Growth and characterization of diamond films on TiN/Si(100) by microwave plasma chemical vapor deposition

Polycrystalline diamond films were deposited on silicon (100) substrate by microwave plasma chemical vapor disposition (MPCVD) using ~ 300 nm thick <001> textured titanium nitride (TiN) films as buffer layer which were prepared by radio-frequency reactive sputtering. The diamond/TiN films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. The results show that no apparent change can be observed for the <100> oriented TiN buffer layers after MPCVD even with a negative bias voltage applied onto the substrates.     

Effect of In/Al ratios on structural and optical properties of InAlN films grown on Si(100) by RF-MOMBE

In _x Al_1-x N films were deposited on Si(100) substrate using metal-organic molecular beam epitaxy. We investigated the effect of the trimethylindium/trimethylaluminum (TMIn/TMAl) flow ratios on the structural, morphological, and optical properties of In _x Al_1-x N films. Surface morphologies and microstructure of the In _x Al_1-x N films were measured by atomic force microscopy, scanning electron microscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM), respectively. Optical properties of all films were evaluated using an ultraviolet/visible/infrared (UV/Vis/IR) reflection spectrophotometer. XRD and TEM results indicated that In _x Al_1-x N films were preferentially oriented in the c-axis direction. Besides, the growth rates of In _x Al_1-x N films were measured at around 0.6 μm/h in average. Reflection spectrum shows that the optical absorption of the In _x Al_1-x N films redshifts with an increase in the In composition.     

Field emission properties and growth mechanism of In2O3 nanostructures

Four kinds of nanostructures, nanoneedles, nanohooks, nanorods, and nanotowers of In₂O₃, have been grown by the vapor transport process with Au catalysts or without any catalysts. The morphology and structure of the prepared nanostructures are determined on the basis of field emission scanning electron microscopy (FESEM), x-ray diffraction (XRD), and transmission electron microscopy (TEM). The growth direction of the In₂O₃ nanoneedles is along the [001], and those of the other three nanostructures are along the [100]. The growth mechanism of the nanoneedles is the vapor-liquid–solid (VLS), and those of the other three nanostructures are the vapor-solid (VS) processes. The field emission properties of four kinds of In₂O₃ nanostructures have been investigated. Among them, the nanoneedles have the best field emission properties with the lowest turn-on field of 4.9 V/μm and the threshold field of 12 V/μm due to possessing the smallest emitter tip radius and the weakest screening effect.     

Effect of plating parameters on the properties of pulse electrodeposited Ni–TiN thin films

The influence of pulse plating parameters on the microstructure, microhardness, and properties of the Ni–TiN thin films was investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), X–ray diffraction (XRD), scanning electron microscopy (SEM), and corrosion and wear tests. The results indicated the Ni–TiN thin films prepared via electrodeposition at 4 A/dm² current density to show an optimum microhardness and TiN content values of 984.7 HV and 8.69 wt%, respectively. The average grain sizes of Ni and TiN in the films obtained at 200 Hz were 127.8 and 48.5 nm, respectively. Numerous large pores can be noticed in the films prepared at pulse frequencies of 200 Hz and 500 Hz, whereas only a few small pits are visible on the surface of the Ni–TiN thin films deposited at 800 Hz. The films prepared at 20% duty cycle experienced the least weight loss.     

Effect of oxygen flow ratio on crystallization and structural characteristics of gallium oxide thin films

Beta-gallium oxide (β-Ga₂O₃) thin films were prepared on a MgO (100) substrate under different oxygen flow ratios via magnetron sputtering. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and UV–visible near-infrared (UV–vis–NIR) analyses were conducted to study how the oxygen flow ratio affected the crystalline quality and the surface topography of the films. Microstructure analysis revealed a clear out-of-plane orientation of β-Ga₂O₃ (100) || MgO (100). The film deposited under an oxygen flow ratio of 1% presented the optimal single-crystalline structure, while excess oxygen was confirmed to negatively impact the crystallization characteristics of the films. SEM measurements indicated that the increase in the oxygen flow ratio reduced the grain size and RMS roughness. The average transmittance of the β-Ga₂O₃ films in the visible range exceeded 83%, with a broad luminescence band exhibited at approximately 485 nm in the photoluminescence (PL) spectra.     

