Unveiling the Role of Ge in CZTSSe Solar Cells by Advanced Micro-To-Atom Scale Characterizations.

Kesterite is an earth-abundant energy material with high predicted power conversion efficiency, making it a sustainable and promising option for photovoltaics. However, a large open circuit voltage Voc deficit due to non-radiative recombination at intrinsic defects remains a major hurdle, limiting device performance. Incorporating Ge into the kesterite structure emerges as an effective approach for enhancing performance by manipulating defects and morphology. Herein, how different amounts of Ge affect the kesterite growth pathways through the combination of advanced microscopy characterization techniques are systematically investigated. The results demonstrate the significance of incorporating Ge during the selenization process of the CZTSSe thin film. At high temperature, the Ge incorporation effectively delays the selenization process due to the formation of a ZnSe layer on top of the metal alloys through decomposition of the Cu-Zn alloy and formation of Cu-Sn alloy, subsequently forming of Cu-Sn-Se phase. Such an effect is compounded by more Ge incorporation that further postpones kesterite formation. Furthermore, introducing Ge mitigates detrimental "horizontal" grain boundaries by increasing the grain size on upper layer. The Ge incorporation strategy discussed in this study holds great promise for improving device performance and grain quality in CZTSSe and other polycrystalline chalcogenide solar cells.

Early contact between late farming and pastoralist societies in southeastern Europe.

Archaeogenetic studies have described two main genetic turnover events in prehistoric western Eurasia: one associated with the spread of farming and a sedentary lifestyle starting around 7000-6000 BC (refs. 1-3) and a second with the expansion of pastoralist groups from the Eurasian steppes starting around 3300 BC (refs. 4,5). The period between these events saw new economies emerging on the basis of key innovations, including metallurgy, wheel and wagon and horse domestication6-9. However, what happened between the demise of the Copper Age settlements around 4250 BC and the expansion of pastoralists remains poorly understood. To address this question, we analysed genome-wide data from 135 ancient individuals from the contact zone between southeastern Europe and the northwestern Black Sea region spanning this critical time period. While we observe genetic continuity between Neolithic and Copper Age groups from major sites in the same region, from around 4500 BC on, groups from the northwestern Black Sea region carried varying amounts of mixed ancestries derived from Copper Age groups and those from the forest/steppe zones, indicating genetic and cultural contact over a period of around 1,000 years earlier than anticipated. We propose that the transfer of critical innovations between farmers and transitional foragers/herders from different ecogeographic zones during this early contact was integral to the formation, rise and expansion of pastoralist groups around 3300 BC.

Frontier Lapita interaction with resident Papuan populations set the stage for initial peopling of the Pacific.

The initial peopling of the remote Pacific islands was one of the greatest migrations in human history, beginning three millennia ago by Lapita cultural groups. The spread of Lapita out of an ancestral Asian homeland is a dominant narrative in the origins of Pacific peoples, and although Island New Guinea has long been recognized as a springboard for the peopling of Oceania, the role of Indigenous populations in this remarkable phase of exploration remains largely untested. Here, we report the earliest evidence for Lapita-introduced animals, turtle bone technology and repeated obsidian import in southern New Guinea 3,480-3,060 years ago, synchronous with the establishment of the earliest known Lapita settlements 700 km away. Our findings precede sustained Lapita migrations and pottery introductions by several centuries, occur alongside Indigenous technologies and suggest continued multicultural influences on population diversity despite language replacement. Our work shows that initial Lapita expansion throughout Island New Guinea was more expansive than previously considered, with Indigenous contact influencing migration pathways and island-hopping strategies that culminated in rapid and purposeful Pacific-wide settlement. Later Lapita dispersals through New Guinea were facilitated by earlier contact with Indigenous populations and profoundly influenced the region as a global centre of cultural and linguistic diversity.

Record-high positive refractive index change in bismuth germanate crystals through ultrafast laser enhanced polarizability.

