SiC-like phase and room-temperature photoluminescence of low-k SiOCH films

Carbon-doped hydrogenated silicon oxide (SiOCH) low-k films have been prepared using 13.56 MHz discharge in trimethylsilane (3MS) - oxygen gas mixtures at 3, 4, and 5 Torr sustained with RF power densities 1.3 - 2.6 W/cm2. The atomic structure of the SiOCH films appears to be a mixture the amorphous SiO2-like and the partially polycrystalline SiC-like phases. Results of the infra-red spectroscopy reflect the increment in the volume fraction of the SiC-like phase from 0.22 - 0.28 to 0.36 - 0.39 as the RF power increment. Steady-state near-UV laser-excited (364 nm wavelength, 40±2 mW) photoluminescence (PL) has been studied at room temperatures in the visible (1.8 eV - 3.1 eV) subrange of photon spectrum. Two main bands of the PL signal (at the photon energies of 2.5 - 2.6 eV and 2.8 - 2.9 eV) are observed. Intensities of the both bands are changed monotonically with RF power, whereas the bandwidth of ∼0.1 eV remains almost invariable. It is likely that the above lines are dumped by the non-radiative recombination involving E1-like centres in the amorphous-nanocrystalline SiC-like phases. Such explanation of the PL intensity dependences on the RF power density is supported by results of experimental studies of defect states spectrum in bandgap of the SiOCH films.

Nano-scale morphology and electron spectrum of defect states in low-k SiOCH films

Results of experimental investigations on the relationship between nanoscale morphology of carbon doped hydrogenated silicon-oxide (SiOCH) low-k films and their electron spectrum of defect states are presented. The SiOCH films have been deposited using trimethylsilane (3MS) - oxygen mixture in a 13.56 MHz plasma enhanced chemical vapor deposition (PECVD) system at variable RF power densities (from 1.3 to 2.6 W/cm2) and gas pressures of 3, 4, and 5 Torr. The atomic structure of the SiOCH films is a mixture of amorphous-nanocrystalline SiO2-like and SiC-like phases. Results of the FTIR spectroscopy and atomic force microscopy suggest that the volume fraction of the SiC-like phase increases from ∼0.2 to 0.4 with RF power. The average size of the nanoscale surface morphology elements of the SiO2-like matrix can be controlled by the RF power density and source gas flow rates. Electron density of the defect states N(E) of the SiOCH films has been investigated with the DLTS technique in the energy range up to 0.6 eV from the bottom of the conduction band. Distinct N(E) peaks at 0.25 - 0.35 eV and 0.42 - 0.52 eV below the conduction band bottom have been observed. The first N(E) peak is identified as originated from E1-like centers in the SiC-like phase. The volume density of the defects can vary from 1011 - 1017 cm-3 depending on specific conditions of the PECVD process.

Aligning off-balance sheet risk, on-balance sheet risk and audit fees: a PLS path modelling analysis

This study focuses on using the partial least squares (PLS) path modelling methodology in archival auditing research by replicating the data and research questions from prior bank audit fee studies. PLS path modelling allows for inter-correlations among audit fee determinants by establishing latent constructs and multiple relationship paths in one simultaneous PLS path model. Endogeneity concerns about auditor choice can also be addressed with PLS path modelling. With a sample of US bank holding companies for the period 2003-2009, we examine the associations among on-balance sheet financial risks, off-balance sheet risks and audit fees, and also address the pervasive client size effect, and the effect of the self-selection of auditors. The results endorse the dominating effect of size on audit fees, both directly and indirectly via its impacts on other audit fee determinants. By simultaneously considering the self-selection of auditors, we still find audit fee premiums on Big N auditors, which is the second important factor on audit fee determination. On-balance-sheet financial risk measures in terms of capital adequacy, loan composition, earnings and asset quality performance have positive impacts on audit fees. After allowing for the positive influence of on-balance sheet financial risks and entity size on off-balance sheet risk, the off-balance sheet risk measure, SECRISK, is still positively associated with bank audit fees, both before and after the onset of the financial crisis. The consistent results from this study compared with prior literature provide supporting evidence and enhance confidence on the application of this new research technique in archival accounting studies.

