Ion Beam Sputtering Research Articles

Half 4-inch wafer-scale 2D MoS2 with high uniformity direct bandgap grown using ion beam sputtering and vulcanization

Half 4-inch wafer-scale 2D MoS2 with high uniformity direct bandgap grown using ion beam sputtering and vulcanization

Non-Fourier thermal spike effect on nanocrystalline Cu phase engineering

The thermal spike effect dominates rapid heating and quenching at the nanoscale in ion beam assisted materials surface phase engineering. This phenomenon often leads to the formation of metastable nanocrystalline phases in the resulting micro-/nanostructures. However, such a non-equilibrium process cannot be accurately described by the conventional Fourier thermal spike model. In this study, a non-Fourier model is proposed to elucidate the dynamics of heat diffusion in sub-keV Cu ion beam sputter deposition. The effects of beam density and energy on the non-equilibrium thermal and stress fields are quantitatively investigated. The influence of high stress field on nanocrystalline Cu phase content is also studied. It is found that the energetic Cu ion beams produce a rapidly oscillating stress field with a maximum of ∼ 10 GPa within 50 ps, which significantly constrains the growth of nanocrystalline Cu phase at a threshold of ∼ 4 GPa. This understanding provides new insights into the formation of metastable nanocrystalline phases in the fabrication and modification of surface micro-/nanostructures using ion beam assisted techniques.

Production of mixed phase Ti3+-rich TiO2 thin films by oxide defect engineered crystallization.

Amorphous TiO2 has insufficient chemical stability that can be enhanced with annealing induced crystallization. However, the crystalline structure is already predetermined by the defect composition of the amorphous phase. In this paper, we demonstrate that the oxide defects, i.e., oxygen vacancies and Ti3+ states, can be created by O2 deficiency during ion-beam sputter deposition without affecting the O/Ti ratio of TiO2. The films are thus stoichiometric containing a variable degree of interstitial O instead of lattice O. Defect-free TiO2 crystallizes into microcrystalline anatase during vacuum annealing, whereas a moderate number density of defects causes crystallization into nanocrystalline rutile. An excessive number density of defects results in a mixed amorphous/nanocrystalline rutile phase that was analyzed by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The number density of defects did not affect the crystallization temperature, which was 400 °C. All crystalline films, including the mixed amorphous/nanocrystalline rutile phase, were chemically stable in 1.0 M NaOH for 80 h. Unlike annealing treatments in oxidizing environments that are typically applied to improve stability, vacuum annealing improves the stability preserving also the Ti3+ gap states that are critical to the charge transfer in protective TiO2-based photoelectrode coatings.

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.

Effect of annealing on ion-beam-sputtered hafnium oxide thin films properties

HfO2 films are high laser damage-threshold and low-absorption thin-films that can be utilized for a broad range of optoelectronic and optical applications. In this study, HfO2 thin films were prepared via dual ion beam sputtering followed by annealing in the atmosphere at temperatures ranging from 200 to 700 °C. The optical properties, microstructure, film stress, and absorption loss of the HfO2 films at various annealing temperatures were then systematically characterized. The results revealed that the properties of the films were improved after annealing at temperatures below 500 °C. Specifically, at an optimal annealing temperature of 400 °C, the residual stress of the films was minimized close to zero and the absorption loss was as low as 1 ppm. However, at annealing temperatures reaching 600 °C, the films began to crystallize, leading to the deterioration of their optical properties. Optimizing the process parameters for HfO2 thin film deposition is crucial for developing the next generation of high-performance laser optics.

Determining the carbon detection limit with magnetic sector dynamic secondary ion mass spectrometry (SIMS)

Dynamic SIMS is often used to evaluate the concentration of impurities in solids because of its high sensitivity, depth profiling capabilities, good depth resolution, and high throughput. Continuous ion beam sputtering with a high-density primary beam provides high sensitivity and reduces the background contribution from residual gases within the analytical chamber. Dynamic SIMS experiments performed with several magnetic sector instruments using various sputtering rate conditions demonstrated a slow decrease of the carbon detection limit with the increase of sputtering rate (SR), when it was varied by changing the sputtering beam density. The dependence data, within the scatter limits, can be fit by a power function of SR with the exponent of about −1/2. The observed detection-limit-dependence curve is common for magnetic sector SIMS instruments, owing to contamination and the design of the analytical chamber. The depth resolution of light-element SIMS analysis (except for oxygen) performed using Cs+ sputtering is limited and cannot be improved by reducing the impact energy of the sputtering beam. A segregation-type depth profile with a long trailing edge was observed in the B, C, and N depth profiles when Cs+ sputtering was employed under ultra-high vacuum conditions. This effect is plausibly associated with preferential sputtering owing to the difference in the surface binding energy, along with the large difference in the mass of the interacting atoms within the collision cascade during sputtering. The depth resolution improved with surface oxidation when Cs + sputtering was combined with backfilling of the analytical chamber using O2. The analytical chamber backfilled with oxygen can be sufficiently replaced with a very low-impact energy-focused oxygen beam, enabling simultaneous oxygen and cesium co-sputtering SIMS analysis. The practical feasibility of using a co-sputtering with focused Cs+ and O2+ sputtering beams to achieve a high depth-resolution for carbon analysis under ultrahigh vacuum conditions was demonstrated.

