Zn Films Research Articles

Molecular Dynamics Analysis of Multi-Factor Influences on Structural Defects in Deposited Mg-Matrix Zn Atom Films.

Mg metal vascular stents not only have good mechanical support properties but also can be entirely absorbed by the human body as a trace element beneficial to the human body, but because Mg metal is quickly dissolved and absorbed in the human body, magnesium metal alone cannot be ideally used as a vascular stent. Since the dense oxide Zn film formed by Zn contact with oxygen in the air has good anti-corrosion performance, the Zn nanolayer film deposited on the Mg matrix vascular scaffold by magnetron sputtering can effectively inhibit the rapid dissolution of Mg metal. However, there are few studies on the molecular dynamic structural defects of Mg-matrix Zn atomic magnetron sputtering, and the atomic level simulation of Mg-matrix Zn thin-film depositions can comprehensively understand the atomic level structural defects in the deposition process of Zn thin films from a theoretical perspective to further guide experimental research. Based on this, this research first studied and analyzed the atomic layer structure defects, surface morphology, surface roughness, atomic density of different deposited layers, radial distribution function, and residual stress of the thin-film deposition layer of 1500 deposited Zn atoms at the initial deposition stage, during and after deposition under Mg-matrix thermal layer 500K and a deposited velocity 5 Å/ps by molecular dynamics. At the same time, the effects of temperature and deposited velocity of the Mg-matrix thermal layer on the surface morphology, roughness, and biaxial stress of the deposited films were studied.

Low-cost deposition of tunable band gap Zn(O,S) as electron transport layer for crystalline silicon heterojunction solar cells

In recent years, the research on silicon heterojunction (HJT) solar cells based on dopant-free contacts has experienced rapid development. Zn(O,S) is a low work function n-type semiconductor compound with tunable band gap that can be used as the electron transport layer (ETL) in HJT solar cells. In our work, we choose Zn(O,S) as ETL and deposit it via the low-cost chemical bath deposition (CBD) method. Uniform and fast growth of Zn(O,S) films can be obtained by regulating the concentration of the complexing agent and the ratio of reactants to reduce the generation of impurities. To further achieve band matching with c-Si, the Zn(O,S) films are processed with air-annealing to modify the elemental ratios. The air-annealing lowers the interfacial electron transport barrier, which promotes charge separation and transport, thus reducing carrier recombination at the interface. Finally, the PCE of HJT solar cell based on CBD-Zn(O,S) ETL is close to 15 %, providing a new potential route for the development of low-cost HJT solar cells.

Recycling Process of Spent Alkaline and Zn-C Batteries for the Re-Utilization in Rechargeable Zn-Ion Battery

The Zn, Mn and C extraction processes from spent primary batteries and the synthesis of recycled Zn film, MnO2 and MnO2/C for Zn-ion battery application were developed in the project. The Zn, Mn and C extraction process involved the acid leaching of Zn and Mn ions from the spent alkaline and Zn-C battery electrodes in the lab-scale was initially investigated using various leaching conditions. The acid leaching using 0.5-2 M HCl and H2SO4 at ambient temperature providing Zn extraction efficiencies in a range of 72.3-95.3%. By introducing an inexpensive reducing agent namely sodium sulfide (Na2S), sodium metabisulfite (Na2S2O5) or hydrogen peroxide (H2O2) in 2M H2SO4, the Mn extraction efficiency for Mn was increased from 21.9% (with no reducing agent) up to 48.4%, 82.8% and 98.9%, respectively. The upscale leaching study was subsequently performed in a 100-L pilot scale reactor demonstrated the Zn and Mn extraction efficiencies of 71% and 65%, respectively. Using the leaching solutions from the upscale hydrometallurgical route, Zn-film fabrication via electrodeposition process, and the MnO2 and MnO2/C synthesis via hydrothermal techniques were performed. Additionally, the one-step synthesis of MnO2/C via one-step hydrothermal method with no acid leaching was also explored in this study. The recycled Zn, MnO2, MnO2/C and C residual were subsequently used as the anode and cathode main components in the CR2032 and pouch-cell rechargeable Zn-ion batteries. The recycled MnO2 and MnO2/C provided similar performance as the commercial products, which indicating the recycled MnO2, MnO2/C could be effectively utilized in the Zn-ion battery, while the utilization of recycled Zn-film provided slightly lower performance compared to that of the commercial Zn foil.

