Enhanced ferroelectric properties of (Pb0.90La0.10)Ti0.975O3 multilayered thin films prepared by RF magnetron sputtering

The (Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PLT/PT), PbTiO₃/(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PT/PLT/PT) multilayered thin films with a PbO_x buffer layer were in situ deposited by RF magnetron sputtering at the substrate temperature of 600 °C. With this method, highly (1 0 0)-oriented PLT/PT and PT/PLT/PT multilayered thin films were obtained. The PbO_x buffer layer leads to the (1 0 0) orientation of the films. The dielectric, ferroelectric and pyroelectric properties of the PLT multilayered thin films were investigated. It is found that highly (1 0 0)-oriented PT/PLT/PT multilayered thin films possess higher remnant polarization 2P_r (44.1 μC/cm²) and better pyroelectric coefficient at room temperature p (p = 2.425 × 10⁻⁸ C/cm² K) than these of PLT and PLT/PT thin films. These results indicate that the design of the PT/PLT/PT multilayered thin films with a PbO_x buffer layer should be an effective way to enhance the dielectric, ferroelectric and pyroelectric properties. The mechanism of the enhanced ferroelectric properties was also discussed.     

Preparation of fluorocarbon thin film deposited by soft X-ray ablation and its electrical characteristics and thermal stability

Fluorocarbon films were deposited by soft X-ray ablation of polytetrafluoroethylene (PTFE) and characterized as low-dielectric-constant interlayer dielectrics. Very rapid deposition of such films at approximately 1500 nm/min could be achieved at room temperature. Fourier-transform infrared spectroscopy (FT-IR) measurement results suggest that the films deposited are primarily formed as one-dimensional chains of (-CF₂-)_n which are partially cross-linked. The cross-link density increases with increasing deposition temperature, which improves the thermal stability. However, the dielectric constant of the films increased abruptly above 300 °C. The dielectric constant and leakage current at 1.0 MV/cm of the film deposited at room temperature were approximately 2.1 and 2.0×10⁻⁹ A/cm², respectively.     

Microstructures and photoluminescence of hydrogenated amorphous carbon films produced by using organic hydrocarbon source

Thin layers of hydrogenated amorphous carbon were prepared by using organic hydrocarbon source, xylene (C₈H₁₀), in plasma-enhanced chemical vapor deposition (PECVD) system. The microstructures were characterized by using Fourier-transform infrared and Raman scattering spectra. The appearance of a sharp vibration signal in 1600 cm^-1 strongly suggests the existence of sp² carbon clusters with aromatic rings. With increasing the deposition rf power, the content of these aromatic structures is increased in the films. In contrast to a broad single PL peak in methane (CH₄)-baseda-C:H films, the PL band of xylene-based a-C:H films contains multiple peaks in blue-green light region, which is influenced by rf power. We tentatively attributed it to the radiative recombination of electron-hole pairs through some luminescent centers associated with aromatic structures. Received: 26 April 2000 / Accepted: 9 May 2000 / Published online: 13 September 2000     

Structure-related infrared optical properties of BaTiO3 thin films grown on Pt/Ti/SiO2/Si substrates

BaTiO₃ thin films with different thickness have been grown on Pt/Ti/SiO₂/Si substrates by a modified sol-gel method. X-ray diffraction analyses show that the BaTiO₃ thin films are polycrystalline. The crystalline quality of the films is improved with increasing thickness. The infrared optical properties of the BaTiO₃ thin films have been investigated using an infrared spectroscopic ellipsometry in the wave number range of 800-4000 cm⁻¹ (2.5-12.5 μm). By fitting the measured pseudodielectric functions with a three-phase model (Air/BaTiO₃/Pt), and a derived classical dispersion relation for the thin films, the optical constants and thicknesses of the thin films have been simultaneously obtained. The refractive index of the BaTiO₃ thin films increases and on the other hand, the extinction coefficient does not change with increasing thickness in the entirely measured wave number range. The dependence of the refractive index on the film thickness has been discussed in detail and was mainly due to both the crystalline quality of the films and packing density. Finally, the absorption coefficient was calculated in the infrared region for applications in the pyroelectric IR detectors.     

