Atomic Layer Deposition Of Thin Films Research Articles

Controlling Pt nanoparticle sintering by sub-monolayer MgO ALD thin films.

Metal nanoparticle (NP) sintering is a major cause of catalyst deactivation, as NP growth reduces the surface area available for reaction. A promising route to halt sintering is to deposit a protective overcoat on the catalyst surface, followed by annealing to generate overlayer porosity for gas transport to the NPs. Yet, such a combined deposition-annealing approach lacks structural control over the cracked protection layer and the number of NP surface atoms available for reaction. Herein, we exploit the tailoring capabilities of atomic layer deposition (ALD) to deposit MgO overcoats on archetypal Pt NP catalysts with thicknesses ranging from sub-monolayers to nm-range thin films. Two different ALD processes are studied for the growth of MgO overcoats on Pt NPs anchored on a SiO2 support, using Mg(EtCp)2 and H2O, and Mg(TMHD)2 and O3, respectively. Spectroscopic ellipsometry and X-ray photoelectron spectroscopy measurements reveal significant growth on both SiO2 and Pt for the former process, while the latter exhibits a drastically lower growth per cycle with an initial chemical selectivity towards Pt. These differences in MgO growth characteristics have implications for the availability of uncoated Pt surface atoms at different stages of the ALD process, as probed by low energy ion scattering, and for the sintering behavior during O2 annealing, as monitored in situ with grazing incidence small angle X-ray scattering (in situ GISAXS). The Mg(TMHD)2-O3 ALD process enables exquisite coverage control allowing a balance between physically blocking the Pt surface to prevent sintering and keeping Pt surface atoms free for reaction. This approach avoids the need for post-annealing, hence also safeguarding the structural integrity of the as-deposited overcoat.

PECVD and PEALD on polymer substrates (part II): Understanding and tuning of barrier and membrane properties of thin films

AbstractThis feature article presents insights concerning the correlation of plasma‐enhanced chemical vapor deposition and plasma‐enhanced atomic layer deposition thin film structures with their barrier or membrane properties. While in principle similar precursor gases and processes can be applied, the adjustment of deposition parameters for different polymer substrates can lead to either an effective diffusion barrier or selective permeabilities. In both cases, the understanding of the film growth and the analysis of the pore size distribution and the pore surface chemistry is of utmost importance for the understanding of the related transport properties of small molecules. In this regard, the article presents both concepts of thin film engineering and analytical as well as theoretical approaches leading to a comprehensive description of the state of the art in this field. Perspectives of future relevant research in this area, exploiting the presented correlation of film structure and molecular transport properties, are presented.

Low temperature plasma-enhanced atomic layer deposition of sodium phosphorus oxynitride with tunable nitrogen content

Atomic layer deposition (ALD) is a key technique in processing new materials compatible with complex architectures. While the processing space for Li-containing ALD thin films has been relatively well explored recently, the space for other alkali metal thin films (e.g., Na) is more limited. Thermal ALD and plasma-enhanced ALD (PEALD) lithium phosphorus oxynitride [Kozen et al., Chem. Mater. 27, 5324 (2015); Pearse et al., Chem. Mater. 29, 3740 (2017)] processes as well as analogous thermal sodium phosphorus oxynitride (NaPON) (Ref. 13) have been previously developed as conformal ALD solid state electrolytes. The main difference between the Na and Li processes is the alkali tert-butoxide precursor (AOtBu, A = Li, Na). One would expect such an isoelectronic substitution with precursors that have similar structure and properties to correlate with a similarly behaved ALD process. However, this work demonstrates that the PEALD NaPON process unexpectedly behaves quite differently from its Li counterpart, introducing some insight into the development of Na-containing thin films. In this work, we demonstrate process development and characterization of an analogous low temperature (250 °C) PEALD of NaPON. This process demonstrates significant tunability of N coordination states by varying plasma nitrogen exposure time. Electrochemical characterization showed an ionic conductivity of 8.2 × 10−9 S/cm at 80 °C and activation energy of 1.03 eV. This first instance of low temperature NaPON deposition by PEALD shows promise for further development and understanding of more versatile processing of Na thin film materials.