A comparative investigation of C6-C15 hydrocarbons emitted from a passenger car powered by unleaded petrol and 10% ethanol fuel

Twenty-three non-methane hydrocarbons were captured from the exhaust of a car operating on unleaded petrol (ULP) and 10% ethanol fuels at steady speed on a chassis dynamometer. The compounds were identified and quantified by GC/MS/FID and their emission concentrations at 60 km/h, 80km/h and idle speed were evaluated. The most abundant compounds in the exhaust included n-hexane, n-heptane, benzene, toluene, ethyl benzene, m- and p-xylenes, and methylcyclopentane. Because of the large number of compounds involved, no attempt was made to compare the emission concentrations of the compounds. Rather the sum of the emission concentrations for the suite of compounds identified was compared when the car was powered by ULP and 10% ethanol fuel. It was evident from the results that the emission concentrations and factors were generally higher with ULP than with 10% ethanol fuel. The total emission concentrations with the ULP fuel were 2.8, 4.2 and 2.6 times the corresponding values for the 10% ethanol fuel at 60km/h, 80km/h and idle speed, respectively. The implications of the results on the environment are discussed in the paper.

Nitrous oxide emissions from fertilized, irrigated cotton (Gossypium hirsutum L.) in the Aral Sea Basin, Uzbekistan : influence of nitrogen applications and irrigation practices

Nitrous oxide emissions were monitored at three sites over a 2-year period in irrigated cotton fields in Khorezm, Uzbekistan, a region located in the arid deserts of the Aral Sea Basin. The fields were managed using different fertilizer management strategies and irrigation water regimes. N2O emissions varied widely between years, within 1 year throughout the vegetation season, and between the sites. The amount of irrigation water applied, the amount and type of N fertilizer used, and topsoil temperature had the greatest effect on these emissions. Very high N2O emissions of up to 3000 μg N2O-N m−2 h−1 were measured in periods following N-fertilizer application in combination with irrigation events. These “emission pulses” accounted for 80–95% of the total N2O emissions between April and September and varied from 0.9 to 6.5 kg N2O-N ha−1.. Emission factors (EF), uncorrected for background emission, ranged from 0.4% to 2.6% of total N applied, corresponding to an average EF of 1.48% of applied N fertilizer lost as N2O-N. This is in line with the default global average value of 1.25% of applied N used in calculations of N2O emissions by the Intergovernmental Panel on Climate Change. During the emission pulses, which were triggered by high soil moisture and high availability of mineral N, a clear diurnal pattern of N2O emissions was observed, driven by daily changes in topsoil temperature. For these periods, air sampling from 8:00 to 10:00 and from 18:00 to 20:00 was found to best represent the mean daily N2O flux rates. The wet topsoil conditions caused by irrigation favored the production of N2O from NO3− fertilizers, but not from NH4+ fertilizers, thus indicating that denitrification was the main process causing N2O emissions. It is therefore argued that there is scope for reducing N2O emission from irrigated cotton production; i.e. through the exclusive use of NH4+ fertilizers. Advanced application and irrigation techniques such as subsurface fertilizer application, drip irrigation and fertigation may also minimize N2O emission from this regionally dominant agro-ecosystem.

Methane and nitrous oxide fluxes in annual and perennial land-use systems of the irrigated areas in the Aral Sea Basin

