Effect of bilayer structure and a SrRuO3 buffer layer on ferroelectric properties of BiFeO3 thin films

Effects of the BiFe_0.95Mn_0.05O₃ thickness and a SrRuO₃ (SRO) buffer layer on the microstructure and electrical properties of BiFeO₃/BiFe_0.95Mn_0.05O₃ (BFO/BFMO) bilayered thin films were investigated, where BFO/BFMO bilayered thin films were fabricated on the SRO/Pt/Ti/SiO₂/Si(100) substrate by a radio frequency sputtering. All thin films are of a pure perovskite structure with a mixture of (110) and (111) orientations regardless of the BFMO layer thickness. Dense microstructure is demonstrated in all thin films because of the introduction of BFMO layers. The SRO buffer layer can also further improve the ferroelectric properties of BFO/BFMO bilayered thin films as compared with those of these thin films without a SRO buffer layer. The BFO/BFMO bilayered thin film with a thickness ratio of 220/120 has an enhanced ferroelectric behavior of 2P _r??165.23???C/cm² and 2E _c??518.56?kV/cm, together with a good fatigue endurance. Therefore, it is an effective way to enhance the ferroelectric and fatigue properties of bismuth ferrite thin films by constructing such a bilayered structure and using a SRO buffer layer.     

Photovoltaic effect of TiO2 thick films with an ultrathin BiFeO3 as buffer layer

The photovoltaic (PV) effect of a bilayer anatase TiO₂/BiFeO₃ (BFO) film has been studied. The 20-nm ultrathin BFO layers were deposited on the fluorine-doped tin oxide (FTO) glass substrates by the chemical solution deposition method. An anatase TiO₂ layer is deposited subsequently on the BFO surface via a screen-printing technique. It is found that the FTO/TiO₂/Au cell exhibits negligible PV effect under solar exposure, while the one after introducing an ultrathin BFO film between TiO₂ and FTO leads to a considerable PV effect with an open-circuit voltage of ?0.58 V and a photocurrent density of 18.27 µA/cm². The FTO/BiVO₄ (BVO)/TiO₂/Au cell was constructed to investigate the underlying mechanism for the observed effect. A negligible PV effect of the FTO/BVO/TiO₂/Au cell indicates that the PV effect of the FTO/BFO/TiO₂/Au cell arises mainly from a built-in electric field in the BFO film induced by the self-polarization. Our work opens up a new path to utilize TiO₂ and may influence the future design of solar cells.     

Bismuth ferrite composite thin films

0.60Bi_0.90La_0.10FeO₃–0.40Pb(Zr_0.52Ti_0.48)O₃ composite thin films were deposited on Pt/TiO₂/SiO₂/Si(100) substrates by radio-frequency sputtering and their ferroelectric and fatigue properties were mainly investigated. The composite thin films have a low dielectric loss, a high dielectric constant, and enhanced ferroelectric properties of 2P _r～122.6 μC/cm² and 2E _c～479.3 kV/cm, together with a fatigue-free behavior at 200 kHz. Their fatigue behavior is strongly dependent on measurement frequencies, and the concentration of oxygen vacancies plays an important role in their fatigue behavior.     

复合薄膜NiFe2 O4-BiFeO3 中的磁电耦合

采用化学溶液沉积法(CSD)在Au/Ti/SiO₂/Si衬底上通过自组装生长制备了BiFeO₃-NiFe₂O₄ (BFO-NFO)多铁性复合薄膜.X射线衍射图谱(XRD)显示形成了分离的钙钛矿结构的铁电相BFO和尖晶石结构的铁磁相NFO. NFO的引入导致复合薄膜的泄漏电流减小,剩余极化强度增加.相比于纯BFO薄膜,0.25NFO-0.75BFO样品泄漏电流下降了约两个数量级,剩余极化强度( M _{关键词： 多铁性复合薄膜 磁电耦合 铁电性 铁磁性}     