Design and fabrication of integrated negative feedback resistor for InGaAs/InP avalanche photodiode

The serial resistor of alloy material can be integrated on negative feedback avalanche diodes to reduce afterpulsing effect. In this work, the influence of parasitic capacitance on the avalanche quenching resistor was theoretically analyzed. By using simulation model of device & circuit mixed-mode, the quenching capability of integrated resistors was evaluated with the parasitic parameters. For the material growth of feedback quenching resistor, thin film based on CrSi alloy was prepared by ion beam sputtering process, realizing the sheet resistance of 3 kΩ/square. The resistor material were sufficiently investigated by characterizing the morphology and element component. CrSi pattern of spiral shape was fabricated on sapphire substrate, realizing a resistor of the order of 500 kΩ in area of diameter 40 μm, which was equivalent to the active area of avalanche diodes. The electrical measurement indicated the excellent temperature stability of this integrated resistor, showing the promising application prospect for preparing high-performance negative feedback avalanche diodes.

Integrated Amorphous Carbon Film Temperature Sensor with Silicon Accelerometer into MEMS Sensor.

Amorphous carbon (a-C) has promising potential for temperature sensing due to its outstanding properties. In this work, an a-C thin film temperature sensor integrated with the MEMS silicon accelerometer was proposed, and a-C film was deposited on the fixed frame of the accelerometer chip. The a-C film was deposited by DC magnetron sputtering and linear ion beam, respectively. The nanostructures of two types of films were observed by SEM and TEM. The cluster size of sp2 was analyzed by Raman, and the content of sp2 and sp3 of the carbon film was analyzed by XPS. It showed that the DC-sputtered amorphous carbon film, which had a higher sp2 content, had better temperature-sensitive properties. Then, an integrated sensor chip was designed, and the structure of the accelerometer was simulated and optimized to determine the final sizes. The temperature sensor module had a sensitivity of 1.62 mV/°C at the input voltage of 5 V with a linearity of 0.9958 in the temperature range of 20~150 °C. The sensitivity of the sensor is slightly higher than that of traditional metal film temperature sensors. The accelerometer module had a sensitivity of 1.4 mV/g/5 V, a nonlinearity of 0.38%, a repeatability of 1.56%, a total thermomechanical noise of 509 μg over the range of 1 to 20 Hz, and an average thermomechanical noise density of 116 µg/√Hz, which is smaller than the input acceleration amplitude for testing sensitivity. Under different temperatures, the performance of the accelerometer was tested. This research provided significant insights into the convenient procedure to develop a high-performance, economical temperature-accelerometer-integrated MEMS sensor.

Simulation of ion beam sputtering with OKSANA and SRIM: A comparative study

The energy distributions and average energies of sputtered particles are calculated using simulation codes OKSANA and SRIM-2013. Most simulations refer to an amorphous Ni target bombarded by normally incident Ar ions of keV energies. Sputtering of Si, Ti, V and Nb targets is also considered. It is shown that SRIM can strongly overestimate the contribution of fast ejected atoms, especially for targets irradiated with lighter ions. The effect is amplified by using the surface binding energies found to fit the measured sputter yields. It is concluded that the enhanced ejection of fast particles is associated with sputtering due to backscattered ions. The role of the first collision of an incident ion with a target atom is particularly noted. A comparison of the OKSANA calculated results with the data of other codes (TRIM.SP, ACAT) and experimental data showed their reasonable agreement.

