Atomistic origins of high-performance in hybrid halide perovskite solar cells

The performance of organometallic perovskite solar cells has rapidly surpassed that of both conventional dye-sensitised and organic photovoltaics. High power conversion efficiency can be realised in both mesoporous and thin-film device architectures. We address the origin of this success in the context of the materials chemistry and physics of the bulk perovskite as described by electronic structure calculations. In addition to the basic optoelectronic properties essential for an efficient photovoltaic device (spectrally suitable band gap, high optical absorption, low carrier effective masses), the materials are structurally and compositionally flexible. As we show, hybrid perovskites exhibit spontaneous electric polarisation; we also suggest ways in which this can be tuned through judicious choice of the organic cation. The presence of ferroelectric domains will result in internal junctions that may aid separation of photoexcited electron and hole pairs, and reduction of recombination through segregation of charge carriers. The combination of high dielectric constant and low effective mass promotes both Wannier-Mott exciton separation and effective ionisation of donor and acceptor defects. The photoferroic effect could be exploited in nanostructured films to generate a higher open circuit voltage and may contribute to the current-voltage hysteresis observed in perovskite solar cells.Comment: 6 pages, 5 figure

Broadband Linear-Dichroic Photodetector in a Black Phosphorus Vertical p-n Junction

The ability to detect light over a broad spectral range is central for practical optoelectronic applications, and has been successfully demonstrated with photodetectors of two-dimensional layered crystals such as graphene and MoS2. However, polarization sensitivity within such a photodetector remains elusive. Here we demonstrate a linear-dichroic broadband photodetector with layered black phosphorus transistors, using the strong intrinsic linear dichroism arising from the in-plane optical anisotropy with respect to the atom-buckled direction, which is polarization sensitive over a broad bandwidth from 400 nm to 3750 nm. Especially, a perpendicular build-in electric field induced by gating in black phosphorus transistors can spatially separate the photo-generated electrons and holes in the channel, effectively reducing their recombination rate, and thus enhancing the efficiency and performance for linear dichroism photodetection. This provides new functionality using anisotropic layered black phosphorus, thereby enabling novel optical and optoelectronic device applications.Comment: 18 pages, 5 figures in Nature Nanotechnology 201

On the Chemical Origin of the Gap Bowing in (GaAs)1−xGe2x Alloys: A Combined DFT–QSGW Study

Motivated by the research and analysis of new materials for photovoltaics and by the possibility of tailoring their optical properties for improved solar energy conversion, we have focused our attention on the (GaAs)1−xGe2x series of alloys. We have investigated the structural properties of some (GaAs)1−xGe2x compounds within the local-density approximation to density-functional theory, and their optical properties within the Quasiparticle Self-consistent GW approximation. The QSGW results confirm the experimental evidence of asymmetric bandgap bowing. It is explained in terms of violations of the octet rule, as well as in terms of the order–disorder phase transition

CGRPα-Expressing Sensory Neurons Respond to Stimuli that Evoke Sensations of Pain and Itch

Calcitonin gene-related peptide (CGRPα, encoded by Calca) is a classic marker of nociceptive dorsal root ganglia (DRG) neurons. Despite years of research, it is unclear what stimuli these neurons detect in vitro or in vivo. To facilitate functional studies of these neurons, we genetically targeted an axonal tracer (farnesylated enhanced green fluorescent protein; GFP) and a LoxP-stopped cell ablation construct (human diphtheria toxin receptor; DTR) to the Calca locus. In culture, 10–50% (depending on ligand) of all CGRPα-GFP-positive (+) neurons responded to capsaicin, mustard oil, menthol, acidic pH, ATP, and pruritogens (histamine and chloroquine), suggesting a role for peptidergic neurons in detecting noxious stimuli and itch. In contrast, few (2.2±1.3%) CGRPα-GFP+ neurons responded to the TRPM8-selective cooling agent icilin. In adult mice, CGRPα-GFP+ cell bodies were located in the DRG, spinal cord (motor neurons and dorsal horn neurons), brain and thyroid—reproducibly marking all cell types known to express Calca. Half of all CGRPα-GFP+ DRG neurons expressed TRPV1, ∼25% expressed neurofilament-200, <10% contained nonpeptidergic markers (IB4 and Prostatic acid phosphatase) and almost none (<1%) expressed TRPM8. CGRPα-GFP+ neurons innervated the dorsal spinal cord and innervated cutaneous and visceral tissues. This included nerve endings in the epidermis and on guard hairs. Our study provides direct evidence that CGRPα+ DRG neurons respond to agonists that evoke pain and itch and constitute a sensory circuit that is largely distinct from nonpeptidergic circuits and TRPM8+/cool temperature circuits. In future studies, it should be possible to conditionally ablate CGRPα-expressing neurons to evaluate sensory and non-sensory functions for these neurons

