Sputter-deposited Films Research Articles

Sputter-deposited TiOx thin film as a buried interface modification layer for efficient and stable perovskite solar cells

Despite perovskite solar cells (PSCs) based on a SnO2 hole-blocking layer (HBL) are achieving excellent performance, the non-perfect buried interface between the SnO2 HBL and the perovskite layer is still an obstacle in achieving further improvement in power conversion efficiency (PCE) and stability. The poor morphology with numerous defects and the energy level mismatch at the buried interface constrain the open circuit voltage and cause instability. Herein, a sputter-deposited TiOx thin film is used as a buried interface modification layer to address the aforementioned issues. Utilizing in situ grazing-incidence small-angle X-ray scattering (GISAXS) during the sputter deposition, we monitor and unveil the growth process of the TiOx thin film, identifying a 10 nm thickness optimum. The defects at the buried interface are passivated through tuning the growth, leading to a suppressed non-radiative recombination and improved PCE (from 22.19 % to 23.93 %). The evolution of the device performance and the degradation process of PSCs using operando grazing-incidence wide-angle X-ray scattering (GIWAXS) under the protocol ISOS-L-1I explains the enhanced stability introduced by the buried interface modification via a sputter-deposited TiOx thin layer. The perovskite decomposition process and the detrimental formation of PbI2 are both slowed down by the TiOx thin layer.

Oxygen plasma-assisted magnetron sputtering deposition of non-stoichiometric Y2O3 films: Influence of oxygen vacancies on etching resistance

Yttrium oxide (Y2O3) films are widely used to protect equipment in plasma etching, a crucial technique in semiconductor processing, due to their exceptional resistance to plasma etching. Since oxygen vacancy affects the performance of Y2O3 and may impact physical etching resistance, the internal relationship necessitates further investigation. In this article, Y2O3 films with varying oxygen vacancy concentrations are prepared by reactive magnetron sputtering with the assistance of oxygen plasma. The formation and development of oxygen vacancies in cubic Y2O3 films and their impact on the physical etching resistance were investigated. The experiment results indicate that the accumulation of oxygen vacancies causes non-stoichiometry and the etching rate is significantly reduced. Combined with density-functional theory, it is revealed that oxygen vacancy distorts the lattice, which increases covalent YO bonding and the formation energy of atoms. Moreover, the vacancy line defects resulting from diffusion and aggregation of oxygen vacancies exert a similar influence on the adjacent yttrium and oxygen layers. The enhancement of physical etching resistance is attributed to the strengthened internal YO bonds led by increasing oxygen vacancy concentration in the cubic Y2O3 films without inducing phase transition. The discovery enriches the understanding of how plasma interacts with Y2O3, and the etching mechanism.

Sputter-Deposited copper iodide thin film transistors with low Operating voltage

This paper reports on a back-gated p-type thin film transistor (TFT) with copper iodide (CuI) as the channel material, a HfO2 gate dielectric layer, and Al2O3 passivation. The γ-CuI channel was deposited from a CuI target using DC magnetron sputtering at room temperature. Our TFT can be fully shut off by VG = 4 V, with a field-effect channel hole mobility μh ∼ 1.5–2 cm2 V−1 s−1. An anneal in forming gas was performed twice, once at 200 °C, then at 250 °C to improve gate control, yielding a final Ion/Ioff current ratio of ∼ 250. The anneal served two purposes: to reduce the oxygen acceptor density in the CuI channel and reduce the concentration of interface states between the CuI, Al2O3 passivation, and HfO2. A model of the device was built in an industrial TCAD simulator, which reproduces the measured characteristics and allows an estimation of interface state densities and channel doping.

Analysis of Heterostructure Formation of Abnormally Oriented Grains in Sputter-Deposited AlScN Films and Its Impact on Bulk Acoustic Wave Devices.

