An Abnormal Photoluminescence Enhancement in (Eu,Yb) Co-doped SiO2 Thin Film

We report on the photoluminescence (PL) properties of europium (Eu) and ytterbium (Yb) co-doped SiO₂ thin film. The Eu (both Eu²⁺ and Eu³⁺) PL and the Yb³⁺ PL is co-related under different temperature annealing. However, upon 1100°C anneal, the Eu PL intensity is significantly stronger than other temperatures anneal. Transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction results, suggest that meta-stable Eu²⁺-related silicates (EuSiO₃) have formed in the oxide as well as the formation of Yb₂Si₂O₇.     

Structural and electrical properties of Sb-doped p-type ZnO thin films fabricated by RF magnetron sputtering

We investigated the Sb-doping effects on ZnO thin film using RF (radio frequency) magnetron sputtering and RTA (rapid thermal annealing). The structural and electrical properties of the thin films were measured by X-ray diffraction, SEM (scanning electron microscope), and Hall effect measurement. Thin films were deposited at a high temperature of 800°C in order to improve the crystal quality and were annealed for a short time of only 3 min. The structural properties of undoped and Sb-doped films were considerably improved by increasing oxygen content in the Ar-O₂ gas mixture. Sb-doping also significantly decreased the electron concentration, making the films p-type. However, the crystallinity and surface roughness of the films degraded and the mobility decreased while increasing Sb-doping content, likely as a result of the formation of smaller grain size. From this study, we observed the transition to the p-type behavior at 1.5 at.% of Sb. The thin film deposited with this doping level showed a hole concentration of 4.412?×?10¹⁷ cm^?3 and thus is considered applicable to p-type ZnO thin film.     

Effects of rapid thermal annealing in different ambients on structural, electrical, and optical properties of ZnO thin films by sol-gel method

We studied the effects of rapid thermal annealing in different ambients on the structural, electrical and optical properties of the sol-gel derived ZnO thin films. All the films after annealing showed highly degree of (002) oriented in the X-ray diffractometry (XRD) patterns. The effects of annealing ambients on electrical properties of the films were studied. Carrier concentration, resistivity and mobility were found to be distinguished after annealed in different ambients. The sample with the lowest resistivity of 0.095 ??·cm and the largest mobility of 105.1 cm²/v·s was achieved after annealing in vacuum. XPS results indicated that more oxygen vacancies existed on the ZnO surface when annealed in vacuum than that in O₂.     

Preparation and characterization of SrBi2Ta2O9 thin films by low-oxygen-concentration annealing technique

SrBi₂Ta₂O₉ thin films were successfully prepared at a low annealing temperature using a low-oxygen-concentration annealing technique. It was possible to obtain a single perovskite phase at 600 °C in 0.7% oxygen concentration and fluorite phase was observed at 600 °C in 100% oxygen. In addition, the SrBi₂Ta₂O₉ thin films annealed at 650 °C in 0.7% oxygen were well crystallized and composed of dense crystal grains with a size of 70 nm. The remanent polarization and leakage current density of the SrBi₂Ta₂O₉ thin film obtained using this new technique were 7 μC/cm² and 3 × 10⁻⁹ A/cm² (at 5 V), respectively. The final remanent polarization after 10⁹ switching cycles was nearly constant. © 1999 Scripta Technica, Electr Eng Jpn, 129(4): 1–6, 1999     

Epitaxial recrystallization and luminescence of CaAl2O4:Eu2+ thin films prepared on sapphire substrates

Eu²⁺ doped CaAl₂O₄ thin films were prepared on c-, a-, and r-plane sapphire substrates by a sputtering method, and then post-annealed for the recrystallization. Post-annealed films have out-of-plane epitaxial orientations of (010) and (001) CaAl₂O₄ on c- and a-plane sapphire substrates, respectively, whereas the films on r-plane were composed of two epitaxial phases of (210) CaAl₂O₄ and (210) CaAl₄O₇. In-plane relationships between films and substrates were also determined by an X-ray pole figure method, demonstrating that the films were epitaxially recrystallized, but not single crystals. The emission wavelengths were independent of the orientations of epitaxial films, showing a blue emission at 448 nm under 325 nm excitation, but the emission intensity depended on the film structure.     

