Orientation dependence of ferroelectricity in pulsed-laser-deposited epitaxial bismuth-layered perovskite thin films

Thin films of bismuth-layered perovskites such as SrBi₂Ta₂O₉, Bi₄Ti₃O₁₂, and BaBi₄Ti₄O₁₅ with preferred orientations were grown by pulsed laser deposition on epitaxial conducting LaNiO₃ electrodes on single-crystalline (100) SrTiO₃ or on top of epitaxial buffer layers on (100) silicon. A morphology and structure investigation by X-ray diffraction analysis, scanning probe microscopy, and scanning and transmission electron microscopy showed that the films consisted of both c-axis-oriented regions and mixed (110)-, (100)-, and (001)-oriented regions. The regions with mixed orientation featured rectangular as well as equiaxed crystalline grains protruding out of a smooth c-oriented background. A closer examination revealed that the regions with mixed orientation actually consisted of a c-axis-oriented sublayer growing directly on the epitaxial LaNiO₃ electrode, on top of which the growth of either (110)-, (100)-, or (001)-oriented grains took place. Macroscopic as well as microscopic measurements of the ferroelectric properties of regions with pure c-orientation and of regions with mixed orientations showed a clear relationship between their ferroelectric properties and their morphology and crystallographic orientation. In the regions with mixed orientation, the films exhibited saturated ferroelectric hysteresis loops with well-defined remnant polarisation P_r and coercive field E_c. The regions having c-axis orientation with a smooth surface morphology in contrast exhibited a linear P-E curve with no hysteretic behaviour for SrBi₂Ta₂O₉ and BaBi₄Ti₄O₁₅ and a weak ferroelectric behaviour for Bi₄Ti₃O₁₂. This clearly showed that the ferroelectric properties of bismuth-layered ferroelectric oxides depended on the crystalline orientation of the film and that the observed ferroelectric hysteresis loops in SrBi₂Ta₂O₉ and BaBi₄Ti₄O₁₅ films were solely due to the (100)- and (110)-oriented grains. The size of the (110)- and (100)-oriented grains being of the order of 100 nm and spontaneous polarisation having been observed and switched in a controlled manner is a demonstration that ferroelectricity can exist in structures of submicrometer size. These results might have a technological impact due to the relevance of bismuth-layered ferroelectric oxides for the fabrication of non-volatile FeRAM memories.     

Pulsed-laser deposition of Ta-doped PZT ferroelectric films for memory applications using conductive oxide La0.25Sr0.75CoO3 and SrRuO3 electrodes

New methods for fabricating highly 𘚡¢-oriented and complete 𘜏¢-textured Pb(Ta_0.05Zr_0.48Ti_0.47)O₃ (PTZT) films on Pt/TiO₂/SiO₂/Si(001) substrates by pulsed-laser deposition have been developed using conductive oxide La_0.25Sr_0.75CoO₃ and SrRuO₃ electrodes. The 𘚡¢-preferred orientated PTZT ferroelectric capacitor was not subjected to loss of its polarization after 1᎒¹⁰ switching cycles at an applied voltage of 5 V and a frequency of 1 MHz, and the 𘜏¢-textured PTZT film capacitor retains 94.7% of its polarization after 1.5᎒¹⁰ switching cycles at 5 V and 50 kHz. The PTZT capacitors using these conductive oxide electrodes have low leakage current dominated by Schottky field emission mechanism.     

SrBi2Ta2O9/Bi4Ti3O12复合铁电薄膜的制备与特性研究

采用溶胶凝胶工艺在p-Si衬底上制备了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合铁电薄膜. 研究了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合薄膜的微观结构与生长行为、铁电性能和疲劳特性. 研究表明: Si衬底Bi₄Ti< 关键词： 2Ta₂O₉')" href="#">SrBi₂Ta₂O₉ 4Ti₃O₁₂')" href="#">Bi₄Ti₃O₁₂ 复合铁电薄膜 溶胶凝胶工艺     

