Distribution in orientation axis of thin film grown by pulsed laser deposition

Orientations of LaNiO₃ (LNO) and Pb(Zr_0.52Ti_0.48)TiO₃ (PZT) films deposited by laser ablation were evaluated using X-ray diffraction. (001)-oriented PZT and LNO films were achieved under optimized deposition conditions. Pole-figure measurements of both LNO and PZT films showed that (001) out-of-plan orientation was affected by plume direction. It was found that the (001) axes of both LNO and PZT films at locations away from the plume center were significantly tilted. The incline angle of tilt increases with the distance away from the center of the plume. The films grown in columnar structures and the column axis coincided with the crystalline orientation. Polarization of the PZT film was slightly affected by the difference in orientation tilt angles of the film investigated.     

Compositionally graded Pb(Zr,Ti)O3 thin films with different crystallographic orientations

Compositionally graded ferroelectric PbZr_xTi_1−xO₃ (PZT) films were deposited using a sputtering method and crystallized in situ at 500 °C. The films showed purely (100) or (111) crystallographic orientation when grown on Si/SiO₂/TiO₂/Pt substrates, while they exhibited c-axis epitaxial microstructure when prepared on MgO/Pt substrates. Their crystallographic orientation was controlled owing to a thin TiO_x layer sputtered on substrates prior to PZT deposition. Analysis performed by Auger depth profile clearly confirmed the variation of composition in the films. Coercive fields from 80 kV/cm to 200 kV/cm and remnant polarization as large as 45 μC/cm² were obtained. However, no typical offset was observed on hysteresis loops, unlike previous works related to graded PZT films.     

Microstructure and electrical properties of Pb(Zr0.52Ti0.48)O3 ferroelectric films on different bottom electrodes

The crystalline quality, dielectric and ferroelectricity of the Pb(Zr_0.52Ti_0.48)O₃ (PZT) films deposited on the LaNiO₃ (LNO), LNO/Pt and Pt bottom electrodes were comparatively analyzed to investigate the possibility for their application. LNO thin films were successfully prepared on Si (100) and Pt(111)/Ti/SiO₂/Si substrates by modified metallorganic decomposition (MOD). The PZT thin films were spin-coated onto the LNO, LNO/Pt and Pt bottom electrodes by sol–gel method. The crystallographic orientation and the microstructure of the resulting LNO films and PZT thin films on the different bottom electrodes were characterized by X-ray diffraction analysis. The dielectric and ferroelectric properties of PZT films on the different bottom electrodes are discussed. The PZT films deposited onto Pt/Ti/SiO₂/Si and LNO/Si substrates show strong (110) and (100) preferred orientation, respectively, while the films deposited onto LNO/Pt/Ti/SiO₂/Si substrates show the peaks of mixed orientations. PZT films on LNO and LNO/Pt bottom electrodes have larger dielectric constant and remnant polarizations compared with those grown on the Pt electrode.     

Preparation of Pb(Zr0.52Ti484848)O3 thin films on silicon-on-insulator substrates by excimer laser deposition combined with rapid thermal annealing

In this paper we report the fabrication of ferroelectric Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films on Si-on-Insulator (SOI) substrates with and without an electrode by pulsed excimer laser deposition combined with rapid thermal annealing. Based on the structural and interfacial characteristics analysis by X-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), cross-sectional transmission electron microscopy (XTEM) and automatic spreading resistance measurement (ASR), the film structure and orientation were revealed to be dependent on the annealing time and annealing temperature as well as deposition temperature. From RBS spectra and XTEM observation it is shown that the PZT thin films did not interact with the top silicon layers of SOI and that the composition of the film was similar to the target. The ASR measurements showed that the electrical properties of PZT/SOI as well as PZT/Pt/SOI were abrupt, and that the electrical properties of the SOI substrates were still good after the PZT growth.     

