镧钛酸铅铁电薄膜成膜机理探讨

采用快速热处理和传统热处理工艺对金属有机物热分解法制备的镧钛酸铅（ＰＬＴ）铁电薄膜进行了热处理，用扫描电镜对不同热处理工艺和不同厚度的ＰＬＴ薄膜的形貌进行了分析。结果表明，快速热处理工艺有利于活性高，较薄膜层的结晶和致密化反应；ＰＬＴ薄膜在传统和快速热处理过程中的形成过程与蒸发和溅射薄膜的核生长型薄膜的形成过程相似，薄膜的形成经历了岛状－网状－连续的过程，即随层数的增加，薄膜逐渐从不连续转变为连续，而热处理工艺只影响形成连续薄膜的厚度。     

Hierarchical Domain Structure and Extremely Large Wall Current in Epitaxial BiFeO3 Thin Films

Erasable electrical conductive domain walls in an insulating ferroelectric matrix provide novel functionalities for applications in logic and memory devices. The crux of such success requires sufficiently high wall currents to drive high‐speed and high‐power nanodevices. This work provides an appealing strategy to increase the current by two orders of magnitude through the careful selection of current flowing paths along the charged walls. The dense walls come into form through the hierarchical evolution of the 71°, 109°, and 180° domains of epitaxial BiFeO₃ films in a planar‐geometry ferroelectric resistance‐switching memory cell. The engineered films grown on SrTiO₃ and GdScO₃ substrates allow the observation of detailed local configurations and the evolution of the different domain types using vector piezo‐force microscopy. The higher local electrical conductivity near the charged domain walls is identified by conductive atomic‐force microscopy. It is shown that 180° domain reversal proceeds by three‐step 71° rotations of the pristine domains. Surprisingly, a maximum current of ≈300 nA is observed for current paths along charge‐uncompensated head‐to‐head hierarchical domain walls connecting the two electrodes on the film surface. Furthermore, the achievable current level can be conveniently controlled by varying the relative directions of the initial polarization and the applied field.     

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 Self‐Poling,Switching, and Monoclinic Domain Configuration in BiFeO3 Thin Films

Self‐poling of ferroelectric films, i.e., a preferred, uniform direction of the ferroelectric polarization in as‐grown samples is often observed yet poorly understood despite its importance for device applications. The multiferroic perovskite BiFeO₃, which crystallizes in two distinct structural polymorphs depending on applied epitaxial strain, is well known to exhibit self‐poling. This study investigates the effect of self‐poling on the monoclinic domain configuration and the switching properties of the two polymorphs of BiFeO₃ (R′ and T′) in thin films grown on LaAlO₃ substrates with slightly different La_0.3Sr_0.7MnO₃ buffer layers. This study shows that the polarization state formed during the growth acts as “imprint” on the polarization and that switching the polarization away from this self‐poled direction can only be done at the expense of the sample's monoclinic domain configuration. The observed reduction of the monoclinic domain size is largely reversible; hence, the domain size is restored when the polarization is switched back to its original orientation. This is a direct consequence of the growth taking place in the polar phase (below T_c). Switching the polarization away from the preferred configuration, in which defects and domain patterns synergistically minimize the system's energy, leads to a domain state with smaller (and more highly strained and distorted) monoclinic domains.     

Interfacial Strain Gradients Control Nanoscale Domain Morphology in Epitaxial BiFeO3 Multiferroic Films

Domain switching pathways fundamentally control performance in ferroelectric thin film devices. In epitaxial bismuth ferrite (BiFeO₃) films, the domain morphology is known to influence the multiferroic orders. While both striped and mosaic domains have been observed, the origins of the latter have remained unclear. Here, it is shown that domain morphology is defined by the strain profile across the film–substrate interface. In samples with mosaic domains, X‐ray diffraction analysis reveals strong strain gradients, while geometric phase analysis using scanning transmission electron microscopy finds that within 5 nm of the film–substrate interface, the out‐of‐plane strain shows an anomalous dip while the in‐plane strain is constant. Conversely, if uniform strain is maintained across the interface with zero strain gradient, striped domains are formed. Critically, an ex situ thermal treatment, which eliminates the interfacial strain gradient, converts the domains from mosaic to striped. The antiferromagnetic state of the BiFeO₃ is also influenced by the domain structure, whereby the mosaic domains disrupt the long‐range spin cycloid. This work demonstrates that atomic scale tuning of interfacial strain gradients is a powerful route to manipulate the global multiferroic orders in epitaxial films.     