Ferromagnetism and optical properties of La1???x Al x FeO3 nanopowders

La_{1 − x} Al _x FeO₃ (x = 0.0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) nanopowders were prepared by polymerization complex method. All prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and UV-vis spectrophotometry (UV-vis). The magnetic properties were investigated using a vibrating sample magnetometer (VSM). The X-ray results of all samples show the formation of an orthorhombic phase with the second phase of α-Fe₂O₃ in doped samples. The crystallite sizes of nanoparticles decreased with increasing Al content, and they are found to be in the range of 58.45 ± 5.90 to 15.58 ± 4.64 nm. SEM and TEM images show the agglomeration of nanoparticles with average particle size in the range of 60 to 75 nm. The FT-IR spectra confirm the presence of metal oxygen bonds of O-Fe-O and Fe-O in the FeO₆ octahedra. The UV-vis spectra show strong absorption peaks at approximately 285 nm, and the calculated optical band gaps are found to be in the range of 2.05 to 2.09 eV with increasing Al content. The M-H loop of the pure sample is antiferromagnetic, whereas those of the doped samples tend to be ferromagnetic with increasing Al content. The magnetization, remanent magnetization, and coercive field of the Al-doped sample with x = 0.5 are enhanced to 1.665 emu/g, 0.623 emu/g, and 4,087.0 Oe, respectively.     

Effect of thickness on the structure,composition and properties of titanium nitride nano-coatings

Titanium nitride (TiN_x) coatings were grown by magnetron sputtering onto Si(100) substrates by varying time of deposition to produce coatings with variable thickness (d_TiN) in the range of 20–120 nm. TiN_x coatings were characterized by studying their structure, composition, and mechanical properties. Nuclear reaction analysis (NRA) combined with Rutherford backscattering spectrometry (RBS) analyses indicate that the grown coatings were stoichiometric TiN. Grazing incidence X-ray diffraction (GIXRD) measurements indicate that the texturing of TiN coatings changes as a function of d_TiN. The (111) and (002) peaks appear initially; (111) becomes intense while (002) disappears with increasing d_TiN. Dense, columnar grain structure was evident for all the coatings in electron microscopy analyses. The residual stress for TiN coatings with d_TiN~120 nm was 1.07 GPa in compression while thinner samples exhibit higher values of stress.     

Ferroelectric BaTiO3/SrTiO3 multilayered thin films for room-temperature tunable microwave elements

Ferroelectric BaTiO₃/SrTiO₃ with optimized c-axis-oriented multilayered thin films were epitaxially fabricated on (001) MgO substrates. The microstructural studies indicate that the in-plane interface relationships between the films as well as the substrate are determined to be (001)_SrTiO3//(001)_BaTiO3//(001)_MgO and [100]_SrTiO3//[100]_BaTiO3//[100]_MgO. The microwave (5 to 18 GHz) dielectric measurements reveal that the multilayered thin films have excellent dielectric properties with large dielectric constant, low dielectric loss, and high dielectric tunability, which suggests that the as-grown ferroelectric multilayered thin films can be developed for room-temperature tunable microwave elements and related device applications.     

Copper pillar and memory characteristics using Al2O3 switching material for 3D architecture

A novel idea by using copper (Cu) pillar is proposed in this study, which can replace the through-silicon-vias (TSV) technique in future three-dimensional (3D) architecture. The Cu pillar formation under external bias in an Al/Cu/Al₂O₃/TiN structure is simple and low cost. The Cu pillar is formed in the Al₂O₃ film under a small operation voltage of <5 V and a high-current-carrying conductor of >70 mA is obtained. More than 100 devices have shown tight distribution of the Cu pillars in Al₂O₃ film for high current compliance (CC) of 70 mA. Robust read pulse endurances of >10⁶ cycles are observed with read voltages of −1, 1, and 4 V. However, read endurance is failed with read voltages of −1.5, −2, and −4 V. By decreasing negative read voltage, the read endurance is getting worst, which is owing to ruptured Cu pillar. Surface roughness and TiO _x N _y on TiN bottom electrode are observed by atomic force microscope and transmission electron microscope, respectively. The Al/Cu/Al₂O₃/TiN memory device shows good bipolar resistive switching behavior at a CC of 500 μA under small operating voltage of ±1 V and good data retention characteristics of >10³ s with acceptable resistance ratio of >10 is also obtained. This suggests that high-current operation will help to form Cu pillar and lower-current operation will have bipolar resistive switching memory. Therefore, this new Cu/Al₂O₃/TiN structure will be benefited for 3D architecture in the future.     

