Variability of Cu 2 ZnSnS 4 nanoparticle hot injection synthesis and modifications by thin film annealing

As a quaternary semiconductor with a direct energy bandgap of around 1.4 eV, Cu2ZnSnS4 is a promising candidate for absorber layers in next generation thin-film solar PV devices. It has the advantage of being based on low cost earth-abundant elements. Solution based synthesis approaches show the greatest potential for scaling up manufacture. Cu2ZnSnS4 devices are currently limited in efficiency because of a large open circuit voltage deficit, arising predominantly from high concentrations of point defects and charge compensation defect complexes. To drive device efficiency robust, reliable and reproducible synthesis protocols are required. We have produced a series of Cu2ZnSnS4 thin films by spin coating nanoparticle ink suspensions fabricated under nominally identical conditions to investigate the inherent variability in hot injection synthesis of Cu2ZnSnS4 nanoparticles by fabricating 11 batches using the same initial conditions. We use two different chemical routes to extratct nanoparticles from solution after synthesis. We find that the lattice constants of the nanocrystalline material do not change significantly. The relative concentration of the constituent elements varies with S having the largest anion variation of ±3.8% as compared to metal cation variations of Zn ±2.4%, Cu ±1.8%, and Sn ±1.4% with Zn having the largest cation variation. We compare data from energy dispersive X-ray (EDX) and inductively coupled plasma mass spectroscopy (ICPMS) chemical analysis methods and find that the ICPMS analysis has a consistently smaller standard deviation, an average of 0.1 lower, as this technique samples a large volume of material. We observe variation in the kesterite tetragonal lattice constants a and c, and energy bandgap Eg across the different samples, although there is no systematic change in the chemical composition. The average bandgap of as-synthesised films is 1.14 eV. We find that annealing in a sulphur rich environment has no systematic impact on the Cu/(Zn + Sn) cation ratio and leads to a decrease of −0.4 in the Zn/Sn ratio. At higher annealing temperatures, 500–600 °C, the bandgap shows a linear increase of +0.15 eV accompanied by the formation of abnormal grains and an increase in the size of the crystalline scattering domain τ, determined from the X-ray spectra, from 30–100 nm. The most dramatic changes occur in the first 0.5 hours of annealing. These findings will help in the design of fabrication strategies for higher efficiency Cu2ZnSnS4 photovoltaic devices

Rearrangement of secondary flow over spanwise heterogeneous roughness

Turbulent flow over a surface with streamwise-elongated rough and smooth stripes is studied by means of direct numerical simulation (DNS) in a periodic plane open channel with fully resolved roughness. The goal is to understand how the mean height of roughness affects the characteristics of the secondary flow formed above a spanwise heterogeneous rough surface. To this end, while the statistical properties of roughness texture as well as the width and spacing of the rough stripes are kept constant, the elevation of the smooth stripes is systematically varied in different simulation cases. Utilizing this variation, three configurations – representing protruding, recessed and an intermediate type of roughness – are analysed. In all cases, secondary flows are present and the skin friction coefficients calculated for all the heterogeneous rough surfaces are meaningfully larger than what would result from the area-weighted average of those of homogeneous smooth and rough surfaces. This drag increase appears to be linked to the strength of the secondary flow. The rotational direction of the secondary motion is shown to depend on the relative surface elevation. The present results suggest that this rearrangement of the secondary flow is linked to the spatial distribution of the spanwise-wall-normal Reynolds stress component, which carries opposing signs for protruding and recessed roughness

