Oxide Thin Films Research Articles

Epitaxial Thin Film Growth on Recycled SrTiO3 Substrates Toward Sustainable Processing of Complex Oxides.

Complex oxide thin films cover a range of physical properties and multifunctionalities that are critical for logic, memory, and optical devices. Typically, the high-quality epitaxial growth of these complex oxide thin films requires single crystalline oxide substrates such as SrTiO3 (STO), MgO, LaAlO3, a-Al2O3, and many others. Recent successes in transferring these complex oxides as free-standing films not only offer great opportunities in integrating complex oxides on other devices, but also present enormous opportunities in recycling the deposited substrates after transfer for cost-effective and sustainable processing of complex oxide thin films. In this work, the surface modification effects introduced on the recycled STO are investigated, and their impacts on the microstructure and properties of subsequently grown epitaxial oxide thin films are assessed and compared with those grown on the pristine substrates. Detailed analyses using high-resolution scanning transmission electron microscopy and geometric phase analysis demonstrate distinct strain states on the surfaces of the recycled STO versus the pristine substrates, suggesting a pre-strain state in the recycled STO substrates due to the previous deposition layer. These findings offer opportunities in growing highly mismatched oxide films on the recycled STO substrates with enhanced physical properties. Specifically, yttrium iron garnet (Y3Fe5O12) films grown on recycled STO present different ferromagnetic responses compared to that on the pristine substrates, underscoring the effects of surface modification. The study demonstrates the feasibility of reuse and redeposition using recycled substrates. Via careful handling and preparation, high-quality epitaxial thin films can be grown on recycled substrates with comparable or even better structural and physical properties toward sustainable process of complex oxide devices.

Enhanced optoelectronic properties of spray deposited antimony-doped tin oxide thin films

Antimony-doped tin oxide (Sb:SnO2) thin films with varying Sb concentrations were deposited using the spray pyrolysis technique. A comprehensive analysis of the films' elemental, structural, and optoelectronic properties is presented. All films possess a polycrystalline single-phase nature and have a tetragonal rutile structure. As Sb concentration increases, the unit cell shrinks continuously, suggesting proper substitution of Sn4+ by Sb5+. This substitution causes a continuous increase in the concentration of charge carriers and a reduction in electron mobility. X-ray photoelectron spectroscopy investigations revealed the presence of asymmetric Sn 3d core-level peaks distinguished by peak splitting, which increases with increasing carrier concentration. Utilizing the plasmon absorption model, an effective mass value of (0.51 ± 0.07)me for the conduction electron at the fermi level is obtained. With increasing Sb concentration, the optical energy gap increases gradually from 3.84 eV for undoped SnO2 to 4.35 eV for 5.0 at. % Sb. After considering the Urbach tailing phenomenon as well as the Moss–Burstein effect, this increase was attributed to the increase in Moss–Burstein energy due to increased charge carrier concentration. Our study revealed that the film doped with 2.0 at. % Sb has the best optoelectronic properties, with a figure of merit of 4.18 (Ω/cm2)−1.

Supercapacitor performance of pure and Ni-doped CuO electrodes prepared by USP

Abstract In this study, the ultrasonic spray pyrolysis (USP) technique was employed to fabricate pure and 3% Ni-doped copper oxide (CuO) thin films (TFs) on In2O3/SnO2 (ITO) coated glass substrates. X-ray diffraction (XRD) analysis revealed that both pure and 3% Ni-doped CuO TFs exhibit a polycrystalline structure with the tenorite phase oriented preferentially along the (111) plane. The morphological properties of these TFs were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM) imaging. Energy dispersive x-ray spectroscopy (EDX) confirmed that the deposited TFs achieved the desired stoichiometry. The electrochemical properties of both pure and 3% Ni-doped CuO TFs were evaluated using cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS). At a current density of 1 A g−1, the specific capacitance of pure CuO TFs was found to be 78 F g−1, decreasing to 2 F g−1 at 10 A g−1. In contrast, Ni-doped CuO TFs exhibited a specific capacitance of 722 F g−1 at 1 A g−1 and 20 F g−1 at 10 A g−1. These results indicate that Ni-doping significantly enhances the specific capacitance values. The superior performance of Ni-doped CuO electrodes is attributed to their uniformly high porosity and improved electrical conductivity, demonstrating Ni-doped CuO as an optimal electrode material for pseudocapacitors.

