Amorphous Films Research Articles

Deposition of hydrogenated amorphous carbon films by CH4/Ar capacitively coupled plasma using tailored voltage waveform discharges

We investigated the effects of tailored voltage waveform (TVW) discharges on the deposition of hydrogenated amorphous carbon (a-C:H) films in CH4/Ar capacitively coupled plasma. TVW discharges employ two driving radio frequencies (13.56 MHz and 27.12 MHz) and control their phase shifts to independently regulate ion bombardment energy (IBE) and ion flux. In this study, a-C:H films were deposited by changing DC-self bias with phase shift and constant applied voltage peak-to-peak. Additionally, we investigated phase-resolved optical emission spectroscopy (PROES) for plasma characterization. As a result, plasma-enhanced CVD (PECVD) for a-C:H films using TVW discharges realize control of film properties such as mass density, sp3 fraction, and H content, while keeping the deposition rate constant. Thus, it is suggested that TVW discharges realize the independent control of IBE and ion flux with high accuracy, highlighting its utility in a-C:H film depositions.

Measuring thermal conductivity using H2-O2 flame on ceramic films prepared by atmospheric chemical vapor deposition

Uneven micron-sized pores on the surface of the polycrystalline alumina (Al2O3) substrates can affect their performance as electrical insulating plates. In this study, we investigated the sealing of these pores with amorphous Al2O3 films deposited via atmospheric chemical vapor deposition. Furthermore, we conducted annealing treatments on the samples. The color change of the deposited Al2O3 films was investigated using the Commission Internationale de I’Eclairage color space. Notably, the deposited films initially changed the sample color from white to orange or brown. However, increasing the annealing temperature and duration reversed this discoloration effectively and restored the original white (colorless) appearance of the sample. We measured thermal conductivity using the flame flash method with the H2-O2 flame to assess the influence of sealing. While the unsealed substrate exhibited a thermal conductivity of 4.66 W/mK in the range of 400–500 °C, the annealed and flattened Al2O3 film deposited on the substrate maintained a comparable thermal conductivity of 4.67 W/mK within the same temperature range. This finding demonstrates that our sealing method successfully filled the pores while having minimal influence on thermal conductivity, which is a crucial property for electrical insulation applications.

Polymer-like hydrogenated amorphous carbon thin films fabricated by plasma-enhanced chemical vapor deposition of cyclohexane precursor

Hydrogenated amorphous carbon (a-C:H) films were fabricated by plasma-enhanced chemical vapor deposition (PECVD) of a cyclohexane precursor at ambient temperature at varying deposition pressures from 19.73 to 38.00 Pa and varying plasma powers from 20 to 80 W. The deposition rate of the a-C:H films was strongly dependent on the deposition conditions. The films were all optically transparent with extinction coefficient below 0.0042. The refractive index as an indicator of the film's density varied depending on the deposition conditions. Their surfaces were all hydrophobic regardless of the deposition conditions. The a-C:H films had wide optical bandgaps ranging from 3.09 to 3.69 eV. The refractive index and FTIR spectra were consistent with those of polymer-like a-C:H films. As the deposition pressure decreased and plasma power increased, the intensity of a dominant peak of CHx stretching mode in the FTIR spectra decreased. The relative hydrogen content of the a-C:H films was estimated from an FTIR analysis and determined to have an inverse relationship with refractive index. These results indicated that the formation of more energetic plasmas during deposition at lower pressures and higher plasma powers led to the a-C:H films with reduced hydrogen content and increased density. The observed film properties could be advantageous for several applications, particularly as protective, wear-resistant, low-friction, or anti-reflective coatings for optical windows.

Binder-free nickel/boron-doped diamond film electrodes for hydrogen evolution reaction in alkaline medium: Effect of nickel catalyst nanostructure on electrochemical performance

Boron-doped diamond (BDD) is a robust electrode material, and Ni metal is a promising alternative electrocatalyst to noble metals for promoting the hydrogen evolution reaction. In this study, binder-free Ni/BDD film electrodes, with Ni acting as a catalyst, were constructed. With thermal annealing temperature regulation, the Ni catalyst exhibited different nanostructures, including amorphous continuous films, partially crystalline corrugated films, and uniformly dispersive nanoparticles. The electrodes were characterized via scanning electron microscopy, grazing-incidence X-ray diffraction, and X-ray photoelectron spectroscopy. Furthermore, the impact of the Ni catalyst fine structure on the hydrogen evolution reaction performance was evaluated. The results highlighted the versatility of BDD as a platform for developing binder-free Ni/BDD electrodes. Through precise adjustment of the nano-scale structure of Ni catalysts on the BDD surface, high hydrogen evolution reaction activity was achieved, with an overpotential as low as 273 mV at 10 mA/cm2 in a 1 M KOH solution.