Epistatic Roles for Pseudomonas aeruginosa MutS and DinB (DNA Pol IV) in Coping with Reactive Oxygen Species-Induced DNA Damage

Pseudomonas aeruginosa is especially adept at colonizing the airways of individuals afflicted with the autosomal recessive disease cystic fibrosis (CF). CF patients suffer from chronic airway inflammation, which contributes to lung deterioration. Once established in the airways, P. aeruginosa continuously adapts to the changing environment, in part through acquisition of beneficial mutations via a process termed pathoadaptation. MutS and DinB are proposed to play opposing roles in P. aeruginosa pathoadaptation: MutS acts in replication-coupled mismatch repair, which acts to limit spontaneous mutations; in contrast, DinB (DNA polymerase IV) catalyzes error-prone bypass of DNA lesions, contributing to mutations. As part of an ongoing effort to understand mechanisms underlying P. aeruginosa pathoadaptation, we characterized hydrogen peroxide (H2O2)-induced phenotypes of isogenic P. aeruginosa strains bearing different combinations of mutS and dinB alleles. Our results demonstrate an unexpected epistatic relationship between mutS and dinB with respect to H2O2-induced cell killing involving error-prone repair and/or tolerance of oxidized DNA lesions. In striking contrast to these error-prone roles, both MutS and DinB played largely accurate roles in coping with DNA lesions induced by ultraviolet light, mitomycin C, or 4-nitroquinilone 1-oxide. Models discussing roles for MutS and DinB functionality in DNA damage-induced mutagenesis, particularly during CF airway colonization and subsequent P. aeruginosa pathoadaptation are discussed

Anisotropy in Oxidation of Zirconium Surfaces from Density Functional Theory Calculations

This work uses density functional theory calculations to analyze the energy barriers for oxygen migration into the basal and prismatic surfaces of zirconium. Specifically, the migration energy barriers between each octahedral site and tetrahedral site in the basal surface, prism surface, and the bulk are determined. The possible oxygen migration paths in each system are also analyzed. Oxygen has higher energy barriers to penetrating the basal surface than the prism surface. It also has a lower energy barrier to escape from basal surface than from the prism surface. This is consistent with the experimental observation that the prism plane of zirconium oxidizes more quickly than the basal plane

Surface structure of (100) and (110) surfaces of ZnO with Density functional theory and atomistic simulation

We have calculated the stability of two of the low-index surfaces known to dominate the morphology of ZnO as a function of stoichiometry. These two surfaces are (100) and (110). In each case, two terminations only are stable for a significant range of oxygen and hydrogen chemical potential: the pure stoichiometric surface and a surface covered in a monolayer of water. The mode by which the water adsorbs is however different for the two surfaces considered. On the (100) surface the close proximity of the water molecules means hydrogen bonding can occur between adjacent chemiabsorbed water molecules and hence there is little difference in the stability of the hydrated and hydroxylated surface, and in fact the most stable surface occurs with a combination of dissociated and undissociated water adsorption. In the case of the (110) surface, it is only when full dissociation has occurred that a hydrogen-bonding network can form. Our results also show good agreement between DFT and atomistic simulations, suggesting that potential based methods can usefully be applied to Zn

First principles study of the stability and the formation kinetics of subsurface and bulk carbon on a Ni catalyst

10.1021/jp711497qJournal of Physical Chemistry C112269679-968