Mn:BiFeO3/Zn:BiFeO3 bilayered thin films of (1 1 1) orientation

Ferroelectric and fatigue behavior of bilayered thin films consisting of Mn⁴⁺-modified BiFeO₃ and Zn²⁺-modified BiFeO₃, which were deposited on SrRuO₃-buffered Pt coated silicon substrates, were systematically investigated. The (1 1 1) orientation is induced for the BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer, due to the introduction of the bottom BiFe_0.95Zn_0.05O₃ layer. With increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer, their leakage current decreases, and the fatigue endurance is greatly improved owing to the introduction of the BiFe_0.95Mn_0.05O₃ layer with a lower fatigue rate. The BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer with the thickness ratio of 3:1 exhibits a larger remanent polarization of 2P_r ∼ 161.0 μC/cm² than those of bilayers with different thickness ratios, while their coercive field slightly increases with increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer.     

Ferroelectric domain structures and polarization switching characteristics of polycrystalline BiFeO3 thin films on glass substrates

We investigated ferroelectric characteristics of BiFeO₃ (BFO) thin films on SrRuO₃ (SRO)/yttria-stabilized zirconia (YSZ)/glass substrates grown by pulsed laser deposition. YSZ buffer layers were employed to grow highly crystallized BFO thin films as well as SRO bottom electrodes on glass substrates. The BFO thin films exhibited good ferroelectric properties with a remanent polarization of 2P_r = 59.6 μC/cm² and fast switching behavior within about 125 ns. Piezoelectric force microscopy (PFM) study revealed that the BFO thin films have much smaller mosaic ferroelectric domain patterns than epitaxial BFO thin films on Nb:SrTiO₃ substrates. Presumably these small domain widths which originated from smaller domain energy give rise to the faster electrical switching behavior in comparison with the epitaxial BFO thin films on Nb:SrTiO₃ substrates.     

Silicon nitride/silicon oxide interlayers for solar cell passivating contacts based on PECVD amorphous silicon

This Letter demonstrates improved passivating contacts for silicon solar cells consisting of doped silicon films together with tunnelling dielectric layers. An improvement is demonstrated by replacing the commonly used silicon oxide interfacial layer with a silicon nitride/silicon oxide double interfacial layer. The paper describes the optimization of such contacts, including doping of a PECVD intrinsic a‐Si:H film by means of a thermal POCl₃ diffusion process and an exploration of the effect of the refractive index of the SiN_x. The n⁺ silicon passivating contact with SiN_x /SiO_x double layer achieves a better result than a single SiN_x or SiO_x layer, giving a recombination current parameter of ～7 fA/cm² and a contact resistivity of ～0.005 Ω cm², respectively. These self‐passivating electron‐selective contacts open the way to high efficiency silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Effect of pore size on ferroelectric properties of multiferroic BiFeO3 films prepared on porous silicon

The ferroelectric properties of BiFeO₃ (BFO) films spray deposited on porous silicon have been studied. The analysis of XRD and FESEM investigations show that the crystalline strain in the BFO films increases with pore size. The BFO films on porous silicon substrate showed improvement in ferroelectric fatigue behavior, remanent polarization and ferroelectric switching time. A maximum memory window of 5.54 V at 1 MHz and a large remanent polarization (P_r) of 13.1 μC/cm² have been obtained at room temperature. The improvement in the ferroelectric properties of these films has been correlated to the crystalline strain.     

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.     

