Effect of film thickness on interface and electric properties of BiFeO3 thin films

Bismuth ferrite (BFO) thin films were fabricated by RF-magnetron sputtering deposition method on Pt/Ti/SiO₂/Si(1 0 0) substrate. The effect of the thickness of BFO films varying from 85 to 280 nm on electrical properties was investigated. Saturated coercive fields were found to increase with the BFO film thickness. The dielectric constant of BFO thin films measured at 1 kHz decreased with decreasing thickness from 98 to 86, while tangent losses increased from 0.013 to 0.021. The presence of bismuth oxide at the interface between BFO films and Pt bottom electrodes was responsible for the high leakage currents in thin BFO thin films as was demonstrated by X-ray diffraction, grazing-incident X-ray diffraction, and secondary ion mass spectroscopy analysis.     

基于BiFeO_3/ITO复合膜表面钝化的黑硅太阳电池性能研究

采用金属银辅助化学刻蚀法在制绒的硅片表面刻蚀纳米孔形成微纳米双层结构,以期获得高吸收率的太阳能电池用黑硅材料.鉴于微纳米结构会在晶硅表面引入大量的载流子复合中心,利用磁控溅射技术在黑硅太阳电池表面制备了BiFeO_3/ITO复合膜,并对其表面性能和优化效果进行了探索.实验制备的具有微纳米双层结构的黑硅纳米线长约180—320 nm,在300—1000 nm波长范围内入射光反射率均在5%以下.沉积BiFeO_3/ITO复合薄膜后的黑硅太阳能电池反射率略有提高,但仍然具有较强的光吸收性能;采用BiFeO_3/ITO复合膜的黑硅太阳能电池开路电压和短路电流密度分别由最初的0.61 V和28.42 mA/cm~2提升至0.68 V和34.57 mA/cm~2,相应电池的光电转化效率由13.3%上升至16.8%.电池综合性能的改善主要是因为沉积BiFeO_3/ITO复合膜提高了电池光生载流子的有效分离,从而增强了黑硅太阳电池短波区域的光谱响应,表明具有自发极化性能的BiFeO_3薄膜对黑硅太阳能电池的表面性能可起到较好的优化作用.     

Influence of heating rate on the crystalline properties of 0.7BiFeO3-0.3PbTiO3 thin films prepared by sol-gel process

0.7BiFeO₃-0.3PbTiO₃ (BFPT7030) thin films were deposited on SiO₂/Si substrates by sol-gel process. The influence of heating rate on the crystalline properties of BFPT7030 thin films were studied by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). XRD patterns of the films showed that a pure perovskite phase exists in BFPT7030 films annealed by rapid thermal annealing (RTA) technique. SEM and AFM observations demonstrated that the BFPT7030 films annealed by RTA at 700 °C for 90 s with the heating rate of 1 °C s⁻¹ could show a dense, crack-free surface morphology, and the films’ grains grow better than those of the films annealed by RTA at the same temperature with other heating rates. XPS results of the films indicated that the ratio of Fe³⁺:Fe²⁺ is about 21:10 and 9:5 for the films annealed by RTA at 700 °C for 90 s with the heating rate of 1 and 20 °C s⁻¹, respectively. That means the higher the heating rate, the higher the concentration of Fe²⁺ in the BFPT7030 thin films.     

Magnetic field annealing effects on self-oriented BiFeO3 thin films prepared by chemical solution deposition

Self-oriented BiFeO₃ (BFO) thin films are prepared via chemical solution deposition method with magnetic field in-situ annealing process. The effects of magnetic annealing on the microstructure, magnetic and dielectric properties as well as magnetoelectric coupling effect of the BFO thin films are investigated. With increasing the annealing magnetic field, the crystallization quality, texture, grain boundary connectivity and densification of the films are enhanced, which is attributed to the improvement of connection and diffusion of components. The magnetization of the field-annealing films and dielectric constant as well as remanent polarization increases with increasing the strength of annealing magnetic field. In addition, it is observed that magnetocapacitance value of the magnetic-field-annealing BFO thin film is higher than the non-field-annealing one. Moreover the BFO thin films annealed at 3 kOe magnetic field show the magnetoelectric effect with 4% under 2 kOe at room temperature.     

Off-stoichiometry effects on BiFeO3 thin films

The effects of Bi and Fe-excess on the structure, ferroelectric, leakage current and magnetic properties of BiFeO₃ (BFO) thin films are reported. BFO with 5% excess exhibits no change in the structure with an improvement in leakage current properties in comparison to stoichiometric BFO. Raman spectroscopy of 10% Bi excess suggests a structural change from monoclinic to rhombohedral accompanied with an improvement of resistivity and ferroelectric polarization switching. A higher Fe-excess leads to the formation of pyrochlore Bi₂Fe₄O₉ and gamma-Fe₂O₃ that cause an increase in conductivity at the macroscopic scale. The results are discussed in terms of Fe and Bi-excess effects on the defect structure of BFO.     

