适用于FBAR的ZnO薄膜制备及压电特性分析

采用射频磁控溅射法在Al电极层上制备了适用于 薄膜体声波谐振器(FBAR)的ZnO薄膜, 研究了溅射功率对ZnO薄膜择优取向、压电响应和极化分布的影响。X射线衍射(XRD)测试结 果 表明,在一定范围内,随着溅射功率的增大,ZnO薄膜的择优取向和结晶质量得到提高;但 溅射功率过大,ZnO薄膜的择优取向变差。压电响应力显微镜(PFM)测量表明,溅射功率对薄 膜的压电性能和极化取向也有很大影响, 在所制备的薄膜中,多数晶粒的自发极化方向均垂直向上,表明所制备ZnO薄膜的表面主要 为O 截止;压电响应的振幅与薄膜的结晶质量和择优取向相关,在溅射功率为150W条件下制备的ZnO 在垂直于表面方向上表现出最大压电响应振幅,同时薄膜极化取向分布的一致性最好。     

Controlling the Polarization in Ferroelectric PZT Films via the Epitaxial Growth Conditions

The integration of thin-film ferroelectrics with reliable properties into oxide electronics requires accomplishing deterministic polarization states. Since ferroelectricity emerges during thin-film synthesis already, it is essential to elucidate how the interplay of different growth parameters affects the polarization. Here, the polarization of fully strained Pb(Zr_0.2Ti_0.8)O₃ (PZT) films is accessed in situ, during epitaxial growth. Surprisingly, it is found that the orientation of the out-of-plane polarization during growth may differ from the one after growth completion and it strongly depends on the substrate temperature and the oxygen partial pressure. Increasing the growth temperature and/or the oxygen partial pressure favors a uniform downward-oriented polarization, independent of the direction of polarization during growth. Specifically, for films with an emerging upward-oriented polarization, a polarization reversal and a downward-oriented polarization after cool-down is observed. The in situ measurements obtained by optical second harmonic generation (SHG) in conjunction with ex situ piezoresponse force microscopy (PFM) and X-ray diffraction (XRD) measurements point to the temperature- and pressure-dependent formation of a charged Pb defect gradient toward the film surface as the responsible mechanism for the polarization reorientation.     

Interesting Evidence for Template‐Induced Ferroelectric Behavior in Ultra‐Thin Titanium Dioxide Films Grown on (110) Neodymium Gallium Oxide Substrates

The first evidence for room‐temperature ferroelectric behavior in anatase‐phase titanium dioxide (a‐TiO₂) is reported. Behavior strongly indicative of ferroelectric characteristics is induced in ultra‐thin (20 nm to 80 nm) biaxially‐strained epitaxial films of a‐TiO₂ deposited by liquid injection chemical vapor deposition onto (110) neodymium gallium oxide (NGO) substrates. The films exhibit significant orthorhombic strain, as analyzed by X‐ray diffraction and high‐resolution transmission electron microscopy. The films on NGO show a switchable dielectric spontaneous polarization when probed by piezoresponse force microscopy (PFM), the ability to retain polarization information written into the film using the PFM tip for extended periods (several hours) and at elevated temperatures (up to 100 °C) without significant loss, and the disappearance of the polarization at a temperature between 180 and 200 °C, indicative of a Curie temperature within this range. This combination of effects constitutes strong experimental evidence for ferroelectric behavior, which has not hitherto been reported in a‐TiO₂ and opens up the possibility for a range of new applications. A model is presented for the effects of large in‐plane strains on the crystal structure of anatase which provides a possible explanation for the experimental observations.     

The Effect of Substrate Material and Postannealing on the Photoluminescence and Piezo Properties of DC-Sputtered ZnO

Abstact Zinc oxide (ZnO) thin films were deposited on various substrates by DC sputtering deposition. Thermal annealing was performed at up to 1,200°C in N₂ for 30 min. The effect was investigated using x-ray diffraction (XRD), photoluminescence (PL) spectra, scanning electron microscopy (SEM), and piezoresponse force microscopy (PFM). The influence on PL response depends both on substrate material and annealing temperature. The PFM images reveal that the ZnO films have inversion domains. While annealing improves the piezoresponse, the inversion domains still persist. The cross-sectional analysis of the inversion domains shows domain boundary widths of approximately 1.5 nm. (Received ...; accepted ...)     