PZT/ZnO薄膜制备及其结构特性研究

利用固相反应制备的ZnO-Li_(2.2%)陶瓷靶和RF射频磁控溅射技术在Si(100)基片上制备了高度c轴择优取向的ZnO薄膜,XRD和电性能分析表明掺杂Li离子改善了ZnO靶材的结构和性能,同时研究了不同RF溅射温度对ZnO薄膜结构与取向的影响;然后采用sol-gel前驱单体薄膜制备方法,以ZnO为过渡层淀积PZT薄膜,探讨高度c轴(002)择优取向ZnO薄膜对PZT薄膜结构与性能的影响,实验发现在PZT/ZnO异质结构中,致密、均匀和高度c轴择优取向的ZnO可作为晶核,促进PZT钙钛矿结构转化、晶粒(110)择优取向生长,相应降低PZT薄膜的退火温度.     

Tailoring in-plane crystallographic orientation of epitaxial YBa2Cu3O7 − x thin films having perpendicular c-axis texture

Control of the in-plane crystallographic orientation of YBa₂Cu₃O_7 − x (YBCO) films on (100) MgO substrates is of significant application value due to the selective enhancement of superconducting properties. In the present work, the preparation, crystallographic and superconducting properties of YBCO films deposited on MgO substrates are reported. Crystallographic in-plane orientation was realized by means of tailoring the pulsed laser deposition conditions and the use of interfacial buffering structures. Superconductiong properties were measured for films having different in-plane orienations. The results indicate that the 0^° in-plane oriented films showed the highest current density of 1.62 MA/cm² that was attributed to the elimination of high-angle grain boudaries. Additionally, the growth mechanism of YBCO films was discussed in terms of crystallographic and thermodynamic theory.     

The thickness effect of Bi3.25La0.75Ti3O12 buffer layer in PbZr0.58Ti0.42O3/Bi3.25La0.75Ti3O12 (PZT/BLT) multilayered ferroelectric thin films

A series of PbZr_0.58Ti_0.42O₃ (PZT) thin films with various Bi_3.25La_0.75Ti₃O₁₂ (BLT) buffer layer thicknesses were deposited on Pt/TiO₂/SiO₂/p-Si(100) substrates by RF magnetron sputtering. The X-ray diffraction measurements of PZT film and PZT/BLT multilayered films illustrate that the pure PZT film shows (111) preferential orientation, and the PZT/BLT films show (110) preferential orientation with increasing thickness of the BLT layer. There are no obvious diffraction peaks for the BLT buffer layer in the multilayered films, for interaction effect between the bottom BLT and top PZT films during annealing at the same time. From the surface images of field-emission scanning electron microscope, there are the maximum number of largest-size grains in PZT/BLT(30 nm) film among all the samples. The growth direction and grain size have significant effects on ferroelectric properties of the multilayered films. The fatigue characteristics of PZT and PZT/BLT films suggest that 30-nm-thick BLT is just an effective buffer layer enough to alleviate the accumulation of oxygen vacancies near the PZT/BLT interface. The comparison of these results with that of PZT/Pt/TiO₂/SiO₂/p-Si(100) basic structured film suggests that the buffer layer with an appropriate thickness can improve the ferroelectric properties of multilayered films greatly.     

Synthesis and electrical properties of Pb(Zr0.52Ti0.48)O3 thick films embedded with ZnO nanoneedles prepared by the hybrid sol–gel method

Pb(Zr_0.52Ti_0.48)O₃ thick films embedded with ZnO nanoneedles (PZT–ZnO_n) were successfully prepared on Pt/Cr/SiO₂/Si substrates by the hybrid sol–gel method via spin-coating ZnO_n suspension and lead zirconate titanate (PZT) sol. To control the orientation of the films, a PbTiO₃ (PT) layer was first deposited as a seed layer. Effects of annealing method and ZnO_n contents on the corresponding orientation and crystallization of PZT–ZnO_n films were investigated by XRD and SEM. The results show that all the PZT–ZnO_n composite thick films have pure perovskite structure and high-quality film surface. The dielectric and ferroelectric properties of the PZT–ZnO_n films are close to the PZT films, and have a little decrease with the increasing of the ZnO_n contents.     

