Pulse-Extended Excimer Laser Crystallisation of Pb(Zr,Ti)O 3 Thin Films for Integration on Low Thermal Budget Substrates

Excimer laser annealing has been used to convert low temperature (non-ferroelectric) deposited lead zirconate titanate (PZT) to the perovskite phase without significantly heating underlying layers. A pulse-extension technique has been used to lengthen the laser pulse duration from 25 ns to 374 ns, lowering the surface temperature and improving the heat distribution in the PZT, as compared to the non-extended case, but still not significantly heating the substrate. Initial experiments are reported which have shown the technique to be capable of crystallising over half a 500 nm thick PZT film to perovskite although a melting effect limited the converted thickness. The thickness crystallised is however of the order of that used in FeRAM devices and modelled temperature profiles suggest that the technique provides a tractable solution for high temperature processing of ferroelectric thin films of thickness 200-300 nm on low thermal budget substrates.     

Pb(Zr,Ti)O3 thin film growth on yttrium-treated Si(100)

Abstract

Pulsed laser ablation has been used to deposit ferroelectric Pb(Zr, Ti)O₃ (PZT) thin films on Si(100) and on yttrium-treated Si(100) substrates. The yttrium (Y) treatment of a Si surface followed by oxidation resulted in formation of a very thin, Y-enhanced SiO₂ antidiffusion barrier layer, thereby suppressing the undesirable PZT/Si interdiffusion. The best PZT film grown on Y-treated Si(100) had a breakdown voltage of 0.6 MV/cm, a coercive field of 71 KV/cm, and a remanent polarization of 18 μC/cm².     

Preparation of Pb(Zr,Ti)O3 Thin Films on Silica Substrate by Metallo-Organic Decomposition

In this study, we report the deposition of crack-free transparent PZT films (up to ～859 nm) by metallo-organic decomposition (MOD) process on amorphous silica substrate. Effect of SrTiO₃ (STO) buffer layer on the growth behavior of PZT thin films deposited on SiO₂-coated silicon substrates was systematically studied. Perovskite phase, which cannot be formed directly on SiO₂/Si substrates, has been obtained when a thin STO film (～150 nm) was used as buffer layer. A SIMS examination indicates that the upward diffusion of Si-species into PZT layer is minimal, although downward diffusion of Pb-species into the SiO₂ layer is still observable.     

Dielectric, ferroelectric and ferromagnetic properties of 0.8PbFe0.5Ta0.5O3-0.2PbTiO3 ceramics

Lead based complex compounds, 0.8PbFe_0.5− Ta_0.5O₃-0.2PbTiO₃ (0.8PFT-0.2PT) ceramics, were prepared by the solid state reaction method, and the corresponding dielectric, ferroelectric and ferromagnetic properties were investigated. As the PT phase was added to the PFT phase, the Curie temperature of 0.8PFT-0.2PT ceramics increased. The ferroelectric P-E and ferromagnetic M-H hysteresis loops were observed at the same time. The ferroelectric properties depend on the formation of the perovskite 0.8PFT-0.2PT phase; however, the ferromagnetic properties depend on the formation of the pyrochlore Pb₃FeTaO₇ phase.     

Water-Immersible Micromachined Pb(Zr, Ti)O3 Thin Film Actuators

We demonstrate a water-immersible thin film lead zirconate titanate, Pb(Zr, Ti)O₃, [PZT] actuator, without special passivation layer, towards in-vivo or in-vitro scanning probe microscope (SPM) measurements of living cells in water or biological fluids. In order to be water-immersible, the electrodes need to be electrically insulated and the piezoelectric layer needs to be protected against direct water contact. This paper describes our design solution with a simple fabrication process for a water-immersible piezoelectric device, which separates the bottom electrode from the top electrode by having a narrow ditch covered with PZT film. The PZT film is then encapsulated with the top metal electrode without insulation layer. In this structure, the PZT is sandwiched between the top and bottom metal electrodes to prevent water permeation. The device is fabricated using lift-off processing for the bottom and top electrodes, sol-gel spinning for the PZT thin film and wet etching for the PZT patterning. The piezoelectric constant, d₃₁, is about –100 pC/N. The dielectric polarization and fatigue properties of the devices were measured in air and water. The spontaneous polarization, remnant polarization, coercive field and dielectric constant are 54 C/cm², 15 C/cm², 60 kV/cm and 1200, respectively. The polarization property of the device was unchanged in either air or water up to 1 × 10⁹ continuous cycles.     