Unification of insertion and supercapacitive storage concepts: Storage profiles in titania

Insertion storage in battery electrodes and supercapacitive storage are typically considered to be independent phenomena and thus are dealt with in separate scientific communities. Using tailored experiments on titanium oxide thin films of various thicknesses, we demonstrate the simultaneous occurrence of both processes. For the interpretation of the entire storage profile encompassing both contributions, the (free) energies of the charge carriers in the mixed conductor and the neighboring phase are the only materials parameters required. The experimental results enable no less than a unification of insertion and supercapacitive storage, the first being dominant for thick films, the latter for thin films or negligible electronic conductivity. Therefore, the size of the storage medium and the nature of the current collecting phases can be used to tune power density versus energy density.

Spectroscopic Analysis of Electrical Phenomena and Oxygen Vacancy Generation for Self-Aligned Fully Solution-Processed Oxide Thin-Film Transistors.

This work unveils critical insights through spectroscopic analysis highlighting electrical phenomena and oxygen vacancy generation in self-aligned fully solution-processed oxide thin-film transistors (TFTs). Ar inductively coupled plasma treatment was conducted to fabricate an amorphous indium zinc oxide (a-InZnO) TFT in a self-aligned process. Results showed that the Ar plasma-activated a-InZnO regions became conductive, which means that a homogeneous layer can act as both channel and electrode in the device. Several techniques were employed to probe specific aspects of the source-drain-channel interface in the fully solution-processed TFTs. X-ray absorption near-edge structure and Extended X-ray absorption fine structure were conducted to investigate the existence of oxygen vacancies, which is the main driving factor in inducing a conductive region. X-ray photoelectron spectroscopy was also used to explain the oxygen refilling mechanism. Ultraviolet Photoelectron Spectroscopy was conducted to analyze the valence band maximum and work function. Integration of these results facilitated the construction of the energy band diagram at the interface, wherein a Schottky barrier height of ∼0.37 eV was observed. By leveraging these techniques, insights into the electronic properties and performance of next-generation transistors are gained, enabling their future widespread adoption.

Revealing Enhanced Optical Modulation and Coloration Efficiency in Nanogranular WO3 Thin Films Through Precursor Concentration Modifications

Electrochromic (EC) materials allow for dynamic tuning of optical properties via an applied electric field, presenting great potential in energy-efficient technologies, such as smart windows for effective light and temperature regulation. The precise control of precursor concentration has proven to be a powerful approach in tailoring the physicochemical properties of semiconducting metal oxides. In this study, we employed a one-step electrodeposition technique to fabricate tungsten oxide (WO3) thin films, systematically exploring how varying precursor concentrations influence the material’s characteristics. X-ray diffraction analysis revealed significant changes in diffraction patterns, reflecting subtle structural modifications due to concentration variations. Additionally, scanning electron microscopy revealed significant changes in the microstructure, showing a progression from small nanogranules to larger agglomerations within the film matrix. The W-25 mM thin film delivered exceptional EC performance, efficiently accommodating lithium ions while showcasing superior EC properties. The optimized electrode, denoted as W-25 mM, showcased exceptional EC metrics, featuring the highest optical modulation at 82.66%, outstanding reversibility at 99%, and a notably high coloring efficiency of 83.01 cm2/C. These findings emphasize the importance of precursor concentration optimization in enhancing the EC properties of WO3 thin films, contributing to the advancement of high-performance, energy-efficient materials.

