Structure Of Thin Films Research Articles

Order-Order Transition in Statistical Copolymer Thin Film Induced by LCST-Type Behavior.

In this paper, we describe the formation of an ordered structure in a copolymer thin film through hydration, which subsequently transitions to a different ordered structure upon dehydration. A statistical copolymer of poly(N-octadecyl acrylamide-stat-hydroxymethyl acrylamide) with a comonomer content ratio of 1:1, denoted as p(ODA50/HEAm50), was synthesized via free radical copolymerization. We prepared a thin film of this copolymer on a solid substrate and annealed it at 60 °C under humid conditions. This treatment formed a side-chain segregated lamellar (SCSegL) structure, in which the ODA and HEAm units are oriented perpendicularly to the polymer backbone and opposite each other. Increasing the annealing temperature to 90 °C led to a transition to a side-chain mixed lamellar (SCMixL) structure, where the ODA and HEAm units are also oriented perpendicularly to the polymer backbone but in both directions. The quartz crystal microbalance (QCM) data indicate that p(ODA50/HEAm50) exhibits LCST-like behavior with a transition temperature of approximately 50 °C. We conclude that the formation of the SCSegL structure at 60 °C is due to pronounced segregation between the water-adsorbed HEAm groups and the hydrophobic ODA. Conversely, dehydration at 90 °C reduces the segregation forces, forming the SCMixL structure, which exhibits lower strain. These results demonstrate that the p(ODA50/HEAm50) film undergoes an order-to-order transition driven by the hydration-dehydration process. Additionally, we found that changes in the lamellar structure significantly alter the swelling properties of the film.

Even-integer quantum Hall effect in an oxide caused by a hidden Rashba effect.

In the presence of a high magnetic field, quantum Hall systems usually host both even- and odd-integer quantized states because of lifted band degeneracies. Selective control of these quantized states is challenging but essential to understand the exotic ground states and manipulate the spin textures. Here we demonstrate the quantum Hall effect in Bi2O2Se thin films. In magnetic fields as high as 50 T, we observe only even-integer quantum Hall states, but there is no sign of odd-integer states. However, when reducing the thickness of the epitaxial Bi2O2Se film to one unit cell, we observe both odd- and even-integer states in this Janus (asymmetric) film grown on SrTiO3. By means of a Rashba bilayer model based on the ab initio band structures of Bi2O2Se thin films, we can ascribe the only even-integer states in thicker films to the hidden Rasbha effect, where the local inversion-symmetry breaking in two sectors of the [Bi2O2]2+ layer yields opposite Rashba spin polarizations, which compensate with each other. In the one-unit-cell Bi2O2Se film grown on SrTiO3, the asymmetry introduced by the top surface and bottom interface induces a net polar field. The resulting global Rashba effect lifts the band degeneracies present in the symmetric case of thicker films.

Charge transfer effects in (HfNbTiVZr)C—Shown by ab initio calculations and X‐ray photoelectron spectroscopy

AbstractConsidering charge transfer effects and the variability of the bonding between elements with different electronegativity opens up a deeper understanding of the electronic structure and as a result many of the properties in high entropy‐related materials. This study investigates the importance of the diverse bonding and chemical environments when discussing multicomponent carbide materials. A combination of ab initio calculations and X‐ray photoelectron spectroscopy (XPS) was used to investigate the electronic structure of multicomponent thin films based on the (HfNbTiVZr)C system. The charge transfer was quantified theoretically using relaxed and nonrelaxed multicomponent as well as binary carbide reference structures, employing a fixed sphere model. High‐resolution XPS spectra from (HfNbTiVZr)C magnetron‐sputtered thin films displayed core‐level binding energy shifts and broadening effects as a result of the complex chemical environment. Charge transfer effects and a changed electronic structure in the multicomponent material, compared with the reference binary carbides, are observed both experimentally and in the density functional theory (DFT) simulations. The observed effects loosely follow electronegativity considerations, leading to a deviation from an ideal solid solution structure assuming nondistinguishable chemically equivalent environments.

