Optimized Ni1-x Al x O hole transport layer for silicon solar cells.

NiO alloyed with aluminum, Ni1-x Al x O, is analyzed in terms of its stoichiometry, electronic and transport properties, as well as interfacial band alignment with Si to evaluate its potential use as a hole transport layer (HTL) in p-i-n type solar cells. The analysis is based on component material and slab structural simulations, as well as simulated and measured angle-resolved valence-band photoemission spectroscopy (PES) data, in order to reveal the best suitable stoichiometry. It is concluded that the ionization energy from the highest occupied states tends to increase with Al content as the simulated work function grows from 4.1 eV for pure NiO to 4.7 eV for heavily alloyed Al0.50Ni0.50O. The electronic structure as a function of the interface design between crystalline silicon and the transport layer is used to assess the band lineup and its correlation with the discontinuity of the affinities. The affinity rule is tested by evaluating the workfunctions of the component layers and justified best for a particular Ni-enriched interface design. Technology Computer-Aided Design (TCAD) device simulations show, that the band offset between oxide and crystalline silicon remains within the range of values to sustain a staggering alignment - a condition suitable for effective charge separation, similar to a situation in a tunneling diode. The self-energy of the hole carriers is estimated by contrasting simulated and measured photoemission data, which in the case of non-annealed Al-rich samples is shown to be an order of magnitude higher due to the disorder effects. The work functions derived from the measured PES data for the epitaxially grown oxide films with nearly identical alloy stoichiometry correlate well with the simulated values. The findings suggest that the optimal HTL is formed by starting with a pure Ni layer, followed by a graded doping Al x Ni1-x O, with x high at contact/oxide interface and low at the oxide/semiconductor.

First principles calculations for defects in U.

Uranium (U) exhibits a high temperature body-centered cubic (bcc) allotrope that is often stabilized by alloying with transition metals such as Zr, Mo, and Nb for technological applications. One such application involves U-Zr as nuclear fuel, where radiation damage and diffusion (processes heavily dependent on point defects) are of vital importance. Several systems of U are examined within a density functional theory framework utilizing projector augmented wave pseudopotentials. Two separate generalized gradient approximations of the exchange-correlation are used to calculate defect properties and are compared. The bulk modulus, the lattice constant, and the Birch-Murnaghan equation of state for the defect free bcc uranium allotrope are calculated. Defect parameters calculated include energies of formation of vacancies in the α and γ allotropes, as well as self-interstitials, Zr interstitials, and Zr substitutional defects for the γ allotrope. The results for vacancies agree very well with experimental and previous computational studies. The most probable self-interstitial site in γ-U is the (110) dumbbell, and the most probable defect location for dilute Zr in γ-U is the substitutional site. This is the first detailed study of self-defects in the bcc allotrope of U and also the first comprehensive study of dilute Zr defects in γ-U.

Aberration-corrected scanning transmission electron microscopy: from atomic imaging and analysis to solving energy problems.

The new possibilities of aberration-corrected scanning transmission electron microscopy (STEM) extend far beyond the factor of 2 or more in lateral resolution that was the original motivation. The smaller probe also gives enhanced single atom sensitivity, both for imaging and for spectroscopy, enabling light elements to be detected in a Z-contrast image and giving much improved phase contrast imaging using the bright field detector with pixel-by-pixel correlation with the Z-contrast image. Furthermore, the increased probe-forming aperture brings significant depth sensitivity and the possibility of optical sectioning to extract information in three dimensions. This paper reviews these recent advances with reference to several applications of relevance to energy, the origin of the low-temperature catalytic activity of nanophase Au, the nucleation and growth of semiconducting nanowires, and the origin of the eight orders of magnitude increased ionic conductivity in oxide superlattices. Possible future directions of aberration-corrected STEM for solving energy problems are outlined.

Role of electronic versus atomic relaxations in Stokes shifts at defects in solids.

Redshifts of luminescence relative to optical absorption bands (Stokes shifts) of molecules and of defects in solids are universally attributed to slow atomic relaxations on the grounds that electronic transitions are fast (Franck-Condon principle). Here we report a novel phenomenon that can occur only in the solid state: Stokes shifts caused by slow electronic relaxations. We demonstrate that the phenomenon occurs in the nonbridging oxygen defect in amorphous SiO2. We predict that another defect (OH group), which can exist in either crystalline or amorphous SiO2, has a similar Stokes shift, but it arises from a mix of lattice and electronic relaxations with manifest differences in the two phases.

Reactions and diffusion of water and oxygen molecules in amorphous SiO2.

Water and oxygen molecules determine many of the properties of amorphous SiO2 used in several technologies, but the underlying atomic-scale processes remain unresolved. We report results of first-principles calculations showing that a wide range of behavior is possible in an amorphous environment, including diffusion of the molecule as a whole and various reactions with the network. Experimental data including oxygen exchange reaction and radiation sensitivity are accounted for. The possibility of H3O+ formation as a source of positive charge is discussed.

Defect generation by hydrogen at the Si- SiO(2) interface.

Hydrogen is known to passivate Si dangling bonds at the Si-SiO(2) interface, but the subsequent arrival of H(+) at the interface causes depassivation of Si-H bonds. Here we report first-principles density functional calculations, showing that, contrary to conventional assumptions, depassivation is not a two-step process, namely, neutralization of H(+) by a Si electron and subsequent formation of an H(2) molecule. Instead, we establish that H(+) is the only stable charge state at the interface and that H(+) reacts directly with Si-H, forming an H(2) molecule and a positively charged dangling bond (P(b) center). As a result, H-induced interface-trap formation does not depend on the availability of Si electrons.