Control of ferroelectric and linear piezoelectric response of PZT films through texture

The high and low field ferroelectric response of freestanding PbZr_0.52Ti_0.48O₃ (PZT) films, with texture varying from 100% (001) to 100% (111) was investigated via 500 nm thick PZT unimorphs deposited on the same substrate. It is shown that the ferroelectric and piezoelectric properties depend strongly on texture, and the effective transverse strain and stress coefficients vary linearly with %(001) and %(111) texture factors. PZT films with 100% (001) orientation displayed 150%, 140%, and 80% larger linear piezoelectric strain coefficient, saturated strain coefficient, and saturated stress coefficient, respectively, compared to films with 100% (111) orientation. As a result, pure (001) textured PZT films with 20% higher dielectric constant have 50% higher figure of merit in sensing than films with pure (111) texture. The piezoelectric and ferroelectric properties of all but one combinations of (001) and (111) texture were shown for the first time to be bounded by the values for 100% (001) and 100% (111) texture. A notable exception was PZT films comprised of 73% (001) and 27% (111) texture which showed stable piezoelectric coefficients at all electric fields, with major technological implication to low power microdevices. Finally, the coercive field was shown to decrease with (001) texture factor and excess‐Pb in the PZT and the PbTiO₃ seed layer.     

Rapid Microwave Annealing of Amorphous Lead Zirconate Titanate Thin Films Deposited by Sol‐Gel Method on LaNiO3/SiO2/Si Substrates

The heating behavior of LaNiO₃ (LNO) films on SiO₂/Si substrate heated by 2.45 GHz microwave irradiation in the microwave magnetic field was first investigated, and then amorphous Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were deposited on LNO‐coated SiO₂/Si substrates by a sol‐gel method and crystallized in the microwave magnetic field. The crystalline phases and microstructures as well as the electrical properties of the PZT films were investigated as a function of the elevated temperature generated by microwave irradiation. The perovskite PZT films with a highly (100)‐preferred orientation can be obtained by microwave annealing at 700°C for only 180 s of total processing time, and have good electrical properties. The results demonstrated that conductive metal oxide LNO as a bottom electrode layer is an advantage for the crystallization of PZT thin films by microwave irradiation in the microwave magnetic field.     

Design,synthesis, microstructure and electrical properties of thermal-strained PZT films

The integration units with functional and structural material components have been developed largely recently. In the present study, 200 nm-thick polycrystalline PbZr_0.52Ti_0.48O₃ (PZT) films with a dense columnar structure were grown on LaNiO₃ (LNO) buffered heat-resistant steel substrates via a low-cost chemical solution approach. The behavior of the functional PZT films when combined with the structural steel was investigated mainly by TEM and electrical measurement. A large in-plane compressive stress was obtained in the PZT films due to the thermal expansion mismatch of about 88.2 % between the thin films and the steel substrates, which intensifies the orientation of the films toward c-axis. Sub-10 nm 90° nanodomains were alternately distributed in [001] grains which is beneficial to the piezoelectric performance, and the equivalent d₃₃ value is ～44.4 pm V^?1. A remnant polarization (P_r) of ～67.3μC/cm² and a dielectric constant of ～425 were obtained. The enhanced electrical properties are associated with the stress-induced improved c-axis spontaneous polarization and crystal orientation in the hybrid system. This work may provide a theoretical basis for further integrating functional elements into metallic materials, which is valuable for covering the gap between academic research and industrial mass production.     

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.     

The influence of chemical passivation on the PZT/Pt electrode interface

It has been recognized that the interdiffusion of atomic species between a PZT film and the Pt bottom electrode leads to the gradual degradation of a PZT capacitor. In order to prevent this interdiffusion, experimental studies on chemical passivation to the bottom electrode surface were carried out by the sulfurization method. It was observed that a sulfur layer was built up on the Pt substrate with small grains, which resulted in a structural change at the Pt surface. Atomic force microscopy (AFM) showed that the film roughness of the Pt surface was increased by sulfur treatment. Pb(Zr_0.5Ti_0.5)O₃(PZT) thin films were prepared on a Pt/Ti/SiO₂Si bottom electrode by spin-coating techniques. The microstructure and the preferred orientation of the PZT films were shown to depend on the sulfur-treated electrode. The PZT capacitor on a clean Pt electrode was confirmed to be ferroelectric with Pr=17.7 μC/cm² and Ec=65 kV/cm from the P-E hysteresis curves. The fatigue behavior of a PZT film capacitor prepared on a sulfur-treated one was observed to be relaxed, but the absolute value of Pr was paid off.     