X‐ray standing wave assisted XANES for depth dependent chemical state analysis of Cr in Cr2O3/Cr bilayer structure

We report the detailed depth‐dependent structural and chemical analysis of the Cr2O3/Cr bilayer structure deposited on Si ˂100˃ substrate. The non‐destructive simultaneous X‐ray reflectivity and grazing incidence X‐ray fluorescence measurements were used for this purpose. Corresponding variation in the chemical state of Cr atoms as a function of depth has been studied using X‐ray standing wave (XSW) assisted X‐ray absorption near edge structure (XANES) measurements. Various oxidation states of Cr atoms present in the Cr2O3/Cr bilayer structure were determined using X‐ray photoelectron spectroscopy (XPS). Depth‐resolved XANES measurements confirmed the presence of chromium oxide (Cr2O3) and hydroxide (Cr (OH)3) at the top surface of the Cr2O3/Cr bilayer structure. The results also reveal the presence of metallic Cr along with its compounds Cr2O3 and Cr (OH)3 at the interface medium, showing significant mixing between the Cr2O3 and Cr layers. Our results clearly demonstrate that the XSW assisted XANES technique is extremely efficient for determining the variation of chemical states at the surface, interface, and different depths of a thin film structure. Such types of analysis are particularly useful for differentiating the presence of a metal from its own oxides, even at higher depths inside a thin film medium.

Voltage control of multiferroic magnon torque for reconfigurable logic-in-memory

Magnons, bosonic quasiparticles carrying angular momentum, can flow through insulators for information transmission with minimal power dissipation. However, it remains challenging to develop a magnon-based logic due to the lack of efficient electrical manipulation of magnon transport. Here we show the electric excitation and control of multiferroic magnon modes in a spin-source/multiferroic/ferromagnet structure. We demonstrate that the ferroelectric polarization can electrically modulate the magnon-mediated spin-orbit torque by controlling the non-collinear antiferromagnetic structure in multiferroic bismuth ferrite thin films with coupled antiferromagnetic and ferroelectric orders. In this multiferroic magnon torque device, magnon information is encoded to ferromagnetic bits by the magnon-mediated spin torque. By manipulating the two coupled non-volatile state variables—ferroelectric polarization and magnetization—we further present reconfigurable logic operations in a single device. Our findings highlight the potential of multiferroics for controlling magnon information transport and offer a pathway towards room-temperature voltage-controlled, low-power, scalable magnonics for in-memory computing.

Phase formation, structure and properties of quaternary MAX phase thin films in the Cr-V-C-Al system: A combinatorial study

Tailoring of individual atomic layers via alloying to synthesize quaternary MAX phases allows for expanding their chemical diversity and fine-tuning of their properties. In this study, Cr-V/C/Al multilayered precursors were deposited via combinatorial magnetron sputtering, creating nanostructured architectures with periodic stacking of nanolayers and varying Cr:V ratios. Their phase transformation and underlying reaction mechanisms during subsequent thermal annealing in argon towards the prospective quaternary solid solution (CrV)n+1AlCn MAX phases formation was systematically studied. Crystallization of (CrV)2AlC starts at approximately 500°C, while growth of higher-ordered (CrV)4AlC3 is observed from 960°C. Notably, intergrowth of (CrV)2AlC and (CrV)4AlC3 structures with coherent interface suggests that (CrV)2AlC acts as template for nucleation of (CrV)4AlC3. Thermal stability and high-temperature oxidation tests found that (CrV)2AlC exhibits higher thermal stability compared to (CrV)4AlC3 and films with Cr72.7V27.3 displayed good oxidation resistance at 1000°C, forming a protective bilayer oxide scale consisting of (Cr,Al)2O3 and Al2O3.

Polyepitaxial grain matching to study the oxidation of uranium dioxide

Although the principal physical behaviour of a material is inherently connected to its fundamental crystal structure, the behaviours observed in the real-world are often driven by the microstructure, which for many polycrystalline materials, equates to the size and shape of the constituent crystal grains. Here we highlight a cutting edge synthesis route to the controlled engineering of grain structures in thin films and the simplification of associated 3-dimensional problems to less complex 2D ones. This has been applied to the actinide ceramic, uranium dioxide, to replicate structures typical in nuclear fission fuel pellets, in order to investigate the oxidation and subsequent transformation of cubic UO2 to orthorhombic U3O8. This article shows how this synthesis approach could be utilised to investigate a range of phenomena, affected by grain morphology, and highlights some unusual results in the oxidation behaviour of UO2, regarding the phase transition to U3O8.

