Ge – Sb – Te alloys are widely used for data recording based on the rapid and reversible amorphous-to-crystalline phase transformation that is accompanied by increases in the optical reflectivity and the electrical conductivity. However, uncertainties about the optical band gaps and electronic transport properties of these phases have persisted because of inappropriate interpretation of reported data and the lack of definitive analytical studies. In this paper we characterize the most widely used composition, Ge2Sb2Te5, in its amorphous, face-centered-cubic, and hexagonal phases, and explain the origins of inconsistent or unphysical results in previous reports. The optical absorption in all of these phases follows the relationship αhν∝(hν−Egopt)2, which corresponds to the optical transitions in most amorphous semiconductors as proposed by Tauc, Grigorovici, and Vancu [Tauc et al., Phys. Status Solidi 15, 627 (1966)], and to those in indirect-gap crystalline semiconductors. The optical band gaps of the amorphous, face-centered-cubic, and hexagonal phases are 0.7, 0.5, and 0.5eV, respectively. The subgap absorption in the amorphous phase shows an exponential decay with an Urbach slope of 81meV. We measured the photoconductivity of amorphous Ge2Sb2Te5 and determined a mobility-lifetime product of 3×10−9cm2∕V. The spectral photoconductivity shows a threshold at about 0.7eV, in agreement with our analysis of the optical band gap. The face-centered-cubic and hexagonal phases are highly conductive and do not show freeze-out; even at 5K the density of free carriers remains at 1019–1020cm−3, so these are degenerate semiconductors in which the Fermi level resides inside a band. In the hexagonal phase, the effect of free electrons on the Hall coefficient is significant at high temperatures. When the Hall data are fitted using the two-carrier analysis, the hole mobility is found to decrease slowly with temperature, as expected. The considerations discussed in this paper can be readily applied to study related chalcogenide materials.

The thermal conductivity of thin films of the phase-change material Ge2Sb2Te5 is measured in the temperature range of 27°C<T<400°C using time-domain thermoreflectance. From the low thermal conductivity of amorphous phase, the conductivity increases irreversibly with increasing temperature and undergoes large changes with phase transformations. Thermal transport in the amorphous and early cubic phases can be described by a random walk of vibrational energy, i.e., the minimum thermal conductivity. In the hexagonal phase, the electronic contribution to the thermal conductivity is larger than the lattice contribution. Crystallization by laser processing produces a cubic phase with a lower thermal conductivity than cubic phases produced by thermal annealing; the authors attribute this difference in conductivity to a larger degree of atomic-scale disorder in films that are crystallized on short time scales.

Phase transformation generally begins with nucleation, in which a small aggregate of atoms organizes into a different structural symmetry. The thermodynamic driving forces and kinetic rates have been predicted by classical nucleation theory, but observation of nanometer-scale nuclei has not been possible, except on exposed surfaces. We used a statistical technique called fluctuation transmission electron microscopy to detect nuclei embedded in a glassy solid, and we used a laser pump-probe technique to determine the role of these nuclei in crystallization. This study provides a convincing proof of the time- and temperature-dependent development of nuclei, information that will play a critical role in the development of advanced materials for phase-change memories.

Phase change memory devices are based on the rapid and reversible amorphous-to-crystalline transformations of phase change materials, such as Ge2Sb2Te5 and AgInSbTe. Since the maximum switching speed of these devices is typically limited by crystallization speed, understanding the crystallization process is of crucial importance. While Ge2Sb2Te5 and AgInSbTe show very different crystallization mechanisms from their melt-quenched states, the nanostructural origin of this difference has not been clearly demonstrated. Here, we show that an amorphous state includes different sizes and number of nanoscale nuclei, after thermal treatment such as melt-quenching or furnace annealing is performed. We employ fluctuation transmission electron microscopy to detect nanoscale nuclei embedded in amorphous materials, and use a pump-probe laser technique and atomic force microscopy to study the kinetics of nucleation and growth. We confirm that melt-quenched amorphous Ge2Sb2Te5 includes considerably larger and more quenched-in nuclei than its as-deposited state, while melt-quenched AgInSbTe does not, and explain this contrast by the different ratio between quenching time and nucleation time in these materials. In addition to providing insights to the crystallization process in these technologically important devices, this study presents experimental illustrations of temperature-dependence of nucleation rate and growth speed, which was predicted by theory of phase transformation but rarely demonstrated.

The phase change material Ge2Sb2Te5 is widely investigated for use in nonvolatile memories. It has been reported that the crystallization speed depends on the thermal history, indicating that structural differences exist between amorphous states. The authors apply fluctuation electron microscopy to quantify differences in the nanometer-scale structural order between several amorphous states of Ge2Sb2Te5. All as-deposited films are found to contain ordered regions. Thermal annealing below the crystallization threshold increases the nanoscale order, and such samples crystallize slightly more rapidly. The authors hypothesize that the nanoscale ordered regions act as the nuclei for crystallization, with the largest regions being the most significant.

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The nanoscale crystal nuclei in an amorphous Ge2Sb2Te5 bit in a phase change memory device were evaluated by fluctuation transmission electron microscopy. The quench time in the device (∼10 ns) afforded more and larger nuclei in the melt-quenched state than in the as-deposited state. However, nuclei were even more numerous and larger in a test structure with a longer quench time (∼100 ns), verifying the prediction of nucleation theory that slower cooling produces more nuclei. It also demonstrates that the thermal design of devices will strongly influence the population of nuclei, and thus the speed and data retention characteristics.

The structures of many disordered materials are not ideally random, but contain structural order on the scale of 1-3 nm. However, such nanoscale order, called medium-range order, cannot be detected by conventional diffraction methods in most cases. Fluctuation transmission electron microscopy (FTEM) has the capability to detect medium-range order in disordered materials based on statistical analysis of nanodiffraction patterns or dark-field images from TEM. FTEM has been successful in demonstrating the theoretically predicted development of nanoscale nuclei in amorphous chalcogenides, as well as in revealing the subtle effect of different preparation routes on the medium-range order in amorphous semiconductors and metals. The fluctuation principle can also be applied to study structural order on longer length scales in polymers and other disordered materials using X-rays or visible light. Further advances in theory and practice of FTEM will greatly increase our understanding of amorphous structures and nucleation phenomena.