Effect of solutions acidity on Haacke’s Figure of Merit of ZnO and ZnO:F thin films deposited by ultrasonic spray pyrolysis

Fluorine-doped zinc oxide (ZnO:F) thin films are valued for their potential as transparent conductive materials, particularly in optoelectronic applications. In this work, the deposition of highly conductive and transparent fluorine-doped ZnO thin films, deposited by chemical spray on glass substrates is reported. The effect of acetic (AcAc) in the initial fresh solution on Haacke’s Figure of Merit (Φ) of both zinc oxide (ZnO) and fluorine-doped zinc oxide (ZnO:F) thin films was studied. The substrate temperature was fixed to 450°C, and two deposition times (8 and 14 min) were tested. Accordingly, the optical and transport properties, as well as the structural and morphological characteristics of the films were measured. The results indicate that the samples are polycrystalline in all cases and exhibit a wurtzite-type structure of ZnO. The variation of AcAc in the starting solution causes a switch in preferential growth from (002) to (001). As the AcAc content increases, the surface morphology of the films reveals the formation of well-defined hexagonal grains, and the grain size increases. Conversely, the transmittance decreases as the acetic acid increases, which can attributed to carbon incorporation into the film. In addition, the band gap values of the films varied from 3.2 to 3.4 eV. Also, as the acetic acid concentration increased, a drop in the electrical resistivity of ZnO thin films on the order of 0.016 Ω⋅ cm was found for the ZnO:F films deposited with fresh solution for 14 min. This can be ascribed to a dense acetic cloud formed during the synthesis process, trapping volatile F species that incorporate into the ZnO lattice. This enhances Haacke’s Figure of Merit of ZnO:F films deposited with a fresh solution, demonstrating their potential use for application as transparent conductive films. This contrasts with other synthesis methods that require longer aging time in the precursor solution, making these findings useful for large-scale and more efficient production of transparent conductive films.

Improving the photoswitching performance of a transistor with amorphous metal oxide semiconductor thin film by a gradient annealing approach

Metal oxides are attracting attention as electronic mate rials in research and industry. Thin films of amorphous indium gallium zinc oxide (a-IGZO) exhibit low absorbance in the visible spectrum, making them ideal components in transparent electronics. To widen the scope of use for thin film transistor (TFT) devices based on a-IGZO in on-chip sensing applications, photoresponsive behavior has been achieved by proper engineering of the active layers by either introducing a photosensitive top layer or using a method to generate localized states inside the band gap. In this paper, we propose a bilayer structured with the use of thermal annealing of a-IGZO film at different temperatures. Thermal annealing has been shown to improve the electrical performance of the TFT devices because of the improved film quality but negatively affects the photoresponsivity by removing tarp sites that play an important role in both charge generation and photomultiplication via the photogating effect. Therefore, here we propose an a-IGZO film with a high temperature-annealed bottom layer and pristine top layer. The bottom layer plays a vital role in the charge transport behavior, resulting in a low threshold voltage and subthreshold swing similar to the device with a fully annealed film, while the photoresponse of the device is driven by the higher density of gap states in the pristine top layer. This proposed method is advantageous to previously published procedures due to the simplicity of using no additional materials and complex steps to introduce trap sites into the photoactive layer, but only differential annealing temperature.

Gold-enhanced aptasensors for highly sensitive dengue detection: a cost-effective approach

The reemergence of diseases such as Dengue has spurred the development of efficient biosensing devices. This study aims to establish a rapid, cost-effective, and efficient platform for Dengue detection. The surface of the sensor was constructed by sputtering gold onto fluorine-doped tin oxide thin films, that were previously deposited on glass substrates. Varied sputtering deposition times were used. Results obtained from X-Ray Diffraction analysis showed that the films with 4-minute deposition time had the best gold surface coverage and the best cost-benefit ratio for sensor fabrication. Subsequently, the gold thin films were functionalized with the co-immobilization of a self-organized monolayer of aptamers and 6-mercapto-1-hexanol (MCH). The monolayer was analysed using the electrochemical impedance spectroscopy technique, and the ratio of 1:25 (aptamer: total thiol) was determined for surface optimization. The performance of the aptasensor was tested for the detection of the non-structural protein 1 of Dengue serotype 4 (NS1-S4). A good sensitivity of 40.2 ± 3.7 % per decade and a low detection limit of 1.25 pg/mL were obtained. The development of this platform represents an advance in the fast fabrication of aptasensors for the detection of emerging diseases such as Dengue, contributing also to the miniaturization process of point-of-care devices.