Voltage effect of corona poling on characteristics of PbZrxTi1−xO3 (PZT) film

The paper investigates the voltage effect of corona poling on the characteristics of PbZr_xTi_1−xO₃ (PZT) thin film. Purchased PZT powder and lab-made PZT solution were mixed together as sol-gel that was spin-coated on titanium (Ti) substrate. X-ray diffractometer (XRD), scanning electron microscopy (SEM), impedance analyzer were utilized to measure the orientation and dielectric characteristics of films for comparison. The experimental results indicated that the poling voltage would not affect the orientation of crystallization, microstructure and grain size of PZT film surface. However, the higher applied poling voltage would result in better charge storage capacity and energy transfer efficiency of the film.     

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.     

PZT thick films on LTCC substrates with an interposed alumina barrier layer

PZT thick films (PbZr_0.53Ti_0.47O₃ with the addition of 6% PbO and 2% Pb₅Ge₃O₁₁) with a low sintering temperature were printed and fired on LTCC substrates (951, Du Pont), covered with an alumina barrier layer. The electrical characteristics (remanent polarisation, coercive field, dielectric constant and dielectric loss) of these PZT thick films, together with sets prepared on “unprotected” LTCC substrates and on alumina substrates were compared. Whereas the electrical characteristics of the films on LTCC substrates deteriorated significantly due to interactions between the LTCC substrates and the PZT layers the values obtained for the LTCC/alumina barrier structures were comparable with those on ceramic alumina substrates.     

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.     

The effect of imprint on remanent piezoelectric properties and ferroelectric aging of PbZr0.52Ti0.48O3 thin films

Ferroelectric films suffer from both aging and degradation under high ac-field drive conditions due to loss of polarization with time. In this study, the roles of defect chemistry and internal electric fields on the long-term stability of the properties of piezoelectric films were explored. For this purpose, lead zirconate titanate (PZT) films with a Zr/Ti ratio of 52/48 doped with Mn- (PMZT) or Nb- (PNZT) were deposited on Pt coated Si substrates by the sol-gel method. It was demonstrated that the magnitude of the internal field is much higher in PMZT films compared to PNZT films after poling in the temperature range of 25-200°C under an electric field of −240 kV/cm. The development of the internal field is thermally activated, with activation energies from 0.5 ± 0.06 to 0.8 ± 0.1 eV in Mn doped films and from 0.8 ± 0.1 to 1.2 ± 0.2 eV in Nb doped films. The different activation energies for imprint suggests that the physical mechanism underlying the evolution of the internal field in PMZT and PNZT films differs; the enhanced internal field upon poling is attributed to (a) alignment of oxygen vacancy—acceptor ion defect dipoles (, ) in PMZT films, and (b) thermionic injection of electron charges and charge trapping in PNZT films. In either case, the internal field reduces back switching, enhances the remanent piezoelectric properties, and dramatically improves the aging behavior. PMZT films exhibited the greatest enhancement, with reduced high temperature (180°C) aging rates of 2%-3%/decade due to improved stability of the poled state. In contrast, PNZT films showed significantly larger high temperature aging rates (15.5%/decade) in the piezoelectric coefficient, demonstrating that the fully poled state was not retained with time.     

Effect of Nb and K doping on the crack propagation behaviour of lead zirconate titanate ceramics

In the present study, we investigated the effect of doping on the crack propagation behaviour of lead zirconate titanate ceramics (PZT), particularly crack growth resistance and slow crack growth. Three PZT grades were processed: an undoped PZT, a soft PZT doped with niobium, PNZT, and a hard PZT doped with potassium, PKZT. The composition was chosen close to that of the morphotropic phase boundary (MPB), known to give excellent electromechanical properties. The soft material showed an important crack growth resistance and its slow crack growth curve V–K_I (crack velocity versus stress intensity factor, K_I) is shifted toward higher values of K_I. The results are discussed in terms of toughening due to ferroelastic domain switching under mechanical loading.     

