在ITO玻璃衬底上制备锆钛酸铅铁电薄膜

利用射频反应性溅射沉积技术在掺的Ｓｎ的Ｉｎ２Ｏ３导电透明膜衬底上制备了钙钛矿型Ｐｂ（Ｚｒ,Ｔｉ）Ｏ３（ＰＺＴ）铁电薄膜。研究了沉积参量与热处理工艺对铁电薄膜结构和性能的影响。运用Ｘ射线衍射、Ｘ射线光电子能谱和扫描电镜等技术,分析了薄膜的晶体结构、表面形貌和表面元素化学状态。测量了不同处理条件下薄膜的铁电性能。结果表明：在掺Ｓｎ的Ｉｎ２Ｏ３导电透明膜衬底上可以得到表面无裂纹,化学计量比符合要求的ＰＺ     

铁电薄膜的材料系统与功能性质

集成铁电体把铁电材料与集成半导体技术联合起来,以发展出一批新的电子器件.铁电薄膜在其中发挥着非挥发性记忆、热释电、压电、光折变、抗辐射、声学的和/或介电的功能性质.在不同的器件应用中,铁电薄膜的材料体系是不相同的.在非挥发性存贮器(NVRAM)中,PZT薄膜面临着SrBi2Ta2O9(SBT)系列铁电体的强力挑战;Ba1-xSrxTiO3(BST)则可能出现在下一代高密度动态随机存贮器(DRAM)中.金属氧化物电极和/或过渡层可以克服Pt电极面临的一些问题,并有助于铁电薄膜的外延生长.     

Improved ferroelectric photovoltaic effect in Mn-doped lead-free K0.5Na0.5NbO3 films

The pure and Mn-doped K_0.5Na_0.5NbO₃ (KNN) films were deposited using solution-gelation method. The crystal structure, ferroelectric properties, spectral response and J-V performance of photovoltaic effect were systematically investigated. Both the ferroelectric and leakage properties are obviously enhanced for Mn-doped KNN films. A fascinating phenomenon is observed that the ferroelectric photovoltaic effect is enhanced in Mn-doped KNN films, which is originated from the improved ferroelectric polarization and narrower band gap. The transition element Nb partially substituted by Mn results in the lattice distortion and further destroys the symmetry space structure, which enhances ferroelectric polarization. And the narrower band gap effectively decreases the internal potential barrier to separate the carriers. This work gives a clear relationship between the lattice distortion, ferroelectric and photovoltaic response. It is certain that lead-free transparent K_0.5Na_0.5NbO₃ films can be potentially applied in viable ferroelectric based solar cells.     

Temperature dependence of ferroelectric property and leakage mechanism in Mn-doped Pb(Zr0.3Ti0.7)O3 films

High-quality ferroelectric films of Mn-doped Pb(Zr_0.3Ti_0.7)O₃ (PMZT) were prepared using the sol-gel method, and the temperature dependence of ferroelectric, dielectric, and leakage current properties (J–E) were explored in detail using the top electrode/ferroelectric films/bottom electrode capacitor heterostructure. The enhancement of polarization and dielectric properties by element doping is clearly observed by 3% Mn-doping. Such enhancement is beneficial for the application of these films in ferroelectric random-access memory. In addition, the analysis of leakage current reveals symmetric behavior with 3% Mn-doping and the leakage current density gradually increases with increasing temperature, which may be due to the movement of domain wall and oxygen vacancy. The dominant leakage current conduction mechanism is bulk-limited ohmic or interface-limited Schottky emission conduction within a wide temperature range. The results might be meaningful for further work on ferroelectric electrical devices with improved ferroelectric and dielectric properties.     

Synthesis and ferroelectric investigations of poly(vinylidene fluoride‐co‐hexafluoropropylene)‐Mg(NO3)2 films

The free‐standing, flexible, and ferroelectric films of poly(vinylidenefluoride‐co‐hexafluoropropylene) [P(VDF‐HFP)] were prepared by spin coating method. The ferroelectric phase of the films was enhanced by adding magnesium nitrate Mg(NO₃)₂ in different wt % as the additive during the film fabrication. The effects on the structural, compositional, morphological, ferroelectric, dielectric, and leakage current behaviors of the films due to the addition of salt were analyzed. Based on the X‐ray diffraction (XRD) patterns and Fourier Transform Infrared (FTIR) spectra, it is confirmed that the addition of Mg(NO₃)₂ promotes the electroactive β phase that induces the ferroelectric property. The fiber‐like topography of the films exhibits a nodule‐like structure, and the roughness of the films increases by the addition of Mg(NO₃)₂. The ferroelectric studies show the higher polarization values for the composite films than that of the plain P(VDF‐HFP) film. The Piezo‐response force microscope images also confirm the domain switching behavior of the samples. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44008.     