Land use and agricultural practices can result in important contributions to the global source strength of atmospheric nitrous oxide (N2O) and methane (CH4). However, knowledge of gas flux from irrigated agriculture is very limited. From April 2005 to October 2006, a study was conducted in the Aral Sea Basin, Uzbekistan, to quantify and compare emissions of N2O and CH4 in various annual and perennial land-use systems: irrigated cotton, winter wheat and rice crops, a poplar plantation and a natural Tugai (floodplain) forest. In the annual systems, average N2O emissions ranged from 10 to 150 μg N2O-N m−2 h−1 with highest N2O emissions in the cotton fields, covering a similar range of previous studies from irrigated cropping systems. Emission factors (uncorrected for background emission), used to determine the fertilizer-induced N2O emission as a percentage of N fertilizer applied, ranged from 0.2% to 2.6%. Seasonal variations in N2O emissions were principally controlled by fertilization and irrigation management. Pulses of N2O emissions occurred after concomitant N-fertilizer application and irrigation. The unfertilized poplar plantation showed high N2O emissions over the entire study period (30 μg N2O-N m−2 h−1), whereas only negligible fluxes of N2O (<2 μg N2O-N m−2 h−1) occurred in the Tugai. Significant CH4 fluxes only were determined from the flooded rice field: Fluxes were low with mean flux rates of 32 mg CH4 m−2 day−1 and a low seasonal total of 35.2 kg CH4 ha−1. The global warming potential (GWP) of the N2O and CH4 fluxes was highest under rice and cotton, with seasonal changes between 500 and 3000 kg CO2 eq. ha−1. The biennial cotton–wheat–rice crop rotation commonly practiced in the region would average a GWP of 2500 kg CO2 eq. ha−1 yr−1. The analyses point out opportunities for reducing the GWP of these irrigated agricultural systems by (i) optimization of fertilization and irrigation practices and (ii) conversion of annual cropping systems into perennial forest plantations, especially on less profitable, marginal lands.

Assessment of cone beam CT registration for prostate radiation therapy : fiducial marker and soft tissue methods

Introduction This investigation aimed to assess the consistency and accuracy of radiation therapists (RTs) performing cone beam computed tomography (CBCT) alignment to fiducial markers (FMs) (CBCTFM) and the soft tissue prostate (CBCTST). Methods Six patients receiving prostate radiation therapy underwent daily CBCTs. Manual alignment of CBCTFM and CBCTST was performed by three RTs. Inter-observer agreement was assessed using a modified Bland–Altman analysis for each alignment method. Clinically acceptable 95% limits of agreement with the mean (LoAmean) were defined as ±2.0 mm for CBCTFM and ±3.0 mm for CBCTST. Differences between CBCTST alignment and the observer-averaged CBCTFM (AvCBCTFM) alignment were analysed. Clinically acceptable 95% LoA were defined as ±3.0 mm for the comparison of CBCTST and AvCBCTFM. Results CBCTFM and CBCTST alignments were performed for 185 images. The CBCTFM 95% LoAmean were within ±2.0 mm in all planes. CBCTST 95% LoAmean were within ±3.0 mm in all planes. Comparison of CBCTST with AvCBCTFM resulted in 95% LoA of −4.9 to 2.6, −1.6 to 2.5 and −4.7 to 1.9 mm in the superior–inferior, left–right and anterior–posterior planes, respectively. Conclusions Significant differences were found between soft tissue alignment and the predicted FM position. FMs are useful in reducing inter-observer variability compared with soft tissue alignment. Consideration needs to be given to margin design when using soft tissue matching due to increased inter-observer variability. This study highlights some of the complexities of soft tissue guidance for prostate radiation therapy.

Design and modification of three-component randomly incorporated copolymers for high performance organic photovoltaic applications

In this study we report the molecular design, synthesis, characterization, and photovoltaic properties of a series of diketopyrrolopyrrole (DPP) and dithienothiophene (DTT) based donor-acceptor random copolymers. The six random copolymers are obtained via Stille coupling polymerization using various concentration ratios of donor to acceptor in the conjugated backbone. Bis(trimethylstannyl)thiophene was used as the bridge block to link randomly with the two comonomers 5-(bromothien-2-yl)-2,5-dialkylpyrrolo[3,4-c]pyrrole-1, 4-dione and 2,6-dibromo-3,5-dipentadecyl-dithieno[3,2-b;2′,3′-d] thiophene. The optical properties of these copolymers clearly reveal a change in the absorption band through optimization of the donor-acceptor ratio in the backbone. Additionally, the solution processability of the copolymers is modified through the attachment of different bulky alkyl chains to the lactam N-atoms of the DPP moiety. Applications of the polymers as light-harvesting and electron-donating materials in solar cells, in conjunction with PCBM as acceptor, show power conversion efficiencies (PCEs) of up to 5.02%.

