Thin Films Research Articles

Effect of Deposition Temperature on Zn Interstitials and Oxygen Vacancies in RF-Sputtered ZnO Thin Films and Thin Film-Transistors

ZnO thin films were deposited using RF sputtering by varying the argon:oxygen gas flow rates and substrate temperatures. Structural, optical and electrical characterization of ZnO thin films were systematically carried out using X-Ray diffraction (XRD), scanning electron microscopy (SEM), UV–visible spectroscopy, X-Ray photoelectron spectroscopy (XPS) and Hall measurements. Film deposited at room temperature and annealed at 300 °C exhibited low O2 incorporation with localized defects and a high percentage of Zn interstitials. A large crystalline size and fewer grain boundaries resulted in a high Hall mobility of 46.09 cm2/V-s Deposition at higher substrate temperatures resulted in improvement in O2 incorporation through the annihilation of localized defects and decrease in oxygen vacancies and Zn interstitials. Urbach tails within the bandgap were identified using the absorption spectrum and compared with the % defects from XPS. Bottom-gate thin-film transistors were subsequently fabricated on a SiO2/p-Si substrate using the combination of RF sputtering, wet etching and photolithography. Variation in the substrate temperature showed performance enhancement in terms of the leakage current, threshold voltage, sub-threshold swing and ION/IOFF ratio. Thin-film transistor (TFT) devices deposited at 300 °C resulted in an O2-rich surface through chemisorption, which led to a reduction in the leakage current of up to 10−12 A and a 10-fold reduction in the sub-threshold swing (SS) from 30 V to 2.8 V. Further TFT optimization was carried out by reducing the ZnO thickness to 50 nm, which resulted in a field-effect mobility of 1.1 cm2/V-s and ION/IOFF ratio of 105.

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.

Macroscopic Monograin Nano-Gyroid Thin Films in 4-inch Scale Through Shear-Rolling and Subsequent Solvent Annealing.

The gyroid structure from self-assembly is highly attractive for optical applications such as photonic crystals and metamaterials. However, due to the direction-dependent nature of these applications, achieving a monograin-level structure over a large area has remained challenging. In this study, the fabrication of unidirectionally oriented anisotropic nanocylinders of polystyrene-block-polydimethylsiloxane (PS-b-PDMS) is reported block copolymer thin films up to a 4-inch scale via a shear-rolling process, followed by solvent annealing to induce phase transition to nearly monograin gyroid structures. Grazing-incidence small-angle X-ray scattering (GISAXS) analysis and cross-sectional scanning electron microscope (SEM) images in the direction parallel to the shear-rolling direction reveal the preferential orientation with the (111) plane onto the YZ axis of the film, while only the (110) plane on the YZ axis of the film is observed in the perpendicular direction, with grain sizes approaching single-grain levels. For metamaterial applications, the PDMS domain is selectively removed, and gold is electroplated to produce monograin gold gyroid films.

Tracing the graphitization of polymers: A novel approach for direct atomic-scale visualization

Due to its excellent physical, chemical, and electrochemical characteristics, pyrolytic carbon has become a promising material for a wide range of advanced technologies. Pyrolytic carbon can be obtained through the pyrolysis of a polymeric carbon precursor at high temperatures and in inert atmosphere. By tuning the pyrolysis conditions, the hybridization of carbon atoms and thus the physicochemical properties of the derived carbon can be tailored. Advancing its development requires a deeper understanding of the graphitization process. In this context, an in situ microstructural analysis of the pyrolysis process is needed. This work presents the microfabrication of suspended polymer thin film structures on transmission electron microscopy heating chips, by two-photon polymerization 3D printing. We visualized graphitization of these films during in situ transmission electron microscopy heating studies. The favorable identified conditions are a thin film with a thickness of around 700 nm pre-pyrolysis, a pyrolysis profile reaching a maximum temperature of 1300°C and a minimum of 2 h of dwell at this temperature. An increase in the number of stacked graphene layers was observed over dwell time. Overall, the developed method has the potential to enable the visualization of graphitization of different polymer precursors and thus help predict the microstructure and properties of pyrolytic carbon depending on its fabrication conditions.

