Tuning electrical properties of PZT film deposited by Pulsed Laser Deposition

The variation of the chemical composition and properties of PZT films as a function of oxygen pressure and laser fluence during pulsed laser deposition is used to tune the electrical properties of the PZT thin films. It is found that the deposition using a 248 nm laser fluence of 1.7 J/cm² and an oxygen pressure of 400 mtorr results the PZT films very similar to that of target material. Changing the laser fluences or oxygen pressure, affects the lead content of the deposited film. In the range of oxygen pressure 50–200 mtorr, the Zr/Zr+Ti and Ti/Zr+Ti ratio varies with oxygen pressure while the Pb/Zr+Ti ratio is almost uniform. Using oxygen pressure as a control parameter to tune the chemical compound and electrical properties of the deposited PZT films, the remnant polarization of the PZT films is tuned in the range of 6.6–42.2 µC/cm², the dielectric constant is controlled in the range of 29–130, and the piezoelectric constant d₃₃ is controlled in the range of 3.82–4.96 pm/V for a 40 nm thick PZT film.     

Preparation and ferroelectric properties of (Na0.5Bi0.5)0.94Ba0.06TiO3 thin films deposited on Pt electrodes using LaNiO3 as buffer layer

(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1) and LaNiO₃/Pt/Ti/SiO₂/Si (1 1 1) substrates by a sol–gel process. The phase structure and ferroelectric properties were investigated. The X-ray diffraction pattern indicated that the (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ thin film deposited on Pt/Ti/SiO₂/Si (1 1 1) substrates is polycrystalline structure without any preferred orientation. But the thin film deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates shows highly (1 0 0) orientation (f ≥ 81%). The leakage current density for the two thin films is about 6 × 10^?3 A/cm² at 250 kV/cm, and thin film deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates possessed a much lower leakage current under high electric field. The hysteresis loops at an applied electric field of 300 kV/cm and 10 kHz were acquired for the thin films. The thin films deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates showed improved ferroelectricity.     

Lead zirconium titanate thin films prepared by thermal annealing of multilayer structures composed of PbO,ZrO2 and TiO2

Lead zirconium titanate [Pb(Zr_xTi_1?x)O₃ or PZT] thin films were prepared by the thermal annealing of multilayer films composed of binary oxide layers of PbO, ZrO₂ and TiO₂. The binary oxides were deposited by metal organic chemical vapor deposition. An interdiffusion reaction for perovskite PZT thin films was initiated at approximately 550 °C and nearly completed at 750 °C for 1 h under O₂ annealing atmosphere. The composition of Pb/Zr/Ti in perovskite PZT could be controlled by the thickness ratio of PbO/ZrO₂/TiO₂ where the contribution of each binary oxide at the same thickness was 1:0.55:0.94. The electrical properties of PZT (Zr/Ti = 40/60, 300 nm) prepared on a Pt-coated substrate included a dielectric constant ?_r of 475, a coercive field E_c of 320 kV/cm, and remnant polarization P_r of 11 μC/cm² at an applied voltage of 18 V.     

Electrophoretic deposition of Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 thick film on Pt wire

0.2PbNi_1/3Nb_2/3–0.8Pb(Zr,Ti)O₃ (PNN–PZT) thick films were deposited on Pt wire with the diameter of 50 μm by electrophoretic deposition (EPD) method. The EPD deposition times on the microstructures of PNN–PZT thick films were investigated. By optimizing the EPD process, the Pt wire can be uniformly wrapped with the PNN–PZT powders. During the sintering process, the as-deposited PNN–PZT/Pt wires were buried in the mixed powders of PbCO₃ and ZrO₂, and then sintered in the optimal temperature to get a dense microstructure. The piezoelectric properties of the thick films were characterized by scanning force microscopy (SFM) method. The results show that the PNN–PZT thick films prepared by EPD method have good piezoelectricity.     

