The recently discovered orthorhombic allotrope of silicon, Si24, is an exciting prospective material for the future of solar energy due to a quasi-direct bandgap near 1.3 eV, coupled with the abundance and environmental stability of silicon. Synthesized via precursor Na4Si24 at high temperature and pressure (∼850 °C, 9 GPa), typical synthesis results have yielded polycrystalline samples with crystallites on the order of 20 μm. Several approaches to increase the crystal size have yielded success, including in-situ thermal spikes and refined selection of the starting materials. Microstructural analysis suggests that coherency exists between diamond silicon (d-Si) and Na4Si24. This hypothesis has led to the successful attempts at single crystal synthesis by selecting large crystals of d-Si along with metallic Na as the precursors rather than powdered and mixed precursor material. The new synthesis approach has yielded single crystals of Na4Si24 greater than 100 μm. These results represent a breakthrough in synthesis that enables further characterization and utility. The promise of Si24 for the future of solar energy generation and efficient electronics is strengthened through these advances in synthesis.

We have measured the 121Sb NMR spectra, which are highly sensitive to the electric field gradients at the nuclear site, for crystalline Sb2Te3, Ge1Sb2Te4, Ge2Sb2Te4, and Ge2Sb2Te5. Estimates of the coupling constants, which are a measure of the field gradient, based on these spectra compare well with compounds containing Sb sites that are approximately 6-fold coordinated. The coupling constants of amorphous phase counterparts are roughly an order of magnitude larger and compare favorably with compounds where the Sb sites are 3-fold coordinated. We argue that the difference in the coupling constants arises primarily from a change in the local coordination, as opposed to the slight differences in the Sb-Te bond lengths and bond angles. The NMR data agree best with a structural model of amorphous phase based upon the “8-N” rule.

We have investigated the localized electronic states in mixed-phase hydrogenated nanocrystalline silicon thin films (nc-Si:H) with electron-spin-resonance (ESR). The dark ESR signal most likely arises from defects at the grain boundaries or within the crystallites. With illumination with photon energies ranging from 1.2 eV to 2.0 eV, there is no evidence of photo-induced carriers trapped in the bandtail states within the amorphous region. Dependence of the light-induced ESR (LESR) upon the exciting photon energy reveals that, at different excitation photon energies, different regions dominate the optical absorption. This behavior may have potential consequences for understanding the light-induced degradation in nc-Si:H.

We have observed the growth of defects caused by optical illumination in liquid nitrogen. We kept the sample in liquid nitrogen over one year. After one year and half the ESR signal reached ∼1018 cm−3 with no evidence of saturation. After that, we step-wise annealed isochronal the sample up to room temperature, where two thirds of original defects were annealed out. After room temperature, the sample was annealing isothermally around 300 K for several months. At this temperature, the defects slowly anneal. After a hundred of hours at 295K, the defect density decreased 10x from its original value at 77K.

Extended abstract of a paper presented at Microscopy and Microanalysis 2007 in Ft. Lauderdale, Florida, USA, August 5 – August 9, 2007

Solid-phase crystallization and the subsequent re-hydrogenation of the amorphous silicon thin films provides a low cost approach for thin-film crystalline Si:H-based photovoltaic devices. During the hydrogen effusion, significant lattice reconstruction occurs, as hydrogen is driven out of the film, accompanied by creation and migration of a large number of dangling bonds. We used electron-spin-resonance (ESR) to study evolution of the local order surrounding these dangling bonds during crystallization. When samples made by both plasma enhanced chemical vapor deposition (PECVD) and the and hot wire CVD (HWCVD) are heated to 560°C, hydrogen effuses within 30 min, giving rise to H-effused defect densities of about 5x1018 cm-3. Further heating at 560°C results in crystallizati°n in the HWCVD sample after about 200 min. On the other hand, PECVD samples crystallize only when heated up to 580°C, and then only after much longer times (Dt ~ 1300 min) [1,2]. ESR defects in both samples persist at the 5x1018 cm-3 level as long as the sample remains amorphous during the grain nucleation period. As the crystallites appear, the defect densities gradually decrease and saturate at about 3x1017 cm-3 as the crystallization is completed, both in HWCVD and PECVD samples.

In the H-effused states before crystallization, the ESR signals for both the HWCVD and PECVD samples show significant exchange-narrowing, suggesting that the defects are probably clustered. As the sample crystallizes, the defect clustering largely disappears, yet the line-widths in fully crystallized films are somewhat narrower than those in typical micro-crystalline silicon thin films as reported earlier [3]. This difference is probably due the specific structures of the grain boundaries in the present study. The effect of re-hydrogenation on both the H-effused amorphous and crystallized states will be discussed.

