Reactive Sputtering Method Research Articles

Effect of abnormally oriented grains on the ferroelectric properties of Al0.65Sc0.35N thin films

The wide bandgap wurtzite Al1-xScxN ferroelectric material is compatible with semiconductor processes and offers advantages such as high remanent polarization (Pr) and high-temperature stability. To clear the relationship between the structure zone model (SZM), abnormally oriented grains (AOGs) and the ferroelectric properties, the Al0.65Sc0.35N films were prepared at various sputtering pressures (0.32–0.90 Pa) and substrate temperatures (200–500 ℃) on low resistance n+-(111) Si substrate by the radio frequency dual-source reactive magnetron sputtering method using Al and Sc targets under pure N2 gas. The introduction of AOGs facilitates compressive stress reduction and promotes ferroelectric switching. However, excessive AOGs will damage the (002) orientation, leading to loss of ferroelectricity. The Al0.65Sc0.35N films synthesized under a sputtering pressure of 0.52 Pa and a substrate temperature of 400 ℃ exhibited a lower leakage current at high electric field, with a Pr value of 154.3 μC/cm2 and a negative coercive field (Ec-) of 3.1 MV/cm at a testing frequency of 1 kHz. The outstanding comprehensive properties support the large potential of Al1-xScxN ferroelectric material for high-performance FeRAM devices.

Thermochromic properties and surface chemical states of reactive magnetron sputtered vanadium oxide thin films at various deposition pressures

Vanadium oxide thin films were prepared using reactive magnetron sputtering method, varying the deposition pressures from 4 to 10 mTorr while maintaining the other sputtering parameters constant. Our investigations revealed sensitive dependence of deposition pressure, chemical states of the V and O atoms, crystal phases, and thermochromic (TC) optical modulation. Specifically, the film deposited at 8 mTorr displayed distinct TC characteristics with a prevalent monoclinic m-VO2 phase according to X-ray diffraction (XRD), supported by X-ray photoelectron spectroscopy (XPS). Optical transmittance modulation and electrical property measurements revealed a metal–insulator transition (MIT), confirming the intimate connection between TC characteristics and presence of the m-VO2 phase. Films deposited at pressures lower or higher than 8 mTorr exhibited typical semiconductor behavior without TC characteristics, further supported by in situ XRD, where (110) plane shifted to lower angle upon heating above τC. Chemical state analysis by XPS revealed a clear correlation between V−O peaks and the presence of a VO2 phase, with the film deposited at 8 mTorr displaying relatively large peak fitted area indicative of the VO2 phase. These findings highlight the critical and sensitive dependence of the deposition conditions in tailoring the properties of vanadium oxide thin films and provide valuable insights for potential applications in chromogenic films.

Effect of N2 reactive gas flow rate on the structural, optical and wettability properties of silicon carbon oxynitride thin films

In the current research, the silicon carbon oxynitride (SiCON) thin film was deposited on the silicon (Si) substrate by radio frequency (RF) reactive magnetron sputtering method. To comprehensively assess the impact of nitrogen flux rate on thin film characteristics, a suite of advanced analytical methods was utilized. The GIXRD analysis confirmed that the SiCON thin film is amorphous in structure. Additionally, Raman spectroscopy detected no graphite nanocrystals within the film. Ellipsometry measurements further showed that the refractive index of the thin films rises with increased nitrogen flux in the reactive gas, indicating a direct correlation between nitrogen concentration during deposition and optical properties. Based on the designs made with McLeod's software, the amount of reflection can be reduced up to 5.7 % at the wavelength of 4 μm and up to 8.5 % in the wavelength range of 3–5 μm for an optimal thickness thin film. The atomic force microscopy (AFM) examination revealed that the surface roughness of the thin films decreases as the nitrogen flux in the reactive gas mixture increases. Additionally, measurements of the water contact angle (WCA) indicated that the SiCON thin films exhibit a hydrophilic state.

