Substrate-induced strain in molybdenum disulfide grown by aerosol-assisted chemical vapor deposition.

Transition metal dichalcogenides have been extensively studied in recent years because of their fascinating optical, electrical, and catalytic properties. However, low-cost, scalable production remains a challenge. Aerosol-assisted chemical vapor deposition (AACVD) provides a new method for scalable thin film growth. In this study, we demonstrate the growth of molybdenum disulfide (MoS2) thin films using AACVD method. This method proves its suitability for low-temperature growth of MoS2thin films on various substrates, such as glass, silicon dioxide, quartz, silicon, hexagonal boron nitride, and highly ordered pyrolytic graphite. The as-grown MoS2shows evidence of substrate-induced strain. The type of strain and the morphology of the as-grown MoS2highly depend on the growth substrate's surface roughness, crystallinity, and chemical reactivity. Moreover, the as-grown MoS2shows the presence of both direct and indirect band gaps, suitable for exploitation in future electronics and optoelectronics.

Transfer of High-Temperature-Sputtered BiFeO3 Thin Films onto Flexible Substrates Using α-MoO3 Layers.

Inducing external strains on highly oriented thin films transferred onto mechanically deformable substrates enables a drastic enhancement of their ferroelectric, magnetic, and electronic performances, which cannot be achieved in films on rigid single crystals. Herein, the growth and diffusion behaviors of BiFeO3 thin films grown at various temperatures is reported on α-MoO3 layers of different thicknesses using sputtering. When the BiFeO3 thin films are deposited at a high temperature, significant diffusion of Fe into α-MoO3 occurs, producing the Fe1.89Mo4.11O7 phase and suppressing the maintenance of the 2D structure of the α-MoO3 layers. Although lowering the deposition temperature alleviates the diffusion yielding the survival of the α-MoO3 layer, enabling exfoliation, the BiFeO3 is amorphous and the formation of the Fe1.89Mo4.11O7 phase cannot be suppressed at the crystallization temperature. High-temperature-grown BiFeO3 thin films are successfully transferred onto flexible substrates via mechanical exfoliation by introducing a blocking layer of Au and measured the ferroelectric properties of the transferred films.

Electrostatic Correlations Lead to High Capacitance in Zwitterion-Containing Thin Films.

A novel zwitterion composed of an imidazolium tethered to an anionic sulfonyl(trifluoromethane sulfonyl)imide group was prepared as an alternative dielectric material to traditional ionic liquids. The zwitterion not only melted below 100 °C but also proved to be nonhygroscopic. High-capacitance organic dielectric materials were obtained by blending this compound with poly(methyl methacrylate) over a range of concentrations and thicknesses. Above a specific temperature and concentration, films exhibit a capacitance nearly equivalent to that of an electrostatic double layer, approximately 10 µF/cm2, regardless of their thickness. Grazing-incidence wide-angle X-ray scattering experiments suggest that the zwitterions adopt a lamellar ordering at their surface above a critical concentration. The observed ordering is correlated with a 1000-fold increase in capacitance. The behavior suggests that the zwitterions exhibit strong electrostatic correlations throughout the film bulk, pointing the way toward a novel class of organic dielectric materials.

Piezoelectric Charge Coefficient of Halide Perovskites.

Halide perovskites are an emerging family of piezoelectric and ferroelectric materials. These materials can exist in bulk, single-crystal, and thin-film forms. In this article, we review the piezoelectric charge coefficient (dij) of single crystals, thin films, and dimension-tuned halide perovskites based on different measurement methods. Our study finds that the (dij) coefficient of the bulk and single-crystal samples is mainly measured using the quasi-static (Berlincourt) method, though the piezoforce microscopy (PFM) method is also heavily used. In the case of thin-film samples, the (dij) coefficient is dominantly measured by the PFM technique. The reported values of dij coefficients of halide perovskites are comparable and even better in some cases compared to existing materials such as PZT and PVDF. Finally, we discuss the promising emergence of quasi-static methods for thin-film samples as well.

Thin Layers of Cerium Oxynitride Deposited via RF Sputtering.