Characterization techniques for thin and thick ferroelectric films

A few measurement techniques are presented for characterization of thin and thick ferroelectric films at microwave frequencies. Broadband reflection type measurements using a probe station are considered for on wafer characterization of thin films. The accuracy of the method is analyzed with respect to measurement residual systematic errors. A test structure is introduced allowing quick and accurate extraction of the film parameters based on the rigorous full-wave model. Two measurement techniques are reported for electrode-less characterization of thick ferroelectric films. The first method (X-band) is based on the reflection type measurement of a resonator established by a layered alumina/ferroelectric sample loaded in a cut-off waveguide. The second method (B-band) utilizes an open resonator (OR) technique. Theoretical and experimental results are presented.     

Crystal Phase and Orientation Control in Integrated Ferroelectric CaBi4Ti4O15 Using a Tailored Liquid of Alkoxides

We used a Ca–Bi–Ti complex alkoxide, in which metal–oxygen bonding was confirmed by spectroscopic analysis, to deposit CaBi₄Ti₄O₁₅ (CBTi144) thin films in various configurations. The phase transition of non-ferroelectric pyrochlore to ferroelectric perovskite in the complex-alkoxy-derived CBTi144 thin films was found to depend on the Pt bottom electrodes. Matching of the atomic arrangement to the Ca–Bi–Ti–O thin films was predominant rather than the strain and crystallinity of the bottom electrode. The thin films crystallized at 650°C on (111)-oriented Pt showed random orientation and ferroelectric P – V hysteresis loops. The endurance property was excellent against a number of switchings. For this reason, CBTi144 thin films would be expected to be excellent for application to ferroelectric random access memories (FeRAM). Polar-axis-oriented CBTi144 films were fabricated on Pt foils using the complex metal alkoxide solution. The 500-nm-thick film had a columnar structure comprising well-developed grains. The a / b -axis orientation of the ferroelectric films is considered to be associated with the preferred orientation of Pt foil. The film showed improved ferro- and piezoelectric properties. The P _r, E _c, and d ₃₃ values were enhanced to become twice those of CBTi144 thin films with random orientation. These polar-axis-oriented CBTi144 films are eminently useful in devices as Pb-free piezoelectric materials.     

Multiferroic nanoscale Bi(2)FeCrO(6) material for spintronic-related applications

We report the control of the growth mode of Bi(2)FeCrO(6) thin and ultrathin films by either tuning the pulsed laser deposition parameters or by using a buffer layer. The films are epitaxial and the heterostructures exhibit very smooth interfaces, thus eliminating the main obstacle in the realization of tunnel junctions. By characterizing the functional properties of thin films we find that Bi(2)FeCrO(6) retains its room temperature multiferroic character even at the nanoscale. The coexistence of these properties in ultra-thin Bi(2)FeCrO(6) films will pave the way to design multifunctional devices for applications in spintronics and electronics, such as ferroelectric tunnel junctions or magnetic tunnel junctions with ferroelectric barriers.     

铁电薄膜的制备工艺及发展趋势

随着陶瓷材料新技术生产发展的需求,多功能的铁电薄膜材料日益引起科研人员的广泛关注,并成为近年来研究的热点。论述了铁电薄膜的发展过程、种类、性能以及应用,着重介绍了铁电薄膜的制备方法,并指出了铁电薄膜的发展趋势。     

Enhanced red photoluminescence in a nanocomposite thin film composed of Bi3.6Eu0.4Ti3O12 and Au-decorated ZnO nanorods

This paper firstly reports on a series of nanocomposite thin films composed of a ferroelectric Bi_3.6Eu_0.4Ti₃O₁₂ (BET) and Au-decorated ZnO nanorods (Au-ZnO), which are prepared by a ultraviolet-induced hybrid chemical solution method. The effects of Au nanoparticles (NPs) and ZnO nanorods on the significantly red photoluminescence enhancement of Eu³⁺ ions are investigated. The results indicate that the larger near band edge (NBE) emission of ZnO by the SPR effect of Au NPs can make an energy transfer from ZnO to Eu³⁺ ions. Simultaneously, the depression of the deep-level emission of ZnO can improve the monochromaticity in the visible range. Furthermore, the dielectric and ferroelectric properties of the thin films are also enhanced. The findings suggest that the nanocomposite thin films of a ferroelectric BET and Au-ZnO could be used as a multifunctional material in the ferroelectric optoelectronic devices with bright light emitting.     