Optical and electrophysical properties of nitride TiAlSiN and carbonitride TiAlSiCN coatings: influence of reactive magnetron deposition regimes

The development of thin-film thermal control coatings for small spacecraft is relevant. Coatings based on titanium nitride are capable of functioning in unfavorable conditions of near and deep space, due to their high resistance to the irradiation by high-energy particles. Using the reactive magnetron sputtering method, the nanostructured TiAlSiN and TiAlSiCN coatings were formed on the substrates of silicon oxide (SiO2), glass-ceramic CT-1 and single-crystalline silicon (Si(100)). A study of the electrophysical and optical properties of the formed coatings was carried out. The deposited coatings demonstrate a good reflectivity in the infrared range of spectrum (700–2000 nm), what is important for reducing the overheating of the spacecraft (SC) under the influence of the direct sunlight. In the visible range of spectrum (400–700 nm), a low level of total Rtotal reflection is observed. This is promising for satellites designed to observe the Earth’s surface. The values of solar absorption coefficients αs, emissivity coefficients ε0, ratios αs/ε0, as well as the equilibrium temperature Tр for the samples under study were obtained. The values of resistivity ρ and surface resistance R□, electron concentration N and electron mobility μ were determined. It has been discovered that TiAlSiN, TiAlSiCN films are electrically conductive: ρTiAlSiN = (92÷4260) ∙ 10–7 Ω ∙ m, ρTiAlSiCN = (51÷2360) ∙ 10–7 Ω ∙ m. It has been found that adding carbon to the coating composition reduces the resistance. The obtained nanostructured coatings of TiAlSiN nitride and TiAlSiCN carbonitride can be used as temperature control coatings for small spacecrafts.

Impact of blocking layers based on TiO2 and ZnO prepared via direct current reactive magnetron sputtering on DSSC solar cells

The optimization of dye-sensitized solar cells (DSSCs) technology towards suppressing charge recombination between the contact and the electron transport layer is a key factor in achieving high conversion efficiency and the successful commercialization of this type of product. An important aspect of the DSSC structure is the front blocking layer (BL): optimizing this component may increase the efficiency of photoelectron transfer from the dye to the semiconductor by reduction charge recombination at the TiO2/electrolyte and FTO/electrolyte interfaces. In this paper, a series of blocking layer variants, based on TiO2 and ZnO:TiO2, were obtained using the reactive magnetron sputtering method. Material composition, structure and layer thickness were referred to each process parameters. Complete DSSCs with structure FTO/BL/m-TiO2@N719/ EL-HSE/Pt/FTO were obtained on such bases. In the final results, verification of opto-electrical parameters of these cells were tested and used for the conclusions on the optimal blocking layer composition. As the conclusion, application of blocking layer consists of neat TiO2 resulted in improvement of device efficiency. It should be noted that for TiO2:ZnO/CuxO and TiO2/CuxO cells, higher efficiencies were also achieved when pure TiO2 was used as window layer. Additionally it was proven that the admixture of ZnO phase inspires Voc and FF growth, but is overall unfavorable compared to pristine TiO2 blocking layer and the reference cell, according to the final cell efficiency.

Performance Improvement of a-In-Ga-Sn-O Thin-Film Transistor with Oxygen Doping by Reactive Sputtering Method

Performance Improvement of a-In-Ga-Sn-O Thin-Film Transistor with Oxygen Doping by Reactive Sputtering Method

Optimization of TiN/TiOxNy Laminated Electrode Films for High-Performance Gene Sequencing Chip

With continuous advancement of the fourth generation nanopore gene sequencing technology, the requirements for performance of the electrode films in gene sequencing chips are increasing. This study utilized the high vacuum reactive magnetron sputtering method to examine the impact of working pressure on the electrical, electrochemical, crystal structure, chemical composition, and surface morphology of TiOxNy thin films in detail. The findings revealed that the TiN thin film deposited at 0.4 Pa exhibited the lowest resistivity of 391.9 μΩ·cm. Additionally, the TiOxNy thin film deposited at 1.6 Pa demonstrated the highest volumetric specific capacitance of 35.37 mF·cm−2·μm−1 at 5 mV·s−1. Utilizing the optimal parameters, TiOxNy laminated electrode thin films were in situ grown. Through measurements and analysis, it was found that the TiOxNy electrode thin film effectively achieves a 29.35% improvement in specific capacitance compared to the single layer TiOxNy electrode thin film. The integration of a TiN current collector with low resistivity effectively reduced the internal resistance of the electrode system and decreased the response time to 0.038 s. The features of low impedance and high specific capacitance of TiOxNy laminated thin films offer promising prospects for the preparation of gene sequencing chip with high throughput.