Fabrication of MFIS diodes using sol-gel derived SBT films and LaAlO3 buffer layers

Abstract

We demonstrate the ferroelectric behavior of Sr_0.8Bi_2.2Ta₂O₉ (SBT) films grown on Si(100) substrates by using lanthanum aluminate (LaAlO₃) buffer layers. LaAlO₃ films were prepared by vacuum evaporation method. Then, they were subjected to ex situ dry N₂ annealing in a rapid thermal annealing (RTA) furnace. From the capacitance-voltage (C-V) measurement, the dielectric constant of LaAlO₃ was estimated to be 20～25. On these substrates, SBT films (210nm) were deposited by sol-gel method and they were characterized by XRD analysis after annealing under various conditions. It was found from C-V characteristics that the memory window of an SBT film annealed at 750°C for 30min in O₂ atmosphere was about 3.0V for the voltage sweep of ±10V. It was also found from the retention measurement that the capacitance values of the SBT film annealed at 750°C did not change over 12hours. It is concluded from these results that the SBT/LaAlO₃/Si(100) structure is one of the most promising structures for realizing MFISFETs (metal-ferroelectric-insulator-semiconductor field-effect-transistors).     

Characteristics of Bi4Ti3O12 thin films on ITO/glass and Pt/Si substrates prepared by R.F. sputtering and rapid thermal annealing

Bi₄Ti₃O₁₂ thin films are deposited on ITO/glass and Pt/Ti/Si(100) substrates by R.F. magnetron sputtering at room temperature. The films are then heated by a rapid thermal annealing (RTA) process conducted in oxygen atmosphere at temperatures ranging from 550–700^∘C. X-ray diffraction examination reveals that the crystalinity of the films grown on Pt/Ti/Si is better than that of the films grown on ITO/glass under the same fabrication conditions. SEM observation shows that the films grown on Pt/Ti/Si are denser than those grown on ITO/glass substrates. Interactive diffusion between the Bi₄Ti₃O₁₂ film and the ITO film increases with the increase of annealing temperature. The optical transmittance of the thin film annealed at 650^∘C is found to be almost 100% when the effect of the ITO film is excluded. The relative dielectric constants, leakage currents and polarization characteristics of the two films are compared and discussed.     

Optical characteristics of Bi4-xEuxTi3O12 ferroelectric thin films on fused silica substrates

Bi_4-xEu_xTi₃O₁₂ (BEuT) ferroelectric thin films were prepared on fused silica substrates by using chemical solution deposition technique. The attained samples had a polycrystalline bismuth-layered perovskite structure, and their optical properties were composition dependent. The thin film samples had good optical transmittance above 500?nm wavelength. A blue shift of the optical absorption edge was observed in the BEuT thin films with increasing Eu³⁺ concentration. The optical band gaps of BEuT thin films were estimated to be about 3.57, 3.60, 3.61, 3.63, and 3.69?eV for the samples with x?=?0.25, 0.40, 0.55, 0.70, and 0.85, respectively. Photoluminescence measurements showed that two emission peaks of BEuT thin films originated from two transitions of ⁵ D ₀????⁷? F ₁ (594?nm) and ⁵ D ₀????⁷? F ₂ (617?nm) had maximum intensities when Eu³⁺ concentration was x?=?0.40. The relatively high quenching concentration of Eu³⁺ content was thought to be related to the layered structure of BEuT thin films. These results suggested that multifunctional BEuT thin film materials could have promising applications in optoelectronic devices.     

Preparation and electrical properties of 0.4Pb(Zn1/3Nb2/3)O3-0.6Pb(Zr0.4Ti0.6)O3 thin films by 2-step annealing method

