Ferroelectric and piezoelectric properties of bismuth titanate thin films grown on different bottom electrodes by soft chemical solution and microwave annealing

Bismuth titanate (Bi₄Ti₃O₁₂, BIT) films were evaluated for use as lead-free piezoelectric thin films in micro-electromechanical systems. The films were grown by the polymeric precursor method on LaNiO₃/SiO₂/Si (1 0 0) (LNO), RuO₂/SiO₂/Si (1 0 0) (RuO₂) and Pt/Ti/SiO₂/Si (1 0 0) (Pt) bottom electrodes in a microwave furnace at 700 °C for 10 min. The domain structure was investigated by piezoresponse force microscopy (PFM). Although the converse piezoelectric coefficient, d₃₃, regardless of bottom electrode is around (∼40 pm/V), those over RuO₂ and LNO exhibit better ferroelectric properties, higher remanent polarization (15 and 10 μC/cm²), lower drive voltages (2.6 and 1.3 V) and are fatigue-free. The experimental results demonstrated that the combination of the polymeric precursor method assisted with a microwave furnace is a promising technique to obtain films with good qualities for applications in ferroelectric and piezoelectric devices.     

Effect of post-deposition annealing on phase formation and properties of RF magnetron sputtered PLZT thin films

In this work, we report the preparation of lanthanum-modified lead zirconate titanate (PLZT) thin films by RF magnetron sputtering on platinized silicon (Pt/Ti/SiO₂/Si) substrate. Sputtering was done in pure argon at 100 W RF power without external substrate heating. X-ray diffraction studies were performed on the films to study the effect of post-deposition furnace annealing temperature and time on the perovskite phase formation of PLZT. Annealing at 650 °C for 2 h was found to be optimum for the preparation of PLZT films in pure perovskite phase. The effect of different annealing conditions on surface morphology of the films was examined using AFM. The dielectric, ferroelectric and electrical properties of these films were also investigated in detail as a function of different annealing conditions. The pure perovskite film exhibits better properties than the other films which have some fraction of unwanted pyrochlore phase. The remanent polarization for pure perovskite film was found to be ∼29 μC/cm² which is almost double compared to the films having mixed phases. The dc resistivity of the pure perovskite film was found to be 7.7 × 10¹⁰ Ω cm at the electric field of ∼80 kV/cm.     

Size effects of polycrystalline lanthanum modified Bi4Ti3O12 thin films

The film thickness dependence on the ferroelectric properties of lanthanum modified bismuth titanate Bi_3.25La_0.75Ti₃O₁₂ was investigated. Films with thicknesses ranging from 230 to 404 nm were grown on platinum-coated silicon substrates by the polymeric precursor method. The internal strain is strongly influenced by the film thickness. The morphology of the film changes as the number of layers increases indicating a thickness dependent grain size. The leakage current, remanent polarization and drive voltage were also affected by the film thickness.     

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.     

Phase stabilization and microstructural studies of lead lanthanum titanate thin films

Thin ferroelectric films of PLTx (Pb_1−xLa_xTi_1−x/4O₃) have been prepared by a sol-gel spin coating process. As deposited films were thermally treated for crystallization and formation of perovskite structure. Characterization of these films by X-ray diffraction (XRD) have been carried out for various concentrations of La (x = 0.04, 0.08 and 0.12) on ITO coated corning glass substrates. For a better understanding of the crystallization mechanism, the investigations were carried out on films annealed at temperatures (350, 450, 550 and 650 °C). Characterization of these films by X-ray diffraction shows that the films annealed at 650 °C exhibit tetragonal phase with perovskite structure. Atomic force microscope (AFM) images are characterized by slight surface roughness with a uniform crack free, densely packed structure. Fourier transform infrared spectra (FTIR) studies of PLTx thin films (x = 0.08) deposited on Si substrates have been carried out to get more information about the phase stabilization.     

