Multiple Exciton Generation in 3D-Ordered Networks of Ge Quantum Wires in Alumina Matrix.

Thin films containing 3D-ordered semiconductor quantum wires offer a great tool to improve the properties of photosensitive devices. In the present work, we investigate the photo-generated current in thin films consisting of an interconnected 3D-ordered network of Ge quantum wires in an alumina matrix. The films are prepared using nitrogen-assisted magnetron sputtering co-deposition of Ge and Al2O3. We demonstrate a strong photocurrent generation in the films, much stronger than in similar films containing Ge quantum dots. The enhanced photocurrent generation is the consequence of the multiple exciton generation and the films' specific structure that allows for efficient carrier transport. Thin film with the largest nitrogen content showed enhanced performance compared to other thin films with 1.6 excitons created after absorption of a single photon at an energy nearly equal to the double bandgap value. The bandgap value depends on the geometrical properties of the quantum wires, and it is close to the maximum of the solar irradiance in this case. In addition, we show that the multiple exciton generation is the most pronounced at the photon energy values equal to multiple values of the thin film bandgap.

Surface Functionalisation of Dental Implants with a Composite Coating of Alendronate and Hydrolysed Collagen: DFT and EIS Studies.

The success of the osseointegration process depends on the surface characteristics and chemical composition of dental implants. Therefore, the titanium dental implant was functionalised with a composite coating of alendronate and hydrolysed collagen, which are molecules with a positive influence on the bone formation. The results of the quantum chemical calculations at the density functional theory level confirm a spontaneous formation of the composite coating on the titanium implant, ∆G*INT = -8.25 kcal mol-1. The combination of the results of X-ray photoelectron spectroscopy and quantum chemical calculations reveals the structure of the coating. The alendronate molecules dominate in the outer part, while collagen tripeptides prevail in the inner part of the coating. The electrochemical stability and resistivity of the implant modified with the composite coating in a contact with the saliva depend on the chemical nature of alendronate and collagen molecules, as well as their inter- and intramolecular interactions. The formed composite coating provides a 98% protection to the implant after the 7-day immersion in the artificial saliva. From an application point of view, the composite coating could effectively promote osseointegration and improve the implant's resistivity in contact with an aggressive environment such as saliva.

Entropy-Driven Self-Healing of Metal Oxides Assisted by Polymer-Inorganic Hybrid Materials.

Enabling self-healing of materials is crucially important for saving resources and energy in numerous emerging applications. While strategies for the self-healing of polymers are advanced, mechanisms for semiconducting inorganic materials are scarce due to the lack of suitable healing agents. Here a concept for the self-healing of metal oxides is developed. This concept consists of metal oxide nanoparticle growth inside the bulk of halogenated polymers and their subsequent entropy-driven migration to externally induced defect sites, leading to recovery of the defect. Herein, it is demonstrated that the pool of self-healing materials is expanded to include semiconductors, thereby increasing the reliability and sustainability of functional materials through the use of metal oxides. It is revealed that electrical properties of tin-doped indium oxide can be partially restored upon healing. Such properties are of immediate interest for the further development of transparent flexible electrodes.

Structural Behavior and Spin-State Features of BaAl2O4 Scaled through Tuned Co3+ Doping.

Pure and Co3+-doped BaAl2O4 [Ba(Al1-xCox)2O4, x = 0, 0.0077, 0.0379] powder samples were prepared by a facile hydrothermal route. Elemental analyses by static secondary ion mass spectrometry (SIMS), X-ray absorption spectroscopy (XAS) measurements at the Co K-edge, and X-ray diffraction studies were fully correlated, thus addressing a complete description of the structural complexity of Co3+-doped BaAl2O4 powder. Powder X-ray diffraction (PXRD) patterns indicated that prepared samples were nanocrystalline with a hexagonal P63 symmetry. The X-ray absorption near-edge structure (XANES) measurements revealed the presence of cobalt in a +3 oxidation state, while the rarely documented, tetrahedral symmetry around Co3+ was extracted from the extended X-ray absorption fine structure (EXAFS) oscillation patterns. Rietveld structure refinements showed that Co3+ preferentially substitutes Al3+ at tetrahedral Al3 sites of the BaAl2O4 host lattice, whereas the (Al3)O4 tetrahedra remain rather regular with Co3+-O distances ranging from 1.73(9) to 1.74(9) Å. The underlying magneto-structural features were unraveled through axial and rhombic zero-field splitting (ZFS) terms. The increased substitution of Al3+ by Co3+ at Al3 sites leads to an increase of the axial ZFS terms in Co3+-doped BaAl2O4 powder from 10.8 to 26.3 K, whereas the rhombic ZFS parameters across the series change in the range from 2.7 to 10.4 K, showing a considerable increase of anisotropy together with the values of the anisotropic g-tensor components flowing from 1.7 to 2.5. We defined the line between the Co3+ doping limit and influenced magneto-structural characteristics, thus enabling the design of strategy to control the ZFS terms' contributions to magnetic anisotropy within Co3+-doped BaAl2O4 powder.