Initiation of a polarized state in thin lithium niobate films synthesized on isolated silicon substrates

The distributions of induced state and surface potential in thin lithium niobate films obtained via the deposition onto a (100)-oriented Si-oxidized substrate by the method of high-frequency magnetron sputtering were mapped using piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM). Using an electrical field applied with a conducting cantilever, the possibility of the formation of an induced polarization state and of its subsequent visualization was shown. The induced state in KPFM measurements was shown to be retained for a much longer time than for PFM.     

Low‐Symmetry Monoclinic Phases and Polarization Rotation Path Mediated by Epitaxial Strain in Multiferroic BiFeO3 Thin Films

A morphotropic phase boundary driven by epitaxial strain has been observed in lead‐free multiferroic BiFeO₃ thin films and the strain‐driven phase transitions have been widely reported as iso‐symmetric Cc‐Cc by recent works. In this paper, it is suggested that the tetragonal‐like BiFeO₃ phase identified in epitaxial films on (001) LaAlO₃ single crystal substrates is monoclinic M_C. This M_C phase is different from the M_A type monoclinic phase reported in BiFeO₃ films grown on low mismatch substrates, such as SrTiO₃. This is confirmed not only by synchrotron X‐ray studies but also by piezoresponse force microscopy measurements. The polarization vectors of the tetragonal‐like phase lie in the (100) plane, not the (11 0) plane as previously reported. A phenomenological analysis is proposed to explain the formation of M_C Phase. Such a low‐symmetry M_C phase, with its linkage to M_A phase and the multiphase coexistence open an avenue for large piezoelectric response in BiFeO₃ films and shed light on a complete understanding of possible polarization rotation paths and enhanced multiferroicity in BiFeO₃ films mediated by epitaxial strain. This work may also aid the understanding of developing new lead‐free strain‐driven morphotropic phase boundary in other ferroic systems.     

Probing Local and Global Ferroelectric Phase Stability and Polarization Switching in Ordered Macroporous PZT

We describe the characterization, ferroelectric phase stability and polarization switching in strain‐free assemblies of PbZr_0.3Ti_0.7O₃ (PZT) nanostructures. The 3‐dimensionally ordered macroporous structures present uniquely large areas and volumes of PZT where the microstructure is spatially modulated and the composition is homogeneous. Variable temperature powder X‐ray diffraction (XRD) studies show that the global structure is crystalline and tetragonal at room temperature and undergoes a reversible tetragonal to cubic phase transition on heating/cooling. The measured phase‐transition temperature is 50–60 °C lower than bulk PZT of the same composition. The local ferroelectric properties were assessed using piezoresponse force spectroscopy that reveal an enhanced piezoresponse from the nanostructured films and demonstrate that the switching polarization can be spatially mapped across these structures. An enhanced piezoresponse is observed in the nanostructured films which we attribute to the formation of strain free films, thus for the first time we are able to assess the effects of crystallite‐size independently of internal stress. Corresponding polarization distributions have been calculated for the bulk and nanostructured materials using a direct variational method and Landau‐Ginzburg‐Devonshire (LGD) theory. By correlating local and global characterization techniques we have for the first time unambiguously demonstrated the formation of tetragonal and ferroelectric PZT in large volume nanostructured architectures. With the wide range of materials available that can be formed into such controlled architectures we conclude that this study opens a pathway for the effective studies of nanoscale ferroelectrics in uniquely large volumes.     