Polarization Switching in (100)/(001) Oriented Epitaxial Pb(Zr, Ti)O3 Thin Films

Thin films made of (100)/(001)-oriented Pb(Zr, Ti)O₃ (PZT) were deposited by liquid-delivery metal-organic chemical vapor deposition on Ir/MgAl₂O₄/SiO₂/Si(100) substrates. For comparison, PZT thin films were also deposited on Ir/MgO(100) substrates. The X-ray scan spectra for the (202) reflections revealed that the PZT films have four-fold symmetry. It indicates that the PZT films were epitaxially grown as a cube-on-cube structure on both substrates. The switchable polarization (Q_sw) of the PZT capacitors on the silicon substrate was only 23 C/cm² at 1.8 V; however, Q_sw of PZT capacitors on MgO was 99 C/cm². In the case of PZT films deposited on silicon, the volume fraction of (001)-oriented domains (which contribute to polarization switching) was 15.1% (calculated from an XRD pattern). This result is due to the lower Q_sw of PZT capacitors on silicon. By piezoresponse-force microscopy, switchable and unswitchable domains could be identified by imaging color contrast, namely, (001) and (100) domains, respectively. Consequently, domain distribution of the PZT film on a silicon substrate indicates that the (001) domain exists in the (100) domain matrix.     

Slow Dielectric Relaxation in Pb(Zr,Ti)O3 and (Ba,Sr)TiO3 Ferroelectric Thin Films

An impedance analysis of Ni/Pb(Zr,Ti)O₃/Pt thin-film structures based on measurements at the frequencies from 100 Hz to 100 MHz, along with the data of Grazing Angles XRD, TEM and photo-electric study, is used to obtain electronic structure of the PZT thin films deposited by sol-gel method on silicone substrates. Both slow capacitance relaxation and charging/discharging currents versus time under step-voltage excitation have been studied in (Ba,Sr)TiO₃ thin films between SrRuO₃ electrodes.     

Pb(Mg1/3Nb2/3)0.97Ti0.03O3 Ferroelectric Thin Films, Deposited by Laser Ablation on TiN Bottom Electrodes

Pb(Mg_1/3Nb_2/3)_0.97Ti_0.03O₃ (PMNT) polycrystalline thin films were deposited on Titanium Nitride electrode at different temperatures by laser ablation, using a wavelength of 248 nm. The morphology of the films was analyzed by scanning electron microscopy (SEM). The nature of the ferroelectric layer-electrode interface is studied by transmission electron microscopy (TEM) as well as the effect of its characteristics in the performance of the multilayer system. The influence of the annealing temperature on the dielectric properties was studied by hysteresis and fatigue measurements.     

Multi-Step Growth of Oriented LiNbO 3 Thin Films

Highly-oriented LiNbO 3 thin films have been successfully synthesized through a refined 2-step growth process consisting of the successive use of a physical technique (r.f. sputtering) and a chemical one (pyrosol). Taking the strict control of processing parameters, a <001>-preferential out-of-plane orientation could be promoted on both <001>-Al 2 O 3 and <111>-Si substrates while the in-plane texture of the deposited layers was found to depend strongly upon the nature of the underlying templates.     

Ferroelectric Properties and Memory Characteristics of Pb(Zr0.52 Ti0.48)O3 Thin Films Crystallized by Hot Isostatic Pressing

Pb(Zr_0.52Ti_0.48)O₃ films with highly uniform c-axis orientation were fabricated on PbTiO₃ (PT)/ Pt(111)/SiO₂/Si(100) substrates by hot isostatic pressing (HIP) from the amorphous state. All the PZT samples HIP-treated 500°C for 1 h under gas pressures of 1.0–2.0 MPa showed the preferred (001) orientation with c-axis orientation, α > 0.80. The relative permittivity tended to decrease gently with increasing HIP pressure, whereas the dielectric loss increased almost linearly in the 1.5–100 MPa. The PZT sample treated at 1.5 MPa had a symmetric and slim hysteresis loop shape with a remanent polarization, P _r = 15 μ C/cm² and coercive field, E _c = 60 kV/cm. Both samples treated at 10 and 100 MPa exhibited almost the fatigue-free behavior that resisted degradation even after 3 × 10¹⁰ cycles.     

Influence of Post-Annealing on the Characteristics of Pb(Zr,Ti)O3 Thin Films Deposited by Liquid Delivery MOCVD Using a Cocktail Solution

Ferroelectric PZT thin films were deposited by liquid delivery MOCVD using a cocktail solution. The cocktail solution consisted of Pb(METHD)₂, Zr(METHD)₄ and Ti(MPD)(METHD)₂ diluted with ethylcyclohexane. The films deposited on Pt/Ti/SiO₂/Si at a substrate temperature of 500°C consisted of PZT, PbO and PbPt_x, and showed poor properties. However, after annealing at 450°C in air for thirty minutes, the PbPt_x phase disappeared while the volume of the PbO phase increased. The hysteresis properties were also improved by annealing at 450°C. After annealing at 600°C in air for thirty minutes, the PbPt_x and the PbO phases disappeared perfectly and the PZT thin films showed good hysteresis properties with the remanent polarization of 30 μC/cm² and the coercive field of 88 kV/cm.     

