We report on the study of single devices of phase-change (Ge2Sb2Te5) memory cells in line cell type devices. Devices were investigated employing an x-ray nanobeam of only about 150 nm diameter, which could be fully contained within the spatial extent of the active area within a single device cell. XANES spectra showing the device in the amorphous and crystalline state have been successfully collected after switching the device in situ at the synchrotron. By monitoring the fluorescence response of the sample constituent materials at a constant photon energy (corresponding to the Ge K-edge absorption edge) as a function of x-ray beam position on the sample 2D maps have been produced.

We introduce a technique to permit x-ray absorption spectroscopy studies focusing on individual phase-change (Ge2Sb2Te5) memory cells in fully integrated PC-RAM structures. Devices were investigated employing an x-ray nanobeam of only about 300 nm diameter, which could be fully contained within the spatial extent of the active area within a single device cell and enabled us to investigate individual devices without interference from non-switching material surrounding the area of interest. By monitoring the fluorescence signals of tungsten and germanium at a photon energy corresponding to the Ge K-edge absorption edge white line position, we were successful in producing 2D area maps of the active cell region, which clearly show the imbedded tungsten heater element and the switched region of the phase change material. Additionally, position dependent changes in the phase change material could be traced by taking an array of XANES spectra at the Ge K-edge on and in the vicinity of individual devices.

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.

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 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.

Epitaxial Ge2Sb2Te5 has been successfully grown on GaSb(001) by molecular beam epitaxy. The films show a tendency for void formation and rough morphology, but at the same time a very strong epitaxial orientation, cubic structure and a sharp interface to the substrate. The layers can be reversibly switched between the crystalline and amorphous phases using short laser pulses.

Chalcogenides, in particular germanium-antimony-tellurium (GeSbTe) and antimony-rich tellurium (R-SbTe) based alloys, are the most technologically significant alloys currently being applied to recordable optical storage as typified by rewritable digital versatile discs (DVD-RW), DVD random access memory, (DVD-RAM). The same alloys are also being applied to nonvolatile random access memory electrical memory in the form of phase change random access memory (PCRAM). In 2004, the phase transition mechanism of GeSbTe was first revealed, demonstrating that the amorphous state is not a random configurational network but is locally well-ordered with the crystalline to amorphous switching process being based upon Ge atoms moving between octahedral and tetrahedral symmetry positions. The kinetic barrier between these two states gives rise to the non-volatile nature of GeSbTe as a storage medium. In contrast, no theoretical analysis has been proposed for SbTe alloys because a Ge-free system. In this paper, the Sb2Te structure has been investigated using the local density approximation (LDA) using a plane-wave basis and compared with experimental results. The effect of external stress on the structure was also investigated. It was found that Sb2Te undergoes two phase-transitions at around 18 GPa (compressive) and −3 GPa (tensile). In the case of negative stress, the c-axis was found to expanded more than the other axes, giving rise a large refractive index change. We report on coherent (uniaxial) melting induced by the breaking a sigma bond between Sb2Te3 and Sb superlattices. We believe this to be the origin of the phase transition that induces a large change in physical properties.

We have grown device-grade Cu(In,Ga)Se2 (CIGS) thin films using a RF-cracked Se-radical beam source. A unique combination of film properties: smooth surface, large grain size and high photovoltaic performance are shown. A competitive energy conversion efficiency of 17 % has been demonstrated from a solar cell fabricated using a CIGS absorber grown with a Se-radical source. In addition to the unique combination of film properties and high photovoltaic performance, a significant improvement in the use of Se source material in comparison with the conventional Se-evaporative sources has been demonstrated.

In this paper we discuss properties of phase-change materials that are crucial for their performance

In addition to their wide-spread application in the re-writable optical memory markets, phase-change memory alloys are also poised to take a prominent role in future non-volatile memory applications due to their potential for low-energy usage and indefinite cyclability compared with their silicon-based flash memory counterparts. In contrast with their widespread use, however, the details of the crystalline to amorphous switching process utilized for memory storage remain an active research topic with many details still lacking. Considering the conflicting requirements for high-speed switching, yet long term data storage integrity, a deeper understanding of these materials is essential for insightful application development. We have used x-ray absorption fine structure spectroscopy (XAFS), a technique equally suitable for amorphous and crystalline phases to elaborate details in structural changes in the phase-change process for a variety of phase-change alloys in static measurements. As the kinetics of the switching process are the linchpin for optimizing switching characteristics, we have recently initialted dynamic measurements of light -induced structural changes in Ge-Sb-Te (GST) alloys. These measurements have been carried out synchronously using both femtosecond and nanosecond laser pump pulses in conjunction with 100~ps x-ray pulses generated by an electron storage ring. By synchronously triggering the laser with a variable sub-nanosecond delay, we have been able to use XAFS to probe details of the dynamics of the switching process. Preliminary results learned from this approach applied to GST alloys are presented.