Energy state of InGaAs quantum dots on SiO2-patterned vicinal substrate

The optical properties of In_0.8Ga_0.2As self-assembled quantum dots (SAQDs) grown on GaAs wire structures formed by utilizing SiO₂-patterned exact and 5°-off (001) GaAs substrates have been studied with micro-photoluminescence (μ-PL). Single PL peak was occurred for In_0.8Ga_0.2As SAQDs grown on SiO₂-patterned exact (001) GaAs, whereas double PL peaks were showed for SAQDs grown on 5°-off (001) GaAs substrates as the width of the opening windows increased. The power-dependent μ-PL spectra show that the first and second peaks of these double peaks were originated from the well-defined ground and excited state, respectively. These results demonstrated that In_0.8Ga_0.2As SAQDs selectively grown by utilizing SiO₂-patterned 5°-off (001) GaAs substrates have well-defined zero-dimensional quantum states.     

Impact of electrically formed interfacial layer and improved memory characteristics of IrOx/high-κx/W structures containing AlOx,GdOx, HfOx,and TaOx switching materials

Improved switching characteristics were obtained from high-κ oxides AlO_x, GdO_x, HfO_x, and TaO_x in IrO_x/high-κ_x/W structures because of a layer that formed at the IrO_x/high-κ_x interface under external positive bias. The surface roughness and morphology of the bottom electrode in these devices were observed by atomic force microscopy. Device size was investigated using high-resolution transmission electron microscopy. More than 100 repeatable consecutive switching cycles were observed for positive-formatted memory devices compared with that of the negative-formatted devices (only five unstable cycles) because it contained an electrically formed interfacial layer that controlled ‘SET/RESET’ current overshoot. This phenomenon was independent of the switching material in the device. The electrically formed oxygen-rich interfacial layer at the IrO_x/high-κ_x interface improved switching in both via-hole and cross-point structures. The switching mechanism was attributed to filamentary conduction and oxygen ion migration. Using the positive-formatted design approach, cross-point memory in an IrO_x/AlO_x/W structure was fabricated. This cross-point memory exhibited forming-free, uniform switching for >1,000 consecutive dc cycles with a small voltage/current operation of ±2 V/200 μA and high yield of >95% switchable with a large resistance ratio of >100. These properties make this cross-point memory particularly promising for high-density applications. Furthermore, this memory device also showed multilevel capability with a switching current as low as 10 μA and a RESET current of 137 μA, good pulse read endurance of each level (>10⁵ cycles), and data retention of >10⁴ s at a low current compliance of 50 μA at 85°C. Our improvement of the switching characteristics of this resistive memory device will aid in the design of memory stacks for practical applications.     

Air-based sputtering deposition of titanium oxynitride-based single,gradient, and multi-layer thin films for photoelectrochemical applications

Titanium oxynitride (TiN_xO_y) thin films exhibiting tunable physical and chemical properties can be used in many fields. Air-based sputtering deposition of the films with diverse O/N ratios was employed to produce gradient and multilayer films. By solely altering the air/Ar flow ratio, obtained TiN_xO_y films could change from a crystalline to a mainly amorphous feature. Moreover, the carrier concentration, Hall mobility, and hence resistivity of the films could be modified to a large range. The optical bandgaps of the films could also be tailored to a wide extent. Based on these results, the gradient TiN_xO_y layer and TiN_xO_y/TiN(O) multilayer were also deposited on TiN(O)-coated glass substrates for the assessment of photoelectrochemical performance. Compared with the TiN_xO_y/TiN(O) bilayer with the best photoelectrochemical performance, the photoelectrochemical currents of gradient TiN_xO_y films could be improved from 99 ± 2 μA⋅cm⁻² to 164 ± 2 μA⋅cm⁻² by taking advantage of bandgap engineering. Additionally, the photoelectrochemical currents of TiN_xO_y/TiN(O) multilayer were further improved to 175 ± 6 μA⋅cm⁻². This is mainly due to conductive nano TiN(O) layers providing multiple high-transport paths while allowing light transmission. The enhancement mechanisms of the gradient and multilayer films have also been elaborated.     