The presence of abnormally oriented grains (AOGs) in sputter-deposited aluminum scandium nitride (AlScN) films significantly degrades their physical properties, compromising the performance of bulk acoustic wave (BAW) devices. This study utilizes first-principles calculations to reveal that in tetrahedral wurtzite AlScN film-doped Sc atoms tend to aggregate at the second nearest-neighbor positions, forming dense ScN octahedral structures. The rock-salt (RS) ScN continued to grow due to further Sc aggregation. However, due to inadequate scandium flux, embryonic RS structures cannot be sustained, resulting in the nucleation of AOGs at the (111) faces of the octahedral ScN structure. Electron microscopy studies indicated that AOGs possess wurtzite structures and originate at tilted grain boundaries. These boundaries were characterized as RS ScN with more Sc atoms. This corroborated the theoretical predictions. BAW resonators and filters fabricated from sputter-deposited AlScN films demonstrate that AOGs degraded the piezoelectricity of AlScN, reducing the resonator's electromechanical coupling coefficient (Keff2). Measurements showed that AOG density increased from edge to center of the 8 in. wafer, resulting in a 3% decrease in average Keff2 in the resonators and a 137 MHz decrease in the filter bandwidth at 5 dB.

Low temperature dependence of electrical resistivity in obliquely sputter-deposited transition metal thin films

Transition metals exhibiting hcp (Ti, Zr, Hf) and bcc (V, Nb, Ta, Cr, Mo, W) crystalline structures are DC sputter-deposited by oblique angle deposition. A constant film thickness of 400 nm is prepared, whereas the deposition angle α is systematically changed from 0 to 85° A columnar structure is produced with column angle reaching β = 50° for the highest deposition angle. Crystallinity and grain size are both reduced with an increasing deposition angle, especially for α higher than 60° DC electrical resistivity vs. temperature in the range 7–300 K shows a typical metallic-like behavior with films becoming more resistive for high deposition angles. For temperatures higher than 100 K, the linear temperature dependence of resistivity is obtained for films prepared with deposition angles lower than 60° The electron-phonon is the main interaction acting on electronic transport mechanism. Oblique deposition angles give rise to an enhancement of electron-phonon interactions with a saturation effect of electrical resistivity for some metals. Resistivity measurements at low temperatures (down to 7 K) show the predominance of electron-defect interactions. Electron-phonon-defect interaction effect is particularly investigated as a function of the deposition angle and a shift of the crossover temperature is brought to the fore.

Anatase to rutile transition in TiO2 thin films: Role of tantalum and oxygen

The present study discusses the optimal solubility limit of tantalum in anatase TiO2 thin films (dopant solubility limit) and its effect on crystal structure transformation to the rutile phase. The study also focuses on the role of lattice oxygen in this structural phase transition. The detailed chemical composition, constitution, and phase of these sputter-deposited thin films are correlated with their electrical and optical properties to understand the disparity between total impurity concentration in these films and actual impurity substitution into the host lattice sites (dopant content). Reduced oxygen vacancies from the oxygen lattice sites and/or Ta substitution in Ti lattice sites are found to hinder the anatase to rutile phase transformation in TiO2 thin films. Our experimental data indicates the solubility limit of Ta being < 5 at% in TiO2. Similar behavior is seen when Ta is replaced with Nb in TiO2 thin films. Moreover, an increased oxygen and/or impurity concentration is found to lead to impurity-rich-oxides in these films, degrading the electrical conductivity.

Cr-induced structural phase transformation in sputter deposited poly-AlN thin film from wurtzite to rocksalt structure and their effect on the optical properties

We report Cr doping-induced structural phase transformation (PT) in sputter-deposited polycrystalline-AlN thin film from wurtzite (w) to rocksalt (r) structure. Rietveld analysis shows that the steady substitution of Al ions by Cr ions in the w-AlN lattice distorts and compresses the wurtzite lattice along the c-axis. The chemical pressure exerted in the w-AlN lattice by the compression from the doped Cr ions causes the PT, similar to the high-pressure-induced PT in AlN. Post the PT, the r-Al1-xCrxN thin film continues to exhibit compressive residual stress, indicating that such sustained stress may also play a role in stabilizing the metastable r-Al1-xCrxN phase. The structural distortion and the PT also affected the optical absorption characteristics of the w-Al1-xCrxN thin films. The w-Al1-xCrxN exhibit a direct inter-band transition and the band gap (Eg) decreases from ∼ 6.06 eV for pure w-AlN to ∼ 4.15 eV for w-Al0.73Cr0.27N. After the PT, the r-Al0.61Cr0.39N thin film, on the other hand, exhibits an indirect inter-band transition with an Eg of ∼ 1.84 eV. In addition to the change in Eg, a prominent defect band appears at ∼ 4 eV at low Cr% and another band appears at ∼ 0.98 eV at higher Cr%.

