Stephan W. H. Eijt

Reduced enthalpy of metal hydride formation for Mg-Ti nanocomposites produced by spark discharge generation.

Spark discharge generation was used to synthesize Mg-Ti nanocomposites consisting primarily of a metastable body-centered-cubic (bcc) alloy of Mg and Ti. The bcc Mg-Ti alloy transformed upon hydrogenation into the face-centered-cubic fluorite Mg1-yTiyHx phase with favorable hydrogen storage properties. Both metal and metal hydride nanocomposites showed a fractal-like porous morphology, with a primary particle size of 10-20 nm. The metal content of 70 atom % (at %) Mg and 30 at % Ti, consistently determined by XRD, TEM-EDS, and ICP-OES, was distributed uniformly across the as-prepared sample. Pressure-composition isotherms for the Mg-Ti-H nanocomposites revealed large differences in the thermodynamics relative to bulk MgH2, with a much less negative enthalpy of formation of the hydride as small as -45 ± 3 kJ/molH2 as deduced from vant Hoff plots. The plateau pressures of hydrogenation were substantially higher than those for bulk MgH2 in the low temperature range from 150 to 250 °C. The reaction entropy was simultaneously reduced to values down to 84 ± 5 J/K mol H2, following a linear relationship between the enthalpy and entropy. Plausible mechanisms for the modified thermodynamics are discussed, including the effect of lattice strains, the presence of interfaces and hydrogen vacancies, and the formation of excess free volume due to local deformations. These mechanisms all rely on the finely interdispersed nanocomposite character of the samples which is maintained by grain refinement.

New Insights in the Nanostructure and Defect States of Hydrogenated Amorphous Silicon Obtained by Annealing

Temperature annealing is used as a tool to study the validity of network models for the nanostructure of hydrogenated amorphous silicon (a-Si:H) and its relation to defect states. The changes in the size of the dominant open volume deficiencies have been studied using Doppler broadening positron annihilation spectroscopy and Fourier transform infrared spectroscopy. It is shown that the dominant open volume deficiencies for as-deposited films are divacancies, which appear to agglomerate into larger open volume deficiencies up to 400 °C. Above this temperature, the largest open volume deficiencies are suggested to be released at the surface of the sample. Fourier transform photocurrent spectroscopy results indicate a dramatic increase in the density of various subgap defect state distributions during temperature annealing. In addition, at least four defect states have been identified. These findings cannot be directly explained by assuming solely dangling bonds as the dominant defects in a-Si:H. We discuss that a model based on an anisotropic disordered network with volume deficiencies does explain our findings better than the classical model based on a continuous random network with solely an isotropic distribution of coordination defects. The claim is made that next to dangling bonds not fully hydrogen-passivated vacancies are significantly contributing to the dominant defect states in a-Si:H.

The Nature and the Kinetics of Light-Induced Defect Creation in Hydrogenated Amorphous Silicon Films and Solar Cells

The nature and the kinetics of light-induced defect creation in hydrogenated amorphous silicon (a-Si:H) films and solar cells are investigated by means of Doppler broadening positron annihilation spectroscopy, Fourier transform photocurrent spectroscopy, and J-V characterization. There is a strong correlation between the open volume deficiencies in a-Si:H and the Staebler-Wronski effect (SWE). The carrier generation and recombination profiles in the absorber layer are spatially correlated, and the recombination due to defects in the top and bottom parts of the absorber layer is different. Furthermore, the various defect distributions in the bandgap have different defect creation kinetics. It is demonstrated that the SWE defect formation kinetics in a solar cell are very complex and can impossibly be described by one time scaling ~ tβ as is often claimed.

Fractal disperse hydrogen sorption kinetics in spark discharge generated Mg/NbOx and Mg/Pd nanocomposites

Isothermal hydrogen desorption of spark discharge generated Mg/NbOx and Mg/Pd metal hydride nanocomposites is consistently described by a kinetic model based on multiple reaction rates, in contrast to the Johnson-Mehl-Avrami-Kolmogorov [M. Avrami, J. Phys. Chem. 9, 177 (1941); W. A. Johnson and R. F. Mehl, Trans. Am. Inst. Min., Metal. Eng. 135, 416 (1939); A. N. Kolmogorov, Izv. Akad. Nauk SSSR, Ser. Mat. 3, 355 (1937); F. Liu, F. Sommer, C. Bos, and E. J. Mittemeijer, Int. Mat. Rev. 52, 193 (2007)] model which is commonly applied to explain the kinetics of metal hydride transformations. The broad range of reaction rates arises from the disperse character of the particle size and the dendritic morphology of the samples. The model is expected to be generally applicable for metal hydrides which show a significant variation in particle sizes, in configuration and/or chemical composition of local surroundings of the reacting nanoparticles.