Role of bismuth precursor in crystallization of SrBi2Ta2O9 thin films

Crystallization of SrBi₂Ta₂O₉ (SBT) thin films was studied as a function of viscosity of bismuth precursor and baking temperature, in order to fabricate capacitors with improved ferroelectric properties. SBT thin films were deposited on to Pt substrates using a chemical solution deposition (CSD) technique. Post-deposition anneal at 750 °C for 1 h in oxygen atmosphere revealed a significant influence of baking temperature and the viscosity of bismuth precursor on the microstructure and the ferroelectric properties of SBT thin films. A high baking temperature (350 °C) and a low viscosity of bismuth precursor (8 cp) yielded larger amounts of Bi₂O₃ secondary phase, smaller SBT grains (104 nm), and lower remanent polarization (P_r=2.0 7c/cm²). Additionally, these films exhibited a very high rate of ageing (>45% reduction in P_r after 7 days). A modified CSD process is suggested, which could suppress the formation of Bi₂O₃ secondary phase. Films fabricated using modified CSD technique exhibited a much larger grain size of 165 nm, higher P_r of 7.2 7c/cm², and significantly improved ageing characteristics (<1% reduction in P_r after 7 days). A qualitative model to describe the ageing in SBT-based capacitors is also suggested.     

Preferential orientation of modified SrBi2Nb2O9 ferroelectric thin films prepared by pulsed laser deposition

We report on the deposition of SrBi₂Nb₂O₉ and Sr_1-xNa_xBi_2-xTe_xNb₂O₉ ferroelectric thin films on Pt/TiO₂/SiO₂/(100)Si substrates using the pulsed laser deposition technique. Deposition on substrates heated to 600-700 °C produces {11l} film texture and dense films with grain sizes up to about 500 nm. The recrystallization at 700 °C of amorphous films deposited at lower temperatures enhances the contribution of the {100} and {010} orientations. These films show smaller grain size, namely 50-100 nm. {11l}-oriented Sr_1-xNa_xBi_2-xTe_xNb₂O₉ films have remnant polarization P_rۆ 7C/cm², a coercive field E_c䏐 kV/cm and dielectric constant, )𪓴. The low value of P_r is probably related to the low fraction of grains with the ferroelectric axis in the direction of the applied field, E. The recrystallized films have more grains with the ferroelectric axis parallel to E; however, they have a low resistivity which so far has prevented electrical characterization.     

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.     

Influence of cationic stoichiometry of the bottom electrode La1-xSrxCoO3 on the microstructures of Pb(Ta0.05Zr0.48Ti0.47)O3 ferroelectric films using Pt/TiO2 conducting barrier

The heterostructures La_1-xSr_xCoO₃/Pb(Ta_0.05 Zr_0.48Ti_0.47)O₃(PTZT)/La_1-x Sr_xCoO₃ have been deposited on SiO₂/Si(001) substrates using Pt/TiO₂ as conductive barrier by pulsed-laser deposition. La_0.25Sr_0.75CoO₃(25/75) bottom electrodes with a pseudo-cubic perovskite structure favors (001)-textured growth of PTZT films. The ferroelectric capacitor LSCO(25/75)/PTZT/LSCO(25/75) remains about 96% of its polarization after 5᎒¹⁰ switching cycles at an applied voltage of 5 V and a frequency of 500 kHz. The cross-section morphology of scanning electron microscopy and Rutherford backscattering spectra show that no obvious interdiffusion occurs across the interfaces.     

Atomic-force microscopy of polarization domains in ferroelectric films

Single-crystal (001)-oriented PbZr_0.47Ti_0.53O₃ and polycrystalline (111)-oriented PbZr_0.47Ti_0.53O₃ thin ferroelectric films were studied using contact electrostatic force microscopy. Local electromechanical response measurements permitted study of the polarization vector distribution in natural and intentionally created polarization nanodomains in films. The principal components of an electromechanical response signal encountered in studies of ferroelectric films (the piezoelectric response and the additional capacitive contribution) were isolated and analyzed. The effect of tip-surface contact stiffness on the capacitive contribution to the electromechanical response signal was demonstrated experimentally and in terms of a model. It was shown that more accurate information on the distribution of the polarization vector in ferroelectric films can be gained by monitoring local variations in the tip-surface contact stiffness.     