Influence of MgO and ZrO2 buffer layers on dielectric properties of Ba(Zr0.20Ti0.80)O3 thin films prepared by sol-gel processing

Ba(Zr_0.20Ti_0.80)O₃ (BZT) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si, MgO and ZrO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel process. The BZT thin films directly grown on Pt(1 1 1)/Ti/SiO₂/Si substrates exhibit highly (1 1 1) preferred orientation, while the films deposited on Pt(1 1 1)/Ti/SiO₂/Si substrates with MgO and ZrO₂ buffer layers show highly (1 1 0) preferred orientation. At 100 kHz, dielectric constants are 417, 311 and 321 for the BZT thin films grown on Pt(1 1 1)/Ti/SiO₂/Si, MgO and ZrO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si substrates, respectively. The difference in dielectric properties of three BZT films can be attributed to the series capacitance effect, interface conditions and their orientations.     

Photoluminescence of Y2O3:Eu thin film phosphors by sol-gel deposition and rapid thermal annealing

Y₂O₃:Eu³⁺ phosphor films have been developed by using the sol-gel process. Comprehensive characterization methods such as Photoluminescent (PL) spectroscopy, X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy were used to characterize the Y₂O₃:Eu³⁺ phosphor films. In this experiment, the XRD profiles show that the Y₂O₃:Eu³⁺ phosphor films crystallization temperature and optimum annealing temperature occur at about 650 and 750 °C, respectively. The optimum dopant concentration is 12 mol% Eu³⁺ and the critical transfer distance (R_c) among Eu³⁺ ions is calculated to be about 0.84 nm. Vacuum environment is more efficient than oxygen and nitrogen to eliminate the OH content and hence yields higher luminescent phosphor films. The PL emission intensity of Y₂O₃:Eu³⁺ phosphor films is also dependent on the annealing time. It was found that the H₂O impurities were effectively eliminated after annealing time of 25 s at 750 °C in vacuum environment. From the experiment results, the schematic energy band diagram of Y₂O₃:Eu³⁺ phosphor films is constructed.     

Structural and optical properties of low temperature synthesized Nanostructured BiFeO3 thin films

Nanostructured bismuth ferrite (BiFeO₃) thin films were deposited on glass substrate by the sol-gel process. The as-fired film at 250 °C was found to be amorphous crystallizing to pure rhombohedral phase after annealing at 450 °C for 2 h in air. The XRD pattern shows that the sample is polycrystalline in nature. The average grain size of the film calculated from the XRD data was found to be 16 nm. The as-fired film show high transmittance that decreases after crystallization. The absorption edge of the films was found to be sharper and shifting towards the lower energy as the annealing temperature increases. The optical energy band gaps of the amorphous and crystalline films were found to be 2.63 and 2.31 eV, respectively. The refractive indices of the amorphous and crystalline films were 2.05 and 2.26, respectively.     

Swift heavy ion irradiation induced modification of BiFeO3 thin films prepared by sol-gel method

We report the preparation of multiferroic BiFeO₃ thin films on ITO coated glass substrates through sol-gel spin coating method followed by thermal annealing and their modification by swift heavy ion (SHI) irradiation. X-ray diffraction and Raman spectroscopy studies revealed amorphous nature of the as deposited films. Rhombohedral crystalline phase of BiFeO₃ evolved on annealing the films at 550°C. Both XRD and Raman studies indicated that SHI irradiation by 200 MeV Au ions result in fragmentation of particles and progressive amorphization with increasing irradiation fluence. The average crystallite size estimated from the XRD line width decreased from 38 nm in pristine sample annealed at 550°C to 29 nm on irradiating these films by 200 MeV Au ions at 1 × 10¹¹ ions cm⁻². Complete amorphization of the rhombohedral BiFeO₃ phase occurs at a fluence of 1 × 10¹² ions.cm⁻². Irradiation by another ion (200 MeV Ag) had the similar effect. For both the ions, the electronic energy loss exceeds the threshold electronic energy loss for creation of amorphized latent tracks in BiFeO₃.     