Studies on chemically deposited CuInSe2 thin films

Nanocrystalline thin films of CuInSe₂ have been prepared by chemical bath deposition technique at temperatures below 60 °C. X-ray diffraction of the films confirmed the identity of CuInSe₂ and with largely broadened peaks indicated the nanocrystalline nature of the films. Images from scanning electron microscope represented spherical nanoparticles.     

Structural, electrical and optical studies of SILAR deposited cadmium oxide thin films: Annealing effect

Successive ionic layer adsorption and reaction (SILAR) method has been successfully employed for the deposition of cadmium oxide (CdO) thin films. The films were annealed at 623 K for 2 h in an air and changes in the structural, electrical and optical properties were studied. From the X-ray diffraction patterns, it was found that after annealing, H₂O vapors from as-deposited Cd(O₂)_0.88(OH)_0.24 were removed and pure cubic cadmium oxide was obtained. The as-deposited film consists of nanocrystalline grains of average diameter about 20-30 nm with uniform coverage of the substrate surface, whereas for the annealed film randomly oriented morphology with slight increase in the crystallite size has been observed. The electrical resistivity showed the semiconducting nature with room temperature electrical resistivity decreased from 10⁻² to 10⁻³ Ω cm after annealing. The decrease in the band gap energy from 3.3 to 2.7 eV was observed after the annealing.     

A study on the electrical properties of Pb(Zr, Ti)O3 thin films crystallized by the electrical resistive heating of Pt thin film

The electrical properties of Pb(Zr, Ti)O₃ thin films annealed by Pt thin film heater were investigated. By the thin film heater, we successfully crystallized Pb(Zr, Ti)O₃ thin films at a high temperature above 750 °C in a few seconds. The thin film heater has some advantages, such as a low thermal budget, little Pb-loss and enhanced surface morphology compared with the conventional furnace because it has a fast heating rate. The electrical properties of the Pb(Zr, Ti)O₃ thin film crystallized by thin film heater improved considerably comparing to those crystallized in conventional furnace. The remanent polarization, breakdown field, and leakage current density measured to be 22.7 μC/cm², 853 kV/cm, and 6.93 × 10⁻⁷ A/cm², respectively.     

Structural and optical characterizations of chemically deposited cadmium selenide thin films

Synthesis of cadmium selenide thin films by CBD method has been presented. The deposited film samples were subjected to XRD, SEM, UV-vis-NIR and TEP characterization. X-ray diffraction analysis showed that CdSe film sample crystallized in zinc blende or cubic phase structure. SEM studies reveal that the grains are spherical in shape and uniformly distributed all over the surface of the substrates. The optical band gap energy of as deposited film sample was found to be in the order of 1.8 eV. The electrical conductivity of the film sample was found to be 10⁻⁶ (Ω cm)⁻¹ with n-type of conduction mechanism.     

Cathodoluminescence of CaWO4 and SrWO4 thin films prepared by spray pyrolysis

Thin films of CaWO₄ and SrWO₄ were prepared on glass substrates by spray pyrolysis. The effects of preparation conditions and monovalent, bivalent and trivalent cation doping on cathodoluminescence (CL) properties of the films were studied. Polycrystalline CaWO₄ and SrWO₄ films formed a scheelite structure after being annealed above 300°C. They exhibited analogous cathodoluminescence consisting of a blue emission band at 447 nm and a blue-green emission band at 487 nm. The blue and blue-green emission intensities increased with substrate and annealing temperature. Annealing atmosphere and doping with Ag⁺, Pb²⁺ and La³⁺ did not influence the characteristics of the blue and blue-green emissions, whereas Eu³⁺ did. The results indicated both the blue and blue-green emissions originated from the WO₄²⁻ molecular complex. The luminance and efficiency for CaWO₄ film were 150 cd/m² and 0.7 lm/W at 5 kV and 57 μA/cm².     