Diffusiophoretically Mediated Nanopatterning by Solvent Nanodroplets on Polystyrene Surfaces.

Dissolution is a ubiquitous process in nature and industry. However, due to technical difficulties, the detailed dissolution process at the nanoscale has seldom been captured experimentally. In this study, we investigated the dissolution dynamics in the confinement of toluene surface nanodroplets on polystyrene (PS) thin films in oversaturated toluene/water mixture solutions. This was achieved by adjusting the immersion durations from several minutes to 9 h. Dissolution takes place upon the deposition of nanodroplets on the PS surfaces, leading to the formation of surface nanostructures. Interestingly, we found that the induced nanostructures underwent complex morphological changes, from complex nanocraters with central bulges and/or multiple rims to simple nanocraters. We speculate that diffusiophoresis plays a key role in the formation of the complex nanocraters, as it facilitates the transportation of dissolved PS molecules inside the nanodroplets. We believe this finding not only enhances our understanding of dissolution dynamics at the nanoscale but also holds promise for applications in dissolution-based nanopatterning.

Reversible Nucleophilic Ring-Opening of Tetraoxapentacene Derivatives: Accessing New Materials for Thermally Activated Delayed Fluorescence.

We report the unexpected nucleophilic ring-opening reaction of electron deficient dioxins in the presence of carbazole under basic conditions. This nucleophilic ring-opening reaction is reversible under basic conditions in the absence of nucleophiles. Further, we demonstrate that this unexpected reactivity can be used to prepare novel donor-acceptor compounds that are emissive in solution and as thin films and exhibit thermally activated delayed fluorescence (TADF).

High-sensitivity fiber temperature sensor based on composite film structure and lossy mode resonance

In this work, we proposed and demonstrated a high-sensitivity optical fiber temperature sensor based on lossy mode resonance (LMR). The sensor is composed of a D-shaped fiber and a thin composite film. The composite film consists of tin dioxide (SnO2) and polydimethylsiloxane (PDMS). PDMS is inserted as an intermediate layer between D-shaped fiber and SnO2 layer, realizing the separation of TM and TE polarization to reduce polarization crosstalk, while also serving as a temperature sensitive layer. The polarization state of the excited LMR can be freely controlled by adjusting the thickness of the composite film. The proposed sensor exhibits a high temperature sensitivity of −1.1883 nm/°C with a measurement range of 10–90 °C. Meanwhile, a fast response time of ∼ 109 ms was observed due to the ultra-thin PDMS interlayer.

Near‐Infinite‐Chain Polymers with Ge=Ge Double Bonds

Despite considerable interest in heteroatom‐containing conjugated polymers, there are only few examples with heavier p‐block elements in the conjugation path. The recently reported heavier acyclic diene metathesis (HADMET) allowed for the synthesis of a polymer containing Ge=Ge double bonds – albeit insoluble and with limited degree of polymerization. By incorporation of long alkyl chains, we now obtained soluble representatives, which exhibit degrees of polymerization near infinity according to diffusion‐ordered NMR spectroscopy (DOSY) and dynamic light scattering (DLS). Analyses of the UV/Vis absorption and the NMR spectroscopic data confirm the presence of σ,π‐conjugation across the silylene‐phenylene linkers between the Ge=Ge double bonds. Favorable intermolecular dispersion interactions lead to ladder‐like cylindrical supramolecular assemblies as confirmed by X‐ray diffraction (XRD), small angle X‐ray scattering (SAXS) and DLS. AFM and TEM images of deposited thin films reveal lamellar ordering of extended polymer bundles.

Recrystallizing Sputtered NiOx for Improved Hole Extraction in Perovskite/Silicon Tandem Solar Cells