Thin Film Based Membrane Electrode Assemblies for Solid-State Ammonia Synthesis

Ammonia is the of the most crucial chemicals and currently primarily produced through the Haber-Bosch process causing the industrial ammonia production to emit more CO2 than any other chemical-making reaction. While the current primary function of ammonia lies within the fertilizer production, it can also be directly used as a fuel for power generation or in the maritime industry. Compared to hydrogen, ammonia has superior storage and transportation capabilities due to its greater volumetric energy density and mild conditions for liquefication. Given the need of reducing global carbon emissions, ammonia could be synthesized electrochemically using air, water and electricity by the Solid-State Ammonia Synthesis (SSAS). Protonic ceramic cells operate within an intermediate temperature regime of around 450 - 550 °C which is well suited for this process. Within our work, we present a tubular membrane electrode unit entirely made of ceramic components based on a barium zirconate thin film electrolyte. An ammonia production rate of 9.06 × 10-10 mol s-1 cm-2 and a Faradaicefficiency of 6.58% were achieved using a NiO-BaZr0.7Ce0.2Y0.1O3- δ | BaZr0.8Y0.2O3- δ | Ru@Ba0.5Sr0.5TiO3-δ cell.A key innovation lies in the production of dense BaZr0.8Y0.2O3-δ electrolyte layers, ranging from 1 to 5 µm in thickness, utilizing a Closed-Field Unbalanced Magnetron Sputtering (CFUMS) process. This technique allows precise adjustments of stoichiometric ratios within the perovskite structure, offering improved sputtering yields compared to conventional methods. Furthermore, the crystallinity, phase purity, and microstructure of sputter-deposited thin films are enhanced through selective laser annealing (SLA), resulting in high-density films composed of single-phase BaZr0.8Y0.2O3-δ with average crystallite sizes of 200 nm while avoiding substrate damage from thermal stress. Electrochemical performance was evaluated through impedance spectroscopy, half-cell tests and full cell tests providing insights into the efficacy of the developed tubular membrane reactor for the electrochemical synthesis of ammonia. The results demonstrate the feasibility of utilizing ceramic proton conductors in SSAS, particularly highlighting the potential of high-pressure operation up to 80 bars in tubular cells at relatively low temperatures around 450 °C, thereby achieving attractive NH3 production rates.This research contributes to the evolving landscape of sustainable ammonia synthesis by presenting a novel approach that integrates advanced materials and manufacturing techniques. Electrification and decentralization of the ammonia supply chain will expand the market by supporting its current use as fertilizer source and enable a new route as green energy carrier paving the way for an ammonia-based economy. Figure 1

Revealing the Role of Mo Leaching in the Structural Transformation of NiMo Thin Film Catalysts upon Hydrogen Evolution Reaction.

NiMo alloys are considered highly promising non-noble Hydrogen Evolution Reaction (HER) catalysts. Besides the synergistic effect of alloying elements, recent attention is drawn to the Mo leaching from the catalyst. This work investigates the role of Mo in NiMo alloys during HER, aiming to understand the interplay between compositional, structural, and electronic factors on the activity, and their effects on the electrode material and catalyst properties. For this purpose, sputter-deposited low roughness NixMo100-x thin films are produced. The investigation of catalyst performance depending on their chemical composition shows a volcano-shaped plot, peaking for the Ni65Mo35 alloy with the highest intrinsic activity in alkaline HER. A comprehensive electrode surface analysis combining transmission electron microscopy, X-ray photoelectron spectroscopy and atomic force microscopy identifies the leaching of Mo on a structural level and indicates the formation of a Ni(OH)2-rich surface area. The ultimate surface characteristics of the NiMo catalysts depend on the initial composition and the electrochemical procedure. Based on the findings, it conclude that the observed catalytic properties of NiMo alloys in HER are determined by a complex interplay of increasing roughness, available surface species and their synergies. The leaching of Mo has a proven structural effect and is considered one of several factors contributing to the enhanced catalyst activity.