In Situ and Ex Situ diagnostics of ALD-Ultrathin Lithium-Ion Films

All solid-state ion layers has an ever-growing interest in order to accomplish on-chip energy storage devices. As such, lithium-ion synaptic transistor to build artificial neural networks, integrated area-enhanced capacitors and lithium-ion microbatteries for energy supply are suitable candidates fulfilling energy-efficient devices. Atomic layer deposition (ALD) is one of the most promising techniques for manufacturing ultrathin layers for lithium-ion devices with exceptional capabilities to enable conformal growth at atomic scale. In this area, in situ diagnostics has become of vital importance for the growth process understanding especially on view of the air-sensitivity character of lithium ultra-thin layers.The purpose of this work is to present an in situ spectroscopic ellipsometry (SE) study of ALD thin films used on the fabrication of lithium-ion devices. We will consider several aspects of ALD ultrathin films growth, such as film thickness, saturation curves and initial films nucleation. We shall compare in situ SE results with those of ex situ diagnostics such as XRR (x-ray reflectometry) and XPS (x-ray photoelectron spectroscopy).We focus on the characterization of 10-100 nm thin lithium phosphate electrolyte with and without nitrogen doping deposited at ALD temperature range 300-350°C using LiHMDS-TMPO and LiHMDS-DEPA precursors, respectively. On the other hand, the realization of silicon integrated lithium ionic devices requires the implementation of essential barrier films to prevent Li-ion into the Si substrate. We will explore here the ability of titanium nitride depositions to act as lithium-ion diffusion barriers. TiN deposition (10-20 nm thin) by ALD process (350°C-400°C) uses TiCl4 and NH3 precursors.First, we investigate the growth process of LiPO, LiPON and TiN intrinsic layers deposited using thermal ALD. Secondly, we apply in situ and ex situ diagnostics on exemplary LiPO/LiPON deposited on top of the 10 nm ALD TiN film (Figure 1: Monitoring of LiPON thickness vs deposition time using in-situ Ellipsometry). The film thickness deduced from in situ SE measurements was corroborated by thickness measurements with XRR technique (Figure 2: Evolution of LiPON thickness vs ALD cycles using Ellipsometry and SE characterization techniques). Ex situ SE was used most often for WiW uniformity evaluating (Figure 3: 8” Wafer thickness mapping of ALD LiPON layers (a: 10nm TiN film; b: 17nm LiPON film). The preliminary results underline the fact that ALD growth rate and nucleation of lithium electrolyte and titanium nitride obviously depends on the ALD process parameters (temperature, pulse and purge times, number of cycles) but on the substrate nature (silicon, thermal oxide, and metallic). In situ and ex situ diagnostics highlight that initial film growth of lithium electrolytes and TiN layers strongly depends on the precursors kind used in the ALD process and the substrate material employed. Figure 1

Evaluation of the Near-Zero Temperature Coefficient of Resistivity (NZ-TCR) of ALD TiSixn Films

Atomic Layer Deposition (ALD) of ternary TiSixN leads to nanocomposites of metallic TiN atomically mixed with insulating Si3N4. Formulating TiSixN films with various Ti:Si ratios lead to the emergence of a temperature regime where resistivity is independent of thermal drift, denoted as near-zero temperature coefficient of resistivity (nz-TCR). Further, the ease with which nanocomposites of TiSixN can be deposited using ALD offer precise tunability in Ti:Si ratio, thickness, mass density, crystallinity and electrical properties.Recently, our group explored TiSixN films deposited using a Eugenus® 300 mm commercial QXP mini-batch system by modulating the ratio of Ti and Si precursors with NH3 as a co-reactant. Si-content was varied from 0 at % (pure TiN) to 24.2 at % Si while maintaining thickness ~ 140 nm. The X-ray reflectivity and grazing incidence X-ray diffraction measurements showed a reduction in film density and transition from nano-crystalline to pure amorphous phase with increase in Si-fraction. Spectroscopic ellipsometry revealed the optical constants, composition, and electrical resistivities and were supported by X-ray photoelectron spectroscopy and electrical measurements. Room-temperature resistivity measurements show an increase in film resistivity with increasing at % Si. Temperature-dependent Van der Pauw measurements found a nz-TCR of -23 ppm K-1 in the temperature range of 298 K – 398 K and at 3.4 at % Si content.We have now discovered that an at % Si = 3.0% induces a nz-TCR of -5.7 ppm K-1 from 80 K – 420 K – one of the best reported nz-TCR values for ALD thin films. Fine tuning the at % Si in TiSixN films, possible only via ALD, significantly elongated the temperature window of nz-TCR behavior. Mapping the local conductivity of individual grains through conductive atomic force microscopy (c-AFM) indicated higher resistance at the grain boundaries. The local composition at the grain boundaries may play a major role in determining the nz-TCR behavior of TiSixN films. In addition, variable temperature Hall effect measurements were performed to provide deeper insights into the nz-TCR mechanism, decoupling carrier concentration from carrier mobility effects while determining film resistivity.Compared to other nz-TCR films, which are deposited using physical vapor deposition techniques, ALD based nz-TCR films presents a unique synthesis platform for interconnect technology in topologically complex, 3D devices, circuits and sensors that undergo large temperature variation during operation but need to maintain stability in their electrical characteristics.