Influence of Ar:O2 Mixing Ratio on Characteristics of Tio2 Nanostructured Thin Films Deposited by DC Reactive Magnetron Sputtering Method

Abstract: In this paper, titanium dioxide nanostructured thin films TiO2 were deposited on unheated glass substrates by applying the DC reactive magnetron sputtering method. Three TiO2 films were deposited using argon sputtering gas with different oxygen ratios: 10%, 25%, and 50%. The resulting films had thicknesses of 200, 184, and 140 nm, respectively. The structural, morphological, optical, and electrical properties of deposited thin films were studied. X-ray diffraction (XRD) data showed that the samples exhibited an amorphous phase. It was found from atomic force microscopy (AFM) that the deposited thin films had a nanostructure, and the heights of their nanograins were 16, 24, and 30 nm, respectively. It was observed from the root-mean-square height RMS values that the films had low roughness. The UV-Vis-NIR spectroscopy showed that the films become more transparent with the increase in oxygen content. The direct band gap ranged between 3.68 and 3.88 eV, while the indirect band gap ranged from 3.3 to 3.66 eV. The highest intensity photoluminescence emission was obtained for the film deposited at 50% O2. In addition, the impedance spectroscopy showed that the films’ resistance did not change with changing oxygen content. Keywords: Magnetron sputtering, Titanium dioxide, X-ray diffraction, Absorption spectra, Atomic Force Microscopy, Photoluminescence, Impedance.

Metal oxide-based gas sensor array for VOCs determination in complex mixtures using machine learning

Detection of volatile organic compounds (VOCs) from the breath is becoming a viable route for the early detection of diseases non-invasively. This paper presents a sensor array of 3 component metal oxides that give maximal cross-sensitivity and can successfully use machine learning methods to identify four distinct VOCs in a mixture. The metal oxide sensor array comprises NiO-Au (ohmic), CuO-Au (Schottky), and ZnO–Au (Schottky) sensors made by the DC reactive sputtering method and having a film thickness of 80–100 nm. The NiO and CuO films have ultrafine particle sizes of < 50 nm and rough surface texture, while ZnO films consist of nanoscale platelets. This array was subjected to various VOC concentrations, including ethanol, acetone, toluene, and chloroform, one by one and in a pair/mix of gases. Thus, the response values show severe interference and departure from commonly observed power law behavior. The dataset obtained from individual gases and their mixtures were analyzed using multiple machine learning algorithms, such as Random Forest (RF), K-Nearest Neighbor (KNN), Decision Tree, Linear Regression, Logistic Regression, Naive Bayes, Linear Discriminant Analysis, Artificial Neural Network, and Support Vector Machine. KNN and RF have shown more than 99% accuracy in classifying different varying chemicals in the gas mixtures. In regression analysis, KNN has delivered the best results with an R2 value of more than 0.99 and LOD of 0.012 ppm, 0.015 ppm, 0.014 ppm, and 0.025 ppm for predicting the concentrations of acetone, toluene, ethanol, and chloroform, respectively, in complex mixtures. Therefore, it is demonstrated that the array utilizing the provided algorithms can classify and predict the concentrations of the four gases simultaneously for disease diagnosis and treatment monitoring.Graphical

Band alignment engineering at ultra-wide bandgap GeO2/SiO2 heterointerfaces

Owing to the tremendous contribution for the carrier transport across the interface, the band alignment engineering in oxide semiconductor heterojunctions (OSHs) is of vital importance for developing oxide semiconductor optoelectronic devices. Here, we have deposited a series of ultra-wide bandgap GeO2 thin films on quartz substrates by the direct-current reactive magnetron sputtering method to construct the OSHs and described the effect of the flow rate ratios of O2 and Ar (O2:Ar) and substrate temperatures on the bandgap energies of GeO2 films and band alignments at the interface of OSHs. Based on the energy loss spectra of O 1 s peaks, the tunable bandgap energies ranging from 4.37 to 5.37 eV have been achieved for GeO2 films. An obvious variation of band alignments has been found in the OSHs, suggesting the dramatically influence of deposition conditions. The valence band offsets are determined to be ranging from 1.85 to 1.96 eV (from 1.88 to 1.95 eV) and the conduction band offsets are calculated to be ranging from 1.88 to 2.78 eV (from 1.74 to 2.19 eV) for the GeO2 films grown at different O2:Ar (substrate temperatures), respectively, due to the nonlocalization of the oxygen vacancies in valence band and the formation of single hexagonal phase in the GeO2 film. Our findings on the band alignment engineering in the GeO2/SiO2 heterointerfaces will open the way for developing GeO2-based optoelectronic devices.