Films of (1−x)Pb(Zn_1/3Nb_2/3)O₃-xPb(Zr_0.4Ti_0.6) O₃ (x = 0.6, 40PZN-60PZT) were deposited on Pt/TiO₂/ SiO₂/Si substrate through spin coating. Using a combination of homogeneous precursor solution preparation and two-step pyrolysis process, we were able to obtain the 40PZN-60PZT thin films of perovskite phase virtually without pyrochlore phase precipitation after annealing above 650^∘C. But since annealing done at the high temperatures for extended time can cause diffusion of Pt, TiO₂ and Si, and precipitation of nonstoichiometric PbO, we adopted 2-step annealing method to circumvent these problems. The 2-step annealed films show dense microstructure than the 1-step films annealed at higher temperature. Furthermore, the root-mean-square surface roughness of 220 nm thick films which are annealed at 720^∘C for 1 min and then annealed at 650^∘C for 5 min was found to be 3.9 nm by atomic force microscopy as compared to the 12 nm surface roughness of the film annealed only at 720^∘C for 5 min. The electrical properties of 2-step annealed films are virtually same and those of the 1-step annealed films annealed at high temperature. The film 2-step annealed at 720^∘C for brief 1 min and with subsequent annealing at 650^∘C for 5 min showed a saturated hysteresis loop at an applied voltage of 5 V with remanent polarization (P _r) and coercive voltage (V _c) of 25.3 μC/cm² and 0.66 V respectively. The leakage current density was lower than 10⁻⁵A/cm² at an applied voltage of 5 V.     

Preparation of TiO<Subscript>2</Subscript> thin films deposited from highly dense targets with multi-oxide glass doping

Glass doped TiO₂ (GTO) thin films were deposited by radio frequency (RF) magnetron sputter at room temperature and annealed in a reductive atmosphere containing 90 % N₂ and 10 % H₂. Highly dense TiO₂ ceramic mixed with glass consisting of multi-metal oxides (as a sintering aid) was used as the sputtering target. This sintering aid allows low temperature densification of TiO₂ target through a liquid phase wetting mechanism, and also works as a doping resource. XRD and FESEM were carried out to characterize the microstructure of the GTO films and the results reveal that the doping of multi-metal ions enhances the crystallization and increases the grain size of TiO₂ films. TEM analysis also showed that these metal ions were dissolved into TiO₂ lattices. The electrical and optical properties of TiO₂ thin films at different glass concentrations were evaluated and compared to the films merely doped with MoO₃. The electrical resistivity of the GTO films reaches 9.1 × 10^–4 Ω·cm at 2 wt% glass doping, corresponding to a carrier density of 8.9 x 10²⁰ cm^-3 and a mobility of 7.1 cm²/Vs. Meanwhile, the electrical resistivity of the TiO₂ film doped with glass was found to be lower than that of MoO₃-doped film. This was mainly attributed to the increase in carrier concentration by double doping effect of glass. The optical band gap of the GTO films ranged from 3.34 to 3.42 eV, which is greater than that of the un-doped TiO₂ film. This blue shift of approximately 0.18 eV was due to the Burstein-Moss effect.     

Sputtered ferroelectric thin films for dynamic random access memory applications

Abstract

A low thermal budget (with 550°C annealing) process with Ti-compensation for sputtered ferroelectric PZT thin films has been developed. PZT films with a composition near the morphotrophic phase boundary (Zr/Ti = 53/47) annealed at 550°C for 1 hr in a N₂ ambient exhibits high charge storage density and low leakage current density, which are the important requirements of dielectric materials for ULSI DRAM cells. It was also found that Ti compensated films show good fatigue endurance in comparison with non-Ti compensated films.     

Structure and properties of Zn-doped CoFe2O4 thin films via a sol–gel method

Zn-doped cobalt ferrite Co_0.9Zn_0.1Fe₂O₄ (CZFO) films with the spinel structure were fabricated on Pt(111)/Ti/SiO₂/Si(100) using a sol-gel method, and the effect of annealing temperature and time on structure and magnetic properties of the CZFO thin films were investigated. The coercivity and saturation magnetization of the films are not sensitive to annealing time, and increase with a rise in the annealing temperature below 800 °C. The CZFO thin films annealed at 800 °C show the best crystallization and the highest coercivity (3.5 kOe), and above 800 °C, the coercivities of the films decrease as a result of formation of multi-domains, while the saturation magnetization comes to stable.     