Inelastic relaxation in tin oxide thin films with an amorphous structure

Inelastic relaxation in amorphous tin oxide thin films obtained by ion-beam sputtering in an argon atmosphere were studied. The films retain an amorphous structure after annealing at temperatures below 623 K for 30 min and crystallization begins after annealing at 673 K with the formation of two phases, where the SnO2 phase predominates over the SnO phase. Annealing at 723 K for 30 min leads to a partial transition of the SnO crystalline phase to the SnO2 phase.The temperature dependence of internal friction revealed maxima at 585 K and 603 K, identified as β - relaxation maxima, as well as at 690 K, identified as α - relaxation maximum. It is assumed that the β - relaxation maxima at 585 K and 603 K are associated with local hopps of oxygen atoms within the defect structure of SnO2 and with local hopps of tin atoms within the defect structure of SnO, respectively. The exponential increase in internal friction up to a temperature of 690 K in the α - relaxation region is associated with the diffusion of nonequilibrium vacancy-like defects of the amorphous structure below the glass transition temperature and equilibrium ones above the glass transition temperature. Estimates of the migration energy and formation energy of vacancy-like defects in amorphous tin oxide were made.

Anisotropic wettability transition on nanoterraced glass surface by Ar ions

Ion beam sputtering (IBS) can induce nanoripple patterns in a short time on variety of materials for wide range of applications. In this work, we describe the nanoripple as well as terrace pattern formation by IBS on soda-lime glass surfaces and the mechanisms leading to such pattern formations. The role of ion energy, ion fluence, and ion incidence angle on the morphology of the structural features is systematically explored. For a range of ion beam parameter values with energy varying from 600 to 1500 eV and fluence in the range 9.7 × 1017 to 2.0 × 1019 ions/cm2 at fixed incidence angle of 45°, transition of ripples to terraces has been observed. The experimental results are explained on the basis of recently modified KS equation which clearly explains the simultaneous role of nonlinear cubic term in the terrace formation. It is also demonstrated how ion beam can be used to tailor the wettability of glass surface and makes it hydrophobic in nature. Due to pattern formation, anisotropic hydrophobicity is observed showing an increasing trend owing to the magnification of the amplitude of nanopatterns developed on the surface.

Nanoscale pattern formation on surfaces by cluster ion beam irradiation

Ion beam sputtering is a solid-surface nanostructuring procedure applicable to any type of material. In this study, we are interested in the bombardment of a metallic surface, specifically, of a Co(110) surface bombarded with Ar clusters at oblique incidence. The bombardment with clusters accentuates the effect of surface ripple formation. Sputter erosion and surface atomic redistribution are the processes that determine the morphological evolution of the surface from the collisional point of view. The importance of these processes was analyzed for different angles of incidence in the bombardment with very small clusters and atoms while always maintaining the same fluence. The sputter yield increases with the number of atoms in the cluster for angles greater than 50°; while for the rest, it barely experiences any increase. Unlike sputtering, displacements increase as the cluster size increases above the critical angle. Moreover, horizontal displacement only shows some sign of saturation for angles close to the normal. An analysis of redistributed volumes and previous data suggest that sputtering drives the ripple effect for grazing angles and ones close to these. It is also responsible for the enhancement effect in the cluster bombardment. For the rest of the angles, the weight of the redistribution is decisive. There is a proportional relationship between the emptied volume and the horizontal displacement.

Tailoring the Lithium Concentration in Thin Lithium Ferrite Films Obtained by Dual Ion Beam Sputtering.

Thin films of lithium spinel ferrite, LiFe5O8, have attracted much scientific attention because of their potential for efficient excitation, the manipulation and propagation of spin currents due to their insulating character, high-saturation magnetization, and Curie temperature, as well as their ultra-low damping value. In addition, LiFe5O8 is currently one of the most interesting materials in terms of developing spintronic devices based on the ionic control of magnetism, for which it is crucial to control the lithium's atomic content. In this work, we demonstrate that dual ion beam sputtering is a suitable technique to tailor the lithium content of thin films of lithium ferrite (LFO) by using the different energies of the assisting ion beam formed by Ar+ and O2+ ions during the growth process. Without assistance, a disordered rock-salt LFO phase (i.e., LiFeO2) can be identified as the principal phase. Under beam assistance, highly out-of-plane-oriented (111) thin LFO films have been obtained on (0001) Al2O3 substrates with a disordered spinel structure as the main phase and with lithium concentrations higher and lower than the stoichiometric spinel phase, i.e., LiFe5O8. After post-annealing of the films at 1025 K, a highly ordered ferromagnetic spinel LFO phase was found when the lithium concentration was higher than the stoichiometric value. With lower lithium contents, the antiferromagnetic hematite (α-Fe2O3) phase emerged and coexisted in films with the ferromagnetic LixFe6-xO8. These results open up the possibility of controlling the properties of thin lithium ferrite-based films to enable their use in advanced spintronic devices.