Ferroelectric Materials: Probing Local and Global Ferroelectric Phase Stability and Polarization Switching in Ordered Macroporous PZT (Adv. Funct. Mater. 5/2011)

We describe the characterization, ferroelectric phase stability and polarization switching in strain‐free assemblies of PbZr_0.3Ti_0.7O₃ (PZT) nanostructures. The 3‐dimensionally ordered macroporous structures present uniquely large areas and volumes of PZT where the microstructure is spatially modulated and the composition is homogeneous. Variable temperature powder X‐ray diffraction (XRD) studies show that the global structure is crystalline and tetragonal at room temperature and undergoes a reversible tetragonal to cubic phase transition on heating/cooling. The measured phase‐transition temperature is 50–60 °C lower than bulk PZT of the same composition. The local ferroelectric properties were assessed using piezoresponse force spectroscopy that reveal an enhanced piezoresponse from the nanostructured films and demonstrate that the switching polarization can be spatially mapped across these structures. An enhanced piezoresponse is observed in the nanostructured films which we attribute to the formation of strain free films, thus for the first time we are able to assess the effects of crystallite‐size independently of internal stress. Corresponding polarization distributions have been calculated for the bulk and nanostructured materials using a direct variational method and Landau‐Ginzburg‐Devonshire (LGD) theory. By correlating local and global characterization techniques we have for the first time unambiguously demonstrated the formation of tetragonal and ferroelectric PZT in large volume nanostructured architectures. With the wide range of materials available that can be formed into such controlled architectures we conclude that this study opens a pathway for the effective studies of nanoscale ferroelectrics in uniquely large volumes.     

Global excitation and local probing of ferroelectric domains

In this work, the macroscopic polarization of a ferroelectric capacitor is correlated with the local domain morphology. To this end, a ferroelectric capacitor of the random copolymer poly(vinylidenefluoride-trifluoroethylene) [P(VDF-TrFE)] is poled to a set polarization state in a Sawyer-Tower setup. After chemically removing the top electrode, the exposed ferroelectric is locally probed with piezoresponse force microscopy. The domains without the top electrode are thermodynamically stable for weeks in ambient environment, as proven by comparing the remanent polarization measured before etching away and after re-depositing the top electrode. Out-of-plane PFM phase images show a random distribution of domains with up and down polarity. We unambiguously demonstrate a linear correlation between the mean PFM phase and the macroscopic polarization. As a demonstration of the insights that the global excitation and local probing method can provide, we show how thermal and electrical depoling can result in identical macroscopic polarization yet completely different domain morphologies.     

Selective orientation of discotic films by interface nucleation

Thin films deposited from solution by the hollow capillary writing technique exhibit macroscopic uniaxial grains with an in-plane arrangement of discotic stacks. We report a method to change the orientation of thin films from in-plane to homeotropic (discotic columns perpendicular to the substrate). It is observed that annealing of open supported films at a temperature 25 °C below the equilibrium LC/isotropic phase boundary induces homeotropic alignment, while rapid cooling leads to predominantly in-plane alignment. A model based on heterogeneous nucleation at the film/substrate interface accounts for the experimental observations.     

Single‐Crystalline Films of the Homologous Series InGaO3(ZnO)m Grown by Reactive Solid‐Phase Epitaxy

Single‐crystalline thin films of the homologous series InGaO₃(ZnO)_m (where m is an integer) are fabricated by the reactive solid‐phase epitaxy (R‐SPE) method. Specifically, the role of ZnO as epitaxial initiator layer for the growth mechanism is clarified. High‐temperature annealing of bilayer films consisting of an amorphous InGaO₃(ZnO)₅ layer deposited at room temperature and an epitaxial ZnO layer on yttria‐stabilized zirconia (YSZ) substrate allows for the growth of single‐crystalline film with controlled chemical composition. The epitaxial ZnO thin layer plays an essential role in determining the crystallographic orientation, while the ratio of the thickness of both layers controls the film composition.     

