The oxygen stoichiometry has a large influence on the physical and chemical properties of complex oxides. Most of the functionality in e.g. catalysis and electrochemistry depends in particular on control of the oxygen stoichiometry. In order to understand the fundamental properties of intrinsic surfaces of oxygen-deficient complex oxides, we report on in situ temperature dependent scanning tunnelling spectroscopy experiments on pristine oxygen deficient, epitaxial manganite films. Although these films are insulating in subsequent ex situ in-plane electronic transport experiments at all temperatures, in situ scanning tunnelling spectroscopic data reveal that the surface of these films exhibits a metal-insulator transition (MIT) at 120 K, coincident with the onset of ferromagnetic ordering of small clusters in the bulk of the oxygen-deficient film. The surprising proximity of the surface MIT transition temperature of nonstoichiometric films with that of the fully oxygenated bulk suggests that the electronic properties in the surface region are not significantly affected by oxygen deficiency in the bulk. This carries important implications for the understanding and functional design of complex oxides and their interfaces with specific electronic properties for catalysis, oxide electronics and electrochemistry.
Magneto-optic Kerr effect can probe the process of magnetization reversal in ferromagnetic thin films and thus be used as an alternative to magnetometry. Kerr effect is wavelength-dependent and the Kerr rotation can reverse sign, vanishing at particular wavelengths. We investigate epitaxial heterostructures of ferromagnetic manganite, La$_{0.7}$Sr$_{0.3}$Mn$_{0.9}$Ru$_{0.1}$O$_3$, by polar Kerr effect and magnetometry. The manganite layers are separated by or interfaced with a layer of nickelate, NdNiO$_3$. Kerr rotation hysteresis loops of trilayers, with two manganite layers of different thi…
We report on multiple fundamental qualitative improvements in the growth of improper ferroelectric hexagonal YMnO$_3$ (YMO) thin films and heterostructures by pulsed laser deposition (PLD). By a combination of pre-growth substrate annealing and low-energy-fluence PLD, we obtain a two-dimensional growth mode of the YMO films on yttria-stabilized zirconia (YSZ) with ultralow roughness and devoid of misoriented nanocrystalline inclusions. By inserting a sacrificial manganite layer capped with conducting indium-tin oxide between the substrate and the final film, the latter is grown in a fully latt…
Epitaxial growth of multiferroic Pb(Zr0.57Ti0.43)O3-Pb(Fe2/3W1/3)O3 solid-solution thin films and their magnetoelectric effects
本文报道了用脉冲激光沉积法外延生长单相[Pb（Zr 0.57 Ti 0.43）O3]0.8[Pb（Fe 2/3 W 1/3）O3]0.2（PZT-PFW）固溶体薄膜。X射线衍射测试表明薄膜具有四方晶系结构。该薄膜在室温下表现出铁电性和弱铁磁响应。磁电效应进行了研究，非线性磁电系数进行了测量，发现是可比的多铁性六方锰氧化物，但至少两个数量级小于多晶PZT-PFW薄膜。
Dynamical control of orbital occupations via a ferroelectric-induced polar state in metallic manganites
在过渡金属阳离子上轨道简并性的破坏以及由此产生的这些轨道的不平等电子占据提供了对金属氧化物中的电子密度和自旋有序的有力杠杆。在这里，我们展示了如何通过切换铁电极化来动态调制铁电/锰氧化物界面处的Mn原子上的轨道布居。轨道占有率的变化可达10%，大大超过了块状锰氧化物的轨道占有率。这种可翻转的轨道分裂在很大程度上是由铁电极性位移到界面区域的传播控制的，这是一种在本体中不存在的结构图案，并且是界面所特有的。我们使用{ \it ab initio}理论，外延薄膜生长，和扫描透射电子显微镜来验证预测的界面极性状态和伴随的轨道分裂。
A detailed nanoscale structural characterization was performed on high-quality La0.66Sr0.33MnO3 (LSMO) thin films of different thicknesses and deposited by pulsed laser deposition onto buffered Si (100) substrates. A multilayered structure built of Y0.13Zr0.87O2 (YSZ) and CeO2 layers was used as buffer in order to optimize the manganite films growth. The stacking of the different layers, their morpholohy, composition and strains were analysed using different experimental techniques. In-situ characterization of the films, performed with reflection high-energy electron diffraction, revealed thei…
