Fabrication of CaLa4(Zr0.05Ti0.95)4O15 thin films by RF magnetron sputtering

Crystalline CaLa₄(Zr_0.05Ti_0.95)₄O₁₅ thin films deposited on n-type Si substrates byRF magnetron sputtering at a fixed RF power of 100 W, an Ar/O₂ ratio of 100/0, an operating pressure of 3 mTorr, and different substrate temperatures were investigated. The surface structural and morphological characteristics analyzed by X-ray diffraction and atomic force microscopy were sensitive to the deposition conditions, such as the substrate temperature. The diffraction pattern showed that the deposited films had a polycrystalline microstructure. As the substrate temperature increased, the quality of the CaLa₄(Zr_0.05Ti_0.95)₄O₁₅ thin films improved, and the kinetic energies of the sputtered atoms increased, resulting in a structural improvement of the deposited CaLa₄(Zr_0.05Ti_0.95)₄O₁₅ thin films. A high dielectric constant of 16.7 (f=1 MHz), a dissipation factor of 0.19 (f=1 MHz), and a low leakage current density of 3.18×10⁻⁷ A/cm² at an electrical field of 50 kV/cm were obtained for the prepared films.     

High-performance (Na0.5Bi0.5)(Ti0.97Fe0.03)O3-based heterostructure thin films for energy storage capacitors

This work presents a simple process to fabricate Na_0.5Bi_0.5(Ti_0.97Fe_0.03)O₃/Ba_(1–x)Sr_xTiO₃–based heterostructure thin films with a compositional graded sequence, and their energy storage properties are investigated systematically. A simulation technique is used to predict the experimental results. Interestingly, improved energy storage properties are obtained in the “up–graded” film, which is associated with the stress/strain. Furthermore, the “up–graded” film after aging with treating exhibits a higher breakdown strength (E_BD = 3176.4 kV/cm), recoverable energy storage density (W_rec = 67.18 J/cm³) and efficiency (η = 75.65%). This can be attributed to the ordered defect dipoles induced by aging with treating driving domain switching, which is favorable for high (P_m–P_r) and large W_rec. These results provide an approach and guidance to design thin film-based devices with optimal energy storage performance.     

Enhanced conductance properties of UV laser/RTA annealed Al-doped ZnO thin films

Thin films comprising 0.5 mol% aluminum-doped zinc oxide (AZO) were prepared on glass substrates by a spin-coating method for transparent conducting oxide (TCO) applications. UV laser was selected for the annealing of AZO thin films, due to the well matched energy bandgap between UV laser and AZO films. After the rapid thermal annealing (RTA) process, post UV laser annealing was carried out by varying the scan speed of the laser beam, and the effects of laser annealing on the structural, morphological, electrical, and optical properties were analyzed. The results indicated that UV laser annealing based on various scan speeds affects the microstructure, sheet resistance, and optical transmittance of the AZO thin films, compared with those of the only RTA processed thin films. X-ray diffraction (XRD) analysis showed that all films that preferentially grew normally on the substrate had a (002) peak. The optical transmittance spectra of the laser/RTA annealed AZO thin films exhibited greater than 83% transmittance in the visible region. Also, the sheet resistance (1.61 kΩ/sq) indicated that optimized UV laser annealing after the RTA process improves film conductance.     

Pyroelectric,ferroelectric, piezoelectric and dielectric properties of Na0.5Bi0.5TiO3 ceramic prepared by sol-gel method

Sodium bismuth titanate (BNT) nanopowder of molar composition 50/50 (Na_0.5Bi_0.5TiO₃) was prepared by a sol-gel processing method. The structure and microstructure of the precursor gel as well as the ferroelectric, pyroelectric, dielectric and piezoelectric properties of the BNT were studied. BNT crystallized in the rhombohedra perovskites structure Na_0.5Bi_0.5TiO₃ was obtained from the precursor gel by heating at 700 °C for 2 h in air. The BNT ceramic at 1100 °C sintering temperature present high crystallinity, good dielectric properties at 1 kHz (ε′=885, tan δ=0.03, T_c=370 °C), piezoelectric properties (k₃₃=0.39, c₃₃=105 GPa, e₃₃=12.6 C/m², d₃₃=120 pC/N), high remnant polarization (P_r=47 μC/cm²) and pyroelectric coefficient ($p$=707 μC/m² K) and low coercive field (E_c=55 kV/cm). Hence, the BNT prepared by sol-gel method could be used for silicon based memory device application where a low synthesis temperature is a key requirement.     

