Direct Visualization of Localized Vibrations at Complex Grain Boundaries.

Grain boundaries (GBs) are a prolific microstructural feature that dominates the functionality of a wide class of materials. The functionality at a GB results from the unique atomic arrangements, different from those in the grain, that have driven extensive experimental and theoretical studies correlating atomic-scale GB structures to macroscopic electronic, infrared optical, and thermal properties. In this work, a SrTiO3 GB is examined using atomic-resolution aberration-corrected scanning transmission electron microscopy and ultrahigh-energy-resolution monochromated electron energy-loss spectroscopy, in conjunction with density functional theory. This combination enables the correlation of the GB structure, nonstoichiometry, and chemical bonding with a redistribution of vibrational states within the GB dislocation cores. The new experimental access to localized GB vibrations provides a direct route to quantifying the impact of individual boundaries on macroscopic properties.

Observation of solid-state bidirectional thermal conductivity switching in antiferroelectric lead zirconate (PbZrO3).

Materials with tunable thermal properties enable on-demand control of temperature and heat flow, which is an integral component in the development of solid-state refrigeration, energy scavenging, and thermal circuits. Although gap-based and liquid-based thermal switches that work on the basis of mechanical movements have been an effective approach to control the flow of heat in the devices, their complex mechanisms impose considerable costs in latency, expense, and power consumption. As a consequence, materials that have multiple solid-state phases with distinct thermal properties are appealing for thermal management due to their simplicity, fast switching, and compactness. Thus, an ideal thermal switch should operate near or above room temperature, have a simple trigger mechanism, and offer a quick and large on/off switching ratio. In this study, we experimentally demonstrate that manipulating phonon scattering rates can switch the thermal conductivity of antiferroelectric PbZrO3 bidirectionally by -10% and +25% upon applying electrical and thermal excitation, respectively. Our approach takes advantage of two separate phase transformations in PbZrO3 that alter the phonon scattering rate in different manners. In this study, we demonstrate that PbZrO3 can serve as a fast (<1 second), repeatable, simple trigger, and reliable thermal switch with a net switching ratio of nearly 38% from ~1.20 to ~1.65 W m-1 K-1.

Observation of grain boundary plasmon and associated deconvolution techniques for low-loss electron energy-loss (EEL) spectra acquired from grain boundaries.

Spatially resolved valence electron energy-loss spectroscopy (VEELS) was used to acquire low-loss EEL spectra from Al grain boundaries (GBs) with different GB energies. The loss signal from the GB is highly delocalized and is mixed with the bulk loss, therefore requiring separation. Three different separation techniques, i.e., Fourier-log, Fourier-ratio deconvolution and direct subtraction, were employed to extract the GB response from the low-loss spectra and produced similar results. The GB response consists of a positive intensity peak from the excitation of GB plasmons (GBP) and a negative intensity begrenzungs (Bgs) peak from reduced scattering from bulk oscillations. Also, lower electron density at the GB reduces the inelastic scattering of the bulk plasmon. The intensity of GBP scattering and begrenzungs peak is found to increase toward the GBs, with maximum intensity when the electron probe is positioned on the GB, connecting the begrenzungs effect with the creation of a GBP.

Emergent interface vibrational structure of oxide superlattices.

As the length scales of materials decrease, the heterogeneities associated with interfaces become almost as important as the surrounding materials. This has led to extensive studies of emergent electronic and magnetic interface properties in superlattices1-9. However, the interfacial vibrations that affect the phonon-mediated properties, such as thermal conductivity10,11, are measured using macroscopic techniques that lack spatial resolution. Although it is accepted that intrinsic phonons change near boundaries12,13, the physical mechanisms and length scales through which interfacial effects influence materials remain unclear. Here we demonstrate the localized vibrational response of interfaces in strontium titanate-calcium titanate superlattices by combining advanced scanning transmission electron microscopy imaging and spectroscopy, density functional theory calculations and ultrafast optical spectroscopy. Structurally diffuse interfaces that bridge the bounding materials are observed and this local structure creates phonon modes that determine the global response of the superlattice once the spacing of the interfaces approaches the phonon spatial extent. Our results provide direct visualization of the progression of the local atomic structure and interface vibrations as they come to determine the vibrational response of an entire superlattice. Direct observation of such local atomic and vibrational phenomena demonstrates that their spatial extent needs to be quantified to understand macroscopic behaviour. Tailoring interfaces, and knowing their local vibrational response, provides a means of pursuing designer solids with emergent infrared and thermal responses.

High In-Plane Thermal Conductivity of Aluminum Nitride Thin Films.