The effects of the PbO content and seeding layers upon the microstructure and orientation of sol-gel derived PZT films

This paper systematically studied the factors including Pb content of precursor, PT seeding layer and TiO₂ and ZrO₂ seeding layers, which influence greatly the crystal orientation of lead zirconate titanate (PZT, Zr/Ti = 52/48) thin films fabricated by a sol-gel process. We find that the PZT films deposited by precursor with 20% mole excess Pb displayed strong (111) preferred orientation, with 5% mole excess Pb showed a little (100) orientation and pyrochlore phase. PT seeding layer was found prompting the PZT films phase transformation with (110) preferred orientation. In addition, the results show that the TiO₂ and ZrO₂ seeding layers had totally different effects on the preferred orientation of PZT films. The films with TiO₂ seeding layer were highly (111) oriented and exhibited better ferroeletric properties (remnant polarization Pr = 14.2 μC⋅ cm⁻², coercive field Ec = 59.1 Kvcm⁻¹) than those of the films with ZrO₂ seeding layer shown (100) orientation (Pr = 7.4 μC⋅cm⁻², Ec = 42.9 Kvcm⁻¹).     

Effects of substrate temperature on Bi0.8La0.2FeO3 thin films prepared by pulsed laser deposition

Bi_0.8La_0.2FeO₃ thin films on Pt/TiO₂/SiO₂/Si substrates at various substrate temperatures from 500 °C to 750 °C are prepared by pulsed laser deposition, and their microstructures and ferroelectric/magnetic properties are carefully investigated using various techniques. It is observed that the crystallographic orientation and Fe-ion valence state depend significantly on the substrate temperature, which consequently influences considerably on the ferroelectric and magnetic properties of the thin films. A considerable improvement of the ferroelectric and magnetic properties of the thin films can be achieved by optimizing the substrate temperature for deposition.     

Preparation and characterization of preferred oriented PZT films on amorphous substrates

The (001) preferred orientation of Nb-doped Pb(Zr_0.52Ti_0.48) O₃ (PZT) thin films was successfully realized on amorphous glass substrate with LaNiO₃(LNO) as electrode by rf-sputtering method. It was found that the LNO film greatly promotes formation of the PZT film with pervoskite phase on amorphous substrate and the preferred orientation of the PZT film depends strongly on the process of preparation. The experimental results show that the dielectric constant and loss of the PZT films with the (001) preferred orientation are 1308 and 0.042, respectively, at 1 kHz, 0.05 V. The remanent polarization (P_r), saturation polarization (P_s) and coercive field (E_c) are 34.5, 43 C/cm² and 105 kV/cm, respectively. The PZT films also show a 33 kV/cm internal bias field due to its (001) preferred orientation. The piezoelectric coefficient d₃₃ of the PZT film without the poled treatment is about 15 pC/N due to its (001) preferred orientation. The effect of the foreign stress on the piezoelectric voltage response of the PZT/LNO/glass was investigated. The results make us consider using the PZT film as an artificial skin to realize the self-diagnosis of amorphous materials under the action of stress.     

Effect of LaNiO3 electrodes and lead oxide excess on chemical solution deposition derived Pb(Zrx,Ti1 − x)O3 films

The effects of LaNiO₃ (LNO) and Pt electrodes on the properties of Pb(Zr_x,Ti_1 − x)O₃ (PZT) films were compared. Both LNO and PZT were prepared by chemical solution deposition (CSD) methods. Specifically, the microstructure of LNO and its influence on the PZT properties were studied as a function of PbO excess. Conditions to minimize the Pyrochlore phase and porosity were found. Remnant polarization, coercive field and fatigue limit were improved in the PZT/LNO films relative to the PZT/Pt films. Additionally, the PZT crystallization temperature over LNO was 500 °C, about ~ 50 °C lower than over Pt. The crystallization temperature reported here is amongst the lowest values for CSD-based PZT films.     

