Pyroelectric characteristics of thin PbTiO3 and la-modified PbTiO3 films on platinum films for infrared sensors

In this work, we grew lead titanate (PbTiO₃) and La-modified PbTiO₃ thin films on platinized silicon (Si(100)) substrates under controlled substrate temperature and ambient by a modified jet-vapor deposition (JVD) process described in this paper. The x-ray diffraction patterns obtained from these films showed a single-phase perovskite structure. We examined locally homogeneity and thickness of these films through the comparative use of laser Raman spectroscopy. We also collected Raman and x-ray data on pure PbTiO₃, as well as prepared lead zirconate titanate (PZT) (54/46), and PZT (50/50) films using the JVD process. This paper discusses the temperature variations of the pyroelectric and dielectric properties of three compositions of La-modified PbTiO₃ films containing 5.2% to 15% of La, respectively, with a view toward studying the effect of La in place of Pb on these electrical properties. We detected significant pyroelectric currents on all three La-modified PbTiO₃ films before performing poling treatments, and observed pyroelectric coefficeints as high as 84 nC/cm²·°C in the poled La-doped PbTiO₃ films containing 5.2% La. The pyroelectric coefficient and dielectric constant varied significantly with La content. We compared the calculated figures of merit, which were based on the measured physical properties, with pure PbTiO₃ as well as PZT and lead lanthanide zirconate titanate (PLZT) films. These properties just described illustrate that these films would be suitable for IR detectors.     

Sol-Gel processing of Nb-doped Pb(Zr,Ti)O3 thin films for ferroelectric memory applications

The ferroelectric properties of Nb-doped PZT thin films prepared by a sol-gel method were evaluated relative to memory device application requirements. Within the range of 0 to 4 mol %, Nb-doping of PZT compositions near the morphotropic phase boundary region (i.e. PZT 53/47) enhanced overall ferroelectric properties by reducing the te-tragonal distortion of the unit cell. A 4 mol % Nb-doped PZT 53/47 thin film (0.26 μm) had a coercivity of 8 V/ μm, a remanence ratio of 0.54, a switchable polarization of 45 μC/cm², and a specific resistivity of 3 x 10⁹ Ω-cm. Nb-doping levels in excess of 5 mol had a detrimental effect on the resulting thin film ferroelectric properties. X-ray diffraction (XRD) analysis of highly doped films showed development of a significant PbO phase accompanied by diffraction line broadening of the perovskite phase. As such, it was postulated that the creation of excessive lead vacancies in the PNZT lattice resulted in PbO accumulation at the grain boundaries which impeded grain growth, and hence, adversely affected ferroelectric switching performance. The fatigue performance of the sol-gel derived thin film capacitor system was a function of switching voltage. At switching fields sufficient to saturate the polarization, the endurance of the thin film capacitor was greater than 10⁹ cycles. Cycling with lower fields reduced endurance values, but in all cases, the switchable polarization decreased linearly with the logarithm of cycles. Nb-doping did not have a significant effect on the fatigue performance.     

Microstructures and electrical properties of SrRuO3 thin films on LaAIO3 substrates

Conductive SrRuO₃ thin films have been deposited using pulsed laser deposition on LaA10₃ substrates at different substrate temperatures. Structural and microstructural properties of the SrRuO₃/LaAlO₃ system have been studied using x-ray diffraction, scanning electron microscopy, and scanning tunneling microscopy. Electrical properties of SrRuO₃ thin films have been measured. It was found that the film deposited at 250°C is amorphous, showing semiconductor-like temperature dependence of electrical conductivity. The film deposited at 425°C is crystalline with very fine grain size (100∼200?), showing both metallic and semiconductor-like temperature dependence of electrical conductivity in different temperature regions. The film deposited at 775°C shows a resistivity of 280 μΩ.cm at room temperature and a residual resistivity ratio of 8.4. Optimized deposition conditions to grow SrRuO₃ thin films on LaA10₃ substrates have been found. Possible engineering applications of SrRuO₃ thin films deposited at different temperatures are discussed. Bulk and surface electronic structures of SrRuO₃ are calculated using a semi-empirical valence electron linear combination of atomic orbitals approach. The theoretical calculation results are employed to understand the electrical properties of SrRuO₃ thin films.     