Analysis of composition homogeneity and polarization orientation of PZT submicron fibers by micro-Raman spectroscopy

Micro-Raman spectroscopy is a convenient tool to probe individual objects with a feature size on the submicron scale. The phase, composition, and orientation of Pb(Zr,Ti)O₃ fibers fabricated via hydrothermal processing have been characterized by this technique, with the working principles given in the paper. It is shown that the prepared PZT submicron fibers are of a tetragonal pervoskite phase, with Zr/(Zr + Ti) varying from 0.05 to 0.25. The spontaneous polarization has been confirmed to be along the length direction and one of its {1 0 0} planes parallel to the substrate plane.     

Enhanced ferroelectric properties of 0.95Pb(Sc0.5Ta0.5)O3–0.05PbTiO3 thin films with Pb(Zr0.52,Ti0.48)O3 seed layer

0.95Pb(Sc_0.5Ta_0.5)O₃–0.05%PbTiO₃ (PSTT5) thin films with and without a Pb(Zr_0.52,Ti_0.48)O₃ (PZT52/48) seed layer were deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering. X-ray diffraction patterns indicate that the PSTT5 film with a PZT52/48 seed layer exhibited nearly pure perovskite crystalline phase with highly (4 0 0)-preferred orientation. Piezoresponse force microscopy observations reveal that a large out-of-plane spontaneous polarization exists in the highly (4 0 0)-oriented PSTT5 thin film. The PSTT5/PZT(52/48) possesses good ferroelectric properties with large remnant polarization P_r (12 μC/cm²) and low coercive field E_c (110 kV/cm). Moreover, The perfect butterfly-shaped capacitance–voltage characteristic curve and the relative dielectric constant as high as 733 is obtained in this PSTT5 thin film at 100 kHz.     

Phase and Texture Evolution in Chemically Derived PZT Thin Films on Pt Substrates

The crystallization of lead zirconate titanate (PZT) thin films was evaluated on two different platinum‐coated Si substrates. One substrate consisted of a Pt coating on a Ti adhesion layer, whereas the other consisted of a Pt coating on a TiO₂ adhesion layer. The Pt deposited on TiO₂ exhibited a higher degree of preferred orientation than the Pt deposited on Ti (as measured by the Full Width at Half Maximum of the 111 peak about the sample normal). PZT thin films with a nominal Zr/Ti ratio of 52/48 were deposited on the substrates using the inverted mixing order (IMO) route. Phase and texture evolution of the thin films were monitored during crystallization using in situ X‐ray diffraction at a synchrotron source. The intensity of the Pt₃Pb phase indicated that deposition on a highly oriented Pt/TiO₂ substrate resulted in less diffusion of Pb into the substrate relative to films deposited on Pt/Ti. There was also no evidence of the pyrochlore phase influencing texture evolution. The results suggest that PZT nucleates directly on Pt, which explains the observation of a more highly oriented 111 texture of PZT on the Pt/TiO₂ substrate than on the Pt/Ti substrate.     

Micro-patterning of PZT thick film by lift-off using ZnO as a sacrificial layer

Micro-pattern of 8.2-μm-thick PZT films was prepared on Pt/Ti/SiO₂/Si (1 0 0) substrate wafer by combining composite sol–gel and a novel lift-off using ZnO as a sacrificial layer. The processes include ZnO sacrificial layer deposition and patterning, PZT film preparation, and final lift-off. The results reveal the micro-pattern was better than that formed by wet etching, the PZT thick films patterned by lift-off possessed similar dielectric characters, better ferroelectric properties, and higher breakdown voltage than those of films patterned by wet etching. The lift-off is suitable for micro-patterning of PZT thick films.     

