The influence of stress on the phase change behaviour of Ge2Sb2Te5 encapsulated by ZnS-SiO2 and TiN is investigated using temperature dependent Extended X-ray Asbsorption Fines Structure and Ellipsometry to determine the crystallisation temperature. The encapsulation material surrounding the Ge2Sb2Te5 has an increasingly dominant effect on the material's ability to change phase and can cause a profound increase in its crystallization temperature. We have experimentally shown that the increased crystallization temperature originates from compressive stress exerted from the encapsulation material. By minimizing the stress we have maintained the bulk crystallization temperature in Ge2Sb2Te5 films just 2 nm thick.

Germanium ion implantation at an energy of 30 keV was used as a different method to re-amorphize thin films of crystalline phase change material Ge2Sb2Te5 (GST). It was found that rather low doses of 5×1013 cm-2 were sufficient to re-amorphize GST. Amorphization was determined by X-ray diffraction (XRD) as well as reflectivity measurements. Re-crystallization characteristics of ion-implantation-amorphized samples was studied using time-resolved XRD. It showed that samples re-crystallize at an increased crystallization temperature with increasing dose compared to as-deposited material. A static laser tester was applied to measure the crystallization times of material that was (1) as–deposited amorphous; (2) crystallized by annealing and re-amorphized by melt-quenching using a laser pulse; and (3) crystallized by annealing and re-amorphized by ion implantation. It was found that as-deposited amorphous and high-dose ion implanted samples had longer crystallization times while melt-quenched amorphous and low-dose ion implanted samples had shorter crystallization times.

Phase-change kinetics, structure evolution and feasibility to phase-change memory (PCM) of Ag2In7Sb64Te27 (AIST) and its nanocomposite comprised of 85 wt.% AIST and 15 wt.% SiO2 were presented. In-situ heating x-ray diffraction (XRD) indicated nanocomposite transforms from amorphous to HCP structure during heating and incorporation of SiO2 increases the recrystallization temperature (Tx) of samples (189°C for AIST and 223°C for nanocomposite). XRD and transmission electron microscopy (TEM) analyses both revealed the grain refinement in nanocomposite. Kissinger's analysis found the increase of activation energy (Ea) of phase transition in nanocomposite, denoting the SiO2 embedment restrains the grain growth of AIST during recrystallization. Johnson-Mehl-Avrami (JMA) theory revealed the decrease of Avrami exponent (n), indicating that the phase transition is prone to be heterogeneous since the dispersed SiO2 particles may provide additional nucleation sites.

Static I–V measurement indicated that the switching threshold voltage (Vth) of nanocomposite device (1.65 V) is higher than that of the AIST device (1.10 V). Increase of dynamic resistance in nanocomposite device leads to the reduction of writing current. I–V analysis also confirmed the retardation of recrystallization in AIST due to the incorporation of SiO2 and the rise of Ea is able to enhance the thermal stability of amorphous state in PCM devices.

Ge-Sb-Te (GST) thin films were deposited by chemical vapor deposition (CVD) and hot-wire chemical vapor deposition (HW CVD). Several precursor sets (tetraethylgermanium - trimethylantimony - dimethyltellurium (TEGe-TMSb-DMTe), tetraisopropylgermanium - triisopropylantimony - di-tertiarybutyltellurium (TiPGe-TiPSb-DtBTe) and tetraallylgermanium - triisopropylantimony - diisopropyltellurium (TAGe-TiPSb-DiPTe)) were tested for CVD. For the TEGe-TMSb-DMTe precursor set tellurium and germanium could be detected in the films for all deposition temperatures investigated, while Sb was found only in the films deposited at elevated temperature higher than 550 °C. The deposition temperature could be reduced by using two other precursor sets (TiPGe-TiPSb-DtBTe and TAGe-TiPSb-DiPTe). The Ge content, however, could not be sufficiently increased to obtain stoichiometric Ge2Sb2Te5 films. Therefore, the hot wire or catalytic method was applied to improve the decomposition of the precursors. In this case, the desired composition (e.g. Ge2Sb2Te5) was obtained at each investigated temperature by adjusting dosing and deposition parameters. Additionally, film roughness (as low as 2 nm) and deposition rates could be optimized by adjusting deposition temperature and pressure.

Phase change memory (PCM) devices are based on the electrically-induced change of phase within an active chalcogenide material. PCM features large resistance window, fast threshold/phase switching and high endurance, thus motivating a broad interest as potential Flash replacement and/or nonvolatile storage class memory. Despite the relatively mature progress of research and technology, there is still a wide debate about the ultimate scaling perspective for PCMs. Structural relaxation, crystallization and noise affecting the amorphous chalcogenide phase need to be addressed by accurate physical models for a realistic scaling projection. This work discusses the scaling of PCM devices in terms of the conduction mechanisms and structural stability of the amorphous chalcogenide phase. Resistance window narrowing, current fluctuations, resistance drift and crystallization in the amorphous phase will be explained by a unified model for thermal excitation of the structure by many-phonon phenomena. The downscaling of the reset current, needed to reduce the cell area in memory arrays, and thermal disturb between adjacent cells during reset will be finally addressed to assess the scaling capability of high-density PCM crossbar architectures.

