnetic matrix turned out to have a detectable influence on the GMR behavior.