Enhanced fatigue property of PZT thin films using LaNiO3 thin layer as bottom electrode

A highly (100)-oriented metallic LaNiO₃ film was prepared directly on a Si substrate by a simple metalorganic decomposition (MOD) technique using lanthanum nitrate and nickel acetate as the starting sources. Subsequent Pb(Zr,Ti)O₃ (PZT) thin films deposited on the LaNiO₃-coated Si substrate were obtained by a modified sol–gel method. It was found that the PZT thin films began to form a single perovskite phase at a low annealing temperature of 530 °C, and exhibited highly (100) orientation. A ferroelectric capacitor of Pt/Pb(Zr,Ti)O₃/LaNiO₃/Si annealed at 600 °C displayed a good P-E hysteresis characteristic and was fatigue-free even after 10¹¹ switching cycles. Received: 25 May 2000 / Accepted: 9 August 2000 / Published online: 30 November 2000     

Photoluminescence characteristics of neodymium oxide nanocrystal/titania/ormosil composite sol-gel thin films

Neodymium (III) oxide nanocrystal/titania/organically-modified silane (ormosil) composite thin films have been prepared using a chemical approach consisting of a combination of inverse microemulsion and sol-gel techniques at low temperature. Transmission electron microscopy shows that the neodymium (III) oxide nanoparticles have a needle-like nanocrystal structure. A strong room temperature emission at 1064 nm, corresponding to the ⁴ F _3/2?⁴ I _11/2 transition, has been observed as a function of the heat treatment temperature used for the production of the composite thin films. In addition to this emission, two other main emissions at 890 nm and at 1336 nm have also been observed. In particular, there was a clear shoulder peak at 1145 nm, probably be due to the host matrix, which was observed in all the measured samples and this shoulder peak gave a maximum intensity after heat treatment at 300 °C. Received: 6 September 2000 / Accepted: 15 November 2000 / Published online: 20 June 2001     

Preparation and assessment of piezo- and pyroelectric poly (vinylidene fluoride-hexafluoropropylene) copolymer films

Films of poly(vinylidene fluoride-hexafluoropropylene) copolymer [P(VDF-HFP)] were cast from a dimethylsulfoxide (DMSO)/acetone solution of Solef?85-15 P(VDF-HFP) copolymer powder grade 21508. Undrawn and uniaxially drawn cast copolymer films were investigated with respect to their piezo- and pyroelectric properties. Quasistatic charge integration was employed for the determination of the poling-field dependence of the piezoelectric d₃₁ and pyroelectric p₃ coefficients. In addition, the thermal stability of the pyroelectric effect was studied with a combination of thermally stimulated discharge (TSD) and temperature-modulation techniques. Cast copolymer films could withstand electrical poling fields of up to 400 MV/m. The maximum values of d₃₁=30 pC/N and p₃=49 μC/(m²K) for uniaxially drawn samples are similar to those found on commercial PVDF films and much higher than those on pure PVDF films cast from solution. Samples kept for 5 min at 150 °C still exhibit 30–40% of the initial pyroelectric effect [up to around 20 μC/(m²K)]. After this annealing step, no further decay of the pyroelectric coefficient could be observed during storage at 120 °C for several hours. Received: 5 July 2001 / Accepted: 27 July 2001 / Published online: 2 October 2001     

Fabrication and electrical properties of sol-gel-derived Ba0.8Sr0.2TiO3 ferroelectric films from a 0.05-M spin-on solution

Barium strontium titanate (Ba_0.8Sr_0.2TiO₃) films with good ferroelectricity have been obtained by a developed sol-gel processing, using a 0.05-M spin-on solution. X-ray diffraction and Raman spectroscopy investigations showed that the Ba_0.8Sr_0.2TiO₃ film exhibited a tetragonal structure at room temperature. Field-emission scanning electron microscopy measurements revealed that large columnar grains with the size of 100 to 200 nm in the film were formed from the highly dilute spin-on solution with layer-by-layer homoepitaxy. Electrical measurements for the prepared Ba_0.8Sr_0.2TiO₃ film showed a remnant polarization of 3.5 μC/cm², a coercive field of 53 kV/cm, two distinctive phase transitions, lower dissipation factor, and good insulating properties. These results indicate the sol-gel-derived Ba_0.8Sr_0.2TiO₃ film from a 0.05-M solution is suitable for uncooled infrared detector applications. Received: 19 August 1999 / Accepted: 11 October 1999 / Published online: 1 March 2000     

Simultaneous interaction of methyl radicals and atomic hydrogen with amorphous hydrogenated carbon films, as investigated with optical in situ diagnostics

