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.     

Epitaxial La0.5Sr0.5CoO3 electrode films for ferroelectric device applications

Abstract

We have grown high quality La_0.5Sr_0.5CoO₃ thin films by Pulsed Laser Deposition. This material is a electrically conducting perovskite which can be used as structurally compatible electrodes for devices using ferroelectric materials such as Pb-La-Zr-Ti-O (PLZT). Oxygen stability was investigated under various annealing conditions. LSCO/PLZT/LSCO heterostructures were grown epitaxially on SrTiO₃ (STO) and MgO substrates. P-E hysteresis loop was observed with P_r = 20 μC/cm² and E_c = 24 kV/cm. Direct observation of the piezoelectric effect in PLZT was made by measuring the PLZT c-axis lattice constant under various electric fields. LSCO/STO superlattice was also grown by PLD. The superlattice showed excellent crystallinity with a Rutherford Backscattering (RBS) channeling minimum yield of only 3.6%.     

Effects of temperature on the ferroelectric properties of PbZr0.53Ti0.53O3-based capacitors prepared by pulsed laser-ablation deposition

Abstract

The effects of elevated temperature on the long and short term ferroelectric properties of La_0.5Sr_0.5Co₃(LSCO)/PbZr_0.53 Ti_0.47O₃(PZT)/La_0.5Co₃(LSCO) heterostructure capacitors are presented in this paper. Capacitors are evaluated in the temperature range of 25°C to 100°C. Polarization values (switched and non-switched), coercive voltages, and PZT resistivity are measured as a function of temperature. Rate of fatigue, tendency to imprint, and retention loss are also investigated in the 25–100°C temperature range. An activation energy for the process responsible for loss of remanent polarization is determined from the fatigue data.     

Preferentially oriented (La,Sr)CoO3/PbLa0.1TiO3 (La,Sr)CoO3 tri-layers on lithium-fluoride and sodium-chloride substrates

Abstract

(La, Sr)CoO₃/PbLa_0.1TiO₃/(La, Sr)CoO₃ tri-layers have been grown in situ using pulsed laser deposition on single crystal LiF and NaCl substrates because of their potential to serve as substrates and sacrificial layers for building suspended infrared detector structures. At growth temperatures around 525°C to 615°C and oxygen partial pressures of ∽25 mTorr, the LaSrCoO₃/PbLaTiO₃/LaSrCoO₃ tri-layers on LiF substrates exhibit preferential orientation, as indicated by x-ray diffraction data. The surface morphology of each successive layer is smooth, as shown in scanning electron microgram. Higher growth temperatures result in better orientations but suffer from substrate out-gassing, while lower growth temperatures lead to polycrystalline film growth. On the NaCl substrates, buffer layers, such as Pt and Pd, are necessary to achieve oriented films by suppressing severe substrate out-gassing at the growth conditions required for stoichiometric (La, Sr)CoO₃/PbLa_0.1TiO₃/(La, Sr)CoO₃ tri-layer growth.     

Fabrication and structural characterization of interdigitated thin film La1 − x Sr x CoO 3 (LSCO) electrodes

For the prospective use as micro-Solid Oxide Fuel Cell (μ-SOFC) cathodes and for the investigation of reaction kinetics, La_{1 − x}Sr_xCoO₃ (LSCO) mixed ionic electronic conducting thin films were deposited by DC and RF sputtering onto a number of different substrate materials and characterized. Standard photolithographic and wet chemical etching methods were utilized to microstructure the LSCO films and XRD, SEM, AFM, WDS, and RBS were used to characterize their structure, topography, and chemistry. Sputtering resulted in very homogeneous and smooth thin crystalline films with Sr deficiency and submicron sized grains. Hydrochloric acid was found to readily etch LSCO with the etching quality strongly dependent on substrate material. LSCO films were most easily etched when deposited directly on silicon substrates, etched at intermediate rates when deposited on Gd:CeO₂ films, and most resistant to etching after deposition onto single crystal yttria stabilized zirconia (YSZ) substrates. Imperfect etching was attributed to interface formation and the presence of impurities.     