High polarization levels in poly(vinylidene fluoride–trifluoroethylene) ferroelectric thin films doped with diethyl phthalate

With a spin‐coating technique, ferroelectric thin films of poly(vinylidene fluoride–trifluoroethylene) copolymer [P(VDF–TrFE; with a content (mol %) ratio of 68/32 vinylidene fluoride/trifluoroethylene] were fabricated on silicon wafers covered with platinum and were doped with a nucleation agent, diethyl phthalate (DEP). The remnant polarization of copolymer thin films increased 70% after doping with DEP, and the coercive field was reduced, which is highly desirable in bistable memory devices. The dielectric constant of thin films also increased after doping. However, the effect of doping on the ferroelectric response was not remarkable in freestanding copolymer films. The results demonstrated that the ferroelectric dipole orientation in P(VDF–TrFE) thin films was significantly enhanced by the presence of DEP because the crystallinity of thin films decreased after doping, as revealed by X‐ray results. The dopant DEP acted as both a nucleation agent during the crystallization process and a plasticizer in the noncrystalline regions, which greatly enhanced the dipole orientation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1416–1419, 2003     

BaTiO3铁电薄膜在硅基片上的取向生长

采用脉冲激光沉积方法,在硅基片上先沉积MgO或CeO2缓冲层后再制备BaTiO3(BTO)铁电薄膜.通过原位反射高能电子衍射来监测MgO,CeO2缓冲层在硅基片上的生长行为.用X射线衍射测定BTO薄膜的结晶取向.并利用压电响应力显微镜观察了铁电薄膜的自发极化形成的铁电畴.结果表明:BTO薄膜在不同的缓冲层硅基片上以不同的取向生长,在织构的MgO/Si(001)基片上为(001)择优,择优程度与MgO织构品质有关,其中在双轴织构MgO缓冲层上为(001)单一取向;在CeO2(111)缓冲层上为(011)单一取向.(001)取向的BTO薄膜具有更大的面外极化,而(011)取向的BTO薄膜具有更大的面内极化.     

Enhanced switchable ferroelectric photovoltaic in BiFeO3 based films through chemical-strain-tuned polarization

Ferroelectric photovoltaic (FE-PV) materials have generated widespread attention due to their unique switchable photovoltaic behavior, but suffering from low photocurrent and remanent polarization. Herein, enhanced ferroelectric polarization and switchable photovoltaic in BiFeO₃ based thin films were achieved by the optimization of Bi content. The compact and uniform films with few defects were obtained by the control of chemical composition. The remanent polarization increased from 3.4 to 73.9 μC cm^?2 showing a qualitative leap. Intriguingly, the control range of photovoltaic signal between two polarization directions of the short-circuit current density (J_SC) and open circuit (V_OC) in present films exhibited an increase of 99.2% and 278.9%, respectively. It is suggested that the ferroelectric polarization was the main driving force for enhancing switchable ferroelectric photovoltaic. Therefore, the present work outstands a simple idea to enhance switchable ferroelectric photovoltaic based on the chemical engineering, providing a promising pathway for the development of photovoltaic devices.     

Ferroelectric properties of ZrO2 films deposited on ITO-coated glass

In this work, the ferroelectric characteristics of ZrO₂ thin films grown on ITO-coated glass have been investigated. The ferroelectric nature of the ZrO₂ films has been studied by polarization-electric field (P-E) hysteresis loops and found to be optimum for the films processed by rapid thermal annealing at 600 °C. The increase in the annealing temperature improves the ferroelectric properties through the increase of the in-plane strain that causes the formation of the ferroelectric orthorhombic phase. The formation of the orthorhombic phase was confirmed through high-resolution transmission electron microscopy. The effect of the electric field on the polarization switching kinetics of ZrO₂ films has been investigated revealing that the switching kinetics follows the nucleation limited switching (NLS) model. The activation fields estimated from the peak values of the polarization currents (i_m) and the time (t_m) at which i_m occurs are in good agreement with the values obtained from the switching characteristic time of the NLS model. This work paves the way towards the integration of (pseudo)-binary oxide thin films on cheap substrates like glass for the next-generation of non-volatile memories.     

Effect of annealing protection atmosphere on the ferroelectric yttrium doped hafnium oxide thin films

The 10 nm thick yttrium doped hafnium oxide (Y:HfO₂) thin films, prepared by chemical solution deposition which using all-inorganic aqueous salt reagents, were fabricated on Si (100) substrates. The crystalline structure, chemical composition and ferroelectric properties of thin films, annealed in protection atmosphere of Air, Ar and N₂, were examined. Result showed that the crystalline structure and ferroelectric properties of films exhibited a strong annealing protection atmosphere dependence. When compared to annealing protection atmosphere of Air and Ar, the films with the N₂ exhibited lowest m-phase fraction of 19.4%, and the highest oxygen vacancy percentage content of 3.06%, accompanied with the highest relative permittivity of 50.9 and the remanent polarization of 14.6 μC/cm². These excellent ferroelectric properties were correlated with asymmetric orthorhombic phase and the concentration of oxygen vacancy introduced from the nitrogen doping concentration.     

