Electromechanics of Ferroelectric‐Like Behavior of LaAlO3 Thin Films

Electromechanical coupling in complex oxide heterostructures opens new possibilities for the development of a broad range of novel electronic devices with enhanced functionality. In this article, the switchable hysteretic electro­mechanical behavior of crystalline epitaxial LaAlO₃ (LAO) thin films associated with polarization induced by electrical and mechanical stimuli is investigated. The field–time‐dependent testing of the induced polarization states along with transport measurements and theoretical modeling suggests that the ferroelectric‐like response of the LAO thin films is mediated by the field‐induced ion migration in the bulk of the film. Comparative analysis of the dynamics of polarization reversal under the electrical field and mechanical stress applied via a tip of a scanning probe microscope demonstrates that both electrical and mechanical stimulus can be used to effectively control polarization at least at the submillisecond timescale. However, the mechanical writing is more localized than the electrical one. A combined electrical/mechanical approach for tuning the physical properties of oxide hetero­structures may potentially facilitate novel memory and logic devices, in which the data bits are written mechanically and read electrically.     

PZT铁电薄膜的印迹研究

印迹(Imprint)是造成铁电存储器失效的一个重要因素,通过分析不同厚度的PZT薄膜电容的界面层后认为,造成印迹的原因是上下电极与铁电薄膜之间界面层厚度的不同,导致了铁电薄膜表面极化钉扎状态的差异。矫顽电压偏移量对铁电薄膜的厚度依赖性,以及矫顽电压的偏移量随时间变化规律,很好地证实了笔者的设想。     

PZT铁电薄膜刻蚀的研究进展

PZT铁电薄膜器件在微电子领域有着广泛的应用，可用于制备微机械系统(MEMS)、DRAM、红外探测器等，而薄膜的微图形化刻蚀技术是制备工艺中重要的环节。该文主要介绍了PZT铁电薄膜刻蚀技术的研究进展和应用，并对各种刻蚀法进行分析和对比。     

Ferroelectric Poling of Methylammonium Lead Iodide Thin Films

Seemingly contradictory reports on polar domains and their origin have surrounded the controversial discussion about the ferroelectricity of the methyl ammonium lead iodide (MAPbI₃) thin films that are commonly employed in perovskite solar cells. In this work, microscopic modulations of the polar domain patterns upon application of an electric poling field are correlated with macroscopic changes to the currents through the MAPbI₃ layer. Piezoresponse force microscopy is used to monitor the widening, narrowing, generation or extinction of polar domains, as well as shifts of the domain walls at room temperature under an in‐plane electric poling field that is applied between two laterally organized electrodes. This poling leads to a net polarization of individual grains and the thin film itself. Macroscopically, this net polarization results in a persistent shift of the diode characteristics that is measured across the channel between the electrodes. Both the modulation of the polar domains upon electric poling and the concurrent persistent shift of the electric currents through the device are the unambiguous hallmarks of ferroelectricity, which demonstrate that MAPbI₃ is a ferroelectric semiconductor.     

现代电阻薄膜

电阻薄膜是一种重要的电子薄膜。本文系统地论述了这种薄膜。     

溶胶—凝胶法制备掺镧钛酸铋铁电薄膜

利用溶胶-凝胶法在Si（100）及Pt/Ti/Si（100）衬底上制备了Bi3.5La0.5Ti3O12(BLT-5）铁电薄膜,研究了在不同退火条件下BLT-5薄膜的结晶性能。经650℃、30min退火处理的BLT-5铁电薄膜的矫顽场Et=67kV/cm,剩余极化强度Pt=11.2μC/cm∧2,BLT-5铁电薄膜呈现较好的抗疲劳特性,可望用于制备高容量铁电随机存取存储器。     

(Bi,Yb)4Ti3O12铁电薄膜的制备

采用稀有金属镱元素对钛酸铋进行掺杂,以期获得性能较好的(Bi,Yb)4Ti3O12铁电薄膜.采用溶胶-凝胶旋涂法在p型Si(100)基底上成功地沉积出(Bi34,Yb06)Ti3O12[BYT]铁电薄膜.用X射线衍射法对其结构及其成份进行了表征,用铁电分析仪(RT66A)测试了其铁电性.并就影响BYT薄膜铁电性能的因素进行了分析.     

Origin of Hysteresis in CH3NH3PbI3 Perovskite Thin Films

Organic–inorganic hybrid perovskite solar cells are attracting the attention of researchers owing to the high level of performance they exhibit in photovoltaic device applications. However, the attainment of an even higher level of performance is hindered by their anomalous current–voltage (I–V) hysteresis behavior. Even though experimental and theoretical studies have suggested that the perovskite materials may have a ferroelectric nature, it is still far from being fully understood. In this study, the origin of the hysteresis behavior in CH₃NH₃PbI₃ perovskite thin films is investigated. The behavior of ferroelectricity using piezoresponse force microscopy is first examined. Then, by comparing the scan‐rate‐dependent nano/macroscopic I–V curves, it is found that ion migration assisted by the grain boundaries is a dominant origin of I–V hysteresis from a macroscopic viewpoint. Consequently, the observations suggest that, even though ferroelectricity exists in the CH₃NH₃PbI₃ perovskite materials, ion migration primarily contributes to the macroscopic I–V hysteresis. The presented results can provide fundamental guidelines to the resolution of hysteresis issues in organic–inorganic hybrid perovskite materials.     