The functional properties of transition metal perovskite oxides are known to result from a complex interplay of magnetism, polarization, strain, and stoichiometry. Here, we show that for materials with a cooperative Jahn-Teller distortion, such as LaMnO$_3$ (LMO), the orbital order can also couple to the defect chemistry and induce novel material properties. At low temperatures, LMO exhibits a strong Jahn-Teller distortion that splits the $e_g$ orbitals of the high-spin Mn$^{3+}$ ions and leads to alternating long, short, and intermediate Mn--O bonds. Our DFT+$U$ calculations show that, as a r…
Epitaxial orthorhombic Hf0.5Zr0.5O2 (HZO) films on La0.67Sr0.33MnO3 (LSMO) electrodes show robust ferroelectricity, with high polarization, endurance and retention. However, no similar results have been achieved using other perovskite electrodes so far. Here, LSMO and other perovskite electrodes are compared. A small amount of orthorhombic phase and low polarization is found in HZO films grown on La-doped BaSnO3 and Nb-doped SrTiO3, while null amounts of orthorhombic phase and polarization are detected in films on LaNiO3 and SrRuO3. The critical effect of the electrode on the stabilized phases…
Contradictory reports about the electronic and magnetic behavior of bulk Nd0:5Ba0:5MnO3 with uniform disorder exist in the literature. In this work, we investigate the thin films of Nd0:5Ba0:5MnO3, grown by pulsed laser deposition. The success of epitaxial growth in a layer-by-layer mode and high quality of the films have been confirmed by in-situ reflection high energy electron diffraction, atomic force microscopy, X-ray reflectivity, and, X-ray diffraction. These films are found to be insulting and exhibit spin-glass behavior at low temperatures. The study offers an opportunity to tune the c…
Interest for layered Ruddlesden-Popper strongly correlated manganites of Pr$_{0.5}$Ca$_{1.5}$MnO$_4$ as well as to their thin film polymorphs is motivated by the high temperature of charge orbital ordering above room temperature. We report on the tailoring of the c-axis orientation in epitaxial RP-PCMO films grown on SrTiO$_3$ (STO) substrates with different orientations as well as the use of CaMnO$_3$ (CMO) buffer layers. Films on STO(110) reveal in-plane alignment of the c-axis lying along to the [100] direction. On STO(100), two possible directions of the in-plane c-axis lead to a mosaic li…
Fundamental understanding of interfacial magnetic properties in ferromagnetic heterostructures is essential to utilize ferromagnetic materials for spintronic device applications. In this paper, we investigate the interfacial magnetic and electronic structures of epitaxial single-crystalline LaAlO$_3$ (LAO)/La$_{0.6}$Sr$_{0.4}$MnO$_3$ (LSMO)/Nb:SrTiO$_3$ (Nb:STO) heterostructures with varying LSMO-layer thickness, in which the magnetic anisotropy strongly changes depending on the LSMO thickness due to the delicate balance between the strains originating from both the Nb:STO and LAO layers, usin…
Atomically engineered oxide heterostructures provide a fertile ground for creating novel states. For example, a two-dimensional electron gas at the interface between two oxide insulators, giant thermoelectric Seebeck coefficient, emergent ferromagnetism from otherwise nonmagnetic components, and colossal ionic conductivity. Extensive research efforts reveal that oxygen deficiency or lattice strain play an important role in determining these unexpected properties. Herein, by studying the abrupt presence of robust ferromagnetism (up to 1.5 uB/Mn) in LaMnO3-based heterostructures, we find the mul…
