Aging is a ubiquitous phenomenon in glasses. In the case of phase-change materials, it leads to a drift in the electrical resistance, which hinders the development of ultrahigh density storage devices. Here we elucidate the aging process in amorphous GeTe, a prototypical phase-change material, by advanced numerical simulations, photothermal deflection spectroscopy and impedance spectroscopy experiments. We show that aging is accompanied by a progressive change of the local chemical order towards the crystalline one. Yet, the glass evolves towards a covalent amorphous network with increasing Peierls distortion, whose structural and electronic properties drift away from those of the resonantly bonded crystal. This behaviour sets phase-change materials apart from conventional glass-forming systems, which display the same local structure and bonding in both phases.

Germanium telluride (GeTe) is one of the most studied phase change materials. Surprisingly, only little is known about the density of states (DOS) in its band gap. In this paper, the DOS of amorphous GeTe films is investigated both experimentally and theoretically. We propose a model for this DOS as well as estimates of some of the transport parameters of this material. Thin films of amorphous GeTe have been deposited by sputtering. Their dark and photoconductivity have been measured as a function of temperature. By means of the modulated photocurrent technique their DOS was probed, while their absorption was investigated by photothermal deflection spectroscopy at room temperature. Numerical calculations were employed to reproduce the experimental results with a proper set of transport parameters and choice of DOS. These data constitute a good basis for further study on the influence of the DOS on the aging of the sample resistance (“resistance drift”).

Structural and calorimetric investigation of Ge(x)Te(100-x) films over wide range of concentration 10 < x < 50 led to evidence two structural singularities at x ∼ 22 at. % and x ∼ 33-35 at. %. Analysis of bond distribution, bond variability, and glass thermal stability led to conclude to the origin of the first singularity being the flexible/rigid transition proposed in the framework of rigidity model and the origin of the second one being the disappearance of the undercooled region resulting in amorphous materials with statistical distributions of bonds. While the first singularity signs the onset of the Ge-Ge homopolar bonds, the second is related to compositions where enhanced Ge-Ge correlations at intermediate lengthscales (7.7 Å) are observed. These two threshold compositions correspond to recently reported resistance drift threshold compositions, an important support for models pointing the breaking of homopolar Ge-Ge bonds as the main phenomenon behind the ageing of phase change materials.

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Understanding the physical origin of threshold switching and resistance drift phenomena is necessary for making a breakthrough in the performance of low-cost nanoscale technologies related to nonvolatile phase-change memories. Even though both phenomena of threshold switching and resistance drift are often attributed to localized states in the band gap, the distribution of defect states in amorphous phase-change materials (PCMs) has not received so far, the level of attention that it merits. This work presents an experimental study of defects in amorphous PCMs using modulated photocurrent experiments and photothermal deflection spectroscopy. This study of electrically switching alloys involving germanium (Ge), antimony (Sb) and tellurium (Te) such as amorphous germanium telluride (a-GeTe), a-Ge 15 Te 85 and a-Ge 2 Sb 2 Te 5 demonstrates that those compositions showing a high electrical threshold field also show a high defect density. This result supports a mechanism of recombination and field-induced generation driving threshold switching in amorphous chalcogenides. Furthermore, this work provides strong experimental evidence for complex trap kinetics during resistance drift. This work reports annihilation of deep states and an increase in shallow defect density accompanied by band gap widening in aged a-GeTe thin films.

Amorphous semiconductors and chalcogenide glasses exhibit a high density of localized states in their bandgap as a consequence of structural defects or due to a lack of long range order. These defect states have a strong influence on the electronic transport properties. Thus, many theories attribute the “resistance drift” or the “threshold switching” effects, both observed in amorphous phase change alloys, to defects within the bandgap. The energetic distribution of states within the bandgap can be probed via modulated photocurrent (MPC) experiments that enable a spectroscopy of the relative density of these defect states by varying the modulation frequency at various temperatures T. It is also a common feature that the bandgap decreases with temperature. Nevertheless, the consequences of a shrinking bandgap with increasing temperature have been neglected in the classical analysis of MPC experiments. In this paper, we propose to add correction terms to the classical MPC energy scaling to take the temperature dependence of the bandgap of the studied material into account to improve the accuracy of the determination of the defect distribution. We illustrate the efficacy of our proposed corrections by applying it to the study of disordered materials such as hydrogenated amorphous silicon a-Si:H, a-GeTe and a-Ge2Sb2Te5.

International audienceIn phase-change materials, the amorphous state resistivity increases with time following a power law q/(t/t0)aRD. This drift in resistivity seriously hampers the potential of multilevel-storage to achieve an increased capacity in phase-change memories. This paper presents the stoichiometric dependence of drift phenomena in amorphous GeSnTe systems (a-GeSnTe) and other known phase-change alloys with the objective to identify low drift materials. The substitution of Ge by Sn results in a systematic decrease of the drift parameter from a-GeTe (alphaRD=0.129) to a-Ge2Sn2Te4 (alphaRD=0.053). Furthermore, with increasing Sn content a decrease in crystallization temperature, trap state density, optical band gap, and activation energy for electronic conduction is observed. In a-GeSnTe, a-GeSbTe, and a-AgInSbTe alloys as well, the drift parameter alphaRD correlates to the activation energy for electronic conduction. This study indicates that low drift materials are characterized by low activation energies of electronic conduction. The correlation found between drift and activation energy of electronic conduction manifests a useful criterion for material optimization

Amorphous chalcogenides usually exhibit a resistivity, which increases with age following a power law ρ ∼ tα. Existing theories link this change in amorphous state resistivity to structural relaxation. Here, the impact of fundamental glass properties on resistance drift phenomena in amorphous GexTe1−x networks is studied. Employing Raman spectroscopy, the Maxwell rigidity transition from flexible to stressed rigid is determined to occur in the compositional range 0.250 &lt; xc &lt; 0.265. Stressed rigid glasses (x &gt; 0.265) exhibit rather strong resistance drift, where the drift parameters increase steadily from α = 0.13 for amorphous GeTe to α = 0.29 for compositions near the stiffness threshold xc. On the other hand, the drift parameter in flexible glasses (x &lt; 0.25) decreases with decreasing Ge content x to values as low as α = 0.05. These findings illustrate the strong impact of the stiffness threshold on resistance drift phenomena in chalcogenides.