Furan containing diketopyrrolopyrrole copolymers : synthesis, characterization, organic field effect transistor performance and photovoltaic properties

In this work, we report design, synthesis and characterization of solution processable low band gap polymer semiconductors, poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-phenylene} (PDPP-FPF), poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene} (PDPP-FNF) and poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-anthracene} (PDPP-FAF) using the furan-containing 3,6-di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBF) building block. As DBF acts as an acceptor moiety, a series of donor-acceptor (D-A) copolymers can be generated when it is attached alternatively with phenylene, naphthalene or anthracene donor comonomer blocks. Optical and electrochemical characterization of thin films of these polymers reveals band gaps in the range of 1.55-1.64 eV. These polymers exhibit excellent hole mobility when used as the active layer in organic thin-film transistor (OTFT) devices. Among the series, the highest hole mobility of 0.11 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices using PDPP-FNF. When these polymers are used as a donor and [70]PCBM as the acceptor in organic photovoltaic (OPV) devices, power conversion efficiencies (PCE) of 2.5 and 2.6% are obtained for PDPP-FAF and PDPP-FNF polymers, respectively. Such mobility values in OTFTs and performance in OPV make furan-containing DBF a very promising block for designing new polymer semiconductors for a wide range of organic electronic applications.

Longitudinal Assessment of Neuropathy in Diabetes using novel ophthalmic MARKers (LANDMark): Baseline findings

Purpose:Over the past decade, corneal nerve morphology and corneal sensation threshold have been explored as potential surrogate markers for the evaluation of diabetic neuropathy. We present the baseline findings of a Longitudinal Assessment of Neuropathy in Diabetes using novel ophthalmic Markers (LANDMark). Methods:The LANDMark Study is a 5-year, two-site, natural history (observational) study of individuals with Type 1 diabetes stratified into those with (T1W) and without (T1WO) neuropathy according to the Toronto criteria, and control subjects. All study participants undergo detailed annual assessment of neuropathy including corneal nerve parameters measured using corneal confocal microscopy and corneal sensitivity measured using non-contact corneal esthesiometry. Results:396 eligible individuals (208 in Brisbane and 188 in Manchester) were assessed: 76 T1W, 166 T1WO and 154 controls. Corneal sensation threshold (mbars) was significantly higher in T1W (1.0 ± 1.1) than T1WO (0.7 ± 0.7) and controls (0.6 ± 0.4) (P=0.002); post-hoc analysis (PHA) revealed no difference between T1WO and controls (Tukey HSD, P=0.502). Corneal nerve fiber length (mm/mm2) (CNFL) was lower in T1W (13.8 ± 6.4) than T1WO (19.1 ± 5.8) and controls (23.2 ± 6.3) (P<0.001); PHA revealed CNFL to be lower in T1W than T1WO, and lower in both of these groups than controls (P<0.001). Corneal nerve branch density (branches/mm2) (CNBD) was significantly lower in T1W (40 ± 32) than T1WO (62 ± 37) and controls (83 ± 46) (P<0.001); PHA showed CNBD was lower in T1W than T1WO, and lower in both groups than controls (P<0.001). Alcohol and cigarette consumption did not differ between groups, although age, BMI, BP, waist circumference, HbA1c, albumin-creatinine ratio, and cholesterol were slightly greater in T1W than T1WO (p<0.05). Some site differences were observed. Conclusions:The LANDMark baseline findings confirm that corneal sensitivity and corneal nerve morphometry can detect differences in neuropathy status in individuals with Type 1 diabetes and healthy controls. Corneal nerve morphology is significantly abnormal even in diabetic patients ‘without neuropathy’ compared to control participants. Results of the longitudinal trial will assess the capability of these tests for monitoring change in these parameters over time as potential surrogate markers for neuropathy.