Preparation of Textured Growth Pb(Zr,Ti)O3 Thin Films on Si Substrate Using SrTiO3 as Buffer Layers

PZT thin films are deposited on SiO₂/Si substrate by metallo-organic decomposition (MOD) process, using SrTiO₃ (STO) as buffer layer for textured growth. The STO layers deposited on SiO₂/Si substrate by pulsed laser deposition process show (100)/(200) preferred orientation, whereas the STO buffer layer deposited on silica substrate using spin-coating technique show random orientation behavior. The use of STO as buffer layers enhanced the crystallization and the preferred orientations of the PZT films. The PZT on STO buffered SiO₂/Si substrates thus obtained possess high refractive index, (n)_PZT/STO = 2.1159, and are of good enough quality for optical waveguide applications.     

NiCr Alloy As Both Absorption Layer and Top Electrode onto Pb(Zr0.3Ti0.7)O3 Thin Films for Infrared Sensors

NiCr alloys prepared by dc magnetron sputtering are considered to apply simultaneously both the absorption layer and the top electrode on PZT thin films for infrared sensors. NiCr alloys deposited with dc powers of Ni 80 and Cr 50 W showed the most stable oxidation resistance even at 600°C in an oxygen ambient. They have a resistivity of approximately 70 μΩ-cm and a rms roughness of 2.0 nm in samples annealed at 600°C for 5 min in O₂. The NiCr/PZT/Pt capacitors showed a well-saturated hysteresis loop having a remanent polarization of 20 μC/cm². Ultra-thin NiCr alloys showed a possibility as a top electrode for infrared sensors.     

Electro-Optic Properties of Heteroepitaxial Pb(Zr,Ti)O3/La0.5Sr0.5CoO3 Film Structures

Vertical ferroelectric Pb(Zr,Ti)O₃ (PZT) 1 μm thick film capacitor was fabricated by pulsed laser deposition technique (PLD) onto conducting La_0.5Sr_0.5CoO₃(LSCO) 100 nm thick bottom electrode on both side polished YAlO₃ + 1% Nd₂O₃ (Nd:YAlO₃) single crystal substrate to operate as a Pockels cell optical modulator. On top of the PZT film, semitransparent 30 nm thick Au electrode was deposited by thermal evaporation. Intensity of the chopped 670 nm polarized laser radiation transmitted through the Au/PZT/LSCO/Nd:YAlO₃ cell was measured at various temperatures and bias voltage applied. Applying 20 V (200 kV/cm) across the capacitive cell, modulation of the transmitted light as high as 3% was achieved while the voltage tunability measured at 1 kHz from C-V characteristics was about 70%. Thermo-optical measurements performed for PZT/Nd:YAlO₃ sample in the range up to 400°C showed the phenomenon of critical opalescence in the vicinity of Curie temperature at 208°C. Optical transmission through the PZT film biased with electric field was studied in the range 400 to 1000 nm. Film thickness, refraction index and absorption coefficient have been determined from the interference pattern observed in the PZT transmission spectrum. A simple model yields the dispersion relation for the electro-optic coefficient.     

Investigation on the Dielectric and Polarization Behavior of Sol-Gel Derived Erbium Doped Pb(Zr 0.53 Ti 0.47 )O 3 Thin Films

We have studied the effect of Er 3+ doping on the dielectric and polarization hysteresis behavior of sol-gel derived Pb 1.05 (Zr 0.53 Ti 0.47 )O 3 thin films. Up to 1 at% Er doping, the dielectric constant of undoped PZT increases from 1245 to 1477 (measured at 50 kHz, 500 mV oscillation voltage), whereas the remnant polarization increases from 30 to 41 w C/cm 2 . Under the subswitching external field, the dielectric permittivities follow the Rayleigh law. The Rayleigh coefficient ( f ) was considered as a measure of the ease of domain wall motion. Up to 1 at% Er doping, the increase of f indicates minimal defect-domain wall interaction due to lower defect concentration. Under the switching field, the irreversible part of the switchable polarization was estimated from the C-V and hysteresis measurements. At the saturation field it was observed that up to 1 at% Er doping the irreversible component at switchable polarization increases and reversible component remains low. The improvements of dielectric and ferroelectric properties for up to 1 at% Er doping have been correlated to the relative site occupancy of Er 3+ as a function of Er content in PZT host lattice.     