Structural and electrical properties of Pb(Zr0.53Ti0.47)O3 films prepared on La0.5Sr0.5CoO3 coated Si substrates

PbZr_0.53Ti_0.47O₃ (PZT) thin films with thickness of 0.9 μm were prepared on La_0.5Sr_0.5CoO₃ (LSCO) coated Si substrates. Both PZT and LSCO were prepared by the sol–gel method. The concentration of LSCO sol was varied from 0.3 to 0.1 mol/L, which could modify the preferential orientation of PZT thin films and consequently affect the dielectric and ferroelectric properties. The LSCO electrode layers derived from lower sol concentration of 0.1 mol/L have much more densified structure, which facilitates the formation of (1 0 0) textured PZT films with smooth and compact columnar grains. PZT thin films prepared on the optimized LSCO films exhibit the enhanced dielectric constant and remnant polarization of 980 and 20 μC/cm², respectively.     

Preparation and tunability properties of Ba(ZrxTi1−x)O3 thin films grown by a sol–gel process

Ba(Zr_xTi_1−x)O₃ (BZT) thin films were deposited via sol–gel process on LaNiO₃, as buffer layer, and Pt-coated silicon substrates. The BZT films were perovskite phase and showed a (1 0 0) preferred orientation dependent upon zirconium content. The grain size decreased and the microstructure became dense with increasing zirconium content. The addition of Zr to the BaTiO₃ lattice decreased the grain size of the crystallized films. The temperature dependent dielectric constant revealed that the thin films have relaxor behavior and diffuse phase transition characteristics that depend on the substitution of Zr for Ti in BaTiO₃. The dependence of electrical properties on film thickness has been studied, with the emphasis placed on dielectric nonlinear characteristics. Ba(Zr_0.35Ti₆₅)O₃ thin films with weak temperature dependence of tunability in the temperature range from 0 to 130 °C could be attractive materials for situations in which precise control of temperature would be either impossible or too expensive.     

Low-temperature crystallization of tantalum pentoxide films under elevated pressure

Ta₂O₅ thin films deposited via a metal-organic decomposition method were crystallized via atmospheric pressure annealing and a high-pressure crystallization (HPC) process. Ta₂O₅ thin films started to become crystallized at 700 °C as subjected to atmospheric pressure annealing. When the HPC process was adopted and annealing at 16.5 MPa was performed, the crystallization temperature of Ta₂O₅ films was greatly dropped to as low as 350 °C. The developed HPC process considerably reduced the thermal budget and energy consumption during film processing. The crystallized Ta₂O₅ phase was found to be homogeneously distributed within the HPC-derived films. With annealing at 700 °C under atmospheric pressure, the silicon species diffused from the substrates into the Ta₂O₅ layers, thereby leading to reduced dielectric constants. The HPC process effectively suppressed the interdiffusion between the substrates and dielectric layers by lowering the required heating temperature, and also significantly increased the dielectric constants of Ta₂O₅ thin films. The HPC process was confirmed to effectively lower the crystallization temperature and improve the dielectric properties of Ta₂O₅ thin films.     

Crystallization of lead zirconate titanate without passing through pyrochlore by new solution process

We report a novel low-temperature crystallization path for perovskite lead zirconate titanate (PZT) from solution. The modification of a PZT solution by monoethanolamine (MEA) resulted in a change in the crystallization behavior. MEA was strongly coordinated to the metal ions, resulting in destroy of multinuclear metal organic complexes. This led to a remarkably increased pyrolysis temperature, and Pb²⁺ was reduced into Pb⁰ because of a reducing environment at 200–300 °C. Nanoscopic separations of Pb⁰ was later transformed into uniformly distributed α-PbO nanocrystals and clusters in the amorphous Zr/Ti–O matrix, and finally the sample crystallized into perovskite at 400–500 °C. On the other hand, pyrochlore phase was observed in the conventional crystallization process. The avoidance of pyrochlore formation is the key for the low-temperature crystallization of perovskite. X-ray absorption fine structure (XAFS) analysis was performed to reveal the structures in solutions and amorphous phases.     