Mixed grains and orientation-dependent piezoelectricity of polycrystalline Nd-substituted Bi4Ti3O12 thin films

Polycrystalline Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were prepared on Pt/Ta/glass substrates by a pulsed laser deposition method. X-ray diffraction measurements revealed that the BNT thin films were preferentially oriented along the (117) direction although they possessed a polycrystalline structure. Good ferroelectric properties of the BNT thin film were observed with a remnant polarization of 13 μC/cm² (2 P_r ~26 μC/cm²). The fatigue resistance test exhibited that the ferroelectric polarization of the BNT thin film degraded significantly after around 10⁹ switching cycles, which can be attributed to its crystal structure. We investigated the surface morphology and ferroelectric domain structure by atomic force microscopy (AFM) and piezoresponse force microscopy (PFM), respectively. Interestingly, mixed grains consisting of long and circular shapes were observed on the BNT film surface, which corresponded to a- and c-axes orientations of crystal growth, respectively. The PFM study revealed that the piezoelectric coefficient (d₃₃) of the long grains was much larger than that of the circular grains.     

Synthesis and photoluminescence properties of CaGd2(MoO4)4:Eu3+ red phosphors

The novel red-emitting Eu³⁺ ions activated CaGd₂(MoO₄)₄ phosphors were prepared by a citrate sol–gel method. The X-ray diffraction patterns confirmed their tetragonal structure when the samples were annealed above 600 °C. The photoluminescence excitation spectra of CaGd₂(MoO₄)₄:Eu³⁺ phosphors exhibited the charge transfer band (CTB) and intense f–f transitions of Eu³⁺ ion. The optimized annealing temperature and Eu³⁺ ion concentration were analyzed for CaGd₂(MoO₄)₄:Eu³⁺ phosphors based on the dominant red (⁵D₀→⁷F₂) emission intensity under NUV (394 nm) excitation. All decay curves were well fitted by the single exponential function. These luminescent powders are expected to find potential applications such as WLEDs and optical display systems.     

Influence of interface structure on microstructure and dielectric properties of bismuth magnesium niobate thin films

Bismuth magnesium niobate (Bi_3/2MgNb_3/2O₇, BMN) thin films were prepared on bare SiO₂/HR-Si and Pt/TiO₂/SiO₂/HR-Si substrates by using sol-gel spin coating technique followed by rapid thermal annealing process. The influence of the interface on crystalline structure and tunable dielectric properties of the two types of BMN films were investigated. It was found that the BMN films prepared on SiO₂/Si substrate with a BMN/SiO₂ interface structure had higher orientation and better crystallinity. The deposited BMN thin films with a BMN/SiO₂ interface structure exhibited superior tunability of 52.5%, while it showed a relative small tunability value of the film with BMN/Pt interface structure. It suggests that the interface state between the films and substrates, electric field distribution, and orientation degree are responsible for the impacts on the microstructure and tunable dielectric properties of the BMN thin films.     

Effects of tungsten thickness and annealing temperature on the electrical properties of W-TiO2 thin films

TiO₂ thin films were prepared by RF magnetron sputtering onto glass substrates and tungsten was deposited onto these thin films (deposition time 15-60 s) to form W-TiO₂ bi-layer thin films. The crystal structure, morphology, and transmittance of these TiO₂ and W-TiO₂ bi-layer thin films were investigated. Amorphous, rutile, and anatase TiO₂ phases were observed in the TiO₂ and W-TiO₂ bi-layer thin films. Tungsten thickness and annealing temperature had large effects on the transmittance of the W-TiO₂ thin films. The W-TiO₂ bi-layer thin films with a tungsten deposition time of 60 s were annealed at 200 °C-400 °C. The band gap energies of the TiO₂ and the non-annealed and annealed W-TiO₂ bi-layer thin films were evaluated using (αhν)^1/2 versus energy plots, showing that tungsten thickness and annealing temperature had major effects on the transmittance and band gap energy of W-TiO₂ bi-layer thin films.     