Sputter-deposited Ni-rich NiTi thin films: Mechanical behavior and composition sensitivity

In this study, we investigated the mechanical behavior of sputter-deposited Ni-rich NiTi thin films with various chemical compositions. Freestanding thin films were successfully produced by employing magnetron sputtering and microfabrication techniques. Notably, films containing Ni within the range of 52.6–57.6 at. % exhibited distinct stress-induced martensitic transformations. Among these, 53.3 at. % and 54.2 at. % Ni–Ti films demonstrated a remarkable combination of strength exceeding 1.5 GPa and elastic strain approaching 5%. Conversely, films with the highest Ni content displayed nearly linear elastic behavior, showcasing an exceptional tensile strength of 2.2 GPa. As the element composition deviated from the equiatomic ratio, the grain size of the deposited films underwent a transition from several micrometers to nano-scale. In addition, the critical stresses showed lower sensitivity to chemical composition compared to bulk alloys, indicating that superelastic behavior persists over a wider composition range in Ni-rich NiTi thin films. By comparing the NiTi matrix and precipitate morphology between bulk alloys and thin films, we discussed the variations in the mechanical behavior of thin films.

Investigation of microstructural and mechanical properties of sputter-deposited Ni3Al films at different substrate temperatures

Ni3Al films were deposited on silicon (100) substrate at different substrate temperatures by DC magnetron sputtering. The evolution of phase, microstructure, surface topography and mechanical properties have been investigated as a function of substrate temperature via XRD, FE-SEM, AFM and nanoindentation respectively. Results revealed that the deposited film possessed the preferred orientation of (111) whereas the crystallite size increased and grain size decreased with increase in the substrate temperature. The results of nanoindentation showed that the hardness of the film increased up to 400 °C after which it abruptly decreased. Maximum hardness of ∼13 GPa was achieved when the film was deposited at the substrate temperature of 400 °C. The surface roughness of the film increases simultaneously with the increase in substrate temperature whereas the static contact angle and mechanical properties declined significantly for the film deposited at the substrate temperature of 600 °C. This study reflects the impact of substrate temperature on the evolution of phase, microstructure and mechanical properties of Ni3Al coatings deposited at different substrate temperatures.

Effect of RF power on analog synaptic behavior of sputter-deposited InGaZnO films for neuromorphic computing applications

We demonstrate that an analog synaptic weight update can be achieved using identical pulses via gradual resistance switching of memristors based on sputter-deposited InGaZnO (IGZO) films. When a positive voltage is applied to the IGZO memristor, oxygen vacancies (Vo) are ionized and electrons that serve as dopants are generated. This lowers the Schottky barrier formed at the interface and decreases the resistance. However, a negative voltage provides electrons from the Pd electrode, annihilating the ionized vacancies. As the barrier is reconstructed, the IGZO memristor exhibits a high-resistance state (HRS). As Vo plays a crucial role in switching, the effect of the radio frequency (RF) power on the memristor during the IGZO deposition is examined. A physical analysis reveals that the Vo concentration in the IGZO is proportional to the RF power, inducing a leaky HRS. However, at the expense of a reduced memory window in the IGZO deposited at a higher power of 200 W, the resultant low-resistance state is reliable over time. The strengthened retention allows the synaptic weights to be linearly decreased even by consecutive negative pulses. Hence, when the IGZO memristors are used for synaptic elements to construct neural networks, a higher recognition accuracy for the MNIST dataset is achieved.

Influence of deposition pressure on the microstructure and mechanical properties of sputter-deposited MoNbTaW refractory multi-principal element alloy thin films

A systematic investigation into the effects of deposition pressure on the microstructure and mechanical properties of MoNbTaW refractory multi-principal element alloy (RMPEA) films deposited on Silicon (100) substrates using direct current magnetron sputtering (DCMS) is presented. The deposition pressure was varied from 3 Pa to 0.3 Pa at a homologous temperature (T/Tm) ≤ 0.1. The crystal structure, surface morphology, cross-sectional microstructure and mechanical properties were studied using X-ray diffraction, scanning and transmission electron microscopy and nanoindentation. X-ray diffraction findings indicate a single-phase BCC structure throughout the pressure range. An evolution in surface morphology was observed, coupled with a transition from a void-rich to a densified microstructure as the deposition pressure decreased, in line with the structure zone model. Additionally, variations in crystallographic orientations were detected, with changes in I(110)/(211) suggesting an interplay between film growth dynamics and crystallographic orientation shifts with the deposition pressure. The mechanical properties have shown significant improvement, with hardness and modulus values increasing from 7GPa to 12 GPa and 135 GPa to 243 GPa, with a decrease in deposition pressure. The study provides insights into the deposition mechanism, highlighting that microstructural changes and variations in crystallographic orientations are influenced by deposition pressure-induced alterations in adatom energy and surface mobility, thus affecting the films' mechanical properties.