Organic Cations Texture Zinc Metal Anodes for Deep Cycling Aqueous Zinc Batteries.

Manipulating the crystallographic orientation of zinc (Zn) metal to expose more (002) planes is promising to stabilize Zn anodes in aqueous electrolytes. However, there remain challenges involving the non-epitaxial electrodeposition of highly (002) textured Zn metal and the maintenance of (002) texture under deep cycling conditions. Herein, a novel organic imidazolium cations-assisted non-epitaxial electrodeposition strategy to texture electrodeposited Zn metals is developed. Taking the 1-butyl-3-methylimidazolium cation (Bmim+) as a paradigm additive, the as-prepared Zn film ((002)-Zn) manifests a compact structure and a highly (002) texture without containing (100) signal. Mechanistic studies reveal that Bmim+ featuring oriented adsorption on the Zn-(002) plane can reduce the growth rate of (002) plane to render the final exposure of (002) texture, and homogenize Zn nucleation and suppress H2 evolution to enable the compact electrodeposition. In addition, the formulated Bmim+-containing ZnSO4 electrolyte effectively sustains the (002) texture even under deep cycling conditions. Consequently, the combination of (002) texture and Bmim+-containing electrolyte endows the (002)-Zn electrode with superior cycling stability over 350h under 20 mAh cm-2 with 72.6% depth-of-discharge, and assures the stable operation of full Zn batteries with both coin-type and pouch-type configurations, significantly outperforming the (002)-Zn and commercial Zn-based batteries in Bmim+-free electrolytes.

Improved plating/stripping in anode-free lithium metal batteries through electrodeposition of lithiophilic zinc thin films

The new concept of anode-free Li batteries (AFLBs) with no excess lithium, while retaining numerous strengths, does come with certain challenges, such as high capacity loss and low coulombic efficiency. These challenges can be addressed through the utilization of modified lithiophilic current collectors to enhance the electrochemical performances. Herein, we investigated the surface modification of the Cu current collector by zinc electrodeposition to provide a lithiophilic thin layer. This process aims to facilitate a smoother plating/stripping process, leading to a uniform and dendrite-free lithium deposition on the LixZny phase formed at the first stages of plating. The zinc-modified current collectors improved cell's performances, including smooth and dense lithium deposition, reduced overpotential at various applied current densities (44.5 mV to 16.8 mV @0.25 mA cm−2), prolonged cycling stability for about 300 cycles and provided high coulombic efficiency of 95 % when compared to bare Cu electrodes. These improvements are attributed to a favorable lithium alloying reaction on the Zn-coated surface. Galvanostatic Intermittent Titration Technique (GITT) and Electrochemical Impedance Spectroscopy (EIS) revealed high diffusion coefficients for lithium (ranging from 10−9 to 10−6 cm² s-1), despite of the solid-state Li diffusion in the Zn film coating. We anticipate that implementing this modified current collector in a half-cell configuration could lead to the realization of a high-performance, anode-free lithium battery. This holistic approach proposes a scalable and cost-effective technique for boosting the performance of AFLBs.

Influence of Deposition Parameters on Performance of Zn(O,S) Buffer Layer Deposited by Solution-Based Continuous Flow Reactor for CIGS Solar Cells

CdS thin films are commonly used as buffer layers in hetero-junction structured CIGS thin film solar cells. However, the toxicity of Cd has raised concerns regarding environmental safety and alternative materials have been explored. ZnS is a leading candidate to replace Cd, with the presence of Zn(O,S) impurities known to be required for efficient CIGS solar cell fabrication. In this study, we synthesized Zn(O,S) films using a solution-based deposition method combining a continuous flow reactor (CFR) with another solutionbased deposition method. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the structural and physicochemical properties of the films, confirming the efficacy of the CFR process for depositing Zn(O,S) thin films in a short period of time. We successfully deposited Zn(O,S) thin films using the combined CFR process. Cd-free B:ZnO/Zn(O,S)/CIGS solar cells were fabricated on Mo-coated glass substrates to investigate the effects of experimental parameters, such as deposition time and method, on the performance of the Zn(O,S) buffer layer in the devices.