Microwave properties of epitaxial large-area Ca-doped YBa2Cu3O7−δ thin films on r-plane sapphire

Ca doping of YBa₂Cu₃O_7−δ (YBCO) is well known to enhance the critical current density in large-angle grain boundaries for example of bicrystals. However, up to now no data are available on microwave properties of epitaxial Ca-doped YBa₂Cu₃O_7−δ thin films on r-plane sapphire with CeO₂ buffer layer.Therefore, first results are presented for large-area pulsed laser deposition (PLD) grown Ca_xY_1−xBa₂Cu₃O_7−δ films on 3-in. diameter sapphire wafers. The PLD process is optimised for undoped YBCO thin films and shows high reproducibility for YBCO. The microwave surface resistance R_s at 8.5 GHz of Ca-doped YBCO (x=0.1) thin films shows clear reduction (up to 20%) with respect to that of YBCO for temperatures from about 20–50 K. In addition, microwave surface resistance R_s of Ca-doped YBCO is lower than that of YBCO even for enhanced microwave surface magnetic field up to about 20 mT for temperatures 20 and 40 K.     

铁电薄膜非制冷红外探测器的技术发展

介绍了课题组在铁电薄膜的制备、特性研究以及非制冷红外探测技术方面的研究结果。研究获得了几种控制铁电薄膜微结构(如晶粒尺寸、晶粒形状、Ba_1-xSr_xTiO₃(BST)和PbZr_xTi_1-xO₃ (PZT)铁电薄膜的择优取向生长等)的新技术;研制出具有高度自极化特性的0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMNT)弛豫铁电薄膜;探索了一种具有将红外转化为可见光机制的新型光读出方式;发明了PZT薄膜的低温(400 °C)生长方法。此外,还介绍了256×1线列铁电薄膜非制冷红外探测器的研制及部分成像结果。     

Deposition and characterization of Pb TiO3 thin films on silicon wafers using metalorganic sources

Ferroelectric PbTiO₃ thin films were deposited on bare silicon and Pt/SiO₂/Si substrates by metalorganic chemical vapor deposition in a temperature range from 270 to 550°C. The deposition of a single phase PbTiO₃ thin film did not occur on bare silicon substrates. Instead a double layer of lead-silicate and PbTiO₃ was formed owing to a serious diffusion of lead and oxygen ions into silicon substrates. But on Pt/SiO₂/Si substrates, a single phase PbTiO₃ oriented parallel to a-and c-axis was grown at a substrate temperature as low as 350°C even without a high temperature post-annealing. To get an optimal film, a precise control of input gas composition and also a deposition in a low temperature range from 350 to 400°C are necessary.     

Comparison of the surface morphology and microstructure of in situ and ex situ derived YBa2Cu3O7−x thin films

The surface morphology and microstructure of in situ and ex situ derived YBa₂Cu₃O_7−x (YBCO) thin films have been investigated. In situ films were deposited by single-target off-axis sputtering and three-target co-sputtering. Ex situ films were derived by metalorganic deposition (MOD) of trifluoroacetate precursors. Surface defects resulting from mixed a-axis and c-axis orientation as well as secondary phases have been identified in these films. Despite these defects, films with excellent electrical properties have been formed. However, defects interfere with film patterning and the fabrication of multi-layered structures. Several secondary phase precipitates have been identified, including CuO, Y₂O₃, Cu-Ba-O, and Y₂Cu₂O₅. Secondary phases resulting from a lack of stoichiometry can be eliminated by direct composition control in the MOD and three-target sputtering techniques, and by composition control through the application of an externally applied magnetic field in single-target off-axis sputtering. Secondary phases caused by contamination were also identified: Cr-Ba-O in off-axis sputtering, resulting from contamination by the oxidized heater block; and BaSO₄ in MOD, resulting from gas phase impurities. These results suggest that cation composition control is not sufficient to prevent the formation of secondary phases and that small levels of contamination may prevent phasepure material from being formed.     