Structural,optical and electrical properties of low temperature grown undoped and (Al,Ga) co-doped ZnO thin films by spray pyrolysis

Aluminum and gallium co-doped ZnO (AGZO) thin films were grown by simple, flexible and cost-effective spray pyrolysis method on glass substrates at a temperature of 230 °C. Effects of equal co-doping with aluminum (Al) and gallium (Ga) on structural, optical and electrical properties were investigated by X-ray diffraction (XRD), UV–vis–NIR spectrophotometry and Current–Voltage (I–V) measurements, respectively. XRD patterns showed a successful growth with high quality polycrystalline films on glass substrates. The predominant orientation of the films is (002) at dopant concentrations ≤2 at% and (101) at higher dopant concentrations. Incorporation of Al and Ga to the ZnO crystal structure decreased the crystallite size and increased residual stress of the thin films. All films were highly transparent in the visible region with average transmittance of 80%. Increasing doping concentrations increased the optical band gap, from 3.12 to 3.30 eV. A blue shift of the optical band gap was observed from 400 nm to 380 nm with increase in equal co-doping. Co-doping improved the electrical conductivity of ZnO thin films. It has been found from the electrical measurements that films with dopant concentration of 2 at% have lowest resistivity of 1.621×10⁻⁴ Ω cm.     

Effect of nickel doping on structural,optical, electrical and ethanol sensing properties of spray deposited nanostructured ZnO thin films

Undoped and nickel (Ni)-doped ZnO thin films were spray deposited on glass substrates at 523 K using 0.1 M of zinc acetate dihydrate and 0.002–0.01 M of nickel acetate tetrahydrate precursor solutions and subsequently annealed at 723 K. The effect of Ni doping in the structural, morphological, optical and electrical properties of nanostructured ZnO thin film was investigated using X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), UV–vis Spectrophotometer and an Electrometer respectively. XRD patterns confirmed the polycrystalline nature of ZnO thin film with hexagonal wurtzite crystal structure and highly oriented along (002) plane. The crystallite size was found to be increased in the range of 15–31 nm as dopant concentration increased. The SEM image revealed the uniformly distributed compact spherical grains and denser in the case of doped ZnO thin films. All the films were highly transparent with average transmittance of 76%. The measured optical band gap was found to be varied from 3.21 to 3.09 eV. The influence of Ni doping in the room temperature ethanol sensing characteristics has also been reported.     

Temperature dependence of electrical and electromechanical properties of Pb(Mg1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 thin films

The electrical and electromechanical properties of Pb(Mg_1/3Nb_2/3)O₃–Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃ (PMN–PNN–PZT, PMN/PNN/PZT = 20/10/70) on Pt/Ti/SiO₂/Si substrates by chemical solution deposition was investigated. The PMN–PNN–PZT films annealed at 650 °C exhibited slim polarization hysteresis curves and a high dielectric constant of 2100 at room temperature. A broad dielectric maximum at approximately 140–170 °C was observed. The field-induced displacement was measured by scanning probe microscopy, the bipolar displacement was not hysteretic, and the effective piezoelectric coefficient (d₃₃) was 66 × 10⁻¹² m/V. The effective d₃₃ decreased with temperature, but the value at 100 °C remained 45 × 10⁻¹² m/V.     

Effects of Mn doping on dielectric properties and energy-storage performance of Na0.5Bi0.5TiO3 thick films

Lead-free Na_0.5Bi_0.5Ti_1−xMn_xO₃ (NBTMn_x, x=0, 0.01, 0.03 and 0.05) ferroelectric thick films have been fabricated on LaNiO₃/Si(100) substrate by using a polyvinylpyrrolidone-modified sol-gel method and the effects of Mn content on their microstructure, dielectric properties and energy-storage performance were investigated. Compared with the pure Na_0.5Bi_0.5TiO₃ (NBT) thick films, NBTMn_x thick films exhibited a large enhancement in dielectric properties and energy-storage performance. Particularly, a giant recoverable energy-storage density (W) of 30.2 J/cm³ and the corresponding efficiency (η) of 47.7% were obtained in NBTMn_0.01 thick film at 2310 kV/cm. Moreover, the NBTMn_0.01 thick film displayed good energy-storage stability over a large temperature range at different frequency.     