Vanadium oxide thin films growth by a chemical solution deposition method and its pH sensor toward bio-sensing devices

Abstract We report on the evaluation of the structure of VOx thin films under different fabrication conditions of the chemical solution deposition method and the pH response of an extended gate field effect transistor (EGFET)-type pH sensor. Polycrystalline V2O5 thin films of 30 and 60 nm thick and amorphous VOx thin films of about 30 nm thick were successfully prepared under different precursor solution conditions. Using polycrystalline V2O5 thin films and amorphous VOx thin films as an extended gate (EG) electrode, protypes of EGFET-type pH sensors were fabricated and investigated their pH response characteristics. The average pH responsibility of 64 mV/pH, which exceeded the theoretical Nernst limit, was observed over a wide pH range from 2.4 to 8.0 in the amorphous VOx extended gate sensor. It was also found that stable pH response measurements could be performed on amorphous VOx film samples.

Temperature-Dependent Surface Anisotropy in (110) Epitaxial Rare Earth Iron Garnet Films.

Ferrimagnetic oxide thin films are important material platforms for spintronic devices. Films grown on low symmetry orientations such as (110) exhibit complex anisotropy landscapes that can provide insight into novel phenomena such as spin-torque auto-oscillation and spin superfluidity. Using spin-Hall magnetoresistance measurements, the in-plane (IP) and out-of-plane (OOP) uniaxial anisotropy energies are determined for a thickness series (5-50nm) of europium iron garnet (EuIG) and thulium iron garnet (TmIG) films epitaxially grown on a gadolinium gallium substrate with (110) orientation and capped with Pt. Pt/EuIG/GGG exhibits an (001) easy plane of magnetization perpendicular to the substrate, whereas Pt/TmIG/GGG exhibits an (001) hard plane of magnetization perpendicular to the substrate with an IP easy axis. Both IP and OOP surface anisotropy energies comparable in magnitude to the bulk anisotropy are observed. The temperature dependence of the surface anisotropies is consistent with first-order predictions of a simplified Néel surface anisotropy model. By taking advantage of the thickness and temperature dependence demonstrated in these ferrimagnetic oxides grown on the low symmetry (110) orientations, the complex anisotropy landscapes can be tuned to act as a platform to explore rich spin textures and dynamics.

Molybdenum-Modified Niobium Oxide: A Pathway to Superior Electrochromic Materials for Smart Windows and Displays

Electrochromic materials enable the precise control of their optical properties, making them essential for energy-saving applications such as smart windows. This study focuses on the synthesis of molybdenum-doped niobium oxide (Mo-Nb2O5) thin films using a one-step hydrothermal method to investigate the effect of Mo doping on the material’s electrochromic performance. Mo incorporation led to distinct morphological changes and a transition from a compact granular structure to an anisotropic rod-like feature. Notably, the MN-3 (0.3% Mo) sample displayed an optimal electrochromic performance, achieving 77% optical modulation at 600 nm, a near-perfect reversibility of 99%, and a high coloration efficiency of 89 cm2/C. Additionally, MN-3 exhibited excellent cycling stability, with only 0.8% degradation over 5000 s. The MN-3 device also displayed impressive control over color switching, underscoring its potential for practical applications. These results highlight the significant impact of Mo doping on improving the structural and electrochromic properties of Nb2O5 thin films, offering improved ion intercalation and charge transport. This study underscores the potential of Mo-Nb2O5 for practical applications in energy-efficient technologies.

Fabrication and Characterization of Aluminum-Doped Nickel Oxide Thin Films for Optoelectronic Applications using the SILAR Method