Nanoscale Characterization of Energy Generation from Piezoelectric Thin Films

We report on the use of nanoindentation to characterize in situ the voltage and current generation of piezoelectric thin films. This work presents the controlled observation of nanoscale piezoelectric voltage and current generation, allowing accurate quantification and mapping of force function variations. We characterize both continuous thin films and lithographically patterned nano­islands with constrained interaction area. The influence of size on energy generation parameters is reported, demonstrating that nanoislands can exhibit more effective current generation than continuous films. This quantitative finding suggests that further research into the impact of nanoscale patterning of piezoelectric thin films may yield an improved materials platform for integrated microscale energy scavenging systems.     

Microdomain Transformations in Mosaic Mesocrystal Thin Films

An easy design route via simple evaporation is reported for macroscopic mosaic thin films comprising the quaternary system of dl ‐lysine·HCl, poly(acrylic acid), water, and EtOH. By depositing droplets of the quaternary dispersions onto hydrophilic cover slips, the formation of macroscopic crack‐free mosaic mesocrystal thin films are produced. The formation follows a multistage crystallization process, which includes the formation of a polymer‐induced liquid‐precursor (PILP) phase, the formation of spherulitic thin films, and the recrystallization of mosaic mesocrystal thin films. A slow cooling rate is noted to be beneficial for the mesocrystal thin films, enabling the films to be crack‐free and to display low surface roughness at the nanoscale.     

脉冲激光沉积技术沉积温度对PZT/LSAT薄膜生长取向的影响

采用固相法分别制备了标准摩尔配比和铅过垦10%的两种靶材.并利用脉冲激光沉积技术(PLD)在镧锶铝钽(LaSrAlTaO3,LSAT)单晶衬底上成功制备了锆钛酸铅(Pb(Zr0.3Ti0.7)O3,PZT)铁电薄膜,在550～750℃沉积温度范围内研究了PZT薄膜的生长取向和铅含最对薄膜生长取向的影响.利用X射线衍射(XRD)仪和原子力显微镜(AFM)表征了薄膜生长取向和表面形貌.XRD测量表明在标准摩尔配比情况下薄膜牛长从550 C近似c轴取向逐渐过渡到750℃近似a轴取向,而在铅过量情况下薄膜生长取向无明显过渡性变化;AFM测量表明PZT薄膜在近似C轴和a轴生长情况下,表面均方根(RMS)粗糙度分别为16.9 nm和13.7 nm,而在混合生长无择优取向的情况下,薄膜表面均方根粗糙度达到68 nm,这可能是两种取向竞争生长的结果.     

ITO玻璃衬底上PLZT铁电薄膜的制备与电性能

用sol-gel法在掺Sn的In2O3导电透明膜(ITO)衬底上,制备了La掺杂的PbZr0.5Ti0.5O3(PLZT)铁电薄膜。研究了La掺杂量对薄膜的铁电、介电和漏电性质的影响。结果表明,x(La)为5%的PLZT薄膜经650℃退火,有优良的铁电特性,外加15V电压下,剩余极化强度为35.4×10–6C/cm2,矫顽场强为111×103V/cm。100kHz时的εr和tgδ分别为984和0.13。在外加电场小于9V时,薄膜的漏电流密度不超过10–8A/cm2。     

光电子薄膜的进展

由于光电子器件的迅速发展,对光电子器件应用的薄膜提出了很高的要求。本文简要地论述了光电子薄膜制备技术的重要进展,同时扼要地介绍了本实验室在这方面所开展的初步工作。     

Electromechanics of Domain Walls in Uniaxial Ferroelectrics

Piezoresponse force microscopy (PFM) is used for investigation of the electromechanical behavior of the head-to-head (H-H) and tail-to-tail (T-T) domain walls on the non-polar surfaces of three uniaxial ferroelectric materials with different crystal structures: LiNbO₃, Pb₅Ge₃O₁₁, and ErMnO₃. It is shown that, contrary to the common expectation that the domain walls should not exhibit any PFM response on the non-polar surface, an out-of-plane deformation of the crystal at the H-H and T-T domain walls occurs even in the absence of the out-of-plane polarization component due to a specific form of the piezoelectric tensor. In spite of their different symmetry, in all studied materials, the dominant contribution comes from the counteracting shear strains on both sides of the H-H and T-T domain walls. The finite element analysis approach that takes into account a contribution of all elements in the piezoelectric tensor, is applicable to any ferroelectric material and can be instrumental for getting a new insight into the coupling between the electromechanical and electronic properties of the charged ferroelectric domain walls.     