Transforming an Ionic Conductor into an Electronic Conductor via Crystallization: In Situ Evolution of Transference Numbers and Structure in (La,Sr)(Ga,Fe)O3‐x Perovskite Thin Films

AbstractMixed‐conducting perovskites are workhorse electrochemically active materials, but typical high‐temperature processing compromises their catalytic activity and chemo‐mechanical integrity. Low‐temperature pulsed laser deposition of amorphous films plus mild thermal annealing is an emerging route to form homogeneous mixed conductors with exceptional catalytic activity, but little is known about the evolution of the oxide‐ion transport and transference numbers during crystallization. Here the coupled evolution of ionic and electronic transport behavior and structure in room‐temperature‐grown amorphous (La,Sr)(Ga,Fe)O3‐x films as they crystallize is explored. In situ ac‐impedance spectroscopy with and without blocking electrodes, simultaneous capturingsynchrotron‐grazing‐incidence X‐ray diffraction, dc polarization, transmission electron microscopy, and molecular dynamics simulations are combined to evaluate isothermal and non‐isothermal crystallization effects and the role of grain boundaries on transference numbers. Ionic conductivity increases by ≈2 orders of magnitude during crystallization, with even larger increases in electronic conductivity. Consequently, as crystallinity increases, LSGF transitions from a predominantly ionic conductor to a predominantly electronic conductor. The roles of evolving lattice structural order, microstructure, and defect chemistry are examined. Grain boundaries appear relatively nonblocking electronically but significantly blocking ionically. The results demonstrate that ionic transference numbers can be tailored over a wide range by tuning crystallinity and microstructure without having to change the cation composition.

Atomic-scale understanding on the influence of sliding angle on the interfacial structure and friction behavior of textured amorphous carbon films

Textured amorphous carbon (T:a-C) films have received great attention in the fields of hard drives, MEMS, and NEMS due to their excellent tribological properties. However, there is still a lack of research on the dependence of its friction behavior on different sliding angles. Especially, owing to the limitations of in-situ characterization in capturing the friction interface information, the potential friction mechanisms are still unclear. Hence, in this work T:a-C film with a rectangular shape was constructed and the impact of different sliding angles on friction behavior under dry friction condition was mainly explored through reactive molecular dynamics simulation. Results unveil that the friction properties of T:a-C films are closely dependent on the sliding angle. When the sliding angle increases from 0° to 45°, the decrease in the number of CC covalent bonds at the friction interface weakens the interfacial crosslinking effect, leading to a decrease in the friction coefficient by 20.11 %. However, as the sliding angle further increases from 45° to 90°, an increase in friction coefficient is observed, which is due to the increase of unsaturated bond content, weakening the interface passivation effect. These results reveal the friction mechanism of T:a-C films, induced by sliding angle, and effectively guide the design and technical application of textured a-C films.

Porous-anodic-alumina-templated Ta-Nb-alloy/oxide coatings via the magnetron-sputtering/anodizing as novel 3D nanostructured electrodes for energy-storage applications

