Impact of vacancy ordering on thermal transport in crystalline phase-change materials.

Controlling thermal transport in solids is of paramount importance for many applications. Often thermal management is crucial for a device's performance, as it affects both reliability and power consumption. A number of intricate concepts have been developed to address this challenge, such as diamond-like coatings to enhance the thermal conductivity or low symmetry complex super-structures to reduce it. Here, a different approach is pursued, where we explore the potential of solids with a high yet controllable degree of disorder. Recently, it has been demonstrated that an unconventionally high degree of structural disorder characterizes a number of crystalline phase-change materials (PCMs). This disorder strongly impacts electronic transport and even leads to disorder induced localization (Anderson localization). This raises the question how thermal transport is affected by such conditions. Here thermal transport in highly disordered crystalline Ge-Sb-Te (GST) based PCMs is investigated. Glass-like thermal properties are observed for several crystalline PCMs, which are attributed to strong scattering by disordered point defects. A systematic study of different compounds along the pseudo-binary line between GeTe and Sb2Te3 reveals that disordered vacancies act as point defects responsible for pronounced phonon scattering. Annealing causes a gradual ordering of the vacancies and leads to a more 'crystal-like' thermal conductivity. While both vibrational and electronic degrees of freedom are affected by disorder, the consequences differ for different stoichiometries. This opens up a pathway to tune electrical and thermal transport by controlling the degree of disorder. Materials with tailored transport properties may not only help to improve power efficiency and scaling in upcoming phase-change memories but are also of fundamental interest in the field of thermoelectric materials.

The power of torque magnetometry: defect induced switching in hexaferrite nano-structures.

The presence of magnetic heterogeneities in ferromagnetic systems can reduce their performances in applications such as data storage media and permanent magnets. The detection and the full characterization of these heterogeneities is difficult especially when they are present in a very low concentration within ferromagnetic systems. Here, torque magnetometry is applied to investigate the magnetism of heterogeneities in two-dimensional hexaferrite structures. The study was conducted on a two-dimensional BaFe12O19 structure with decoupled nano-platelets grown on oxidized silicon buffered with ZnO. Measured torque curves reveal anomalous effects manifested by the presence of reversible and hysteretic kinks at large and low magnetic fields respectively. These kinks represent the contribution of magnetic heterogeneities to the global anisotropy of the film in addition to the two-fold symmetry of the major perpendicular anisotropy component. The heterogeneities consist of two types of nano-metric crystallites with the same magnitude of anisotropy as the major magnetic phase, but tilted about -74° and 74° from the normal to the film plane. These results are supported by various types of material characterization (SEM, XPS, XRD, MFM and VSM) and are well reproduced with a simple theoretical model that replicates the symmetry, switching and the easy axes alignment of the heterogeneities magnetization.

Role of vacancies in metal-insulator transitions of crystalline phase-change materials.

The study of metal-insulator transitions (MITs) in crystalline solids is a subject of paramount importance, both from the fundamental point of view and for its relevance to the transport properties of materials. Recently, a MIT governed by disorder was observed in crystalline phase-change materials. Here we report on calculations employing density functional theory, which identify the microscopic mechanism that localizes the wavefunctions and is driving this transition. We show that, in the insulating phase, the electronic states responsible for charge transport are localized inside regions having large vacancy concentrations. The transition to the metallic state is driven by the dissolution of these vacancy clusters and the formation of ordered vacancy layers. These results provide important insights on controlling the wavefunction localization, which should help to develop conceptually new devices based on multiple resistance states.

Disorder-induced localization in crystalline phase-change materials.

Localization of charge carriers in crystalline solids has been the subject of numerous investigations over more than half a century. Materials that show a metal-insulator transition without a structural change are therefore of interest. Mechanisms leading to metal-insulator transition include electron correlation (Mott transition) or disorder (Anderson localization), but a clear distinction is difficult. Here we report on a metal-insulator transition on increasing annealing temperature for a group of crystalline phase-change materials, where the metal-insulator transition is due to strong disorder usually associated only with amorphous solids. With pronounced disorder but weak electron correlation, these phase-change materials form an unparalleled quantum state of matter. Their universal electronic behaviour seems to be at the origin of the remarkable reproducibility of the resistance switching that is crucial to their applications in non-volatile-memory devices. Controlling the degree of disorder in crystalline phase-change materials might enable multilevel resistance states in upcoming storage devices.

Adaptive modulations of martensites.

Modulated phases occur in numerous functional materials like giant ferroelectrics and magnetic shape-memory alloys. To understand the origin of these phases, we employ and generalize the concept of adaptive martensite. As a starting point, we investigate the coexistence of austenite, adaptive 14M phase, and tetragonal martensite in Ni-Mn-Ga magnetic shape-memory alloy epitaxial films. We show that the modulated martensite can be constructed from nanotwinned variants of the tetragonal martensite phase. By combining the concept of adaptive martensite with branching of twin variants, we can explain key features of modulated phases from a microscopic view. This includes metastability, the sequence of 6M-10M-14M-NM intermartensitic transitions, and the magnetocrystalline anisotropy.

Magnetostriction and magnetic heterogeneities in iron-gallium.

Iron-gallium alloys Fe(1-x)Ga(x) exhibit an exceptional increase in magnetostriction with gallium content. We present small-angle neutron scattering investigations on a Fe(0.81)Ga(0.19) single crystal. We uncover heterogeneities with an average spacing of 15 nm and with magnetizations distinct from the matrix. The moments in and around the heterogeneities are observed to reorient with an applied magnetic field or mechanical strain. We discuss the possible roles played by nanoscale magnetic heterogeneities in the mechanism for magnetostriction in this material.

Effect of crystallographic compatibility and grain size on the functional fatigue of sputtered TiNiCuCo thin films.

The positive influence of crystallographic compatibility on the thermal transformation stability has been already investigated extensively in the literature. However, its influence on the stability of the shape memory effect or superelasticity used in actual applications is still unresolved. In this investigation sputtered films of a highly compatible TiNiCuCo composition with a transformation matrix middle eigenvalue of 1±0.01 are exposed to thermal as well as to superelastic cycling. In agreement with previous results the thermal transformation of this alloy is with a temperature shift of less than 0.1 K for 40 cycles very stable; on the other hand, superelastic degradation behaviour was found to depend strongly on heat treatment parameters. To reveal the transformation dissimilarities between the differently heat-treated samples, the microstructure has been analysed by transmission electron microscopy, in situ stress polarization microscopy and synchrotron analysis. It is found that good crystallographic stability is not a sufficient criterion to avoid defect generation which guarantees high superelastic stability. For the investigated alloy, a small grain size was identified as the determining factor which increases the yield strength of the composition and decreases the functional degradation during superelastic cycling.This article is part of the themed issue 'Taking the temperature of phase transitions in cool materials'.