Ferroelectric properties of pure ZrO2 thin films by chemical solution deposition

Ferroelectricity in pure zirconia (ZrO₂) thin films, manufactured on Si (100) substrates via the chemical solution deposition method using all-inorganic aqueous salt precursor, has been demonstrated for the first time. The influence of thickness on the crystalline structure and ferroelectric properties of the thin films were measured and showed that they were strongly affected by the film thickness. The structural data indicated that as the film thickness increased from 30 nm to 50 nm, the m-phase fraction increased, and a phase transition from orthorhombic to cubic and then tetragonal occurred near the main diffraction peak of 30.7°. The lowest m-phase fraction of 15.4% was obtained in the pure ZrO₂ film with a thickness of 30 nm, and after 10³ field cycling, it exhibited the highest relative permittivity of 39.6 as well as the highest residual polarization of 8.5 μC/cm².     

Preparation by chemical solution deposition and transparent conducting properties of LaRh1-xNixO3 thin films

Transparent conducting thin films have been widely used in lots of fields. The absence of high-performance hole-type transparent conducting thin films, however, seriously limits the wider applications. LaRhO₃ as a type of perovskite material shows hole-type conduction with semiconductor-like properties and no investigations have been carried out about transparent conducting properties on LaRhO₃ thin films. Here, LaRh_1-xNi_xO₃ (x = 0, 0.05, 0.1) thin films were firstly deposited by chemical solution deposition, showing epitaxial growth on single crystal SrTiO₃ (001) substrates with the epitaxial relationship of LaRhO₃(001)[110]||SrTiO₃(001)[110]. With the doping of Ni element, the surface morphology became denser. Hall measurements confirmed that the hole concentration was enhanced with Ni doping, resulting in the decreased resistivity. Low resistivity of 17.3 mΩ cm at 300K was obtained for the LaRh_0.9Ni_0.1O₃ thin films. The electrical transport mechanisms were investigated, showing thermal activation at high temperatures and variable range hopping model for the doped thin films at low temperatures. The transmittance within the visible range for all thin films was higher than 50%. The results will provide a feasible route to deposit hole-type transparent conducting LaRhO₃-based thin films.     

Preferentially oriented BaTiO3 thin films deposited on silicon with thin intermediate buffer layers

Barium titanate (BaTiO₃) thin films are prepared by conventional 2-methoxy ethanol-based chemical solution deposition. We report highly c-axis-oriented BaTiO₃ thin films grown on silicon substrates, coated with a lanthanum oxynitrate buffer layer of 8.9 nm. The influence of the intermediate buffer layer on the crystallization of BaTiO₃ film is investigated. The annealing temperature and buffer layer sintering conditions are optimized to obtain good crystal growth. X-ray diffraction measurements show the growth of highly oriented BaTiO₃ thin films having a single perovskite phase with tetragonal geometry. The scanning electron microscopy and atomic force microscopy studies indicate the presence of smooth, crack-free, uniform layers, with densely packed crystal grains on the silicon surface. A BaTiO₃ film of 150-nm thickness, deposited on a buffer layer of 7.2 nm, shows a dielectric constant of 270, remnant polarization (2P_r) of 5 μC/cm², and coercive field (E_c) of 60 kV/cm.     

Color tunable up-conversion emission of ZrO2:Yb3+, Er3+ thin films prepared by chemical solution deposition

The color-tunable up-conversion (UC) emission was observed in ZrO₂:Yb³⁺, Er³⁺ thin films synthesized on fused silica substrates using a chemical solution deposition method. The crystal structure, surface morphology image and optical transmittance of ZrO₂:Yb³⁺, Er³⁺ thin films were detected in the matter of Yb³⁺/Er³⁺ doping content. Under excitation by 980?nm infrared light, intense UC emission can be obtained from ZrO₂:Yb³⁺, Er³⁺ thin films. Photoluminescence study shows that there are two emission bands centered at 548?nm and 660?nm in the UC luminescence spectra, which can be owing to (²H_11/2,⁴S_3/2)→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺ ions, respectively. In addition, the color coordinate of UC emission between green-red can be tuned by properly adjusting the dopant concentration, because the composition of Yb³⁺/Er³⁺ affect the red/green ratio via the process of cross relaxation and energy back transfer. Our study suggests that ZrO₂:Yb³⁺, Er³⁺ thin films can be considered as promising materials for new photoluminescence devices.     

