High Resolution Imaging of Chalcogenide Superlattices for Data Storage Applications:Progress and Prospects

Phase-change materials (PCMs) based on Ge–Sb–Te alloys are a strong contender for next-generation memory technology. Recently, PCMs in the form of GeTe–Sb 2 Te 3 superlattices (CSLs) have shown superior performance compared to ordinary PCM memory, which relies on switching between amorphous and crystalline phases. Although detailed atomic structure switching models have been developed with the help of ab-initio simulations, there is still fierce scientific debate concerning the experimental verification of the actual crystal structures pertaining to the two CSL memory states. One of the strongest techniques to provide this information is (scanning) transmission electron microscopy ((S)TEM). The present article reviews the analyses of CSLs using TEM-based techniques published during the last seven years since the seminal 2011 Nature Nanotechnology paper of Simpson et al., showing the superior performance of the CSL memory. It is critically reviewed what relevant information can be extracted from the (S)TEM results, also showing the impressive progress that has been achieved in a relatively short time frame. Finally, an outlook is given including several open questions. Although debate on actual switching mechanism in CSL memory is clearly not settled, still there is consensus in this field that CSL research has a bright future

Pulsed laser deposited stoichiometric GaSb films for optoelectronic and phase change memory applications

Phase-change memory (PCM) holds great potential in realizing the combination of DRAM-like speeds with non-volatility and large storage capacity for future electronic devices including in-memory computing. However, various (reliability) issues related to e.g. too high programming current (power consumption), resistance drift, data retention (low crystallization temperature), phase separation and density change upon switching stand in the way to make PCM really attractive. GaSb thin films have interesting optical and electrical properties which are attractive for optoelectronic and PCM applications but so far reported stoichiometric GaSb compositions are Sb-rich which produced reliability issues in PCM devices. In this study, we managed to deposit stoichiometric GaSb thin films using pulsed laser deposition (PLD) by varying deposition parameters and conditions. Using electron microscopy, the morphology of deposited films and target surface and the compositional deviation from exact stoichiometry have been investigated. We show that the directional nature of laser-target interaction is directly responsible for film quality in PLD in which particulates with high number density are generated due to directional pillar formation. Suppressing this pillar formation, by a simple 180° target rotation, showed an increase in deposition yield by 60%, exact stoichiometric transfer from target to substrate, and large reduction in particulate density. Moreover, from XRD analysis, we show that exact stoichiometric transfer from target to substrate is crucial for structural integrity of the produced films. Temperature induced structural transformation from resistivity vs. temperature measurements show a high crystallization temperature of 250 °C for stoichiometric GaSb thin film. We believe the exact stoichiometric GaSb thin films with reduced particulate densities and favorable structural and (opto)electronic properties are attractive for future PCM devices

Resolving hydrogen atoms at metal-metal hydride interfaces

Hydrogen as a fuel can be stored safely with high volumetric density in metals. It can, however, also be detrimental to metals causing embrittlement. Understanding fundamental behavior of hydrogen at atomic scale is key to improve the properties of metal-metal hydride systems. However, currently, there is no robust technique capable of visualizing hydrogen atoms. Here, we demonstrate that hydrogen atoms can be imaged unprecedentedly with integrated differential phase contrast, a recently developed technique performed in a scanning transmission electron microscope. Images of the titanium-titanium monohydride interface reveal remarkable stability of the hydride phase, originating from the interplay between compressive stress and interfacial coherence. We also uncovered, thirty years after three models were proposed, which one describes the position of the hydrogen atoms with respect to the interface. Our work enables novel research on hydrides and is extendable to all materials containing light and heavy elements, including oxides, nitrides, carbides and borides

Real space imaging of hydrogen at a metal - metal hydride interface

Hydrogen as a prospective fuel can be stored safely with high volumetric density in metals. It can, however, also be detrimental to metals causing embrittlement. For a better understanding of these metal-metal hydride systems, and in particular their interfaces, real-space imaging of hydrogen with atomic resolution is required. However, hydrogen has not been imaged before at an interface. Moreover, to date, a robust technique that is capable to do such light-element imaging has not been demonstrated. Here, we show that integrated Differential Phase Contrast (iDPC), a recently developed imaging technique performed in an aberration corrected scanning transmission electron microscope, has this capability. Atomically sharp interfaces between hexagonal close-packed titanium and face-centered tetragonal titanium monohydride have been imaged, unambiguously resolving the hydrogen columns. Exploiting the fact that this monohydride has two types of columns with identical surrounding of the host Ti atom we have, 30 years after they were first proposed, finally resolved which one of the proposed structural models holds for the interface. Using both experimental and simulated images, we compare the iDPC technique with the currently more common annular bright field (ABF) technique, showing that iDPC is superior regarding complicating wave interference effects that may lead to erroneous detection of light element columns

