Comparison of the effect of PLT and PZT buffer layers on PZT thin films for ferroelectric materials applications

In order to study the effect of different buffer layers on the Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films, 10-nm thick (Pb_0.72La_0.28)Ti_0.93O₃ (PLT) and Pb(Zr_0.52Ti_0.48)O₃ buffer layers have been deposited on the Pt(1 1 1)/Ti/SiO₂/Si substrates by pulsed laser deposition, respectively. The top buffer layers were also deposited on PZT thin films with the same thickness of the seed layers in order to enhance the fatigue characteristics of PZT thin films. We compared the results of dielectric constant, hysteresis loops and fatigue resistance characteristics. It was found that the dielectric properties of PZT thin films with PLT buffer layers were improved by comparing with PZT thin films with PZT buffer layers. The polarization characteristics of PZT thin films with PLT buffer layers were observed to be superior to those of PZT thin films using PZT buffer layers. The remanent polarization of PZT thin films showed 36.3 μC/cm² and 2.6 μC/cm² each in the case of use PLT and PZT buffer layers. For the switching polarization endurance analysis, PZT thin films with PLT buffer layers showed more excellent result than that of PZT thin films with PZT buffer layers.     

Energy band modulation of GaAs/Al0.26Ga0.74As quantum well in 3D self-assembled nanomembranes

In this study, we investigate the modulation of energy band in 3D self-assembled nanomembranes containing GaAs/Al_0.26Ga_0.74As quantum wells (QWs). Photoluminescence (PL) characterizations demonstrate that the self-assembled structures have different optical transition properties and the modulation of the energy band is thus realized. Detailed spectral analyses disclose that the small strain change in structures with different curvatures cannot cause remarkable change in energy bands in Al_0.26Ga_0.74As layer. On the other hand, the optical transitions of GaAs QW layer is influenced by the strain evolution in term of light emission intensity. We also find the first order Stark effect in rolled-up nanomembrane with diameter of 150 μm, which is closely connected with the coupling effect between the deformation potential and the piezoelectric potential. Our work may pave a way for the fabrication of high performance rolled-QW infrared photo-detectors.     

Influence of plasma pressure on the growth characteristics and ferroelectric properties of sputter-deposited PZT thin films

PZT thin films of thickness (320-1040) nm were synthesized on Si/SiO₂/Ti/Pt multilayered substrates by radio frequency magnetron sputtering. The influence of plasma pressure in the range of (0.24-4.9) Pa, during deposition, on the structural, electrical and ferroelectric properties of the PZT films was systematically studied. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and cross-sectional transmission electron microscopy (XTEM) were employed for structural study. Nano-probe Energy Dispersive (EDX) line scanning was employed to investigate the elemental distribution across the film-bottom electrode interface. I-V characteristics and polarization-electric field (P-E) hysteresis loop of the films were measured. The study reveals that the plasma pressure has a strong influence on the evolution and texture of the ferroelectric perovskite phase and microstructure of the films. At an optimum plasma pressure of 4.1 Pa, PZT films are grown with 93% perovskite phase with (1 1 1) preferred orientation and uniform granular microstructure. These films show a saturation polarization of 67 μC/cm², remnant polarization of 30 μC/cm² and coercive field of 28 kV/cm which, according to the literature, seem to be suitable for device applications.Transmission electron microscopy (TEM) study shows that at a plasma pressure of 4.1 Pa, the PZT/bottom Pt interface is sharp and no amorphous interlayer is formed at the interface. At a higher plasma pressure of 4.9 Pa, poor I-V and P-E hysteresis loop are observed which are interpreted as due to an amorphous interlayer at the film-bottom electrode interface which is possibly enriched in Pb, Zr, O and Pt.     