钇掺杂锆钛酸铅铁电薄膜的电性能研究

对采用Sol-Gel法制备的钇掺杂锆钛酸铅铁电薄膜的电性能进行了研究。实验结果表明，由于钇离子（Y^3 ）的引入造成晶格畸变，使掺钇后的PZT铁电薄膜比未掺钇时具有更大的剩余极化强度、更小的矫顽场和漏电流。此外，钇掺杂锆钛酸铅铁电薄膜具有良好的介电性能，在室温和10kHz频率下，其介电常数和介电损耗分别为437和0．043。     

Declamped Piezoelectric Coefficients in Patterned 70/30 Lead Magnesium Niobate–Lead Titanate Thin Films

Lateral subdivision of blanket piezoelectric thin films increases the functional properties through both increased domain wall mobility and declamping of the intrinsic response. This work presents the local effects of substrate declamping on the piezoelectric coefficient d _33,f of 300 nm thick, rhombohedral, {001}‐oriented lead magnesium niobate–lead titanate thin films at the 70/30 composition (70PMN–30PT). Films grown by chemical solution deposition on platinized Si substrates are patterned into strip structures ranging from 0.75 to 9 µm in width. The longitudinal piezoelectric coefficient, d _33,f, is interrogated as a function of position across the patterned structures by three approaches: finite element modeling, piezoresponse force microscopy, and nanoprobe synchrotron X‐ray diffraction. It is found that d _33,f increases from the clamped value of 40–50 to ≈160 pm V^?1 at the free sidewall under 200 kV cm^?1 excitation. The sidewalls partially declamp the piezoelectric response 500–600 nm into the patterned structure, raising the piezoelectric response at the center of features with lateral dimensions less than 1 µm (3:1 width to thickness aspect ratio). The normalized data from all three methods are in excellent agreement, with quantitative differences providing insight to the field dependence of the piezoelectric coefficient and its declamping behavior.     

掺钐钛酸铅铁电薄膜的制备和主要性质

采用金属有机分解法(MOD)在P型Si(111)衬底上制备了Pb0.85Sm0.1TiO3(PST)薄膜。用X-射线衍射技术研究了退火温度对薄膜的结构和结晶性的影响。同时还研究了薄膜的介电、铁电和绝缘性能。结果发现在600°C下退火1h的PST薄膜呈钙钛矿结构;在0～16V范围内,薄膜的漏电流小于1.17×10-7A;在±10V的偏压范围内,电容-电压(C-V)记忆窗口宽度为4.5V;在室温10kHz下,其介电常数为37.25,介电损耗为0.042。     

(Pb,La)TiO3薄膜电畴生长的压电响应力显微镜研究

压电响应力显微镜为铁电薄膜电畴的研究提供了一种有效的检测方法.本实验用压电响应力显微镜(PFM)对不同退火温度的(Pb,La)TiO3铁电薄膜进行表征,得到了各个样品相应的形貌像、面外电畴像和面内电畴像.结果表明,随退火温度升高,(Pb,La)TiO3铁电薄膜的表面形貌表现出从粘连到结晶较好,到出现抱团的变化过程;此外,随退火温度升高,铁电薄膜的自发极化强度先增强后减弱.通过对这一系列铁电薄膜电畴进一步研究得到:在625℃退火1 h后,(Pb,La)TiO3铁电薄膜以非铁电相为主;而在650℃和675℃退火1 h后,(Pb,La)TiO3铁电薄膜以铁电相为主.     

Nanoscale Insight Into Lead‐Free BNT‐BT‐xKNN

Piezoresponse force microscopy (PFM) is used to afford insight into the nanoscale electromechanical behavior of lead‐free piezoceramics. Materials based on Bi_1/2Na_1/2TiO₃ exhibit high strains mediated by a field‐induced phase transition. Using the band excitation technique the initial domain morphology, the poling behavior, the switching behavior, and the time‐dependent phase stability in the pseudo‐ternary system (1–x)(0.94Bi_1/2Na_1/2TiO₃‐0.06BaTiO₃)‐xK_0.5Na_0.5NbO₃ (0 <= x <= 18 mol%) are revealed. In the base material (x = 0 mol%), macroscopic domains and ferroelectric switching can be induced from the initial relaxor state with sufficiently high electric field, yielding large macroscopic remanent strain and polarization. The addition of KNN increases the threshold field required to induce long range order and decreases the stability thereof. For x = 3 mol% the field‐induced domains relax completely, which is also reflected in zero macroscopic remanence. Eventually, no long range order can be induced for x >= 3 mol%. This PFM study provides a novel perspective on the interplay between macroscopic and nanoscopic material properties in bulk lead‐free piezoceramics.     

层状钙钛矿铁电薄膜的结构及性能研究

介绍了ＳｒＢｉ２Ｔａ２Ｏ９系列层状钙钛矿铁电薄膜的结构、性能、制备方法以及研究进展。