High thermal conductivity materials show promise for thermal mitigation and heat removal in devices. However, shrinking the length scales of these materials often leads to significant reductions in thermal conductivities, thus invalidating their applicability to functional devices. In this work, we report on high in-plane thermal conductivities of 3.05, 3.75, and 6 µm thick aluminum nitride (AlN) films measured via steady-state thermoreflectance. At room temperature, the AlN films possess an in-plane thermal conductivity of ∼260 ± 40 W m-1 K-1, one of the highest reported to date for any thin film material of equivalent thickness. At low temperatures, the in-plane thermal conductivities of the AlN films surpass even those of diamond thin films. Phonon-phonon scattering drives the in-plane thermal transport of these AlN thin films, leading to an increase in thermal conductivity as temperature decreases. This is opposite of what is observed in traditional high thermal conductivity thin films, where boundaries and defects that arise from film growth cause a thermal conductivity reduction with decreasing temperature. This study provides insight into the interplay among boundary, defect, and phonon-phonon scattering that drives the high in-plane thermal conductivity of the AlN thin films and demonstrates that these AlN films are promising materials for heat spreaders in electronic devices.

Interface controlled thermal resistances of ultra-thin chalcogenide-based phase change memory devices.

Phase change memory (PCM) is a rapidly growing technology that not only offers advancements in storage-class memories but also enables in-memory data processing to overcome the von Neumann bottleneck. In PCMs, data storage is driven by thermal excitation. However, there is limited research regarding PCM thermal properties at length scales close to the memory cell dimensions. Our work presents a new paradigm to manage thermal transport in memory cells by manipulating the interfacial thermal resistance between the phase change unit and the electrodes without incorporating additional insulating layers. Experimental measurements show a substantial change in interfacial thermal resistance as GST transitions from cubic to hexagonal crystal structure, resulting in a factor of 4 reduction in the effective thermal conductivity. Simulations reveal that interfacial resistance between PCM and its adjacent layer can reduce the reset current for 20 and 120 nm diameter devices by up to ~ 40% and ~ 50%, respectively. These thermal insights present a new opportunity to reduce power and operating currents in PCMs.

Photoconductive mechanism of IR-sensitive iodized PbSe thin films via strong hole-phonon interaction and minority carrier diffusion.

Photoconductive PbSe thin films are highly important for mid-infrared imaging applications. However, the photoconductive mechanism is not well understood so far. Here we provide additional insight on the photoconductivity mechanism using transmission electron microscopy, x-ray photoelectron microscopy, and electrical characterizations. Polycrystalline PbSe thin films were deposited by a chemical bath deposition method. Potassium iodide (KI) was added during the deposition process to improve the photoresponse. Oxidation and iodization were performed to sensitize the thin films. The temperature-dependence Hall effect results show that a strong hole-phonon interaction occurs in oxidized PbSe with KI. It indicates that about half the holes are trapped by KI-induced self-trapped hole centers (Vk center), which results in increasing dark resistance. The photo Hall effect results show that the hole concentration increases significantly under light exposure in sensitized PbSe, which indicates the photogenerated electrons are compensated by trapped holes. The presence of KI in the PbSe grains was confirmed by I 3d5/2 core-level x-ray photoelectron spectra. The energy dispersive x-ray spectra obtained in the scanning transmission electron microscope show the incorporation of iodine during the iodization process on the top of PbSe grains, which can create an iodine-incorporated PbSe outer shell. The iodine-incorporated PbSe releases electrons to recombine with holes in the PbSe layer so that the resistance of sensitized PbSe is about 800 times higher than that of PbSe without the iodine-incorporated layer. In addition, oxygen found in the outer shell of PbSe can act as an electron trap. Therefore, the photoresponse of sensitized PbSe is from the difference between the high dark resistance (by KI addition and iodine incorporation) and the low resistance after IR exposure due to electron compensation (by electron traps at grain boundary and electron-hole recombination in KI hole traps).

Determining the Volume Expansion at Grain Boundaries Using Extended Energy-Loss Fine Structure Analysis.

Grain boundaries (GBs) play an important role in material behavior, so considerable effort has gone into determining their structure and properties. Studies of GBs have revealed a correlation between the GB energy and expansion of the planes normal to the GB, or the so-called normal volume expansion. In this investigation, the volume expansion at several GBs was experimentally determined using extended energy-loss fine structure (EXELFS) analysis in a scanning/transmission electron microscope, allowing changes in the nearest-neighbor (n.n.) distances to be determined with nanometer spatial resolution. EXELFS performed on three-model GBs showed that the average n.n. distances at the GBs increased with increasing GB energy. Additionally, the total volume expansion at the GBs, calculated using complementary plasmon energy profiles, showed excellent agreement with volume expansions measured using other experimental techniques. Hence, this study demonstrates that EXELFS is a useful technique to measure the normal volume expansion at GBs. When combined with the results from complementary studies on the same GBs using valence electron energy-loss spectroscopy, this work further shows that the GB energy increases in relation to both the decrease in electron density at the GB and an accompanying increase in specific volume expansion at the GB.