Versatile r.f. magnetron sputtering doping method to produce aluminum‐doped zinc oxide films

AbstractAluminum‐doped zinc oxide Al:ZnO (AZO) is a non‐toxic material applied as a transparent conductive oxide film. In this study, we report on the structural, optical, and electrical properties of AZO films obtained by thermally oxidizing aluminum‐doped Zn films produced by a versatile and low‐cost method of doping using the magnetron sputtering technique deposition. We use aluminum wire above the zinc target to produce Al:Zn films. The influence of r.f. power and different Al wire lengths on the AZO film properties were studied. The resulting AZO films exhibited Al concentrations of up to 2.85% and an optical gap between 3.22 and 3.29 eV. The transmittance was greater than 80% for all samples, and the electrical resistivity decreased by two orders of magnitude with Al doping. As a result, the sample with an aluminum concentration of approximately 1% had the lowest resistivity. In this work, it was possible to relate the lower resistivity with larger grain size and smaller concentrations of defects or vacancies.

Modulation of the microstructure, optical properties and electrical properties of zinc-doped nickel oxide films via direct current sputtering power

Zinc-doped NiO (NiO:Zn) films were direct-current-magnetron sputtered on the glass substrates. The modulation of the properties of the films via sputtering powers (Pspu) was especially studied. The conducting transition from p to n type was also proposed in mechanism. The NiO:Zn films are all preferentially 〈111〉 oriented. The films with high Pspu almost have small lattice distortion due to the improved crystallization caused by the thermal effect and the Zn element doping. The films begin to exhibit the n-type conduction at 90 W Pspu. The conducting transition from p to n type is mainly attributed to the occupation of Ni vacancies by Zn2+ and the interstitial Zn, and the improved n-type conduction in Pspu range of 140 W through 160 W to the increase in content of the interstitial Zn atoms. The absorption edge of the NiO:Zn films remaining at about 3.7 eV is slightly affected by the increase in Pspu, showing that the doping of the Zn element in the NiO is not mainly in the form of the Ni vacancies occupying ions.

NEW ZINC-BONE APATITE FILMS SHOW ANTI-TUMOUR EFFICACY AGAINST BONE METASTASES IN VITRO

Decreasing the chance of local relapse or infection after surgical excision of bone metastases is a main goals in orthopedic oncology. Indeed, bone metastases have high incidence rate (up to 75%) and important cross-relations with infection and bone regeneration. Even in patients with advanced cancer, bone gaps resulting from tumor excision must be filled with bone substitutes. Functionalization of these substitutes with antitumor and antibacterial compounds could constitute a promising approach to overcome infection and tumor at one same time. Here, for the first time, we propose the use of nanostructured zinc-bone apatite coatings having antitumor and antimicrobial efficacy. The coatings are obtained by Ionized Jet Deposition from composite targets of zinc and bovine-derived bone apatite. Antibacterial and antibiofilm efficacy of the coatings is demonstrated in vitro against S. Aureus and E. Coli. Anti-tumor efficacy is investigated against MDA- MB-231 cells and biocompatibility is assessed on L929 and MSCs.A microfluidic based approach is used to select the optimal concentration of zinc to be used to obtain antitumor efficacy and avoid cytotoxicity, exploiting a custom gradient generator microfluidic device, specifically designed for the experiments. Then, coatings capable of releasing the desired amount of active compounds are manufactured. Films morphology, composition and ion-release are studies by FEG- SEM/EDS, XRD and ICP. Efficacy and biocompatibility of the coatings are verified by investigating MDA, MSCs and L929 viability and morphology by Alamar Blue, Live/Dead Assay and FEG-SEM at different timepoints. Statistical analysis is performed by SPSS/PC + Statistics TM 25.0 software, one-way ANOVA and post-hoc Sheffe? test. Data are reported as Mean ± standard Deviation at a significance level of p <0.05.Results and Discussion. Coatings have a nanostructured surface morphology and a composition mimicking the target. They permit sustained zinc release for over 14 days in medium. Thanks to these characteristics, they show high antibacterial ability (inhibition of bacteria viability and adhesion to substrate) against both the gram + and gram – strain.The gradient generator microfluidic device permits a fine selection of the concentration of zinc to be used, with many potential perspectives for the design of biomaterials. For the first time, we show that zinc and zinc-based coatings have a selective efficacy against MDA cells. Upon mixing with bone apatite, the efficacy is maintained and cytotoxicity is avoided. For the first time, new antibacterial metal-based films are proposed for addressing bone metastases and infection at one same time. At the same time, a new approach is proposed for the design of the coatings, based on a microfluidic approach. We demonstrated the efficacy of Zn against the MDA-MB-231 cells, characterized for their ability to form bone metastases in vivo, and the possibility to use nanostructured metallic coatings against bone tumors. At the same time, we show that the gradient-generator approach is promising for the design of antitumor biomaterials. Efficacy of Zn films must be verified in vivo, but the dual-efficacy coatings appear promising for orthopedic applications.