Fabrication of antiferroelectric PLZT films on metal foils

Fabrication of high-dielectric-strength antiferroelectric (AFE) films on metallic foils is technically important for advanced power electronics. To that end, we have deposited crack-free Pb_0.92La_0.08Zr_0.95Ti_0.05O₃ (PLZT 8/95/5) films on nickel foils by chemical solution deposition. To eliminate the parasitic effect caused by the formation of a low-permittivity interfacial oxide, a conductive buffer layer of lanthanum nickel oxide (LNO) was coated by chemical solution deposition on the nickel foil before the deposition of PLZT. Use of the LNO buffer allowed high-quality film-on-foil capacitors to be processed in air. With the PLZT 8/95/5 deposited on LNO-buffered Ni foils, we observed field- and thermal-induced phase transformations of AFE to ferroelectric (FE). The AFE-to-FE phase transition field, E_AF = 225 kV/cm, and the reverse phase transition field, E_FA = 190 kV/cm, were measured at room temperature on a ≈1.15 μm-thick PLZT 8/95/5 film grown on LNO-buffered Ni foils. The relative permittivities of the AFE and FE states were ≈600 and ≈730, respectively, with dielectric loss ≈0.04 at room temperature. The Curie temperature was ≈210 °C. The thermal-induced transition of AFE-to-FE phase occurred at ≈175 °C. Breakdown field strength of 1.2 MV/cm was measured at room temperature.     

A study on the structural and mechanical properties of nanocrystalline CuS thin films grown by chemical bath deposition technique

We report a chemical route for the deposition of nanocrystalline thin films of CuS, using aqueous solutions of Cu(CH₃COO)₂, SC(NH₂)₂ and N(CH₂CH₂OH)₃ [triethanolamine, i.e. TEA] in proper concentrations and ratios. The films were structurally characterized using X-ray diffraction technique (XRD), field emission scanning electron microscopy (FESEM) and optical analysis [both photo luminescence (PL) and ultraviolet-visible (UV-vis)]. Optical studies showed a large blue shift in the band gap energy of the films due to quantum confinement effect exerted by the nanocrystals. From both XRD and FESEM analyses, formation of CuS nanocrystals with sizes within 10-15 nm was evident. A study on the mechanical properties was carried out using nanoindentation and nanoscratch techniques, which showed good mechanical stability and high adherence of the films with the bottom substrate. Such study on the mechanical properties of the CuS thin films is being reported here for the first time. Current-voltage (I-V) measurements were also carried out for the films, which showed p-type conductivity.     

Investigation of size dependent structural and optical properties of thin films of CdSe quantum dots

Cadmium selenide (CdSe) quantum dots were grown on indium tin oxide substrate using wet chemical technique for possible application as light emitting devices. The structural, morphological and luminescence properties of the as deposited thin films of CdSe Q-dot have been investigated, using X-ray diffraction, transmission electron microscopy, atomic force microscopy and optical and luminescence spectroscopy. The quantum dots have been shown to deposit in an organized array on ITO/glass substrate. The as grown Q-dots exhibited size dependent blue shift in the absorption edge. The effect of quantum confinement also manifested as a blue shift of photoluminescence emission. It is shown that the nanocrystalline CdSe exhibits intense photoluminescence as compared to the large grained polycrystalline CdSe films.     

Preparation and characterization of indium doped CdS0.2Se0.8 thin films by spray pyrolysis

The CdS_0.2Se_0.8 and indium doped CdS_0.2Se_0.8 thin films have been deposited onto the amorphous glass and fluorine doped tin oxide coated glass substrates by spray pyrolysis. The doping concentration of indium has been optimized by photoelectrochemical characterization technique. The structural, surface morphological, optical and electrical properties of CdS_0.2Se_0.8 and indium doped CdS_0.2Se_0.8 thin films have been studied. X-ray diffraction studies reveal that the films are polycrystalline in nature with hexagonal crystal structure. Scanning electron microscopy studies reveal that the grains are uniform with uneven spherically shaped, distributed over the entire substrate surface. The complete surface morphology has been changed after doping. In optical studies, the transition of the deposited films is found to be direct allowed with optical energy gaps decreasing from 1.91 to 1.67 eV with indium doping. Semiconducting behavior has been observed from resistivity measurements. The thermoelectric power measurements reveal that the films exhibit n-type conductivity.     