Application of ALD Thin Films on the Surface of the Surgical Scalpel Blade

The article describes biomaterials and surgical instruments, in particular surgical cutting tools. In addition, the functions of coatings and the layer vapor deposition methods are described. In the experimental component of the study, zinc oxide thin film was deposited on the surgical knife blades by the atomic layer deposition (ALD) method with a varying number of cycles. The structures of the deposited thin films were investigated using a Raman spectrometer and the surface topography of the samples was examined using atomic force microscopy and scanning electron microscopy. The adhesion of the thin films was tested using the micro-scratch method. The corrosion resistance was also tested. Surgical instruments coated with non-allergenic metal oxide coatings, containing metal structures that reduce the growth of bacteria, could significantly decrease the risk of undesirable reactions of the body during and after surgery.

Understanding the roles of atomic layer deposition in improving the electrochemical performance of lithium-ion batteries

Rechargeable lithium-ion batteries have been widely used as energy storage devices in electric vehicles and other smart devices due to their excellent properties, such as high energy and power densities, long-term service life, and acceptable cost. The electrochemical performance of the materials in a lithium-ion battery system determines the performance of the battery, so it is essential that the electrochemical properties of these materials be improved. Atomic layer deposition is a versatile thin film coating technique for surface functionalization that can deposit a highly uniform thin film of nanoscale thickness on battery components, and it has been proven to improve the electrochemical performance of materials that operate in a lithium-ion battery system, such as rate capability, interface stability, and cycling life. This review paper focuses on recent advances of application of atomic layer deposition in lithium-ion batteries and summarizes the roles of such thin film coatings in improving the electrochemical performance of batteries. The present review summarizes and classifies the latest understanding of improvement mechanisms proposed by researchers according to different components in lithium-ion batteries, including cathodes, anodes, separators, and solid electrolytes. This review will not only help researchers in this field to comprehend the roles of atomic layer deposition thin film coating for improving the performance of various components in a battery system, but will also help them choose appropriate coating materials on battery components. In addition, we briefly discuss the limitations of atomic layer deposition in lithium-ion battery applications and the challenges that it faces in the future.

Impact of Different Intermediate Layers on the Morphology and Crystallinity of TiO2 Grown on Carbon Nanotubes by Atomic Layer Deposition

AbstractNanocomposites of TiO2 and carbon nanotubes (CNTs) have been extensively studied in photocatalysis, sensing, and energy conversion and storage over the last decade. The unique properties of these nanocomposites are greatly dependent on the morphology, crystallinity, and homogeneity of the TiO2 coating. However, a fine control of the film microstructure is still challenging due to limited understanding of early stages of the TiO2 growth. The presence of an intermediate buffer layer can induce remarkable changes in the morphological and structural characteristics of the coatings. Here, TiO2 films deposited by atomic layer deposition (ALD) on CNTs without and with different intermediate layers (Al2O3 and ZnO) have been systematically investigated. Compared to bare CNTs, it is suggested that these two intermediate layers with higher surface energy can lead to a delay of the TiO2 crystallization, ultimately resulting in the growth of conformal and crystalline TiO2 films. This study demonstrates a strategy to tailor the microstructure and the properties of thin films via ALD by applying intermediate layers and provides information about the role of surface energy of the substrate in crystallization and growth behavior of ALD thin films.

Is Poly(methyl methacrylate) (PMMA) a Suitable Substrate for ALD?: A Review.