Inverse problems in resonant ultrasound spectroscopy based on spectra perturbation

In RUS, the fit between the experimental resonant spectrum and the result of the inversion procedure is usually worse than the inaccuracy of the experimental measurement of the resonant frequencies. Thus, it can be problematic to extract any valuable information from slight perturbation of experimental spectra, where the experimental frequency shift falls well below the accuracy of this fit. However, the inverse procedure can be reformulated and instead of fitting the resonant frequencies itself, it can be based on the direct fitting of the frequency perturbations. In this contribution, we show two examples of the use of this approach (i) quantitative RUS evaluation of the elasticity of micrometric and submicrometric surface layers from frequency differences measured before and after layer deposition [1] and (ii) in situ characterization of the thermal degradation of the bonding layer in a bimetallic system [2]. [1] Thomasová M. et al. Young's moduli of sputter-deposited NiTi films determined by resonant ultrasound spectroscopy: Austenite, R-phase, and martensite (2015) Scripta Materialia, 101, pp. 24–27. [2] Janovská M. et al Characterization of bonding quality of a cold-sprayed deposit by laser resonant ultrasound spectroscopy (2020) Ultrasonics, 106, art. no. 106140.

Annealing Effects of ZnO Thin Film on Photocatalytic Performances of Graphene Composites

The hybrid structure of Graphene and ZnO (Graphene/ZnO) is emerging as a novel material used to achieve the high performance of photocatalysis. In this study, we examined the ZnO characteristics that affect the photocatalytic activity of graphene/ZnO using a lamellar structure of graphene and ZnO thin films. Graphene samples were synthesized via chemical vapor deposition, and a typical wet process was applied to transfer them on sputter-deposited ZnO thin films with and without annealing. We confirmed that graphene-deposited ZnO demonstrated more efficient photocatalytic behavior toward the decomposition of methylene blue (as a model organic compound) with ordinary sputtered ZnO thin films. Again, ZnO thin films annealed at 1000 °C in an N2 gas atmosphere with graphene performed better than unannealed films. XRD analysis confirmed that pre-thermal treatment of a ZnO thin film promoted re-crystallization, which had less impact on the photocatalytic improvement. The attachment of graphene to the film is considered to contribute to the enhancement. Raman analysis revealed that the graphene coverage areas on the post-annealed ZnO increased by two times compared to that of an unannealed film where the unannealed film had a higher graphene layer. The results presented in this study demonstrate that an annealed ZnO thin film forms a better attachment with graphene, resulting in a larger graphene coverage area with fewer multilayers, which effectively improves the photocatalytic activity in composite structures.

In situ compositional analysis of ZnO films deposited using sputtering

Metal oxide films are widely used in various industrial products, such as solar cell electrodes and flat panel displays, and they are typically produced using sputter deposition. In situ elemental analysis of metal oxide films improves their reliability because a slight difference in the film compositions affects their properties. Herein, an in situ elemental analysis method of sputter-deposited metal oxide films was developed based on optical emission spectroscopy. The possibility of determining the compositions of the ZnO films based on the emission intensities of the Zn and O I lines during sputter deposition was investigated, and the selection procedures of the emission lines suitable for determining the film composition were proposed. This was achieved by evaluating the linearity (R2 value) between the emission intensity ratio of the Zn I lines to the O I line and the Zn/O atomic ratio in the films. The Zn I lines with R2 values higher than 0.950 did not virtually overlap with other emission lines, and their emission intensity exhibited a dependence on the chamber pressure and the input power to the target similar to that of the O I 777.3 nm line. The highest R2 value (0.992) was obtained for a combination of the Zn I 481.1 nm and O I 777.3 nm lines. The results indicate that obtaining emission spectra during the sputtering of a ZnO target can improve the reliability of ZnO films.