The Ta-52 at.%Nb thin alloy films were magnetron sputter-deposited over a low-aspect-ratio nanoporous anodic-alumina template formed in 0.05 M tartaric acid solution at 250 V and modified by the pore-widening technique to enlarge the pores up to ∼500 nm. The alloy coated the pores evenly, thus forming a 3D continuous conducting nanofilm on the template. Partially anodizing the templated alloy in a borate buffer solution of pH 7.5 generated a compact amorphous mixed-oxide anodic film thickening proportionally to the applied voltage. It was revealed that the oxide on the Ta-52 at.%Nb alloy grows with a slower migration of Ta5+ ions relative to Nb5+ ions, resulting in mixing Ta2O5 and Nb2O5 in the film depth and forming a few-nm-thick Nb2O5 outmost layer. The unique migration of Ta4+, Ta3+, Nb4+, and Nb3+ ions is assumed accountable for forming corresponding suboxides in the 3D anodic film in contrast to a flat Ta-52 at.%Nb alloy film used as a reference. The 3D anodic films behave as an n-type semiconductor with a low donor density Nd = ∼2 × 1018 cm−3, appropriate for dielectric applications. An unusual two-layered structure with a sharp electrical interface revealed in the 3D oxide films anodized to 30–130 V, comprising a low-resistivity layer superimposed on the high-resistivity layer, is explained by an immobile negative space charge in the outer film part. The air-annealing at moderate temperatures releases the space charge and transforms the two layers into a high-resistivity single layer having substantially improved dielectric properties and thermostable (up to 250 °C) capacitance of 1.2 μF cm−2 achieved for the film anodized to practical 50 V. The 3D films having up to 4.5 times enlarged effective surface area can be utilized as novel metal/oxide nanostructured electrodes for electrolytic microcapacitors suitable for classical electronic circuits and energy-storage applications.

Suppression of crack formation in wafer-scale amorphous SiNx films by residual hydrogen-ligands manipulation

Plasma-Enhanced Chemical Vapor Deposition (PECVD) of amorphous silicon nitride (SiNx) thin films is a critical procedure in microelectronics serving as a surface passivation layer and dielectric barrier. However, intrinsic film stress continuously builds up along with PECVD growth, leading to film cracking. How to achieve crack-free PECVD amorphous SiNx film within a large thickness range remains a critical unresolved challenge in semiconductor industry. In this study, we revealed that high residual NH ligands from the NH3 precursor could induce excessive tensile strain at the SiNx/Si wafer interface and consequently aggravate SiNx film crack formation. With a heating pretreatment on the wafer, residual H ligands were effectively reduced to achieve homogenous chemical composition in SiNx film. As a result, the crack number declined ∼42% and the remaining crack length was substantially shorter in contrast to the original SiNx film. This work demonstrates the crucial role of residual ligands on internal strain regulation and points out a pathway to achieve crack-free PECVD SiNx films in industrial manufacturing.

Revealing the low-temperature friction behavior and mechanisms of hydrogenated amorphous carbon films with Al/Cr/Si doping

Hydrogenated amorphous carbon (a-C:H) film has emerged as a significant contender for solid lubrication applications in low-temperature environments. Here, a set of a-C:H films doped with varying contents of elements (Al, Cr, Si) (AlCrSi/a-C:H) were fabricated, and their low-temperature frictional evolution pattern and mechanisms were explored. The results revealed that the films maintained a superlubricity state as the temperature decreased to − 40 °C, and when the temperature further decreased, the coefficient of friction increased followed by a significant fluctuation. It was related to the competition between shear graphitization, abrasive wear, transfer film formation, and film embrittlement in different low temperature ranges. This work provides new evidence for understanding the carbon film low-temperature friction behavior.

Ultrastable Zn3N2 Thin Films via Integration of Amorphous GaN Protection Layers

AbstractZinc nitride (Zn3N2) is a promising semiconductor for a range of optoelectronic and energy conversion applications, offering a direct bandgap of 1.0 eV, large carrier mobilities, and abundant constituent elements. However, the material is prone to bulk oxidation in ambient environments, which has thus far impeded its practical deployment. While previous approaches have focused on stabilizing the material via integration of ZnO surface layers, these strategies introduce additional challenges regarding elevated processing temperatures and limited control of interface properties. In this study, it is shown that amorphous GaN thin films can serve as highly stable protection layers on Zn3N2 surfaces and can be deposited at the same growth temperature and in the same deposition system as the underlying semiconductor. The GaN‐capped Zn3N2 structures exhibit long‐term stability, surviving over 3 years of exposure to ambient conditions with no discernible alterations in composition, structure, or electrical properties. Notably, the amorphous GaN coatings can even impede Zn3N2 oxidation under prolonged aqueous exposure. Thus, this study offers a solution to stabilize Zn3N2 in ambient conditions, providing a viable pathway to its utilization in robust and high‐performance electronic devices, such as thin film transistors and solar energy conversion systems.