Enhanced resistive switching memory characteristics and mechanism using a Ti nanolayer at the W/TaOx interface

Enhanced resistive memory characteristics with 10,000 consecutive direct current switching cycles, long read pulse endurance of >10⁵ cycles, and good data retention of >10⁴ s with a good resistance ratio of >10² at 85°C are obtained using a Ti nanolayer to form a W/TiO_x/TaO_x/W structure under a low current operation of 80 μA, while few switching cycles are observed for W/TaO_x/W structure under a higher current compliance >300 μA. The low resistance state decreases with increasing current compliances from 10 to 100 μA, and the device could be operated at a low RESET current of 23 μA. A small device size of 150 × 150 nm² is observed by transmission electron microscopy. The presence of oxygen-deficient TaO_x nanofilament in a W/TiO_x/TaO_x/W structure after switching is investigated by Auger electron spectroscopy. Oxygen ion (negative charge) migration is found to lead to filament formation/rupture, and it is controlled by Ti nanolayer at the W/TaO_x interface. Conducting nanofilament diameter is estimated to be 3 nm by a new method, indicating a high memory density of approximately equal to 100 Tbit/in.².     

Modification of crystal anisotropy and enhancement of magnetic moment of Co-doped SnO2 thin films annealed under magnetic field

Co-doped SnO₂ thin films were grown by sputtering technique on SiO₂/Si(001) substrates at room temperature, and then, thermal treatments with and without an applied magnetic field (H_TT) were performed in vacuum at 600°C for 20 min. H_TT was applied parallel and perpendicular to the substrate surface. Magnetic M(H) measurements reveal the coexistence of a strong antiferromagnetic (AFM) signal and a ferromagnetic (FM) component. The AFM component has a Néel temperature higher than room temperature, the spin axis lies parallel to the substrate surface, and the highest magnetic moment m =7 μ_B/Co at. is obtained when H_TT is applied parallel to the substrate surface. Our results show an enhancement of FM moment per Co⁺² from 0.06 to 0.42 μ_B/Co at. for the sample on which H_TT was applied perpendicular to the surface. The FM order is attributed to the coupling of Co⁺² ions through electrons trapped at the site of oxygen vacancies, as described by the bound magnetic polaron model. Our results suggest that FM order is aligned along [101] direction of Co-doped SnO₂ nanocrystals, which is proposed to be the easy magnetization axis.     

Efficient preparation of hybrid nanocomposite coatings based on poly(vinyl alcohol) and silane coupling agent modified TiO2 nanoparticles

In the present investigation, at first, the surface of titanium dioxide (TiO₂) nanoparticles was modified with γ-aminopropyltriethoxy silane as a coupling agent. Then a new kind of poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposites coating with different modified TiO₂ loading were prepared under ultrasonic irradiation process. Finally, these nanocomposites coating were used for fabrication of PVA/TiO₂ films via solution casting method. The resulting nanocomposites were fully characterized by Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), thermogravimetric analysis/derivative thermal gravimetric (TGA/DTG), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The TEM and SEM results indicated that the surface modified nanoparticles were dispersed homogeneously in PVA matrix on nanoscale and based on obtained results a possible mechanism was proposed for ultrasonic induced nanocomposite fabrication. TGA confirmed that the heat stability of the nanocomposite was improved. UV–vis spectroscopy was employed to evaluate the absorbance and transmittance behavior of the PVA/TiO₂ nanocomposite films in the wavelength range of 200–800 nm. The results showed that this type of films could be used as a coating to shield against UV light.     

Formation of self-organized Zircaloy-4 oxide nanotubes in organic viscous electrolyte via anodization

This work reports the formation of self-organized Zircaloy-4 (Zr-4) oxide nanotubes in viscous organic ethylene glycol (EG) electrolyte containing a small amount of fluoride salt and deionized (DI) water via an electrochemical anodization. The structure, morphology, and composition of the Zr-4 oxide nanotubes were studied using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), EDX, and XPS. SEM results showed that the length of the nanotubes is approximately 13 μm, and TEM results showed that the inner diameter of the Zr-4 oxide nanotubes is approximately 20 nm with average wall thickness of approximately 7 nm. XRD and selected area electron diffraction pattern (SAED) results confirmed that the as-anodized Zr-4 oxide nanotubes have cubic crystalline structure. Both cubic and monoclinic phases were found after annealing of Zr-4 oxide nanotubes. The tubular structure morphology of Zr-4 oxide nanotubes did not remain intact after annealing which is attributed to the elimination of F species from the annealed nanotubes.     