Real space imaging of hydrogen at a metal - metal hydride interface

Hydrogen as a prospective fuel can be stored safely with high volumetric density in metals. It can, however, also be detrimental to metals causing embrittlement. For a better understanding of these metal-metal hydride systems, and in particular their interfaces, real-space imaging of hydrogen with atomic resolution is required. However, hydrogen has not been imaged before at an interface. Moreover, to date, a robust technique that is capable to do such light-element imaging has not been demonstrated. Here, we show that integrated Differential Phase Contrast (iDPC), a recently developed imaging technique performed in an aberration corrected scanning transmission electron microscope, has this capability. Atomically sharp interfaces between hexagonal close-packed titanium and face-centered tetragonal titanium monohydride have been imaged, unambiguously resolving the hydrogen columns. Exploiting the fact that this monohydride has two types of columns with identical surrounding of the host Ti atom we have, 30 years after they were first proposed, finally resolved which one of the proposed structural models holds for the interface. Using both experimental and simulated images, we compare the iDPC technique with the currently more common annular bright field (ABF) technique, showing that iDPC is superior regarding complicating wave interference effects that may lead to erroneous detection of light element columns

Reversible amorphous-crystalline phase changes in a wide range of Se1-xTex alloys studied using ultrafast differential scanning calorimetry

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 T-m as a composition indicator. The glass transition T-g and crystallization temperature T-c could be determined accurately, allowing the construction of extended phase diagrams. It was found that T-m and T-g increase (but T-g/T-m decrease slightly) with increasing Te-concentration. Contrarily, the T-c 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. (C) 2014 AIP Publishing LLC

S-Rich PbS Quantum Dots:A Promising p-Type Material for Optoelectronic Devices

PbS colloidal quantum dots (CQDs) are versatile building blocks for bottom-up fabrication of various optoelectronic devices. The transport properties of thin films of this class of materials depend on the size of the CQDs, their surface ligands, and stoichiometry. The most common synthetic methods yield PbS CQDs with an excess of Pb atoms, which induces n-type transport properties in CQD films. In this work, we developed a new synthesis, which offers S-rich PbS CQDs. Thanks to their sufficient colloidal stability in nonpolar solvents, we established a protocol for the integration of these CQDs into thin field-effect transistors and found strong hole-dominated transport with a hole mobility of about 1 × 10–2 cm2/Vs. Moreover, we were able to enhance the electron mobility for almost two orders of magnitude while keeping the hole mobility nearly the same. This approach allows us to obtain reliably p-doped PbS CQDs, which can be used for the fabrication of various electronic and optoelectronic devices.ISSN:0897-475

Controlling phase separation in thermoelectric Pb1-xGexTe to minimize thermal conductivity

Intensive studies have been carried out over the past decade to identify nanostructured thermoelectric materials that allow the efficient conversion of waste heat to electrical power. However, less attention has been paid to the stability of such materials under operating temperatures, typically 400 degrees C or higher. Conventionally nanostructured ceramics tend to undergo grain growth at high temperature, lowering the density of interfaces and raising the thermal conductivity, which is detrimental to device performance. Therefore it is preferable to identify materials with stable nanostructures, for example systems that undergo spontaneous phase separation. Here we investigate PbTe-GeTe alloys, in which spinodal decomposition occurs on initial cooling from above 580 degrees C, forming complex nanostructures consisting of Ge-rich and Pb-rich domains on different size scales. The resulting dense arrangement of interfaces, combined with mass fluctuation associated with Pb-Ge mixing, enhances phonon scattering and strongly reduces the thermal conductivity. Here we focus on the nominal composition Pb0.49Ge0.51Te and show that by tuning the synthesis procedure, we are able to control the pattern of compositional domains and the density of interfaces between them. This allows low lattice thermal conductivities to be maintained even after thermal cycling over the operating temperature range

Free-standing nanolayers based on Ru silicide formation on Si(100)

Free-standing layers of nanoscale thickness are essential in numerous applications but challenging to fabricate for all but a small selection of materials. We report a versatile, chemical-free pathway of exfoliating centimeter-sized free-standing nanolayers from Si(100) with native oxide based on the spontaneous delamination of thin Ru and Ru-based films upon annealing at temperatures as low as 400 °C. Combining results from X-ray photoelectron spectroscopy (XPS), and transmission and scanning electron microscopy (TEM, SEM), we identify that the element Ru, a thin SiO2 layer, and the Si(100) substrate are essential ingredients for the delamination and propose a stress-based mechanism to explain the effect. The diffusion of Si into the layer upon annealing leads to the formation of a Ru-Si compound at the thin-film side of the Ru/Si(100) interface and pyramidal cavities in the Si(100) substrate. Moreover, the uptake of Si results in an increase in layer thickness and the buildup of in-plane compressive stress, which is reduced by local buckling and finally by the separation of the full layer from the substrate at the SiO2-Si(100) interface. The use of a thin Ru-buffer layer allows us to apply this delamination process to produce free-standing nanolayers of Mo and HfMoNbTiZr in this simple, chemical-free, and vacuum-compatible manner. These results indicate the potential of the reported effect for the fabrication of free-standing layers using a wide range of compositions, deposition techniques, and growth conditions below the onset temperature of delamination