A study on microstructure and electrical property of cerium (Ce)-doped Ge2Sb2Te5 (GST) layers for phase-change memory (PCM) application were presented. Ce doping does not suppress the resistivity of amorphous GST and the resistivity ratio of amorphous and crystalline GST remains at about 105. Further, Ce-doping escalates the recrystallization temperature (Tx) of GST from 159 to 236°C. Such a unique behavior would greatly benefit the preservation of signal contrast as well as the high-density signal storage and will not cause the increase of device writing current. X-ray diffraction (XRD) indicated that Ce doping stabilizes amorphous GST and suppresses the formation of hexagonal phase. Transmission electron microscopy (TEM) revealed Ce doping refines the grain size of GST. Kissinger's analysis found that Tx and activation energy (Ea) of phase transition for doped-GST both increase with the increase of Ce content. Isothermal experiment found the Ce doping increases temperature for 10-yr data retention from 76 and 170°C. This is attributed to the presence of Ce solutes in GST matrix that inhibits the grain growth during recrystallization.

Static-mode electrical test on PCM device containing doped GST as the programming layer found that Ce incorporation indeed increases the switching threshold voltage (Vth). This confirmed that Ce doping effectively retards the crystallization of GST and improves the stability of amorphous GST.

Ab Initio calculations of various configurations of In2Se3 compounds are used to gain insight into the transition from crystalline to amorphous phase. The structures considered are based on wurzite structures with 1/3 of indium sites vacant as observed experimentally. From extensive calculations for possible vacancy configurations in In2Se3 compounds, predictions based on the local coordination of In/Se atoms are made for the energetically favorable vacancy ordering structures. Results indicate that in the most stable In vacancy configurations, Se atoms have coordination of either 2 or 3 (In atoms have coordination of 4). Other coordinations lead to significantly higher formation energies. Results from analyzing the total energy and electronic structure of a range of off-stoichiometry, including vacancies, interstitials and anti-site, configurations, suggest that the energetically most favorable way to form In-rich material is via incorporation of Se vacancies, while Se occupying a vacant site is the most favorable for formation of Se-rich phase. Based on these calculations, predictions are made on how stoichiometry deviations impact structural evolution during phase change.

100 nm-thick GeSbN films with high Sb content were investigated by XRD and TEM in order to investigate crystalline phases. We observe the crystallization of the two phases separatly. First, Sb rhomboedral crystallizes at 250°C and then cubic Ge appears at 340°C according to Reflectivity and X-Ray Diffraction measurements. With the incorporation of nitrogen in the thick films, a delay to crystallization of the two phases is observed. Grain size measurements with Scherrer formula support the decrease of grain crystallization with N content. Moreover, TEM observations show clearly the separation of the two phases in the layer and the reduction in size of the grains with nitrogen content. This allows a better re-amorphization than films without nitrogen.

We demonstrate, both experimentally and by computer simulation, that while the metastable face-centered cubic (fcc) phase of Ge-Sb-Te becomes amorphous under hydrostatic compression at about 15 GPa, the stable trigonal phase remains crystalline. We present evidences that the pressure-induced amorphisation phenomenon strongly depends on the concentration of vacancies included in the Ge/Sb sublattice, but is thermally insensitive. Upon higher compression, a body-centered cubic phase is obtained in both cases at around 30 GPa. Upon decompression, the amorphous phase is retained when starting with the fcc phase while the initial structure is recovered when starting with the trigonal phase. We argue that the presence of vacancies and the associated subsequent large atomic displacements lead to nanoscale phase separation and the loss of the initial structure memory in the fcc staring phase of Ge-Sb-Te. We futher compare the amorphous phase obtained via the pressure route with the melt quenched amorphous phase.

The crystallization kinetics of nano-structured amorphous Ge2Sb2Te5 (GST) regions (20-100 nm in diameter) obtained by Electron Beam Lithography (EBL) and 40 KeV Ge+ 1014/cm2 ion irradiation of crystalline 20 nm thick films was investigated. The amorphous regions, surrounded by crystalline cubic (fcc) or hexagonal (hcp) phase, were recrystallized by isothermal annealing in the temperature range 80°C - 120°C and by focused electron beam irradiation. The process was followed in situ by transmission electron microscope (TEM). The recrystallization is governed by the growth of the surrounding f.c.c. crystalline interface with a velocity of 2×10-2 nm/s at 110°C. The interface velocity is higher in the h.c.p. substrate less than a factor ten. Local focused electron beam irradiation induces instead crystalline nucleation inside the nano amorphous regions. Similar experiments have been performed on planar ion amorphized thin films lying on both GST crystalline phases. In both cases the recrystallization is mainly associated to the movement of the amorphous-crystalline interface. These results indicate that the stability of the amorphous region, generated by ion irradiation, is severely affected by the adjacent crystalline structure and by the size of the amorphous area, critically involved in the scaling of the PCM-based devices.