Long-term evolution of Ti-Cu amorphous film: Agglomeration and crystallization behaviors of Cu

Sometimes the films deposited by magnetron sputtering are in a metastable state. The films tend to transition to the equilibrium phase, which is crucial for the stability of the microstructure and properties of the films in practical applications. In this study, Ti-Cu films were deposited using a high-power pulsed magnetron sputtering technique, and the evolution of the microstructure of the film under natural aging and thermal aging conditions was systematically investigated. The results showed that the as-deposited Ti-Cu film was amorphous, and as the aging time increased, particles comprising Cu agglomerates and crystalline phases were gradually formed in the film. During aging treatments, Cu agglomerates at the Ti-Cu film led to strong scattering and absorption of the incident light, resulting in reflectance losses. Cu agglomerates at the film was more intense under thermal aging conditions than under natural aging conditions, which was attributed to the fact that the provision of additional temperature could accelerate the diffusion of the smaller Cu atoms in the Ti-Cu amorphous film. Exploring the long-term evolution of the Ti-Cu film structure will provide theoretical guidance for the stability of films in practical applications.

Field-free transformations of topological spin textures in ferrimagnetic TbFeCo films

The generation of topological spin textures under ultrafast laser pulse excitations and field-free manipulation of topological transitions between different spin textures has attracted enormous interest from the perspective of spintronic applications. Here, we utilize ultrafast electron microscopy to showcase the femtosecond laser pulses excitation on magnetic materials and have generated multiple topological spin textures in an amorphous ferrimagnetic TbFeCo film. Furthermore, the following field-free topological transitions between skyrmions and bubbles with diversified topology are identified via in situ heating the sample in Lorentz transmission electron microscopy. The critical role of uniaxial anisotropy variation on changing the magnetic textures during the heating process is confirmed by micromagnetic simulations. Our results provide a perspective on the generation and transformation of topological spin textures.

Regulating the structure and performance of amorphous carbon-based films by introducing different interlayers for applications in PEMFC bipolar plates

In this work, the effects of inserting an interlayer on the anti-corrosion performance of amorphous carbon (a-C) films in a simulated Proton Exchange Membrane Fuel Cell (PEMFC) environment have been systematically studied. Four a-C films with different interlayers, namely CCr, C-Cr-N, CrN and Cr, were prepared on 316L stainless steel substrates using unbalanced magnetron sputtering. The surface/fractural morphologies, carbon bonding structure and the anti-corrosion performance of the 4 films were observed/characterized in detail. The nanostructure and composition evolution from the film surface down to the film-substrate interface before and after electrochemical tests were also analysed via high resolution transmission electron microscopy (HRTEM). Results indicate that a-C films with CCr and C-Cr-N interlayers display superior corrosion resistance compared to undoped samples and those lacking an interlayer, with the lowest self-corrosion current density (i.e. 2.1 × 10−7 A/cm2, C-Cr-N interlayer) being nearly two orders of magnitude lower than that of the substrate (i.e. 1.1 × 10−5 A/cm2). The doped C-Cr-N interlayer plays a vital role in the corrosion resistance of the samples by accelerating oxidation of surface defect locations, inhibiting the continuous penetration of electrolyte, and improving corrosion resistance. Additionally, a-C films with a C-Cr-N interlayer exhibited an outstanding interface contact resistance (ICR) value (~3.5 mΩ/cm2) than that with a CrN interlayer (~30 mΩ/cm2) or the 316L substrate (~100 mΩ/cm2) at a typical contact pressure of 1.5 MPa. All 4 films demonstrate obviously improved hydrophobicity (contact angles against distilled water under room temperature up to 94.2°) compared to the substrate (75.8° under identical condition). In a word, this study proves that the strategy of inserting an appropriately designed interlayer (with the ternary C-Cr-N being most promising) to a-C films could alter and enhance the anti-corrosion, ICR and hydrophobic properties of 316L, proposing valuable solutions for high-performance bipolar plates (BPs) in the PEMFC industry.