Experimental, theoretical and numerical simulation-based investigations on the fabricated Cu2ZnSn thin-film-based Schottky diodes with enhanced electron transport for solar cell

Copper-zinc-tin Cu2ZnSn (CZT) thin films are promising materials for solar cell applications. This thin film was deposited on a fluorine-doped tin oxide (FTO) using an electrochemical deposition hierarchy. X-ray diffraction of thin-film studies confirms the variation in the structural orientation of CZT on the FTO surface. As the pH of the solution is increased, the nature of the CZT thin-film aggregate changes from a fern-like leaf CZT dendrite crystal to a disk pattern. The FE-SEM surface micrograph shows the dendrite fern leaf and sharp edge disks. The 2-D diffusion limitation aggregation under slippery conditions for ternary thin films was performed for the first time. The simulation showed that by changing the diffusing species, the sticking probability was responsible for the pH-dependent morphological change. Convincingly, diffusion-limited aggregation (DLA) simulations confirm that the initial structure of copper is responsible for the final structure of the CZT thin films. An experimental simulation with pH as a controlled parameter revealed phase transition in CZT thin films. The top and back contact of Ag-CZT thin films based on Schottky behavior give a better electronic mechanism in superstrate and substrate solar cells.

Impact of deposition parameters on the optical properties of Fe2O3 thin films prepared by SILAR method

In order to explore the structures, morphology, and optical features of Fe2O3 nanofilms, the successive ionic layer adsorption and reactions (SILARs) technique was utilized to deposit the nanofilms onto glassy slides at varying concentrations of the precursor. Three precursor concentrations (0.025, 0.05 and 0.075) M were used. Analysis using X-ray diffraction (XRD) presented the crystalline structure of the Fe2O3 thin films. Field emission-scanning electron microscopy (FE-SEM) was used to evaluate the morphological features of the films. The results demonstrate that the surfaces of the films are nonporous and that there is a good distribution for spherical nanosize particles. The number of cycles is another important parameter that has been tested and its effect on the optical properties of prepared films was evaluated. The optical properties like optical absorption and energy gaps are affected directionally by changing the concentration and cycle numbers during the preparation. The latest objective of our study is to determine the role of precursor concentrations and deposition cycles in preparing thin films that have electronic applications such as sensors and solar cells.

On the enhanced electrochromic performance of nano-structured V2O5 thin films developed by substrate temperature induced orientated Growth

Electrochromic society is keen to develop devices with multicolor displays with high stability, using eco-friendly inorganic materials. In the present research, Influence of substrate temperature on the electrochromic V2O5 active electrodes deposited using automated nebulizer spray pyrolysis was examined to demonstrate V2O5 nanostructured films with good cyclic stability, high color contrast, and a robust memory effect. The structural characterization of the V2O5 thin films was conducted through R-ray diffraction and thermogravimetric analysis to assess material stability. Nanostructure morphology under different conditions was analysed using SEM and TEM. The electrochromic studies revealed that the higher optical modulation (ΔT) was achieved (with 70.8 % at 550 nm) in a very short switching time. Feature studies on V2O5 under different potentials were conducted to understand the capacitive and diffusion effects. The electrochromic response V2O5 thin films to various potentials was analysed using ex-situ XRD, elucidates phase changes from V2O5 to LiVO5 and V4O9, and a 2000-cycle CV measurement comprehended the material stability. The significantly improved electrochromic performance is primarily attributed to the nanosheet structure of the V2O5 thin films, since the structures enhance the material stability during lithium-ion intercalation/deintercalation processes.