Nanoscale Origins of Nonlinear Behavior in Ferroic Thin Films

The nonlinear response of a ferroic to an applied field has been studied through the phenomenological Rayleigh Law for over a hundred years. Yet, despite this, the fundamental physical mechanisms at the nanoscale that lead to macroscopic Rayleigh behavior have remained largely elusive, and experimental evidence at small length scales is limited. Here, it is shown using a combination of scanning probe techniques and phase field modeling, that nanoscale piezoelectric response in prototypical Pb(Zr,Ti)O₃ films appears to follow a distinctly non‐Rayleigh regime. Through statistical analysis, it is found that an averaging of local responses can lead directly to Rayleigh‐like behavior of the strain on a macroscale. Phase‐field modeling confirms the twist of the ferroelastic interface is key in enhancing piezoelectric response. The studies shed light on the nanoscale origins of nonlinear behavior in disordered ferroics.     

BST溶胶及其纳米晶铁电薄膜特性研究

考察了在溶胶-凝胶(Sol-Gel)工艺中化学添加剂对钛酸锶钡(BST)溶胶的粒度分布的影响。通过对化学添加剂的优选,制备出具有优异电性能的BST薄膜。X-射线衍射(XRD)表明在Pt/Cr/SiO2/Si衬底上制备的BST薄膜具有完整的钙钛矿结构,AFM表面形貌显示BST薄膜表面致密、平整、无裂纹,平均晶粒尺寸约50 nm。漏电流测试表明BST薄膜在0~9 V的外加偏压下始终保持着较低的漏电流,在外加偏压为8.8 V时,漏电流密度为2.9×10-6A/cm2。     

Influence of a Single Grain Boundary on Domain Wall Motion in Ferroelectrics

Epitaxial tetragonal 425 and 611 nm thick Pb(Zr_0.45Ti_0.55)O₃ (PZT) films are deposited by pulsed laser deposition on SrRuO₃‐coated (100) SrTiO₃ 24° tilt angle bicrystal substrates to create a single PZT grain boundary with a well‐defined orientation. On either side of the bicrystal boundary, the films show square hysteresis loops and have dielectric permittivities of 456 and 576, with loss tangents of 0.010 and 0.015, respectively. Using piezoresponse force microscopy (PFM), a decrease in the nonlinear piezoelectric response is observed in the vicinity (720–820 nm) of the grain boundary. This region represents the width over which the extrinsic contributions to the piezoelectric response (e.g., those associated with the domain density/configuration and/or the domain wall mobility) are influenced by the presence of the grain boundary. Transmission electron microscope (TEM) images collected near and far from the grain boundary indicate a strong preference for (101)/(01) type domain walls at the grain boundary, whereas (011)/(01) and (101)/(01) are observed away from this region. It is proposed that the elastic strain field at the grain boundary interacts with the ferro‐electric/elastic domain structure, stabilizing (101)/(01) rather than (011)/(01) type domain walls, which inhibits domain wall motion under applied field and decreases non‐linearity.     

BST薄膜铁电移相器研究进展

钛酸锶钡(BST)薄膜因其具有高的介电调谐量,相对低的损耗tgδ和快的开关速度,在微波移相器的应用中显示出巨大优势。介绍了改善BST薄膜的介电性能的有效方法,衬底材料的选择,以及BST薄膜铁电移相器的结构类型和研究进展。     

Nanoscale Observation of Time‐Dependent Domain Wall Pinning as the Origin of Polarization Fatigue