Improved barium fluoride process YBa2Cu3)7-x films via post-anneal monitoring

The continuous monitoring of the conversion, of Y, Cu and BaF₂ precursors to form superconductor thin films has been achieved using a fluorine-specific-ion electrode immersed in an effluent gas-washing cell. High-quality thin films of YBa₂Cu₃O_7-x deposited on NdGaO₃, LaA10₃ and LaGaO₃, have been produced by limiting the wet oxygen annealing phase of the post-deposition anneal. When the films were over-annealed in humidified oxygen the superconducting transition temperature as measured by inductive methods and the crystal quality, determined by x-ray rocking curves were degraded.     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

Recent progress of (Ba,Sr)TiO<Subscript>3</Subscript> thin films for tunable microwave devices

The (Ba_1−xSr_x)TiO₃ (BST) ferroelectric thin films exhibit outstanding dielectric properties, even at high frequencies (>1 GHz), and large, electric-field dielectric tunability. This feature makes them suitable for developing a new class of tunable microwave devices. The dielectric properties and dielectric tuning property of BST thin films are closely related to the film compositions, substrate types, and post-deposition process. The successful implementation of BST films as high-frequency dielectrics in electrically tunable microwave devices requires a detailed understanding of both their processing and material properties. This paper will review the recent progress of BST thin films as active dielectrics for tunable microwave devices. The technical aspects of BST thin films, such as processing methods, post-annealing process, film compositions, film stress, oxygen defects, and interfacial structures between film and substrate, are briefly reviewed and discussed with specific samples from the recent literature. The major issues requiring additional investigations to improve the dielectric properties of BST thin films for tunable microwave applications are also discussed.     

Effects of excess Bi concentration, buffered Bi2O3 layer, and Ta doping on the orientation and ferroelectricity of chemical-solution-deposited Bi3.25La0.75Ti3O12 films

Effects of excess Bi concentration, buffered Bi₂O₃ layer, and Ta doping on the orientation and ferroelectricity of chemical-solution-deposited (CSD) Bi_3.25La_0.75Ti₃O₁₂ (BLT) films on Pt/SiO₂/Si(100) were studied. The optimum concentration of excess Bi added to the BLT films to achieve a larger remanent polarization (2Pr) was 10 mol.%. The buffered Bi₂O₃ layers could reduce the temperature for c-axis-oriented growth of BLT films from 850°C to 700°C. However, two-step annealing, i.e., first annealed at 650°C and then annealed at a temperature of 700–850°C, could effectively suppress the c-axis-oriented growth and thus improve the 2Pr of BLT films. The improvement of the 2Pr of BLT films can be explained in terms of the large polarization along the a-axis orientation and buffered Bi₂O₃ layers, which compensate the BLT films for Bi evaporation during annealing. The Ta doping can induce two contrary effects on the 2Pr of BLT films. For the (Bi_3.25La_0.75)(Ti_3−xTa_x)O₁₂ (BLTTx) films with x=0.005, the effect of a decrease of oxygen vacancies would be dominant, resulting in the improvement of 2Pr. Because the Ta concentration (x) in the BLTTx films exceeds 0.01, the effect of a decrease of grain size would become dominant, resulting in the degradation of 2Pr.     

LaNiO3 and Cu3Ge contacts to YBa2Cu3O7-x films

Metallization of high-T_c superconductors using low resistivity metal oxides and Cu-Ge alloys has been investigated on high quality pulsed laser deposited epitaxial YBa₂Cu₃O_7-x (YBCO) films. Epitaxial LaNiO₃ (LNO) thin films have been grown on YBCO films at 700°C using pulsed laser deposition. The specific resistivity of LNO was measured to be 50 μΩ-cm at 300K which decreases to 19 μΩ-cm at 100K indicating good metallicity of the LNO films. The contact resistance of LNO-YBCO thin film interface was found to be reasonably low (of the order of 10^-4Ω-cm² at 77K) which suggests that the interface formed between the two films is quite clean and LNO can emerge as a promising metal electrode-material to YBCO films. A preliminary investigation related to the compatibility of Cu₃Ge alloy as a contact metallization material to YBCO films is discussed. The usage of other oxide based low resistivity materials such as SrRuO₃ (SRO) and SrVO₃ (SVO) for metallization of high-T_c YBCO superconductor films is also discussed.     