Si基Bi4Ti3O12铁电薄膜的制备与特性研究

采用sol-gel工艺, 在分层快速退火的工艺条件下成功地制备了高质量Si基Bi_{4Ti3O12铁电薄膜. 研究了Si基Bi4Ti3O12薄膜的生长行为、铁电性能、C-V特性和疲劳特性. 研究表明: Si基Bi4Ti3O12薄膜具有随退火温度升高沿c轴择优生长的趋势; 退火温度通过影响薄膜的晶粒尺寸、生长取向和薄膜中载流子的浓度来改变Si基Bi关键词： sol-gel法 铁电薄膜 4Ti3O12')" href="#">Bi4Ti3O12 C-V特性}     

Ferroelectric properties of bilayer structured Pb(Zr0.52Ti0.48)O3/SrBi2Ta2O9 (PZT/SBT) thin films on Pt/TiO2/SiO2/Si substrates

Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films with large remanent polarization and SrBi₂Ta₂O₉ (SBT) thin films with excellent fatigue-resisting characteristic have been widely studied for non-volatile random access memories, respectively. To combine these two advantages_, bilayered Pb(Zr_0.52Ti_0.48)O₃/SrBi₂Ta₂O₉ (PZT/SBT) thin films were fabricated on Pt/TiO₂/SiO₂/Si substrates by chemical solution deposition method. X-ray diffraction patterns revealed that the diffraction peaks of PZT/SBT thin films were completely composed of PZT and SBT, and no other secondary phase was observed. The electrical properties of the bilayered structure PZT/SBT films have been investigated in comparison with pure PZT and SBT films. PZT/SBT bilayered thin films showed larger remanent polarization (2P_r) of 18.37 μC/cm² than pure SBT and less polarization fatigue up to 1 × 10⁹ switching cycles than pure PZT. These results indicated that this bilayered structure of PZT/SBT is a promising material combination for ferroelectric memory applications.     

Ag/Bi4Ti3O12栅n沟道铁电场效应晶体管制备及存储特性

在溶胶-凝胶工艺获得高质量Bi₄Ti₃O₁₂薄膜的基础上 ，制备了Ag/Bi₄Ti₃O₁₂栅n沟道铁电场效应晶体管. 研 究了Si基Bi₄Ti₃O₁₂薄膜的生长特性及其对铁电薄膜/ 硅的界面状态和铁电场效应晶体管存储特性的影响. 研究表明，在合理的工艺条件下可以获 得具有较高c-轴择优取向的纯钙钛矿相Si基Bi₄Ti₃O₁₂ 铁电薄膜并有利于改善Bi₄Ti₃O₁₂/Si之间的界面特性; 顺时针回滞的C-V特性曲线和C-T曲线表明Ag/Bi₄Ti₃O_{12栅n沟道铁电场效应晶体管具有极化存储效应和一定的极化电荷保持能力; 器件的转移(I< sub>sd}-V_G)特性曲线显示Ag/Bi₄Ti₃O_{12栅n沟道铁电场效应晶体管具有明显的栅极化调制效应. 关键词： 铁电场效应晶体管 4}Ti₃O₁₂')" href="#">Bi₄Ti₃O₁₂ 存储 特性 溶胶-凝胶工艺     

Film structure and ferroelectric properties of in situ grown SrBi2Ta2O9 films

Ferroelectric SrBi₂Ta₂O₉ (SBT) films were grown by pulsed-laser deposition (PLD) at different substrate temperatures and fluences. A correlation between film structure and ferroelectric properties is established. The dielectric function ε^′ of thin SBT films shows a Curie–Weiss behavior well below the peak temperature T_max and relaxor-like behavior in the vicinity of T_max. Domain walls have a strong influence on the dielectric and ferroelectric properties and on the polarization fatigue of SBT films below 100 °C. The formation of ferroelectric phases is favored at lower substrate temperatures by incorporating Bi₂O₃ template layers into the structure. Received: 18 March 1999 / Accepted: 19 March 1999 / Published online: 5 May 1999     