Solution-processed BiFeO3 thin films with low leakage current

Bismuth ferrite (BiFeO₃) is an attractive multiferroic material that shows strong ferroelectric and antiferromagnetic properties. Nevertheless, producing high-quality oriented BiFeO₃ on technology-important platinized silicon substrates by low-cost solution deposition methods is still challenging. In this work, polycrystalline Mn and Ti co-doped BiFeO₃ (BFO) thin films were fabricated on platinized silicon substrates by a solution deposition method. PbTiO₃ nanocrystals were used as a seed layer between the electrode and the BFO thin films to induce a preferential (100) pseudocubic orientation. We show that the introduction of a PbTiO₃ seed layer strongly reduces the leakage current. The films show excellent room-temperature ferroelectric properties at low frequencies (300 Hz), with epitaxial-like remanent polarization as high as 51 μC/cm² and coercive field of 500 kV/cm.     

The effect of crystallographic orientation and solution aging on the electrical properties of sol–gel derived Pb(Zr0.45Ti0.55)O3 thin films

Lead zirconate titanate—Pb(Zr_0.45Ti_0.55)O₃ thin films are grown on Pt_1 1 1/Ti/SiO₂/Si_1 0 0 substrates by a sol–gel method with 1 0 0/0 0 1 and 1 1 1 preferred orientations. Film orientation was controlled mainly by the annealing process and temperature. Films with 1 0 0/0 0 1 orientation consist of a uniform microstructure with micron size grains, whereas films with 1 1 1 orientation contain sub-micron grains. The electrical properties were influenced markedly by the microstructure and orientation of the films. The 1 1 1 oriented films exhibit a square-like hysteresis loop with remnant polarization (P_r) reaching 46 μC/cm² under 550 kV/cm, whereas 1 0 0/0 0 1 oriented films have a P_r of 20 μC/cm² with more slim hysteresis curves. Aging of the precursor solutions resulted in films growing with 1 0 0/0 0 1 texture and displaying inferior electrical properties.     

Interface-layer-assisted reliable ferroelectricity in BiFeO3 thin films by chemical solution deposition

BiFeO₃ thin films, specifically those fabricated by chemical solution deposition, suffer from severe leakage that hinder the acquirements of their intrinsic high polarizations and are thus normally not considered for use in practical electronics. The controlled fabrication of thin films with reduced leakage is of vital importance. In the present work, BiFeO₃ films (with thicknesses below ~300 nm), assisted by an interfacial amorphous layer, were fabricated by chemical solution deposition on Pt/Ti/SiO₂/Si substrates. This facile method facilitates the growth of the mentioned amorphous layer, and the ferroelectric properties of the obtained films were greatly enhanced. The conducting mechanisms of both types of thin films were systematically investigated to understand the impact of the designed interface. The results not only advance the potential use of BiFeO₃ thin films in electromechanical devices but also promote chemical solution deposition as a promising methodology for the fabrication of high-quality ferroelectric films with compressed leakage.     

Enhanced multiferroic properties in Pr-doped BiFe0.97Mn0.03O3 films

Bi_1−xPr_xFe_0.97Mn_0.03O₃ (x=0.00, 0.05, 0.10, 0.15, 0.20) thin films were deposited on FTO/glass substrate using chemical solution deposition. The influences of Pr doping on the crystalline structure and multiferroic properties were investigated. In the X-ray diffraction and Raman spectra results, the crystal structures of Bi_1−xPr_xFe_0.97Mn_0.03O₃ films revealed a gradual transformation from the trigonal structure to the tetragonal structure. The leakage current densities of Bi_1−xPr_xFe_0.97Mn_0.03O₃ films are one order of magnitude lower than that of BiFeO₃. Compared with unsaturated polarization-electric field hysteresis loop of BiFeO₃ film, the Pr and Mn co-doped BFO films have significantly improved ferroelectric properties. The improved remnant polarization (Pr=91.3 µC/cm²) and the positive switching current (I=0.028 A) have been observed in Bi_0.85Pr_0.15Fe_0.97Mn_0.03O₃ film. The improved electrical properties are attributed to the structure transformation, increasing grain boundaries, low oxygen vacancies ratio and increasing Fe³⁺ concentration. In addition, the saturation magnetization of Bi_0.85Pr_0.15Fe_0.97Mn_0.03O₃ film is 1.81 emu/cm³, which is approximately three times higher than pure BiFeO₃ (M_s=0.67 emu/cm³).     