The microscopic mechanism of polarization fatigue (i.e., a loss of switchable polarization under electrical cycling) remains one of the most important long‐standing problems in ferroelectric communities. Although there are numerous proposed fatigue models, a consensus between the models and experimental results is not reached yet. By using modified‐piezoresponse force microscopy, nanoscale domain switching dynamics are visualized for different fatigue stages in epitaxial PbZr_0.4Ti_0.6O₃ capacitors. Systematic time‐dependent studies of the domain nucleation and evolution reveal that domain wall pinning, rather than nucleation inhibition, is the primary origin of fatigue. In particular, the evolution of domain wall pinning process during electrical cycling, from the suppression of sideways domain growth in early fatigued stages to the blockage of forward domain growth in later stages, is directly observed. The pinning of forward growth results in a nucleation‐limited polarization switching and a significant slowdown of the switching time in the severely fatigued samples. The direct nanoscale observation of domain nucleation and growth dynamics elucidates the importance of evolution of the domain wall pinning process in the fatigue of ferroelectric materials.     

Observation of Unconventional Dynamics of Domain Walls in Uniaxial Ferroelectric Lead Germanate

Application of scanning probe microscopy techniques such as piezoresponse force microscopy (PFM) opens the possibility to re‐visit the ferroelectrics previously studied by the macroscopic electrical testing methods and establish a link between their local nanoscale characteristics and integral response. The nanoscale PFM studies and phase field modeling of the static and dynamic behavior of the domain structure in the well‐known ferroelectric material lead germanate, Pb₅Ge₃O₁₁, are reported. Several unusual phenomena are revealed: 1) domain formation during the paraelectric‐to‐ferroelectric phase transition, which exhibits an atypical cooling rate dependence; 2) unexpected electrically induced formation of the oblate domains due to the preferential domain walls motion in the directions perpendicular to the polar axis, contrary to the typical domain growth behavior observed so far; 3) absence of the bound charges at the 180° head‐to‐head (H–H) and tail‐totail (T–T) domain walls, which typically exhibit a significant charge density in other ferroelectrics due to the polarization discontinuity. This strikingly different behavior is rationalized by the phase field modeling of the dynamics of uncharged H–H and T–T domain walls. The results provide a new insight into the emergent physics of the ferroelectric domain boundaries, revealing unusual properties not exhibited by conventional Ising‐type walls.     

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。     

衬底温度对ZnO薄膜氧缺陷的影响

采用射频磁控溅射在石英玻璃和单晶硅Si(100)衬底上制备了ZnO薄膜，研究了衬底温度对ZnO薄膜中氧缺陷的影响。实验发现，ZnO薄膜c轴取向性随温度的升高而增强；当衬底温度达到550。C时，XRD谱上仅出现一个强的(002)衍射峰和一个弱的(004)衍射峰，显示ZnO具有优异c轴取向性。同时，随着温度的升高，ZnO薄膜的紫外透射截止边带向高波长方向漂移，其电导率也随衬底温度的升高逐渐增大，表明薄膜中的氧缺陷逐渐增多。这种氧缺陷是由于ZnO的氧平衡分压高于Zn所致，可通过提高溅射气体中氧含量来改善。     

Sub‐Picosecond Processes of Ferroelectric Domain Switching from Field and Temperature Experiments

After calculations of various domain‐switching current transients under the pulse from electrical circuit parameters, the field dependence of domain‐switching speeds is accurately estimated over five orders of magnitude in a wide temperature range of 5.4–280 K from the height of domain‐switching current in Pb(Zr_0.4Ti_0.6)O₃ thin films. These estimations are extended following Merz's equation [W. J. Merz, Phys. Rev. 1954 , 95 , 690] and an ultimate domain‐switching current density of 1.4 × 10⁸ A cm^?1 is extracted at the highest field of 0.20 MV cm^?1. From classical domain‐nucleation models with thermal fluctuations, an ultimate (asymptotic high‐field) nucleation time of 0.47 ps is derived when the domain sideways motion is kink‐nucleation‐rate limited.     