Radical-triggered cross-linking for molecular layer deposition of SiAlCOH hybrid thin films.

Here, we report on a simultaneous growth and radical-initiated cross-linking of a hybrid thin film in a layer-by-layer manner via molecular layer deposition (MLD). The cross-linked film exhibited a self-limiting MLD growth behavior and improved properties like 12% higher film density and enhanced stability compared to the non-cross-linked film.

Biomass bottom ash & dolomite similarly ameliorate an acidic low-nutrient soil, improve phytonutrition and growth, but increase Cd accumulation in radish.

One of negative side-effects of usage of bio-renewables might be generation of mineral (ash) material, potential source of environmental pollution. A hypothesis was that bottom ash (BA; from biomass cogeneration facility) could be efficiently (re) used in soil chemical conditioning similarly to widely-used dolomite-based soil conditioner (DO; from Croatian Dinaric-coastal region) which we tested by: i) physicochemical characterisation of BA and DO, and ii) bioassay with Raphanus sativus cultivated in acidic soil amended with BA or DO. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) confirmed complex chemical/physical structures and morphology between amendments, X-ray diffraction (XRD) showed their distinctive mineralogy with predominantly dolomite (in DO) vs. quartz and calcite (in BA), while secondary ion mass spectrometry (SIMS) revealed their diverse elemental/isotopic composition. The BA or DO amendments ameliorated soil acidity, increased available P, K and most other nutrients, but not Cd. The BA or DO amendments improved vegetative growth and edible hypocotyl yield. However, both amendments also increased Cd accumulation in all radish tissues, which was unexpected given the alkaline matrix of bio-ash and dolomite that would be likely to facilitate retention and immobilisation of toxic Cd. Thus, thorough characterisation and evaluation of BA- and/or DO-based materials and relevant soils (with an emphasis on metal sorption/immobilisation) prior to application in (agro) ecosystems is crucial for producing food clean of toxic metals.

Omniphobic Etched Aluminum Surfaces with Anti-Icing Ability.

In this work, omniphobic surfaces are developed by combining chemical etching and surface modification of aluminum. In the first step, hierarchical micro/nanostructuring is carried out by chemical etching. Thereafter, a perfluoropolyether is grafted onto the corrugated aluminum substrate, decreasing its surface free energy and turning the system omniphobic. The morphology and chemical composition of the developed surfaces are characterized. We observed a low affinity toward liquids, regardless of their chemical nature and surface tension. The surface shows superhydrophobic properties with a water contact angle of 160° and simultaneously strong oleophobic properties with a hexadecane contact angle of 141°. Furthermore, these omniphobic surfaces significantly delay the freezing time of water droplets to 5100 s, which is about 20-fold of the freezing time on pristine aluminum (260 s), and they even inhibit ice growth by repelling the incoming droplets prior to ice nucleation.

A New Insight into Coating's Formation Mechanism Between TiO2 and Alendronate on Titanium Dental Implant.

Organophosphorus compounds, like bisphosphonates, drugs for treatment and prevention of bone diseases, have been successfully applied in recent years as bioactive and osseoinductive coatings on dental implants. An integrated experimental-theoretical approach was utilized in this study to clarify the mechanism of bisphosphonate-based coating formation on dental implant surfaces. Experimental validation of the alendronate coating formation on the titanium dental implant surface was carried out by X-ray photoelectron spectroscopy and contact angle measurements. Detailed theoretical simulations of all probable molecular implant surface/alendronate interactions were performed employing quantum chemical calculations at the density functional theory level. The calculated Gibbs free energies of (TiO2)10-alendronate interaction indicate a more spontaneous exergonic process when alendronate molecules interact directly with the titanium surface via two strong bonds, Ti-N and Ti-O, through simultaneous participation common to both phosphonate and amine branches. Additionally, the stability of the alendronate-modified implant during 7 day-immersion in a simulated saliva solution has been investigated by using electrochemical impedance spectroscopy. The alendronate coating was stable during immersion in the artificial saliva solution and acted as an additional barrier on the implant with overall resistivity, R ~ 5.9 MΩ cm2.

Molecular layer deposition of hybrid siloxane thin films by ring opening of cyclic trisiloxane (V3D3) and azasilane.

