We show that the average parameters of conductive filaments and the related characteristics of threshold switches can be described thermodynamically based on the system free energy. In particular, we derive analytical expressions for the filament radius as a function of applied bias, and its current-voltage characteristics, the observations of which have remained without mathematical description for about 30 years. Our theory is extendible to filament transients and allows for efficient numerical simulations of arbitrary switching structures. This new understanding may be important in the advancement of novel technologies that combine threshold switches with phase change memory, such as 3D architectures.

Ion implantation of Ge2Sb2Te5 (GST) enables localized doping of the film by using conventional lithography. Although the doped region dimensions and the doping concentration profile are defined by the opening in the mask and the ion energy, longitudinal and lateral straggling of implanted ions leads to a spread in the ions final location. Additionally, a thermal treatment such as one that induces a phase transition may lead to redistribution of the implanted dopants and further increase the spread. In this work we demonstrate doping of GST by ion implantation. Using Secondary Ion Mass Spectrometry (SIMS) we studied the as-implanted doping profiles obtain by ion implantation of carbon and silicon into GST. We also investigated by SIMS the dopant redistribution following a recrystallization annealing. The as-implanted ion profiles were found to be in fair agreement with TRIM simulation. The dopants profiles show little change after a crystallization annealing at 200°C for silicon doping and at 350°C for carbon doping.

The origin of sub-diffraction-limit apertures in Sb-based thin films is discussed. Electromagnetic energy can be channeled by these apertures thus allowing near-field focussing- the Super-RENS effect. The aperture formation within Sb, Sb2Te3, Sb2Te, SbTe and Ge2Sb2Te5 is investigated by time resolved optical pump-probe techniques and found to occur without melting. Density functional calculations have shown that these materials exhibit a thresholdlike change in their optical properties below their melting temperatures. The threshold is shown to be a consequence of thermally induced misalignment of p-orbital bonds. It is the non-linearity of this process that leads to the formation of the sub-diffraction-limit apertures.

Phase change materials along the GeTe-Sb2Te3 pseudobinary line (GST) are grown by molecular beam epitaxy (MBE) on Si(111). The growth on (111) oriented substrates leads to greatly increased crystal quality compared to (001) oriented substrates, even for a high lattice mismatch. This holds true even for Si substrates which have a lattice mismatch of around 10% with respect to GST. The growth is controlled in situ via line of sight quadrupole mass spectrometer (QMS). Structural characterization is performed in situ by X-ray diffraction (XRD), which reveals a clear cubic symmetry of the film and a lattice slightly rhombohedrally distorted along the [111] direction.

The physical modeling of carrier conduction and material-related effects such as crystallization, structural relaxation (SR), electromigration and ion migration in chalcogenide materials is a key challenge toward the development and scaling of phase change memory (PCM) devices. In particular, future scaling to 10 nm and below may require addressing variability effects in the programming, switching and retention properties of the cell. Variability is deeply linked with the nanometer-scale fluctuations of potential, atomic structure and material composition that affect conduction, structure relaxation and crystallization. Therefore, the physical modeling of conduction and reliability in PCM devices requires energy landscape models, describing the random fluctuations of e.g. the potential energy dictating the carrier transport and the free energy controlling the atomic rearrangement of the amorphous chalcogenide structure. This work discusses energy landscape models for a physical description of (i) electrical conduction in the amorphous phase and (ii) SR responsible for resistance drift in the amorphous chalcogenide phase. The link between the effective energy barrier in conduction and relaxation will be clarified, and analytical models for the prediction of drift depending on time and temperature will be introduced. These models provide the first comprehensive approach for a physics-based prediction of resistance window, resistance drift and their corresponding statistical variability within large PCM arrays.