Raman spectroscopic investigations of epitaxial BiFeO3 thin films on rare earth scandate substrates

BiFeO₃ epitaxial thin films fabricated by pulsed laser deposition on different scandate substrates were investigated by means of Raman spectroscopy. We observed periodic changes in Raman position, full width at half maximum and intensity for some phonon modes as a function of the azimuthal angle ϕ. Further analysis revealed the possibility to assign the so far controversial discussed Raman modes at low wavenumbers (<250 cm⁻¹) through rotational Raman measurements at different azimuthal angles, which show high sensitivity to the aforementioned parameters. Furthermore, the ferroelectric/ferroelastic domain structure shown by piezo‐response force microscopy investigations of the samples was confirmed. Our results are supported by symmetry‐based calculations including the analysis of Raman scattering geometry as well as the dielectric function of BiFeO₃ in the infrared range. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of CuAlO2 thin film prepared by rapid thermal annealing of an Al2O3/Cu2O/sapphire structure

CuAlO₂ thin film was successfully prepared by rapid thermal annealing of an Al₂O₃/Cu₂O/sapphire structure in air above 1000 °C. The film was mostly with single crystalline structure as verified by X-ray diffraction methods. We found that crystal quality and electrical conductivity of the films were affected by the cooling rate after annealing. The highest conductivity obtained in this work was 0.57 S/cm. Optical gap of this film was determined to be 3.75 eV.     

CO2 sensing properties of semiconducting copper oxide and spinel ferrite nanocomposite thin film

A new active layer for CO₂ sensing based on semiconducting CuO-Cu_xFe_3−xO₄ (with 0 ≤ x ≤ 1) nanocomposite was prepared by radiofrequency sputtering from a delafossite CuFeO₂ target using a specific in situ reduction method followed by post annealing treatment in air. The tenorite-spinel ferrite nanocomposite layer was deposited on a simplified test device and the response in a carbon dioxide atmosphere was measured by varying the concentration up to 5000 ppm, at different working temperatures (130-475 °C) and frequencies (0.5-250 kHz). The results showed a high response of 50% (Rair/RCO₂=1.9) at 250 °C and 700 Hz for a CO₂ concentration of 5000 ppm.     

Effects of annealing on morphological,structural and electrical properties of thermally evaporated WO3 thin films

Tungsten trioxide (WO₃) thin films were prepared by thermal evaporation method onto quartz substrates at room temperature. Effect of annealing temperature (from 200 to 800 °C) to morphology, crystallographic structure and electrical properties were investigated. In order to investigate the temperature dependant resistivity properties of the films dark current–voltage measurements were done at the temperatures of 30, 60, 90, 120 and 150 °C. From the AFM pictures it is seen that the increasing annealing temperature causes an increase in grain sizes. At elevated temperatures the grains combine to each other and thus form continuous and homogenous surfaces. From the XRD patterns it was seen that the as-prepared and annealed films at 200, 300, 310 and 320 °C were amorphous. On the other hand at 330 °C and higher temperatures the films were found as in crystallized structures (monoclinic phase). From the current–voltage measurements it was seen that the contacts areohmic and the current increased with increasing temperatures. From the calculated values it was seen that the produced films shows good semiconducting nature.     

Orientation-dependent dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films prepared by sol-gel method

The orientation-dependent dielectric properties of barium stannate titanate (Ba(Sn_0.15Ti_0.85)O₃, BTS) thin films grown on (1 0 0) LaAlO₃ single-crystal substrates through sol-gel process were investigated. The nonlinear dielectric properties of the BTS films were measured using an inter-digital capacitor (IDC). The results show that the in-plane dielectric properties of BTS films exhibited a strong sensitivity to orientation. The upward shift of Curie temperature (T_c) of the highly (1 0 0)-oriented BTS thin films is believed to be attributing to a tensile stress along the in-plane direction inside the film. A high tunability of 47.03% was obtained for the highly (1 0 0)-oriented BTS films, which is about three times larger than that of the BTS films with random orientation, measured at a frequency of 1 MHz and an applied electric field of 80 kV/cm. This work clearly reveals the highly promising potential of BTS films for application in tunable microwave devices.     

Effects of annealing temperature on the structural and photoluminescence properties of nanocrystalline ZrO2 thin films prepared by sol-gel route

Highly transparent nanocrystalline zirconia thin films were prepared by the sol-gel dip coating technique. XRD pattern of ZrO₂ thin film annealed at 400 °C shows the formation of tetragonal phase with a particle size of 13.6 nm. FT-IR spectra reveal the formation of Zr-O-Zr and the reduction of OH and other functional groups as the temperature increases. The transmittance spectra give an average transmittance greater than 80% in the film of thickness 262 nm. Photoluminescence (PL) spectra give intense band at 391 nm and a broad band centered at 300 nm. The increase of PL intensity with elevation of annealing temperature is related to reduction of OH groups, increase in the crystallinity and reduction in the non-radiative related defects. The luminescence dependence on defects in the film makes it suitable for luminescent oxygen-sensor development. The “Red shift” of excitation peak is related to an increase in the oxygen content of films with annealing temperature. The “Blue shift” of PL spectra originates from the change of stress of the film due to lattice distortion. The defect states in the nanocrystalline zirconia thin films play an important role in the energy transfer process.     