Photoluminescence and electron-beam excitation induced cathodoluminescence properties of novel green-emitting Ba4La6O(SiO4)6:Tb3+phosphors

Tb³⁺ions activated Ba₄La₆O(SiO₄)₆ (BLSO:Tb³⁺) phosphors were synthesized by a citrate sol-gel method. The X-ray diffraction pattern confirmed their oxyapatite structure. The field-emission scanning electron microscope image established that the BLSO:Tb³⁺phosphor particles were closely-packed and acquired irregular shapes. The photoluminescence (PL) excitation spectra of BLSO:Tb³⁺phosphors showed intense f–d transitions along with low intense peaks corresponding to the f–f transitions of Tb³⁺ions in the lower energy region. The PL emission spectra displayed the characteristic emission bands of Tb³⁺ions, and the optimized concentrations were found to be at 1 and 6 mol% for blue and green emission peaks, respectively. The cathodoluminescece (CL) spectra exhibited a similar behavior that was observed in the PL spectra except the intensity variations in the blue and green regions. The CL spectra of the BLSO:6 mol% Tb³⁺phosphor unveiled accelerating voltage induced luminescent properties.     

Ultraviolet pulsed laser crystallization of Ba0.8Sr0.2TiO3 films on LaNiO3-coated silicon substrates

In this work, Ba_0.8Sr_0.2TiO₃ (BST) films on LaNiO₃-buffered SiO₂/Si (LNO/SiO₂/Si) substrates were crystallized by pulsed laser irradiation. Solution-derived amorphous barium–strontium–titanate precursor layers were crystallized with a KrF excimer laser in oxygen ambient at fluences ranging from 50 to 75 mJ cm⁻². With the substrate temperature set to 500 °C, the number of pulses and film thickness were varied until high-quality crystallinity could be achieved. It was found that films with a thickness of 40 nm are fully crystallized with a uniaxial {00l} orientation which is predetermined by the LaNiO₃ orientation. On the other hand, for 160 nm thick films, crystallization was observed after 12,000 pulses in the 70 nm close to the surface, while the rest of the film remained amorphous. The large temperature difference between the film surface and interface due to the low thermal conductivity of the amorphous BST is suggested as the origin of this behavior. Films thicker than 80 nm cracked on crystallization due to the stress caused by the different thermal expansion coefficients of film and substrate, as well as the large temperature variations within the BST film.     

Influence of the composition-induced structure evolution on the electrocaloric effect in Bi0.5Na0.5TiO3-based solid solution

The present work investigated the influence of the composition induced structure evolution on the electrocaloric effect in lead-free (0.935−x)Bi_0.5Na_0.5TiO₃–0.065BaTiO₃–xSrTiO₃ (BNBST, BNBSTx) ceramics. It was found that broad ∆T peak could be observed for all compositions and the electrocaloric strength α (α=ΔT_max/ΔE) in BNBST0.02 could reach as high as 0.27 K mm/kV. The increase of the SrTiO₃ concentration led to a shift of ∆T_max to a lower temperature, resulting in a large near room-temperature electrocaloric strength α of 0.17 K mm/kV in BNBST0.22.     

Phase transition induced morphotropic phase boundary behavior and the electric properties in strontium modulated Bi4.5Na0.5Ti4O15 lead-free ceramics