Study’s Excerpt The effect of varying annealing times on 10% Aluminum-doped Nickel Oxide (ANO) thin films, deposited via the SILAR technique is presented. SEM and RBS analyses were used for detailed correlation between annealing time and the film's microstructural improvements. ANO thin films could be used for advanced technological applications. Full Abstract The effect of varying the annealing time of %10 aluminium-doped Nickel Oxide thin film was studied to understand the possible effect on the optical, structural, and electrical properties of %10 aluminium-doped Nickel Oxide (ANO) for possible application. The thin films were deposited on glass substrates using the successive ionic layer adsorption reaction (SILAR) deposition technique. The samples formed were annealed at 3000C, and the annealing time varied at 1.35 hrs., 1.45 hrs., 1.55 hrs., and 2 hrs, respectively. The deposited films were characterized to obtain the optical, electrical, and structural characteristics and the compositional constituent of the film using the double beam photo spectrometer, Four-Point Probe, Scanned electron Microscope, Energy Dispersion Spectroscopy, and X-ray Diffractometer. The films were observed to have low absorbance in the range of 0.1 to 0.01 and high % transmittance within the range of 80% - 98% in the visible region of the spectrum. The reflectance of the film was observed to decrease with an increase in annealing time in the range of 10% - 2.5%, all in the visible region of the spectrum. The crystallite size of the deposited films decreased with increased annealing time with the structural formation of simple cubic phase NiO thin film. SEM micrograph of the thin films reveals that an increase in annealing time improved the crystallinity of the films with the grain size evenly distributed. The EDS result of the deposited films revealed the presence of nickel, aluminum and Oxygen as the major constituent of the deposited films. The Ruther Ford Backscattering (RBS) analysis of the thickness of the films shows an increase in the thickness with an increase in annealing time. Clearer compositions of the films were also seen from the RBS analysis. Their electrical properties revealed that the films formed had low electrical resistivity and high conductivity, so they could be useful in making optoelectronics devices and corrosion resistance.

Cr2O3–NiO mixed oxides thin films for p-type transparent conductive electrodes

The Cr2O3–NiO mixed oxides’ thin films were formed by means of the layer-by-layer magnetron sputtering deposition of Cr2O3, NiO, and Cr2O3 layers on c-plane sapphire substrates. These thin-film structures, subjected to subsequent annealing, constituted a combination of the monocrystalline (0001) Cr2O3 and nonordered nickel oxide phase, which was a mixture of NiO and Ni2O3. The annealing at 900 and 1000 °С in air facilitated the diffusion of Ni and Cr atoms into the layers. Varying the annealing time allowed us to control the uniformity of the Ni and Cr distribution, the microrelief of the film surface, the transmittance in the visible region, and the sheet resistance of the Cr2O3–NiO thin-film structures. Thus, the films annealed at 900 °C during 30 min were characterized by a uniform distribution, a relatively weakly developed surface, a low sheet resistance, and the highest Haacke's Figure of Merit of 1.49 × 10–9 Ω–1. The formation of mixed Cr2O3–NiO oxides by the proposed approach was found to be an effective way to improve the performances of Cr2O3 based p-type transparent conductive electrodes.

A study on the high mobility and improved reliability of pr-doped indium zinc oxide thin film transistors

Abstract It is generally accepted that there is a trade-off relationship between mobility and stability for oxide thin film transistor (TFT) devices. Different doping ratios of Ln praseodymium (Pr) into indium (In) zinc (Zn) oxide have been employed as the active layer to get 1# and 2# amorphous oxide semiconductor (AOS) TFTs in this work. The 1#-based TFTs exhibited a high mobility of 49.84 cm2 V−1 s−1 due to the increased concentration of In. By further elevating the Pr doping ratio and adjusting In/Zn ratio of the film, the 2#-based TFT obtained both a good mobility of 26.65 cm2 V−1 s−1, and a promising stability, showing a positive-bias temperature stress stability of ΔV TH = 1.56 V and a negative-bias temperature illumination stress stability of ΔV TH = −1.47 V. It was revealed that the low energy charge transfer state of Pr in 2# film absorbs the visible light, leading to suppressed photo-induced carriers and thus a good illumination reliability of the 2#-based TFTs. In practice, the LCD panel based 2# ACT TFT shows a well stable performance even under 10 000-nit illumination. The result indicates a promising strategy to accelerate the commercialization of AOS TFTs to large-panel display production.