Realization of low specific-contact-resistance on N-polar GaN surfaces using heavily-Ge-doped n-type GaN films deposited by low-temperature reactive sputtering technique

We developed a low-temperature ohmic contact formation process for N-polar GaN surfaces. Specific-contact-resistances of 9.4 × 10−5 and 2.0 × 10−5 Ω cm2 were obtained using Ti/Al metal stacks on heavily-germanium-doped GaN films, which were deposited at 500 °C and 600 °C using a radical-assisted reactive sputtering method, respectively. The electrode sintering temperature was as low as 475 °C. Carrier concentrations for the 500 °C and 600 °C samples were 2.6 × 1020 and 1.8 × 1020 cm−3, respectively. These results suggest that this method is highly effective in reducing the contact resistance of GaN devices with low thermal budgets.

The Influence of Nitrogen Flow on the Stoichiometric Composition, Structure, Mechanical, and Microtribological Properties of TiN Coatings.

Utilizing reactive DC magnetron sputtering method, TiN coatings were deposited on the silicon substrates at different nitrogen flows and powers. A study of the X-ray phase composition of the coatings was carried out. The stoichiometric composition of the coatings was determined using energy dispersive x-ray spectroscopy. The structure of the surface, cross-section, and thickness of the coatings were determined using scanning electron (SEM) and atomic force microscopy (AFM). A significant change in the surface structure of TiN coatings was established with changes in deposition power and nitrogen flow. SEM images of cross-sections of all coated samples showed that the formation of coatings occurs in the form of a columnar structure with a perpendicular orientation relative to the silicon substrate. The mechanical properties (elastic modulus E and microhardness H) of TiN coatings of the first group demonstrate a maximum at a nitrogen flow of 3 sccm and are 184 ± 11 GPa and 15.7 ± 1.3 GPa, respectively. In the second group, the values of E and H increase due to a decrease in the size of the structural elements of the coating (grains and crystallites). In the third group, E and H decrease. Microtribological tests were carried out in 4 stages: at a constant load, multi-cycle for 10 and 100 cycles, and with increasing load. The coefficient of friction (CoF) and specific volumetric wear ω depend on the roughness, topology, and mechanical properties of the resulting coatings. Fracture toughness was determined using nanoscratch and depends on the mechanical properties of TiN coatings. Within each group, coatings with the best mechanical and microtribological properties were described: in the first group-TiN coating at 3 sccm (with (29.6 ± 0.1) at.% N), in the second group-TiN coating at 2 sccm (with (40.8 ± 0.2) at.% N), and in the third group-TiN coating at 1 sccm (c (37.3 ± 0.2) at.% N).

Growth mechanism and field emission of B doped AlN films

This paper highlights the effect of boron dopant on the field emission and growth mechanism of AlN films. The films have been grown by reactive RF magnetron sputtering method. For undoped films, columnar AlN structure was obtained. In the case of boron doped AlN films, the structure growth proceeded gradually through four layers of different thicknesses and structures. It was found that boron favors the formation of an amorphous layer within which oxygen and boron based precipitates develops, retarding the growth of columnar morphology. Depth profiling X-ray photoelectron spectroscopy analyses confirm the presence of B-O, B-N, Al-B and Al-O groups.The study on the field emission (FE) properties of undoped and B doped AlN films on Si substrates indicates that the addition of boron allow to improve FE properties with low turn on field of 2.6 V/μm and low threshold filed of 3.07 V/μm. Such good field emission properties can be attributed to the formation of densely nanograined surface and the appearance of boron based groups.

