Composition-Dependent Structural and Transport Properties of Amorphous Transparent Conducting Oxides

Structural properties of amorphous In-based oxides, In-X-O with X=Zn, Ga, Sn, or Ge, are investigated using ab initio molecular dynamics liquid-quench simulations. The results reveal that indium retains its average coordination of 5.0 upon 20% X fractional substitution for In, whereas X cations satisfy their natural coordination with oxygen atoms. This finding suggests that the carrier generation is primarily governed by In atoms, in accord with the observed carrier concentration in amorphous In-O and In-X-O. At the same time, the presence of X affects the number of six-coordinated In atoms as well as the oxygen sharing between the InO6 polyhedra. Based on the obtained interconnectivity and spatial distribution of the InO6 and XOx polyhedra in amorphous In-X-O, composition-dependent structural models of the amorphous oxides are derived. The results help explain our Hall mobility measurements in In-X-O thin films grown by pulsed-laser deposition and highlight the importance of long-range structural correlations in the formation of amorphous oxides and their transport properties

Post-Kala-azar Dermal Leishmaniasis in Nepal: A Retrospective Cohort Study (2000–2010)

Post-kala-azar dermal leishmaniasis (PKDL) is a skin disorder seen in patients treated for Leishmania donovani visceral leishmaniasis (VL), a neglected tropical disease that is fatal if left untreated. In the Indian subcontinent, PKDL is seen in 5–10% of all past VL cases and is also reported in some without history of VL. As persons with PKDL do not feel sick, the disease has only cosmetic significance for the individual and treatment is rarely sought. However, PKDL lesions harbour parasites and therefore could represent a source of transmission, through the bite of female sand flies. Our study shows that the occurrence of PKDL in patients with past treated VL is low in Nepal compared to neighboring countries. Treatment of the original VL episode with SSG (sodium stibogluconate), inadequate treatment and treatment on ambulatory basis were significantly associated with PKDL. Though SSG has since been replaced by other drugs, counseling and supervision of adherence to the prescribed VL treatment is of vital importance to reduce risk of treatment failure and relapse as well as later development of PKDL. Policy makers should include surveillance and case management of PKDL in the VL elimination program

Properties of Amorphous Transparent Conducting and Semiconducting Oxides from First Principles

Amorphous transparent conducting and semiconducting oxides possess properties superior or comparable to their crystalline counterparts. The structure-property relationship in amorphous oxides is not nearly as well understood as in the case of the crystalline transparent conducting oxides. We have employedab initio molecular dynamics and a liquid quench approach to simulate amorphous oxide structures and performed density functional-based calculations to study the electronic properties of several amorphous conducting and semiconducting oxides with various cation compositions. The effect of amorphization in oxides was investigated by taking indium oxide as a progenitor of the system. From the thorough study it was confirmed that the distribution and connectivity of naturally coordinated indium polyhedra (InO6) depend on the cooling rates used in the quenching process. Also, it was shown experimentally that the transport properties depend strongly on the deposition temperature, in particular, the carrier Hall mobility is enhanced at the onset of the amorphous region to become similar to the mobility in crystalline In2O3. Our results have shown that the corresponding amorphous structure exhibits a long chain of the InO6 connected primarily via corner sharing, thus, highlighting the importance of the medium/long-range structural characteristics. To understand the effect of chemical composition on the structure and properties of amorphous oxides, In-X-O with X=Sn, Zn, Ga, Cd, Ge, Sc, Y, or La, were studied. The results reveal that the short-range structure of the metal-O polyhedra is preserved in the amorphous oxides; therefore, the extended nature of the conduction band, the key feature of transparent conducting oxide, is maintained. Unlike the case of crystalline transparent oxides, additional cation in amorphous oxides does not act as a dopant. Instead, the presence of X affects the number of naturally coordinated In atoms as well as the oxygen sharing between metal-oxygen polyhedra which ultimately affects the transport properties --Abstract, page iv