Methyl radicals (CH₃) and atomic hydrogen (H) are dominant radicals in low-temperature plasmas from methane. The surface reactions of these radicals are believed to be key steps leading to deposition of amorphous hydrogenated carbon (a-C:H) films or polycrystalline diamond in these discharges. The underlying growth mechanism is studied, by exposing an a-C:H film to quantified radical beams of H and CH₃. The deposition or etching rate is monitored via ellipsometry and the variation of the stoichiometry is monitored via isotope labeling and infrared spectroscopy. It was shown recently that, at 320 K, methyl radicals have a sticking coefficient of 10^-4 on a-C:H films, which rises to 10^-2 if an additional flux of atomic hydrogen is present. This represents a synergistic growth mechanism between H and CH₃. From the interpretation of the infrared data, a reaction scheme for this type of film growth is developed: atomic hydrogen creates dangling bonds by abstraction of bonded hydrogen within a surface layer corresponding to the range of H in a-C:H films. These dangling bonds serve at the physical surface as adsorption sites for incoming methyl radicals and beneath the surface as radicalic centers for polymerization reactions leading to carbon–carbon bonds and to the formation of a dense a-C:H film. Received: 18 July 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Luminescence properties from erbium oxide nanocrystals dispersed in titania/organically modified silane composite sol–gel thin films

Luminescence properties from erbium (III) oxide nanocrystals dispersed in titania/organically modified silane composite thin films were studied. Erbium oxide nanocrystals were prepared by an inverse microemulsion technique. A strong room-temperature photoluminescence was observed at 1.531 μm, with the full width at half maximum (FWHM) of 22 nm due to intra-atomic transitions between ⁴ I _13/2 and ⁴ I _15/2 levels in the erbium (III) ion. The shape, peak position, and FWHM of the photoluminescence signals from the composite thin films were quite comparable to those prepared by other methods. The photoluminescence peak of the composite thin films showed a maximum intensity at the heat-treatment temperature of 300 °C. A room-temperature green up-conversion emission at 543 nm (⁴ S _3/2?⁴ I _15/2) was observed for the composite thin films with different heat-treatment temperatures upon excitation at 993 nm. The up-conversion emission mechanism was explained by means of an energy-level diagram and the lifetime of the visible up-conversion emission was measured. Received: 10 July 2000 / Accepted: 11 July 2000 / Published online: 5 October 2000     

High-performance pyroelectric single crystals for uncooled infrared detection applications

Uncooled pyroelectric infrared detectors based on ferroelectric single crystals 0.74Pb(Mg_1/3Nb_2/3)O₃–0.26PbTiO₃ (PMN–0.26PT) were fabricated. The performances of pyroelectric detectors dependence on detector fabrication temperature, absorption layer, and element thickness were compared. The room-temperature voltage responsivity (R_v) of 200 V/W and specific detectivity (D^*) of 10⁸ cm Hz^1/2/W at 12.5 Hz have been achieved. The results reveal that the better pyroelectric response can be expected by controlling temperature below 70 °C during the fabrication of the pyroelectric detectors, selecting absorption layer with high absorption coefficient, and decreasing the thickness of the elements.     

Structural and magnetic properties of Co-C composite films and Co/C multilayer films

CoC composite films and Co/C multilayer films have been prepared by a method incorporating ion beam sputtering and plasma chemical vapor deposition. It has been found that the structure and magnetic properties of both the Co-C composite and the Co/C multilayer films depend strongly on the substrate temperature during deposition. The Co-C composite film deposited at room temperature is amorphous, with relatively low saturation magnetization and coercivity. On the other hand, the film deposited at 250 °C is composed of fine Co crystallites separated by amorphous C or Co-C phase. As a result, both the saturation magnetization and coercivity are increased compared with the film deposited at room temperature. When deposited at room temperature, the Co/C multilayer film exhibits good periodicity, with a period of 70 nm (Co: 40 nm, C: 30 nm) and sharp and flat Co-C interfaces. High magnetization (602 emu/cm³) and low coercivity (1.6 Oe) are obtained for such a film. However, increasing the substrate temperature to 250 °C was found to be detrimental to the magnetic properties due to the formation of cobalt carbide at the Co-C interface. Received: 11 July 2000 / Accepted: 13 July 2000 / Published online: 30 November 2000     

The effect of potential of impedance in the pulsed-laser-deposited SrBi2Ta2O9 thin film

Ferroelectrics SrBi₂Ta₂O₉ (SBTO) thin films were grown on a highly oriented Pt/Ti/SiO₂/Si substrates using the pulsed laser ablation. The ac impedance of SBTO thin films have been measured at room temperature both in the frequency range from 10⁻¹ to 10⁶ Hz and bias voltage range from −6 to 6 V. The ac impedance dispersion was observed at low frequency with increasing bias voltage, which was interpreted based on a blocked charge. We can explain that the blocking interface gives rise to constant phase element (CPE) response, and we give an impedance model function that can fit data along the low frequency range when such a CPE is found. The low frequency dispersion phenomena of SBTO thin film are related to a charge diffusion process at the surface of thin film.     