Preparation of ultrathin PZT films by a chemical solution deposition method from a polymeric citrate precursor

Ultrathin PZT film was prepared using a chemical solution deposition method from polymeric citrate precursors. The PZT solution was spin-coated on an amorphous silica layer formed on a Si(1 0 0) substrate. The films were thermally treated from the substrate side with a low heating rate (1°/min) up to 700 °C and finally annealed for 10 h. Ultrathin PZT films without microstructural instability were prepared in spite of high temperature and long annealing time. AFM and HRTEM investigations revealed the formation of a well-developed dense microstructure consisting of spherical crystallites (4–7 nm). Low roughness (2.2 nm) of a ～26 nm thick layer was obtained for a two-layered PZT film. The grazing incidence X-ray diffraction (GIXRD) measurements confirmed the polycrystalline structure of ultrathin PZT films. Also, GIXRD and electron energy dispersive X-ray (EDS) analysis showed that compositional variations were smaller than expected, in spite of the long annealing time.     

Orientation control and electrical properties of PZT/LNO capacitor through chemical solution deposition

This paper describes the deposition of PZT/lanthanum nickel oxide (LNO) electrode thin-film capacitor on a Si(1 0 0) substrate with a chemical solution deposition (CSD). Highly (1 0 0)-oriented LNO film with a perovskite structure was deposited by annealing at 700 °C from a precursor solution of La(NO₃)₃ and Ni(CH₃COO)₂. In addition, highly (1 0 0)&(0 0 1)-oriented PZT/LNO capacitor was deposited on LNO/Si substrate by annealing at 600 °C, showing P_r = 18 μC/cm² and E_c = 36 kV/cm. Furthermore, the resultant PZT/LNO thin-film capacitor exhibited no fatigue up to 10⁸ switching cycles.     

The effects of deposition temperature on structure and dielectric properties of Ba0.6Sr0.4TiO3 thin films produced by pulsed laser deposition

The effects of deposition temperature on orientation, surface morphology and dielectric properties of the thin films for Ba_0.6Sr_0.4TiO₃ thin films deposited on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition were investigated. X-ray diffraction patterns revealed a (2 1 0) preferred orientation for all the films. With rising substrate temperature from 650 °C to 700 °C, the crystallinity and crystal grain size of the films increase, the relative dielectric constant increases, but the dielectric losses have not obvious difference. The film deposited at 350 °C and annealed at 700 °C has strongly improved roughness and dielectric permittivity compared with the film only deposited directly at 700 °C. Three distinct relaxation processes within tan(δ) were found for the Ba_xSr_1?xTiO₃ film: a broadened process of the film relaxation, an intermediate peak which originates from Maxwell–Wagner–Sillars polarization, and an extremely slow process ascribed to leak current. The complex dielectric permittivity and loss can be fitted by an improved Cole–Cole model corresponding to a stretched relaxation function.     

Structure and dielectric properties of barium titanate thin films for capacitor applications

BaTiO₃ is a typical ferroelectric material with high relative permittivity and has been used for various applications, such as multilayer ceramic capacitors (MLCCs). With the tendency of miniaturization of MLCCs, the thin films of BaTiO₃ have been required. In this work, BaTiO₃ thin films have been deposited on Pt-coated Si substrates by RF magnetron sputtering under different deposition conditions. The films deposited at the substrate temperature from 550 °C–750 °C show a pure tetragonal perovskite structure. The films deposited at 550 °C–625  °C exhibit (111) preferential orientation, and change to (110) preferential orientation when deposited above 650 °C. The film morphologies vary with working pressure and substrate temperature. The film deposited at 625 °C and 4.5 Pa has the relative permittivity of 630 and the loss tangent of 2% at 10 kHz.     