Surface energy and stress driven growth of extremely long and high-density ZnO nanowires using a thermal step-oxidation process.

Formation of highly crystalline zinc oxide (ZnO) nanowires with an extremely high aspect ratio (length = 60 μm, diameter = 50 nm) is routinely achieved by introducing an intermediate step-oxidation method during the thermal oxidation process of thin zinc (Zn) films. High-purity Zn was deposited onto clean glass substrates at room temperature using a vacuum-assisted thermal evaporation technique. Afterwards, the as-deposited Zn layers were thermally oxidized under a closed air ambient condition at different temperatures and durations. Structural, morphological, chemical, optical and electrical properties of these oxide layers were investigated using various surface characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoemission spectroscopy (XPS). It was noticed that the initial thermal oxidation of Zn films usually starts above 400 °C. Homogeneous and lateral growth of the ZnO layer is usually preferred for oxidation at a lower temperature below 500 °C. One-dimensional (1D) asymmetric growth of ZnO started to dominate thermal oxidation above 600 °C. Highly dense 1D ZnO nanowires were specifically observed after prolonged oxidation at 600 °C for 5 hours, followed by short-step oxidation at 700 °C for 30 minutes. However, direct oxidation of Zn films at 700 °C resulted in ZnO nanorod formation. The formation of ZnO nanowires using step-oxidation is explained in terms of surface free energy and compressive stress-driven Zn adatom kinetics through the grain boundaries of laterally grown ZnO seed layers. This simple thermal oxidation process using intermittent step-oxidation was found to be quite unique and very much useful to routinely grow an array of high-density ZnO nanowires. Moreover, these ZnO nanowires showed very high sensitivity and selectivity towards formaldehyde vapour sensing against few other VOCs.

Effect of Water on Zn Electrodeposition from a Deep Eutectic Solvent

The electrodeposition of Zn films from a deep eutectic solvent (DES) of ZnCl2 and formamide and its mixture with water was studied. From spectroscopic analyses it was observed that water up to 30 v/v% does not change the Zn coordination in the electrolyte after which significant change in the coordination was observed. Electrochemical studies showed that with increase in water concentration in the DES, higher deposition/stripping current was achieved which was related to lowering of viscosity. The Zn deposit morphology changed significantly with water concentration. At low concentrations of water (up to 20 v/v%), porous Zn nanoplates formed whereas the morphology changed to a dense hexagonal structure on increasing the water concentration. X-ray diffraction results confirmed that at low water concentrations (up to 20 v/v%) Zn-Cu alloy formed. Above 20 v/v% water concentration in the DES, Zn peaks evolved with Zn-Cu alloy forming a shoulder. Based on the electrochemical and spectroscopic studies, it appears that 20–30 v/v% water is the critical region wherein significant changes occur from a DES rich region to a water-rich region.

The microstructure and protective properties of electroplating zinc films on NdFeB from a chloride-free nonaqueous bath.