Poly (methyl methacrylate) (PMMA) is a thermoplastic synthetic polymer, which displays superior characteristics such as transparency, good tensile strength, and processability. Its performance can be improved by surface engineering via the use of functionalized thin film coatings, resulting in its versatility across a host of applications including, energy harvesting, dielectric layers and water purification. Modification of the PMMA surface can be achieved by atomic layer deposition (ALD), a vapor-phase, chemical deposition technique, which permits atomic-level control. However, PMMA presents a challenge for ALD due to its lack of active surface sites, necessary for gas precursor reaction, nucleation, and subsequent growth. The purpose of this review is to discuss the research related to the employment of PMMA as either a substrate, support, or masking layer over a range of ALD thin film growth techniques, namely, thermal, plasma-enhanced, and area-selective atomic layer deposition. It also highlights applications in the selected fields of flexible electronics, biomaterials, sensing, and photocatalysis, and underscores relevant characterization techniques. Further, it concludes with a prospective view of the role of ALD in PMMA processing.

Phosphites as precursors in atomic layer deposition thin film synthesis

We here demonstrate a new route for deposition of phosphorous based materials by atomic layer deposition (ALD) using the phosphites Me3PO3 or Et3PO3 as precursors. These contain phosphorous in the oxidation state (III) and are open for deposition of reduced phases by ALD. We have investigated their applicability for the synthesis of LiPO and AlPO materials and characterized their growth by means of in situ quartz crystal microbalance. Phosphites are good alternatives to the established phosphate-based synthesis routes as they have high vapor pressure and are compatible with water as a coreactant during deposition. The deposited materials have been characterized using XPS, x-ray fluorescence, and ion beam analysis for composition analysis, spectroscopic ellipsometry for thickness, and FTIR for local structure.

The effect of surface preparation on the protective properties of Al2O3 and HfO2 thin films deposited on cp-titanium by atomic layer deposition

Atomic layer deposition (ALD), a method that allows the formation of thin and conformal films on substrates of interest, was employed to prepare thin films of alumina (Al2O3) and hafnia (HfO2), with the aim of protecting the surface of the commercially pure titanium (cp-Ti) used in biomedical applications. Prior to deposition, cp-Ti specimens have been prepared in two ways – grinding and grinding followed by polishing. Such surfaces have been denoted as rough and smooth, respectively. The thickness, composition, morphology and topography of alumina and hafnia films have been determined using ellipsometry, focused ion beam microscopy with energy dispersive X-ray spectroscopy, time-of-flight secondary ion mass spectrometry and 3D profilometry. A homogeneous stoichiometric composition of alumina and hafnia was obtained with a layer thickness of ca. 150 nm. The anti-corrosive properties of ALD thin films were measured in simulated body fluid solution, using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves. The roughness of the cp-Ti surface plays an important role in the protective properties of these films, especially those of hafnia. In general, when deposited on a smooth surface, ALD films with better anti-corrosive properties were obtained, as evidenced by EIS long-term, 40-day tests. ALD films showed very low porosity, calculated from electrochemical parameters, and significantly lower corrosion current densities, compared with those from bare cp-Ti specimens. Lower porosity and slightly better protective properties were provided by films of hafnia. On the other hand, according to EIS long-term tests, alumina retained slightly greater impedance values than hafnia. Since both alumina and hafnia are biocompatible materials, this study confirms the possibility of their use to reduce the risk of failure of medical implants made of cp-Ti, in the human body environment.

An Advanced Dual‐Function MnO2‐Fabric Air Filter Combining Catalytic Oxidation of Formaldehyde and High‐Efficiency Fine Particulate Matter Removal

AbstractComprehensive treatment of indoor contaminants such as volatile organic compounds (VOCs) and fine particulate matter (PM2.5) using transition metal oxide catalysts or functional fibrous filters has gained substantial attention recently. However, coupling VOC oxidation catalysts into high‐performance filter systems remains a challenge. Herein, an overall solution to strongly bind manganese dioxide (MnO2) nanocrystals onto polypropylene (PP) nonwoven fabrics is provided. For the first time, uniform heterogeneous nucleation and growth of MnO2 onto PP nonwoven fabrics using intermediate inorganic nucleation films, including Al2O3, TiO2, and ZnO, formed conformally on the fabrics via atomic layer deposition (ALD) are demonstrated. How different ALD thin films influence the crystallinity, morphology, surface area, and surface oxygen species of the MnO2 grown ALD‐coated PP fibers is further investigated. In addition to uniformity and integrity, ZnO thin films give rise to MnO2 crystals with the largest fraction of available surface oxygen, enabling 99.5% catalytic oxidation of formaldehyde within 60 min. Moreover, the metal oxide filters provide excellent PM removal efficiencies (ePM), achieving ePM2.5 90% and ePM10 98%, respectively, making the approach an outstanding method to produce fully dual‐functional filtration media.