Examination of the electronic structure of crystalline and liquid Al versus temperature by in situ electron energy-loss spectroscopy (EELS).

Electron energy-loss near-edge structure (ELNES) analysis using in situ heating in a transmission electron microscope (TEM) was performed to compare the electronic structure of crystalline and liquid Al versus temperature. It was found that the ELNES features in the L2,3 edges of crystalline and liquid Al are qualitatively similar, but that the edge threshold is modified and certain features in the energy range between 102 and 115eV vanish in the liquid, indicating that partial DOS is quantitatively different. Broadening of the L2,3 edge maximum for Al with temperature indicates a decay in the centrifugal barrier for the 2p electrons with increasing temperature. Comparison between the ELNES edge in supercooled liquid and crystalline Al at the same temperature of 600°C shows that the degree of order, i.e., crystallinity, plays an important role in determining the DOS. The ELNES edge of supercooled liquid Al closely resembles that of superheated liquid Al.

The influence of spatial and temporal averaging on interpretation of HRTEM images of solid-liquid interfaces.

The effects of spatial and temporal averaging on high-resolution transmission electron microscope (HRTEM) images and associated intensity profiles of a solid-liquid Al interface were investigated using atomic coordinates obtained from molecular dynamics simulations. It was found that intensity profiles obtained by spatial averaging across the solid-liquid interface capture the variation in structural features nearly as well as time-averaged intensity profiles. This suggests that adequate spatial averaging of a single HRTEM image can be used to study the contrast from interfaces, and thereby, the structural details, without the need for more time-consuming, computer-intensive time averaged analyses. The limitations of this method are also discussed.

Are electron tweezers possible?

Positively answering the question in the title, we demonstrate in this work single electron beam trapping and steering of 20-300nm solid Al nanoparticles generated inside opaque submicron-sized molten Al-Si eutectic alloy spheres. Imaging of solid nanoparticles and liquid alloy in real time was performed using energy filtering in an analytical transmission electron microscope (TEM). Energy-filtering TEM combined with valence electron energy-loss spectroscopy enabled us to investigate in situ nanoscale transformations of the internal structure, temperature dependence of plasmon losses, and local electronic and optical properties under melting and crystallization of individual binary alloy particles. For particles below 20nm in size, enhanced vibrations of the dynamic solid-liquid interface due to instabilities near the critical threshold were observed just before melting. The obtained results indicate that focused electron beams can act as a tool for manipulation of metal nanoparticles by transferring linear and angular mechanical momenta. Such thermally assisted electron tweezers can be utilized for touchless manipulation and processing of individual nano-objects and potentially for fabrication of assembled nanodevices with atomic level sensitivity and lateral resolution provided by modern electron optical systems. This is by three orders of magnitude better than for light microscopy utilized in conventional optical tweezers. New research directions and potential applications of trapping and tracking of nano-objects by focused electron beams are outlined.

Laser synthesis of bimetallic nanoalloys in the vapor and liquid phases and the magnetic properties of PdM and PtM nanoparticles (M = Fe, Co and Ni).

In this work, we present several examples of the synthesis and characterization of bimetallic nanoparticle alloys using the Laser Vaporization Controlled Condensation (LVCC) method. In the first example, the vapor phase synthesis of Au-Ag, Au-Pd, and Au-Pt nanoparticle alloys are presented. The formation of nanoalloys is concluded from the observation of one plasmon absorption band at a wavelength that varies linearly with the gold mole fraction in the nanoalloy. Both XRD data and HRTEM-EDX data confirm the formation of nanoparticle alloys and not simply mixtures of the two metal nanoparticles. Irradiation of a mixture of Au/Ag nanoparticles dispersed in water with the 532 nm unfocused laser results in efficient alloying while the 1064 nm laser radiation results only in evaporation and size reduction of the unalloyed nanoparticles. Selective absorption of the femtosecond 780 nm radiation by large Au aggregates results in the formation of smaller aggregates with fractal structures, and no evidence for the Au-Ag alloy formation. The synthesis of palladium and platinum nanoparticles alloyed with transition metals such as iron and nickel using the LVCC method is also presented. The alloyed nanoparticles (FePd, FePt, NiPd, NiPt, and FeNi) are found to be superparamagnetic.

In situ determination of the nanoscale chemistry and behavior of solid-liquid systems.

Many fundamental questions in crystal-growth behavior remain unanswered because of the difficulties encountered in simultaneously observing phases and determining elemental concentrations and redistributions while crystals nucleate and grow at the nanoscale. We show that these obstacles can be overcome by performing energy-dispersive x-ray spectroscopy on partially molten Al-Si-Cu-Mg alloy particles during in situ heating in a transmission electron microscope. Using this technique, we were able to (i) determine that the aluminum and silicon concentrations change in a complementary and symmetric manner about the solid-liquid interface as a function of temperature; (ii) directly measure the solid- and liquid-phase compositions at equilibrium and in highly undercooled conditions for quantitative comparison with thermodynamic calculations of the liquidus and solidus phase boundaries; and (iii) provide direct evidence for homogeneous nucleation of the aluminum-rich solid.