Piezoresponse force microscopy characterization of rare-earth doped BiFeO3 thin films grown by the soft chemical method

The multiferroic behavior with ion modification using rare-earth cations on crystal structures, along with the insulating properties of BiFeO₃ (BFO) thin films was investigated using piezoresponse force microscopy. Rare-earth-substituted BFO films with chemical compositions of (Bi_1.00−xRE_xFe_1.00O₃ (x=0; 0.15), RE=La and Nd were fabricated on Pt (111)/Ti/SiO₂/Si substrates using a chemical solution deposition technique. A crystalline phase of tetragonal BFO was obtained by heat treatment in ambient atmosphere at 500 °C for 2 h. Ion modification using La³⁺ and Nd³⁺ cations lowered the leakage current density of the BFO films at room temperature from approximately 10⁻⁶ down to 10⁻⁸ A/cm². The observed improved magnetism of the Nd³⁺ substituted BFO thin films can be related to the plate-like morphology in a nanometer scale. We observed that various types of domain behavior such as 71° and 180° domain switching, and pinned domain formation occurred. The maximum magnetoelectric coefficient in the longitudinal direction was close to 12 V/cm Oe.     

Microstructures and ferroelectric properties of PbTiO3/PbZrO3 superlattices deposited by pulse laser deposition

In general, the strain effect and the electrostatic effect are important factors influencing the electrical properties of ferroelectric superlattices. However, the interfacial diffusion may also greatly influence the electrical properties of ferroelectric superlattices. Here, we deposited PbTiO₃/PbZrO₃ (PTO/PZO) superlattices on Nb-doped SrTiO₃ (NSTO) single-crystal substrates by pulse laser deposition with the same deposition processes but different cooling processes to explore the effects of interface diffusion on the structural and electrical properties of the superlattices. The experimental results showed that with increasing the holding time in the cooling process after deposition, the ferroelectric and dielectric properties were enhanced, meanwhile, the leakage current density was reduced. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) results showed that the PTO/PZO interfaces became blurred with increasing cooling time. Therefore, the increase in ferroelectric and dielectric properties and the decrease in leakage current density may be due to the interdiffusion of Ti and Zr ions at the PTO/PZO interfaces resulting in the formation of Pb(Zr_xTi_1-x)O₃ (PZT) and the decrease of interface defects at the PTO/PZO interfaces. Our results demonstrate that besides the strain and electrostatic effects, the interdiffusion of the elements at the interfaces is also an important factor that influences the electrical properties of ferroelectric superlattices.     

Structural and electrical properties of LaNiO3 thin films grown on (1 0 0) and (0 0 1) oriented SrLaAlO4 substrates by chemical solution deposition method

LaNiO₃ thin films were deposited on SrLaAlO₄ (1 0 0) and SrLaAlO₄ (0 0 1) single crystal substrates by a chemical solution deposition method and heat-treated in oxygen atmosphere at 700 °C in tube oven. Structural, morphological, and electrical properties of the LaNiO₃ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and electrical resistivity as temperature function (Hall measurements). The X-ray diffraction data indicated good crystallinity and a structural preferential orientation. The LaNiO₃ thin films have a very flat surface and no droplet was found on their surfaces. Samples of LaNiO₃ grown onto (1 0 0) and (0 0 1) oriented SrLaAlO₄ single crystal substrates reveled average grain size by AFM approximately 15–30 nm and 20–35 nm, respectively. Transport characteristics observed were clearly dependent upon the substrate orientation which exhibited a metal-to-insulator transition. The underlying mechanism is a result of competition between the mobility edge and the Fermi energy through the occupation of electron states which in turn is controlled by the disorder level induced by different growth surfaces.     

Tuning of BiFeO3 multiferroic properties by light doping with Nb

Bulk ceramic samples of BiFeO₃ were light doped (up to 1%) with Nb⁵⁺ in the place of Fe³⁺ (B-site doping) and their multiferroic properties were investigated using XRD, SEM, polarization (PMTS) and magnetization (SQUID) techniques. It is shown that even the small percentages of doping can notably change electric and magnetic behavior. Electric conductivity differs by two orders of magnitude between samples doped with 0.2% and 1% Nb. The ferroelectric behavior strongly depended on conduction mechanism, and transition from space-charge-limited current (SCLC) conduction to trap-filled limited (TFL) conduction regime reflected on a change in hysteresis patterns, particularly for the samples with 0.2% and 0.5% Nb. Separation of ZFC-FC magnetization curves occurred for all Nb concentrations and increased with Nb doping. Weak ferromagnetic behavior and the increase of remnant magnetization with Nb concentration was observed from the hysteresis measurements. Coercive field changed drastically compared to the pure BiFeO₃, namely, the sample with 1% Nb exhibited very high coercive magnetic field of ~ 10?kOe.     

