XRD TEM EELS Studies on Memory Device Structures

Over the past decade, numerous emerging memory technologies are being considered as contenders to displace either or both NAND flash and DRAM as scaling limitations of these conventional memories are perceived for applications in mobile devices. Some of these include Magnetic and Spin Transfer Torque Random Access Memory MRAM, STTRAM , Phase Change RAM PCRAM , Ferroelectric RAM and Resistive RAM memories. These technologies can be classified as relying on one of the movements atomic, ionic, electron charge or spin in nanoscale thin films comprising of a variety of materials. The literature shows about 50 elements of the periodic table being investigated for these memory applications owing to their unique physical and chemical properties. Engineering memory devices requires nanoscale characterizations of film stacks for their chemical compositions and crystalline nature in addition to electronic properties such as resistance, magnetization and polarization depending upon the principle involved. This paper focuses on how x ray diffraction XRD , transmission electron microscopy TEM and electron energy loss spectroscopy EELS techniques have been employed to obtain insight into engineering magnetic tunnel junctions MTJ and PCM device

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

Influence of the electrode nano/microstructure on the electrochemical properties of graphite in aluminum batteries

Herein we report on a detailed investigation of the irreversible capacity in the first cycle of pyrolytic graphite electrodes in aluminum batteries employing 1-ethyl-3-methylimidazolium chloride:aluminum trichloride (EMIMCl:AlCl3) as electrolyte. The reaction mechanism, involving the intercalation of AlCl4- in graphite, has been fully characterized by correlating the micro/nanostructural modification to the electrochemical performance. To achieve this aim a combination of X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and computed tomography (CT) has been used. The reported results evidence that the irreversibility is caused by a very large decrease in the porosity, which consequently leads to microstructural changes resulting in the trapping of ions in the graphite. A powerful characterization methodology is established, which can also be applied more generally to carbon-based energy-related materials

Crystallization of Ge2Sb2Te5 films by amplified femtosecond optical pulses

Copyright © 2012 American Institute of PhysicsThe phase transition between the amorphous and crystalline states of Ge2Sb2Te5 has been studied by exposure of thin films to series of 60 femtosecond (fs) amplified laser pulses. The analysis of microscope images of marks of tens of microns in size provide an opportunity to examine the effect of a continuous range of optical fluence. For a fixed number of pulses, the dependence of the area of the crystalline mark upon the fluence is well described by simple algebraic results that provide strong evidence that thermal transport within the sample is one-dimensional (vertical). The crystalline mark area was thus defined by the incident fs laser beam profile rather than by lateral heat diffusion, with a sharp transition between the crystalline and amorphous materials as confirmed from line scans of the microscope images. A simplified, one-dimensional model that accounts for optical absorption, thermal transport and thermally activated crystallization provides values of the optical reflectivity and mark area that are in very good quantitative agreement with the experimental data, further justifying the one-dimensional heat flow assumption. Typically, for fluences below the damage threshold, the crystalline mark has annular shape, with the fluence at the centre of the irradiated mark being sufficient to induce melting. The fluence at the centre of the mark was correlated with the melt depth from the thermal model to correctly predict the observed melt fluence thresholds and to explain the closure and persistence of the annular crystalline marks as functions of laser fluence and pulse number. A solid elliptical mark may be obtained for smaller fluences. The analysis of marks made by amplified fs pulses present a new and effective means of observing the crystallization dynamics of phase-change material at elevated temperatures near the melting point, which provided estimates of the growth velocity in the range 7-9 m/s. Furthermore, finer control over the crystallization process in phase-change media can be obtained by controlling the number of pulses which, along with the laser fluence, can be tailored to any medium stack with relaxed restrictions on the thermal properties of the layers in the stack

Threshold switching via electric field induced crystallization in phase-change memory devices

Copyright © 2012 American Institute of PhysicsPhase-change devices exhibit characteristic threshold switching from the reset (off) to the set (on) state. Mainstream understanding of this electrical switching phenomenon is that it is initiated electronically via the influence of high electric fields on inter-band trap states in the amorphous phase. However, recent work has suggested that field induced (crystal) nucleation could instead be responsible. We compare and contrast these alternative switching “theories” via realistic simulations of device switching both with and without electric field dependent contributions to the system free energy. Results show that although threshold switching can indeed be obtained purely by electric field induced nucleation, the fields required are significantly larger than experimentally measured values

Kinetics of liquid-mediated crystallization of amorphous Ge from multi-frame dynamic transmission electron microscopy

The kinetics of laser-induced, liquid-mediated crystallization of amorphousGe thin films were studied using multi-frame dynamic transmission electron microscopy (DTEM), a nanosecond-scale photo-emission transmission electron microscopy technique. In these experiments, high temperature gradients are established in thin amorphousGe films with a 12-ns laser pulse with a Gaussian spatial profile. The hottest region at the center of the laser spot crystallizes in ∼100 ns and becomes nano-crystalline. Over the next several hundred nanoseconds crystallization continues radially outward from the nano-crystalline region forming elongated grains, some many microns long. The growth rate during the formation of these radial grains is measured with time-resolved imaging experiments. Crystal growth rates exceed 10 m/s, which are consistent with crystallization mediated by a very thin, undercooled transient liquid layer, rather than a purely solid-state transformation mechanism. The kinetics of this growth mode have been studied in detail under steady-state conditions, but here we provide a detailed study of liquid-mediatedgrowth in high temperature gradients. Unexpectedly, the propagation rate of the crystallization front was observed to remain constant during this growth mode even when passing through large local temperature gradients, in stark contrast to other similar studies that suggested the growth rate changed dramatically. The high throughput of multi-frame DTEM provides gives a more complete picture of the role of temperature and temperature gradient on laser crystallization than previous DTEM experiment

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 amp; 8242; 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 island

Influence of the electrode nano microstructure on the electrochemical properties of graphite in aluminum batteries

Herein we report on a detailed investigation of the irreversible capacity in the first cycle of pyrolytic graphite electrodes in aluminum batteries employing 1 ethyl 3 methylimidazolium chloride aluminum trichloride EMIMCl AlCl3 as electrolyte. The reaction mechanism, involving the intercalation of AlCl4 in graphite, 3 has been fully characterized by correlating the micro nano modification to the electrochemical performance. To achieve this aim a combination of X ray diffraction XRD , small angle X ray scattering SAXS and computed tomography CT has been used. The reported results evidence that the irreversibility is caused by a very large decrease in the porosity, which consequently leads to microstructural changes resulting in the trapping of ions in the graphite. A powerful characterization methodology is established, which can also be applied more generally to carbon based energy related material

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 application