A shield for reducing the thermal signal from heating holders during in situ energy-dispersive X-ray spectroscopy analysis.

This article describes a simple shield that can be placed on typical commercial heating holders to reduce the thermal signal during heating to reasonable levels for in situ energy-dispersive X-ray spectroscopy analysis. The improved temperature capability provided by the shield is demonstrated by initial compositional analysis results obtained across a solid-liquid interface on Al-Si-Cu-Mg alloy powder particles. Considerations in the design of and improvement for the shield are discussed.

High-resolution and analytical TEM investigation of metastable-tetragonal phase stabilization in undoped nanocrystalline zirconia.

Submicron and nano-sized nanocrystalline pure zirconia (ZrO2) powders having metastable tetragonal and tetragonal-plus-monoclinic crystal structures, respectively, were synthesized using the sol-gel technique. The as-precipitated and the calcinated ZrO2 powders were analyzed for their morphology, nanocrystallite size and structures, aggregation tendency, local electronic properties, and elemental compositions by conventional and high-resolution transmission electron microscopy and field-emission analytical electron microscopy, including energy-dispersive X-ray and electron energy-loss spectroscopies. The results from this study indicate that a combination of nanocrystallite size, strain-induced grain-growth confinement, and the simultaneous presence of the monoclinic phase can lead to stabilization of the metastable tetragonal-phase in undoped ZrO2. As a result, the tetragonal phase is stabilized within ZrO2 nanocrystallites up to 100 nm in size, which is 16 times larger than the previously reported critical size of 6 nm.

Application of valence electron energy-loss spectroscopy and plasmon energy mapping for determining material properties at the nanoscale.

Measuring material properties at the nanoscale is critical to understanding the behavior of nanostructured materials. In this paper, we demonstrate a novel technique that allows direct determination and imaging of physical properties of individual nanoprecipitates and nanoparticles using energyfiltering transmission electron microscopy combined with valence electron energy-loss spectroscopy (VEELS). We show that strong scaling correlations exist between the plasmon energy and elastic properties, hardness, valence electron density and cohesive energy. We apply these scaling relationships to characterize the elastic properties of metastable nanoprecipitates in a Ti-based structural alloy and the hardness of diesel-engine soot particles. We also discuss additional factors that need to be considered when using plasmons as a quantitative tool for nanoscale property measurement. The results show that VEELS has the potential to determine multiple solid-state properties of materials at the nanoscale, establishing a new capability for analytical electron microscopy.

Effects of heat and electron irradiation on the melting behavior of Al-Si alloy particles and motion of the Al nanosphere within.

In situ heating and electron-beam irradiation in the transmission electron microscope were performed to study melting of Al-11.6 at.% Si alloy submicron particles supported on an amorphous-C thin film. It was found that electron irradiation could be used to melt the particles, even when the hot-stage specimen holder was kept at a much lower temperature than the bulk melting point (i.e. the eutectic temperature) of the particles. The critical current densities required to achieve partial melting increased linearly with the incident electron-beam energy for a given temperature. Comparison between this behavior and analytical calculations indicates that melting under electron-beam irradiation is caused by a temperature rise due to electron thermal spikes in the particles and poor thermal conduction away from the particles. The motion of the crystalline Al nanosphere inside the partially molten particles was also investigated, using the electron beam to both stimulate and observe the motion of the nanosphere. The irregular motion observed was quantified as antipersistent fractional Brownian motion. Analysis of possible phenomena contributing to the motion demonstrates that the incident electrons provide the fractional force that moves the Al nanosphere, and that gravity and the oxide shell on the partially molten particle cause the antipersistent behavior. Another interesting phenomenon observed in this study was that the crystalline Al nanosphere inside the partially molten Al-Si alloy particle followed a focused electron beam as it was moved about on the partially molten particle. This observation suggests that it may be possible to manipulate metallic nanospheres inside opaque liquids using an electron beam.

Use of plasmon spectroscopy to evaluate the mechanical properties of materials at the nanoscale.

Relationships between volume plasmon excitations and mechanical properties of various materials are considered. Based on systematic evaluation of available data, correlations between the volume plasmon energy, Ep, Young's modulus, Ym, bulk modulus, Bm, shear modulus, Gm, and microhardness, Hm, are established. The resulting correlations indicate that plasmon energies potentially can be used to predict and/or determine the local mechanical properties of technologically important materials, such as metal alloys, semiconductors, and ceramics at the nanometer level.