Effect of rare earth doping on sol-gel derived PZT thin films

We have studied the effect of rare earth dopants (Nd, Gd and Ce) on the phase formation behavior and electrical properties of sol-gel derived Pb_1.05(Zr_0.53Ti_0.47)O₃ thin films. In all these films the perovskite phase is obtained up to 5 at% doping and beyond that pyrochlore phase was found to coexist with the perovskite phase. Ce and Gd doping(1-2 at%) exhibited improved ferroelectric and dielectric properties as compared to the undoped PZT films. Nd doping (2 at%) was found to be effective to increase the retained switchable polarization of undoped PZT from 63% to 84%. The transition temperature of undoped PZT film was found to be reduced with Nd doping. The Nd doped films also exhibited typical relaxor behavior and a diffuse phase transition, characteristic of the relaxor material. Introduction of Nd into the PZT lattice probably introduces disorder in the B site of ABO₃ lattice which causes the observed relaxor behavior     

Ferroelectric properties of PZT/BFO multilayer thin films prepared using the sol-gel method

In this study, Pb(Zr_0.52Ti_0.48)O₃/BiFeO₃ [PZT/BFO] multilayer thin films were fabricated using the spin-coating method on a Pt(200 nm)/Ti(10 nm)/SiO₂(100 nm)/p-Si(100) substrate alternately using BFO and PZT metal alkoxide solutions. The coating-and-heating procedure was repeated several times to form the multilayer thin films. All PZT/BFO multilayer thin films show a void-free, uniform grain structure without the presence of rosette structures. The relative dielectric constant and dielectric loss of the six-coated PZT/BFO [PZT/BFO-6] thin film were approximately 405 and 0.03%, respectively. As the number of coatings increased, the remanent polarization and coercive field increased. The values for the BFO-6 multilayer thin film were 41.3 C/cm² and 15.1 MV/cm, respectively. The leakage current density of the BFO-6 multilayer thin film at 5 V was 2.52 × 10^-7 A/cm².     

Metalorganic chemical vapor deposition of ferroelectric Pb(ZrxTi1- xO3thin films

Ferroelectric Pb(Zr_xTi_1-x)O₃ (PZT) thin films were successfully deposited on Pt/Ti/SiO₂Si substrates by metalorganic chemical vapor deposition (MOCVD). Pb(C₂H₅)₄, Zr(O-t-C₄H₉)₄, and Ti(O-i-C₃H₇)₄ were used as metalorganic precursors. Variations in crystalline structure, surface morphology, and grain size of deposited films were systematically investigated as a function of process parameters by using X-ray diffraction and scanning electron microscopy. The deposition temperature and gas composition in the reactor are the main parameters that control the microstructure and composition of films. An interrelationship between the grain orientation and surface roughness of the films was found. Films with (111) preferred orientation are significantly smoother than films with other preferred orientations. The ferroelectric properties of the films were also measured by RT66A ferroelectric tester for hysteresis loop and fatigue property. Electrical measurements revealed that the films had good ferroelectric characteristics with the high remanant polarization (32 μC/cm₂) and low coercive voltage (1.1 V).     

Thermally stimulated depolarization current measurements on degraded lead zirconate titanate films

Charge transport mechanisms governing DC resistance degradation in ferroelectric films are influenced by defects, particularly oxygen vacancies. This paper demonstrates that oxygen vacancies migrate in lead zirconate titanate (PZT) films under a DC bias field and contribute to resistance degradation. Model PZT thin films were developed in which the concentration and distribution of oxygen vacancies were controlled via (a) changing the dopant type and concentration from 1%–4% Mn (acceptor) to 1%–4% Nb (donor) or (b) annealing undoped PZT films at varying partial pressures of PbO. The presence of associated (immobile) and dissociated (mobile) oxygen vacancies was distinguished by thermally stimulated depolarization current (TSDC) measurements. The impact of mobile oxygen vacancies on local defect chemistry and associated charge transport mechanisms was explored by electron energy loss spectroscopy (EELS). For Mn-doped PZT films, following resistance degradation, TSDC studies revealed only one depolarization peak with an activation energy of 0.6–0.8 eV; this peak was associated with ionic space charge presumably due to migration of oxygen vacancies. The magnitude of the depolarization current peak increased with increasing degradation times. A similar depolarization current peak attributed to the existence of mobile oxygen vacancies was also observed for undoped and Nb-doped PZT films; the magnitude of this peak decreased as the Nb or PbO contents in PZT films increased. An additional TSDC peak associated with polaron hopping between Ti³⁺ and Ti⁴⁺ was found in both Nb-doped PZT films and undoped PZT films annealed under low PbO partial pressure. Degraded Nb-doped samples exhibited a chemical shift in the TiL_2,3 peak to lower energy losses and the appearance of shoulders on the t_2g and e_g peaks, implying a reduction of Ti cations in regions near the cathode.     