Study on ferroelectric polarization induced resistive switching characteristics of neodymium-doped bismuth ferrite thin films for random access memory applications

The present work reports on resistive switching (RS) characteristics of Neodymium (Nd)-doped bismuth ferrite (BFO) layers. The Nd (2–10 at%) doped BFO thin film layers were deposited using a spray pyrolysis method. The structural analysis reveals that a higher Nd doping concentration in BFO leads to significant distortion of the prepared Nd:BFO thin films from rhombohedral to tetragonal characteristics. The morphological analysis shows that all the deposited Nd:BFO thin films have regularly arranged grains. The X-ray photoelectron spectroscopy (XPS) analysis reveals that the prepared Nd:BFO thin films have a higher Fe ³⁺/Fe ²⁺ratio and less oxygen vacancy (V_O) defects which enriches the ferroelectric characteristics in Nd:BFO layers. The polarization-electric field (P-E) and RS characteristics of the fabricated Nd:BFO-based RS device were examined. It was observed that the Nd (7 at%) doped BFO RS device shows large remnant polarization (P _r) of 0.21 μC/cm² and stable RS characteristics.     

Synthesis of α-In 2 Te 3 thin films from In/Te bilayer by Si ion irradiation

In this work, In/Te bilayer thin films were prepared using sequential thermal evaporation method and subsequently irradiated using swift heavy ions (SHIs) of 100 MeV silicon (Si) with different fluences (1×10¹³ to 5×10¹³/cm²). The inter-diffusion of In and Te layers was highly controlled by SHI irradiation and the In₂Te₃ formation capability was compared with that of the conventional annealing method. The structural as well as optical properties of a post-sintered SHI-irradiated In/Te bilayer were investigated using X-ray diffraction (XRD) measurements and UV–visible spectroscopy, respectively. We found that irradiated samples showed single-phase In₂Te₃ under post-annealed conditions at 150 °C unlike that prepared using the conventional thermal annealing method, which showed mixed phases under similar conditions. This confirms the effective inter-diffusion in bilayer films by SHI irradiation toward the formation of single-phase In₂Te₃. The estimated optical band gap energy was found to be 1.1±0.5 eV and strongly corroborated the XRD results. In addition, the estimated refractive index (n) value of the SHI-irradiated sample (～3.3) was higher than that of the sample obtained through the conventional annealing method (～2.8). This proves that SHI offers a highly compact nature even at low temperatures. This work has a wide scope for achieving single-phase alloyed films through bilayer mixing by SHI irradiation.     

Multiferroic properties of Bi0.8La0.2FeO3/CoFe2O4 multilayer thin films

Bi_0.8La_0.2FeO₃/CoFe₂O₄ (BLFO/CFO) multilayer thin films (totally 20 layers BLFO and 19 layers CFO) were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition. X-ray diffraction and transmission electron microscope measurements show that the films are polycrystalline and consisted of multilayered structure. Ferroelectric hysteresis loops with remnant polarization and saturated polarization of 4.2 and 13.3 μC/cm², respectively, were observed. On the other hand, the films show well-shaped magnetization hysteresis loops with saturated and remnant magnetization of 34.7 and 11.4 emu/cm³, respectively, which are significantly larger than pure BLFO thin films deposited under the same conditions. These results indicate that constructing epitaxial superlattice might be a promising way to fabricate multiferroics with improved properties.     

Enhanced electrical and ferroelectric properties in a multiferroic (BiFeO3/Bi0.5Na0.5TiO3)3/LaNiO3 superlattices structure

Artificial multiferroic superlattices (SL), consisting of BiFeO₃ (16 nm)/Bi_0.5Na_0.5TiO₃ (5 nm) (BFO/BNT SL), were grown on (001) SrTiO₃ single crystal by pulsed laser deposition method. The cross-sectional, surface morphology, and crystallographic structure of BFO/BNT SL and BFO single layer were investigated. It was found that the electrical, ferroelectric, and magnetic properties of BFO/BNT SL exhibit a remarkably enhancement compared with BFO single layer. The influence of BNT buffering layer, lattice strain, and interfaces interplay of the SL structure are supposed to benefit their ferroelectric and ferromagnetic properties. Our works suggested the BFO/BNT SL with an improved multiferroic characteristics have a promising application for the future informational storage devices.     