The appearance of optically or electrically induced defects in hydrogenated amorphous silicon (a-Si:H), especially those that contribute to the Staebler-Wronski effect, has been the topic of numerous studies, yet the mechanism of defect creation and annealing is far from clarified. We have been observing the growth of defects caused by tritium decay in tritiated a Si-H instead of inducing defects optically. Tritium decays to 3He, emitting a beta particle (average energy of 5.7 keV) and an antineutrino. This reaction has a half âlife of 12.5 years. In these 7 at.% tritium-doped a-Si:H samples each beta decay will create a defect by converting a bonded tritium to an interstitial helium, leaving behind a silicon dangling bond. We use ESR (electron spin resonance) and PDS( photothermal deflection spectroscopy) to track the defects. First we annealed these samples, and then we used ESR to determine the initial defect density around 1016 to 1017 /cm3 , which is mostly a surface spin density. After that we have kept the samples in liquid nitrogen for almost two years. During the two years we have used ESR to track the defect densities of the samples. The defect density increases without saturation to a value of 3x1019/cm3 after two years, a number smaller than one would expect if each tritium decay were to create a silicon dangling bond (2x1020/cm3). This result suggests that there might be either an annealing process that remains at liquid nitrogen temperature, or tritium decay in clustered phase not producing a dangling bond due to bond reconstruction and emission of the hydrogen previously paired to Si-bonded tritium atom. After storage in liquid nitrogen for two years, we have annealed the samples. We have stepwise annealed one sample at temperatures up to 200°C, where all of the defects from beta decay are annealed out, and reconstructed the annealing energy distribution. The second sample, which was grown at 150°C, has been isothermally annealing at 300 K for several months. The defects remain well above their saturation value at 300 K, and the shape of decay suggests some interaction between the defects.

Ge2Sb2Te5 is under intense investigation for phase-change memory devices, including rewriteable DVDs where optical illumination is used to switch between the glassy and crystalline states. We investigate the influence of optical irradiation on amorphous phase. Many chalcogenides display photo-oxidation, photodarkening or photo-bleaching, but little has been reported on the Ge-Sb-Te system. Using spectroscopic ellipsometry (SE) and secondary ion mass spectrometry, we determine that the samples have a strong tendency to photo-oxidize; if this is not accounted for, then the analysis of SE data appears to show photodarkening. Other authors recently reported photodarkening in nonstoichiometric GexSb20-xTe80 [Pamukchieva et al., Proc. SPIE 5581, 608 (2004); Pamukchieva et al., J. Optoelectron. Adv. Mater 7, 1277 (2005)], but our analysis suggests that the changes were also the result of photo-oxidation. The oxide has lower value of (n, k) than Ge2Sb2Te5, and can be etched by hydrofluoric acid or water. The photo-oxidation is presumably the result of free carrier generation in the Ge2Sb2Te5. Our observation of negligible photodarkening is consistent with previous works that found less photodarkening in tellurides compared with selenides or sulfides, and that an increase in the mean coordination number, here by Ge addition, further reduces the photodarkening effect.

We investigated the temperature dependence of the production and annealing kinetics of the light induced defect states in a:Si:H by electron spin resonance (ESR). At low temperatures (T ∼ 25 K) the silicon dangling bond production is about half as efficient as it is at 300 K. Defects, which are created below about 100 K, almost entirely anneal at room temperature. A sample of a-Si:H, which is subjected to several photo-excitation and annealing cycles, shows a very slow increase of both the degraded and annealed defect densities. The difference in the spin densities between the annealed and degraded states decreases with an increasing number of degradation/annealing cycles.

Iron doped lithium niobate (Fe:LiNbO3) in a simple focal plane geometry has demonstrated efficient optical limiting through two-beam coupling. The performance is largely independent of the total Fe concentration and the oxidation state of the Fe ions, providing the linear optical transmission of uncoated crystals is between 30% and 60%. Fe has been found to be the best dopant for LiNbO3, giving the widest spectral coverage and the greatest optical limiting. Optical limiting in Fe:LiNbO3 has been shown to be very much greater than predicted by simple diffusion theory. The reason for this is a higher optical gain than expected. It is suggested that this may be due to an enhancement of the space-charge field arising from the photovoltaic effect. The standard two-beam coupling equations have been modified to include the effects of the dark conductivity. This has produced a theoretical intensity dependence on the ΔOD which closely follows the behaviour observed in the laboratory. A further modification to the theory has also shown that the focusing lens f-number greatly affects the optical limiting characteristics of Fe:LiNbO3. A lens f-number of approximately 20 gives the best results.

Although there are some significant exceptions, most important glass-forming systems contain elements from the sixth, or chalcogenide, column of the periodic table (oxygen, sulfur, selenium, or tellurium). The glasses which contain oxygen are typically insulators, while those which contain the heavier chalcogen elements are usually semiconductors. Even though oxygen is technically a chalcogen element, the term “chalcogenide glass” is commonly used to denote those largely covalent, semiconducting glasses which contain sulfur, selenium, or tellurium as one of the constituents.

The chalcogenide glasses are called semiconducting glasses because of their electrical properties. The electrical conductivity in these glasses depends exponentially on the temperature with an activation energy which is approximately one half of the optical gap. In this sense these glasses exhibit electrical properties similar to those in intrinsic crystalline semiconductors. The analogy is by no means perfect. The mobilities for the charge carriers in these glasses are very low (< 10 cm2/V-s) compared to crystalline semiconductors, and there are even discrepancies in determining the sign of the charge carriers from measurements of the Hall effect and the Seebeck effect.

The first detailed studies of the chalcogenide glasses were performed about 30 years ago. For many years the prototype compositions have been selenium (Se), arsenic triselenide (As2Se3) or arsenic trisulfide (As2S3), and germanium diselenide (GeSe2) or germanium disulfide (GeS2).