Thin films of transition metal oxides and oxynitrides have proven highly effective in protecting stainless steels against corrosion in both chemically aggressive environments and biological fluids. In the present work, cerium zirconium oxynitride thin films were deposited to enhance the corrosion resistance of surgical-grade stainless steel to be used in osteosynthesis processes. Two techniques were employed: co-sputtering and radiofrequency (RF) sputtering, and the morphology and corrosion efficiency of the coatings deposited by each technique were evaluated. X-ray diffraction, X-ray photoelectron spectroscopy and field emission transmission electron microscopy were used to characterize the morphological and chemical structure, respectively. Additionally, the corrosion resistance of the oxynitride-coated surgical grade stainless steel system (ZrCeOxNy-AISI 316L) was assessed using Hank's solution as the corrosive electrolyte, to determine its resistance to corrosion in biological media. The results show that ZrCeOxNy coatings increase the corrosion resistance of surgical grade stainless steel by two orders of magnitude and that the Ce(III)/Ce(IV) equilibrium decreases the corrosion rate, thereby increasing the durability of the steel in a biological environment. The results show that Ce coatings increase the corrosion resistance of surgical grade stainless steel by two orders of magnitude and that the Ce(III)/Ce(IV) equilibrium decreases the corrosion rate, thereby increasing the durability of the steel in a biological environment.

Structure and Selected Properties of SnO2 Thin Films.

Magnesium and its alloys are attractive temporary implants due to their biocompatibility and biodegradability. Moreover, Mg has good mechanical and osteoinductive properties. But magnesium and Mg alloys have one significant disadvantage: poor corrosion resistance in a physiological environment. Hence, a deposition of various layers on the surface of Mg alloys seems to be a good idea. The purpose of the article is to analyze the structure and morphology of two MgCa2Zn1 and MgCa2Zn1Gd3 alloys coated by SnO2 ALD (atomic layer deposition) films of various thickness. The studies were performed using scanning electron microscopy (SEM), X-ray fluorescence (XRF), and an X-ray diffractometer. The corrosion activity of the thin films and substrate alloys in a chloride-rich Ringer's solution at 37 °C was also observed. The corrosion tests that include electrochemical, immersion measurements, and electrochemical impedance spectroscopy (EIS) were evaluated. The results indicated that SnO2 had a heterogeneous crystal structure. The surfaces of the thin films were rough with visible pores. The corrosion resistance of SnO2 measured in all corrosion tests was higher for the thicker films. The observations of corrosion products after immersion tests indicated that they were lamellar-shaped and mainly contained Mg, O, Ca, and Cl in a lower concentration.

Rare Earth Material for Hydrogen Gas Sensing: PtGd Alloy Thin Films as a Promising Frontier.

At the focus of our investigation lies the precision fabrication of ultrathin platinum-gadolinium (PtGd) alloy films, with the aim to use these films for resistive hydrogen gas sensing. The imperative for sensitive and selective sensors to harness hydrogen's potential as an alternative energy source drives our work. Applying rare earth materials, we enhance the capabilities of hydrogen gas sensing applications. Our study pioneers PtGd alloy thin films for hydrogen gas sensing, addressing a gap in existing literature. Here, we demonstrate the functional characteristics of 2 nm thick PtxGd100'x (x = 25, 50 and 75) alloy films, analyzing their hydrogen gas sensing properties, comprehensively examining the interplay between alloy composition, temperature fluctuation and hydrogen concentration. The effect of composition and structural properties on the sensing response were assessed using EDX and XPS. The films are tested at a temperature range between 25 °C and 150 °C with hydrogen gas concentrations ranging from 10 ppm to 5%. Hydrogen gas sensing mechanisms in PtGd alloy ultrathin films are explained by surface scattering. The unique combination of Pt and Gd offers promising characteristics for gas sensing applications, including high reactivity with hydrogen gas and tunable sensitivity based on the alloy composition.

Effect of repeating hydrothermal growth processes and rapid thermal annealing on CuO thin film properties.