Rapid Thermal Annealing of Oxide Electrodes for Nonvolatile Ferroelectric Memory Structures

We report on the properties of a ferroelectric stack comprising (La_0.5Sr_0.5)CoO₃ (LSCO)/Pb(Nb,Zr,Ti)O₃ (PNZT)/LSCO deposited on 4 inch diameter platinized Si wafers (Pt/Ti/SiO₂/Si). The LSCO electrodes were deposited at room temperature by pulsed laser ablation and the ferroelectric layer was deposited by the sol-gel technique. Rutherford backscattering was performed to confirm the uniformity in composition, thickness and stoichiometry of LSCO across the wafers. Conventional furnace or rapid thermal annealing was performed to crystallize the electrodes. The oxidation resistance of the conducting barrier layers, Pt/Ti, was found to be dependent on the annealing procedure adopted for the bottom electrode. In the case where the bottom LSCO was crystallized by rapid thermal annealing, Rutherford backscattering analysis and transmission electron microscopy studies revealed that there was no oxidation of the Pt/Ti conducting barrier composite. This is in contrast to the observations for in-situ deposition or conventional furnace annealing of the bottom electrode. The resistivity, coercive field and polarization of the ferroelectric stack were uniform across the 4-inch wafers. The ferroelectric capacitors showed no fatigue up to 10¹¹ cycles and no imprint at 100°C. The ferroelectric properties were independent of the annealing procedure used for crystallizing the electrodes.     

Effect of seed layer on electrical properties of Pb(Zr,Ti)O3 films grown by metalorganic chemical vapor deposition

Abstract

Pb(Zr_xTi_1?x)O₃ (PZT) ferroelectric thin films were prepared by metalorganic chemical vapor deposition (MOCVD) on Pt/Ti/SiO₂/Si substrate. Very thin PZT films, which were deposited at a lower temperature and post-annealed at higher temperature for crystallization, were used as a seed layer. PZT films grown on the seed layer exhibited superior characteristics in the crystalline structure and electrical properties, compared to those deposited without seed layer. Depending on the deposition conditions of PZT seed layer, a wide variation of surface morphology and stoichiometry was found between samples, whereas chemical composition was found to be very similar.     

Studies on Al-doped ZnO thin-film transistors with Pb(Zr0.3Ti0.7)O3 gate insulator

We report the fabrication of Al-doped ZnO thin-film transistors (FeFETs) on the ferroelectric Pb(Zr_0.3Ti_0.7)O₃ (PZT) gate insulator for the application of nonvolatile random access memory. The results demonstrate the basic principle of Al-doped ZnO resistive switching between the high and low resistive states upon the polarization switching of ferroelectric layer. Own to the good ferroelectric property and high reliability of PZT, such as fatigue, high speed of signal reading and writing, low coercive electric field, etc., this device has an excellent electrical performance. The memory device exhibits a source-drain current modulation with an ON/OFF current ratio close 10³.     

The Effect of La-Doped Bi4Ti3O12 Buffer Layer on Crystallinity and Ferroelectric Properties of PbZr0.58Ti0.42O3/Bi3.25La0.75Ti3O12 Multilayered Thin Films

PbZr_0.58Ti_0.42O₃ (PZT) ferroelectric thin films with Bi_3.25La_0.75Ti₃O₁₂ (BLT) buffer layer of various thickness were fabricated on Pt/TiO₂/SiO₂/p-Si(100) substrates by rf-magnetron sputtering method. The pure PZT film showed (111) preferential orientation in the XRD patterns, and the PZT/BLT films showed (110) preferential orientation with increasing thickness of the BLT layer. There were no obvious diffraction peaks for the BLT buffer layer, for its thin thickness in PZT/BLT multilayered films. There were the maximum number of largest-size grains in PZT/BLT(30 nm) film among all the samples from the surface images of FESEM. The growth direction and grain size had significant effects on ferroelectric properties of the multilayered films. The fatigue characteristics suggested that 30-nm-thick BLT was just an effective buffer layer enough to alleviate the accumulation of oxygen vacancies near the PZT/BLT interface. The comparison of these results suggests that the buffer layer with an appropriate thickness can improve the ferroelectric properties of multilayered films greatly.     

Epitaxial growth of multilayered (Bi,La)4Ti3O12/Pb(Zr,Ti)O3 ferroelectric thin films with different orientations

Epitaxial (Bi,La)₄Ti₃O₁₂ (BLT) thin films, epitaxial Pb(Zr,Ti)O₃ (PZT) thin films, and epitaxial multilayered BLT/PZT ferroelectric thin films with different orientations were prepared on SrTiO₃ (STO) single crystal substrates by pulsed laser deposition. From X-ray pole-figures and electron diffraction patterns, the epitaxial orientation relationships between BLT layers, PZT layers, and STO substrates were identified to be (1) BLT(001)//PZT(001)//STO(001), and BLT[110]//PZT[100]//STO[100] for the multilayered thin films on (001)-oriented STO substrates, and (2) BLT(118)//PZT(011)//STO(011), and $ {\text{BLT}}{\left[ {\overline{1} \overline{1} 0} \right]}//{\text{PZT}}{\left[ {100} \right]}//{\text{SrTiO}}_{3} {\left[ {100} \right]} $ for the multilayered films on (011)-oriented STO substrates. Tri-layered films of the same compositions showed well-defined hysteresis loops as well as a high fatigue resistance up to 1?×?10¹⁰ switching cycles.     