Exploring Retinal Markers of Diabetic Neuropathy

Purpose : To investigate the application of retinal nerve fibre layer (RNFL) thickness as a marker for severity of diabetic peripheral neuropathy (DPN) in people with Type 2 diabetes. Methods : This was a cross-sectional study whereby 61 participants (mean age 61 [41-75 years], mean duration of diabetes 14 [1-40 years], 70% male) with Type 2 diabetes and DPN underwent optical coherence tomography (OCT) scans. Global and 4 quadrant (TSNI) RNFL thicknesses were measured at 3.45mm around the optic nerve head of one eye. Neuropathy disability score (NDS) was used to assess the severity of DPN on a 0 to 10 scale. Participants were divided into three age-matched groups representing mild (NDS=3-5), moderate (NDS=6-8) and severe (NDS=9-10) neuropathy. Two regression models were fitted for statistical analysis: 1) NDS scores as co-variate for global and quadrant RNFL thicknesses, 2) NDS groups as a factor for global RNFL thickness only. Results : Mean (SD) RNFL thickness (µm) was 103(9) for mild neuropathy (n=34), 101(10) for moderate neuropathy (n=16) and 95(13) in the group with severe neuropathy (n=11). Global RNFL thickness and NDS scores were statistically significantly related (b=-1.20, p=0.048). When neuropathy was assessed across groups, a trend of thinner mean RNFL thickness was observed with increasing severity of neuropathy; however, this result was not statistically significant (F=2.86, p=0.065). TSNI quadrant analysis showed that mean RNFL thickness reduction in the inferior quadrant was 2.55 µm per 1 unit increase in NDS score (p=0.005). However, the regression coefficients were not statistically significant for RNFL thickness in the superior (b=-1.0, p=0.271), temporal (b=-0.90, p=0.238) and nasal (b=-0.99, p=0.205) quadrants. Conclusions : RNFL thickness was reduced with increasing severity of DPN and the effect was most evident in the inferior quadrant. Measuring RNFL thickness using OCT may prove to be a useful, non-invasive technique for identifying severity of DPN and may also provide additional insight into common mechanisms for peripheral neuropathy and RNFL damage.

Experimental assessment of the effects of sublethal salinities on growth performance and stress in cultured tra catfish (Pangasianodon hypophthalmus)

The effects of a range of different sublethal salinities were assessed on physiological processes and growth performance in the freshwater ‘tra’ catfish (Pangasianodon hypophthalmus) juveniles over an 8-week experiment. Fish were distributed randomly among 6 salinity treatments [2, 6, 10, 14 and 18 g/L of salinity and a control (0 g/L)] with a subsequent 13-day period of acclimation. Low salinity conditions from 2 to 10 g/L provided optimal conditions with high survival and good growth performance, while 0 g/L and salinities[14 g/L gave poorer survival rates (p\0.05). Salinity levels from freshwater to 10 g/L did not have any negative effects on fish weight gain, daily weight gain, or specific growth rate. Food conversion ratio, however, was lowest in the control treatment (p\0.05) and highest at the maximum salinities tested (18 g/L treatment). Cortisol levels were elevated in the 14 and 18 g/L treatments after 6 h and reached a peak after 24-h exposure, and this also led to increases in plasma glucose concentration. After 14 days, surviving fish in all treatments appeared to have acclimated to their respective conditions with cortisol levels remaining under 5 ng/ mL with glucose concentrations stable. Tra catfish do not appear to be efficient osmoregulators when salinity levels exceed 10 g/L, and at raised salinity levels, growth performance is compromised. In general, results of this study confirm that providing culture environments in the Mekong River Basin do not exceed 10 g/L salinity and that cultured tra catfish can continue to perform well.

Efficiently capturing large, complex cultural heritage sites with a handheld mobile 3D laser mapping system