Structural phase transition,electrical and photoluminescent properties of Pr3+-doped (1-x)Na0.5Bi0.5TiO3-xSrTiO3 lead-free ferroelectric thin films

Lead-free ferroelectric Pr³⁺-doped (1-x)Na_0.5Bi_0.5TiO₃-xSrTiO₃ (x?=?0–0.5) (hereafter abbreviated as Pr-NBT-xSTO) thin films were prepared on Pt/Ti/SiO₂/Si and fused silica substrates by a chemical solution deposition method combined with a rapid thermal annealing process at 700?°C, and their structural phase transition, dielectric, ferroelectric, and photoluminescent properties were investigated as a function of STO content. Raman analysis shows that with increasing STO content, the phase structures evolve from rhombohedral phase to coexistence of rhombohedral and tetragonal phases (i.e. morphotropic phase boundary), and then to tetragonal phase. The structural phase transition behavior has been well confirmed by temperature- and frequency- dependent dielectric measurements. Meanwhile, the variation in photoluminescence intensity of Pr³⁺ ions with different STO content in the NBT-xSTO thin films also indicates that there exists a clear structural phase transition when the film composition is close to the morphotropic phase boundary. Superior dielectric and ferroelectric properties are obtained in the Pr-NBT-0.24STO thin films due to the formation of morphotropic phase boundary. Our study suggests that Pr-NBT-xSTO thin films be promising multifunctional materials for optoelectronic device applications.     

Thickness dependence of microstructure,dielectric and leakage properties of BaSn0.15Ti0.85O3 thin films

The BaSn_0.15Ti_0.85O₃ (BTS) thin films are prepared on Pt-Si substrates with thickness ranging from ~ 60?nm to ~ 380?nm by radio frequency magnetron sputtering. The effects of thickness on microstructure, surface morphologies and dielectric properties of thin films are investigated. The thickness dependence of dielectric constant is explained based on the series capacitor model that the BTS thin film is consisted by a BTS bulk layer and an interfacial layer (dead layer) between the BTS and bottom electrode. The thin films with thickness of 260?nm give the largest figure of merit of 76.9@100?kHz, while the tunability and leakage current density are 64.6% and 7.46?×?10^?7 A/cm² at 400?kV/cm, respectively.     

Synthesis and electrical properties of lead-free piezoelectric Bi0.5Na0.5TiO3 thin films prepared by Sol-Gel method

Lead-free Bi_0.5Na_0.5TiO₃ (BNT) piezoelectric thin films were deposited on Pt/TiO_x/SiO₂/Si substrates by Sol-Gel method. A dense and well crystallized thin film with a perovskite phase was obtained by annealing the film at 700 °C in a rapid thermal processing system. The relative dielectric constant and loss tangent at 12 kHz, of BNT thin film with 350 nm thickness, were 425 and 0.07, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 9 μC/cm² and a coercive field of 90 kV/cm. Piezoelectric measurements at the macroscopic level were also performed: a piezoelectric coefficient (d_33effmax) of 47 pm/V at E = 190 kV/cm was obtained. The piezoresponse force microscopy data confirmed that BNT thin films present ferroelectric and piezoelectric behavior at the nanoscale level.     

Tuning magnetic properties of BiFeO3 thin films by controlling Mn doping concentration

Mn-doped BiFeO₃ (BiFe_1–xMn_xO₃, x = 0, 0.03, 0.05, 0.10, 0.15 and 0.20) polycrystalline multiferroic thin films were successfully synthesized using the facile sol-gel spin-coating method. The crystal structures, surface features, elements valences, and magnetic properties of as-prepared samples were systematically explored. X-ray diffraction and Raman spectroscopy studies revealed the substitutions of Mn into the Fe site and a rhombohedral-to-orthorhombic phase transition. The Field Emission Scanning Electron Microscopy showed a decrease in the average particle sizes and an improvement of surface morphology with increasing the concentration of the substitutes. Energy-dispersive X-ray spectroscopy confirmed the doping concentration of Mn²⁺ in the samples. X-ray photoelectron spectroscopy indicated the co-existence of Mn²⁺/Mn³⁺ ions in the doped films. The remnant magnetization value of BiFe_0.90Mn_0.10O₃ thin film was found to be approximately six times than that of pure BiFeO₃ thin film under a magnetic field of 10 kOe. The enhanced magnetic property of BiFe_0.90Mn_0.10O₃ thin film was mainly ascribed to the structural distortion of spin cycloid and the enhancement of super-exchange interaction between the Fe³⁺ (Mn²⁺) and O^2- ions.     