Effect of excess Pb on crystallinity and ferroelectric properties of PZT(40/60) films on LaNiO3 coated Si substrates by MOD technique

Pb(Zr_0.4Ti_0.6)O₃ [PZT(40/60)] films were deposited onto LaNiO₃ (LNO) coated Si substrates by metal-organic decomposition (MOD) technique. Excess Pb was incorporated in the film by using excess Pb (2%–15%) in the solution. The crystallinity and ferroelectric properties of PZT films were investigated by using X-ray diffraction (XRD), RT66A test system and HP4194 impedance analyzer, respectively. Rayleigh law was employed to analyze the defect concentration in the films. The results show that all the PZT films show the (1 0 0) preferential orientation with complete perovskite structure except for the 2% film displaying some pyrochlore phase. The (1 0 0) preferential orientation is mainly attributed to LNO bottom electrode, which has the highly (1 0 0) preferential orientation. The 10% film shows the best polarization and dielectric properties. The remnant polarization and coercive field are about 10.1 μC/cm² and 73 kV/cm under an electric field around 330 kV/cm, respectively. And the dielectric constant and dissipation factor are about 656 and 0.022 at a frequency of 1 kHz, respectively. The good ferroelectric properties of the 10% film are mainly attributed to the low defect concentration in the film.     

Optical limiting properties of zinc phthalocyanines in solution and solid PMMA composite films

The nonlinear absorption and optical limiting (OL) performance of tetra- and octasubstituted zinc phthalocyanine complexes were described in solution and in the solid state using the open-aperture Z-scan technique. The measurements were performed using collimated 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The polymeric films exhibit a much larger effective nonlinear absorption coefficient in comparison with solution. However, the parameters of the ratio of the excited to ground state absorption cross section and energy-dependent saturation in solution are much better compared to properties in the polymeric film. In terms of the ratio of the excited to ground state absorption cross section, the peripherally substituted complexes show better OL performance than the non-peripherally substituted derivative.     

Fabrication and comparison of PMN-PT single crystal, PZT and PZT-based 1-3 composite ultrasonic transducers for NDE applications

This paper describes fabrication and comparison of PMN-PT single crystal, PZT, and PZT-based 1-3 composite ultrasonic transducers for NDE applications. As a front matching layer between test material (Austenite stainless steel, SUS316) and piezoelectric materials, alumina ceramics was selected. The appropriate acoustic impedance of the backing materials for each transducer was determined based on the results of KLM model simulation. Prototype ultrasonic transducers with the center frequencies of approximately 2.25 and 5 MHz for contact measurement were fabricated and compared to each other. The PMN-PT single crystal ultrasonic transducer shows considerably improved performance in sensitivity over the PZT and PZT-based 1-3 composite ultrasonic transducers.     

Cd0.5Zn0.5Se wide range composite thin films for solar cell buffer layer application

Cd_0.5Zn_0.5Se composite thin films were obtained on glass substrate using aqueous alkaline solution at low temperature using cadmium acetate and zinc acetate as Cd²⁺ and Zn²⁺ and Se²⁻ ion sources. Different phases of individuals i.e. CdSe and ZnSe, spherical and needle shape surface morphology and good elemental chemical stoichiometric ratio were observed from X-ray diffraction, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) studies, respectively. The band gap and electrical resistivity of the composite film were 2.35 eV and about 10⁷ Ω cm, respectively.     

Effects of repetitive polarization switching on the coercive voltage of Pt/Pb(Zr0.52Ti0.48)O3/Pt thin films analyzed using impedance spectroscopy

We investigated the effect of repetitive switching of polarization on the ferroelectric Pt/Pb(Zr_0.52Ti_0.48)O₃/Pt thin film capacitor by using impedance spectroscopy. From the Cole-Cole plot, the equivalent circuit is described as a combination of the bulk part (a capacitor), the interface part (the constant phase element (CPE), and a parallelly-connected resistor). The circuit parameters were analyzed at various stages of switching. An early increase and a subsequent decrease of the bulk capacitance may represent the wake-up and fatigue phenomena, respectively. The change in the interface part was characterized by an increase in resistance and the growth of n, the exponent of CPE, which may have come from a reduction of defects and the diminished inhomogeneity in the interfacial layer, respectively. The change in the resistance and the coefficient of the CPE in the interface part collectively resulted in an increase in the interfacial impedance. The coercive voltage, which may have intrinsically increased due to the repetitive switching, was even larger as a result of the increased interfacial impedance.     