Formation of silver nanocrystals in Ag-Si composite films obtained by ion beam sputtering

Nanostructured composite films based on Ag-Si containing silver nanoparticles are used as a material for SERS (Surfaceenhanced Raman spectroscopy) substrates, plasmonic back reflector, nanoplasmonic sensors, nonlinear optics devices, memristor structures, etc. Due to the widespread use of nanocomposite films based on Ag-Si, there is a need to develop simple and affordable methods for their production compatible with semiconductor technology. Therefore, this work is devoted to the production of an Ag80Si20 nanocomposite film with a high silver content (80 at.%) by ion-beam sputtering with simultaneous control of the morphology, structure, phase composition and electrical properties of the manufactured sample. As a result of complex studies using X-ray diffraction, ultra-soft X-ray emission spectroscopy, SEM and AFMmicroscopy, it was found that the film is a nanocomposite material based on silver nanoparticles with an average size of ~15÷30 nm. At the same time, some silver nanoparticles are in direct contact, while some Ag nanoparticles are isolated from each other by a shell of silicon dioxide SiO2 and amorphous silicon a-Si. Such a nanogranulated structure of the Ag80Si20 film causes the presence in the test sample of the effect of switching from a high-resistance state (880 Ohm) to a lowresistance state (~1 Ohm) under the action of a voltage of ~ 0.2 V. As a result of the formation of conductive filaments (CF) of Ag atoms in the dielectric layer between the silver granules

Magnetic contrast layers with functional SiO2 coatings for soft-matter studies with polarized neutron reflectometry

This study introduces silicon substrates with a switchable magnetic contrast layer (MCL) for polarized neutron reflectometry (PNR) experiments at the solid–liquid interface to study soft-matter surface layers. During standard neutron reflectometry (NR) experiments on soft-matter samples, structural and compositional information is obtained by collecting experimental data with different isotopic contrasts on the same sample. This approach is normally referred to as contrast matching, and it can be achieved by using solvents with different isotopic contrast, e.g. different H2O/D2O ratios, and/or by selective deuteration of the molecules. However, some soft-matter systems might be perturbed by this approach, or it might be difficult to implement, particularly in the case of biological samples. In these scenarios, solid substrates with an MCL are an appealing alternative, as the magnetic contrast with the substrate can be used for partial recovery of information on the sample structure. More specifically, in this study, a magnetically soft Fe layer coated with SiO2 was produced by ion-beam sputter deposition on silicon substrates of different sizes. The structure was evaluated using X-ray reflectometry, atomic force microscopy, vibrating sample magnetometry and PNR. The collected data showed the high quality and repeatability of the MCL parameters, regardless of the substrate size or the thickness of the capping SiO2 layer. Previously proposed substrates with an iron MCL used an Au capping layer. The SiO2 capping layer proposed here allows reproduction of the typical surface of a standard silicon substrate used for NR experiments and is compatible with a large variety of soft-matter samples. This application is demonstrated with ready-to-use 50 × 50 × 10 mm substrates in PNR experiments for the characterization of a lipid bilayer in a single solvent contrast. Overall, the article highlights the potential of PNR with an MCL for the investigation of soft-matter samples.

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.

Magnetic properties and magnetoresistance of hybrid multilayer nanostructures {[(Co40Fe40B20)34(SiO2)66]/[ZnO]}n

The structural, electrical, magnetic, magneto-optical properties and magnetoresistance of {[(Co40Fe40B20)34(SiO2)66]/[ZnO]}n multilayer structures, where n = 50 is the number of bilayers (Co40Fe40B20)34(SiO2)66 nanocomposite and ZnO have been studied. The thicknesses of (Co40Fe40B20)34(SiO2)66 nanocomposite layers as well as ZnO spacers were varied in a wide range. The samples were synthesized by ion-beam sputtering onto glass ceramic substrates. The (Co40Fe40B20)34(SiO2)66 composite have an amorphous structure and the semiconductor ZnO interlayers have a hexagonal crystalline structure with the p63mc symmetry group. The nanocomposite layers containing a ferromagnetic component far from the percolation threshold are in a superparamagnetic state. The presented in the paper data of magnetization, magneto-optical transverse Kerr effect and magnetoresistance indicates that long-range ferromagnetic order does not form down to 77 K both for references ZnO films and studied multilayers with thin and thick ZnO interlayers. An increase in the magneto-optical signal in multilayers compared to references (Co40Fe40B20)34(SiO2)66 composite films has been detected at 1.2 eV. The magnetoresistance of {[(Co40Fe40B20)34(SiO2)66]/[ZnO]}n multilayers with thick (>32 nm) ZnO interlayers is lower than in reference (Co40Fe40B20)34(SiO2)66 nanocomposite, while at thin ZnO interlayers magnetoresistance is significantly higher and reaches 12 % at temperatures of 77 К. Possible mechanisms of ferromagnetic and antiferromagnetic ordering, enhancement of the magneto-optical response and magnetoresistance in {[(Co40Fe40B20)34(SiO2)66]/[ZnO]}n multilayer nanostructures are discussed.