The role of composition, morphology and crystalline structure in the electrochemical behaviour of TiNx thin films for dry electrode sensor materials

A morphological, structural and electrochemical study of titanium nitride (TiN_x) thin films, obtained by DC reactive sputtering on titanium substrates, was carried out for a wide range of compositions (0 < x < 1.34) aiming a selection of the best coatings for dry biomedical electrodes. The films displayed a columnar-type structure, with morphologies strongly dependent on the composition: a compact and smooth surface was found for the Ti-rich films, (x < 1), whereas the N-rich films, (x ≥ 1) displayed a rough and porous structure. The electrochemical study of the TiN_x films was performed in synthetic sweat, aiming at simulating the contact with the skin. The voltammetric analysis showed anodic currents higher for TiN_x films than for titanium for low and medium polarization potentials, whereas for potentials beyond 2 V the blocking behaviour of the TiN_x films allowed them to display lower current values. The passive dissolution currents in the sub-μA/cm² range and the charge transfer resistances of the order of the MΩ proved the excellent stability of all films in sweat conditions. Finally, the electrochemical noise analysis showed that the near-stoichiometric and N-rich films display the lowest noise, being therefore the most suitable for electrode applications, where signals in the microvolt range, such as the electroencephalographic (EEG) signals, are to be monitored.     

Self-compliance RRAM characteristics using a novel W/TaO x /TiN structure

Self-compliance resistive random access memory (RRAM) characteristics using a W/TaO _x /TiN structure are reported for the first time. A high-resolution transmission electron microscope (HRTEM) image shows an amorphous TaO _x layer with a thickness of 7 nm. A thin layer of TiO _x N _y with a thickness of 3 nm is formed at the TaO _x /TiN interface, owing to the oxygen accumulation nature of Ti. This memory device shows 100 consecutive switching cycles with excellent uniformity, 100 randomly picked device-to-device good uniformity, and program/erase endurance of >10³ cycles. It is observed that the 0.6-μm devices show better switching uniformity as compared to the 4-μm devices, which is due to the thinner tungsten (W) electrode as well as higher series resistance. The oxygen-rich TaO _x layer at the W/TaO _x interface also plays an important role in getting self-compliance resistive switching phenomena and non-linear current-voltage (I-V) curve at low resistance state (LRS). Switching mechanism is attributed to the formation and rupture of oxygen vacancy conducting path in the TaO _x switching material. The memory device also exhibits long read endurance of >10⁶ cycles. It is found that after 400,000 cycles, the high resistance state (HRS) is decreased, which may be due to some defects creation (or oxygen moves away) by frequent stress on the switching material. Good data retention of >10⁴ s is also obtained.     

Synthesis of AuPd alloyed nanoparticles via room-temperature electron reduction with argon glow discharge as electron source

Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl₄ and PdCl₂ on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-temperature electron reduction operates in a dry way and requires neither hydrogen nor extra heating nor chemical reducing agent. The analyses using X-ray photoelectron spectroscopy (XPS) confirm all the metallic ions have been reduced. The characterization with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) shows that AuPd alloyed nanoparticles are formed. There also exist some highly dispersed Au and Pd monometallic particles that cannot be detected by XRD and transmission electron microscopy (TEM) because of their small particle sizes. The observed AuPd alloyed nanoparticles are spherical with an average size of 14 nm. No core-shell structure can be observed. The room-temperature electron reduction can be operated in a larger scale. It is an easy way for the synthesis of AuPd alloyed nanoparticles.     

Comparison of resistive switching characteristics using copper and aluminum electrodes on GeOx/W cross-point memories

Comparison of resistive switching memory characteristics using copper (Cu) and aluminum (Al) electrodes on GeO_x/W cross-points has been reported under low current compliances (CCs) of 1 nA to 50 μA. The cross-point memory devices are observed by high-resolution transmission electron microscopy (HRTEM). Improved memory characteristics are observed for the Cu/GeO_x/W structures as compared to the Al/GeO_x/W cross-points owing to AlO_x formation at the Al/GeO_x interface. The RESET current increases with the increase of the CCs varying from 1 nA to 50 μA for the Cu electrode devices, while the RESET current is high (>1 mA) and independent of CCs varying from 1 nA to 500 μA for the Al electrode devices. An extra formation voltage is needed for the Al/GeO_x/W devices, while a low operation voltage of ±2 V is needed for the Cu/GeO_x/W cross-point devices. Repeatable bipolar resistive switching characteristics of the Cu/GeO_x/W cross-point memory devices are observed with CC varying from 1 nA to 50 μA, and unipolar resistive switching is observed with CC >100 μA. High resistance ratios of 10² to 10⁴ for the bipolar mode (CCs of 1 nA to 50 μA) and approximately 10⁸ for the unipolar mode are obtained for the Cu/GeO_x/W cross-points. In addition, repeatable switching cycles and data retention of 10³ s are observed under a low current of 1 nA for future low-power, high-density, nonvolatile, nanoscale memory applications.