AbstractSputtering nickel oxide (NiOx) is a production‐line‐compatible route for depositing hole transport layers (HTL) in perovskite/silicon tandem solar cells. However, this technique often results in films with low crystallinity and structural flaws, which can impair electronic conductivity. Additionally, the complex surface chemistry and inadequate Ni3+/Ni2+ ratio impede the effective binding of self‐assembled monolayers (SAMs), affecting hole extraction at the perovskite/HTL interface. Herein, these issues are addressed using a recrystallization strategy by treating sputtered NiOx thin films with sodium periodate (NaIO4), an industrially available oxidant. This treatment improved crystallinity and increased the Ni3+/Ni2+ ratio, resulting in a higher content of nickel oxyhydroxide. These enhancements strengthened the SAM's anchoring capability on NiOx and improved the hole extraction at the perovskite/HTL interface. Moreover, the NaIO4 treatment facilitated Na+ diffusion within the perovskite layer and minimized phase separation, thus improving device stability. As a result, single‐junction perovskite solar cells with a 1.68 eV bandgap achieve a power conversion efficiency (PCE) of 23.22% for an area of 0.12 cm2. Perovskite/silicon tandem cells with an area of 1 cm2 reached a PCE of 30.48%. Encapsulated tandem devices retained 95% of their initial PCE after 300 h of maximum power point tracking under 1‐sun illumination at 25 °C.

Near-Infinite-Chain Polymers with Ge=Ge Double Bonds.

Despite considerable interest in heteroatom-containing conjugated polymers, there are only few examples with heavier p-block elements in the conjugation path. The recently reported heavier acyclic diene metathesis (HADMET) allowed for the synthesis of a polymer containing Ge=Ge double bonds - albeit insoluble and with limited degree of polymerization. By incorporation of long alkyl chains, we now obtained soluble representatives, which exhibit degrees of polymerization near infinity according to diffusion-ordered NMR spectroscopy (DOSY) and dynamic light scattering (DLS). Analyses of the UV/Vis absorption and the NMR spectroscopic data confirm the presence of σ,π-conjugation across the silylene-phenylene linkers between the Ge=Ge double bonds. Favorable intermolecular dispersion interactions lead to ladder-like cylindrical supramolecular assemblies as confirmed by X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and DLS. AFM and TEM images of deposited thin films reveal lamellar ordering of extended polymer bundles.

Optimization of parameters for the preparation of AlN powder/thin films by tris(N,N,n’,n’-tetramethylethylenediamine) al(III) chloride precursor

The single source precursor tris(N,N,N’,N’-tetramethylethylenediamine)Al(III)Cl3 has been synthesized by the reaction of N,N,N’,N’-tetramethylethylenediamine (TMEDA) with AlCl3 in 3:1 molar ratio in ethanol. The precursor is stable for long periods of time and cleanly generated aluminum nitride upon pyrolysis. The pyrolysis process was optimized by varying parameters such as temperature, pressure, and the flow rate of gases (N2 and Ar). Thin films of AlN were prepared by spin coating the precursor onto Si(100) and quartz substrates followed by pyrolysis under optimized CVD conditions obtained from bulk pyrolysis. Pyrolyzed powders and films were characterized with a variety of techniques. X-ray diffraction (XRD) showed 8.5 nm grain size with a dominant 220 orientation. UV-Vis spectroscopy indicated a band gap for the AlN films of ∼5.7 eV, which is close to bulk AlN (6.1 eV). FESEM showed a smooth and homogeneous film surface and EDAX showed a 1.4:1 ratio of Al:N, respectively.

Enhanced Crystallinity of SrTiO3 Films on a Silicon Carbide Substrate: Structural and Microwave Characterization

Thin films of strontium titanate, which reveal high structure quality and tunable properties prospective for microwave applications at room temperature, were grown on a semi-insulating silicon carbide substrate using magnetron sputtering for the first time. The films’ growth mechanisms were studied using medium-energy ion scattering, and the films’ structures were investigated using X-ray diffraction. The electrical characteristics of planar capacitors based on strontium titanate films were measured at a frequency of 2 GHz using a high-precision resonance technique. It is shown that the tendency to improve the crystalline structure of strontium titanate film with an increase in the substrate temperature is most pronounced for films deposited at elevated working gas pressure under low supersaturation conditions. Planar capacitors formed on the basis of oriented SrTiO3 films on silicon carbide showed tunability n = 36%, with a loss tangent of 0.008–0.009 at a level of slow relaxation of capacitance, which is significantly lower than the data published currently regarding planar tunable ferroelectric elements. This is the first successful attempt to realize a planar SrTiO3 capacitor on a silicon carbide substrate, which exhibits a commutation quality factor more than 2500 at microwaves.