Si基Bi3.25La0.75Ti3O12铁电薄膜的制备与特性研究

采用Sol-Gel工艺低温制备了Si基Bi_3.25La_0.75Ti₃O₁₂铁电薄膜.研究了退火温度对薄膜微观结构、介电特性与铁电性能的影响.500℃退火处理的Bi_3.25La_0.75Ti₃O₁₂薄膜未能充分晶化，晶粒细小且有非晶团聚，介电与铁电性能均较差.高于550℃退火处理的Bi_3.25La_{0.75 关键词： 铁电薄膜 3.25}La_0.75Ti₃O₁₂')" href="#">Bi_3.25La_0.75Ti₃O₁₂ Sol-Gel工艺     

Correlation between local hysteresis and crystallite orientation in PZT thin films deposited on Si and MgO substrates

(0 0 1)-Oriented tetragonal ferroelectric PbZr_0.53Ti_0.47O₃ (PZT) thin films (90 nm of thickness) have been grown on TiO_x/Pt/TiO₂/SiO₂/Si and TiO_x/Pt/MgO substrates. The existence of (1 0 0)-oriented crystallites in the c-axis matrix of the (0 0 1)-oriented films has been evidenced by using four circles X-ray diffraction. Depending on the substrate, the ratio of the lattice parameters c/a was found to be 1.02 (Si) and 1.07 (MgO) and this was correlated with the coercive field values. Local piezoelectric hysteresis loops produced by atomic force microscopy have been taken with profit to characterize the switching properties of the ferroelectric domains at the scale of individual crystallites. In each case, (1 0 0)-oriented crystallites require much higher voltage than (0 0 1)-oriented crystallites for switching. These results are explained by taking into account the strain imposed by the substrate in the film. We conclude that piezoelectric hysteresis loops produced by atomic force microscopy provide very rich information for addressing the local switching property of individual crystallites in PZT thin films.     

Artificial Modulation of Ferroelectric Thin Films into Antiferroelectric through H+ Implantation for High-Density Charge Storage

Hydrogen ions are implanted into Pb（Zro.3Tio.7）03 1014 ions/cm^2. Pseudo-antiferroelectric behaviour in thin films at the energy of 40keV with a flux of 5 x the implanted thin films is observed, as confirmed by the measurements of polarization versus electric hysteresis loops and capacitance versus voltage curves. X-ray diffrac- tion patterns show the film structures before and after H＋ implantation both to be perovskite of a tetragonal symmetry. These findings indicate that hydrogen ions exist as stable dopants within the films. It is believed that the dopants change domain-switching behaviour via the boundary charge compensation. Meanwhile, time dependence of leakage current density after time longer than lOs indicates the enhancement of the leakage cur- rent nearly in one order for the implanted film, but the current at time shorter than i s is mostly the same as that of the original film without the ionic implantation. The artificial tailoring of the antiferroelectric behaviour through H＋ implantation in ferroelectric thin films is finally proven to be achievable for the device application of high-density charge storage.     

Microstructures and impedance studies of Bi<Subscript>3.15</Subscript>Nd<Subscript>0.85</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Microstructures and impedance characteristics of chemical-solution-derived Bi_3.15Nd_0.85Ti₃O₁₂ thin films were studied as functions of temperature. A dielectric anomaly was found at around 450°C, corresponding to the paraelectric to ferroelectric transition. Via complex impedance studies, grain and grain boundary contributions to the impedance were separated. The resistance of grain and grain boundaries is found governed by the same kind of space charge with an activation energy around 1.1 eV, close to that of oxygen vacancies in perovskite ferroelectrics. The low temperature ac conductance of BNdT thin films shows a frequency dispersion, which can also be ascribed to space charges mainly due to oxygen vacancies. The results were compared with SrBi₂Ta₂O₉ in terms of oxygen vacancy conductivity.     