Accurate three-dimensional representations of cultural heritage sites are highly valuable for scientific study, conservation, and educational purposes. In addition to their use for archival purposes, 3D models enable efficient and precise measurement of relevant natural and architectural features. Many cultural heritage sites are large and complex, consisting of multiple structures spatially distributed over tens of thousands of square metres. The process of effectively digitising such geometrically complex locations requires measurements to be acquired from a variety of viewpoints. While several technologies exist for capturing the 3D structure of objects and environments, none are ideally suited to complex, large-scale sites, mainly due to their limited coverage or acquisition efficiency. We explore the use of a recently developed handheld mobile mapping system called Zebedee in cultural heritage applications. The Zebedee system is capable of efficiently mapping an environment in three dimensions by continually acquiring data as an operator holding the device traverses through the site. The system was deployed at the former Peel Island Lazaret, a culturally significant site in Queensland, Australia, consisting of dozens of buildings of various sizes spread across an area of approximately 400 × 250 m. With the Zebedee system, the site was scanned in half a day, and a detailed 3D point cloud model (with over 520 million points) was generated from the 3.6 hours of acquired data in 2.6 hours. We present results demonstrating that Zebedee was able to accurately capture both site context and building detail comparable in accuracy to manual measurement techniques, and at a greatly increased level of efficiency and scope. The scan allowed us to record derelict buildings that previously could not be measured because of the scale and complexity of the site. The resulting 3D model captures both interior and exterior features of buildings, including structure, materials, and the contents of rooms.

Metal artifacts from titanium and steel screws in CT, 1.5T and 3T MR images of the tibial Pilon: A quantitative assessment in 3D

Radiographs are commonly used to assess articular reduction of the distal tibia (pilon) fractures postoperatively, but may reveal malreductions inaccurately. While Magnetic Resonance Imaging (MRI) and Computed Tomography (CT) are potential 3D alternatives they generate metal-related artifacts. This study aims to quantify the artifact size from orthopaedic screws using CT, 1.5T and 3T MRI data. Three screws were inserted into one intact human cadaver ankle specimen proximal to and along the distal articular surface, then CT, 1.5T and 3T MRI scanned. Four types of screws were investigated: titanium alloy (TA), stainless steel (SS) (Ø = 3.5 mm), cannulated TA (CTA) and cannulated SS (CSS)(Ø = 4.0 mm, Ø empty core = 2.6 mm). 3D artifact models were reconstructed using adaptive thresholding. The artifact size was measured by calculating the perpendicular distance from the central screw axis to the boundary of the artifact in four anatomical directions with respect to the distal tibia. The artifact sizes (in the order of TA, SS, CTA and CSS) from CT were 2.0 mm, 2.6 mm, 1.6 mm and 2.0 mm; from 1.5T MRI they were 3.7 mm, 10.9 mm, 2.9 mm, and 9 mm; and 3T MRI they were 4.4 mm, 15.3 mm, 3.8 mm, and 11.6 mm respectively. Therefore, CT can be used as long as the screws are at a safe distance of about 2 mm from the articular surface. MRI can be used if the screws are at least 3 mm away from the articular surface except SS and CSS. Artifacts from steel screws were too large thus obstructed the pilon from being visualised in MRI. Significant differences (P < 0.05) were found in the size of artifacts between all imaging modalities, screw types and material types, except 1.5T versus 3T MRI for the SS screws (P = 0.063). CTA screws near the joint surface can improve postoperative assessment in CT and MRI. MRI presents a favourable non-ionising alternative when using titanium hardware. Since these factors may influence the quality of postoperative assessment, potential improvements in operative techniques should be considered.

Expression and crystallization of SeDsbA, SeDsbL and SeSrgA from Salmonella enterica serovar Typhimurium

Pathogens require protein-folding enzymes to produce functional virulence determinants. These foldases include the Dsb family of proteins, which catalyze oxidative folding in bacteria. Bacterial disulfide catalytic processes have been well characterized in Escherichia coli K-12 and these mechanisms have been extrapolated to other organisms. However, recent research indicates that the K-12 complement of Dsb proteins is not common to all bacteria. Importantly, many pathogenic bacteria have an extended arsenal of Dsb catalysts that is linked to their virulence. To help to elucidate the process of oxidative folding in pathogens containing a wide repertoire of Dsb proteins, Salmonella enterica serovar Typhimurium has been focused on. This Gram-negative bacterium contains three DsbA proteins: SeDsbA, SeDsbL and SeSrgA. Here, the expression, purification, crystallization and preliminary diffraction analysis of these three proteins are reported. SeDsbA, SeDsbL and SeSrgA crystals diffracted to resolution limits of 1.55, 1.57 and 2.6 Å and belonged to space groups P21, P21212 and C2, respectively.