This paper presents an investigation into the influence of repeating cycles of hydrothermal growth processes and rapid thermal annealing (HT+RTA) on the properties of CuO thin films. An innovative hydrothermal method ensures homogeneous single-phase films initially. However, their electrical instability and susceptibility to cracking under the influence of temperature have posed a challenge to their utilization in electronic devices. To address this limitation, the HT+RTA procedure has been developed, which effectively eliminated the issue. Comprehensive surface analysis confirmed the procedure's ability to yield continuous films in which the content of organic compounds responsible for the formation of cracks significantly decreases. Structural analysis underscored the achieved improvements in the crystalline quality of the films. The implementation of the HT+RTA procedure significantly enhances the potential of CuO films for electronic applications. Key findings from Kelvin probe force microscopy analysis demonstrate the possibility of modulating the work function of the material. In addition, scanning capacitance microscopy measurements provided information on the changes in the local carrier concentration with each repetition. These studies indicate the increased usefulness of CuO thin films obtained from the HT+RTA procedure, which expands the possibilities of their applications in electronic devices.

Se-Elemental Concentration Gradient Regulation for Efficient Sb2(S,Se)3 Solar Cells with High Open-Circuit Voltages.

Antimony selenosulfide (Sb2(S,Se)3), featuring large absorption coefficient, excellent crystal structure stability, benign non-toxic characteristic, outstanding humidity and ultraviolet tolerability, has recently attracted enormous attention and research interest regarding its photoelectric conversion properties. However, the open-circuit voltage (Voc) for Sb2(S,Se)3-based photovoltaic devices is relatively low, especially for the device with a high power conversion efficiency (η). Herein, an innovative Se-elemental concentration gradient regulation strategy has been exploited to produce high-quality Sb2(S,Se)3 films on TiO2/CdS substrates through a thioacetamide(TA)-synergistic dual-sulfur source hydrothermal-processed method. The Se-elemental gradient distribution produces a favorable energy band structure, which suppresses the energy level barriers for hole transport and enhances the driving force for electron transport in Sb2(S,Se)3 film. This facilitates efficient charge transport/separation of photogenerated carriers and boosts significantly the Voc of Sb2(S,Se)3 photovoltaic devices. The champion TA-Sb2(S,Se)3 planar heterojunction (PHJ) solar cell displays an considerable η of 9.28% accompanied by an exciting Voc rising to 0.70 V that is currently the highest among Sb2(S,Se)3-based solar cells with efficiencies exceeding 9.0%. This research is anticipated to contribute to the preparation of high-quality Sb2(S,Se)3 thin film and the achievement of efficient inorganic Sb2(S,Se)3 PHJ photovoltaic device.

Magnetic anisotropy and GGG substrate stray field in YIG films down to millikelvin temperatures.

Quantum magnonics investigates the quantum-mechanical properties of magnons, such as quantum coherence or entanglement for solid-state quantum information technologies at the nanoscale. The most promising material for quantum magnonics is the ferrimagnetic yttrium iron garnet (YIG), which hosts magnons with the longest lifetimes. YIG films of the highest quality are grown on a paramagnetic gadolinium gallium garnet (GGG) substrate. The literature has reported that ferromagnetic resonance (FMR) frequencies of YIG/GGG decrease at temperatures below 50 K despite the increase in YIG magnetization. We investigated a 97 nm-thick YIG film grown on 500 µm-thick GGG substrate through a series of experiments conducted at temperatures as low as 30 mK, and using both analytical and numerical methods. Our findings suggest that the primary factor contributing to the FMR frequency shift is the stray magnetic field created by the partially magnetized GGG substrate. This stray field is antiparallel to the applied external field and is highly inhomogeneous, reaching up to 40 mT in the center of the sample. At temperatures below 500 mK, the GGG field exhibits a saturation that cannot be described by the standard Brillouin function for a paramagnet. Including the calculated GGG field in the analysis of the FMR frequency versus temperature dependence allowed the determination of the cubic and uniaxial anisotropies. We find that the total crystallographic anisotropy increases more than three times with the decrease in temperature down to 2 K. Our findings enable accurate predictions of the YIG/GGG magnetic systems behavior at low and ultralow millikelvin temperatures, crucial for developing quantum magnonic devices.