Modelling spanwise heterogeneous roughness through a parametric forcing approach

Inhomogeneous rough surfaces in which strips of roughness alternate with smooth-wall strips are known to generate large-scale secondary motions. Those secondary motions are strongest if the strip width is of the order of the half-channel height and they generate a spatial wall shear stress distribution whose mean value can significantly exceed the area-averaged mean value of a homogeneously smooth and rough surface. In the present paper it is shown that a parametric forcing approach (Busse & Sandham, J. Fluid Mech., vol. 712, 2012, pp. 169–202; Forooghi et al., Intl J. Heat Fluid Flow, vol. 71, 2018, pp. 200–209), calibrated with data from turbulent channel flows over homogeneous roughness, can capture the topological features of the secondary motion over protruding and recessed roughness strips (Stroh et al., J. Fluid Mech., vol. 885, 2020, R5). However, the results suggest that the parametric forcing approach roughness model induces a slightly larger wall offset when applied to the present heterogeneous rough-wall conditions. Contrary to roughness-resolving simulations, where a significantly higher resolution is required to capture roughness geometry, the parametric forcing approach can be applied with usual smooth-wall direct numerical simulation resolution resulting in less computationally expensive simulations for the study of localized roughness effects. Such roughness model simulations are employed to systematically investigate the effect of the relative roughness protrusion on the physical mechanism of secondary flow formation and the related drag increase. It is found that strong secondary motions present over spanwise heterogeneous roughness with geometrical height difference generally lead to a drag increase. However, the physical mechanism guiding the secondary flow formation, and the resulting secondary flow topology, is different for protruding roughness strips and recessed roughness strips separated by protruding smooth surface strips

A New Point of View on Skin-Friction Contributions in Adverse-Pressure-gradient Turbulent Boundary Layers

Skin-friction decompositions such as the so-called FIK identity (Fukagata et al., 2002) are useful tools in identifying relevant contributions to the friction, but may also lead to results difficult to interpret when the total friction is recovered from cancellation of multiple terms with large values. We propose a new formulation of the FIK contributions related to streamwise inhomogeneity, which is derived from the convective form of the momentum equation and using the concept of dynamic pressure. We examine turbulent boundary layers subjected to various pressure-gradient conditions, including cases with drag-reducing control. The new formulation distinguishes more precisely the roles of the free-stream pressure distribution, wall-normal convection, and turbulent fluctuations. Our results allow to identify different regimes in adverse-pressure-gradient turbulent boundary layers, corresponding to different proportions of the various contributions, and suggest a possible direction towards studying the onset of mean separation

Screw dislocation in zirconium: An ab initio study

Plasticity in zirconium is controlled by 1/3 screw dislocations gliding in the prism planes of the hexagonal close-packed structure. This prismatic and not basal glide is observed for a given set of transition metals like zirconium and is known to be related to the number of valence electrons in the d band. We use ab initio calculations based on the density functional theory to study the core structure of screw dislocations in zirconium. Dislocations are found to dissociate in the prism plane in two partial dislocations, each with a pure screw character. Ab initio calculations also show that the dissociation in the basal plane is unstable. We calculate then the Peierls barrier for a screw dislocation gliding in the prism plane and obtain a small barrier. The Peierls stress deduced from this barrier is lower than 21 MPa, which is in agreement with experimental data. The ability of an empirical potential relying on the embedded atom method (EAM) to model dislocations in zirconium is also tested against these ab initio calculations

Secondary flow impact on velocity and thermal fields of a structured turbulent channel flow

Surface structuring in form of streamwise elongated triangular ridges is investigated in a framework of a fully developed turbulent channel flow at Reb = 18000. The ridges generate a strong large-scale secondary motion and hence alter momentum and heat transfer in the channel. A comparison of the obtained skin friction and heat transfer coefficients reveals a 30% enhancement for both quantities relatively to the smooth channel. Tripe decomposition analysis of the total stress and heat flux results in an observation of different mechanisms behind this enhancements: while the skin friction coefficient is mainly increased by the secondary-motion-related contribution, the heat flux is similarly enhanced by the secondary motion and modification of turbulent properties of the flow

Filamentary structure in chemical tracer distributions near the subtropical jet following a wave breaking event