Polarization retention and switching in ferroelectric nanocapacitors with defects on tensile substrates

We analyze the effect of defects on the polarization stability and switching of epitaxial nanocapacitor ferroelectric films on tensile substrates using a thermodynamic approach. Defects are either frozen-in dipoles of the p-type or trapped space charges. The retention of the in-plane ferroelectric polarization does not suffer nearly at all from the possible presence of dead layers or polar defects but is dramatically impacted by relatively high densities of space charge. Switching is a strong function of defects as well as the presence of a bottom electrode. The out-of-plane dielectric displacement exhibits a spike during switching of the in-plane polarization in films with bottom electrodes but nearly disappears otherwise. Such an effect during polarization reorientation along the film plane could be tailored as a sensing signal. The hysteresis and domain characteristics as a function of interface conditions and defects are discussed for BaTiO₃ strained on tensile substrates.     

Mechanically Driven Reversible Polarization Switching in Imprinted BiFeO3 Thin Films

Mechanically driven polarization switching via scanning probe microscopy provides a valuable voltage-free strategy for designing ferroelectric nanodomain structures. However, it is still challenging to realize reversible polarization switching with mechanical forces. Here, the mechanically driven reversible polarization switching observed in imprinted ferroelectric BiFeO₃ thin films is reported, i.e., up-to-down switching by a sharp scanning tip and down-to-up switching by a blunt tip. Free energy calculations, phase-field simulations, and piezoresponse force microscopy reveal that reversible mechanical switching arises from the interplay among the flexoelectric effect, the piezoelectric effect, and the internal upward built-in field in BiFeO₃ films. This study gains a deeper insight into the mechanism and control of mechanically driven polarization switching, and provides guidance for exploring potential ferroelectric-based electro-mechanical microelectronics.     

Deterministic Manipulation of Multi-State Polarization Switching in Multiferroic Thin Films

Deterministically controllable multi-state polarizations in ferroelectric materials are promising for the application of next-generation non-volatile multi-state memory devices. However, the achievement of multi-state polarizations has been inhibited by the challenge of selective control of switching pathways. Herein, an approach to selectively control 71° ferroelastic and 180° ferroelectric switching paths by combining the out-of-plane electric field and in-plane trailing field in multiferroic BiFeO₃ thin films with periodically ordered 71° domain wall is reported. Four-state polarization states can be deterministically achieved and reversibly controlled through precisely selecting different switching paths. These studies reveal the ability to obtain multiple polarization states for the realization of multi-state memories and magnetoelectric coupling-based devices.     

Unraveling Deterministic Mesoscopic Polarization Switching Mechanisms: Spatially Resolved Studies of a Tilt Grain Boundary in Bismuth Ferrite

The deterministic mesoscopic mechanism of ferroelectric domain nucleation is probed at a single atomically‐defined model defect: an artificially fabricated bicrystal grain boundary (GB) in an epitaxial bismuth ferrite film. Switching spectroscopy piezoresponse force microscopy (SS‐PFM) is used to map the variation of local hysteresis loops at the GB and in its immediate vicinity. It is found that the the influence of the GB on nucleation results in a slight shift of the negative nucleation bias to larger voltages. The mesoscopic mechanisms of domain nucleation in the bulk and at the GB are studied in detail using phase‐field modeling, elucidating the complex mechanisms governed by the interplay between ferroelectric and ferroelastic wall energies, depolarization fields, and interface charge. The combination of phase‐field modeling and SS‐PFM allows quantitative analysis of the mesoscopic mechanisms for polarization switching, and hence suggests a route for unraveling the mechanisms of polarization switching at a single defect level and ultimately optimizing materials properties through microstructure engineering.     

Carrier mobility in pentacene as a function of grain size and orientation derived from scanning transmission X-ray microscopy

Pentacene field-effect transistors were prepared on silicon nitride membranes for scanning transmission X-ray microscopy (STXM) investigations. The membranes were modified by different self-assembled monolayers (SAMs). Pentacene was deposited atop the SAM-treated membrane and the in-plane orientation of the grains were subsequently investigated by polarization dependent STXM measurements. The grain sizes were determined and compared to those obtained from atomic force microscopy (AFM) measurements. Statistical analysis of the grain orientation was correlated with the charge carrier mobility of the films, in which we observed an increase in the mobility with increasing grain size and decreasing surface roughness of the SAM.     