Unlike other crystals, the counter intuitive response of bismuth germanate crystals ([Formula: see text], BGO) to form localized high refractive index contrast waveguides upon ultrafast laser irradiation is explained for the first time. While the waveguide formation is a result of a stoichiometric reorganization of germanium and oxygen, the origin of positive index stems from the formation of highly polarisable non-bridging oxygen complexes. Micro-reflectivity measurements revealed a record-high positive refractive index contrast of [Formula: see text]. The currently accepted view that index changes [Formula: see text] could be brought about only by engaging heavy metal elements is strongly challenged by this report. The combination of a nearly perfect step-index profile, record-high refractive index contrast, easily tunable waveguide dimensions, and the intrinsic high optical non-linearity, electro-optic activity and optical transparency up to [Formula: see text] of BGO make these waveguides a highly attractive platform for compact 3D integrated optics.

Revisiting ultrafast laser inscribed waveguide formation in commercial alkali-free borosilicate glasses.

Alkali-free borosilicate glasses are one of the most used dielectric platforms for ultrafast laser inscribed integrated photonics. Femtosecond laser written waveguides in commercial Corning Eagle 2000, Corning Eagle XG and Schott AF32 glasses were analyzed. They were studied in depth to disclose the dynamics of waveguide formation. We believe that the findings presented in this paper will help bridge one of the major and important gaps in understanding the ultrafast light-matter interaction with alkali-free boroaluminosilicate glass. It was found that the waveguides are formed mainly due to structural and elemental reorganization upon laser inscription. Aluminum along with alkaline earth metals were found to be responsible for the densification and silicon being the exchanging element to form a rarefied zone. Strong affinity towards alkaline earth elements to form the densified zone for waveguides written with high feed rate (>200 mm/min) were identified and explained. Finally we propose a plausible solution to form positive refractive index change waveguides in different glasses based on current and previous reports.

Effect of selective-precipitations process on the corrosion resistance and hardness of dual-phase high-carbon steel.

It is commonly known that precipitation of secondary phase in non-ferrous alloys will affect the mechanical properties of them. But due to the nature of dual-phase low-alloy high-carbon steel and its high potential of precipitation of cementite, there is limited study on tailoring the mechanical and corrosion properties of this grade of steel by controlling the precipitation of different phases. Predicting and controlling precipitation behaviour on this grade of steel is of great importance towards producing more advanced applications using this low-cost alloy. In this study the new concept of selective-precipitation process for controlling the mechanical and corrosion behaviour of dual-phase low-alloy high-carbon steel has been introduced. We have investigated the precipitation of different phases using in-situ observation ultra-high temperature confocal scanning laser microscopy, image analyser - ImageJ, scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) and electron probe microanalysis (EPMA). Volume fraction of each phase including retained austenite, martensite and precipitated phases was determined by X-ray diffraction (XRD), electrochemical corrosion test by Tafel extrapolation method and hardness performance by nanoindentation hardness measurement. The experimental results demonstrated that, by controlling the precipitations inside the matrix and at grain boundaries through heat treatment, we can increase the hardness of steel from 7.81 GPa to 11.4 GPa. Also, corrosion resistance of steel at different condition has been investigated. This new approach will open new possibility of using this low-cost steel for high performance applications.

Functionalisation of Polydimethylsiloxane (PDMS)- Microfluidic Devices coated with Rock Minerals.

Fluid flow in porous rocks is commonly capillary driven and thus, dependent on the surface characteristics of rock grains and in particular the connectivity of corners and crevices in which fluids reside. Traditional microfluidic fabrication techniques do not provide a connected pathway of crevices that are essential to mimic multiphase flow in rocks. Here, geo-material microfluidic devices with connected pathways of corners and crevices were created by functionalising Polydimethylsiloxane (PDMS) with rock minerals. A novel fabrication process that provides attachment of rock minerals onto PDMS was demonstrated. The geo-material microfluidic devices were compared to carbonate and sandstone rocks by using energy dispersive X-ray spectroscopy, scanning electron microscopy (SEM), contact angle measurements, and a surface profilometer. Based on SEM coupled with energy-dispersive X-ray spectrometry (SEM-EDS) analyses, roughness measurements, contact angle, wettability, and roughness were comparable to real rocks. In addition, semivariograms showed that mineral deposition across the different geo-material devices was nearly isotropic. Lastly, important multiphase flow phenomena, such as snap-off and corner flow mechanisms, equivalent to those occurring in reservoir rocks have been visualised. The presented approach can be used to visualise rock-fluid interactions that are relevant to subsurface engineering applications, such as hydrocarbon recovery and CO2 sequestration.