Facile preparation of ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) thick films by solution casting

We investigated the effects of annealing temperature and vacuum treatment on the crystallinity and ferroelectric properties of solution‐casted poly(vinylidenefluoride‐co‐trifluoroethylene), P(VDF‐TrFE), thick films. We varied the annealing temperature from 70°C to 150°C and achieved high‐quality ferroelectric thick films annealed at 130°C. Ferroelectric domains and their properties were confirmed using X‐ray diffraction, Fourier transform infrared spectroscopy with attenuated total reflection mode and ferroelectric/piezoelectric measurement systems. Drying and/or annealing in the vacuum allowed for the improvement of crystallinity and ferroelectric/piezoelectric properties. Importantly, the piezoelectric coefficient, d₃₃, of our optimal P(VDF‐TrFE) films after sufficient poling treatment was 36 pC/N and our P(VDF‐TrFE) power generator produced an output voltage of ～6 V under periodic bending and unbending motions. POLYM. ENG. SCI., 54:466–471, 2014. © 2013 Society of Plastics Engineers     

(001)-oriented BiFeO3 films integrated on Si with enhanced electrical performances

Highly (001)-oriented pure-phase BFO films were prepared on traditional Si substrates via radio frequency magnetron sputtering (RFMS). The crystallinity of the films is found to be increased, that is, higher degree of (001) texture, larger grain size, less grain boundary, denser surface morphology, and better thickness uniformity, with increased film thickness. These factors have significant influences on the electrical properties of BFO films, that is, dielectric response, as well as ferroelectric polarization and leakage current characteristics. The 240-nm-thick film exhibits relatively poor electrical properties compared with other three thicker films, which is mainly due to its small grain, the enhancement of the clamping effect of neighboring grains, and the absence of domain walls. The essential roles of the evolution and distribution of grains/domains and defect charges in leakage mechanism and ferroelectric switching polarization were also investigated systematically. It was found that 600-nm-thick BFO film has the lowest leakage current density (as low as 1.8 × 10⁻⁶ A / cm² @ 90 kV/cm) and followed a mixed SE or SCLC conduction behavior, while the leakage behavior in other films is dominated by SE and P-F currents. All (001)-BFO films have a giant electrical polarization which is solely originated from the contribution of ferroelectric domain switching, and it has lower switching voltage and faster switching rate in thicker films.     

SrBi_4Ti_4O_(15)陶瓷薄膜的铁电性能研究

利用溶胶-凝胶法制备了CaxSr1-xBi4Ti4O15铁电陶瓷薄膜,并研究了Ca掺杂量、退火温度以及保温时间对SrBi4Ti4O15陶瓷薄膜铁电性能的影响。研究结果表明,当Ca掺杂含量为0.4%,退火温度为750℃,保温时间为5 min时,样品的铁电性能最好。     

Breakdown field enhancement and energy storage performance in four-layered Aurivillius films

In dielectric capacitors, ferroelectric thin films with slim polarisation electric (P-E) hysteresis loops, which are mainly characterised by small residual polarisation (P_r) and large saturation polarisation (P_s) are expected to obtain high recoverable energy density (U_r) and efficiency (η). However, a lower breakdown in ferroelectric thin films usually impedes this result. Here, through the co-doping of La³⁺ and Pr³⁺ ions, a larger U_r of 54.27 J/cm³ and high η of 85.6% were obtained in four-layered Aurivillius phase ferroelectric thin films capacitors due to the enhanced breakdown electric field. The doped films annealed at relatively low temperatures showed similar energy storage properties compared with those of the prototype and higher energy storage efficiency compared with that of higher annealing films. In addition, the obtained thin film shows excellent energy storage properties in a wide frequency range, fatigue durability and good thermal stability. These results indicated that four-layered Aurivillius films are promising candidate materials for dielectric energy storage capacitors. The co-doping of double ions was an effective way to improve energy storage performance.     

Effect of electrode and substrate on the fatigue behavior of PZT thick films fabricated by aerosol deposition

10 μm-thick lead zirconate titanate (PZT) films with identical LaNiO₃ (LNO) top and bottom electrodes were fabricated on silicon and yttria-stabilized zirconia (YSZ) substrates by aerosol deposition (AD). A Pt electrode was also made for comparison. The dielectric, ferroelectric and fatigue behaviors at different fields were investigated. The PZT films on YSZ/LNO showed the highest dielectric and ferroelectric properties and good fatigue behavior under various fields. PZT films with a Pt electrode also showed good fatigue behavior up to 10⁸ cycles as thicker film can minimize the effect of defect entrapment near the interface.