In this work, we report the first ring opening vapor to solid polymerization of cyclotrisiloxane and N-methyl-aza-2,2,4-trimethylsilacyclopentane by molecular layer deposition (MLD). This process was studied in situ with a quartz crystal microbalance and the thin film was characterized by X-ray photoelectron spectroscopy, ATR-FTIR and high-resolution transmission electron microscopy.

Magnetic oxygen stored in quasi-1D form within BaAl2O4 lattice.

Inorganic materials that enable a link between the storage and release of molecular oxygen offer a fertile ground in continuous quest for the applications that can potentially reduce energy consumption and thus minimize adverse effects on the environment. Herein, we address reversible intake/release of an oxygen within the BaAl2O4 material as evidenced by unexpected magnetic ordering. Magnetic measurements unveil that an oxygen is stored in the form of condensed matter, creating a kind of low dimensional, chain-like assembly within the tunnels of BaAl2O4 structure. We demonstrate that oxygen is adsorbed simply by staying in air, at ambient conditions, and released relatively quickly by staying in the He or other gas atmosphere of several millibars pressure even at 300 K.

Preparation of non-oxidized Ge quantum dot lattices in amorphous Al2O3, Si3N4 and SiC matrices.

The preparation of non-oxidized Ge quantum dot (QD) lattices embedded in Al2O3, Si3N4, SiC matrices by self-assembled growth was studied. The materials were produced by magnetron sputtering deposition, using different substrate temperatures. The deposition regimes leading to the self-assembled growth type and the formation of three-dimensionally ordered Ge QD lattices in different matrices were investigated and determined. The oxidation of the Ge QDs in different matrices was monitored and the best conditions for the production of non-oxidized Ge QDs were found. The optical properties of the Ge QD lattices in different matrices show a strong dependence on the Ge oxidation and the matrix type.

Ta2N3 nanocrystals grown in Al2O3 thin layers.

Tantalum nitride nanoparticles (NPs) and cubic bixbyite-type Ta2N3 nanocrystals (NCs) were grown in (Ta-N+Al2O3)/Al2O3 periodic multilayers (MLs) after thermal treatment. The MLs were prepared by magnetron deposition at room temperature and characterized using grazing incidence small-angle X-ray scattering (GISAXS), X-ray reflectivity (XRR), grazing incidence X-ray diffraction (GIXRD), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). We found amorphous tantalum nitride NPs at 600-800 °C, with a high degree of ordering along the surface normal and short-range ordering within the layers containing tantalum (metallic layers). At an even higher annealing temperature of 900 °C the NPs crystallize in the rare and relatively unexplored Ta2N3 phase. However, the environment, morphology and spatial ordering of the NCs depend on the thickness of the metallic layers. For 12 nm thick metallic layers, the Ta2N3 NCs have an average diameter of 6 nm and they are confined and short-range ordered within the metallic layers. When the metallic layers are thinner, the NCs grow over 20 nm in diameter, show no spatial ordering, while the periodic structure of the ML was completely destroyed. The results presented here demonstrate a self-assembly process of tantalum nitride NPs, the morphological properties of which depend on the preparation conditions. This can be used as a generic procedure to realize highly tunable and designable optical properties of thin films containing transition-metal nitride nanocrystals.

Mechanically activated catalyst mixing for high-yield boron nitride nanotube growth.

Boron nitride nanotubes (BNNTs) have many fascinating properties and a wide range of applications. An improved ball milling method has been developed for high-yield BNNT synthesis, in which metal nitrate, such as Fe(NO3)3, and amorphous boron powder are milled together to prepare a more effective precursor. The heating of the precursor in nitrogen-containing gas produces a high density of BNNTs with controlled structures. The chemical bonding and structure of the synthesized BNNTs are precisely probed by near-edge X-ray absorption fine structure spectroscopy. The higher efficiency of the precursor containing milling-activated catalyst is revealed by thermogravimetric analyses. Detailed X-ray diffraction and X-ray photoelectron spectroscopy investigations disclose that during ball milling the Fe(NO3)3 decomposes to Fe which greatly accelerates the nitriding reaction and therefore increases the yield of BNNTs. This improved synthesis method brings the large-scale production and application of BNNTs one step closer.

Decoration of nitrogen vacancies by oxygen atoms in boron nitride nanotubes.

Decoration of nitrogen vacancies by oxygen atoms has been studied by near-edge X-ray absorption fine structure (NEXAFS) around B K-edge in several boron nitride (BN) structures, including bamboo-like and multi-walled BN nanotubes. Breaking of B-N bonds and formation of nitrogen vacancies under low-energy ion bombardment reduces oxidation resistance of BN structures and promotes an efficient oxygen-healing mechanism, in full agreement with some recent theoretical predictions. The formation of mixed O-B-N and B-O bonds is clearly identified by well-resolved peaks in NEXAFS spectra of excited boron atoms.