Synthesis and characterization of nanocrystalline TiO<Subscript>2</Subscript> thin films

Nanocrystalline thin films of TiO₂ have been synthesized by sol gel spin coating technique Thin films of TiO₂ annealed at 700 °C were characterized by X-ray diffraction(XRD), Atomic Force Microscopy, High resolution TEM and Scanning Electron Microscopy (SEM), The XRD shows formation of tetragonal anatase and rutile phases with lattice parameters a = 3.7837 Å and c = 9.5087 Å. The surface morphology of the TiO₂ films showed that the nanoparticles are fine with an average grain size of about 60 nm. Optical studies revealed a high absorption coefficient (10⁴ cm^?1) with a direct band gap of 3.24 eV. The films are of the n type conduction with room temperature electrical conductivity of 10^?6 (Ω cm)^?1.     

Cu doping effect on the resistive switching behaviors of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> thin films

Spin-coated Cu_xCo_1?xFe₂O₄ (x = 0, 0.2, 0.4, 0.6, and 0.8) thin films were prepared on Pt/TiO₂/SiO₂/Si substrates. Pt/Cu_xCo_1?xFe₂O₄/Pt structures were fabricated to investigate the effect of Cu doping concentration on the resistive switching behaviors. Structural and morphology characterizations revealed that Cu doping improved the crystallization of the thin films as compared to undoped CoFe₂O₄. Current–voltage characterization showed that all Cu_xCo_1?xFe₂O₄ thin films showed unipolar resistance switching, but the distribution range of the set voltage, reset voltage, and resistances were much reduced by Cu doping. Clear improvement in the stability of these parameters started to appear with x = 0.4, and the optimized performance was observed in the Pt/Cu_0.6Co_0.4Fe₂O₄/Pt structure. The improved stability of the switching parameters was attributed to the enhancement of hopping process between the Fe ions and the Cu ions in the spinel lattice. Our results indicated that appropriate adjustment of the doping elements in oxides can be a feasible approach in achieving stable resistance switching memory devices.     

Characterization of Zn doped MgTiO<Subscript>3</Subscript> ceramics: an approach for RF capacitor applications

In the present study the effect of Zn substitution on densification, microstructure, microwave and broad band dielectric properties of MgTiO₃ ceramics were investigated. The (Mg_1?x Zn _x )TiO₃ (x?=?0.01–0.07) ceramics have been prepared by the conventional solid-state reaction method. The sintering conditions were optimized to obtain the best dielectric properties with maximum relative densities. The microwave dielectric properties are heavily influenced by the amount of x concentration. The optimum dielectric properties of ε _r ~ 17.34, Q?×?f _o ~ 274 THz, τ _f ~ -40.3 ppm/^oC is obtained for (Mg_0.95Zn_0.05)TiO₃ ceramics sintered at 1275?°C. The broad band dielectric properties of (Mg_0.95Zn_0.05)TiO₃ ceramics were measured in the frequency range of 1–100 MHz, and temperature range of 133–483 K. Interestingly, the broad band dielectric properties show relaxation behaviour with frequency. The higher temperature dielectric spectrum of (Mg_0.95Zn_0.05)TiO₃ (MZT) ceramics displayed a distinct dispersion, which is shifting towards a lower frequency side. The observed dielectric relaxation behavior is analyzed using Cole–Cole plot. Furthermore, voltage dependent capacitance behavior at different frequencies is studied for the MZT sample, and it’s interesting to note that the capacitance is stable with the variation in voltage. The electrical conductivity study is carried out as a function of frequency and temperature for MZT sample and the activation energy is calculated by using Arrhenius equation, which is found to be 0.07 eV at 10 MHz. The obtained dielectric response of MZT ceramics are suitable for dielectric resonator and type-1 RF capacitor applications.     