Lead-free (Bi_0.5Na_0.5)_1-xSr_xBi₄Ti₄O₁₅ ceramics (x = 0–0.9) are fabricated by solid state reaction process. XRD analysis shows the symmetry divergence from tetragonal to orthorhombic phase accompanied by morphotropic phase boundary with increasing strontium content. Raman spectra confirm the incorporation of strontium into (Bi_2.5Na_0.5Ti₄O₁₃)^2- layers. SEM graphs exhibit the typical plate-like morphology with regular variation of grain size and crystallization as strontium increases. Multistage ferroelectric transition is observed with x = 0.2–0.4. Piezoelectric performance measurements present the well thermal stability at x = 0.4. The dielectric properties display a shifting of Curie temperature towards low temperature with increasing strontium ions. It can be due to the crystal lattice distortion by larger radius of strontium and the increasing tolerance factor. ac conductivity and impedance measurements suggest that electron hopping mainly contributes to the low temperature region. Ionization conductivity by oxygen vacancy migration including first-ionization and double-ionization plays the dominating role in the middle and high temperature region. The controllable properties indicate the potential applications for electric devices of (Bi_0.5Na_0.5)_1-xSr_xBi₄Ti₄O₁₅ ceramic.     

Effects of the sulfurization temperature on sol gel-processed Cu2ZnSnS4 thin films

As a promising and alternative solar absorber material, the copper–zinc–tin–sulfide compound (Cu₂ZnSnS₄) has been drawing attention in recent years for the production of cheap thin-film solar cells owing to the high natural abundance and non-toxicity of all the constituents, a tunable direct-band-gap energy and a large optical absorption coefficient. In addition, to overcome the problem of expensive vacuum-based methods, solution-based approaches are being developed for Cu₂ZnSnS₄ deposition. In this study, we have produced Cu₂ZnSnS₄ thin films via the sol–gel technique and subsequent sulfurization. The effects of the sulfurization temperature on the structural, morphological, compositional and optical properties of the films were investigated. X-ray diffraction and Raman spectroscopy analyses confirmed the formation of phase-pure CZTS films. The crystallinity of the films increased with an increasing sulfurization temperature. From the surface images and the results of the composition analysis, it was found that the films are uniform, composed of homogenously distributed grains and have compositions with Cu deficit. The values of the optical absorption coefficients for the films were found to be 10⁴ cm^?1 based on absorbance spectroscopy. The optical band-gap values were estimated to be between 1.32 and 2.27 eV depending on the sulfurization temperature.     

Enhanced dielectric tunability properties of Ba(ZrxTi1−x)O3 thin films using seed layers on Pt/Ti/SiO2/Si substrates

The compositionally graded and homogeneous Ba(Zr_xTi_1−x)O₃ (BZT) thin films were fabricated on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si and Pt/Ti/SiO₂/Si substrates by a sol–gel deposition method, respectively. These films crystallized into a single perovskite phase. The BZT thin films deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates had a highly (1 0 0) preferred orientation and exhibited a preferred (1 1 0) orientation when the thin films were deposited on Pt/Ti/SiO₂/Si substrates. The LNO and Ba(Zr_0.30Ti_0.70) served as seed layer on Pt/Ti/SiO₂/Si substrates and analyze the relationship of seed layer, microstructure and dielectric behavior of the thin films. The compositionally graded thin films from BaTiO₃ to BaZr_0.35Ti_0.65O₃ were fabricated on LNO/Pt/Ti/SiO₂/Si substrates. The tunability behavior of compositionally graded films was analyzed in order to produce optimum effective dielectric properties. The dielectric constant of BaZr_xTi_1−xO₃ compositionally graded thin films showed weak temperature dependence. This kind of thin films has a potential in a fabrication of a temperature stable tunable device.     

Structural,electrical, and optical properties of Sb-doped SnO2 transparent conductive oxides fabricated using an electrospray technique

Sb-doped SnO₂ (ATO) thin films, for use as transparent conductive oxides (TCOs), were synthesized using an electrospray technique, and their structural, electrical, and optical properties were investigated. To elucidate the optimum fabrication conditions for the best electrical and optical properties, ATO thin films were calcined using four different temperatures, 450 °C, 550 °C, 650 °C, and 750 °C. When calcined at 650 °C, ATO thin films exhibit excellent resistivity (~8.14×10⁻³ Ω cm), superior transmittance (~91.4% at 550 nm), and good figure of merit (~11.4×10⁻⁴ Ω⁻¹) compared to the other samples. The enhanced properties of ATO thin films are attributed to high densification without formation of cracks, and the increased grain size of ATO nanoparticles.