Five-fold twin structures in sputter-deposited nickel alloy films

The deposition of a Ni-1at. % P film resulted in the facilitation of several quintuple twin junctions that give rise to a five-fold twin structure along the film's growth direction. This type of grain growth promoted a pentagonal pyramid surface topology. Upon increasing the deposition rate or the addition of cobalt to reduce the stacking fault energy, an increase in the areal density of such features was observed. Correlated atomic contrast imaging by electron microscopy with atom probe tomography revealed the preference of phosphorus and residual oxygen Cottrell atmospheres around a dislocation network that would be required to accommodate the misorientation strain from a five-fold twin structure filling space. The ability to tune these structures, over a large area of material, offers grain boundary engineering opportunities to readily create novel surface topologies that can act, for example, as an array of field emitters or textured surfaces.

Understanding ion and atom fluxes during high-power impulse magnetron sputtering deposition of NbCx films from a compound target

A combination of time-averaged mass spectroscopy (MS), time-averaged optical emission spectroscopy (OES), and plasma transport modeling was employed to understand the transport processes of ions and atoms in high-power impulse magnetron sputtering discharges resulting in changes in the stoichiometry of NbCx films during their deposition from a stoichiometric NbC compound target at different repetition frequencies and duty cycles. Mass spectrometry showed that the fluxes of ions originating from the elements of the target increase with increasing pulse power density (and decreasing pulse length) due to an increasing electron density and, thus, electron-impact ionization probability. Due to the higher ionization energy and much lower ionization cross section of C (compared to Nb), it was found that the contribution of C+ ions to the deposition flux is practically negligible. Additionally, OES tracked the densities of ions and atoms at different distances from the target. The OES analysis revealed that the atom densities decreased as the pulse power density increased. In contrast, the ion densities exhibited an increase, which is consistent with the findings of MS. Using the data from MS, OES, and modeling, we were able to estimate the fluxes of atoms to the substrate. Our observations demonstrated a transition from C-rich toward Nb-rich flux of film-forming species with increasing pulse power density, corresponding to changes in the film composition. We further discuss the role of internal plasma processes that are responsible for this transition.

The effect of Ar:O2 gas ratios on the structural and optical properties of RF sputter-deposited La2O3-doped ZnO thin films

Due to their unique scintillation, phosphorescence, magnetic, and catalytic properties, rare earth oxide compounds have recently become one of the most in-demand materials used in different ways. The current study investigated the impact of Ar:O2 gas flow variation on the deposition of La2O3-doped zinc oxide thin films (TFs) on silicon dioxide (SiO2) substrates using the radio frequency sputtering technique. FE-SEM analysis has shown a smooth surface topology and purity of La2O3-doped ZnO TFs. X-ray diffraction analysis exhibited a single-phase hexagonal wurtzite-type structure in TFs. A UV–Vis–IR spectrophotometer examined the optical characteristics of ZnO and La2O3-doped ZnO TFs in 300–800 nm wavelength range. The bandgap of La2O3 doped ZnO TFs changed from 2.9 to 3.1 eV as argon and oxygen concentrations in (Ar:O2) gas flow changed. A variation in optical constants such as dielectric constants, refractive index, and extinction coefficient was observed when ZnO and La2O3-doped ZnO TFs were exposed to variable (Ar:O2) gas flow ratios. The photoluminescence analysis of ZnO and La2O3-doped ZnO TFs was performed at an excitation wavelength of 330 nm. Atomic force microscopy further revealed that La2O3 doping resulted in smoother surfaces and smaller grain sizes. This comprehensive study provides valuable insights into the relationship between doping, gas composition, and the optical and structural properties of ZnO TFs. The obtained results on the optimal flow rate of argon gas provide valuable insights for determining the appropriate deposition conditions of La2O3-doped ZnO TFs, specifically for their application in solar thermal systems.

Experimental electronic stopping cross-section of tungsten bulk and sputter-deposited thin films for slow protons, deuterons and helium ions

Experimental electronic stopping cross-section of tungsten bulk and sputter-deposited thin films for slow protons, deuterons and helium ions