Amphiphilic Nanoscale Antifog Coatings: Improved Chemical Robustness by Continuous Assembly of Polymers.

Designing effective antifog coatings poses challenges in resisting physical and chemical damage, with persistent susceptibility to decomposition in aggressive environments. As their robustness is dictated by physicochemical structural features, precise control through unique fabrication strategies is crucial. To address this challenge, a novel method for crafting nanoscale antifog films with simultaneous directional growth and cross-linking is presented, utilizing solid-state continuous assembly of polymers via ring-opening metathesis polymerization (ssCAPROMP). A new amphiphilic copolymer (specified as macrocross-linker) is designed by incorporating polydimethylsiloxane, poly(2-(methacryloyloxy)ethyl) trimethylammonium chloride (PMETAC), and polymerizable norbornene (NB) pendant groups, allowing ssCAPROMP to produce antifog films under ambient conditions. This novel approach results in distinctive surface and molecular characteristics. Adjusting water-absorption and nanoscale assembly parameters produced ultra-thin (≤100 nm) antifog films with enhanced durability, particularly against strong acidic and alkaline environments, surpassing commercial antifog glasses. Thickness loss analysis against external disturbances further validated the stable surface-tethered chemistries introduced through ssCAPROMP, even with the incorporation of minimal content of cross-linkable NB moieties (5 mol%). Additionally, a potential zwitter-wettability mechanism elucidates antifog observations. This work establishes a unique avenue for exploring nanoengineered antifog coatings through facile and robust surface chemistries.

Classical Concept of Semiconductor Heterojunctions in the Approach to Nanohybrid Catalysts.

Recalling the well-established theory of heterojunction formation between two different semiconductors or a semiconductor and a metal can elucidate the remarkable catalytic properties of nanohybrid systems employed in thermal catalysis. Upon the creation of heterojunctions, involved nanoparticles or nanometer-sized thin films, as a result of their dimensions, may become entirely filled with space charges generated from the development of depletion or accumulation regions. This phenomenon dictates the nature of catalytic sites and consequently affects the catalytic activity of such nanohybrids. The following perspective presents this concept and examples of experimental results that substantiate its validity, along with an extremely effective tool, cold plasma deposition, for designing and realizing in a controlled manner the structure of nanohybrids with heterojunctions. This approach will undoubtedly broaden the view of the contemporary "alchemy" of nanocatalysts.

Covalent organic frameworks in tribology - A perspective.

Two-dimensional covalent organic frameworks (2D COFs) are an emerging class of crystalline porous materials formed through covalent bonds between organic building blocks. COFs uniquely combine a large surface area, an excellent stability, numerous abundant active sites, and tunable functionalities, thus making them highly attractive for numerous applications. Especially, their abundant active sites and weak interlayer interaction make these materials promising candidates for tribological research. Recently, notable attention has been paid to COFs as lubricant additives due to their excellent tribological performance. Our review aims at critically summarizing the state-of-art developments of 2D COFs in tribology. We discuss their structural and functional design principles, as well as synthetic strategies with a special focus on tribology. The generation of COF thin films is also assessed in detail, which can alleviate their most challenging drawbacks for this application. Subsequently, we analyze the existing state-of-the-art regarding the usage of COFs as lubricant additives, self-lubrication composite coatings, and solid lubricants at the nanoscale. Finally, critical challenges and future trends of 2D COFs in tribology are outlined to initiate and boost new research activities in this exciting field.

High-Throughput Micro-Combinatorial TEM Phase Mapping of the DC Magnetron Sputtered YxTi1-xOy Thin Layer System.

