Structural and optical properties of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films prepared by chemical solution methods

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films have been grown on Pt/Ti/SiO₂/Si substrates by chemical solution methods. X-ray diffraction analysis shows that BLT thin films are polycrystalline with (171)-preferential orientation. Atomic force microscopy investigation shows that they have large grains about 120 nm in size. A Pt/BLT/Pt capacitor has been fabricated and showed excellent ferroelectricity, with a remnant polarization and coercive field of 24 μC/cm² and 116 kV/cm, respectively. The capacitor shows no polarization fatigue up to 10⁹ switching cycles. The optical constants (n,k) of the BLT thin films in the wavelength range 0.35–1.7 μm were obtained by spectroscopic ellipsometry measurements, and the band-gap energy was found to be about 3.25 eV. Received: 16 October 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/65830-734, E-mail: gswang@mail.sitp.ac.cn     

Ferroelectric properties of Nd-substituted bismuth titanate thin films processed at low temperature

Nd-substituted bismuth titanate Bi_3.54Nd_0.46Ti₃O₁₂ (BNT) thin films were prepared on (111)Pt/Ti/SiO₂/Si substrates by a sol–gel method. The BNT thin films processed at a low annealing temperature of ∼600 °C showed good ferroelectric properties. The randomly oriented BNT single phases and the improved ferroelectric properties were confirmed by X-ray diffraction and polarization–electric field hysteresis loops, respectively. The remanent polarization of the BNT thin films is 64 μC/cm², which is larger than that of Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films. After 10¹⁰ read/write switching cycles, the effective non-volatile charges showed no polarization fatigue. Regardless of the low annealing temperature of 600 °C, the BNT thin films had good ferroelectric properties with high remanent polarizations and strong fatigue resistances. PACS 77.84.Dy     

Infrared Optical Characterization of PLT Thin Films for Applications in Uncooled Infrared Detectors

Lanthanum-modified lead titanate (PLT) thin films have been grown directly on Pt/Ti/SiO₂/Si (100) and LaNiO₃/Si (100) substrates by a modified sol-gel method. X-ray diffraction analysis shows that the PLT thin films are polycrystalline. The infrared optical properties of the thin films were investigated using infrared spectroscopic ellipsometry (IRSE) in the spectral range of 2.5–12.5 m. By fitting the measured ellipsometric parameter (tan and cos) data with a three phase model (air/PLT/Pt) for the PLT thin films on Pt/Ti/SiO₂/Si (100) and a four phase model (air/PLT/LNO/Si) for the PLT thin films on LaNiO₃/Si (100) substrates, 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 and extinction coefficient of the PLT thin films on Pt/Ti/SiO₂/Si (100) substrates are slightly larger than those on LaNiO₃/Si (100) substrates. Given the infrared semitransparent metal of Nickel currently used, the absorption of the Ni/PLT/Pt and Ni/PLT/LNO/Si multilayer thin films in this study is very large around 3.0 m and 5.7 m wavelength range and decrease to 15% or 20% in the 8–12.5 m wavelength region.     

Hydrogen gas-sensing properties of Pt/WO<Subscript>3</Subscript> thin film in various measurement conditions

A well-known gasochromic material is Pt particle-dispersed tungsten trioxide (Pt/WO₃). Its optical properties could make it effective as a hydrogen gas sensor. In this study, Pt nanoparticle-dispersed WO₃ thin films were prepared using the sol–gel process, and their optical and electrical properties dependent on the working environment (i.e., temperature, hydrogen gas concentration, oxygen partial pressure, etc.) were investigated. The Pt/WO₃ thin films prepared at 400 °C showed the largest change in optical transmittance and electrical conductivity when exposed to hydrogen gas compared with the films prepared at other temperatures. The optical absorbance and electrical conductivity were found to be dependent on the hydrogen and oxygen gas concentration in the atmosphere because generation and disappearance of W⁵⁺ in the thin films depend on the equilibrium reaction between injection and rejection of H⁺ into and from the thin films. In addition, the equilibrium reaction depends on the hydrogen and oxygen gas concentrations.     