Preparation and electrochromism of amorphous Bi-doped TiO2 film for aqueous-based electrochromic device

Amorphous Bi–TiO2 films with improved electrochromic properties have been successfully fabricated by a facile sol-gel spin-coating technology. The influence of dopant bismuth (Bi) content and sol amount on the electrochromic performance of Bi–TiO2 films was studied. The optimized Bi–TiO2 films show outstanding electrochromic properties, including wide transmittance modulation (ΔT = 74.26 % at 640 nm), short switching times (2.6 s/3 s for bleaching and coloring), and large coloration efficiency (52.77 cm2 C−1). A proton-based electrochromic device was prepared by the amorphous Bi–TiO2 film as the electrochromic film and Cu sheet as the counter electrode. The prepared device has a small operating potential range (1.0 V) in aqueous electrolyte due to the excellent electrochromic performance and high proton activity for the amorphous Bi–TiO2 film. In addition, the device shows excellent performance (ΔT = 67.41 %, 2.5 s/3.9 s for bleaching and coloring), providing an important reference value for the development of high-efficiency electrochromic device.

Polyester degradation by soil bacteria: identification of conserved BHETase enzymes in Streptomyces

The rising use of plastic results in an appalling amount of waste which is scattered into the environment. One of these plastics is PET which is mainly used for bottles. We have identified and characterized an esterase from Streptomyces, annotated as LipA, which can efficiently degrade the PET-derived oligomer BHET. The Streptomyces coelicolorScLipA enzyme exhibits varying sequence similarity to several BHETase/PETase enzymes, including IsPETase, TfCut2, LCC, PET40 and PET46. Of 96 Streptomyces strains, 18% were able to degrade BHET via one of three variants of LipA, named ScLipA, S2LipA and S92LipA. SclipA was deleted from S. coelicolor resulting in reduced BHET degradation. Overexpression of all LipA variants significantly enhanced BHET degradation. All variants were expressed in E. coli for purification and biochemical analysis. The optimum conditions were determined as pH 7 and 25 °C for all variants. The activity on BHET and amorphous PET film was investigated. S2LipA efficiently degraded BHET and caused roughening and indents on the surface of PET films, comparable to the activity of previously described TfCut2 under the same conditions. The abundance of the S2LipA variant in Streptomyces suggests an environmental advantage towards the degradation of more polar substrates including these polluting plastics.

Single-crystalline hole-transporting layers for efficient and stable organic light-emitting devices

Efficient charge-carrier injection and transport in organic light-emitting devices (OLEDs) are essential to simultaneously achieving their high efficiency and long-term stability. However, the charge-transporting layers (CTLs) deposited by various vapor or solution processes are usually in amorphous forms, and their low charge-carrier mobilities, defect-induced high trap densities and inhomogeneous thickness with rough surface morphologies have been obstacles towards high-performance devices. Here, organic single-crystalline (SC) films were employed as the hole-transporting layers (HTLs) instead of the conventional amorphous films to fabricate highly efficient and stable OLEDs. The high-mobility and ultrasmooth morphology of the SC-HTLs facilitate superior interfacial characteristics of both HTL/electrode and HTL/emissive layer interfaces, resulting in a high Haacke’s figure of merit (FoM) of the ultrathin top electrode and low series-resistance joule-heat loss ratio of the SC-OLEDs. Moreover, the thick and compact SC-HTL can function as a barrier layer against moisture and oxygen permeation. As a result, the SC-OLEDs show much improved efficiency and stability compared to the OLEDs based on amorphous or polycrystalline HTLs, suggesting a new strategy to developing advanced OLEDs with high efficiency and high stability.

Structure and optical properties of amorphous [formula omitted] thin films prepared by spin-coating using mixed n-propylamine-based solutions of [formula omitted] glass and [formula omitted] powder

Engineering new chalcogenide solids improves the desired functionality of the materials and may open the way for new applications. Here we discuss the preparation of AsxS100−x amorphous thin films modified with WS3 by the sol–gel method. We show that the formation of homogeneous, transparent, and stable n-propylamine-based solutions by mixing 0.02M AsxS100−x and 0.02M (NH4)2WS4 solutions is feasible for the As content in the chalcogenide glass precursor x ≤ 25 at.%. Above this limit, rapid and massive precipitation occurs in the solutions. We further demonstrate the preparation of amorphous thin films along the pseudo-binary AsS3- WS3 tie-line and provide information about the role of WS3 on optical properties and the structure of tungsten-based chalcogenide thin films. Due to a significant etching contrast between annealed AsS3− WS3 thin films at 70 and 240∘C, we propose tungsten-based chalcogenide thin films as a suitable platform for application in wet-lithography.