We have investigated the stability of nano-amorphous region of Ge2Sb2Te5 (GST), fabricated by Electron Beam Lithography (EBL), dry etching, and ion implantation. Nano-structures, less than 100 nm in diameter and 20 nm thick, were either embedded in a crystalline environment or just isolated. We have observed nano-structure crystallization by in situ Transmission Electron Microscopy (TEM) in the 75°C-150°C temperature range. Re-crystallization of amorphous dots embedded in a crystalline region (either in the cubic or hexagonal phase) occurs by the movement of the interface at relatively low temperature (about 90°C). Instead, in the isolated structures the transition occurs at about 145°C by nucleation and growth. These results might be of relevance for the data retention of sub-50nm devices. Indeed, the more stable amorphous phase in self-standing regions indicates the better retention properties of isolated cells with respect to the traditional mushroom cell configuration.

The electrical properties of chalcogenide thin films, both pristine Ge2Sb2Te5 (GST) and cerium-doped GST (Ce-GST), were investigated by in-situ AC impedance spectroscopy. In conjunction with the brick layer model, the contributions of both the grain and the grain boundary to the phase-transition behaviors of chalcogenide samples could be distinguished; the results illustrated the dominance of the grain boundary in the phase transition process. Moreover, impedance analysis applied to characterize the effects of doping on the phase-transition kinetics yielded results similar to those obtained by conventional methods. Therefore, in-situ AC impedance spectroscopy is a feasible tool for analyzing the phase transitions of chalcogenides.

Ion implantation of germanium and carbon ions into thin films of Ge2Sb2Te5 (GST) and GeTe was applied to modify the properties of these phase change materials. It was found that it is possible to amorphize crystalline GST and GeTe using ion implantation for optimized ion doses and energies which depend on the film thickness, ion species and capping layer. A relatively low minimum dose is required for complete amorphization as judged by the absence of diffraction peaks in x-ray diffraction (XRD) scans. It is 4–5×1013 cm−2 for germanium implantation into GST, and slightly higher (1014 cm−2) for germanium implantation into GeTe. The properties of the re-amorphized films depend on ion species, dose and energy. The re-crystallization temperature of re-amorphized GST by ion implantation is comparable or higher than as-deposited amorphous GST. Carbon implantation in particular leads to a large increase in the crystallization temperature Tx. A carbon dose of 1016 cm−2 implanted into 20 nm amorphous GST yielded a crystallization temperature of 300 ºC, much higher than the crystallization temperature of 160 ºC we recorded for as-deposited, amorphous GST. Similarly, high dose carbon implantation into amorphous GeTe leads to large increase in Tx. We recorded a shift in Tx from 195 ºC for as-deposited GeTe to 400 ºC for C-implanted GeTe. Crystalline GeTe re-amorphized by a low dose germanium ion implantation exhibits a re-crystallization temperature below Tx of as-deposited amorphous GeTe and Tx increased with the implanted Ge dose to a crystallization temperature above that of unimplanted GeTe. Ion implantation can be regarded an additional tool to create phase change materials with different and improved switching properties that cannot be achieved by conventional sputter deposition.

Phase-change materials undergo a change in bonding mechanism upon crystallization, which leads to pronounced modifications of the optical properties and is accompanied by an increase in average bond lengths as seen by extended x-ray absorption fine structure (EXAFS), neutron and x-ray diffraction. The reversible transition between a crystalline and an amorphous phase and its related property contrast are already employed in non-volatile data storage devices, such as rewritable optical discs and electronic memories. The crystalline phase of the prototypical material GeSb2Te4 is characterized by resonant bonding and pronounced disorder, which help to understand their optical and electrical properties, respectively. A change in bonding, however, should also affect the thermal properties, which will be addressed in this study. Based on EXAFS data analyses it will be shown that the thermal and static atomic displacements are larger in the meta-stable crystalline state. This indicates that the bonds become softer in the crystalline phase. At the same time, the bulk modulus increases upon crystallization. These observations are confirmed by the measured densities of phonon states (DPS), which reveal a vibrational softening of the optical modes upon crystallization. This demonstrates that the change of bonding upon crystallization in phase-change materials also has a profound impact on the lattice dynamics and the resulting thermal properties.