High-throughput methods are extremely important in today's materials science, especially in the case of thin film characterization. The micro-combinatorial method enables the deposition and characterization of entire multicomponent thin film systems within a single sample. In this paper, we report the application of this method for the comprehensive TEM characterization of the Y-Ti-O layer system. Variable composition samples (YxTi1-xOy) were prepared by dual DC magnetron sputtering, covering the entire (0 ≤ x ≤ 1) concentration range. The structure and morphology of phases formed in both as-deposited and annealed samples at 600, 700, and 800 °C were revealed as a function of Y-Ti composition (x). A comprehensive map showing the appropriate amorphous and crystalline phases, and their occurrence regions of the whole Y-Ti-O layer system, was revealed. Thanks to the applied method, it was shown with ease that at the given experimental conditions, the Y2Ti2O7 phase with a pyrochlore structure forms already at 700 °C without the TiO2 and Y2O3 by-phases, which is remarkably lower than the required temperature for most physical preparation methods, demonstrating the importance and benefits of creating phase maps in materials science and technology.

Ring-shaped colloidal patterns on saline water films.

HYPOTHESIS: Electrostatically stabilised colloidal particles destabilise when brought into contact with cations causing the particles to aggregate in clusters. When a drop with stabilised colloidal partices is deposited on a liquid film containing cations the delicate balance between the fluid-mechanical and physicochemical properties of the system governs the spreading dynamics and formation of colloidal particle clusters. EXPERIMENTS: High-speed imaging and digital holographic microscopy were used to characterise the spreading process. FINDINGS: We reveal that a spreading colloidal drop evolves into a ring-shaped pattern after it is deposited on a thin saline water film. Clustered colloidal particles aggregate into larger trapezoidally-shaped 'supraclusters'. Using a simple model we show that the trapezoidal shape of the supraclusters is determined by the transition from inertial spreading dynamics to Marangoni flow. These results may be of interest to applications such as wet-on-wet inkjet printing, where particle destabilisation and hydrodynamic flow coexist.

Wafer Scale Insulation of High Aspect Ratio Through-Silicon Vias by iCVD.

In microelectronics, one of the main 3D integration strategies consists of vertically stacking and electrically connecting various functional chips using through-silicon vias (TSVs). For the fabrication of the TSVs, one of the challenges is to conformally deposit a low dielectric constant insulator thin film at the surface of the silicon. To date, there is no universal technique that can address all types of TSV integration schemes, especially in the case requiring a low deposition temperature. In this work, an organosilicate polymer deposited by initiated chemical vapor deposition (iCVD) was developed and integrated as an insulating layer for TSVs. Process studies have shown that poly(1,3,5-trivinyl-1,3,5-trimethyl cyclotrisiloxane) (P(V3D3)) can present good conformality on high aspect ratio features by increasing the substrate temperature up to 100 °C. The trade-off is a moderate deposition rate. The thermal stability of the polymer has been investigated, and we show that a thermal annealing at 400 °C (with or without ultraviolet exposure) allows the stabilization of the dielectric films by removing residual oligomers. Then, P(V3D3) was integrated in high aspect ratio TSV (10 × 100 µm) on 300 mm silicon wafers using a standard integration flow for TSV metallization. Functional devices were successfully fabricated (including daisy chains of 754 TSVs) and electrically characterized. Our work shows that the metallization barrier should be carefully selected to eliminate the appearance of voids at the top corner of the TSV after the Cu annealing step. Moreover, an appropriate integration process should be used to avoid the appearance of cohesive cracks in the liner. This work constitutes a first proof of concept of the use of an iCVD polymer in a quasi-industrial microelectronic environment. It also highlights the benefit of iCVD as a promising technique to deposit conformal dielectric thin films in a microelectronic pilot line environment.

Enhanced Spectroscopic Insight into Acceptor-Modified Barium Strontium Titanate Thin Films Deposited via the Sol-Gel Method.