Determination of the nanoscale dielectric properties in ferroelectric lead zirconate titanate (PZT) thin films

We report on nanoscale experiments with <100 nm lateral resolution being able to differentiate the effective dielectric polarisation P_z, deposited charge density σ, surface dielectric constant ε_surface, its voltage dependence ε_surface(U), as well as the built-in electric bias voltage U_int in ferroelectric lead zirconate titanate (PZT) thin films. This is possible by combining piezoresponse force microscopy (PFM) and pull-off force spectroscopy (PFS), both methods based on scanning force microscopy (SFM). The differentiation becomes possible since both P_z and σ contribute additively in PFS, while they are subtractive in PFM, hence allowing the two contributions to be separated. ε_surface can be quantified by means of the experimental PFS data and the calculated effective penetration depth of PFM developed in a finite element modelling. Finally, U_int and ε_surface(U) are derived by an absolute matching of the P_z values measured by PFM and PFS.Our nanoscale results obtained on PZT thin films reveal values for the above specified quantities that have the same order of magnitude as those obtained from macroscopic measurements reflecting the integral response using large electrode areas. However, we stress that the data reported here reveal physical properties deduced on the nanometer scale. Furthermore, they are recorded during one single experimental investigation, using one single set-up only.     

Polarization modification of PZT thin films by means of electric fields and stress in scanning force microscopy

Polarization switching in scanning force microscopy (SFM) is influenced by both electric fields and stress, whereby the latter can arise inherently from Maxwell stress. We discuss the influence of electric charges and of the polarization asymmetry on the switching behaviour. For single crystallites of PZT(53/47) thin films, the sectors for ferroelectric, ferroelastoelectric and ferroelastic switching are represented in a field-stress map. The influence of stress on the second harmonic of the SFM is also discussed.     

Temperature-electric field hysteresis loop of multicaloric effects in PbZr0.8Ti0.2O3 thin films

The Multicaloric effect in the PbZr_0.8Ti_0.2O₃ thin films is investigated with the application of sine wave electric field, dc electric field and stress using a phase field method combined with the thermodynamic analysis. The simulation results show that the adiabatic temperature change-electric field curve presents a shape of butterfly in the presence of the sine wave electric field. In order to detect the effect of the sine wave electric field, the multicaloric effect and the domain structures under the direct electric field and the sine wave electric field are compared. It is found that the domain switching behaviors are quite different under the different applied electric fields. And the negative multicaloric effect in the PbZr_0.8Ti_0.2O₃ thin film is attribute to the domain switching under the external field.     

Optical limiting properties of trimeric metallo-phthalocyanines/polymer composite films

The nonlinear absorption and optical limiting properties of two trimeric metallo-phthalocyanines namely, 2,4,6-tris[2-oxa-9,10,16,17,23,24-hexa(hexylthio) phthalocyaninato M(II)]-s-triazine (M=Zn for compound ZnPc and Cu for compound CuPc) doped polyvinyl chloride (PVC) thin film in the nanosecond regime were investigated by using the open-aperture Z-scan technique. The measurements were performed using 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. OL parameters of the ratio of the excited state to ground state absorption cross-sections κ, the effective nonlinear absorption coefficient β_eff, the linear absorption coefficient α₀ and the saturation density or energy density F_sat values were determined. The results show that MPc/PVC composite displays much larger nonlinear absorption coefficient and lower saturable fluence for optical limiting when compared to the same Pc molecules in solution. The results indicated that both compounds exhibited good OL performances. ZnPc shows slightly better OL parameters than that of CuPc.     

Increased surface roughness by oxygen plasma treatment of graphite/polymer composite

The technology of selective plasma etching was applied to increase the surface roughness of graphite/polymer composite. Etching was performed with a low pressure weakly ionised oxygen plasma created with a RF generator of the output power of 200 W and frequency of 27.12 MHz. The density of charged particles, density of neutral oxygen atoms and the electron temperature was about 1×10¹⁶ m⁻³, 4×10²¹ m⁻³, and 5 eV, respectively. The effects of plasma treatment were observed by scanning electron microscope (SEM), electron microprobe (EMPA) and Talysurf. It was found that the surface roughness was increased by approximately 15 times, from a virgin sample at the roughness of R_a=0.27 μm to a very rough surface with R_a=4 μm. The roughness increased with increasing plasma exposure time. The EMPA results showed that the amount of sulphur in the surface layer decreased with increasing etching time indicating that PPS polymer was the material etched preferentially.     

