Disorder induced band gap lowering in kesterite type Cu2ZnSnSe4and Ag2ZnSnSe4: a first-principles and special quasirandom structures investigation.

Quaternary chalcogenides, i.e. Cu2ZnSnS4, crystallising in the kesterite crystal structure have already been demonstrated as potential building blocks of thin film solar cells, containing only abundant elements and exhibiting power conversion efficiencies of about 14.9% so far. However, due to the potential presence of several structurally similar polymorphs, the unequivocal identification of their ground state crystal structures required the application of more elaborate neutron diffraction experiments. One particular complication arose from the later identified Cu-Zn disorder, present in virtually all thin film samples. Subsequently, it has been shown experimentally that this unavoidable Cu-Zn disorder leads to a band gap lowering in the respective samples. Additional theoretical investigations, mostly based on Monte-Carlo methods, tried to understand the atomistic origin of this disorder induced band gap lowering. Here, we present theoretical results from first-principles calculations based on density functional theory for the disorder induced band gap lowering in kesterite Cu2ZnSnSe4and Ag2ZnSnSe4, where the Cu-Zn and Ag-Zn disorder is modelled via a supercell approach and special quasirandom structures. Results of subsequent analyses of structural, electronic, and optical properties are discussed with respect to available experimental results, and will provide additional insight and knowledge towards the atomistic origin of the observed disorder induced band gap lowering in kesterite type materials.

Elucidation of the reaction mechanism for the synthesis of ZnGeN2 through Zn2GeO4 ammonolysis.

Ternary II-IV-N2 materials have been considered as a promising class of materials that combine photovoltaic performance with earth-abundance and low toxicity. When switching from binary III-V materials to ternary II-IV-N2 materials, further structural complexity is added to the system that may influence its optoelectronic properties. Herein, we present a systematic study of the reaction of Zn2GeO4 with NH3 that produces zinc germanium oxide nitrides, and ultimately approach stoichiometric ZnGeN2, using a combination of chemical analyses, X-ray powder diffraction and DFT calculations. Elucidating the reaction mechanism as being dominated by Zn and O extrusion at the later reaction stages, we give an insight into studying structure-property relationships in this emerging class of materials.

Electronic and optical properties of spinel zinc ferrite: ab initio hybrid functional calculations.

Spinel ferrites in general show a rich interplay of structural, electronic, and magnetic properties. Here, we particularly focus on zinc ferrite (ZFO), which has been observed experimentally to crystallise in the cubic normal spinel structure. However, its magnetic ground state is still under dispute. In addition, some unusual magnetic properties in ZFO thin films or nanostructures have been explained by a possible partial cation inversion and a different magnetic interaction between the two cation sublattices of the spinel structure compared to the crystalline bulk material. Here, density functional theory has been applied to investigate the influence of different inversion degrees and magnetic couplings among the cation sublattices on the structural, electronic, magnetic, and optical properties. Effects of exchange and correlation have been modelled using the generalised gradient approximation (GGA) together with the Hubbard '+U' parameter, and the more elaborate hybrid functional PBE0. While the GGA+U calculations yield an antiferromagnetically coupled normal spinel structure as the ground state, in the PBE0 calculations the ferromagnetically coupled normal spinel is energetically slightly favoured, and the hybrid functional calculations perform much better with respect to structural, electronic and optical properties.

Self-Consistent Hybrid Functional Calculations: Implications for Structural, Electronic, and Optical Properties of Oxide Semiconductors.

The development of new exchange-correlation functionals within density functional theory means that increasingly accurate information is accessible at moderate computational cost. Recently, a newly developed self-consistent hybrid functional has been proposed (Skone et al., Phys. Rev. B 89:195112, 2014), which allows for a reliable and accurate calculation of material properties using a fully ab initio procedure. Here, we apply this new functional to wurtzite ZnO, rutile SnO2, and rocksalt MgO. We present calculated structural, electronic, and optical properties, which we compare to results obtained with the PBE and PBE0 functionals. For all semiconductors considered here, the self-consistent hybrid approach gives improved agreement with experimental structural data relative to the PBE0 hybrid functional for a moderate increase in computational cost, while avoiding the empiricism common to conventional hybrid functionals. The electronic properties are improved for ZnO and MgO, whereas for SnO2 the PBE0 hybrid functional gives the best agreement with experimental data.