Effect of excess Bi content on electrical properties of BiFe<Subscript>0.95</Subscript>Cr<Subscript>0.05</Subscript>O<Subscript>3</Subscript> thin films

The Bi_1?+?xFe_0.95Cr_0.05O₃ (BFCO) (x?=?0, 5, 10, 15 and 20%) thin films are fabricated on FTO/glass substrate using a chemical solution deposition method and sequential-layer annealing process. The effects of the excess Bi content on crystalline structure, morphology, and electrical performance of BFCO thin films are investigated. All the BFCO thin films are crystallized into polycrystalline perovskite structure and belonging to the space group of R3c. The BFCO thin films with 5 and 10% excess Bi contents possess no impurity phase. Especially, a dense surface morphology and columnar crystal structure can be obtained for the film with 5% excess Bi content. Especially, the one possesses superior ferroelectricity with a relative high remnant polarization (P _r) of 69.8 µC/cm² and low coercive electric field (E _c) of 291 kV/cm at 1 kHz due to the relatively low leakage current density of 3.04?×?10^??5 A/cm² at 200 kV/cm.     

Structure and electrical properties of MnO doped (Ba<Subscript>0.96</Subscript>Ca<Subscript>0.04</Subscript>)(Ti<Subscript>0.92</Subscript>Sn<Subscript>0.08</Subscript>)O<Subscript>3</Subscript> lead free ceramics

In this work, (Ba_0.96Ca_0.04)(Ti_0.92Sn_0.08)O₃–xmol MnO (BCTS–xMn) lead-free piezoelectric ceramics were fabricated by the conventional solid-state technique. The composition dependence (0 ≤ x ≤ 3.0 %) of the microstructure, phase structure, and electrical properties was systematically investigated. An O–T phase structure was obtained in all ceramics, and the sintering behavior of the BCTS ceramics was gradually improved by doping MnO content. In addition, the relationship between poling temperature and piezoelectric activity was discussed. The ceramics with x = 1.5 % sintering at temperature of 1330 °C demonstrated an optimum electrical behavior: d ₃₃ ~ 475 pC/N, k _p ~ 50 %, ε _r ~ 4060, tanδ ~ 0.4 %, P _r ~ 10.3 μC/cm², E _c ~ 1.35 kV/mm, T _C ~ 82 °C, strain ~0.114 % and \(d_{33}^{*}\) ~ 525 pm/V. As a result, we achieved a preferable electric performance in BaTiO₃-based ceramics with lower sintering temperature, suggesting that the BCTS–xMn material system is a promising candidate for lead-free piezoelectric ceramics.     

Growth and magnetic properties of spin coated Co<Subscript>0.6</Subscript>Zn<Subscript>0.4</Subscript>Mn<Subscript>0.3</Subscript>Fe<Subscript>1.7</Subscript>O<Subscript>4</Subscript> ultrathin films on silicon (100), (110) and (111) substrates

This paper reports growth of Co_0.6Zn_0.4Mn_0.3Fe_1.7O₄ (CZFMO) ultrathin films (thickness: 23–30 nm) by spin coating technique on silicon (100), (110) and (111) substrates. The deposited films were annealed at 700 °C for 1 h in the oxygen environment. All the films were found to be polycrystalline in nature. The CZFMO films were found to have minimal residual stress (13–50 MPa), which could be an encouraging feature for novel microwave miniaturized device applications. Room temperature magnetic measurements demonstrated completely saturated hysteresis loop with the highest squareness ratio (M _R /M _S )?~?60% for the film grown on Si (110) substrate. On the other hand CZFMO films on Si (100) and Si (111) substrates showed unsaturated hysteresis loops with M _R /M _S ~ 10 and 5%, respectively. The reason for the better magnetic properties of the ultrathin CZFMO film on Si (110) substrate seems to be its better crystalline quality and larger grain size compared to those of other films.     

Influence of Nd doping on microwave dielectric properties of SrTiO<Subscript>3</Subscript> ceramics

Sr_1?x Nd _x TiO₃ (x?=?0.08–0.14) ceramics were prepared by conventional solid-state methods. The analysis of crystal structure suggested Sr_1?x Nd _x TiO₃ ceramics appeared to form tetragonal perovskite structure. The relationship between charge compensation mechanism, microstructure feature and microwave dielectric properties were investigated. Trivalent Nd³⁺ substituting Sr²⁺ could effectively decrease oxygen vacancies. This reduction and relative density were critical to improve Q?×?f values of Sr_1?x Nd _x TiO₃ ceramics. For ε _r values, incorporation of Nd could restrain the rattling of Ti⁴⁺ cations and led to the reduction of dielectric constant. The τ _f values were strongly influenced by tilting of oxygen octahedral. The τ _f values decreased from 883 to 650 ppm/°C with x increasing from 0.08 to 0.14. A better microwave dielectric property was achieved for composition Sr_0.92Nd_0.08TiO₃ at 1460 °C: ε _r ?=?160, Q?×?f?=?6602 GHz, τ _f ?=?883 ppm/°C.     