The traditional aqueous electroplating of zinc film causes significant corrosion of NdFeB during the electroplating process, which is accompanied by hydrogen evolution reactions. In this study, electroplating zinc film is carried out from a chloride-free nonaqueous bath using zinc acetate (Zn(OAc)2) as the main salt, sodium acetate (NaOAc) as the conducting salt, and ethylene glycol (EG) as the solvent. The electrochemical properties of the EG bath with Zn(OAc)2 and NaOAc are characterized by means of cyclic voltammetry (CV) and linear sweep voltammetry (LSV) together with a Hull cell test on brass. The results of the experiment show that the Zn(OAc)2 concentration, current density, and temperature significantly impact the deposition behavior of zinc. Moreover, the open circuit potential (OCP) test and scanning electron microscopy (SEM) results demonstrated that the corrosion of NdFeB in the EG bath containing 0.7 M Zn(OAc)2 and NaOAc is effectively inhibited compared to when using the traditional aqueous zinc plating bath. A dense zinc film with a metallic appearance is successfully deposited on the NdFeB surface from the EG bath containing 0.7 M Zn(OAc)2 and NaOAc at 6 mA cm-2 and 60 °C. Comparative experiments demonstrate that the as-deposited Zn film exhibits superior protective performance and exerts less damage to NdFeB compared to the aqueous electroplating film.

Electrodeposited Lithiophilic Zn Thin Film on the Current Collector for Improved Cyclability of Anode-Free Lithium Metal Battery

Anode-free lithium metal batteries (AFMBs) are recently presented as the new generation of Li metal batteries benefiting high gravimetric and volumetric energy densities due to the zero excess lithium. However, poor electrochemical stability and maximum cyclability of around 40-50 cycles due to the zero excess Lithium prevent the AFLMBs to be functional1. Here, lithiophilic electrodeposited Zn thin film on the current collector is reported in order to decrease the lithium nucleation overpotential and improve the plating/stripping process during alloying and dealloying. Moreover, columbic efficiency is increased by applying more zinc coated on the cupper current collector and by providing a more hospitable site for Li nuclei to plate2. Due to the alloy formation of Li-Zn, more conformal Li growth on the current collector is provided and homogeneous Li distribution and smooth morphology are observed by SEM images. The cells in different zinc thin layer coating are cycled with different current densities as well as long-term cycling by galvanostatic cycling charge-discharge cycling. As a result, increasing the thin film thickness up to 1 micron significantly enhances the electrochemical stability of the cells such as higher columbic efficiency and cyclability, lower Li nucleation overpotential. Finally, the Li-ion chemical diffusion coefficients DLi, are evaluated by galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) and the results are compared to each other3.References Maddukuri, S. et al. On the challenge of large energy storage by electrochemical devices. Electrochim Acta 354, 136771 (2020).Merso, S. K. et al. An in-situ formed bifunctional layer for suppressing Li dendrite growth and stabilizing the solid electrolyte interphase layer of anode free lithium metal batteries. J Energy Storage 56, 105955 (2022).Xie, J. et al. Determination of Li-ion diffusion coefficient in amorphous Zn and ZnO thin films prepared by radio frequency magnetron sputtering. Thin Solid Films 519, 3373–3377 (2011).

Room-temperature gas sensing properties of Zn, Sn and Cu-doped TiO2 films

Room-temperature gas sensing properties of Zn, Sn and Cu-doped TiO2 films

Hybrid Organic-Inorganic Additive for Robust Al Anode in Alkaline Aluminum-Air Battery.

Aluminum-air batteries (AABs), known for their high energy density, environmental friendliness, and cost-effectiveness, show immense promise in the realm of energy conversion applications. Nonetheless, their commercialization has encountered inherent challenges of Al anode corrosion and material degradation. In this study, economical hybrid electrolyte additives to inhibit the Al corrosion are developed, safeguarding the integrity of the Al anode. Due to the synergistic interplay between the organic compound dithiothreitol, and inorganic compounds zinc chloride, a robust zinc film is formed on the Al surface This Zn film plays a pivotal role in quelling parasitic hydrogen evolution reactions that typically can plague the Al electrode. Consequently, the as-prepared hybrid additive culminates in a remarkable enhancement to AABs, delivering exceptional discharge capacity of 1793.37mAhg-1 , high energy density of 2047Whkg-1 , and excellent battery longevity (over 20h in on/off cycling tests). This study, therefore, introduces a novel approach in utilizing hybrid electrolyte additives to effectively counteract corrosion-related challenges and boost the stability and performance of AABs.