Effect of measuring factors on ferroelectric properties of?Bi3.15Nd0.85Ti3O12 thin films prepared by sol–gel method for?non-volatile memory

Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by the sol–gel method. The phase composition was detected by XRD, the microstructure was characterized by AFM, and the effect of measuring factors (such as environmental temperature, working frequency, and voltage) on the ferroelectric properties was investigated. The films show the single Bi-layered Aurivillius phase with random orientation. At room temperature, the remanent polarization (2P _r) and the coercive field (2E _c) are 39.1 μC/cm² and 160.5 kV/cm, respectively, and a BNT capacitor shows fatigue-free behavior and memory retention. With the decrease of temperature, 2V _c increases, J decreases slightly, and the general trend of 2P _r is decreased. With the increase of frequency, 2P _r declines and 2V _c increases.     

Structural, ferroelectric and optical properties of Bi2VO5.5 thin films deposited on platinized silicon {(100) Pt/TiO2/SiO2/Si} substrates

Bismuth vanadate (Bi₂VO_5.5, BVO) thin films have been deposited by a pulsed laser ablation technique on platinized silicon substrates. The surface morphology of the BVO thin films has been studied by atomic force microscopy (AFM). The optical properties of the BVO thin films were investigated using spectroscopic ellipsometric measurements in the 300–820 nm wavelength range. The refractive index (n), extinction coefficient (k) and thickness of the BVO thin films have been obtained by fitting the ellipsometric experimental data in a four-phase model (air/BVO_rough/BVO/Pt). The values of the optical constants n and k that were determined through multilayer analysis at 600 nm were 2.31 and 0.056, respectively. For fitting the ellipsometric data and to interpret the optical constants, the unknown dielectric function of the BVO films was constructed using a Lorentz model. The roughness of the films was modeled in the Brugmann effective medium approximation and the results were compared with the AFM observations. PACS 78.20.-e; 77.84.-s; 77.55.+f     

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     

Low-macroscopic field emission from nanocrystalline Al doped SnO<Subscript>2</Subscript> thin films synthesized by sol–gel technique

We have observed low-macroscopic field electron emission from wide bandgap nanocrystalline Al doped SnO₂ thin films deposited on glass substrates. The emission properties have been studied for different anode-sample spacings and for different Al concentrations in the films. The turn-on field and approximate work function were calculated and we have tried to explain the emission mechanism from this. The turn-on field was found to vary in the range 5.6–7.5 V/μm for a variation of anode sample spacing from 80–120 μm. The turn-on field was also found to vary from 4.6–5.68 V/μm for a fixed anode-sample separation of 80 μm with a variation of Al concentration in the films 8.16–2.31%. The Al concentrations in the films have been measured by energy dispersive X-ray analysis. Optical transmittance measurement of the films showed a high transparency with a direct bandgap ∼3.98 eV. Due to the wide bandgap, the electron affinity of the film decreased. This, along with the nanocrystalline nature of the films, enhanced the field emission properties. PACS 81.20.Fw; 61.10.-i; 79.70.+q     

Investigation on optical properties of Bi<Subscript>2.85</Subscript>La<Subscript>0.15</Subscript>TiNbO<Subscript>9</Subscript> thin films by prism coupling technique

Layered-perovskite ferroelectric Bi_2.85La_0.15TiNbO₉ (LBTN) optical waveguiding thin films were grown on fused silica substrates by pulsed laser deposition (PLD). X-ray diffraction (XRD) revealed that the film is highly (00l) textured. We observed sharp and distinct transverse electric (TE) and transverse magnetic (TM) multimodes and measured the refractive indices of LBTN thin films at 632.8 nm. The ordinary and extraordinary refractive indices were calculated to be n _TE=2.358 and n _TM=2.464, respectively. The film homogeneity and the film-substrate interface were analyzed using an improved version of the inverse Wentzel–Kramer–Brillouin (iWKB) method. The refractive index of the film remains constant at n ₀ within the waveguiding layer. The average transmittance of the film is 70% in the wavelength range of 400–1400 nm and the optical waveguiding properties were evaluated by the optical prism coupling method. Our results showed that the LBTN films are very good electro-optical active material.     