Preparation and electrical properties of Bi2Zn2/3Nb4/3O7 thin films deposited at room temperature for embedded capacitor applications

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited at room temperature on Pt/Ti/SiO₂/Si(1 0 0) and polymer-based copper clad laminate (CCL) substrates by pulsed laser deposition. Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited in situ with no intentional heating under an oxygen pressure of 4 Pa and then post-annealed at 150 °C for 20 min. It was found that the films are still amorphous in nature, which was confirmed by the XRD analysis. It has been shown that the surface roughness of the substrates has a significant influence on the electrical properties of the dielectric films, especially on the leakage current. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates exhibit superior dielectric characteristics. The dielectric constant and loss tangent are 59.8 and 0.008 at 10 kHz, respectively. Leakage current density is 2.5 × 10^?7 A/cm² at an applied electric field of 400 kV/cm. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited on CCL substrates exhibit the dielectric constant of 60 and loss tangent of 0.018, respectively. Leakage current density is less than 1 × 10^?6 A/cm² at 200 kV/cm.     

Tailoring of morphology and orientation of LaNiO3 films from polymeric precursors

The aim of this work was to prepare lanthanum nickel oxide (LaNiO₃, LNO) thin films of different morphology and orientation. The precursor solutions were prepared by a chemical method from citric salts of lanthanum and nickel. Films were deposited using spin-on technique on Si (1 0 0) substrates. Tailoring of the films orientation and morphology has been attained through two thermal treatment processes with different heating devices: tubular furnace (process 1) and hot plate (process 2). Films were annealed at 600 and 700 °C, with heating rates: 20 °C/min (process 1) and 1 °C/min (process 2). Annealing times were from 30 min to 20 h. LNO films were characterized by AFM and X-ray diffraction analysis. Depending on the heating process applied, the obtained films showed very different structures, from completely amorphous to well crystallized and highly oriented. Films treated by process 1 were polycrystalline, had smaller oval grains and lower roughness parameters than films heated on a hot plate. Due to the low heating rate and heating from the substrate side, films obtained through process 2 were highly (1 1 0) oriented with elongated grains aligned along one direction.     

Microwave dielectric properties of bismuth zinc niobate thin films deposited on alumina by pulsed laser deposition

Bi₂Zn_2/3Nb_4/3O₇ thin films were prepared on Al₂O₃ substrates by pulsed laser deposition. The phase compositions and microstructures were characterized by X-ray diffraction and atomic force microscopy. The as-deposited films were all amorphous in nature. All films were crystallized after the post annealing at the temperature range of 700–900 °C for 30 min in air. The texture characteristics change with annealing temperature. A split post dielectric resonator method was used to measure the microwave dielectric performance at the resonant frequencies of 10, 15 and 19 GHz. For the films annealed at 900 °C, the preferential orientation is similar to the monoclinic BZN bulk. The microwave dielectric constants at 10, 15 and 19 GHz are 69.4, 58.9 and 47.9, respectively, which are closer to these of the monoclinic BZN bulk.     

Fine-patterning of sol-gel derived PZT film by a novel lift-off process using solution-processed metal oxide as a sacrificial layer

Sub-5 µm pattern of sol-gel derived lead-zirconium-titanate (PZT) film with a thickness of 80–390 nm was successfully prepared on Pt(111)/TiO_x/SiO₂/Si (100) substrate by a novel lift-off process using solution-processed metal oxides as a sacrificial layer. The process is simply divided into three steps: In-Zn-O (IZO) sacrificial layer spin-coating and patterning, PZT film formation followed by lift-off process. The results suggested that the IZO layer is effective in preventing PZT crystallization because of its thermal stability during PZT post-annealing, and its barrier-effects between the spin-coated PZT precursor and the Pt/TiO_x substrate. Consequently, the micro-pattern of lift-off PZT exhibited better properties than that formed by wet-etching. In particular, the lift-off PZT films possessed better ferroelectric properties, higher break-down voltage, and more well-defined shape than those of films patterned by conventional wet-etching. This lift-off process shows great promise for highly integrated devices due to its fine pattern-ability.