Effect of graphene oxide coatings on the optical properties of pulsed laser deposited ZnO:Zn thin films

Highly c-axis orientated ZnO:Zn thin films were successfully prepared by pulsed laser deposition and coated with graphene oxide (GO) using nebulizer spray coating. The structural, morphological, and optical properties of the films were studied before and after annealing under different conditions to produce reduced GO (rGO). Following deposition on the surface of the ZnO:Zn films, the GO sheets showed non-uniform and defective textures. Heavily crumbled sheets were observed for rGO annealed in Ar, while wrinkled sheets were observed for rGO annealed in Ar/H2. The uncoated ZnO:Zn exhibited ultraviolet emission at ∼390 nm attributed to the recombination of excitons and a broad band in the range 400–600 nm centred at ∼450 nm attributed to zinc interstitials. The blue emission at ∼450 nm of ZnO:Zn was enhanced after coating with GO and/or rGO, which was attributed to the coupling of the light-emitting centres with localized surface plasmon resonances from the GO/rGO sheets. However, it was found that annealing of uncoated films also improved their luminescence intensity. These results showed that rGO/ZnO films may be useful for some optoelectronic or photoluminescence applications requiring ultraviolet and blue/green light.

Construction of small Zn-air batteries by dendrite-free Zn electrodeposition using renewable electricity

In this work, the possibility to make small, handy but efficient Zn-air batteries has been studied. Battery anode has been constructed by dendrite-free Zn electrodeposition on conductive substrates made of either carbon cloth or brass. Brass was an alloy containing 71% Cu and 21% Zn. Zn electrodeposition has been monitored by applying several (negative) electric potentials ranging between 0 and −0.5 V. Dendrite-free deposits were obtained for voltages ranging between 0 and −0.2 V while extensive dendrite formation was observed with voltages equal to −0.5 V. Uniform Zn deposits were obtained by using the brass substrate. Zn electrodeposition could be realized with a renewable electricity source, in particular by using a photocatalytic fuel cell or a photovoltaic cell. The substrate (electrode) with deposited Zn film was subsequently employed as anode electrode in a Zn-air battery and the battery characteristics have been monitored. The procedures followed in this work support solar energy conversion and storage in a Zn-air battery.

Native defects association enabled room-temperature p-type conductivity in β-Ga2O3

The room temperature hole conductivity of the ultra-wide bandgap semiconductor β-Ga2O3 is a pre-requisite for developing the next-generation electronic and optoelectronic devices based on this oxide. In this work, high-quality p-type β-Ga2O3 thin films grown on r-plane sapphire substrate by metalorganic chemical vapor deposition (MOCVD) exhibit ρ = 5 × 104 Ω·cm resistivity at room temperature. A low activation energy of conductivity as Ea2 = 170 ± 2 meV was determined, associated to the VO++−VGa−native acceptor defect complex. Further, taking advantage of cation (Zn) doping, the conductivity of Ga2O3:Zn film was remarkably increased by three orders of magnitude, showing a long-time stable room-temperature hole conductivity with the conductivity activation energy of around 86 meV. VO++−ZnGa− defect complex has been proposed as a corresponding shallow acceptor.

Effect of prolonged annealing on the morphology and optical properties of ZnO films produced by magnetron sputtering

The effect of annealing time on the structural and optical properties of ZnO films, which are formed from Zn films obtained by magnetron sputtering followed by oxidation in air, is described. Thermal oxidation in air was carried out for 7 and 24 hours, respectively, in a programmable muffle furnace at T = 750°C. A change in the structure of the film surface depending on the annealing time of the Zn film and the substrate material was found, which manifests itself in the optical properties of the films.

Effects of high temperature annealing on sputtered Zn(O,S) films for CdTe solar cells

Effects of high temperature annealing on sputtered Zn(O,S) films for CdTe solar cells