Biochar aging in contaminated soil promotes Zn immobilization due to changes in biochar surface structural and chemical properties.

Adding biochar to Zn-contaminated soil can immobilize excess Zn and promote plant biomass growth. This was seen previously over the course of a 180-day planted pot trial involving two types of biochar (cattle manure, CM, and grain husk, GH) in a Zn-contaminated soil. Both biochars alleviated Zn-induced phytotoxicity to Ficus by immobilizing Zn and reducing its uptake by the plant, but to different extents. The aim of the current study was to delve into the in-soil mechanisms involved in biochar-mediated Zn immobilization. Biochar particles were excavated from the pot soils. Fresh and aged biochar particles were examined by high-resolution scanning electron microscope (SEM) coupled with energy dispersive X-ray spectroscopy (EDS), field-emission electron probe micro-analyzer (EPMA), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). The physical and chemical properties of the biochars had changed over the 180 days. SEM-EDS and EPMA indicated that organo-mineral micro-agglomerates had formed on biochar surfaces and in pores. Some of the Zn immobilized by the biochars was bound in the organo-mineral complexes of these agglomerates. XPS and FTIR showed that the complexes had a high concentration of oxygenated functional groups which facilitated Zn binding and encapsulation. The micro-agglomerates were similar in structure and composition to those observed on biochars having resided for much longer times in soils, or having been subjected to accelerated aging. Overall, Zn immobilization by the CM biochar was greater than by the GH biochar, due to its higher alkalinity, higher concentration of available negatively charged groups, and greater accretion of organo-mineral layers. These findings are suggestive that biochar-assisted phytorestoration of heavy metal-contaminated soils can be optimized through selection of biochar having such traits. It is hypothesized that metals may be continually taken up in such micro-agglomerates, since they continue to form over the lifetime of the biochar in the soil.

Enhancing steel properties through in situ formation of ultrahard ceramic surface.

Abrasion and corrosion resistant steel has attracted considerable interest for industrial application as a means of minimising the costs associated with product/component failures and/or short replacement cycles. These classes of steels contain alloying elements that increase their resistance to abrasion and corrosion. Their benefits, however, currently come at a potentially prohibitive cost; such high performance steel products are both more technically challenging and more expensive to produce. Although these methods have proven effective in improving the performance of more expensive, high-grade steel components, they are not economically viable for relatively low cost steel products. New options are needed. In this study, a complex industrial waste stream has been transformed in situ via precisely controlled high temperature reactions to produce an ultrahard ceramic surface on steel. This innovative ultrahard ceramic surface increases both the hardness and compressive strength of the steel. Furthermore, by modifying the composition of the waste input and the processing parameters, the ceramic surface can be effectively customised to match the intended application of the steel. This economical new approach marries industry demands for more cost-effective, durable steel products with global imperatives to address resource depletion and environmental degradation through the recovery of resources from waste.

Materials design considerations involved in the fabrication of implantable bionics by metallization of ceramic substrates.

The Pt metallization of co-fired Al2O3/SiO2 substrates containing Pt feedthroughs was shown to be a suitable means to construct implantable bionics. The use of forge welding to join an electrode to such a metallized feedthrough was demonstrated and subsequently evaluated through the use of metallography and electron microscopy. Metallurgical phenomena involved in forge welding relevant to the fabrication of all types of biomedical implants are discussed within this paper. The affect of thermal profiles used in brazing or welding to build implantable devices from metal components is analysed and the case for considered selection of alloys in implant design is put forward.

Evidence for implication of tryptophan hydroxylase in the regulation of melatonin synthesis in ovine pinealocytes in culture.

1. Tryptophan hydroxylase (TPOH) is the first enzyme in the melatonin synthesis pathway and the rate-limiting enzyme in serotonin synthesis. We established in this study an in vitro model of ovine pinealocytes to investigate the role of TPOH in melatonin production. 2. We demonstrated that TPOH is highly expressed both in vivo and in vitro at the protein and mRNA levels. In vitro pinealocytes show ultrastructural features similar to those previously described in vivo. 3. Moreover, our in vitro model allowed us to study the regulation mechanisms for melatonin synthesis in sheep pinealocytes and to demonstrate that both transcriptional and posttranscriptional mechanisms are involved. 4. In particular, our results suggest that TPOH plays an essential role in the regulation of melatonin synthesis.