Photoacoustic spectroscopy of thin films of As<Subscript>2</Subscript>S<Subscript>3</Subscript>, As<Subscript>2</Subscript>Se<Subscript>3</Subscript> and GeSe<Subscript>2</Subscript>

Photoacoustic spectroscopy (PAS) is one of the important branches of spectroscopy, which enables one to detect light-induced heat production following the absorption of pulsed radiation by the sample. As₂S₃, As₂Se₃ and GeSe₂ exhibit a wide variety of photo-induced phenomena that enable them to be used as optical imaging or storage medium and various electronic devices, including electro-optic information storage devices and optical mass memories. Therefore, accurate measurement of thermal properties of semiconducting films is necessary to study the memory density. The thermal conductivity of thin films of As₂S₃ (thickness 100 μm and 80 μm), As₂Se₃ (thickness 100 μm and 80 μm) and GeSe₂ (thickness 120 μm and 100 μm) has been measured using PAS technique. Our result shows that the thermal conductivity of thicker films is larger than the thinner films. This can be explained by the thermal resistance effect between the film and the surface of the substrate.      

Dielectric anomaly in Li-doped zinc oxide thin films grown by sol–gel route

Sol–gel route was employed to grow polycrystalline thin films of Li-doped ZnO thin films (Zn_1-xLi_xO, x=0.15). Polycrystalline films were obtained at a growth temperature of 400–500 °C. Ferroelectricity in Zn_0.85Li_0.15O was verified by examining the temperature variation of the real and imaginary parts of dielectric constant, and from the C–V measurements. The phase transition temperature was found to be 330 K. The room-temperature dielectric constant and dissipation factor were 15.5 and 0.09 respectively, at a frequency of 100 kHz. The films exhibited well-defined hysteresis loop, and the values of spontaneous polarization (P_s) and coercive field were 0.15 μC/cm² and 20 kV/cm, respectively, confirming the presence of ferroelectricity. PACS 77.22Ch; 77.22Ej; 77.80Bh     

Growth and properties of epitaxial rare-earth scandate thin films

Epitaxial rare-earth scandate thin films of 100–1500 nm in thickness have been prepared by pulsed laser deposition on SrTiO₃(100) and MgO(100) substrates. Stoichiometry and crystallinity were investigated by Rutherford backscattering spectrometry/channelling (RBS/C), transmission electron microscopy, and X-ray diffraction. Electrical measurements on microstructured capacitors with a SrRuO₃ bottom electrode and Au top contacts reveal dielectric constants of 20 to 27, leakage currents of 0.85 to 6 μA/cm² at 250 kV/cm, and breakdown fields of 0.6 to 1.2 MV/cm. The optical bandgaps of the films range from 5.5 to 6 eV. The results substantiate the high potential of rare-earth scandates as alternative gate oxides. PACS 73.61.Ng; 73.40.Rw; 77.22.Ch; 77.55.+f; 78.40.Ha     

Effects of thickness on the infrared optical properties of Ba<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> ferroelectric thin films