Annealing temperature effect on ferroelectric and magnetic properties in Mn-added polycrystalline BiFeO3 films

We fabricated 5 at.% Mn-added polycrystalline BiFeO₃ films and investigated the annealing temperature effect on structural, ferroelectric and magnetic properties. In the x-ray diffraction patterns, only the diffraction peaks due to the BiFeO₃ structure were observed and no secondary phase could be observed at annealing temperatures between 773 and 923 K. Adding Mn suppressed the leakage current density in the high electric field region when compared to pure BiFeO₃ films. The conduction mechanism of the Mn-added BiFeO₃ films was dominated by Ohmic conduction. Remanent polarization of the Mn-added polycrystalline BiFeO₃ films for an applied electric field of approximately 1.5 mV/cm was 63 μC/cm² for the specimen annealed at 773 K and 46 μC/cm² for the specimen annealed at 923 K, although the remanent polarization still exhibited a tendency to increase with an increase in the electric field. Spontaneous magnetization was obtained at high annealing specimens. This study revealed that the annealing temperature strongly affected the ferroelectric and magnetic properties in Mn-added polycrystalline BiFeO₃ films. In addition, by optimizing the annealing temperature, we realized multiferroics coexistent with spontaneous magnetization and spontaneous polarization at room temperature in the Mn-added polycrystalline BiFeO₃ film.     

Preparation and characterization of PZT ferroelectric thin films by plasma enhanced metalorganic chemical vapor deposition

Abstract

PZT thin films with a uniform distribution of components were prepared by plasma enhanced chemical vapor deposition (PECVD) using Pb(C₂H₅)₄, Z (O-i-C₄H₉)₄, Ti(O-i-C₃H₇)₄, and oxygen. The crystallization of films was occure after annealing in the temperature range between 450 and 550°C under O₂ ambient for 1 hr. The significant change of Pb concentration in PECVD PZT thin films was not observed in the relation to annealing temperature and time. The dielectric constant PECVD PZT thin films increased with the Ti content, showed the maximum value in the vicinity of morphotropic phase boundary (MPB) composition of PZT material, and decreased with the Ti content. The leakage current density of PZT (65/35) thin film of 180 nm in thickness was 3·37 × 10^?7 A/cm² at the applied voltage of 3 V. Remanent polarization increased with increasing of Zr content in the film and coercive field was nearly independent of the composition. The typical values of electrical properties were ε_r = 570, E_c = 90 kV/cm, and P_r = 19 μC/cm² in the PECVD PZT (54/46) thin film of 220 nm in thickness.     

Effect of heat treatment of sputter deposited ZnO films co-doped with H and Al

ZnO films co-doped with H and Al (HAZO) were prepared by sputtering ZnO targets containing Al₂O₃ dcontent of 1 (HA₁ZO series) and 2 wt.% (HA₂ZO series) on Corning glass (Eagle 2000) at substrate temperature of 150 °C with Ar and H₂/Ar gas mixtures. The effects of hydrogen addition to Al-doped ZnO (AZO) films with different Al contents on the electrical, optical and structural properties of the as-grown films as well as the vacuum- and air-annealed films were examined. For the as-deposited films, the free carrier number in both series of HAZO films increased with increasing H₂ content in sputter gas. HA₂ZO film series prepared from target containing 2 wt.% Al₂O₃ showed better crystallinity and higher carrier concentration than HA₁ZO film series deposited using target containing 1 wt.% Al₂O₃. The crystallinity and the Hall mobility of HA₂ZO film series decreased with increasing H₂ content in sputter gas, while those of HA₁ZO film series showed a reversed behavior. Although HA₂ZO film series yielded lower resistivity than HA₁ZO film series due to higher carrier concentrations, the higher figure of merit (expressed as 1?/?ρα, where ρ and α represents the resistivity and absorption coefficient, respectively) was observed for HA₁ZO film series because of substantially low absorption loss in these films. When annealed in air ambient, HA₁ZO film series showed much stronger stability than HA₂ZO film series. Vacuum-annealing resulted in drop of the carrier concentrations as well as large shrinkage in lattice constant, which indicated that the hydrogen dopants are in relatively volatile state and can be removed easily from the films upon annealing.     

A study on the characteristics of hydrated La2O3 thin films with different oxidation gases on the various annealing temperature

In order to investigate the structural and electrical properties of La₂O₃ films deposited by O₂ and O₃, films were hydrated in DI-water and annealed at 600 and 900 °C. La₂O₃ films deposited by O₃ showed better hydration resistance than those deposited by O₂. The thickness of both hydrated films decreased after annealing at 600 °C and increased after annealing at 900 °C. The dielectric constants of the La₂O₃ films deposited by O₃ were greater than films deposited by O₂ after annealing at 600 °C and slightly less after annealing at 900 °C. The leakage current density of the La₂O₃ films deposited by O₃ was lower than those by O₂ after annealing at 900 °C. To this end, La₂O₃ films deposited by O₃ showed better dissolution resistance than O₂ for hydration experiment as a function of dipping time.     