End-Hall与APS离子源辅助沉积制备的薄膜特性

利用离子束辅助沉积(IAD)技术制备了单层HfO2薄膜,离子源分别为End-Hall与APS离子源。采用Lambda900分光光度计、可变角光谱椭圆偏振仪(V-VASE)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、ZYGO干涉仪和激光量热计测试了薄膜的透射光谱、光学常数、晶体结构、表面形貌和吸收(1064nm)。实验结果表明,薄膜特性与辅助离子源及起始膜料有着密切的关系。End-Hall离子源辅助沉积制备的薄膜出现轻微的折射率不均匀性。两种离子源辅助沉积制备的薄膜折射率均较高,吸收损耗小,薄膜均为单斜晶相。不同离子源辅助沉积条件下,利用金属Hf为起始膜料制备的薄膜表面平整度较好,其均方根粗糙度和总积分散射均相对较小。与End-Hall离子源相比,APS离子源辅助沉积制备的薄膜吸收相对较小。     

Continuous Control of Charge Transport in Bi‐Deficient BiFeO3 Films Through Local Ferroelectric Switching

It is demonstrated that electric transport in Bi‐deficient Bi_1‐δFeO₃ ferroelectric thin films, which act as a p‐type semiconductor, can be continuously and reversibly controlled by manipulating ferroelectric domains. Ferroelectric domain configuration is modified by applying a weak voltage stress to Pt/Bi_1‐δFeO₃/SrRuO₃ thin‐film capacitors. This results in diode behavior in macroscopic charge‐transport properties as well as shrinkage of polarization‐voltage hysteresis loops. The forward current density depends on the voltage stress time controlling the domain configuration in the Bi_1‐δFeO₃ film. Piezoresponse force microscopy shows that the density of head‐to‐head/tail‐to‐tail unpenetrating local domains created by the voltage stress is directly related to the continuous modification of the charge transport and the diode effect. The control of charge transport is discussed in conjunction with polarization‐dependent interfacial barriers and charge trapping at the non‐neutral domain walls of unpenetrating tail‐to‐tail domains. Because domain walls in Bi_1‐δFeO₃ act as local conducting paths for charge transport, the domain‐wall‐mediated charge transport can be extended to ferroelectric resistive nonvolatile memories and nanochannel field‐effect transistors with high performances conceptually.     

组分和应力不均匀分布对薄膜铁电性的影响

采用组合靶射频溅射的方法、制备后慢速降温的途径在（１１１）Ｓｉ基板上制备出了成膜较好的ＰｂＴｉＯ３薄膜,通过测试分析发现在薄膜中形成了一个缓解应力的过渡层,薄膜中的Ｐｂ、Ｔｉ组分比沿着薄膜生长的方向成非线性增长,并在薄膜表面形成一个富Ｐｂ层,薄膜的Ｃ－Ｖ特性曲线中存在负方向的位移和畸变。结合实验结果对薄膜的生长机理进行了探讨,并且对薄膜的应力和不均匀分布组分对薄膜铁电特性的影响进行了理论上的分析,     

均匀设计法研究PZT铁电薄膜制备工艺的优化

应用射频磁控溅射工艺在Pt/Ti/SiO2/Si衬底上制备具有钙钛矿结构的PZT铁电薄膜。对影响PZT薄膜性能、形貌的工作气压、基片温度、氧/氩 氧之比、溅射功率、退火温度5个主要因素进行分析,在其允许范围和精度内设置5个水平,并根据均匀设计理论对该5因素及5水平进行均匀设计。不同温度下退火之后测定了PZT薄膜的厚度、SEM表面形貌、电容、介电损耗、电滞回线(包括矫顽场强、饱和极化强度、剩余极化强度)等。最后对响应结果进行多元二次线性回归,得出了回归方程。探讨达到最优化薄膜特性所需要的工艺条件。     

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。     

Domain Selectivity in BiFeO3 Thin Films by Modified Substrate Termination

Ferroelectric domain formation is an essential feature in ferroelectric thin films. These domains and domain walls can be manipulated depending on the growth conditions. In rhombohedral BiFeO₃ thin films, the ordering of the domains and the presence of specific types of domain walls play a crucial role in attaining unique ferroelectric and magnetic properties. In this study, controlled ordering of domains in BiFeO₃ film is presented, as well as a controlled selectivity between two types of domain walls is presented, i.e., 71° and 109°, by modifying the substrate termination. The experiments on two different substrates, namely SrTiO₃ and TbScO₃, strongly indicate that the domain selectivity is determined by the growth kinetics of the initial BiFeO₃ layers.