SCAPS numerical modeling of novel CBTS/WO₃ thin film solar cell

SCAPS numerical modeling of novel CBTS/WO₃ thin film solar cell

Dual efficacy of potassium-doping in perovskite solar cells: Reducing hysteresis and boosting open-circuit voltage

The incorporation of potassium into perovskite solar cells (PSCs) has been empirically validated to mitigate hysteresis phenomena and boost the power conversion efficiency (PCE). However, the doping mechanism of potassium ions in the perovskite film and their effect on photocarrier recombination remains a topic of debate. Here, we grew doped MAPbI3: K single crystals by inverse temperature crystallization using KI as a dopant, and then perovskite thin films were spin-coated with dissolved MAPbI3: K crystals as a precursor. The doped MAPbI3: K perovskite films exhibit better crystal quality with large columnar grains and lower defect density. Employing Hall effect, ultraviolet photoelectron spectroscopy, and Kelvin probe force microscopy measurements, we definitively demonstrate that K-doping transforms the conductivity type of the perovskite film from a marginally N-type to a distinct P-type semiconductor. Furthermore, this doping strategy induces a concurrent downward shift in both the conduction band minimum and valence band maximum. As a result, the PCE of the PSCs increases from 15.15% to an impressive 20.66%, and the J–V curve hysteresis almost disappears. Additionally, theoretical simulations using SCAPS-1D software reveal a profound modification in the device's energy band diagram after K+-doping. Specifically, the energy level offset between the perovskite layer and the electron transport layer diminishes from 0.24 to 0.14 eV, with a result of bigger quasi-Fermi energy level splitting. This, in turn, elevates the open-circuit voltage (Voc) of the doped perovskite solar cell, underscoring the profound impact of potassium doping on enhancing PSC performance.

Gradually Thermal Diffusing of Silver on Amorphous GeSe Thin Film; Structural and Optical Properties

Gradually Thermal Diffusing of Silver on Amorphous GeSe Thin Film; Structural and Optical Properties

Unraveling the Oxygen Vacancy-Performance Relationship in Perovskite Oxides at Atomic Precision via Precise Synthesis.

Understanding the fundamental effect of the oxygen vacancy atomic structure in perovskite oxides on catalytic properties remains challenging due to diverse facets, surface sites, defects, etc. in traditional powder catalysts and the inherent structural complexity. Through quantitative synthesis of tetrahedral (LaCoO2.5-T), pyramidal (LaCoO2.5-P), and octahedral (LaCoO3) epitaxial thin films as model catalysts, we demonstrate the reactivity orders of active-site geometrical configurations in oxygen-deficient perovskites during the CO oxidation model reaction: CoO4 tetrahedron > CoO6 octahedron > CoO5 pyramid. Ambient-pressure Co L-edge and O K-edge XAS spectra clarify the dynamic evolutions of active-site electronic structures during realistic catalytic processes and highlight the important roles of defect geometrical structures. In addition, in situ XAS and resonant inelastic X-ray scattering spectra and density functional theory calculations directly reveal the nature of high reactivity for CoO4 sites and that the derived shallow-acceptor defect levels in the band structure facilitate the adsorption and activation of reactive gases, resulting in more than 23-fold enhancement for catalytic reaction rates than CoO5 sites.

Catalytically Active Gold Nanoparticles on Star Block Co-polymer Matrix: Synthesis of Nanocomposite Film Exploring the Langmuir-Blodgett Technique.

Nanocomposites with metal nanoparticles and block copolymers distributed in a stable and robust thin film are preferred for various applications. Here, synthesis of such a nanocomposite is reported, which is composed of gold nanoparticles (AuNPs) embedded in a tetronic 701 (T701) and 90R4 (T90R4) thin film matrix generated using the Langmuir-Blodgett (LB) thin film technique. Tetronics contain a monoprotonated central ethylenediamine group at pH 5 due to the presence of chloroauric acid (HAuCl4) in the subphase, along with poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) blocks, both of which have the capacity to serve as the reducing agent toward chloroaurate anion (AuCl4-). Calorimetric experiments have shown that T90R4 has a better interaction with AuCl4-, probably due to its better electrostatic interaction with AuCl4- ions due to the higher % of the hydrophilic PEO group. On the other hand, the T701-AuNP interaction turned out to be more spontaneous due to the higher hydrophobicity of T701 (higher PPO/PEO ratio). The optical properties and structure/morphology of these nanocomposites are characterized by UV-vis spectroscopy, FTIR spectroscopy, XRD, and TEM. The composite thin film has the ability to catalyze the organic electron transfer process between p-nitrophenol and p-aminophenol in the presence of sodium borohydride. A clear correlation has been found between the reaction rates and the kind of tetronic present in the nanocomposite, which acted as a matrix and stabilizer toward AuNPs.