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.     

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.     

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.     

Effect of excess-PB and prenucleation layer on properties of Pb(ZryTi1-y)O3 thin films prepared by mod process

Abstract

A modified metal-organic decomposition process, MOD has been successfully utilized to improve the ferroelectric properties of Pb(Zr_0.52Ti_0.48)O₃, PZT, thin films. Multilayer PZT/Pt(Si) films, which contain 0.12 μm layer of spin coated PbO-excess (10 mol%) precursors on top of 0.12 μm layer of stoichiometric PZT precursors, exhibit superior ferroelectric properties (P_r=14.2 μC/cm²; E_c=62 kV/cm) to the single layer PZT/Pt(Si) films of the same thickness (0.24 μm), which are either stoichiometric or 10 mol% Pb-enriched. The ferroelectric properties are further improved when the PZT films were synthesized using a thin pulsed laser deposited (PLD) prenucleation layer (0.06 μm). The subsequently MOD-prepared PZT films posses high remanent polarization (P_r=23.2–26.6 μC/cm²) and low coercive field (E_c=62.9–69.0 kV/cm).     

PZT Capacitors on Top of CrTiN/TiN Double Barrier Layers

In this paper we investigated the thermal stability of a novel CrTiN/TiN double barrier, compared to those of TiN and CrTiN single layer barriers. The CrTiN/TiN double layer was stable against heat treatments at higher than 700°C in oxygen ambient for 30 min. However, the double layer showed a severe Pt and Cr interdiffusion issue after crystallization annealing for PZT. We found that pre-annealing treatments prior to deposition of Pt significantly reduced the interdiffusion. In addition, we also demonstrated ferroelectric characteristics of PZT capacitors on top of Pt/CrTiN/TiO₂/Si bottom electrode system for ultra-high density memory applications.     

Recent progress in sputtering PZT thin films for ferroelectric memories

Abstract

This paper describes amorphous Pb(Zr, Ti)O₃ (PZT) thin films deposited by cosputtering Pb(Zr_0.5 Ti_0.5)O₃ and PbO targets. By optimizing the amount of the excess Pb and the deposition temperature, PZT thin films with a single perovskite phase were obtained successfully on Ir substrates and Pt substrates at 520°C. 250-nm-thick PZT films crystallized by rapid thermal annealing (RTA) at 600°C for 20 s exhibited excellent ferroelectric properties: a coercive voltage of 1.0 V, a remanent polarization density of about 40 μC/cm², and a polarization switching endurance over 1x109 cycles. Although a heat treatment in a reductive ambient causes degradation of ferroelectric properties of PZT thin films, their degraded ferroelectric properties can be easily recovered from by a 1-min RTA in an oxygen at 400°C.     

Determination of Cross Sectional Variation of Ferroelectric Properties for Thin Film (Ca. 500 nm) PZT (30/70) via PFM