Level set simulation of focused ion beam sputtering of a multilayer substrate.

The evolution of a multilayer sample surface during focused ion beam processing was simulated using the level set method and experimentally studied by milling a silicon dioxide layer covering a crystalline silicon substrate. The simulation took into account the redeposition of atoms simultaneously sputtered from both layers of the sample as well as the influence of backscattered ions on the milling process. Monte Carlo simulations were applied to produce tabulated data on the angular distributions of sputtered atoms and backscattered ions. Two sets of test structures including narrow trenches and rectangular boxes with different aspect ratios were experimentally prepared, and their cross sections were visualized in scanning transmission electron microscopy images. The superimposition of the calculated structure profiles onto the images showed a satisfactory agreement between simulation and experimental results. In the case of boxes that were prepared with an asymmetric cross section, the simulation can accurately predict the depth and shape of the structures, but there is some inaccuracy in reproducing the form of the left sidewall of the structure with a large amount of the redeposited material. To further validate the developed simulation approach and gain a better understanding of the sputtering process, the distribution of oxygen atoms in the redeposited layer derived from the numerical data was compared with the corresponding elemental map acquired by energy-dispersive X-ray microanalysis.

Metal oxides for electronics and the SPQEO journal

This article discusses the main trends in the physics and preparation of metal oxides and summarizes the results of research published by SPQEO in this area over the past decade. The main metal oxides studied include ZnO, Zn1-xCdxO, Zn1-xCoxO, MgxZn1–xO, ZnO:Mn, VO2, ZrO2–Y2O3, TiO2, WO3, Gd2O3, Er2O3, WO3–CaO–SiO2–B2O3: Tb3+, Dy2O3, NiO, FexOy, Ga2O3, Al2O3, ITO, Ag2O and graphene oxide. These oxides were obtained by the following methods: sintering in air or in a stream of various gases, magnetron sputtering, atomic layer deposition, explosive evaporation, sol-gel, spin coating, spray pyrolysis, rapid thermal annealing, green synthesis from plant solutions, melt quenching, rapid thermal annealing, self-ignition, ion-plasma co-sputtering, vacuum sputtering, reactive ion beam sputtering, and the Hammer method. The electrical and optical properties of the studied oxides are illustrated.

Paper-based immunosensor integrated with bioinspired Cu-polydopamine nanozyme for voltammetric detection of CA-15-3 tumor marker

This manuscript describes the fabrication and characterization of a highly conductive paper-based nanoplatform for immobliztion of anti-CA 15-3 antibodies. For this purpose, cellulosic filter paper (FP) was first coated with Cu nanosponges (CuNSs) through ion beam sputtering deposition (IBSD) method and then covered with Cu-doped polydopamine nanospheres (Cu-PDA). Polydopamine doped with copper exhibited laccase (multi-copper oxidase)-mimicking properties. Bioinspired by the structure of the active site and the electron transfer mechanism of laccase, Cu-PDA nanozyme catalyzed the oxidation of hydroquinone (HQ) signal probe. In this design, CA-15-3, a prognostic biomarker in the breast cancer, was chosen as a model target. To the best of our knowledge, this is the only paper on the design of an electrochemical biosensor based on dense and uniform CuNSs produced by IBSD. More importantly, Cu-PDA is biocompatible and biodegradable, which makes it a potential competitor in the point-of-care (POC) biosensing applications. Thus, this paper-based sensing strategy can be used in designing cost-effective flexible chips consisting of electrodes printed on paper for in-situ and real-time monitoring biomarkers under clinical conditions. In addition to these outstanding features, the LOD (1.3 mU mL 1) and LOQ (4.3 mU mL 1) of the Ab/HQ/Cu-PDA/CuNSs/FP-based immunosensor was significantly lower than the clinically relevant cut-off level (30 U mL 1). In the practical applications, one of the key superiorities of this immuosensor is the wide DLR (5 mU mL 1–280 U mL 1) which covers the ultimate value of healthy and patient individuals.