Preparation and Characterization of Nanostructured ITO Thin Films by Spray Pyrolysis Technique: Dependence on Annealing Temperature

Transparent conducting oxides (TCOs) like Indium tin oxide (ITO) have wide attention from all scientists which have low resistance and high visible light transmittance, used as transparent electrodes in many optoelectronic devices such as liquid crystal displays, touch screens, light emitting diodes, and solar cells. In this research, the relationship between the crystallization, optical transmittance, and surface roughness of nanostructured ITO thin films and the change in annealing temperature was investigated. To enhance the efficiency of this material in optoelectronic applications, both the optical transmittance in the visible region and the crystallite size must be increased. These results can be obtained by the heat treatment of the films. Nanostructured ITO thin layer films have been successfully prepared at a substrate temperature equal to (350)℃ by chemical spray pyrolysis (CSP) technique. The physical characterizations of nanostructured ITO thin layer films were investigated at different annealing temperatures (400,450 and 500)℃. The presence of diffraction peaks indicates that the as-deposited and post annealed films are polycrystalline cubic structure and the peak (400) is a preferred growth orientation. For all samples the value of intensity of diffraction peaks increases with increasing substrate temperature. The crystallite size of nanostructured ITO thin films is strongly related to the annealing temperature. The crystallite size estimated from XRD was found to rise with rising annealing temperature. The surface roughness of nanostructured ITO thin layer films increases with rising annealing temperature. High values of transmittance have been measured in the visible region 550 nm equal to (70, 82, 84 and 88)% corresponding to annealing temperature (350,400,450 and 500)℃ respectively.

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.

Solar Cells: Applications and Current Opinion

Due to the manufacturing process, silicon-based solar cells have conquered the marketplace, but their cost is not economic. As a result, thin-film manufacturing was done with low-cost, appealing materials generated using less expensive, scalable, and manufacturable procedures. The motivation behind this work is to develop low-cost, high-efficiency solar cells using chemical and electrochemical techniques. Thin film solar cell structure could be presented as glass, Cu structure, CdS window material, TCO, and CdTe absorber material. The absorber and window materials include layers such as CdS and CdTe, while Cu and TCO are the back and front contacts. By using CSS and chemical bath deposition (CBD), The usual method of making this structure is to grow window (CdS) and absorber (CdTe) materials. CBD is a batch method that generates enormous quantities of Cd-containing waste solutions each time, adding to the production process's high cost. Sputtering or PVD, including high vacuum conditions, is performed with back and front contacts. This research program focuses on developing an "all chemical-solar cell" structure. This study showed that CdS and CdTe materials may be employed and electrodeposited in thin-film solar cell systems, CBD and electroless techniques. Furthermore, the back and front contacts can be coated using the CdS electrolytic bath, which is utilized for seven months without being discarded, but the CBD bath lasts 2-3 days. The deposition rate of the thin films was about 50 - 100 times greater than reported values in the literature. The efficiency of the manufactured cells was between 1 and 6%, which was reduced by the duration of time. Twenty days after manufacturing a TCO, CdS, CdTe, the short-circuit current, Cu-Ag solar cell, and open-circuit voltage deposited by all chemical and electrochemical deposition techniques were 0.8 mA/cm2 and 8.8 mV, respectively. However, consistency and reproducibility remain unresolved. The growth of CdTe nanocrystalline thin film is one of the reasons it has been identified as having nanosized tracks. High-quality CdTe layers should be developed, or in cadmium solar cells, its layered structure is the form of a cadmium window and a zinc oxide buffer layer to increase the consistency of the solar cell efficiency.