Using infrared spectroscopic ellipsometry (IRSE), the optical properties of the Ba_0.9Sr_0.1TiO₃ (BST) ferroelectric thin films with different film thicknesses on Pt/Ti/SiO₂/Si substrates prepared by a modified sol-gel method have been investigated in the 2.5–12.6 m wavelength range. By fitting the measured ellipsometric parameter ( and ) data with a three-phase model (Air/BST/Pt) and the classical dispersion relation for the BST thin films, the optical constants and thicknesses of the thin films have been obtained. The average thickness of the single layer decreases with increasing film thickness. The refractive index of the BST films decreases with increasing thickness in the wavelength range 2.5–11 m, and increases with increasing thickness in the wavelength range 11–12.6 m. However, the extinction coefficient of the BST films monotonously decreases with increasing thickness. It is closely associated with the crystallinity of the thin films, the crystalline size effect and the influence of the interface layer. The absorption coefficient of the BST films with different thicknesses decreases with increasing thickness. PACS 77.55.+f; 78.20.Ci; 78.30.Am; 81.70.Fy; 81.40.Tv     

The influence of lithium excess in the target on the properties and compositions of Li<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>2</Subscript>O<Subscript>4−<Emphasis Type="Italic">δ</Emphasis></Subscript> thin films prepared by PLD

Li–Mn–O thin films were deposited by pulsed laser deposition (PLD) onto stainless steel substrates using targets containing different concentrations of added Li₂O. The influence of the target composition on the stoichiometry of the resulting thin films, the surface morphology and the electrochemical properties was studied. The application of the target with added 7.5 mol% Li₂O results in an almost ideal lithium content, while all films were still oxygen deficient. The thin films were applied as electrodes in Li//Li_1+x Mn₂O_4−δ cells (i.e. model cells for a rechargeable Li-ion battery) and characterized by cyclic voltammetry and galvanostatic charge/discharge experiments. The electrochemical measurements of the thin films confirmed that the thin films can serve as good model systems and that they show a sufficient cyclability.     

Epitaxial growth of ferroelectric PLZT thin film and their optical properties

A series of experiments for growing epitaxial PLZT thin films has been made with rf sputtering. X-ray and electron diffraction analyses confirm that the fabricated films grow epitaxially on SrTiO₃ and MgO crystals. A good transparency in the region above 0.4 μm to infrared with good ferroelectric properties is obtained. Propagation loss of He−Ne laser light is less than 6 dB/cm, and the PLZT thin film is a promising candidate for the optical modulator and other functional elements for integrated optics.     

Structure,transport and field-emission properties of compound nanotubes: CN<Subscript>x</Subscript> vs. BNC<Subscript>x</Subscript> (<Emphasis Type="Italic">x</Emphasis><0.1)

Transport and field-emission properties of as-synthesized CN_x and BNC_x (x<0.1) multi-walled nanotubes were compared in detail. Individual ropes made of these nanotubes and macrofilms of those were tested. Before measurements, the nanotubes were thoroughly characterized using high-resolution and energy-filtered electron microscopy, electron diffraction and electron-energy-loss spectroscopy. Individual ropes composed of dozens of CN_x nanotubes displayed well-defined metallic behavior and low resistivities of ∼10–100 kΩ or less at room temperature, whereas those made of BNC_x nanotubes exhibited semiconducting properties and high resistivities of ∼50–300 MΩ. Both types of ropes revealed good field-emission properties with emitting currents per rope reaching ∼4 μA(CN_x) and ∼2 μA (BNC_x), albeit the latter ropes se- verely deteriorated during the field emission. Macrofilms made of randomly oriented CN_x or BNC_x nanotubes displayed low and similar turn-on fields of ∼2–3 V/μm. 3 mA/cm² (BNC_x) and 5.5 mA/cm² (CN_x) current densities were reached at 5.5 V/μm macroscopic fields. At a current density of 0.2–0.4 mA/cm² both types of compound nanotubes exhibited equally good emission stability over tens of minutes; by contrast, on increasing the current density to 0.2–0.4 A/cm², only CN_x films continued to emit steadily, while the field emission from BNC_x nanotube films was prone to fast degradation within several tens of seconds, likely due to arcing and/or resistive heating. Received: 29 October 2002 / Accepted: 1 November 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