Acyclic sesquiterpenes released by Candida albicans inhibit growth of dermatophytes.

It is unresolved as to whether fungi that share a common skin habitat might in principal interact. In in vitro screening tests with Candida albicans, Trichophytum rubrum and other common dermatophytes, we found C. albicans releases volatile compounds that inhibit growth of the dermatophytes. By applying (enantioselective) gas chromatography combined with mass spectrometry we identified 8 compounds among which stereochemically pure (3R,6E)-2,3-dihydrofarnesol (R-DHF) and (2E,6E)-farnesol (F-ol) were the main components. Synthetic R-DHF and its enantiomer, (3S,6E)-2,3-dihydrofarnesol (S-DHF), as well as F-ol were tested for their capacity to inhibit growth of dermatophytes in microtiter-plate assays over 62 h. All three compounds showed significant and concentration-dependent, to a certain extent even species-specific, inhibitory effects on T. rubrum, T. mentagrophytes, Microsporum canis and Epidermophyton floccosum. In general, S-DHF and F-ol had a pronounced effect on the dermatophytes, similar to or even stronger than that of fluconazole. E. floccosum was completely suppressed by 12.5 µg/ml dihydrofarnesol, as was the inhibition caused by 50 µg/ml fluconazole. Similarly, S-DHF- was more active against T. rubrum than fluconazole. To the best of our knowledge, 2,3-dihydrofarnesol has not yet been described as a volatile generated by microorganisms, and its inhibitory effect on dermatophytes is new to science. However, the relevance of this compound in interfungal interference in situ is unknown. In contrast, farnesol is a well-known semiochemical of C. albicans with intraspecific effects and a clear impact on other microorganisms. Mutual intermicrobial communication based on fungal volatiles therefore appears to be an exciting field for future investigations.

Osteoclastic bioresorption of biomaterials: two- and three-dimensional imaging and quantification.

PURPOSE: Bioresorbable materials have been developed in the hope that the body will replace them with newly formed tissue. The first step of this remodeling process in bone is the bioresorption of the material by osteoclasts. The aim of this study was to analyze osteoclastic resorption of biomaterials in vitro using the commonly used two-dimensional methods of light-microscopy (LM) and scanning electron microscopy (SEM) in comparison with infinite focus microscopy (IFM), a recently developed imaging method allowing for three-dimensional surface analysis. METHODS: Human hematopoietic stem cells were cultivated in the presence of the cytokines M-CSF and RANK-L for 4 weeks directly on dentin and a calcium phosphate cement. Osteoclast development was surveyed with standard techniques. After removal of the cells, resorption was characterized and quantified by LM, SEM and IFM. RESULTS: Osteoclast cultures on the biomaterials presented the typical osteoclast-specific markers. On dentin samples LM, SEM as well as IFM allowed for discrimination of resorption. Quantification of the resorbed area showed a linear correlation between the results (LM vs. SEM: r=0.996, p=0.004; SEM vs. IFM: r=0.989, p=0.011; IFM vs. LM: r=0.995). It was not possible to demarcate resorption pits on GB14 using LM or SEM. With IFM, resorption on GB14 could be visualized and quantified two- and three-dimensionally. CONCLUSIONS: In this paper we introduce IFM as a technology for three-dimensional visualization and quantification of resorption of biomaterials. Better understanding of the bioresorption of biomaterials may help in the design of better materials and might therefore constitute an important step on the avenue to the development of artificial bone.

Co dimers on hexagonal carbon rings proposed as subnanometer magnetic storage bits.