Long-Range Structural Correlations in Amorphous Ternary In-based Oxides

Systematic investigations of ternary In-based amorphous oxides, In–X–O with X = Sn, Zn, Ga, Cd, Ge, Sc, Y, or La, are performed using ab-initio molecular-dynamics liquid-quench simulations. The results reveal that the local M–O structure remains nearly intact upon crystalline to amorphous transition and exhibit weak dependence on the composition. In marked contrast, the structural characteristics of the metal–metal shell, namely, the M–M distances and M–O–M angles that determine how MO polyhedra are connected into a network, are affected by the presence of X. Complex interplay between several factors such as the cation ionic size, metal–oxygen bond strength, as well as the natural preference for edge, corner, or face-sharing between the MO polyhedra, leads to a correlated behavior in the long-range structure. These findings highlight the mechanisms of the amorphous structure formation as well as the specifics of the carrier transport in these oxides

Role of Chemistry and Crystal Structure on the Electronic Defect States in Cs-Based Halide Perovskites

The electronic structure of a series perovskites ABX3 (A = Cs; B = Ca, Sr, and Ba; X = F, Cl, Br, and I) in the presence and absence of antisite defect XB were systematically investigated based on density-functional-theory calculations. Both cubic and orthorhombic perovskites were considered. It was observed that for certain perovskite compositions and crystal structure, presence of antisite point defect leads to the formation of electronic defect state(s) within the band gap. We showed that both the type of electronic defect states and their individual energy level location within the bandgap can be predicted based on easily available intrinsic properties of the constituent elements, such as the bond-dissociation energy of the B–X and X–X bond, the X–X covalent bond length, and the atomic size of halide (X) as well as structural characteristic such as B–X–B bond angle. Overall, this work provides a science-based generic principle to design the electronic states within the band structure in Cs-based perovskites in presence of point defects such as antisite defect

Investigations on the electronic properties and effect of chitosan capping on the structural and optical properties of zinc aluminate quantum dots

Quantum confined uncapped and chitosan capped nanoparticles of ZnAl2O4 synthesized by microwave-assisted sol–gel method were investigated by structural analysis and optical techniques. X-ray diffraction studies confirmed the formation of cubic spinels with crystallite size 4.5 nm and 3.4 nm, respectively for uncapped and chitosan capped ZnAl2O4 nanoparticles. Chitosan capping produced a blue shift in bandgap energy (3.84 to 3.94 eV) agreeing with size effects according to the Brus equation. A blue shift in emission peak and enhancement in photoluminescence intensity was also observed upon chitosan capping. The electronic band structure and the density of states of the bulk spinel were also calculated using density functional theory. The effective masses of electrons and holes estimated based on the band structure were used to extract the excitonic Bohr radius

Cation Size Effects on the Electronic and Structural Properties of Solution-Processed In-X-O Thin Films

The nature of charge transport and local structure are investigated in amorphous indium oxide-based thin films fabricated by spin-coating. The In-X-O series where X = Sc, Y, or La is investigated to understand the effects of varying both the X cation ionic radius (0.89-1.17 Å) and the film processing temperature (250-300 °C). Larger cations in particular are found to be very effective amorphosizers and enable the study of high mobility (up to 9.7 cm2 V-1 s-1) amorphous oxide semiconductors without complex processing. Electron mobilities as a function of temperature and gate voltage are measured in thin-film transistors, while X-ray absorption spectroscopy and ab initio molecular dynamics simulations are used to probe local atomic structure. It is found that trap-limited conduction and percolation-type conduction mechanisms convincingly model transport for low- and high-temperature processed films, respectively. Increased cation size leads to increased broadening of the tail states (10-23 meV) and increased percolation barrier heights (24-55 meV) in the two cases. For the first time in the amorphous In-X-O system, such effects can be explained by local structural changes in the films, including decreased In-O and In-M (M = In, X) coordination numbers, increased bond length disorder, and changes in the MO x polyhedra interconnectivity

Selective Crystal Growth and Structural, Optical, and Electronic Studies of Mn₃Ta₂O₈

Mn3Ta2O8, a stable targeted material with an unusual and complex cation topology in the complicated Mn-Ta-O phase space, has been grown as a ≈3-cm-long single crystal via the optical floating-zone technique. Single-crystal absorbance studies determine the band gap as 1.89 eV, which agrees with the value obtained from density functional theory electronic-band-structure calculations. The valence band consists of the hybridized Mn d-O p states, whereas the bottom of the conduction band is formed by the Ta d states. Furthermore, out of the three crystallographically distinct Mn atoms that are four-, seven-, or eight-coordinate, only the former two contribute their states near the top of the valence band and hence govern the electronic transitions across the band gap. (Graph Presented)