Crystallization behavior and domain structure in textured Pb(Zr0.52Ti0.48)O3 thin films by different annealing processes

Amorphous Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were prepared on the Pt/Ti/SiO₂/Si substrates by radio-frequency magnetron sputtering at room temperature. After rapid thermal annealing (RTA) and conventional furnace annealing (CFA) at different temperatures, the films were transformed into polycrystalline PZT thin films with (111) and (100) orientation, respectively. The phase formation and ferroelectric domains correlated with different orientation were systematically investigated by X-ray diffraction and piezoresponse force microscopy. The results showed that the perovskite PZT crystal with [111] orientation hetero-nucleated preferentially on top of the PtPb intermetallic phase at the PZT/Pt interface during RTA process. It is of interest to find that the domain self-organized into a structure with rounded shape at the early stage of crystallization. While the nucleation of the films treated by CFA dominantly homo-nucleated, thus the (100) orientation grains with minimum surface energy were easy to grow. The texture effects on ferroelectric properties of PZT films were also discussed in relation to the domain structure.     

Orientation controlling of Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> thin films prepared on silicon substrates with the thickness of La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> electrodes

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on La_0.5Sr_0.5CoO₃ (LSCO) coated Si substrates by a sol–gel route. The thickness of LSCO electrode was found to modify the preferential orientation of PZT thin films, which consequently affected the dielectric and ferroelectric properties. (100) textured PZT films with dense columnar structure could be obtained on the top of (110) textured LSCO with thickness of 230 nm. PZT thin films prepared on the optimized LSCO films exhibit the enhanced dielectric constant and remnant polarization of 980 and 20 μC/cm², respectively.     

Effects of preferred orientation on the piezoelectric properties of Pt/Pb(Zr0.3Ti0.7)O3/Pt thin films grown by sol–gel process

Tetragonal lead zirconate titanate (PZT) films with different orientations and 200 nm film thicknesses were prepared on platinized silicon substrates. Types of substrate and control of thermal processes, such as layer-by-layer and one-crystallization heat treatments, result in highly (111) or (100)-oriented PZT films. The piezoelectric, dielectric, and ferroelectric properties of polycrystalline PZT films have been investigated as a function of preferred orientation. The property difference between (111) and (100)-oriented films appears to be induced by the effect of ferroelastic domain existence (90° domain in tetragonal composition). From a modified phenomenological equation, the higher electrostrictive coefficient value of 5.6 × 10⁻² m⁴/C² for (100)-oriented PZT may be responsible for the larger piezoelectric coefficients in (100)-oriented polycrystalline PZT films of 44 pm/V in comparison to (111)-oriented PZT films with about 3.1 × 10⁻² m⁴/C² of Q ₃₃ and 40 pm/V of d _33,f . It was also observed that two (100)-oriented films prepared by different heat treatments showed different values in piezoelectric, dielectric, and ferroelectric properties even though only (100) orientation was characterized for both cases. This process-induced difference may also play an important role in determining both intrinsic and extrinsic contribution to the properties, even though these parameters seem to be more responsible for extrinsic components, such as domain wall motion.     

Pb(Zr0.52Ti0.48)O3/TiNi multilayered heterostructures on Si substrates for smart systems

Ferroelectric/shape memory alloy thin film multilayered heterostructures possess both sensing and actuating functions and are considered to be smart. In this article, Pb(Zr_0.52Ti_0.48)O₃ (PZT) ferroelectric thin films and Ti-riched TiNi shape memory alloy thin films have been deposited on Si and SiO₂/Si substrates in the 400-600 °C temperature range by pulsed laser deposition technique. Deposition processing, microstructure and surface morphology of these films are described. The TiNi films deposited at 500 °C had an austenitic B2 structure with preferred (110) orientation. The surfaces of the films were very smooth with the root-mean-square roughness on a unit cell level. The structure of the TiNi films had a significant influence on that of the subsequently deposited PZT films. The single B2 austenite phase of the TiNi favored the growth of perovskite PZT films. The PZT/TiNi heterostructures with the PZT and TiNi films respectively deposited at 600 and 500 °C exhibited a polarization-electric field hysteresis behavior with a leakage current of about 2 × 10^− 6 A/cm².     