A semi-transparent thermoelectric glazing nanogenerator with aluminium doped zinc oxide and copper iodide thin films

To address the pressing need for reducing building energy consumption and combating climate change, thermoelectric glazing (TEGZ) presents a promising solution. This technology harnesses waste heat from buildings and converts it into electricity, while maintaining comfortable indoor temperatures. Here, we developed a TEGZ using cost-effective materials, specifically aluminium-doped zinc oxide (AZO) and copper iodide (CuI). Both AZO and CuI exhibit a high figure of merit (ZT), a key indicator of thermoelectric efficiency, with values of 1.37 and 0.72, respectively, at 340 K, demonstrating their strong potential for efficient heat-to-electricity conversion. Additionally, we fabricated an AZO-CuI based TEGZ prototype (5 × 5 cm²), incorporating eight nanogenerators, each producing 32 nW at 340 K. Early testing of the prototype showed a notable temperature differential of 22.5 °C between the outer and inner surfaces of the window glazing. These results suggest TEGZ could advance building energy efficiency, offering a futuristic approach to sustainable build environment.

Improved transparency and charge matching of electrochromic devices with Ce-doped NiO counter electrode

The quest for cost-effective and efficient electrochromic electrodes, featuring high color contrast and rapid response times, has sparked increasing interest in research of metal oxides for electrochromic applications. In this study, nickel oxide thin films with various cerium dopant concentrations are synthesized, with the optimized doping concentration identified as 1 at%. X-ray diffraction analysis confirmed that the dopant successfully reduces crystal size and alters the preferred orientation to (111). The 1 % Ce:NiO thin film exhibits enhanced electrochromic performance, with a transmittance modulation increase of 27.4 % at 633 nm, a 27.1 % rise in coloration efficiency and faster response time (tb=9.64 s and tc=6.76 s) compare to the undoped NiO. Importantly, the charge density of 1 % Ce:NiO thin film increases from 4.86 to 8.14 mC cm−2, representing a 67.5 % improvement, which becomes a better charge matching with WO3 in electrochromic devices. The incorporation of Ce into the NiO thin films not only leads to increased transmittance in the bleached state and optical modulation in the electrochromic devices but also contributes to a rise in the optical band gap of the NiO thin films and improved charge balance matching. These results underscore the positive impact of cerium doping on microstructure and electrochromic performance, indicating a promising future for electrochromic devices.

Photon echo on excitons for the development of nanoelectronic devices based on a quantum-size structures in a thin zinc oxide films

The relaxation decays of photon echo signals in thin zinc oxide films produced by magnetron sputtering have been studied. Echo signals are excited at a wavelength of 800 nm at transitions between quantum levels that arise when excitonic states are localized in quantum-sized structures in the two-photon absorption mode of laser pulses with a wavelength of 800 nm.

Ultraviolet-Sensor Based on Tin-Doped Zinc Oxide Thin Films Grown by Spray Pyrolysis

Ultraviolet-Sensor Based on Tin-Doped Zinc Oxide Thin Films Grown by Spray Pyrolysis

Thermovoltaic response in two-layered thin-film zinc oxide structures

A method of measuring the thermovoltaic effect in heterogeneous media with gradient doping impurity distributions producing gradient carrier distributions has been proposed. Iron doped zinc oxide specimens have been produced using ion beam sputtering on thin foil tantalum substrates for thermovoltaic effect measurements, glass-ceramic substrates for Hall measurements and silicon substrates for structural study. The doping impurity concentration хFe in the specimens has been varied from 0.34 to 4.18 at.%. X-ray phase analysis has shown that all the specimens have a hexagonal zinc oxide crystal structure. The films have preferential [002] orientation. The carrier concentration in the experimental specimen layers according Hall data obtained on an ECOPIA 5500 measurement system in a 0.5 T DC magnetic field has varied in the 1016–1020 cm-3 range. The specimens have an n-type conductivity. Thermovoltaic measurements have been carried out for two-layered iron doped zinc oxide specimens with different carrier and iron doping impurity concentrations using the method proposed. The maximum thermovoltaic response (U ~ 80 μV) has been observed in the two-layered thin-film specimen with the carrier concentration difference between the layers (Δn ≈ 2∙103 cm-3). The observed saturation of the thermovoltaic response has been attributed to the establishment of dynamic equilibrium between carrier diffusion from the high carrier concentration layer to the low carrier concentration layer and carrier drift due to internal electric field.