Piezoelectric and Pyroelectric Properties of Pb(Zr,Ti)O3 Films for Micro-Sensors and Actuators

The piezoelectric and the pyroelectric properties of PZT films are systematically investigated for tetragonal (Zr/Ti = 30/70), morphotropic (52/48), and rhombohedral (70/30) compositions. The magnitude of the effective longitudinal piezoelectric coefficient (d₃₃) and pyroelectric coefficient (p) of these films is measured by atomic force microscopy and Byer-Roundy method, respectively. All films are consistently highly textured (111) orientation and have dense microstructures. Slightly less degree of texture in higher Zr-rich composition is observed due to the lattice mismatch between PZT and Pt bottom electrode and higher activation energy for nucleation. Squareness of polarization hysteresis loops is optimized in tetragonal composition, which indicates the tetragonal PZT is closer to the ideal hysteresis behavior than other compositions. It is shown that the piezoelectric coefficient and the pyroelectric figure of merit are dependent on the dielectric properties of the films. The morphotropic PZT films with high dielectric constant and low pyroelectric figure of merit show the largest piezoelectric coefficient values, while the tetragonal PZT films with low dielectric constant and high remanent polarization values show the largest pyroelectric figure of merit compared to other compositions, which indicate the suitability for PIR sensor devices.     

Bilayered Pb(Zr,Ti)O3/(Bi,Nd)4Ti3O12 thin films

Bilayered thin films consisting of Pb(Zr_0.52Ti_0.48) O₃ (PZT) and (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) layers are successfully deposited on Si(100)/SiO₂/Ti/Pt substrate by a combined process involving sol-gel and RF-sputtering. Their dielectric properties cannot be described by the simple rule of mixture on the basis of the series connection model. There occurs a dielectric layer of lower dielectric permittivity in the bilayered thin film, which degrades the polarization behaviors. The bilayered film gives rise to an improvement in fatigue resistance up to 10¹⁰ switching cycles. Moreover, the domain pinning effect after polarization switching is reduced greatly as compared to that of single layered PZT and BNT thin films.     

Self-polarization effect in Pb(Zr,Ti)O3 thin films

Abstract

The self-polarization effect is investigated in Pb(Zr,Ti)O₃ (PZT) thin films deposited by sol-gel and magnetron sputtering techniques. The effective piezoelectric coefficient of as-grown films, which is proportional to their initial polarization (self-polarization), is measured by a sensitive interferometric technique as a function of the annealing temperature, PZT composition, film thickness and bottom electrode material. The results indicate that the films are self-polarized by an internal bias field upon cooling through the phase transition temperature. It is suggested that a built-in field of a Schottky barrier between the PZT film and the bottom electrode is responsible for the observed effect. Self-polarization of the films is found to be very stable and in some cases to be as high as 90% of that produced by the subsequent room temperature poling. This property is very useful for piezoelectric and pyroelectric applications of PZT films since the poling procedure can be avoided. The properties of self-polarization are found to be similar for the films produced by sol-gel and sputtering techniques, suggesting that the same mechanism is operative in both cases.     

Bilayered Pb(Zr,Ti)O3/(Bi,Nd)4Ti3O12 thin films

Bilayered ferroelectric thin films consisting of Pb(Zr_0.52Ti_0.48)O₃ (PZT) and (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) have been successfully synthesized on Pt/Ti/SiO₂/Si substrates, via a combined sol–gel and rf-sputtering route. Their ferroelectric and dielectric properties are critically dependent on the phases present, film texture and in particular layer and film thicknesses. Due to the coupling of PZT and BNT bilayers, there requires an optimized thickness combination of the two ferroelectric layers, in order to give rise to the wanted ferroelectric and dielectric properties, while the phenomenon can not be accounted for by the simple series connection model.     

Orientation Control of (Bi,La) 4 Ti 3 O 12 Thin Films by Addition of Silicates and Germanates

Orientation of crystallites in (Bi,La) 4 Ti 3 O 12 (BLT) thin films were successfully controlled by adding such silicates and germanates as Bi 2 SiO 5 , ZrSiO 4 and La 2 GeO 5 . The ferroelectric films were formed by spin-coating mixed sol-gel solutions of BLT and silicate or germanate on a Pt/Ti/SiO 2 /Si structure. It was found from XRD analysis that the preferred orientation of crystallites in the BLT films was changed by the additives. That is, the orientation of crystallites in a Bi 2 SiO 5 -added BLT film was random, while it was almost perfectly c-axis-oriented in La 2 GeO 5 -added BLT and it was strongly (117)-oriented when ZrSiO 4 was added to BLT. It was also found that the remnant polarization and coercive field changed reflecting these different orientations.