It is demonstrated by means of density functional and ab initio quantum chemical calculations, that transition-metal-carbon systems have the potential to enhance the presently available area density of magnetic recording by 3 orders of magnitude. As a model system, Co2 benzene with a diameter of 0.5 nm is investigated. It shows a magnetic anisotropy of the order of 0.1 eV per molecule, large enough to store permanently 1 bit of information at temperatures considerably larger than 4 K. A similar performance can be expected, if cobalt dimers are deposited on graphene or on graphite.

Transition metal dimers as potential molecular magnets: A challenge to computational chemistry.

Dimers are the smallest chemical objects that show magnetic anisotropy. We focus on 3d and 4d transition metal dimers that have magnetic ground states in most cases. Some of these magnetic dimers have a considerable barrier against re-orientation of their magnetization, the so-called magnetic anisotropy energy, MAE. The height of this barrier is important for technological applications, as it determines, e.g., the stability of information stored in magnetic memory devices. It can be estimated by means of relativistic density functional calculations. Our approach is based on a full-potential local-orbital method (FPLO) in a four-component Dirac-Kohn-Sham implementation. Orbital polarization corrections to the local density approximation are employed. They are discussed in the broader context of orbital dependent density functionals. Ground state properties (spin multiplicity, bond length, harmonic vibrational frequency, spin- and orbital magnetic moment, and MAE) of the 3d and 4d transition metal dimers are evaluated and compared with available experimental and theoretical data. We find exceptionally high values of MAE, close to 0.2 eV, for four particular dimers: Fe(2), Co(2), Ni(2), and Rh(2).

In vitro generation of cartilage-carrier-constructs on hydroxylapatite ceramics with different surface structures.

Tissue engineering approaches for healing cartilage defects are partly limited by the inability to fix cartilage to bone during implantation. To overcome this problem, cartilage can be - already in vitro - generated on a ceramic carrier which serves as bone substitute. In this study, the influence of a hydroxylapatite carrier and its surface structure on the quality of tissue engineered cartilage was investigated. Application of the carrier reduced significantly biomechanical and biochemical properties of the generated tissue. In addition, slight changes in the quality of the formed matrix, in the adhesive strength between cartilage and biomaterial and in attachment and proliferation of a chondrocyte monolayer could be observed for commercial grade carriers, with respect to modified topographies obtained by smooth grinding/polishing. These first results demonstrated an influence of the carrier and its surface structure, but further research is needed for explaining the described effects and for optimization of cartilage-carrier-constructs.

Deformable M-Reps for 3D Medical Image Segmentation.

M-reps (formerly called DSLs) are a multiscale medial means for modeling and rendering 3D solid geometry. They are particularly well suited to model anatomic objects and in particular to capture prior geometric information effectively in deformable models segmentation approaches. The representation is based on figural models, which define objects at coarse scale by a hierarchy of figures - each figure generally a slab representing a solid region and its boundary simultaneously. This paper focuses on the use of single figure models to segment objects of relatively simple structure. A single figure is a sheet of medial atoms, which is interpolated from the model formed by a net, i.e., a mesh or chain, of medial atoms (hence the name m-reps), each atom modeling a solid region via not only a position and a width but also a local figural frame giving figural directions and an object angle between opposing, corresponding positions on the boundary implied by the m-rep. The special capability of an m-rep is to provide spatial and orientational correspondence between an object in two different states of deformation. This ability is central to effective measurement of both geometric typicality and geometry to image match, the two terms of the objective function optimized in segmentation by deformable models. The other ability of m-reps central to effective segmentation is their ability to support segmentation at multiple levels of scale, with successively finer precision. Objects modeled by single figures are segmented first by a similarity transform augmented by object elongation, then by adjustment of each medial atom, and finally by displacing a dense sampling of the m-rep implied boundary. While these models and approaches also exist in 2D, we focus on 3D objects. The segmentation of the kidney from CT and the hippocampus from MRI serve as the major examples in this paper. The accuracy of segmentation as compared to manual, slice-by-slice segmentation is reported.