There is much speculation about the origin of fatigue in ferroelectric thin films that have been grown by sol-gel on various substrates. One of the most important substrates for growing thin film ferroelectric materials is native SiO₂. After the deposition of suitable electrode, most common are Ti-Pt, a thin film of a ferroelectric material can be grown on the substrate. Procedures to grow thin film lead zirconate titanate (PZT 30-70) have been well publicized and it is now routine that almost 100% [111] orientated PZT with a columnar structure of ca. 100 nm is grown on SiO₂ substrates. Recent studies using PFM have shown that it is possible to determine a variation in hysteresis loops with a spatial accuracy of 50 nm on the surface of a ferroelectric material. This study was to determine the variation in d₃₃ for a thin film sample of ferroelectric in terms of a depth profile. It was not suitable to just turn the sample on it's side and analyze the d₃₃ in terms of depth as the continuous back electrode would mean that the resulting vibration of the ferroelectric surface would be a combination of d₃₃ and d₃₁. The de-convolution of this signal was outside the scope of the current investigation. In order to determine the d₃₃ of the material in terms of depth the sample was machined (with an accuracy of 10 nm) to release the ferroelectric from the underlying electrode and electroded in the correct orientation for d₃₃ to be investigated in cross section. Samples of perovskite PZT(30/70) have been produced via sol-gel using a spin coating technique that are ca. 500 nm in cross sectional thickness on Pt/Ti/SiO₂ back electrodes. The PZT is shown to be highly [111] orientated and has in the past been well characterized both at the macro and nanoscale using a variety of techniques. Using focused ion beam (FIB) milling the PZT layer has been released from the SiO₂/Ti/Pt substrate and electroded in such a way as to determine the δ₃₃ properties of the film in terms of thickness of the as-deposited film. Figure 1 indicates the machining process used to generate the free standing PZT block. In Fig. 2, the results of the FIB machining process are shown. The ‘bridge’ structure has the dimensions of 500 nm in cross section and is long enough to ensure that electrode cross talk between the d₃₃ and d₃₁ modes is reduced. Hysteresis loops have been generated using the technique of piezo force microscopy (PFM) at discrete locations across the surface of the film corresponding to a depth profile of the as-deposited PZT. Variations in the shape of the hysteresis loops, calculated δ₃₃ and coercive field for the film have been related to the variation in oxygen defect density in the film. This study shows that the PZT thin film has a variety of fundamental piezoelectric constants that are associated with the variation in local crystal chemistry.     

MOCVD of Pb(Zr x Ti1-x )O3 thin films on MgTiO3/Si substrates and their electrical properties

Abstract

Pb(Zh _x , Ti_1-x )O₃(PZT) thin films were deposited on Si substrates using MgTiO₃ as the buffer layer and the electrical properties of those MFIS structures were investigated. PZT and MgTiO₃ films were made by MOCVD using ultrasonic spraying technique. Perovskite PZT films have been succesfully made at the substrate temperature of 550 to 600°C only when using MgTiO₃ buffer layer. AES depth profile analysis and RBS analysis revealed that there is no remarkable interdiffusion and no formation of reaction layer between PZT and MgTiO₃ and/or between MgTiO₃ and Si substrate. The capacitance-voltage (C-V) curves of the MFIS structure which were made with PZT and MgTiO₃buffer layer have shown the hysteresis resulted from the ferroelectric switching of the PZT films.     

Ferroelectric PbZr0.2Ti0.8O3 thin films on epitaxial Y-Ba-Cu-O

Abstract

Using a combination of pulsed laser deposition and sol-gel processing, we have fabricated epitaxial PbZr_0.2Ti_0.8O₃/YBa₂Cu₃O₇-x heterostructures on single crystalline [001] LaAlO₃. Rutherford back-scattering studies show the composition to be the same as the nominal starting composition. Transmission electron microscopy shows the existence of a randomly oriented polycrystalline microstructure in the PZT layer with a grain size of about 500–1000Å. Microscopic pores were also observed in the PZT layer. The PZT film exhibits ferroelectric hysteresis with a saturation polarization of 22–25μC/cm² (at 7.5V, 1kHz), a remanence of 5–6μC/cm² and a coercive field of about 40kV/cm.     

Dielectric properties and morphotropic phase boundaries in the xPb(Zn1/3Nb2/3)O3−(1−x)Pb(Zr0.5Ti0.5O3 pseudo-binary system

Ceramics in the xPb(Zn_1/3Nb_2/3)O₃−(1−x)Pb(Zr_0.5Ti_0.5)O₃ [xPZN–(1−x)PZT] solid solution system are expected to display excellent dielectric, piezoelectric, and ferroelectric properties in compositions close to the morphotropic phase boundary (MPB). The dielectric behavior of ceramics with x = 0.1−0.6 has been characterized in order to identify the MPB compositions in this system. Combined with X-ray diffraction results, ferroelectric hysteresis measurements, and Raman reflectivity analysis, it was consistently shown that an MPB exists between x = 0.2 and x = 0.3 in this binary system. When x ≤ 0.2, the tetragonal phase dominates at ambient temperatures. In the range of x ≥ 0.3, the rhombohedral phase dominates. For this rhombohedral phase, electrical measurements reveal a profound frequency dispersion in the dielectric response when x ≥ 0.6, suggesting a transition from normal ferroelectric to relaxor ferroelectric between 0.5 ≤ x ≤ 0.6. Excellent piezoelectric properties were found in 0.3PZN–0.7PZT, the composition closest to the MPB with a rhombohedral structure. The results are summarized in a PZN–PZT binary phase diagram.