We have demonstrated that certain chalcogenide layers within a spinning super-RENS optical disc allow to squeeze the 650 nm laser beam to a spot size as fine as 50 nm using a 15-nm chalcogenide film. The near-field light was focused at a depth of just over 30 nm after passing through a chalcogenide film. Finite-difference time-domain (FDTD) simulations also reproduced these results. We suggest that a conductive ring aperture generated in the chalcogenide layers plays an important role in the localized light focusing.

Epitaxial CuGaSe2 films were grown on GaAs substrates under Cu-excess conditions to obtain stoichiometric compositions. The films were annealed in Ar, Sex or O2 ambients with or without a Cu or Cu-Se cap layer with the intention of changing the intrinsic defect concentrations. Samples were evaluated using low-temperature photoluminescence (PL) measurements. Annealing of the samples dramatically changed the PL spectra indicating that not only interdiffusion had occurred, but defect species and populations were changed. Comprehensive consideration of the changes led to the conclusion that the emissions at 1.62 eV, 1.66 eV and in the range from 1.2 to 1.4 eV are related to specific defects of Se vacancies, Cu vacancy-Se vacancy complexes and interstitial Cu, respectively.

CuGaSe2 (CGS) is a promising material for high efficiency thin film solar cells though predicted device performance has not been realized. Understanding the difference in the chemical nature between CuInSe2 (CIS) and CGS is critical for improving Cu (In, Ga) Se2 solar cells with high Ga concentrations. In this work, we have investigated the effects of oxygen-annealing on Ga-rich CGS epitaxial films focusing on compositional changes and secondary phase formations. The photoluminescence (PL) spectrum of Ga-rich films after oxygen-annealing was observed to always change into a spectrum characteristic of CGS grown under Cu-excess conditions. Electron probe micro-analysis (EPMA) measurements indicate the formation of Ga-O after oxygen-annealing. Selective etching of the Ga-O phase showed the composition of the CGS phase became close to stoichiometric. The oxygen-annealed films showed multiple pits ∼ 100 nm in depth and ∼ 2.5 μm in width. The Ga-O phase is founded in a layer formed on the surface of the CGS phase and in a columnar form rising from the bottom of the pits to the film/substrate interface. The above results suggest that excess Ga in Ga-rich CGS tends to react with oxygen to form Ga-O, thus the composition of the remaining CGS approaches stoichiometry consistent with the changes observed in PL.

ZnO films were grown by radical-source molecular beam epitaxy (RS-MBE) on sapphire and glass substrates, and they were characterized in terms of Hall mobility and optical transmission. Undoped ZnO films exhibit a low intrinsic defect density and optical properties close to bulk ZnO. By Ga doping, a resistance ρ as low as 2×10−4 Ωcm could be achieved. Balancing high conductivity and low transmission losses due to free carrier absorption in the infrared, the optimum was obtained for ρ=3.4×10−4Ωcm, electron mobility μe=37 cm2/Vs and an average transmission T of 96% in the wavelength range 400-1100 nm. Polycrystalline growth on glass yields slightly reduced but still good film quality (μe=30 cm2/Vs, T=90%). By the incorporation of Mg, conducting Mg0.3Zn0.7O films with an increased band gap up to ∼ 4eV were realized.

ZnO films were grown directly on epitaxial CuInSe2 (001) (CIS) by radical-source molecular beam epitaxy (RS-MBE). The substrate-film interdiffusion was investigated dependent on the ZnO growth temperature. Secondary Ion Mass Spectroscopy (SIMS) profiles indicate the mutual temperature-activated diffusion of Zn and In at a growth temperature of 440°C which is absent at 250°C. Zn indiffusion into the CIS substrate leads to characteristic changes in the photoluminescence (PL) properties, whereas the In outdiffusion into the growing ZnO film causes an increased carrier concentration.

The piezoelectric photoacoustic (PPA) spectra for Cu-rich CuGaSe2 (CGS)/GaAs epitaxial layers were successfully observed between liquid nitrogen and room temperatures for the first time. Bandgap energy of CGS (A band) is estimated to be 1.72 eV at liquid nitrogen temperature. The activation energies of three possible intrinsic defect levels are estimated to be about 80, 130 and 190 meV.