Effect of sintering temperature on microstructures and microwave dielectric properties of Ba<Subscript>2</Subscript>MgWO<Subscript>6</Subscript> ceramics

The microwave dielectric properties of Ba₂MgWO₆ ceramics were investigated with a view to the use of such ceramics in mobile communication. Ba₂MgWO₆ ceramics were prepared using the conventional solid-state method with various sintering temperatures. Dielectric constants (? _r ) of 16.8–18.2 and unloaded quality factor (Q _u  × f) of 7000–118,200 GHz were obtained at sintering temperatures in the range 1450–1650 °C for 2 h. A maximum apparent density of 6.76 g/cm³ was obtained for Ba₂MgWO₆ ceramic, sintered at 1650 °C for 2 h. A dielectric constant (? _r ) of 18.4, an unloaded quality factor (Q _u  × f) of 118,200 GHz, and a temperature coefficient of resonant frequency (τ _f ) of ?34 ppm/°C were obtained when Ba₂MgWO₆ ceramics were sintered at 1650 °C for 2 h.     

Characterization of CuInGeSe<Subscript>4</Subscript> thin films and Al/n–Si/p–CuInGeSe<Subscript>4</Subscript>/Au heterojunction device

CuInGeSe₄ thin films of various thicknesses were prepared on a glass substrate by thermal evaporation followed by selenization at 700 K. Energy dispersive X-ray analysis shows that the CuInGeSe₄ thin films are near stoichiometric. The X-ray diffraction patterns indicate that the as-deposited CuInGeSe₄ thin films are amorphous, while the CuInGeSe₄ thin films annealed at 700 K are polycrystalline with the chalcopyrite phase. The structure of the films was further investigated by transmission electron microscopy and diffraction, with the results verifying the X-ray diffraction data. High-resolution scanning electron microscopy images show well-defined grains that are nearly similar in size. The surface roughness increases with film thickness, as confirmed by atomic force microscopy. The optical transmission and reflection spectra of the CuInGeSe₄ thin films were recorded over the wavelength range of 400–2500 nm. The variation of the optical parameters of the CuInGeSe₄ thin films, such as the refractive index n and the optical band gap E_g, as a function of the film thickness was determined. The value of E_g decreases with increasing film thickness. For the studied films, n were estimated from the Swanoepl’s method and were found to increase with increasing film thickness as well as follow the two-term Cauchy dispersion relation. A heterojunction with the configuration Al/n–Si/p–CuInGeSe₄/Au was fabricated. The built-in voltage and the carrier concentration of the heterojunction was determined from the capacitance–voltage measurements at 1 MHz and were found to be 0.61 V and 3.72?×?10¹⁷ cm^?3, respectively. Under 1000 W/m² solar simulator illumination, the heterojunction achieved a conversion efficiency of 2.83%.     

Electrophoretic deposition of Sn-doped TiO<Subscript>2</Subscript> nanoparticles and its optical and photocatalytic properties

In this research, Sn-doped TiO₂ (Sn–TiO₂) nanoparticles were synthesized by a simple sol–gel method. The structure and composition of the as-prepared sample were investigated using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible absorption spectroscopy. Electrophoretic deposition (EPD) technique was used to deposit thin films of Sn–TiO₂ on 316L stainless steel (316L SS) substrate. In order to achieve a fine and high-quality layer on the electrode surface, N-phenyl-p-phenylenediamine (NPPDA) was used as a new dispersant and charging agent in ethanolic suspensions. Based on zeta potential and conductivity measurements of the suspensions, an optimum concentration of the NPPDA dispersant was found to be 3.0 g l^?1. The in-situ EPD kinetics was also studied. The prepared Sn–TiO₂ film was used for the photodegradation of methylene blue (MB) under UV, visible and sun lights. The results revealed that the Sn–TiO₂ film could be able to degrade the MB under sunlight. The calculated degradations were 44, 65, and 73% after 2, 4 and 5 h, respectively. The relation between \(\ln \left( {\frac{{{{\text{A}}_0}}}{{\text{A}}}} \right)\) and time was linear, so it was proved that the photocatalytic degradation of MB can be characterized by pseudo-first order reaction kinetics.     