Photocontrol of magnetization in Al-substituted Fe3O4 thin films

Thin films of (111)-oriented spinel ferrite Al_0.5Fe_2.5O₄ have been prepared by a pulsed-laser deposition (PLD) technique on α-Al₂O₃ (0001) substrates. The films exhibit cluster-glass behaviors with a spin-freezing temperature, T_g, near or above room temperature. The magnetization was found to increase following light irradiation below T_g, which indicates the photoinduced melting of cluster-glass states. An analysis comparing the dynamic behavior of magnetic response to light irradiation between zero-field-cooled (ZFC) states and field-cooled (FC) states at 10 K under various light intensities, I, revealed that the direct photoexcitation of spins occurs when I≤0.78 mW/mm², while the thermal heating effect following the light absorption of the samples also contributes to the enhancement of magnetization when I≥1.22 mW/mm². The magnetization of the films could be controlled by light irradiation even at room temperature. This suggests the possibility of utilizing these films in the development of novel magneto-optical memory devices.     

ZrN, ZrxAlyN and ZrxGayN thin films – novel materials for hard coatings grown using pulsed laser deposition

High-quality thin films of ZrN, Zr_xAl_yN and Zr_xGa_yN have been grown by pulsed reactive crossed-beam laser ablation using Zr, Zr-Al and Zr-Ga ablation targets, respectively, and a N₂ gas pulse. The films were characterized for their chemical, crystallographic and tribological properties. All the films had very low impurity levels and a cubic rock salt crystal structure over the entire investigated temperature range between room temperature and 600 °C. High-quality epitaxial films could be grown on Si (001) at 400 °C, though the crystallinity was disrupted at 525 °C by Si diffusion into the film bulk and the formation of ZrSi₂ crystallites. Films grown on stainless steel were polycrystalline. The ratios of the metals in the alloy targets were in general not equal to those in the films: the Al content in the Zr_xAl_yN films was lower than the target value, which we attribute to differential scattering in the ablation plume. The Ga content in the Zr_xGa_yN films fell with increasing substrate temperature, indicative of re-evaporation of Ga from the substrate surface. Those Zr_xGa_yN films with the highest Ga content, grown at the lowest temperatures, were particularly nitrogen-deficient, which we attribute to the low reactivity of Ga with N₂. The Zr_xAl_yN films had an exceptionally low coefficient of friction (0.20) versus steel and the greatest nanohardness of 28 GPa. Received: 9 November 2000 / Accepted: 14 November 2000 / Published online: 28 February 2001     

Texture control and its impact on the properties of SrBi2Ta2O9 thin films prepared by pulsed laser deposition

SrBi₂Ta₂O₉ (SBT) ferroelectric thin films with different preferred orientations were deposited by pulsed laser deposition (PLD). Several methods have been developed to control the preferred orientation of SBT thin films. For SBT films deposited directly on Pt/TiO₂/SiO₂/Si substrates and in situ crystallized at the deposition temperature, the substrate temperature has a significant impact on the orientation and the remnant polarization (Pr) of the films; a higher substrate temperature benefits the formation of (115) texture and larger grain size. The films deposited on Pt/TiO₂/SiO₂/Si substrates at 830 °C are (115)-oriented and exhibit 2Pr of 6 μC/cm². (115)- and (200)-predominant films can be formed by using a La_0.85Sr_0.15CoO₃ (LSCO) buffer layer or by annealing amorphous SBT films deposited on Pt/TiO₂/SiO₂/Si substrates at 450 °C using rapid thermal annealing (RTA). These films exhibit good electric properties; 2Pr of the films are up to 12 μC/cm² and 17 μC/cm², respectively. The much larger 2Pr of the films deposited on the LSCO buffer layer and of the films obtained by RTA than 2Pr of the films deposited on Pt/TiO₂/SiO₂/Si substrates at 830 °C is attributed to a stronger (200) texture. Received: 30 January 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

A novel time-integral type laser energy meter based on anisotropic Seebeck effect