Complex oxide functionality, such as ferroelectricity, magnetism or superconductivity is often achieved in epitaxial thin-film geometries. Oxygen vacancies tend to be the dominant type of defect in these materials but a fundamental understanding of their stability and electronic structure has so far mostly been established in the bulk or strained bulk, neglecting interfaces and surfaces present in a thin-film geometry. We investigate here, via density functional theory calculations, oxygen vacancies in the model system of a SrMnO$_3$ (SMO) thin film grown on a SrTiO$_3$ (STO) (001) substrate. …
We demonstrate that kinetics play an important role in the epitaxial growth of Fe$_3$GeTe$_2$ (FGT) van der Waals (vdW) ferromagnetic films by molecular beam epitaxy. By varying the deposition rate, we control the formation or suppression of an initial tellurium-deficient non-van der Waals phase (Fe$_3$Ge$_2$) prior to realizing epitaxial growth of the vdW FGT phase. Using cross-sectional scanning transmission electron microscopy and scanning tunneling microscopy, we optimize the FGT films to have atomically smooth surfaces and abrupt interfaces with the Ge(111) substrate. The magnetic propert…
Lead free, silicon compatible materials showing large electromechanical responses comparable to, or better than conventional relaxor ferroelectrics, are desirable for various nanoelectromechanical devices and applications. Defect-engineered electrostriction has recently been gaining popularity to obtain enhanced electromechanical responses at sub 100 Hz frequencies. Here, we report record values of electrostrictive strain coefficients (M31) at frequencies as large as 5 kHz (1.04 x 10-14 m2 per V2 at 1 kHz, and 3.87 x 10-15 m2 per V2 at 5 kHz) using A-site and oxygen-deficient barium titanate t…
We investigate structural and transport properties of highly Ru-deficient SrRu0.7O3 thin films prepared by molecular beam epitaxy on (001) SrTiO3 substrates. To distinguish the influence of the two types of disorders in the films, Ru vacancies within lattices and disorders near the interface, SrRu0.7O3 thin films with various thicknesses (t = 1-60 nm) were prepared. It was found that the influence of the former dominates the electrical and magnetic properties when t > 5-10 nm, while that of the latter does when t < 5-10 nm. Structural characterizations revealed that the crystallinity, in terms…
Electronic phase transitions in Pr$_{0.5}$Ca$_{0.5}$MnO$_3$ epitaxial thin films revealed by resonant soft x-ray scattering
研究了在（LaAl O $_3$）$_{0.3}$ -（SrAl $_{0.5}$ Ta $_{0.5}$ O $_3$）$_{0.7}$（LSAT）（011）$_c$上生长的Pr $_{0.5}$ Ca $_{0.5}$ MnO $_3$外延薄膜的磁性和轨道有序.在一个新的实验方法中，极化和能量依赖性的共振软X射线散射被用来揭示显着修改的磁序在膜相比，散装，即（i）不同的磁有序波矢量，（ii）不同的磁易轴和（iii）在低温下的额外的磁重排过渡。这些观察结果表明，强烈的影响的外延应变的自旋顺序，这是介导的轨道自由度，并提供了一个有前途的路线，以调整磁性能的锰氧化物薄膜。我们的研究结果进一步表明，共振软X射线散射是一个非常合适的技术来研究磁性的薄膜，中子散射不能很容易地应用于由于小的样品体积。
Reversible topotactic transitions between oxygen-vacancy-ordered structures in transition metal oxides provide a promising strategy for active manipulation of material properties. While transformations between various oxygen-deficient phases have been attained in bulk ABO$_{3-δ}$ perovskites, substrate clamping restricts the formation of distinct ordering patterns in epitaxial films. Using in-situ scanning transmission electron microscopy (STEM), we image a thermally driven reversible transition in La$_{0.5}$Sr$_{0.5}$CoO$_{3-δ}$ films on SrTiO$_3$ from a multidomain brownmillerite (BM) struct…