Understanding of post deposition annealing and substrate temperature effects on structural and electrical properties of Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> MOS capacitor

The purpose of this study is to understand the effects of substrate temperature (ST) and post deposition annealing (PDA) on the structural-electrical properties of Gd₂O₃ film and to evaluate the electrical performances of the MOS based devices formed with this dielectric. The Gd₂O₃/Si structures were annealed at 500, 600, 700, and 800 °C under N₂ ambient after the films were grown on heated p-Si substrate at various temperatures ranged from 20 to 300 °C by RF magnetron sputtering. For any given ST, the crystallization/grain size increased with increasing PDA temperature. The bump in the accumulation region or continuous decrease in the capacitance values of the inversion region of the C–V curves for 800 °C PDA was not observed. The lowest effective oxide charge density (Q _eff ) value was obtained to be ??1.13?×?10¹¹ cm^?2 from the MOS capacitor with Gd₂O₃, which is grown on heated Si at 300 °C and annealed at 800 °C. The density of the interface states (D _it ) was found to be in the range of 0.84?×?10¹¹ to 1.50?×?10¹¹ eV^?1 cm^?2. The highest dielectric constant (ε) and barrier height \(({\Phi _B})\) values were found to be 14.46 and 3.68, which are obtained for 20 °C ST and 800 °C PDA. The results show that the negative charge trapping in the oxide layer is generally more than that of the positive, but, it is reverse of this situation at the interface. The leakage current density decreased after 20 °C ST, but no significant change was observed for other ST values.     

Effects of sintering temperature on the properties of Mn/Y codoped Ba<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>TiO<Subscript>3</Subscript> ceramics for tunable application

(Ba_0.67Sr_0.33)_1?3x/2Y _x Ti_1?y/2Mn _y O₃ [BST(Mn + Y), x = 0.006, y = 0.005] ceramics were fabricated by using citrate–nitrate combustion derived powder. Microstructure and dielectric properties of the BST(Mn + Y) ceramic samples were investigated within the sintering temperature ranged from 1220 to 1300 °C. Sintering temperature has a great influence on the microstructure and electrical properties of the ceramic samples. The dielectric properties, ferroelectric properties, and tunability are enhanced by optimizing sintering temperature. The relatively high tunability of 40 % (1.5 kV/mm DC field, 10 kHz) was obtained, and relatively low dielectric loss, <0.0052 (at 10 kHz, 20 °C) was acquired for BST(Mn + Y) samples sintered at 1275 °C for 3 h. Both the low dielectric loss and enhanced tunable properties of BST(Mn + Y) are useful for tunable devices application.     

Epitaxial growth and magnetic properties of <Emphasis Type="Italic">h</Emphasis>-LuFeO<Subscript>3</Subscript> thin films

In this paper, the epitaxial hexagonal LuFeO₃ (h-LuFeO₃) thin films with c-axis-oriented single phase, smooth surface were grown on YSZ (111) substrates by pulsed laser deposition method. Furthermore, a structural distortion of increased lattice constant of c is found in the epitaxial h-LuFeO₃ thin films. Moreover, the epitaxial h-LuFeO₃ thin films show room-temperature ferromagnetism. The coercive field and remnant magnetization of the epitaxial h-LuFeO₃ thin film decrease with the increase in the test temperature from 50 to 300 K. The study would be of benefit to the room-temperature single-phase multiferroic materials.     