Investigation on FR(LT)–FR(HT) phase transition and pyroelectric properties of pulsed laser deposited Pb(Zr0.93Ti0.07)O3 thin films

The preparation process, crystallinity and electrical properties of pulse laser deposited Pb(Zr_xTi_1−x)O₃ (PZT) thin films were investigated in this paper. PZT (x = 0.93) thin film samples deposited at different substrate temperatures were prepared. Si (1 1 0) was the substrate; Ag and YBCO were the top electrode and the bottom electrode respectively. The bottom electrode YBCO was deposited on the Si substrate by pulsed laser deposition (PLD), and then PZT was epitaxially deposited on YBCO also by PLD. After annealing, the top electrode Ag was prepared on PZT by thermal evaporation, and then the Ag/PZT/YBCO/Si structured thin films were obtained. The XRD and the analysis of their electrical characters showed that, when the substrate temperature was elevated from 600 °C to 800 °C, the crystallinity and electrical properties of PZT thin films became better and better, and the F_R(LT)–F_R(HT) phase transition of PZT (x = 0.93) thin films occurred at 62 °C. The PZT film deposited at 800 °C had the best pyroelectric properties, and when the F_R(LT)–F_R(HT) phase transition of this film occurred, the peak value of pyroelectric coefficient (p) was obtained, with a value of 1.96 × 10⁻⁶ C/(cm² K). The PZT film deposited at 800 °C had the highest remnant polarization (P_r) and the lowest coercive field (E_c), with the values of 34.3 μC/cm² and 41.7 kV/cm respectively.     

Annealing effects on the surface morphologies of thin PS/PMMA blend films with different film thickness

The surface morphology evolution of three thin polystyrene (PS)/polymethyl methacrylate (PMMA) blend films (<70 nm) on SiO_x substrates upon annealing were investigated by atomic force microscopy (AFM) and some interesting phenomena were observed. All the spin-coated PS/PMMA blend films were not in thermodynamic equilibrium. For the 67.1 and the 27.2 nm PS/PMMA blend films, owing to the low mobility of the PMMA-rich phase layer at substrate surfaces and interfacial stabilization caused by long-range van der Waals forces of the substrates, the long-lived metastable surface morphologies (the foam-like and the bicontinuous morphologies) were first observed. For the two-dimensional ultrathin PS/PMMA blend film (16.3 nm), the discrete domains of the PS-rich phases upon the PMMA-rich phase layer formed and the secondary phase separation occurred after a longer annealing time.     

Pattern guided structure formation in polymer films of asymmetric blends

Two off-critical blends of poly(2-vinylpyridine) and polystyrene, 2:3 and 3:2 (w:w) PVP:PS, were spin-cast (with varied domain scale R) onto periodically (λ = 4 μm) patterned substrate. The pattern consisted of two alternating symmetric stripes: Au attracting PVP and neutral self-assembled monolayer. The resulting droplet-type morphologies were recorded with Scanning Force Microscopy and examined with integral geometry approach. PVP-rich islands of the 2:3 PVP:PS films form, for a wide R/λ range, strongly anisotropic morphologies. They show up, for R/λ ∼ 0.5, a weak λ/2-substructure of smaller PVP droplets in addition to the domains periodic with λ. The 3:2 blend exhibits morphologies with dominant λ-structure of PVP ribbons, which encircle PS droplets. For R/λ ∼ 0.5, smaller PS domains are also present but no λ/2-substructure is formed. The |χ_E|-values of droplet surface density are reduced, as compared to homogeneous substrate, for the 3:2 blend (with |χ_E| → 0 for R ∼ λ). This effect is absent for the 2:3 mixture.     

A comparative study of fibre-textured and epitaxial Nb-doped Pb(Zr0.53Ti0.47)O3 thin films on different substrates