Ionic Space‐Charge Depletion in Lithium Fluoride Thin Films on Sapphire (0001) Substrates

Lithium fluoride thin films with various thicknesses have been grown on c‐plane sapphire substrates by radio‐frequency sputtering. The thin films are granular with a preferential [111] orientation of the grains. Thickness‐dependent measurements allow the separation of bulk and interface conductions. The normalized conductance decreases linearly with decreasing LiF layer thickness with a negative extrapolated intercept. DC polarization, AC impedance spectroscopy and electromotive force measurement indicate depletion of lithium ion vacancies as majority charge carriers and hence a negative space‐charge potential. A generalized Mott–Schottky approach within the model of heterogeneous doping fully explains the entire boundary defect chemistry.     

三维相移电子散斑干涉中的位移场分离研究

提出一种可将离面位移与面内位移分离的方法。在双光束电子散斑干涉(ESPI)中增加参考光,使其为两光束所共用。实验时,两束光各自独立地对变形物体进行测量,结合相移技术,可分别得到包含离面和面内位移信息的2幅相位图。理论分析表明,只需简单的相位运算就能够将面内位移场与与离面位移场分离。典型的3点弯曲梁实验证实了该方法的可行性。     

Structural origin of anisotropic transport in electrically conducting dichloroacetic acid-treated polymers

The post-deposition treatment of water-processable, polymer acid-templated conducting polymers with dichloroacetic acid has recently been shown to enhance in-plane conductivity by orders of magnitude. Here, we evaluate both the in-plane and out-of-plane conductivities of dichloroacetic acid-treated conducting polymer films, and track the accompanying evolution of film structure and composition. Films of poly(ethylene dioxythiophene)–poly(styrene sulfonic acid), PEDOT–PSS, exhibit improvements in both in-plane and out-of-plane conductivities following dichloroacetic acid treatment, associated with the removal of excess PSS from the surface. Conversely, polyaniline–poly(2-acrylamido-2-methyl-1-propanesulfonic acid), PANI–PAAMPSA, films are characterized by high anisotropies in conductivity, with the in-plane conductivity being orders of magnitude higher following DCA treatment and the out-of-plane conductivity substantially lower after the same treatment. Our experiments indicate that this unusual electrical anisotropy results from a vertically inhomogeneous composition profile.     

Multiferroic Clusters: A New Perspective for Relaxor‐Type Room‐Temperature Multiferroics

Multiferroics are promising for sensor and memory applications, but despite all efforts invested in their research no single‐phase material displaying both ferroelectricity and large magnetization at room‐temperature has hitherto been reported. This situation has substantially been improved in the novel relaxor ferroelectric single‐phase (BiFe_0.9Co_0.1O₃)_0.4–(Bi_1/2K_1/2TiO₃)_0.6, where polar nanoregions (PNR) transform into static‐PNR as evidenced by piezoresponse force microscopy (PFM) and simultaneously enable congruent multiferroic clusters (MFC) to emerge from inherent strongly magnetic Bi(Fe,Co)O₃ rich regions as verified by magnetic force microscopy (MFM) and secondary ion mass spectrometry. The material's exceptionally large Néel temperature T_N = 670 ± 10 K, as found by neutron diffraction, is proposed to be a consequence of ferrimagnetic order in MFC. On these MFC, exceptionally large direct and converse magnetoelectric (ME) coupling coefficients, α ≈ 1.0 × 10^?5 s m^?1 at room‐temperature, are measured by PFM and MFM, respectively. It is expected that the non‐ergodic relaxor properties which are governed by the Bi_1/2K_1/2TiO₃ component to play a vital role in the strong ME coupling, by providing an electrically and mechanically flexible environment to MFC. This new class of non‐ergodic relaxor multiferroics bears great potential for applications. Especially the prospect of a ME nanodot storage device seems appealing.