Harnessing ion beam erosion engineering for controlled self-assembly and tunable magnetic anisotropy in epitaxial films

The engineering of the surface morphology and the structure of the thin film is one of the essential technological assets for regulating the physical properties and functionalities of thin film-based devices. This study presents an easy and handy approach to tailor the surface structure of epitaxial thin films utilizing low-energy ion beam. Here, we investigate the evolution of the surface structure and magnetic anisotropy (MA) in epitaxial Fe/MgO (001) model systems subjected to multiple cycles of ion beam erosion (IBE) after thin film growth. The growth of Fe film occurs in the form of three–dimensional islands and exhibits intrinsic biaxial MA. Following a few cycles of IBE, an induced uniaxial magnetic anisotropy leads to a split in the hysteresis loop, and the film displays almost uniaxial magnetic switching behavior. More distinctly, we present a clear and conclusive evidence of (2 × 2) reconstruction of the Fe surface due to the atomic rearrangement by IBE. Furthermore, 57Fe isotope sensitive nuclear resonance scattering measurement provides insight into the depth-resolved magnetic information due to the modified surface topography. We also demonstrate that thermal annealing can reversibly tune the surface reconstruction and induced UMA. The feasibility of the IBE technique by adequately selecting IBE parameters for surface structure modification has been highlighted apart from conventional tailoring of the morphology for the tuning of UMA and introduces a new dimension to our understanding of self-assembled surface morphology evolution by IBE.

NiO thin films fabricated using spray-pyrolysis technique: structural and optical characterization and ultrafast charge dynamics studies

Nickel (II) oxide, NiO, is a wide band gap Mott insulator characterized by strong Coulomb repulsion between d-electrons and displays antiferromagnetic order at room temperature. NiO has gained attention in recent years as a very promising candidate for applications in a broad set of areas, including chemistry and metallurgy to spintronics and energy harvesting. Here, we report on the fabrication of polycrystalline NiO using spray-pyrolysis technique, which is a deposition technique able to produce quite uniform films of pure and crystalline materials without the need of high vacuum or inert atmospheres. The composition and structure of the NiO thin films were then studied using x-ray diffraction, and atomic force and scanning electron microscopies (SEM). The phononic and magnonic properties of the NiO thin films were also studied via Raman spectroscopy, and the ultrafast electron dynamics by using optical pump probe spectroscopy. We found that the NiO samples display the same phonon and magnon excitations expected for single crystal NiO at room temperature, and that electron dynamics in our system is like those of previously reported NiO mono- and polycrystalline systems synthesized using different techniques. These results prove that spray-pyrolysis can be used as affordable and large-scale fabrication technique to synthesize strongly correlated materials for a large set of applications.

Structural, morphological, optical and electrical characterization of MgO thin films grown by sputtering technique on different substrates

Magnesium Oxide (MgO) thin film structures were deposited on glass and n-Si substrates by means of RF magnetron sputtering technique. Structural, morphological, optical characteristics of MgO thin film were determined by XRD, AFM and UV–Vis spectrometer techniques. The optical properties like absorption coefficient and optical band gap were extracted using optical transmittance and absorption spectra. The band-gap of MgO thin film was determined for direct electronic transition. Additionally, electric parameters like ideality factor, saturation current and barrier height of the Au/MgO/n-Si device were computed from the forward I–V data in dark state. The ideality factor was found to be greater than one. This indicates that the I–V characteristics of the device exhibits non-ideal attitude. The results show that the MgO thin film can be applied to both optical and electronic device applications.

Heteroepitaxial growth of Ga2O3 thin films on Al2O3(0001) by ion beam sputter deposition

Deposition of epitaxial oxide semiconductor films using physical vapor deposition methods requires a detailed understanding of the role of energetic particles to control and optimize the film properties. In the present study, Ga2O3 thin films are heteroepitaxially grown on Al2O3(0001) substrates using oxygen ion beam sputter deposition. The influence of the following relevant process parameters on the properties of the thin films is investigated: substrate temperature, oxygen background pressure, energy of primary ions, ion beam current, and sputtering geometry. The kinetic energy distributions of ions in the film-forming flux are measured using an energy-selective mass spectrometer, and the resulting films are characterized regarding crystalline structure, microstructure, surface roughness, mass density, and growth rate. The energetic impact of film-forming particles on the thin film structure is analyzed, and a noticeable decrease in crystalline quality is observed above the average energy of film-forming Ga+ ions around 40 eV for the films grown at a substrate temperature of 725 °C.