Hysteretic properties of Mn-doped Pb(Zr,Ti)O3 thin films

Pb(Zr,Ti)O₃ (PZT 30/70) and Mn-doped Pb(Zr,Ti)O₃ (PMZT 30/70) thin films have been fabricated on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition technique. The experiments found that the addition of Mn in PZT thin films greatly improves the ferroelectric properties of thin films. It is demonstrated that the Mn-doped (1 mol%) PZT showed fatigue-free characteristics at least up to 10¹⁰ switching bipolar pulse cycles under 10 V and excellent retention properties. The Mn-doped PZT thin films also exhibited well-defined hysteresis loops with a remnant polarization (Pr) of 34 μC/cm² and a coercive field (Ec) of 100 kV/cm for the thickness of 300 nm. Dielectric constant and loss (tanδ) for Mn doped PZT thin films are 214 and 0.008, respectively. These figures compare well with or exceed the values reported previously. In this paper, the mechanism by which Mn influences on the ferroelectric properties of PZT thin films has also been discussed.     

Fabrication and function examination of PZT-based MEMS accelerometers

In this study, a hybrid sol-gel method was used to fabricate Pb(Zr_0.52Ti_0.48)_0.98Nb_0.02O₃ (PNZT) piezoelectric thick films. By preparing Pb(Zr_0.52Ti_0.48)_0.98Nb_0·02O₃ sol-gel solutions and mixing them with PZT-5A piezoelectric powders, therefore, the thickness of single layer coating can be increased and reduce the risk of film cracks. The proposed PNZT films have the dielectric constant of 1750, dielectric loss of 0.063, remnant polarization of 58 μC/cm², and d₃₃ of 133 p.m./V. Piezoelectric cantilever beam MEMS accelerometers were then designed, simulated and fabricated via photolithography methods on Si substrates. The sensitivity and natural frequency of the cantilever beam accelerometer are 16.8 mV/g and 200Hz, respectively. Finally, a cantilever beam accelerometer is successfully applied for the server hard-drive fault detection.     

Effect of electrode interfaces on peak-drift switching current of PZT thin films

In this study, we investigated the impact of electrodes on the structural, crystal orientation, and electrical characteristics of lead zirconate titanate [Pb(Zr_0.52Ti_0.48)O₃, PZT] thin films, that were deposited on Pt, Au, and LaNiO₃ (LNO) electrodes through sol-gel processes. The peak voltage, that is, the voltage corresponding to the maximum switching current point, was developed to depict the novel peak-drift electric characteristics in ferroelectric thin films. It increases in the positive ferroelectric peak voltage, and decreases in the negative peak voltage with an increase in the driving voltage amplitude. Based on space-charge-limited bulk conduction, we evaluated the peak-drift phenomenon, Schottky contact and their influences on the switching current. When polarization orientation is reversed, the Schottky contact disappears at one side of the PZT/electrode, and forms at the other side synchronously. Our results indicate that the formation of a Schottky contact affects the shape of the switching curves, and its disappearance influences the magnitude of the current characteristics.     

Lead germanium oxide sinter-assisted PZT composite thick films

Thick films of niobium doped lead zirconate titanate (PNZT) were prepared from a sol-gel/PZT powder composite slurry. The effects of adding different amounts of sol-gel derived lead germanium oxide (PGO) as sintering aid were examined. Four layers of composite, with intermediate sol infiltrations, were deposited by spinning onto Pt/Ti/SiO₂/Si substrates followed by drying and annealing. Addition of PGO enhanced the densification process at a temperature as low as 770 °C. It resulted in an increase in the film properties that depended upon the level of PGO addition. Film properties were assessed by measuring the capacitance and dielectric loss. d_33,f and e_31,f piezoelectric coefficient measurements were carried out after poling at 10 V/μm for 5 min at 130 °C. A maximum relative permittivity of 500 was observed between 5 and 8 wt.% PGO addition. The maximum in d_33,f was found to be about 40 pC/N. Additions between 7 and 10 wt.% PGO led to the maximum e_31,f piezoelectric coefficient of about −1.5 C/m².     

Microwave enhanced sintering of tape-cast ferroelectric films

Porous Pb(Zr_xTi_1−x)O₃(PZT) thick films that had been prepared by tape casting were densified by microwave energy. The microwave absorption effect is substantially correlated with the film thickness. In microwave-processed PZT thick films, rapid particle necking causes densification with no grain growth nearly in a short treatment time of 20 min at 820 °C. The same porous PZT thick films are difficult to densify in a conventional process. A 30-μm-thick PZT thick film has a pure perovskite structure. Self-supporting PZT thick films with a crack-free and uniform microstructure formed in a microwave process have larger coercive field than conventionally processed bulk PZT. The polarization, 14 μC/cm², of PZT thick films in a microwave process exceeds that, 7 μC/cm², of PZT bulk formed in a conventional process.