Pyroelectric properties of BiFeO3 ceramics prepared by a modified solid-state-reaction method

BiFeO₃ (BFO) ceramics were prepared by a modified solid-state-reaction method which adopts a higher heating/cooling rate during the sintering process than usually used. It was found that the calcination temperature T _cal (from 400 to 750°C) does not influence the BFO phase formation, while the sintering temperature T _sin (from 815 to 845°C) dominates the phase purity. The optimum sintering temperature was in the range from 825 to 835°C. The optimized samples exhibit saturated ferroelectric hysteresis loops with a remnant polarization of 13.2 μC/cm². The measured piezoelectric coefficient d ₃₃ was 45 pC/N. No remnant magnetization was observed in all of the samples. The pyroelectric properties were studied as a function of temperature and frequency. A pyroelectric coefficient as high as 90 μC/m² K was obtained at room temperature in the optimized sample. An abrupt decrease of the pyroelectric coefficient was observed at temperatures between 70 and 80°C. On the basis of our results, BFO may have the potential for pyroelectric applications.     

Transport studies of carbon-rich a-SiC x :H film through admittance and deep-level transient spectroscopy measurements

An intrinsic, carbon-rich a-SiC _x :H thin film, prepared by the plasma-enhanced chemical vapour deposition (PECVD) technique, has been studied mainly by AC admittance and small-pulse deep-level transient spectroscopy (DLTS) measurements on an Al/a-SiC _x :H/p-Si metal–insulator–semiconductor (MIS) structure. The effects of measurement temperature, voltage and small-signal AC modulation frequency on the MIS capacitor are qualitatively and quantitatively described. The kinetics of charge injection from the silicon substrate into the a-SiC _x :H film, as a function of temperature and voltage bias stresses, are reported. Nearest-neighbour and variable-range hopping mechanisms are considered. An activation energy of ～?0.09?eV, and a density of states (DOS) of about 10¹⁹?cm^?3/eV were found. The value of the DOS is in agreement with the effective interface DOS of above 10¹²?cm^?2/eV assessed by both capacitance and DLTS measurements. The frequency (or temperature) dependence of the MIS capacitor over the whole DC voltage range is considered in detail. Single- and double-step carrier exchange mechanisms between the a-SiC _x :H film and the silicon substrate, in the accumulation and depletion voltage regimes, respectively, are proposed.     

Photovoltaic effect in BiFeO3/BaTiO3 multilayer structure fabricated by chemical solution deposition technique

Photovoltaic (PV) properties of bismuth ferrite (BFO) and barium titanate (BTO) multilayered ferroelectric BFO/BTO/BFO/BTO thin film structure deposited on Pt/Ti/SiO₂/Si substrates using chemical solution deposition technique are presented. X-ray diffraction analysis confirms pure phase polycrystalline nature of deposited perovskite multilayered structures. Simultaneously both distorted rhombohedral (R3c) and tetragonal phases (P4mm) of the respective BFO and BTO components are also well retained. The ferroelectric sandwiched structures grown on fused quartz substrates exhibit high optical transmittance (~70%) with an energy band gap 2.62 eV. Current–voltage characteristics and PV response of multilayered structures is determined in metal-ferroelectric-metal (MFM) capacitor configuration. Considerably low magnitude of dark current density 1.53×10⁻⁷ A at applied bias of 5 V establish the resistive nature of semi-transparent multilayered structure. Enhanced PV response with 40 nm thin semitransparent Au as top electrode is observed under solid-state violet laser illumination (λ – 405 nm, 160 mW/cm²). The short circuit current density and open circuit voltage are measured to be 12.65 µA/cm² and 1.43 V respectively with a high retentivity. The results obtained are highly encouraging for employing artificial multilayered engineering to improve PV characteristics.     