Preparation and gas-sensing properties of α-Fe2O3 thin films

Haematite (α-Fe₂O₃) thin films are prepared by two different chemical vapor deposition (CVD) processes: the atmospheric pressure CVD (APCVD) and the plasma enhanced CVD (PECVD). The films are analyzed by x-ray diffraction and scanning electron microscopy; their gas-sensing properties are also investigated. Experimental results show that APCVD α-Fe₂O₃ films are highly sensitive and selective to smoke while PECVD films are highly sensitive and selective to alcohol. A certain amount of quadrivalent metal in the films has an effect on their sensitivity and selectivity to gases. It is found that the films will “break down” under certain conditions.     

Preparation of PbTiO3 thin films by plasma enhanced MOCVD and the effect of rapid thermal annealing

Dielectric PbTiO₃-thin films were prepared on p-Si(100) substrate by plasma enhanced metalorganic chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄, Pb(tmhd)₂, and oxygen. As-deposited films were post-treated by rapid thermal annealing method, and the effect of annealing was examined under various conditions. The deposition process was controlled by mixed-control scheme at temperatures lower than 350°C, but controlled by heterogeneous surface reaction at temperatures greater than 350°C. The as-deposited films showed PbO structure at 350∼400°C, but (100) and (101) PbTiO₃ orientations started to appear at 450°C. The deposition rate was increased with rf power due to the enhanced dissociation of Ti and Pb precursors. It was found that the concentration of oxygen plays an important role in crystallization of PbTiO₃ during the rapid thermal annealing. A linear relationship was obtained between the dielectric constant of PbTiO₃ films and the annealing temperature. However, the surface roughness and leakage current density increased mainly due to the defects caused by volatilization of lead and the interface layer formed during the high temperature annealing.     

Electrical properties of metal-ferroelectric-insulator-semiconductor structure using BaxSr1−xTiO3 for ferroelectric-gate field effect transistor

Perovskite ferroelectric Ba_xSr_1−xTiO₃ (x = 0.5, 0.6, 0.7 and 0.8) thin films have been fabricated as metal-ferroelectric-insulator-semiconductor (MFIS) configurations using a sol-gel technique. The C-V characteristics for different Ba-Sr ratios and different film thicknesses have been measured in order to investigate the ferroelectric memory window effect. The results show that the memory window width increases with the increase both of Ba content and film thickness. This behavior is attributed to the grain size and dipole dynamics effect. It is found also that the memory window increases as the applied voltage increases. In addition, the leakage current density for the films is measured and it is found to be of the order of 10⁻⁸ A/cm² for all tested samples, indicating that the films have good insulating characteristics.     

Microstructural study of the effect of an excess of Y2BaCuO5 and BaSnO3 doping on the texturing process of YBa2Cu3O7−x bulk superconductors

Melt texture process of YBCO leads to a YBa₂Cu₃O_7−x matrix where Y₂BaCuO₅ particles are observed. The Y₂BaCuO₅ inclusions size and distribution depend upon several parameters: YBa₂Cu₃O_7-x grain size in the presintered, heating rate, dopants. The influence of an excess of Y₂BaCuO₅ and/or BaSnO₃ on these Y₂BaCuO₅ particles are observed in the liquid phase and in the texture domain. According to the dopant used, two kinds of coarsening of Y₂BaCuO₅ can be observed: an isotropic and an anisotropic. The control of the distribution of Y₂BaCuO₅ particle size is of primary interest to improve the efficiency of the MTG process. In particular large cooling rate (5°C/h) during the texture formation could be used by adding Y₂BaCuO₅ + BaSnO₃ to YBa₂Cu₃O_7−x composition.     