Study of High Transmittance of SiO2/Nb2O5 Multilayer Thin Films Deposited by Plasma-Assisted Reactive Magnetron Sputtering

SiO2/Nb2O5 multilayer thin films were designed for the special application of an aviation lighting system emitting green light. For optical components in this system to meet requirements such as a high transmittance and durability, SiO2/Nb2O5 multilayer thin films of 60 individual layers were fabricated by a plasma-assisted reactive magnetron sputtering method. As a result, the transmittance spectra were confirmed to have a flat top surface and a square bandwidth. The transmittances of the SiO2/Nb2O5 multilayer thin films in the range of 500 nm to 550 nm was approximately 96.14%. The reason for high transmittance was attributed to the almost matching between the designed and fabricated SiO2/Nb2O5 multilayer thin films. It was found that there was little difference in the total thickness between the designed and fabricated SiO2/Nb2O5 multilayer thin films without interlayer diffusion. The surface roughness and hardness of the SiO2/Nb2O5 multilayer thin films on a glass substrate was 2.32 nm ± 0.19 nm and 6.6 GPa, respectively. These results indicate that SiO2/Nb2O5 multilayer thin films can be applied not only to the optical filters used in aviation lighting devices, but also to various optics applications because of high transmittance.

Gas pressure dependence of optical and mechanical properties in a SiCO thin film for optical waveguide by reactive sputtering method

AbstractIn this study, the gas pressure dependence of optical and mechanical characteristics in reactive sputtered SiCO thin films for optical guided‐wave pressure sensors was experimentally investigated. Thin films were fabricated by varying the gas pressure from 0.3 to 1.0 Pa at an oxygen flow ratio of 6%, and the gas pressure dependences was clarified. As the gas pressure increased, the optical bandgap of the SiCO thin film increased, resulting in a transparent SiCO films. On the other hand, the refractive index, young's modulus, and hardness decreased with increasing gas pressure. Combining this dependence with the oxygen inflow ratio dependence of the previous study, the first‐order approximation formula for the gas pressure and oxygen flow rate ratio for various film characteristics was obtained. Based on this equation, trajectories of equal bandgaps and equal young's moduli on the oxygen flow ratio—gas pressure plane were created on the oxygen influx ratio‐gas pressure coordinates, making it easy to fabricate waveguides with desired characteristics.

Reliable Accessibility of Intermediate Polarization States in Textured Ferroelectric Al0.66Sc0.34N Thin Film

AbstractFerroelectric materials are promising candidates for neuromorphic computing synaptic devices due to the nonvolatile multiplicity of spontaneous polarization. To ensure a sufficient memory window, ferroelectric materials with a large coercivity are urgently required for practical applications in highly scaled multi‐bit memory devices. Herein, a remarkable reliability of intermediate ferroelectric polarization states is demonstrated in a textured Al0.66Sc0.34N thin film with a coercive field of 2.4 MV cm−1. Al0.66Sc0.34N thin films are prepared at 300 °C on Pt (111)/Ti/SiO2/Si substrates using a radio frequency reactive sputtering method. Al0.66Sc0.34N thin films exhibit viable ferroelectricity with a large remanent polarization value of &gt;100 µC cm−2. Through the conventional current–voltage characteristics, polarization switching kinetics, and temperature dependence of coercivity, the reproducibility of multiple polarization states with apparent accuracy is attributed to a small critical volume (3.7 × 10−28 m3) and a large activation energy (3.3 × 1027 eV m−3) for nucleation of the ferroelectric domain. This study demonstrates the potential of ferroelectric Al1‐xScxN for synaptic weight elements in neural network hardware.

Fabrications of metal-insulator nanocomposite TiOx thin films and their dielectric properties

The nanocomposite titanium oxides (TiOX) films were grown on the glass substrate using the reactive DC sputtering method. A solid-state disproportionation process led to the development of a multi-phase structure, consisting of nanocrystalline dioxies (TiO2) and suboxides (TinO2n-1) embedded with an amorphous TiO2-δ matrix. As the plasma discharge impedance decreased during the sputtering growth, a sequence of TiO2 crystallites, sesquioxides (Ti2O3), and eventually monoxides (TiO) were formed. This progression came at the expense of compromising the quality of the TiO2 crystallites and resulted in the reduction of oxygen vacancies in the a-TiO2-δ matrix. Furthermore, the frequency-dependent impedance measurements revealed that the metal-insulator nanocomposite TiOx films containing TiO crystallites exhibited a remarkable permittivity above 106 in the frequency range of 102 ∼106 Hz. We believe that the observed colossal permittivity is primarily attributed to the interface polarization within the composite constituents, in addition to the electrode effects.