The electrical resistance on the crystallization process of sputtered-deposited Ge1Cu2Te3 film was investigated by two-point probe method. It was found that the amorphous Ge1Cu2Te3 film crystallizes into a single Ge1Cu2Te3 phase with a chalcopyrite structure, which leads to a large resistance drop. The crystallization temperature of the Ge1Cu2Te3 amorphous film was about 250 °C, which is about 70 °C higher than the conventional Ge2Sb2Te5 amorphous film. The activation energy for the crystallization of the Ge1Cu2Te3 amorphous film was higher than that of the Ge2Sb2Te5 amorphous film. The Ge1Cu2Te3 compound with a low melting point can be expected to be suitable as the phase change material for PCRAM.

The electrical resistance change of amorphous SixTe100-x (x: 10-23) films during heating was investigated by a two-point probe method. The SixTe100-x films showed two-stage crystallization processes. The film was firstly crystallized to Te and subsequently crystallized to Si2Te3 with an electrical resistance drop. The first crystallization temperature Tx1st slightly increased with increasing Si content, while the second crystallization temperature Tx2nd was independent on the composition and was a constant temperature of 310 °C. In all films, the electrical resistance once increased in the temperature range from 250 to 295 °C before the crystallization of the Si2Te3. This temporal resistance increase could be explained by considering a formation of high-resistivity Si-rich amorphous phase.

By virtue of their unique electronic properties, nanometer-diameter sized single-walled carbon nanotubes represent ideal candidates to function as active parts of nanoelectronic memory storage devices. We show for the first time that GeTe, a phase change material, currently considered to be one of the most promising materials for data-storage applications, can efficiently be encapsulated within single-walled carbon nanontubes of 1.4 nm diameter. Structural investigations on the encapsulated GeTe nanowires have been carried out by high resolution transmission electron microscopy. The electronic interactions between the filling material and the host nanotube have been examined using ultraviolet photoelectron spectroscopy experiments and show that the electronic structure of the encapsulating nanotube and that of the encased filling are not perturbed by the presence of each of the other component.

The newly formed hybrids offer potential to operate as active elements in non-volatile electronic memory storage devices.

We discuss possible mechanisms for Poole-Frenkel type of non-ohmic conduction in chalcogenide glasses in the range of room temperatures. Overall, we list 8 such mechanisms, only one of which (Schottky emission) can be ruled out as inconsistent with the observations. Seven others can give more or less satisfactory fits of the observed non-linear IV curves. Our analysis calls upon indicative facts that would enable one to discriminate between the various alternative models.

Selective Chemical Vapor Deposition of Crystalline Ge-Sb-Te alloys initiating at the bottom metal contact of vias of various sizes has been accomplished. The method is based on selecting Sb and Te precursors which do not decompose on dielectric surfaces in the utilized temperature range.

The results of calorimetric and electrical studies of bulk Ge2Sb2Te5 and GeSb2Te4 alloys around melting temperature Tm are presented together with characteristics of phase-change memory devices from such alloys. The endothermic melting region is wider in Ge2Sb2Te5 than GeSb2Te4. Electrical resistivities of the alloys in this region have semiconductor characteristics. The width of the melting region correlates with breadth of set to reset transition in devices. This empirical correlation is probably important for alloy selection for multi-level memory cells.

Amorphous films of Ge1-xTex (x=0.37, 0.51, 0.64) prepared by sputtering, by melt quenching or by ion irradiation were annealed up to 450°C. Different phase stability, i.e. crystallization temperature, was observed varying the amorphous status in stoichiometric and Te-rich alloys while no variation was obtained in the Ge-rich alloy. Laser and ion irradiated stoichiometric alloy exhibits lower stability with respect to the sputtered film while irradiated amorphous Te-rich samples are more stable than the as deposited amorphous sample. An enhancement of edge-sharing GeTe4 tetrahedra Raman signal at the expenses of Ge-rich tetrahedra signal occurs in the irradiated samples with respect to the as-deposited amorphous layers both in the stoichiometric and in the Te-rich alloy. The crystallization temperature decreases in GeTe since the system during irradiation is promoted to a state closer to the crystalline phase while in Te-rich alloy the stability increases with the density of Ge-Te bonds since this local rearrangement delays Te precipitation and the subsequent GeTe crystallization. Irradiation does not affect the stability of Ge rich alloy in which crystallization is limited by the Ge mobility and the induced local rearrangements is probably prevented by the low atomic diffusivity.

This work presents an analytical model of crystalline phase formation in nanoglasses of phase change memory. We describe a data loss mechanism when the cell resistance changes significantly at elevated temperatures over long periods of time with no electrical bias applied. Unlike the standard approach, which relates crystalline shunt formation to aggregates of crystalline particles forming the percolation cluster, we look at the rare events of almost rectilinear path formation in very thin structures. They can occur at crystalline volume fractions considerably lower than the critical volume fraction required for percolation. We find the characteristic parameters which can describe statistics of these rare events.