Ferroelectric Properties of Bi3.25La0.75Ti3O12 Thin Films Crystallized inDifferent N2/O2 Ambients

Bi3.25La0.75 Ti3O12 （BLT） ferroelectric thin films are deposited by sol-gel method and annealed for crystallizaion in total l eccm N2/02 mixed gas with various ratio at 750℃ for 30rain. The effect of crystallization ambient on the structural and ferroelectric properties of the BLT films is studied. The growth direction and grain size of BLT film are revealed to affect ferroeleetric properties. Alter the BLT film is annealed in 20%O2, the largest P~ value is obtained, which is ascribed to an increase of random orientation and large grain size. The fatigue property is improved with the concentration of oxygen in the ambient increasing, which is ascribed to annealing in the ambient with high concentrated oxygen adequately decreasing the defects related to lack of oxygen.     

Low-temperature preparation of SrxBi2+yTa2O9 ferroelectric thin film by pulsed laser deposition and its application to a metal–ferroelectric–nitride–oxide–semiconductor structure

Preferentially (105)-oriented Sr_xBi_2+yTa₂O₉ (SBT) thin films on SiN/SiO₂/p-Si(100) prepared by the pulsed laser deposition (PLD) method at a temperature as low as 400 °C, which is the lowest process temperature for growing SBT ferroelectric thin films on a silicon nitride film. Excess Bi promotes crystallization of the SBT film. A metal-ferroelectric-nitride-oxide-semiconductor (MFNOS) structure, which is very important in ferroelectric gate memory FET, has been fabricated by depositing the SBT film on silicon nitride-oxide-silicon. The MFNOS structures show capacitance-voltage (C-V) hysteresis corresponding to ferroelectric hysteresis. A memory window of the C-V hysteresis is improved, to be as high as 3.5 V in the SBT(400 nm)/SiN_x(7 nm)/SiO₂(18 nm)/Si compared with the window of 2.7 V in the SBT(400 nm)/SiO₂(27 nm)/Si (MFOS), where the thicknesses of their insulator layers are nearly the same. Little degradation is induced in the C-V characteristics of the SiN_x/SiO₂/p-Si structure when depositing the SBT film by PLD at low temperature. It is also found that the SiN_x layer acts as a diffusion barrier against component atoms in the SBT film during its deposition. Finally, the MFNOS structure prepared at the low temperature is very promising for a next-generation ferroelectric gate memory FET.     

Dielectric properties of Bi4Ti3O12–SrBi4Ti4O15 intergrowth ceramics synthesized by a modified oxalate route

In this study, Bi₄Ti₃O₁₂–SrBi₄Ti₄O₁₅ (BIT–SBTi) intergrowth ferroelectric ceramics was synthesized by a modified oxalate route. The phase formation behaviour, structure, morphology and electrical properties of the intergrowth ceramics were also investigated. The phase formation takes place through intermediate phases like SrBi₂O₄ and Bi₁₂TiO₂₀. The precursor mostly changes to Bi₄Ti₃O₁₂ at 600°C and to BIT–SBTi intergrowth at 800°C. Rietveld analysis of the X-ray diffraction pattern showed that the structure of the intergrowth compound was orthorhombic with lattice parameters a = 5.4408(3), b = 5.4505(1) and c = 74.0851(4) Å. The intergrowth ferroelectrics showed a phase transition at 610°C and a frequency-stable permittivity and dielectric loss behaviour. The intergrowth ferroelectrics also showed a larger 2P_r than their constituents BIT and SBTi.     

Influence of oxygen pressure on structural and optical properties of Al2O3 optical waveguides prepared by pulsed laser deposition

Pure and europium doped alumina waveguides have been prepared by Pulsed Laser Deposition using a KrF excimer laser at oxygen pressures in the range from 10^-7 to 0.1 mbar. The composition of the films and the doping ion concentration were determined by Rutherford Backscattering Spectroscopy. From X-ray diffraction measurements, a progressive growth of %-Al₂O₃ crystallites is observed as the oxygen pressure decreases. After annealing treatment, the alumina films are constituted of !-Al₂O₃ crystallites while europium doped alumina films remain constituted of %-Al₂O₃ crystallites. The films have optical waveguiding properties. The mean refractive index of the film increases as oxygen pressure decreases.