Annealing effects on the chemical deposited CdS films and the electrical properties of CdS/CdTe solar cells

CdS layers grown by chemical bath deposition (CBD) are annealed in the oxygen and argon-hydrogen atmosphere respectively. It has been found that the open circuit voltage of the CdS/CdTe solar cell increases when the CBD CdS is annealed with oxygen before the deposition of CdTe by close spaced sublimation (CSS), while the performance of the solar cell decreases when the CBD CdS is annealed with argon-hydrogen. Electronic properties of the CdS films are investigated using X-ray photo-electron spectroscopy (XPS), which indicates that the Fermi level is shifting closer to the conduction band after annealing in the oxygen and consequently a higher open circuit voltage of the solar cell can be obtained.     

Luminescent properties of Gd2Ti2O7: Eu phosphor films prepared by sol-gel process

Gd₂Ti₂O₇: Eu³⁺ thin film phosphors were fabricated by a sol-gel process. X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800 °C and the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free phosphor films were obtained, which mainly consisted of grains with an average size of 70 nm. The doped Eu³⁺ showed orange-red emission in crystalline Gd₂Ti₂O₇ phosphor films due to an energy transfer from Gd₂Ti₂O₇ host to them. Both the lifetimes and PL intensity of the Eu³⁺ increased with increasing the annealing temperature from 800 to 1000 °C, and the optimum concentrations for Eu³⁺ were determined to be 9 at.%. of Gd³⁺ in Gd₂Ti₂O₇ film host.     

Enhanced ferroelectric properties of Pb(Zr0.80Ti0.20)O3/PbO thin films prepared by radio frequency magnetron sputtering

The Pb(Zr_0.80Ti_0.20)O₃ (PZT) thin films with and without a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by radio frequency (rf) magnetron sputtering method. The PbO buffer layer improves the microstructure and electrical properties of the PZT thin films. High phase purity and good microstructure of the PZT thin films with a PbO buffer layer were obtained. The effect of the PbO buffer layer on the ferroelectric properties of the PZT thin films was also investigated. The PZT thin films with a PbO buffer layer possess better ferroelectric properties with higher remnant polarization (P_r = 25.6 μC/cm²), and lower coercive field (E_c = 60.5 kV/cm) than that of the films without a PbO buffer layer (P_r = 9.4 μC/cm², E_c = 101.3 kV/cm). Enhanced ferroelectric properties of the PZT thin films with a PbO buffer layer is attributed to high phase purity and good microstructure.     

Growth of PbS nanopyramidal particulate films for potential applications in quantum-dot photovoltaics and nanoantennas

We report a simple interfacial process called the liquid-liquid interface reaction technique (LLIRT) that leads to the formation of nanosized PbS particulate films with hitherto unreported pyramidal morphology. The resultant PbS films were characterized by transmission electron microscopy (TEM) with selected area electron diffraction (SAED), X-ray diffractometery (XRD), atomic force microscopy (AFM), near field scanning optical microscopy (NSOM) and UV-vis spectroscopy. The pyramidal morphology is speculated to originate from the preferred orientation of the 2 2 0 plane of cubic PbS. Our nanopyramidal PbS particulate films display remarkably sharp excitonic peak centered around 656 nm that accounts for a band gap of 1.8 eV suggesting, in turn, their potential application in QD photovoltaics. Interestingly, the feasibility of such nanopyramids to potentially act as nanoantennas (as revealed by the NSOM) is also suggested.     

Synthesis of luminescent SrMoO4 thin films by a non-reversible galvanic cell method

Well-crystallized SrMoO₄ thin films were synthesized directly on a molybdenum substrate by a non-reversible galvanic cell method through 150 h electrochemical reaction at room temperature. The as-synthesized thin films are a single phase SrMoO₄ with a scheelite-type structure and show uniform and homogeneous surfaces. When excited by 290 nm ultraviolet ray at room temperature, the thin films emit the maximum peaks at 485 nm. The densification, chemical-physical and photoluminescence properties of the SrMoO₄ thin films synthesized by the non-reversible galvanic cell method are significantly improved.