Effect of crystalline phases on the ferroelectric properties of HoMnO3 thin films

Ferroelectric HoMnO₃ thin films were deposited on the Si (100) substrates at 700°C for 2 h by metal–organic chemical vapor deposition. When the films were post-annealed at 800°C for 1 h in air, the single phase of hexagonal HoMnO₃ was detected, and the remnant polarization (Pr) and coercive field (Ec) were decreased due to the decrease of c-axis orientation. With an increase of annealing time, the crystalline phase of HoMnO₃ was changed from the single hexagonal to the mixtures of the hexagonal and orthorhombic phases of HoMnO₃, and/or HoMn₂O₅. Leakage current density was related with charge valence of Mn ion and surface roughness of thin film. Pr of hexagonal HoMnO₃ thin films with high c-axis orientation was 136 nC/cm² and the leakage current density was 10^?6 A/cm².     

Structures and luminescence properties of Eu2+- doped α-sialon phosphors for UV-LED

Eu²⁺-doped α-sialon phosphor was synthesized and structures and various luminescence properties were studied. High crystalline Ca_0.8Al_2.8Si_9.2O_1.169N_14.94 phase was successively obtained for undoped and Eu²⁺-doped samples. Eu²⁺-doped α-sialon phosphor exhibited wide absorption in ultra violet (UV) and visible range, and high broad emission band peaking at from 570 to 582 nm. The optimum compositions and process conditions was obtained from 0.75 mol% Eu²⁺–doped Ca_0.8Al_2.8Si_9.2O_1.169N_14.94 fired at 1650 °C for 2 h in 30% H₂–70% N₂ atm. In addition, fabrication of UV-light emitting diode (LED) lamp using this phosphor was conducted and the optical properties were measured. Relative quantum efficiency of the phosphor and luminous efficiency of the lamp were 83.66% and 35.28 lm/W, respectively. Those results indicated that Eu²⁺-doped α-sialon phosphor in this study was a good candidate for UV-LED light source.     

Characterization of PT ferroelectric thin films on porous silica for pyroelectric IR detectors

Ferroelectric PbTiO₃ thin films were deposited on Pt/DS/PS/SiO₂/Si substrates by sol–gel technique. Porous silica (PS) thin film was used as thermal-insulation layer and dense silica (DS) thin film was a buffer layer to reduce surface roughness of PS layer. Root mean square surface roughness can be effectively reduced from 9.7 to 3.5 nm after PS buffer layer was prepared. The average grain size of PT thin films decreased slightly with increasing thickness of porous silica. Dielectric constant of PT increased from 107 to 171 at 1 KHz as thickness of PS layer increased from 0 to 2,000 nm. PT thin film prepared on 2,000 nm porous silica exhibited good dielectric property. The leakage current density was less than 1.6?×?10^-6 A/cm² when the applied electrical field was 200 kV/cm. The composite film is suitable for preparing pyroelectric IR detectors.     

Influence of Annealing Temperature on Structural,Morphological and NH3 Sensing Properties of Nanostructured WO3 Porous Films

The tungsten trioxide (WO₃) precursor was prepared by sol-gel method with tungsten powder as the raw material, and the WO₃ gas sensing films were obtained by a dip coating method and annealing precursor in air. X-ray diffraction (XRD) spectra indicate that with increasing annealing temperature the triclinic structure of as-prepared sample was transformed into monoclinic or orthorhombic phase. The images of scanning electron microscopy (SEM) exhibit that the WO₃ grain sizes increase from less than 100 nm to several micrometers with increasing annealing temperature. The influences of applied frequency, annealing and operating temperature on NH₃ gas sensing properties of the nanostructured WO₃ porous films were investigated. The results indicate that the gas sensing film annealed at 500°C express high sensitivity, fast response and recovery speed to NH₃ at operating temperature 250°C.