Component regulation and high-entropy engineering for enhanced antioxidant and high-temperature mechanical properties of protective films

Transition metal nitrides (TMNs) have gained widespread application in protecting structural components due to their high strength and hardness. However, TMNs still have the challenge of structural instability and mechanical deterioration caused by oxidation under harsh high temperature conditions. Herein, we present a strategy combining component regulation with high-entropy engineering to develop an advanced high-temperature Al-containing high-entropy nitrides (HENs) material. To prevent the phase decomposition of AlN within the (NbMoTaWAl)N, theoretical simulations were employed to determine a critical atomic percent of 25.0% Al for maintaining the stability of the high-entropy structure. Ensuing experimental synthesis creates three NbMoTaWAlN films with varying Al content: a high-entropy film with 0.0% Al (HEN), a high-entropy film with 21.2% Al (HEN-Al), and an amorphous transition metal nitride film with 30.2% Al (a-TMN-Al), validating key high-entropy engineering benchmarks. It is found that the unique HEN-Al film exhibits excellent oxidation resistance and high-temperature hardness, attributed to the uniform distribution of Al atoms in the robust high-entropy structure, which creates conditions for forming a dense and continuous Al2O3 barrier layer, effectively hindering the diffusion of oxygen into the film interior. This study provides new insights to develop a new generation of high-temperature protective materials.

Hybrid amorphous strontium titanate and terahertz metasurface for ultra-sensitive temperature sensing

In this study, a hybrid amorphous strontium titanate (STO) and terahertz metasurface were studied. Because of the excellent physical properties of amorphous STO, such as its dielectric properties and high transmittance in the terahertz region, it plays a core role in realizing a novel terahertz (THz) temperature sensor with high performance in the temperature range of 500–608 K. A blue shift of the absorption peaks appeared for the THz wave as the temperature increased, which confirmed the temperature-sensing function. The physical mechanisms underlying this phenomenon were also investigated. After optimization, the best THz temperature sensor with a sensitivity of 2.08 GHz/K was obtained, in which the thickness of the amorphous strontium titanate film was approximately 0.36 µm. This study provides a new opportunity for amorphous STO materials to be applied in THz sensors and demonstrates the realization of amorphous STO-based THz temperature sensors with high performance, low cost, and simple processes.

Crystalline as-deposited TiO 2 anatase thin films grown from TDMAT and water using thermal atomic layer deposition with in situ layer-by-layer air annealing

We report a new thermal atomic layer deposition (thermal-ALD) process including an air exposure as a third precursor to deposit crystalline TiO2 anatase thin films from tetrakis(dimethylamido)titanium(IV) (TDMAT) and water at deposition temperatures as low as 180 °C and film thicknesses as low as 10 nm. This ALD process enables TiO2-antase crystal growth during the deposition at low temperatures (< 220 °C). This additional oxidant pulse is used to fully oxidize the Ti to a 4+ state in the amorphous film, lowering the barrier to crystalline anatase formation. This new approach is informed by preliminary studies of post-deposition annealing (PDA) of thermal ALD films in both nitrogen and air atmospheres, which demonstrate the importance of having an oxidizing atmosphere to achieve the nucleation of the crystalline anatase phase. This oxidizing atmosphere is subsequently introduced into the ALD cycle as a third precursor and is shown to be more effective and efficient in promoting the crystalline transformation than even by post-deposition annealing. The crystalline anatase phase is verified by Raman spectroscopy and grazing incidence X-ray diffraction (GIXRD). The mechanism for crystallization during the TDMAT/H2O/air ALD cycle is probed by chemical state analysis via X-ray photoelectron spectroscopy (XPS). We propose that sub-oxidation in TiO2 thin films deposited by the thermal-ALD process inhibits crystallization during ALD from TDMAT/H2O chemistry. Scanning electron microscopy (SEM) is used to investigate the microstructure of these TiO2 thin films as a function of thickness (5 nm to 50 nm) and deposition temperature (180 °C to 220 °C). The reported layer-by-layer air anneal process is found to crystallize entire films in shorter total process times than thermal-ALD with ex situ post deposition annealing at identical temperatures, presumably due to the improved surface diffusion kinetics accessed during the deposition process.