Epitaxial growth of nano-texturized NiO films on MgO (001) substrates by a reactive magnetron sputtering method

Epitaxial films with nanostructures are of great significance for some special applications. In this work, nano-texturized NiO films are epitaxially grown on MgO (001) substrates by a reactive magnetron sputtering method. The evolution in morphology is studied as a function of deposition time, and the influences of substrate temperature, oxygen partial pressure, and the substrate treatment before deposition of NiO on the formation of nano-texturized NiO films are explored. It is found that the non-symmetrically epitaxial growth of nano-texturized NiO films can be linked with the surface damages of MgO (001) substrate, which leads to the coalescence of adjacent NiO grains preferentially occurs along the direction of 〈100〉 and 〈010〉, but they do not coalesce simultaneously following the other directions. In addition, the optical property of nano-texturized NiO films is studied using the Cauchy model.

The structure and micromechanical properties of TiAlSiN, TiAlSiCN coatings formed by the method of reactive magnetron sputtering

Nanostructured nitride TiAlSiN and carbonitride TiAlSiCN coatings are herein formed by reactive magnetron sputtering on various types of substrates: single-crystal silicon (100) and Titanium Grade2. To control and manage the coating process, the developed modular gas flow control complex (MGFCC) is used. The elemental composition is studied byenergy dispersive X-ray spectroscopy (EDX), the structure by X-ray diffraction (XRD), the morphology by scanning electron microscopy (SEM), whereas the micromechanical properties by nanoindentation. It is discovered that the formed coatings over the entire range of parameters α = 0.421–0.605 have a single-phase structure (Ti,Al)N, which is a disordered solid solution with a face-centered cubic (fcc) lattice. The average crystallite size of the (Ti,Al)N phase varies in the range (20–30) ± 5 nm. It is found that a decrease in the degree of reactivity α from α = 0.605 to α = 0.421 leads to an increase in the rate of deposition of nitride TiAlSiN and carbonitride TiAlSiСN coatings on silicon substrates by 200–300 %. The hardness of the formed coatings varies in the range H = 28.74–48.99 GPa, Young’s modulus E = 324.97–506.12 GPa. TiAlSiN, TiAlSiCN coatings demonstrate high values of impact strength indices H/E* = 0.07–0.12 and plastic deformation resistance indices H3/E*2 = 0.13–0.72. It is detected that the degree of reactivity α has a significant effect on the micromechanical properties of the formed coatings. The structure and micromechanical properties of the formed nanostructured nitride and carbonitride TiAlSiN, TiAlSiCN coatings are suitable for use in space technology applications.

High-temperature oxidation resistance of CrAlN thin films prepared by DC reactive magnetron sputtering

CrAlN thin films were prepared by using the reactive DC unbalanced magnetron sputtering method from the single alloy target on a silicon substrate. The effect of annealing temperature in the air which ranges from 500℃ to 900℃ for 1 h on phase structure, film composition, surface morphology, microstructure, and hardness was investigated by XRD, EDS, FE-SEM, and Nanoindentation techniques, respectively. The high-temperature (up to 900℃) oxidation resistance of the thin film was also evaluated. The result shows that solid solutions of (Cr,Al)N with (111), (200), and (220) planes for the as-deposited film and no oxide phase were found after annealing with different temperatures. The O content slightly increases with an increase in the annealing temperature with various Cr, Al, and N contents found by the EDS. From the FE-SEM result, as increased annealing temperature, the evolution of cross-sectional morphology from dense to compact columnar structure was exhibited but the oxides layer was not detected. These results concluded that the as-deposited thin film showed good oxidation resistance when annealed in air at an elevated temperature reaching 900℃. Moreover, the film’s hardness decreased from 61.19 GPa to 50.11 GPa with increasing the annealing temperature observed by the Nanoindentation technique.