We have posed the design of a time-integral type laser energy meter based on anisotropic Seebeck effect for the first time. Anisotropic Seebeck effect is responsible for the laser-induced thermoelectric voltage effect in high temperature superconductor (HTSC) cuprates and colossal magnetoresistance (CMR) manganites thin films grown on tilted single crystal substrates. In this study, for an example, an epitaxial La_2/3Ca_1/3MnO₃ thin film prepared on a tilted LaAlO₃ substrate by standard pulsed-laser deposition (PLD) method is tested with a 1064-nm Q-switched Nd:YAG laser and its 2nd (532 nm), 3rd (355 nm), and 4th (266 nm) harmonics from room temperature to 16 K. The integral of the voltage signal with time shows a good linear relation with the laser energy per pulse in the measured wavelength and temperature range, which confirms the theoretical analysis given in this letter and can be used to design a time-integral type laser energy meter. The sensitivity increases as the film thickness increases or as the thermal diffusion constant decreases, which makes the time-integral type laser energy meter low cost as compared with the peak-voltage type. It operates with fast (nanosecond range) and broad-spectrum (from infrared to ultraviolet) response in wide temperature range (from room temperature to 10s K), and can be useful replacements for pyroelectric power/energy meters.     

Crystalline and photoluminescence characteristics of YVO4:Sm thin films grown by pulsed laser deposition under oxygen pressure

YVO₄:Sm³⁺ films were deposited on Al₂O₃ (0 0 0 1) substrates at various oxygen pressures changing from 13.3 to 46.6 Pa by using the pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by means of X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The XRD pattern confirmed that YVO₄:Sm³⁺ film has zircon structure and the AFM study revealed that the films consist of homogeneous grains ranging from 100 to 400 nm. The room temperature photoluminescence (PL) spectra showed that the emitted radiation was dominated by a reddish-orange emission peak at 602 nm radiating from the transition of (⁴G_5/2→⁶H_7/2). The crystallinity, surface morphology, and photoluminescence spectra of thin-film phosphors were highly dependent on the deposition conditions, in particular, the substrate temperature. The surface roughness and photoluminescence intensity of these films showed similar behavior as a function of oxygen pressure.     

Synthesis of carbon nitride films by direct current plasma assisted pulsed laser deposition

Carbon nitride films were deposited by pulsed laser ablation of a graphite target under a nitrogen atmosphere at room temperature. A direct current discharge apparatus was used to supply active nitrogen species during the deposition of carbon nitride films. The composition and bonding structure of carbon nitride films were determined by Fourier-transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy. The incorporation of nitrogen atoms in the films is greatly improved by the using of a dc glow discharge. The ratio N/C can reach 0.34 at the discharge voltage of 400 V. Six peaks centered at 1025 cm^-1, 1226 cm^-1, 1381 cm^-1, 1534 cm^-1, 1629 cm^-1, and 2200 cm^-1 can be clearly distinguished from the FTIR spectra of the deposited films, which indicates the existence of C–N, C=N, and C≡N bonds. The fraction of sp² C, C≡N bonds, and C=N bonds in the deposited films increases with increasing discharge voltage. Deconvolution results of C 1s and N 1s spectra also indicate that nitrogen atoms in the films are chemically bonded to sp¹ C, sp² C, and sp³ C atoms. Most of the nitrogen atoms are bonded to sp² C atoms. Increasing the discharge voltage leads to a decrease of the fraction of nitrogen atoms bonded to sp² C and the fraction of amorphous carbon; however, it leads to an increase of the fraction of nitrogen atoms bonded to sp³ C and the fraction of sp² C and sp³ C atoms bonded to nitrogen atoms. Received: 7 June 2000 / Accepted: 19 February 2001 / Published online: 27 June 2001     

Synthesis and properties of In2(Se1-xTex)3 thin films: a new semiconductor compound

In₂(Se_1-xTe_x)₃ polycrystalline films were prepared by a dual-source thermal evaporation technique. The depositions onto glass and SnO₂-coated glass substrates were carried out in a vacuum chamber and followed by an annealing in neutral ambient (Ar or N₂). The structural, morphological and compositional studies of the films were made by X-ray diffraction, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman scattering and optical transmission. Optimum conditions are investigated for the formation of the ternary compound In₂(Se_1-xTe_x)₃ in order to tune the band gap by changing the Te concentration. The film properties as a function of Te amount are discussed. It is shown that single-phase, textured and homogeneous layers of In₂(Se_1-xTe_x)₃ can be grown with x≤0.2 at optimal deposition and heat treatment conditions. For x≅0.17 these films showed an energy band gap of about 1.45 eV and an electrical conductivity at room temperature six orders of magnitude higher than that of the binary γ-In₂Se₃ thin films. Received: 9 July 1999 / Accepted: 25 November 1999 / Published online: 13 July 2000