Etch damage evaluation on (Bi4−xLax)Ti3O12 thin films during the etch process using inductively coupled plasma sources

The etching mechanism of (Bi_4−xLa_x)Ti₃O₁₂ (BLT) thin films in Ar/Cl₂ inductively coupled plasma (ICP) and plasma-induced damages at the etched surfaces were investigated as a function of gas-mixing ratios. The maximum etch rate of BLT thin films was 50.8 nm/min of 80% Ar/20% Cl₂. From various experimental data, amorphous phases on the etched surface existed on both chemically and physically etched films, but the amorphous phase was thicker after the 80% Ar/20% Cl₂ process. Moreover, crystalline “breaking” appeared during the etching in Cl₂-containing plasma. Also the remnant polarization and fatigue resistances decreased more for the 80% Ar/20% Cl₂ etch than for pure Ar plasma etch.     

Optical and electrochromic properties of annealed lithium-molybdenum-bronze thin films

Optical band gaps, Urbach inverse slopes, and coloration bands of various samples of annealed, microcrystalline Li_xMoO₃-bronze thin films in the concentration range 0<x<0.6 were determined over the photon energy range from 0.4 eV to 4.2 eV. On investigation, it is learned that the measured, optical band gaps do not shift rigidly over the annealing temperature range 293≤T≤423 K and, therefore, do not reveal the Burstein-Moss effect or reflect any stable, crystallographic phase transformation during any investigated annealing cycle. A model relating the temperature-dependent optical gap to the real part of the refractive index has also been developed, and this model fits very well to the annealed data within a maximum error of about 20%. Next, using an oscillator model, a phonon energy of ∼0.08 eV was obtained, which is very close to the characteristic phonon energy of the material, MoO₃. Using this model, it becomes more certain that the contributions to the Urbach absorption edge for the annealed-molybdenum bronzes are coming from the structural and compositional disorder. In another finding, it was found that the absorption-peak energy for the annealed data was about 1.5–1.6 eV, which is still broad and asymmetrical, and therefore, it is almost of the Mo⁶⁺ (or Mo⁴⁺)-Mo⁵⁺ intervalence or polaronic type. Using the polaron model, the half-bandwidth of the coloration bands of investigated, annealed Li_xMoO₃-thin films was found to be almost constant, which is consistent with the nonrigid band behavior.     

Processing of large YBa2 Cu3Ox domains for levitation applications by a Nd1+x Ba2−x Cu3 Oy-Seeded melt-growth technique

YBa₂Cu₃O_x domains for levitation applications have been produced by a seeding technology that includes Nd_1+x Ba_2−x Cu₃O_y seeds and melt-processing technologies such as conventional melt-textured growth, melt-texturing with PtO₂ and Y₂BaCuO₅ additions, and the new solid-liquid-melt-growth technology. Large domains (∼20 mm) with high levitation forces (F₁ up to 8.2 N) have been produced. The reproducibility of the results is good, and the capability of producing a large number of pellets in a single batch indicates good potential for the production of large amounts of this material.     

Microstructure and Characteristics of Thin-Film La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>Co<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>O<Subscript>3</Subscript>/ZnO:Al Heterocontact CO Sensors Prepared by RF Magnetron Sputtering

Highly sensitive CO gas sensors based on heterocontacts of ZnO:Al on La_0.8Sr_0.2Co_0.5Ni_0.5O₃ (LSCNO) were fabricated successfully. La_0.8Sr_0.2Co_0.5Ni_0.5O₃ thin films were coated on (100) silicon wafers by a sol-gel method including the Pechini process followed by a spin-coating procedure. Then, ZnO:Al films prepared by radiofrequency (RF) magnetron sputtering at various oxygen partial pressures and deposited on as-deposited La_0.8Sr_0.2Co_0.5Ni_0.5O₃ films were investigated. The results revealed that the CO sensing ability of the film prepared with the ratio of O₂/Ar = 5/5 (ratio of volume flow rate) was the worst, owing to the highest (002) plane orientation in the ZnO:Al film. In contrast, the ZnO:Al film prepared with O₂/Ar = 3/7 exhibited better CO sensitivity. Furthermore, all two-layer samples showed higher CO sensitivities than single-layer samples. The CO sensitivity of ZnO:Al/La_0.8Sr_0.2Co_0.5Ni_0.5O₃ thin film was 45% for 500 ppm CO at a sensing temperature of 200°C.