Patterning functional oxides: Some failures and solutions in fabricating a Hall bar

Functional oxides exhibit diverse useful properties, opening attractive prospects for electronic, magnetic, and optoelectronic devices. However, the chemical instability of these oxides with some microfabrication processes, especially when dealing with thin films (<40 nm) or micrometer-scale lateral dimensions, can pose a considerable challenge. Here, we describe the fabrication process of a Hall bar device used as a test structure for thin functional oxide films. This process employs photolithography and dry etching, utilizing standard clean-room materials and methods. The device layout and fabrication process are described in detail, including conclusions and lessons gained from several failed attempts during process development. A key lesson is the advantage of employing an ultrathin protective layer to protect the oxide film surface. In addition, we encountered two additional fabrication challenges: photoresist hardening during dry etching and edge accumulation of photoresist during spin-coating. Effective solutions to these issues are described. We hope that our lessons and conclusions, not limited to functional oxides, will help to shorten the process development for other materials and devices.

Effect of vacuum-ultraviolet irradiation on structure and resistivity of epitaxial copper oxide thin films

Effect of vacuum-ultraviolet irradiation on structure and resistivity of epitaxial copper oxide thin films

Development of a Flexible Thin-Film Radio-Absorbing Structure for UHF and SHF Microwave Range

Development of a Flexible Thin-Film Radio-Absorbing Structure for UHF and SHF Microwave Range

Preparation of Sn-Doped Ga2O3 Thin Films and MSM Ultraviolet Detectors Using Magnetron Co-Sputtering.

Sn-doped Ga2O3 thin films and metal-semiconductor-metal (MSM) ultraviolet detectors were prepared using the co-sputtering method to enhance their photoelectric performance. The results revealed that Sn doping can effectively change the optical and electrical properties of thin films, greatly improving the photoelectric responsiveness of the devices. Through microstructure testing results, all of the thin film structures were determined to be monoclinic beta phase gallium oxide. At a DC power of 30 W, the thickness of the Sn-doped thin film was 430 nm, the surface roughness of the thin film was 4.94 nm, and the carrier concentration, resistivity, and mobility reached 9.72 × 1018 cm-3, 1.60 × 10-4 Ω·cm, and 45.05 cm3/Vs, respectively. The optical results show that Sn doping clearly decreases the transmission of thin films and that the bandgap can decrease to 3.91 eV. Under 30 W DC power, the photo dark current ratio of the detector can reach 101, time responses of tr = 31 s and tf = 22.83 s were obtained, and the spectral responsivity reached 19.25 A/W.

Atom Probe Tomography of the LiFePO4-Electrolyte Interface Enabled by Thin Film Electrodes

Atom probe tomography (APT) can yield three-dimensional tomographic images at atomic-scale resolution and low-AMU elements such as Li are readily observed, making it a powerful tool for exploring battery materials interfaces. However, it is difficult to prepare APT specimen tips containing the interface of interest starting with typical particle-based battery electrodes. Here we demonstrate a methodology for reliable APT imaging of battery interfaces in which a thin film electrode geometry is used to provide well-controlled planar interfaces that are ideal for APT sample preparation and imaging. LiFePO4 (LFP) thin film electrodes, synthesized using pulsed laser deposition (PLD), were studied as an example system, with standard Li-salt electrolytes. For the results to be applicable to conventional particulate electrodes, it is important to obtain representative thin film structure and electrochemical characteristics. Thus, the effects of PLD conditions including substrate temperature, substrate crystallinity, target composition, and deposition time (number of laser pulses) on the thin film’s crystallographic texture, morphology, and electrochemical performance were studied. Optimized LFP film showed good crystallinity with low-C-rate capacity of ∼90 mAh g−1. Initial APT three-dimensional imaging of the LFP/electrolyte interface shows an ∼10 nm cathode-electrolyte interphase layer that is enriched in F and Li.

The influence of aluminum on the morphological, optical properties and electronic structure of ZnO thin films

The influence of aluminum on the morphological, optical properties and electronic structure of ZnO thin films