Investigation of Tb-doping on structural transition and multiferroic properties of BiFeO3 thin films

Pure BiFeO₃ (BFO) and Bi_1−xTb_xFeO₃ (BTFO) thin films were successfully prepared on FTO (fluorine doped tin oxide) substrates by the sol–gel spin-coating method. The effects of Tb-doping on the structural transition, leakage current, and dielectric and multiferroic properties of the BTFO thin films have been investigated systematically. XRD, Rietveld refinement and Raman spectroscopy results clearly reveal that a structural transition occurs from the rhombohedral (R3c:H) to the biphasic structure (R3c:H+R-3m:R) with Tb-doping. The leakage current density of BTFO_x=0.10 thin film is two orders lower than that of the pure BFO, i.e. 5.1×10⁻⁷ A/cm² at 100 kV/cm. Furthermore, the electrical conduction mechanism of the BTFO thin films is dominated by space-charge-limited conduction. The two-phase coexistence of BTFO_x=0.10 gives rise to the superior ferroelectric (2P_r=135.1 μC/cm²) and the enhanced ferromagnetic properties (M_s=6.3 emu/cm³). The optimal performance of the BTFO thin films is mainly attributed to the biphasic structure and the distorted deformation of FeO₆ octahedra.     

Annealing temperature dependence of local piezoelectric response of (Pb,Ca)TiO3 ferroelectric thin films

In this work, we have systematically investigated the piezo/ferroelectric response of (Pb, Ca)TiO₃ thin films prepared by polymeric precursor method using simultaneously topography, piezoresponse force microscopy (PFM) and local piezoelectric hysteresis loop measurements. The thin films were grown on Pt/Ti/SiO₂/Si substrates and annealed at 400, 500 and 600 °C and subjected to structural characterization using x-ray diffraction, infrared and micro-Raman spectroscopy. The ferroelectric domains structure and the piezoelectric response evolved as a function of thermal annealing temperature as well as the density of active grains (number of switchable domains) progressively increased. Another important characteristic of these films is the onset of large area showing the coexistence of active (stronger piezoresponse signal) and inactive (weak or non piezoresponse signal) grains embedded in the polycrystalline perovskite matrix. A combination of out-of-plane (OP) and in-plane (IP) PFM images revealed local features of polarization component magnitudes in samples surface. Well-defined local piezoelectric hysteresis loop was achieved on top of individual nanometer-scale grains in both samples annealed at 500 and 600 °C, and the switching behavior is evident.     

Assessment of Cr doping on TiO2 thin films deposited by a wet chemical method

Undoped and Cr-doped TiO₂ thin films were synthesized by the dip-coating sol-gel process with titanium isopropoxide and chromium (III) chloride hexahydrate being used as the precursors. The chromium concentrations changed for different molar ratios, namely, 2, 4, and 8 wt.%. The samples, coated on glass substrates, were later annealed in air at 450 °C for 60 min. The influence of Cr doping on the structural, surface chemical, and optical properties of the samples was studied by several techniques, including EDS, Raman, UV–Vis, RT-PL, and XPS spectroscopies, as well as SEM and XRD. The diffraction patterns indicated that all the films displayed the anatase structure with the crystallite size decreasing with chromium doping. The same structure was confirmed by Raman spectroscopy measurements. UV–Vis absorption spectra of the samples showed a red shift of the fundamental absorption edge in the visible range following the increase of Cr doping concentration. In addition, the RT-PL study revealed that the dopant incorporation causes a decrease in the PL intensity. The EDS analysis revealed the presence of Ti, O, and Cr in the materials. Moreover, from high-resolution XPS Ti 2p spectra, titanium was found to be in the Ti⁴⁺ oxidation state evidencing the formation of TiO₂, while the Cr 2p fitting analysis showed that chromium is present in the Cr (III) and Cr-metal states.