Fibre-textured and epitaxial Nb-doped Pb(Zr_0.53Ti_0.47)O₃ (PNZT) thin films were grown on the different substrates by a sol-gel process. The [1 0 0]- and [1 1 1]-fibre-textured polycrystalline PNZT films were obtained on platinized silicon substrates by introducing PbO and TiO₂ seeding layers, while the [0 0 1]- and [1 1 1]-oriented epitaxial PNZT films were formed directly on Nb-doped SrTiO₃ (Nb:STO) single-crystal substrates with (1 0 0) and (1 1 1) surfaces, respectively. The preferential orientation and phase structure of the fibre-textured and epitaxial PNZT films, as well as their influences on the electrical properties were investigated. Higher remnant polarization (P_r) and piezoelectric coefficient (d₃₃) were obtained for the epitaxial PNZT films on Nb:STO substrates than that for the fibre-textured ones on platinized silicon substrates. For both fibre-textured and epitaxial cases, the PNZT films with [1 0 0]/[0 0 1] orientations show higher piezoelectric responses than [1 1 1]-oriented ones, whereas better ferroelectric properties can be obtained in the latter. The intrinsic and extrinsic contributions were discussed to explain the difference in electrical properties for differently oriented fibre-textured and epitaxial PNZT films on different substrates.     

Synthesis of cauliflower-like ZnO-TiO2 composite porous film and photoelectrical properties

A series of cauliflower-like TiO₂-ZnO composite porous films with various molar ratios of Zn/Ti were prepared by the screen printing technique on the fluorine-doped SnO₂ (FTO) conducting glasses. The composite films were characterized by field-emission scanning electron microscopy (FE-SEM), X-ray energy-dispersive spectrometry (EDS) and UV-vis transmittance spectrum. The results showed composite film electrode had a novel cauliflower-like morphology, which could effectively increase the dye absorption. The corresponding dye-sensitized solar cells (DSCs) were made by the composite film, and effects of ZnO incorporation on the photovoltaic performances of the DSCs were studied. With the Zn/Ti molar ratio not more than 3% in ZnO-TiO₂ composite film of about 5 μm-thickness, the photocurrent density (J_sc) and the solar-to-electricity conversion efficiency (η) were greatly improved compared with those of the DSC based on bare TiO₂ film of same thickness. This increases in efficiency and J_sc were attributed to high electron conductivity of ZnO, the improved dye adsorption and large light transmittance of composite film.     

Cu(In,Sn)Se2 thin films for absorption of energy from infrared radiation

In this study, we sought to lower the bandgap of thin film solar cells by replacing the Ga used in the absorber layer of Cu(In,Ga)Se₂ with Sn (bandgap of 0.07?eV) to form Cu(In,Sn)Se₂. The proposed scheme was shown to reduce the bandgap of the absorber layer from 1.0?eV to 0.88?eV. Sn films of various thicknesses were deposited using precursors of Sn–In–Cu metal in order to study the effects of Sn/(In?+?Sn) ratio (SIR) on the structure of the material and photoelectrical characteristics of the Cu(In,Sn)Se₂ absorber layer. Experiment results revealed that a higher SIR following selenization increased the grain size and surface roughness of the absorber layer. It increased the quantity of secondary phases of SnSe₂ and Cu₂SnSe₃ and improved the distribution of Cu and In in the absorber layer. A higher SIR was also shown to increase electron mobility while decreasing carrier concentration and conductivity. When SIR≧0.25, the replacement of In³⁺ with Sn⁴⁺in the Cu⁺ vacancies decreased the electron strength of In. We speculate that an increase in SIR caused a relative increase in the quantity of Sn²⁺ compared to Sn⁴⁺, thereby increasing the electron strength of Sn and switching the absorber layer from a p-type to an n-type semiconductor.     

Electrical,optical, and structural characterization of polymer blend (PVC/PMMA) electrolyte films

Ion-conducting solid polymer blend electrolytes based on polyvinyl chloride (PVC)/poly methyl methacrylate (PMMA) complexed with sodium perchlorate (NaClO₄) were prepared in various concentrations by solution cast technique. The features of complexation of the electrolytes were studied by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. DC conductivity of the films was measured in the temperature range 303–398 K. Transference number measurements were carried out to investigate the nature of charge transport in the polymer blend electrolyte system. The electrical conductivity increased with increasing dopant concentration, which is attributed to the formation of charge transfer complexes. The polymer complexes exhibited Arrhenius type dependence of conductivity with temperature. In the temperature range studied, two regions with different activation energies were observed. Transference number data showed that the charge transport in this system is predominantly due to ions. Optical properties like absorption edge, direct band gap, and indirect band gap were estimated for pure and doped films from their optical absorption spectra in the wavelength region 200–600 nm. It was found that the energy gap and band edge values shifted to lower energies on doping with NaClO₄ salt. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamil Nadu, India, Dec. 7–9, 2006.