Laser ablation and micropatterning of thin TiN coatings

Laser ablation of thin TiN films deposited on steel substrates has been studied under wide-range variation of irradiation conditions (pulsewidth, wavelength, energy density and spot size). It has been demonstrated that both picosecond (150–300 ps) and nanosecond (5–9 ns) laser pulses were suitable for controllable ablation and microstructuring of a 1-μm-thick TiN film unlike longer 150-ns pulses. The ablation rate was found to be practically independent of the wavelength (270–1078 nm) and pulsewidth (150 ps–9 ns), but it increased substantially when the size of a laser spot was reduced from 15–60 μm to 3 μm. The laser ablation technique was applied to produce microstructures in the thin TiN films consisting of microcraters with a typical size of 3–5 μm in diameter and depth less than 1 μm. Tests of lubricated sliding of the laser-structured TiN films against a steel ball showed that the durability of lubricated sliding increased by 25% as compared to that of the original TiN film. Received: 28 July 1999 / Accepted: 17 April 2000 / Published online: 20 September 2000     

Enhancement of polarization in bismuth titanate thin films co-modified by La and Nd for non-volatile memory applications

Bismuth titanate thin films co-modified by La and Nd, Bi_3.15(La_0.425Nd_0.425)Ti₃O₁₂ (BLNT) were grown on Pt/Ti/SiO₂/Si(100) substrates by metalorganic solution decomposition method. The co-substitution leads to structural distortion with enhanced remanent polarization. The BLNT film capacitor with a top Pt electrode showed a large remanent polarization (2P_r) of 90 μC/cm² at an applied voltage of 10 V, which is higher than that of highly c-axis oriented BLT, and comparable with BNdT thin films. The BLNT films exhibited a fatigue-free behavior up to 1×10⁹ switching cycles at a frequency of 1 kHz. These experimental results reveal that BLNT thin films can be used as capacitors in ferroelectric random access memory applications. PACS 73.40.Rw; 73.61.-r; 77.55. +F; 77.80.-E; 81.20.Fw     

Carbon nanotubes as nanoparticles collector

This communication reports on a new method for the collection of nanoparticles using carbon nanotubes (CNT) as collecting surfaces, by which the problem of agglomeration of nanoparticles can be circumvented. CNT (10–50 nm in diameter, 1–10 μm in length) were grown by thermal CVD at 923 K in a 7 v/v% C₂H₂ in N₂ mixture on electroless nickel-plated copper transmission electron microscopy (TEM) grids and Monel coupons. These samples were then placed downstream of an arc plasma reactor to collect individual copper nanoparticles (5–30 nm in diameter). It was observed that the Cu nanoparticles preferentially adhere onto CNT and that the macro-particles (diameter >1 μm), a usual co-product obtained with metal nanoparticles in the arc plasma synthesis, are not collected. Cu–Ni nanoparticles, a catalyst for CNT growth, were deposited on CNT to grow multibranched CNT. CNT-embedded thin films were produced by re-melting the deposited nanoparticles.     

Electrical and optical properties of vacuum deposited MnPc thin films

Sandwich and planar structures were fabricated using manganese phthalocyanine (MnPc) as active layer and gold (Au) as electrodes by thermal evaporation method. The permittivity ε of MnPc was determined from the dependence of capacitance on film thickness. J-V characteristics of Au/MnPc/Au structure at room temperature were performed. Thermally generated hole concentration p₀, hole mobility μ_p, total trap concentration N_t and depth of the trap level were estimated. The activation energies of MnPc films were determined from the Arrhenius plots of ln σ versus 1000/T. The absorption and reflectance spectra of MnPc thin film deposited at room temperature were recorded in the spectral range 300–900 nm. The optical band gap of MnPc thin film was determined from the α² versus hν graph. The optical constants n and k were found. The real and imaginary parts of the optical dielectric constant ε₁ and ε₂ were calculated.