Enhancing the microwave dielectric properties of Sr<Subscript>2</Subscript>Ca<Subscript>3</Subscript>Ta<Subscript>4</Subscript>TiO<Subscript>17</Subscript> ceramics by Zr Substitution

The compositions in Sr₂Ca₃Ta₄Ti_1?xZr_xO₁₇ (0?≤?x?≤?0.12) series were designed and fabricated by solid state sintering method. All the compositions formed single phases and crystallized in an orthorhombic crystal structure. Zr substitution led to the enhancing of the microwave dielectric properties by tuning the τ_f value through zero and increased the Q_uf_o value from 12,540 to 14,970 GHz with a slight decrease in ε_r. In the present study, a good combination of ε_r ~?51, Q_uf_o ~?145,43 GHz and τ_f ~ 3 ppm/°C were obtained for Sr₂Ca₃Ta₄Ti_0.90Zr_0.1O₁₇ ceramic sintered at 1575 °C for 4 h.     

Crystal structures of Ln<Subscript>2</Subscript>TiO<Subscript>5</Subscript> (Ln = Gd,Dy) polymorphs

Single crystals of four Ln₂TiO₅ polymorphs have been grown, and their structures have been determined: orthorhombic (Gd₂TiO₅, a = 10.460(5), b = 11.317(6), c = 3.750(3) Å, Pnam, Z = 4), hexagonal (Gd_1.8Lu_0.2TiO₅, a = 3.663(3), c = 11.98(1) Å, P6₃/mmc, Z = 1.2), cubic (Dy₂TiO₅, a = 10.28(1) Å, Fd3m, Z = 10.4), and monoclinic (Dy₂TiO₅, a = 10.33(1), b = 3.653(5), c = 7.306(6) Å, β = 90.00(7)°, B2/m, Z = 2.4). The last polymorph has been identified for the first time.     

Ultralow thermal conductivity of cerium-doped Nd<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> over a wide doping range

In this paper, we report an ultralow thermal conductivity and a high-temperature phase stability of the (Nd_1?x Ce _x )₂Zr₂O_7+x system over the temperature range from room temperature to 1600 °C and over a wide composition range (0.2 ≤ x ≤ 0.8), and the (Nd_1?x Ce _x )₂Zr₂O_7+x system is therefore considered a strong candidate material for the fabrication of next-generation high-temperature thermal barrier coatings. The observed thermal conductivities (0.65–1.0 W/mK) are about 60–40% lower than those of undoped Nd₂Zr₂O₇ over the same temperature range (100–700 °C) and indicate a glass-like behavior. For comparison, the variation in the thermal conductivity with the temperature of the (Gd_1?x Ce _x )₂Zr₂O_7+x system with similar point defects was also measured, and the observed behavior was almost the same as that of undoped Gd₂Zr₂O₇ and was mostly determined by phonon–phonon scattering (λ ∝ 1/T). The effect of point defect scattering and strong phonon scattering sources (rattlers) on the thermal conductivity is also discussed in this paper. The results of this study suggest that the ultralow thermal conductivity of (Nd_1?x Ce _x )₂Zr₂O_7+x can be attributed to the presence of rattlers because of the large difference between the ionic radii of the Nd³⁺ and Ce⁴⁺ ions.     

Effects of NiNb<Subscript>2</Subscript>O<Subscript>6</Subscript> doping on dielectric property,microstructure and energy storage behavior of Sr<Subscript>0.97</Subscript>La<Subscript>0.02</Subscript>TiO<Subscript>3</Subscript> ceramics

Sr_0.97La_0.02TiO₃ ceramics with samll amounts of NiNb₂O₆ additives were prepared by the traditional solid state sintering method, and the phase purity, microstructure, dielectric properties and energy storage behavior of the NiNb₂O₆-added Sr_0.97La_0.02TiO₃ ceramics were investigated. The results show that the grain size of the ceramics firstly decreases and then increases with increasing NiNb₂O₆ concentration. The average grain size reaches 0.55 um for the sample with 4.5 wt% NiNb₂O₆. Moreover, impedance spectroscopy (IS) analysis was employed to study the electrical conductive behavior of NiNb₂O₆-doped Sr_0.97La_0.02TiO₃ ceramics. IS results reveale that the NiNb₂O₆-doped Sr_0.97La_0.02TiO₃ ceramic has large R _gb /(R _gb  + R _g ) ratios due to the decreased grain sizes. The breakdown strength is notably improved, and the highest breakdown strength of 324 kV/cm can be achieved for the sample with 4.5 wt% NiNb₂O₆ additive. The Sr_0.97La_0.02TiO₃ sample with 4.5 wt% NiNb₂O₆ possesses the maximum theoretical energy density of 1.36 J/cm³, which is about 2 times higher than that of pure SrTiO₃ in the literature. And its energy storage efficiency reaches 91.4 % under applied electric field of 80 kV/cm. This study provides the NiNb₂O₆ added ceramic as an attractive candidate for making high-energy density capacitors.     