Large piezoresponse of lead-free Bi0.5(Na0.85K0.15)0.5TiO3 thin film

0.85Bi_0.5Na_0.5TiO₃-0.15Bi_0.5K_0.5TiO₃ (BNKT15) lead-free thin films were prepared on Pt(111)/TiO₂/SiO₂/Si(100) substrates by the chemical solution deposition method. BNKT15 are MPB composition in the Bi_0.5Na_0.5TiO₃-Bi_0.5K_0.5TiO₃ (BNT-BKT) system. The maximum piezoelectric coefficient (d_33,f) value of BNKT15 thin film is approximately 75 pm/V, which is comparable to that of polycrystalline PZT thin films. These results suggest that BNKT15 thin film can be used as an alternative for PZT films in piezoelectric micro-electromechanical systems.     

Magnetic properties of hydrothermally synthesized BiFeO3 nanoparticles

BiFeO₃ nanoparticles with diameters in the range 65–90 nm were prepared using a hydrothermal technique. Low-temperature magnetic measurements showed ferromagnetic behavior of the samples below a certain temperature. The magnetization values were drastically reduced in the case of samples having larger diameters. This was explained as arising due to a reduction of the number of uncompensated spins associated with Fe³⁺ ions as particle diameter was increased. A surface spin disorder is believed to be responsible for this property.     

SrBi4Ti4O15铁电薄膜的制备工艺及薄膜生长机理 研究

以氯化锶，硝酸铋和钛酸丁酯为原料，柠檬酸为络合剂，乙二醇为交联剂，无水乙醇为钛酸 丁酯的溶剂，盐酸为硝酸铋的溶剂，去离子水为氯化锶的溶剂，配制了稳定的SrBi_{4Ti4O15(SBTi)前驱液.采用溶胶凝胶工艺，在Pt/Ti/SiO2 /Si基片上制备了a轴取向增强的SBTi铁电薄膜.研究了一次性晶化快速退火工艺、两 层晶化快速退火工艺、逐层晶化快速退火工艺以及成膜次数对薄膜结晶性、微观结构和生长 行为的影响.实验结果表明，逐层快速退火工艺可有效抑制焦绿石相的形成；随着涂覆次数 的增加，薄膜的结晶性变好；由于SBTi晶体生长的各向异性及单层膜厚对晶体沿(119)方向 生长的限制，随着涂覆次数的增加，SBTi薄膜(119)峰和(200)峰的强度逐渐增大，而(00l) 峰的强度反而略有减小，从而使I(200)/I(119)，I(200)/I(0010)，I(119)/I(0010)逐渐增 大. 关键词： 铁电薄膜 钛酸锶铋 逐层快速退火工艺 生长行为}     

Morphology and orientation of iron oxide precipitates in epitaxial BiFeO3 thin films grown under two non-optimized oxygen pressures

Microstructures of multiferroic BiFeO₃ thin films epitaxially grown on SrRuO₃-buffered SrTiO₃ (001) substrates by laser molecular-beam epitaxy under two non-optimized oxygen pressures were characterized by means of transmission electron microscopy. The results showed that the films grown under oxygen pressures of 1 Pa and 0.3 Pa contain a secondary phase embedded in the BiFeO₃ matrix. High-angle annular dark-field imaging, elemental mapping and composition analysis in combination with selected area electron diffraction revealed that the parasitic phase is mainly antiferromagnetic α-Fe₂O₃. The α-Fe₂O₃ particles are semi-coherently embedded in the BiFeO₃ films, as confirmed by high-resolution transmission electron microscopy. In addition to the α-Fe₂O₃ phase, ferromagnetic Fe₃O₄ precipitates were found in the BiFeO₃ films grown under 0.3 Pa and shown to accumulate in areas near the film/substrate interfaces. In our heteroepitaxy systems, very low density misfit dislocations were observed at the interfaces between the BiFeO₃ and SrRuO₃ layers implying that their misfit strains may be relieved by the formation of the secondary phases. Using X-ray photoelectron spectroscopy it was found that Fe exists in the +3 oxidation state in these films. The possible formation mechanisms of the secondary phases are discussed in terms of film growth conditions.     

Relevancy of phase separation between electrical and thermal properties in La0.8Sr0.2MnO3 thin films

For the purpose of finding the relevancy of phase separation between electrical and thermal properties, La_0.8Sr_0.2MnO₃ thin films, deposited on quartz glass substrates, were studied for temperature dependent resistance and thermal emittance. Based on the phase separation concept, metal phase volume fraction f was calculated from the temperature dependence of resistance and emittance properties by a phenomenological model and two-energy-level Boltzmann distribution, respectively. The two sets of f coincide with each other very well. The results show f plays an important role in the electrical transportation and thermal properties, and the two properties are essentially correlated by f.