Polycrystalline GaSb films prepared by the coevaporation technique

Gallium antimonide (GaSb) films were deposited onto fused silica and n-Si (100) substrates by coevaporating Ga and Sb from appropriate evaporation sources. The films were polycrystalline in nature. The size and the shape of the grains varied with the change in the substrate temperature during deposition. The average surface roughness of the films was estimated to be 10 nm. Grain boundary trap states varied between 2×10¹² and 2.2×10¹² cm^?2 while barrier height at the grain boundaries varied between 0.09 eV and 0.10 eV for films deposited at higher temperatures. Stress in the films decreased for films deposited at higher temperatures. XPS studies indicated two strong peaks located at ～543 eV and ～1121 eV for Sb 3d_3/2 and Ga 2p_3/2 core-level spectra, respectively. The PL spectra measured at 300 K was dominated by a strong peak located ～0.55 eV followed by two low intensity peaks ～0.63 eV and 0.67 eV. A typical n-Si/GaSb photovoltaic cell fabricated here indicated V _oc～311 mV and J～29.45 mA/cm², the density of donors (N _d)～3.87×10¹⁵ cm^?3, built in potential (V _bi)～0.48 V and carrier life time (τ)～28.5 ms. Impedance spectroscopy measurements indicated a dielectric relaxation time ～100 μs.     

Enhancing the efficiency of TiO2–perovskite heterojunction solar cell via evaporating Cs2CO3 on TiO2

In a TiO₂–perovskite heterojunction solar cell (TiO₂–PHSC), besides the perovskite CH₃NH₃PbX₃, TiO₂ as one side of the TiO₂/CH₃NH₃PbX₃ heterojunction also plays an important role in the photovoltaic effect. In order to improve the performance of the TiO₂–PHSC with the structure of glass/FTO/compact TiO₂/mesoporous TiO₂/CH₃NH₃PbI_3–xCl_x /poly‐TPD (poly(N,N ′‐bis(4‐butylphenyl)‐N,N ′‐bis(phenyl)benzidine))/Au, a 2 nanometer thick Cs₂CO₃ layer is thermally evaporated on the mesoporous TiO₂ layer. The short‐circuit current density (J_sc) raises from 17.7 mA cm^–2 to 18.9 mA cm^–2, the open‐circuit voltage (V_oc) from 0.81 V to 0.87 V, and the fill factor (FF) from 55.2% to 67.3%; as a result, the power conservation efficiency (PCE) increases from 8.0% to 11.1% under AM 1.5G solar illumination (100 mW cm^–2). Moreover, in a TiO₂–PHSC free of mesoporous TiO₂, where Cs₂CO₃ is evaporated on the compact TiO₂ layer, the J_sc, V_oc, FF and PCE values increase from 16.0 mA cm^–2, 0.83 V, 50.8% and 6.7% to 17.9 mA cm^–2, 0.90 V, 59.3%, and 9.5%, respectively. The reasons of the PCE increase for either the first kind of TiO₂–PHSC or the mesoporous‐TiO₂‐free TiO₂–PHSC with a nanometer‐thick Cs₂CO₃ layer on mesoporous TiO₂ or compact TiO₂ are discussed. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

(Ba, Ca)(Ti, Zr)O3-BiFeO3 lead-free piezoelectric ceramics

Effects of BiFeO₃ (BFO) content on the microstructure and electrical properties of Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ (BCTZ) ceramics prepared by normal sintering in air were investigated. A stable solid solution is formed between BCTZ and BFO. The grain size gradually becomes smaller, and the ceramics become denser with increasing the BFO content. The Curie temperature, dielectric constant, and dielectric loss of BCTZ ceramics decrease simultaneously with the introduction of BFO. Moreover, the remanent polarization reaches a maximum at x = 0.2 mol%, and the coercive field continuously increases with increasing the BFO content due to the introduction of BFO with a higher coercive field. Improved piezoelectric properties (d₃₃ ∼ 405 pC/N and k_p ∼ 0.44) are demonstrated for the BCTZ ceramic with x = 0.2 mol%.