Applications of Titania Atomic Layer Deposition in the Biomedical Field and Recent Updates

Atomic Layer Deposition (ALD) is a promising technique to precisely deposit nanometer-thick films on inorganic and organic substrates. ALD is known for the deposition of uniform, conformal, and pinhole-free thin films with a controllable thickness with sequential and self-limiting gaseous reactions on the substrate surface of interest. ALD thin films have a wide range of applications, from semiconductor industries to medical devices. In many studies, ALD thin films are used to modify the biomaterial surface properties for particular biomedical applications. Here, polymethyl methacrylate, titanium-based alloys, and collagen were chosen as substrates for this review; thanks to their biocompatibility, these substrates have several applications in the dental, medical, and biomedical fields. The ALD of Titanium (IV) oxide (TiO2) films has been selected for this review as a biocompatible material which has attracted increasing attention in biomedical applications. Selected publications focusing on the modification of the surface of these biomaterials with TiO2 ALD are discussed.

Atomic layer deposition of thermoelectric layered cobalt oxides

Layered cobalt oxides based on the hexagonal CoO2 layer, e.g., NaxCoO2 and [CoCa3O3]0.62CoO2 (or “Ca3Co4O9”), are promising thermoelectric materials. Here, the authors investigate the atomic layer deposition (ALD) of these materials in a thin-film form; this is not trivial, in particular, for the former compound, as both Na and Co are little challenged as components of ALD thin films. The authors employ diketonate precursors for all the metal constituents and ozone as the source of oxygen. In both cases, a postdeposition heat-treatment in O2 is applied to get crystalline coatings; the processes are found amazingly robust in terms of metal precursor pulsing ratios. A striking difference between the two processes is the resultant morphology: while the Ca3Co4O9 films grow highly homogeneous and smooth, the NaxCoO2 coatings exhibit a rather unique reproducible 10–20 μm scale channel-like island structure for all x values investigated. Finally, the authors characterized their ALD Ca3Co4O9 films for their chemical, structural, and physical property details not previously reported.

Probing the Atomic-Scale Structure of Amorphous Aluminum Oxide Grown by Atomic Layer Deposition.

Atomic layer deposition (ALD) is a well-established technique for depositing nanoscale coatings with pristine control of film thickness and composition. The trimethylaluminum (TMA) and water (H2O) ALD chemistry is inarguably the most widely used and yet to date, we have little information about the atomic-scale structure of the amorphous aluminum oxide (AlOx) formed by this chemistry. This lack of understanding hinders our ability to establish process-structure-property relationships and ultimately limits technological advancements employing AlOx made via ALD. In this work, we employ synchrotron high-energy X-ray diffraction (HE-XRD) coupled with pair distribution function (PDF) analysis to characterize the atomic structure of amorphous AlOx ALD coatings. We combine ex situ and in operando HE-XRD measurements on ALD AlOx and fit these experimental data using stochastic structural modeling to reveal variations in the Al-O bond length, Al and O coordination environment, and extent of Al vacancies as a function of growth conditions. In particular, the local atomic structure of ALD AlOx is found to change with the substrate and number of ALD cycles. The observed trends are consistent with the formation of bulk Al2O3 surrounded by an O-rich surface layer. We deconvolute these data to reveal atomic-scale structural information for both the bulk and surface phases. Overall, this work demonstrates the usefulness of HE-XRD and PDF analysis in improving our understanding of the structure of amorphous ALD thin films and provides a pathway to evaluate how process changes impact the structure and properties of ALD films.

Operating pressure influences over micro trenches in exposure time introduced atomic layer deposition

Tremendous interest has been placed on the atomic layer deposition (ALD) process as a thin film deposition technique capacity to deposit quality thin films. However, further comprehension of the ALD process is mandatory to increase the probability of achieving the necessary improvement, which can have a substantial impact on devices’ requiring properties that involve size, performance, and durability. It has been reported that pressure tends to impact growth per cycle. However, little has been done to investigate the specific effects of the – operating pressure on the mechanistic, species transport and reaction rates. Moreover, the effect of these prior properties due to complex topology elements, such as micro-trenches, has rarely been investigated. Hence, this study focuses on numerically investigating the effect between 1 and 10 Torr operating pressure along the ALD process using the computational fluid dynamic approach. A two-dimensional numerical simulation producing Al2O3 ALD thin film over a surface with micro-trenches is studied. Trimethyl-Aluminium and Ozone were utilized as the metal and oxidation source reactants. To assist in the precursor reaction process, a 2.5 s exposure time is added within the ALD sequence. The findings illustrated the fluid flow velocity, surface coverage, mass fraction, deposition rate and growth of the thin-film process.