Migration of Open Volume Deficiencies in Hydrogenated Amorphous Silicon During Annealing

The nanostructure of hydrogenated amorphous silicon (a-Si:H) is studied by means of doppler broadening positron annihilation spectroscopy (DB-PAS) and Fourier transform infrared (FTIR) spectroscopy. The evolution of open volume deficiencies is monitored during annealing, demonstrating that small vacancies and other small vacancy clusters that are initially present in the a-Si:H nanostructure agglomerate into larger vacancy clusters. The migration of open volume deficiencies is less pronounced for a-Si:H deposited at higher hydrogen-to-silane gas flow rate ratio, R. FTIR spectroscopy reveals the presence of a peculiar peak in the refractive index in the infrared—and hence the calculated mass density—which occurs just before H effusion from the films starts. The combined results of DB-PAS and FTIR spectroscopy indicate that a stress buildup caused by the accumulation of H2 in agglomerating vacancies during annealing can explain the sudden mass density increase. At higher temperatures, stress is released with the onset of H effusion. The H effusion consists of a two-stage process involving small open volume deficiencies and nanosized voids, contrasting earlier interpretations. The reduced amount of hydrogen migration and enhanced hydrogen passivation degree are suggested as key factors to the reduced light-induced degradation associated with increased R values.

Annealing of SnO2 thin films by ultra-short laser pulses

Post-deposition annealing by ultra-short laser pulses can modify the optical properties of SnO₂ thin films by means of thermal processing. Industrial grade SnO₂ films exhibited improved optical properties after picosecond laser irradiation, at the expense of a slightly increased sheet resistance [Proc. SPIE 8826, 88260I (2013)]. The figure of merit ϕ = T¹⁰ / R(sh) was increased up to 59% after laser processing. In this paper we study and discuss the causes of this improvement at the atomic scale, which explain the observed decrease of conductivity as well as the observed changes in the refractive index n and extinction coefficient k. It was concluded that the absorbed laser energy affected the optoelectronic properties preferentially in the top 100-200 nm region of the films by several mechanisms, including the modification of the stoichiometry, a slight desorption of dopant atoms (F), adsorption of hydrogen atoms from the atmosphere and the introduction of laser-induced defects, which affect the strain of the film.

Ligand-surface interactions and surface oxidation of colloidal PbSe quantum dots revealed by thin-film positron annihilation methods

Positron Two Dimensional Angular Correlation of Annihilation Radiation (2D-ACAR) measurements reveal modifications of the electronic structure and composition at the surfaces of PbSequantum dots(QDs),deposited as thin films, produced by various ligands containing either oxygen or nitrogen atoms. In particular, the 2D-ACAR measurements on thin films of colloidalPbSeQDs capped with oleic acid ligands yield an increased intensity in the electron momentum density (EMD) at high momenta compared to PbSequantum dots capped with oleylamine. Moreover, the EMD of PbSeQDs is strongly affected by the small ethylenediamine ligands, since these molecules lead to small distances between QDs and favor neck formation between near neighbor QDs, inducing electronic coupling between neighboring QDs. The high sensitivity to the presence of oxygen atoms at the surface can be also exploited to monitor the surface oxidation of PbSeQDs upon exposure to air. Our study clearly demonstrates that positron annihilation spectroscopy applied to thin films can probe surface transformations of colloidal semiconductor QDs embedded in functional layers.

New insights into the nanostructure of innovative thin film solar cells gained by positron annihilation spectroscopy

Recent studies showed that positron annihilation methods can provide key insights into the nanostructure and electronic structure of thin film solar cells. In this study, positron annihilation lifetime spectroscopy (PALS) is applied to investigate CdSe quantum dot (QD) light absorbing layers, providing evidence of positron trapping at the surfaces of the QDs. This enables one to monitor their surface composition and electronic structure. Further, 2D-Angular Correlation of Annihilation Radiation (2D-ACAR) is used to investigate the nanostructure of divacancies in photovoltaic-high-quality a-Si:H films. The collected momentum distributions were converted by Fourier transformation to the direct space representation of the electron-positron autocorrelation function. The evolution of the size of the divacancies as a function of hydrogen dilution during deposition of a-Si:H thin films was examined. Finally, we present a first positron Doppler Broadening of Annihilation Radiation (DBAR) study of the emerging class of highly efficient thin film solar cells based on perovskites.