Thickness-dependent electrical properties of sol–gel derived Pb(Zr0.52Ti0.48)O3 thick films using PbTiO3 buffer layers

Pb(Zr_0.52Ti_0.48)O₃ (PZT) thick films, with thickness up to 4 μm, using PbTiO₃ (PT) buffer layers were successfully prepared on silicon-based substrates by a sol–gel method. Thermal analysis (thermogravimetric–differential thermal analysis) of PT and PZT sols were used to determine the pyrolysis and annealing temperatures. X-ray diffraction results show that the PZT/PT composite thick films possess perovskite structure and the dominant crystalline orientation changes from (100) to (110) with increasing the film thickness. Furthermore, the composite thick films exhibit thickness-dependent ferroelectric and dielectric properties, i.e., the coercive field decreases while dielectric constant increases as the thickness increases. Theoretical analysis shows that the thickness-dependent electrical properties are mainly attributed to the low dielectric constant of PT buffer layer and the relaxation of internal stress in PZT films.     

Damping properties of epoxy-based composite embedded with sol–gel-derived Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> thin film annealed at different temperatures

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on Pt/Ti/SiO₂/Si substrate by sol–gel method. The effect of annealing temperature on microstructure, ferroelectric and dielectric properties of PZT films was investigated. When the films were annealed at 550–850 °C, the single-phase PZT films were obtained. PZT films annealed at 650–750 °C had better dielectric and ferroelectric properties. The sandwich composites with epoxy resin/PZT film with substrate/epoxy resin were prepared. The annealing temperature of PZT films influenced their damping properties, and the epoxy-based composites embedded with PZT film annealed at 700 °C had the largest damping loss factor of 0.923.     

Effect of annealing ambient on structure and ferroelectric properties of Pb(Zr0.4Ti0.6)O3 thin films on LaNiO3 coated Si substrates

Pb(Zr_0.4Ti_0.6)O₃ [PZT(40/60)] thin films were deposited onto LaNiO₃ (LNO) coated Si substrates by sol-gel technique. Three kinds of gases, air, O₂ and N₂, were used as the annealing ambient. The effect of the annealing ambient on their structure and ferroelectric properties was investigated. The results showed that both the films annealed in air and O₂ were the complete perovskite phase with (1 0 0) preferential orientation, while those annealed in N₂ were random orientation including some pyrochlore phases. As compared with the air ambient, either too much O₂ or too much N₂ was detrimental to the ferroelectric properties of PZT films. The difference in structure and ferroelectric properties was mainly associated with the intermediate phases and the concentration of domain pinning centers in the films.     

Effect of heat-treatment on LaNiO3 film electrode of PZT thin films derived by a sol–gel method

Lanthanum nickel oxide (LaNiO₃ or LNO) conducting thin films that could be used as electrodes for improving fatigue and aging properties of ferroelectric thin films were investigated. In this paper, LNO films were directly spin-coated onto SiO₂/Si(1 0 0) substrates followed by thermal treatment in air and in oxygen. It was found that crack-free dense and uniform films with good crystallinity and medium grains were obtained, preferentially (1 0 0)-oriented LNO thin films could be formed at a lower annealing temperature of 550 °C and that with the increase in thermal annealing temperature the LNO thin film possessed better electrical properties especially at 750 °C. However, the LNO film displayed a structure transformation above 850 °C. A phenomenon was found that the first heat-treatment temperature and time played a key role to determine the crystallite size of LNO films. A subsequent deposition of a sol–gel derived Pb(Zr_0.53Ti_0.47)O₃ (PZT53/47) thin film on the LNO-coated SiO₂/Si(1 0 0) substrates was also found to have a (1 0 0)-oriented texture. Moreover, the Au/PZT/LNO capacitor was found to significantly improve the fatigue and the effects of the LNO electrodes to the fatigue were discussed.