Demonstration of Sputtering Atomic Layer Augmented Deposition: Aluminum Oxide-Copper Dielectric-Metal Nanocomposite Thin Films.

Designing a thin-film structure often begins with choosing a film deposition method that employs a specific process by which chemical species are formed and transported; in other words, a film deposition system in which two deposition methods are hybridized should lead to new ways of designing thin-film structures. This premise inspires us to combine atomic layer deposition (ALD) and magnetron sputtering (SPU) within a single chamber-supttering atomic layer augmented deposition (SALAD). SALAD takes full advantage of both ALD's precise and accurate precursor delivery and SPU's versatility in choosing chemical elements. A SALAD system is designed based on knowledge obtained from computational fluid dynamics with the goal of conceiving a film deposition system that satisfies deposition conditions distinctive for both ALD and SPU. As a demonstration, the SALAD system is utilized to deposit a unique nanocomposite made of aluminum oxide (Alox) thin films by ALD and copper (Cu) thin films by SPU-AlOx-Cu nanocomposite thin films. Spectroscopic reflectivity collected on AlOx-Cu nanocomposite thin films shows unique dispersion features to which conventional effective medium theories used for describing optical properties of composites made of a dielectric host that contains metallic inclusions do not seem to simply apply.

Atomic Layer Deposition on Dental Materials: Processing Conditions and Surface Functionalization to Improve Properties - a Critical Review

Atomic Layer Deposition (ALD) is a well-established thin film deposition technique. It is being used for surface functionalization in different technologies and biological related applications. In the current work, ALD is elaborated as a promising method for surface modification of dental materials. Different aspects of conventional dental materials that can be enhanced using ALD are discussed. Also, the influence of different ALD thin films and their microstructure on the surface properties, corrosion-resistance, antibacterial activity, biofilm formation, and osteoblast compatibility are addressed. Depending on the stage of advancement for the studied materials reported in the literature, these studies are then categorized into four stages: fabrication & characterization, in vitro studies, in vivo studies, and human tests. Materials coated with ALD thin films with potential dental applications are also presented here and they are categorized as stage 1. The current study can serve as a guide for future work on using ALD for surface functionalization and resulting property tuning of materials in real world dental applications.

Protective Fabrics: Metal-Organic Framework Textiles for Rapid Photocatalytic Sulfur Mustard Simulant Detoxification

Summary Metal-organic frameworks (MOFs) can catalyze toxic chemical decontamination, but new MOF materials and synthesis strategies are needed to improve performance, particularly in field-usable MOF-textile formats. This article reports for the first time the exceptional photocatalytic reactivity of Al-PMOF (Al-porphyrin-based MOF), composed of an earth-abundant metal-containing Al(OH)O4 cluster bridged by H2TCPP (5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin) chromophores, against the toxic sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES) under visible-light irradiation. Furthermore, Al-PMOF is strongly immobilized into polymeric fibers via well-controlled Al2O3 solid film conversion using dimethylformamide/water cosolvent. The approach enables a secure integration of conformal Al-PMOF films onto polymer fibers at a relatively low synthesis temperature (120°C). In addition, on a per-unit mass of MOF basis, the surface-bound Al-PMOF films enable extremely rapid CEES detoxification turnover frequency, up to 170 mol CEES mol chromophore − 1 min − 1 , more than 10-fold faster than the best MOF powders and 2-fold better than MOF films reported to date.

Improved corrosion protection of CrN hard coating on steel sealed with TiOxNy-TiN composite layers

Based on the excellent conformality and uniformity of atomic layer deposition (ALD), ALD thin films can seal the defects in magnetron sputtered CrN coating. In this work, atomic layer deposited TiN layer is adopted to seal CrN to improve its anti-corrosion properties. The oxidization of TiN forms TiOxNy-TiN composite layer including TiN bottom layer and TiOxNy upper layer, which can limit the charge transport, inhibit the diffusion of corrosive media, such as chlorine ions. Therefore, the addition of TiOxNy-TiN sealing layer significantly improves the corrosion resistance of CrN coated steel, and decreases its corrosion current density, due to the synergistic effect of TiOxNy and TiN in the composite sealing layer.