This paper presents a set of observations and analyses of trace gas cross sections in the extratropical upper troposphere/lower stratosphere (UTLS). The spatially highly resolved (&approx;0.5 km vertically and 12.5 km horizontally) cross sections of ozone (O₃), nitric acid (HNO₃), and peroxyacetyl nitrate (PAN), retrieved from the measurements of the CRISTA-NF infrared limb sounder flown on the Russian M55-Geophysica, revealed intricate layer structures in the region of the subtropical tropopause break. The chemical structure in this region shows an intertwined stratosphere and troposphere. The observed filaments in all discussed trace gases are of a spatial scale of less than 0.8 km vertically and about 200 km horizontally across the jet stream. Backward trajectory calculations confirm that the observed filaments are the result of a breaking Rossby wave in the preceding days. An analysis of the trace gas relationships between PAN and O₃ identifies four distinct groups of air mass: polluted subtropical tropospheric air, clean tropical upper-tropospheric air, the lowermost stratospheric air, and air from the deep stratosphere. The tracer relationships further allow the identification of tropospheric, stratospheric, and the transitional air mass made of a mixture of UT and LS air. Mapping of these air mass types onto the geo-spatial location in the cross sections reveals a highly structured extratropical transition layer (ExTL). Finally, the ratio between the measured reactive nitrogen species (HNO₃ + PAN + ClONO₂) and O₃ is analysed to estimate the influence of tropospheric pollution on the extratropical UTLS. <br><br> In combination, these diagnostics provide the first example of a multi-species two-dimensional picture of the inhomogeneous distribution of chemical species within the UTLS region. Since Rossby wave breaking occurs frequently in the region of the tropopause break, these observed fine-scale filaments are likely ubiquitous in the region. The implications of the layered structure for chemistry and radiation need to be examined, and the representation of this structure in chemistry-climate models is discussed

Nonequilibrium brittle fracture propagation: Steady state, oscillations and intermittency

A minimal model is constructed for two-dimensional fracture propagation. The heterogeneous process zone is presumed to suppress stress relaxation rate, leading to non-quasistatic behavior. Using the Yoffe solution, I construct and solve a dynamical equation for the tip stress. I discuss a generic tip velocity response to local stress and find that noise-free propagation is either at steady state or oscillatory, depending only on one material parameter. Noise gives rise to intermittency and quasi-periodicity. The theory explains the velocity oscillations and the complicated behavior seen in polymeric and amorphous brittle materials. I suggest experimental verifications and new connections between velocity measurements and material properties.Comment: To appear in Phys. Rev. Lett., 6 pages, self-contained TeX file, 3 postscript figures upon request from author at [email protected] or [email protected], http://cnls-www.lanl.gov/homepages/rafi/rafindex.htm

Iatrogenic Spinal Cord Injury Resulting From Cervical Spine Surgery.

STUDY DESIGN: Retrospective cohort study of prospectively collected data. OBJECTIVE: To examine the incidence of iatrogenic spinal cord injury following elective cervical spine surgery. METHODS: A retrospective multicenter case series study involving 21 high-volume surgical centers from the AOSpine North America Clinical Research Network was conducted. Medical records for 17 625 patients who received cervical spine surgery (levels from C2 to C7) between January 1, 2005, and December 31, 2011, were reviewed to identify occurrence of iatrogenic spinal cord injury. RESULTS: In total, 3 cases of iatrogenic spinal cord injury following cervical spine surgery were identified. Institutional incidence rates ranged from 0.0% to 0.24%. Of the 3 patients with quadriplegia, one underwent anterior-only surgery with 2-level cervical corpectomy, one underwent anterior surgery with corpectomy in addition to posterior surgery, and one underwent posterior decompression and fusion surgery alone. One patient had complete neurologic recovery, one partially recovered, and one did not recover motor function. CONCLUSION: Iatrogenic spinal cord injury following cervical spine surgery is a rare and devastating adverse event. No standard protocol exists that can guarantee prevention of this complication, and there is a lack of consensus regarding evaluation and treatment when it does occur. Emergent imaging with magnetic resonance imaging or computed tomography myelography to evaluate for compressive etiology or malpositioned instrumentation and avoidance of hypotension should be performed in cases of intraoperative and postoperative spinal cord injury