Influence of amorphous carbon interlayers on nucleation and early growth of lithium metal at the current collector-solid electrolyte interface.

Nucleation and early growth of Li metal is critical to the performance of anode-free solid-state batteries. We report the use of amorphous carbon deposited by direct current magnetron sputtering as an intermediate layer between the Cu current collector and the Lipon solid electrolyte. The density, conductivity, and microstructure of the carbon interlayer are varied and their influence on the reversible formation and removal of the Li metal anode is investigated. It is shown that thin films of amorphous carbon act as seed layers, reducing the overpotential for Li plating and increasing the critical current density for Li plating and stripping from 2 up to 8 mA cm-2. It is further demonstrated that the ionic conductivity of the Li ions in the carbon interlayers determines their optimum thickness to be 100 nm or less, and that the initial Li loss due to interphase formation can be reduced to a few tens of nm by decreasing the density of the carbon films.

Solution Processing and Self-Organization of PbS Quantum Dots Passivated with Formamidinium Lead Iodide (FAPbI3).

Solution-processed lead sulfide quantum dots (PbS QDs) are very attractive as NIR-active semiconductors for the fabrication of cost-efficient optoelectronic devices. To control the thin film carrier transport, as well as stability, surface passivation is of crucial importance. Here, we present the successful surface passivation of PbS QDs by the formamidinium lead iodide (FAPbI3) ligand. An effective procedure for the fabrication of FAPbI3-passivated PbS QDs through a binary-phase ligand exchange protocol in hexane and n-methylformamide is demonstrated. It is shown that this solution-processed ligand exchange drastically changes the photoluminescence intensity, exciton recombination dynamics, and carrier lifetime of the nanocrystals. The solution casting of the ligand-exchanged nanocrystals into thin films results in the periodic ordering of QDs in a square superlattice with close contacts. Planar graphene/QD photodetectors fabricated with PbS QDs passivated with FAPbI3 show substantially increased thermal stability as compared to similar devices using PbS QDs passivated with commonly used methylammonium lead iodide.

Understanding the microstructural evolution and mechanical properties of transparent Al-O-N and Al-Si-O-N films.

Optically transparent, colorless Al-O-N and Al-Si-O-N coatings with discretely varied O and Si contents were fabricated by reactive direct current magnetron sputtering (R-DCMS) from elemental Al and Si targets and O2 and N2 reactive gases. The Si/Al content was adjusted through the electrical power on the Si and Al targets, while the O/N content was controlled through the O2 flow piped to the substrate in addition to the N2 flow at the targets. The structure and morphology of the coatings were studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM), while the elemental composition was obtained from Rutherford backscattering spectrometry (RBS) and heavy ion elastic recoil detection analysis (ERDA). The chemical states of the elements in the coatings were analyzed by X-ray photoelectron spectroscopy (XPS). Based on analytical results, a model describing the microstructural evolution of the Al-O-N and also previously studied Al-Si-N [1, 2, 3, 4] coatings with O and Si content, respectively, is established. The universality of the microstructural evolution of these coatings with the concentration of the added element is attributed to the extra valence electron (e-) that must be incorporated into the AlN wurtzite host lattice. In the case of Al-O-N, this additional valence charge arises from the e - acceptor O replacing N in the AlN wurtzite lattice, while the e - donor Si substituting Al fulfills that role in the Al-Si-N system. In view of future applications of ternary Al-O-N and quaternary Al-Si-O-N transparent protective coatings, their mechanical properties such as residual stress (σ), hardness (HD) and Young's modulus (E) were obtained from the curvature of films deposited onto thin substrates and by nanoindentation, respectively. Moderate compressive stress levels between -0.2 and -0.5 GPa, which suppress crack formation and film-substrate delamination, could be obtained together with HD values around 25 GPa.

Corrosion fatigue in DLC-coated articulating implants: an accelerated methodology to predict realistic interface lifetime.

We present a methodology to accelerate and estimate the lifetime of an interlayer under dynamic loading in body-like media. It is based on accelerating corrosion fatigue processes taking place at the buried interface of a Si-based adhesion-promoting interlayer in articulating implants on a CoCrMo biomedical alloy; the implants are coated with diamond-like carbon (DLC). The number of interface loading cycles to delamination is determined by reciprocal loading in corrosive fluid. Its dependence on the load is summarized in a Wöhler-like curve of a DLC/DLC-Si/CoCrMo system in body working conditions: cyclic stresses at 37 °C in phosphate buffered saline (PBS). The presence of oxygen as a contaminant strongly affects the lifetime of the interface under corrosion fatigue. The main parameters acting on the prediction, with a special emphasis on simulated in vivo conditions, are analyzed and discussed: the media (PBS, Milli-Q water, NaCl, Ringers' solution and bovine calf serum), the load, the frequency and the composition of the interface determined by X-ray photoelectron spectroscopy.

Photochemical Creation of Covalent Organic 2D Monolayer Objects in Defined Shapes via a Lithographic 2D Polymerization.