The Effect of Substrate Temperature on Magnetic and Electrical Properties of (CeO<Subscript>2</Subscript>)<Subscript>14</Subscript>Fe<Subscript>86</Subscript> Films

(CeO₂)₁₄Fe₈₆ films were fabricated by a radio frequency magnetron sputtering method at different substrate temperature. The results reveal that the films deposited at substrate temperature lower than 773 K exhibit a strong perpendicular anisotropy, and the correlated dynamic permeability spectrum measured over the frequency range of 0.5–7 GHz shows a high resonance frequency. The study on the relation R～T shows that the resistivity of the thin film has a minimum near room temperature and tends to saturation as the temperature approaches zero, exhibiting a behavior reminiscent of Kondo scattering. However, as the substrate temperature increases to 973 K, the films possess an in-plane anisotropy and lower H _c. The resistivity exhibits a transition from metal to insulator characterized by a maximum of resistivity at 220 K.     

Magnetization reversal and tunable exchange bias behavior in Mn-substituted NiCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single phase samples of Ni(Cr_1?xMn _x )₂O₄ (x = 0–0.50) were synthesized by using sol–gel route. Investigation of structural, magnetic, exchange bias and magnetization reversal properties was carried out in the bulk samples of Ni(Cr_1?xMn _x )₂O₄. Rietveld refinement of the X-ray diffraction patterns recorded at room temperature reveals the tetragonal structure for x = 0 sample with I4₁/amd space group and cubic structure for x ≥ 0.05 samples with \( {\text{Fd}\bar{3}\text{m}} \) space group. Magnetization measurements show that all samples exhibit ferrimagnetic behavior, and the transition temperature (T_C) is found to increase from 73 K for x = 0 to 138 K for x = 0.50. Mn substitution induces magnetization reversal behavior especially for 30 at% of Mn in NiCr₂O₄ system with a magnetic compensation temperature of 45 K. This magnetization reversal is explained in terms of different site occupation of Mn ions and the different temperature dependence of the magnetic moments of different sublattices. Study of exchange bias behavior in x = 0.10 and 0.30 samples reveals that they exhibit negative and tunable positive and negative exchange bias behavior, respectively. The magnitudes of maximum exchange bias field of these samples are found to be 640 and 5306 Oe, respectively. Exchange bias in x = 0.10 sample originates from the anisotropic exchange interaction between the ferrimagnetic and the antiferromagnetic components of magnetic moment. The tunable exchange bias behavior in x = 0.30 sample is explained in terms of change in domination of one sublattice moment over the other as the temperature is varied.     

Microwave dielectric properties of ZnO–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–<Emphasis Type="Italic">x</Emphasis>TiO<Subscript>2</Subscript> ceramics prepared by reaction-sintering process

The ZnO–Nb₂O₅–xTiO₂ (1 ≤ x ≤ 2) ceramics were fabricated by reaction-sintering process, and the effects of TiO₂ content and sintering temperature on the crystal structure and microwave dielectric properties of the ceramics were investigated. The XRD patterns of the ceramics showed that ZnTiNb₂O₈ single phase was formed as x ≤ 1.6 and second phase Zn_0.17Nb_0.33Ti_0.5O₂ appeared at x ≥ 1.8. With the increase of TiO₂ content and sintering temperature, the amount of the second phase Zn_0.17Nb_0.33Ti_0.5O₂ increased, resulting in the increase of dielectric constant, decrease of Q × f value, and the temperature coefficient of resonant frequency (τ _f ) shifted to a positive value. The optimum microwave dielectric properties were obtained for ZnO–Nb₂O₅–2TiO₂ ceramics sintered at 1075 °C for 5 h: ε _r  = 45.3, Q × f = 23,500 GHz, τ _f  = +4.5 ppm/°C.