In the present paper, composite thin films of barium strontium titanate (BaxSr1-xTiO3) with an acceptor modifier (magnesium oxide-MgO) were deposited on metal substrates (stainless steel type) using the sol-gel method. The composite thin films feature BaxSr1-xTiO3 ferroelectric solid solution as the matrix and MgO linear dielectric as the reinforcement, with MgO concentrations ranging from 1 to 5 mol%. Following thermal treatment at 650 °C, the films were analyzed for their impedance response. Experimental impedance spectra were modeled using the Kohlrausch-Williams-Watts function, revealing stretching parameters (ß) in the range of approximately 0.78 to 0.89 and 0.56 to 0.90 for impedance and electric modulus formalisms, respectively. Notably, films modified with 3 mol% MgO exhibited the least stretched relaxation function. Employing the electric equivalent circuit method for data analysis, the "circle fit" analysis demonstrated an increase in capacitance from 2.97 × 10-12 F to 5.78 × 10-10 F with the incorporation of 3 mol% MgO into BST-based thin films. Further analysis based on Voigt, Maxwell, and ladder circuits revealed trends in resistance and capacitance components with varying MgO contents, suggesting non-Debye-type relaxation phenomena across all tested samples.

Optimization of Magnetic Tunnel Junction Structure through Component Analysis and Deposition Parameters Adjustment.

In this work, we focus on a detailed study of the role of each component layer in the multilayer structure of a magnetic tunnel junction (MTJ) as well as the analysis of the effects that the deposition parameters of the thin films have on the performance of the structure. Various techniques including atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to investigate the effects of deposition parameters on the surface roughness and thickness of individual layers within the MTJ structure. Furthermore, this study investigates the influence of thin films thickness on the magnetoresistive properties of the MTJ structure, focusing on the free ferromagnetic layer and the barrier layer (MgO). Through systematic analysis and optimization of the deposition parameters, this study demonstrates a significant improvement in the tunnel magnetoresistance (TMR) of the MTJ structure of 10% on average, highlighting the importance of precise control over thin films properties for enhancing device performance.

Fe(Se,Te) Thin Films Deposited through Pulsed Laser Ablation from Spark Plasma Sintered Targets.

Iron-based superconductors are under study for their potential for high-field applications due to their excellent superconducting properties such as low structural anisotropy, large upper critical fields and low field dependence of the critical current density. Between them, Fe(Se,Te) is simple to be synthesized and can be fabricated as a coated conductor through laser ablation on simple metallic templates. In order to make all the steps simple and fast, we have applied the spark plasma sintering technique to synthesize bulk Fe(Se,Te) to obtain quite dense polycrystals in a very short time. The resulting polycrystals are very well connected and show excellent superconducting properties, with a critical temperature onset of about 16 K. In addition, when used as targets for pulsed laser ablation, good thin films are obtained with a critical current density above 105 A cm-2 up to 16 T.

The Potential of Spot Size Control in Shaping the Thickness Distribution in Ultrashort Laser Deposition.

The availability of new-generation femtosecond lasers capable of delivering pulses with energies in the hundreds of mJ, or even in the joules range, has called for a revision of the effect of scaling spot size on the material distribution within the plasma plume. Employing a state-of-the-art Szatmári-type hybrid dye-excimer laser system emitting 248 nm pulses with a maximum energy of 20 mJ and duration of 600 fs, copper films were grown in the classical pulsed laser deposition geometry. The exceptionally clean temporal profile of the laser pulses yielded a femtosecond component of 4.18 ± 0.19 mJ, accompanied by a 0.22 ± 0.01 mJ ASE pedestal on the target surface. While varying the spot sizes, the plasma plume consistently exhibited an extremely forward-peaked distribution. Deposition rates, defined as peak thickness per number of pulses, ranged from 0.030 to 0.114 nm/pulse, with a gradual narrowing of the thickness distribution as the spot area increased from 0.085 to 1.01 mm2 while keeping the pulse energy constant. The material distribution on the silicon substrates was characterized using the f(Θ) = AcoskΘ + (1 - A)cospΘ formalism, revealing exponents characterizing the forward-peaked component of the thickness profile of the film material along the axes, ranging from k = 15 up to exceptionally high values exceeding 50, as the spot area increased. Consequently, spot size control and outstanding beam quality ensured that majority of the ablated material was confined to the central region of the plume, indicating the potential of PLD (pulsed laser deposition) for highly efficient localized deposition of exotic materials.