In this work we prepare Langmuir-Blodgett monolayers with a trifunctional amphiphilic anthraphane monomer. Upon spreading at the air/water interface, the monomers self-assemble into 1 nm-thin monolayer islands, which are highly fluorescent and can be visualized by the naked eye upon excitation. In situ fluorescence spectroscopy indicates that in the monolayers, all the anthracene units of the monomers are stacked face-to-face forming excimer pairs, whereas at the edges of the monolayers, free anthracenes are present acting as edge groups. Irradiation of the monolayer triggers [4 + 4]-cycloadditions among the excimer pairs, effectively resulting in a two-dimensional (2D) polymerization. The polymerization reaction also completely quenches the fluorescence, allowing to draw patterns on the monomer monolayers. More interestingly, after transferring the monomer monolayer on a solid substrate, by employing masks or the laser of a confocal scanning microscope, it is possible to arbitrarily select the parts of the monolayer that one wants to polymerize. The unpolymerized regions can then be washed away from the substrate, leaving 2D macromolecular monolayer objects of the desired shape. This photolithographic process employs 2D polymerizations and affords 1 nm-thin coatings.

Carboxylate Functional Groups Mediate Interaction with Silver Nanoparticles in Biofilm Matrix.

Biofilms causing medical conditions or interfering with technical applications can prove undesirably resistant to silver nanoparticle (AgNP)-based antimicrobial treatment, whereas beneficial biofilms may be adversely affected by the released silver nanoparticles. Isolated biofilm matrices can induce reduction of silver ions and stabilization of the formed nanosilver, thus altering the exposure conditions. We thus study the reduction of silver nitrate solution in model experiments under chemically defined conditions as well as in stream biofilms. Formed silver nanoparticles are characterized by state-of-the art methods. We find that isolated biopolymer fractions of biofilm organic matrix are capable of reducing ionic Ag, whereas other isolated fractions are not, meaning that biopolymer fractions contain both reducing agent and nucleation seed sites. In all of the investigated systems, we find that silver nanoparticle-biopolymer interface is dominated by carboxylate functional groups. This suggests that the mechanism of nanoparticle formation is of general nature. Moreover, we find that glucose concentration within the biofilm organic matrix correlates strongly with the nanoparticle formation rate. We propose a simple mechanistic explanation based on earlier literature and the experimental findings. The observed generality of the extracellular polymeric substance/AgNP system could be used to improve the understanding of impact of Ag+ on aqueous ecosystems, and consequently, to develop biofilm-specific medicines and bio-inspired water decontaminants.

Solar Hydrogen Production by Amorphous Silicon Photocathodes Coated with a Magnetron Sputter Deposited Mo2C Catalyst.

Coupling of Earth-abundant hydrogen evolution catalysts to photoabsorbers is crucial for the production of hydrogen fuel using sunlight. In this work, we demonstrate the use of magnetron sputtering to deposit Mo2C as an efficient hydrogen evolution reaction catalyst onto surface-protected amorphous silicon (a-Si) photoabsorbers. The a-Si/Mo2C photocathode evolves hydrogen under simulated solar illumination in strongly acidic and alkaline electrolytes. Onsets of photocurrents are observed at potentials as positive as 0.85 V vs RHE. Under AM 1.5G (1 sun) illumination, the photocathodes reach current densities of -11.2 mA cm(-2) at the reversible hydrogen potential in 0.1 M H2SO4 and 1.0 M KOH. The high photovoltage and low-cost of the Mo2C/a-Si assembly make it a promising photocathode for solar hydrogen production.

On interlayer stability and high-cycle simulator performance of diamond-like carbon layers for articulating joint replacements.

Diamond like carbon (DLC) coatings have been proven to be an excellent choice for wear reduction in many technical applications. However, for successful adaption to the orthopaedic field, layer performance, stability and adhesion in physiologically relevant setups are crucial and not consistently investigated. In vitro wear testing as well as adequate corrosion tests of interfaces and interlayers are of great importance to verify the long term stability of DLC coated load bearing implants in the human body. DLC coatings were deposited on articulating lumbar spinal disks made of CoCr28Mo6 biomedical implant alloy using a plasma-activated chemical vapor deposition (PACVD) process. As an adhesion promoting interlayer, tantalum films were deposited by magnetron sputtering. Wear tests of coated and uncoated implants were performed in physiological solution up to a maximum of 101 million articulation cycles with an amplitude of ±2° and -3/+6° in successive intervals at a preload of 1200 N. The implants were characterized by gravimetry, inductively coupled plasma optical emission spectrometry (ICP-OES) and cross section scanning electron microscopy (SEM) analysis. It is shown that DLC coated surfaces with uncontaminated tantalum interlayers perform very well and no corrosive or mechanical failure could be observed. This also holds true in tests featuring overload and third-body wear by cortical bone chips present in the bearing pairs. Regarding the interlayer tolerance towards interlayer contamination (oxygen), limits for initiation of potential failure modes were established. It was found that mechanical failure is the most critical aspect and this mode is hypothetically linked to the α-ß tantalum phase switch induced by increasing oxygen levels as observed by X-ray diffraction (XRD). It is concluded that DLC coatings are a feasible candidate for near zero wear articulations on implants, potentially even surpassing the performance of ceramic vs. ceramic.