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.     

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.     

Multifunctional Nanocrystalline Thin Films of Er2O3: Interplay between Nucleation Kinetics and Film Characteristics

In this study, thin films of Er₂O₃ are deposited by low‐pressure metal–organic chemical vapor deposition (MOCVD) using a tris(isopropylcyclopentadienyl)erbium precursor and O₂ on various substrates, including p‐type Si(100), Si(111), Corning glass, and c‐axis‐oriented α‐Al₂O₃(0001). The resulting films are extensively characterized in order to demonstrate their applicability as antireflective and protective coatings and as high‐k gate dielectrics. The interplay existing among the substrate, the nucleation kinetics, and the resulting structural, morphological, optical, and electrical properties of Er₂O₃ thin films is explored. Fast nucleation governed by surface energy minimization characterizes the growth of (111)‐oriented Er₂O₃ on Si(100), glass, and α‐Al₂O_3. Conversely, nonhomogeneous nucleation leads to polycrystalline Er₂O₃ on Si(111) substrates. Er₂O₃ films grown on Si(100) possess superior characteristics. A high refractive index of 2.1 at 589.3 nm, comparable to the value for bulk single crystalline Er₂O₃, a high transparency in the near UV‐vis range, and an optical bandgap of 6.5 eV make Er₂O₃ interesting as an antireflective and protective coating. A static dielectric constant of 12–13 and a density of interface traps as low as 4.2 × 10¹⁰ cm² eV^–1 for 5–10 nm thick Er₂O₃ layers grown on Si(100) render the present Er₂O₃ films interesting also as high‐k dielectrics in complementary metal oxide semiconductor (CMOS) devices.     

氧压对ZnO薄膜电阻温度系数的影响

采用脉冲激光沉积(PLD)技术,在不同氧气氛下,在Si(lll)衬底上生长了ZnO薄膜,使用X线衍射仪分析了ZnO薄膜的结晶质量.计算了不同氧气氛下生长的ZnO薄膜的电阻温度系数(TCR)值,发现随着氧分压降低,ZnO薄膜的TCR值增大;ZnO薄膜的TCR值最高可达-8%/K.这为研究ZnO薄膜的导电特性提供了新的途径,开辟了ZnO薄膜在室温非制冷红外微测辐射热计材料中的应用潜力.     

Formation of Hierarchically Structured Thin Films

Here, we report the preparation of hierarchically structured polymer brushes with well‐defined geometries via multiple step microcontact printing (MS‐µCP) of inks containing different ratios of initiator‐terminated thiols and non‐reactive alkylthiols. Thick (and dense), polymer brushes grew from self‐assembled monolayers (SAMs) with high concentration of initiator‐terminated thiols, and these brushes exhibited high chemical etch‐resistance, compared to thin (and less dense), brushes grown from more dilute initiator‐terminated SAMs. Upon etching, patterned crosslinking polymer brush films decorated with thin layers of Au, could be lifted off the surface to form geometrically well‐defined free‐standing hierarchical films. These polymer brush films showed interesting buckling instabilities when compressed. Areas with different brush thicknesses and Au backing showed markedly different buckling behavior, leading to unusual patterns of wrinkles with different wavelengths and orientations toward the force field.     

Enhanced Dielectric and Crystalline Properties in Ferroelectric Barium Titanate Thin Films

A chemical solution synthesis technique incorporating barium titanate and a high‐temperature liquid phase is developed. In a temperature range conventional to thin‐film growth, the presence of the liquid phase dramatically enhances grain growth, densification, and overall crystalline quality. By controlling the liquid‐phase stoichiometry and molar fraction, thin films with grain sizes greater than 10 μm that pronounce X‐ray peak splitting, low loss, and permittivity values in excess of 3000 at room temperature can be produced. These properties are comparable, and in some cases superior, to those observed in well‐prepared bulk barium titanate. As such, the historical difficulty in reproducing bulklike properties in polycrystalline barium titanate is overcome. These results have broad implications for the expanded use of ferroelectric thin films by demonstrating bulk properties in thin layers and by providing a means of achieving these properties with low thermal budgets.     

3D Hexagonal (R‐3m) Mesostructured Nanocrystalline Titania Thin Films: Synthesis and Characterization

A straightforward and reproducible synthesis of crack‐free large‐area thin films of 3D hexagonal (R‐3m) mesostructured nanocrystalline titania (meso‐nc‐TiO₂) using a Pluronic triblock copolymer (P123)/1‐butanol templating system is described. The characterization of the films is achieved using a combination of electron microscopy (high‐resolution scanning electron microscopy and scanning transmission electron microscopy), grazing‐incidence small‐angle X‐ray scattering, in situ high‐temperature X‐ray diffraction, and variable‐angle spectroscopic ellipsometry. The mesostructure of the obtained films is found to be based upon a 3D periodic array of large elliptically shaped cages with diameters around 20 nm interconnected by windows of about 5 nm in size. The mesopores of the film calcined at 300 °C are very highly ordered, and the titania framework of the film has a crystallinity of 40 % being composed of 5.8 nm sized anatase crystallites. The film displays high thermal stability in that the collapse of the pore architecture is incomplete even at 600 °C. The accessible surface area of 3D hexagonal meso‐nc‐TiO₂ estimated by the absorption of methylene blue is nearly twice as large as that of 2D hexagonal meso‐nc‐TiO₂ at the same annealing temperature.     

Initiated and Oxidative Chemical Vapor Deposition of Polymeric Thin Films: iCVD and oCVD

The techniques of initiated chemical vapor deposition (iCVD) and oxidative chemical vapor deposition (oCVD) enable the fabrication of chemically well‐defined thin polymeric films on complex objects with micro‐ and nano‐scale features. By depositing polymers from the vapor phase, many wetting and solution effects are avoided, and conformal films can be created. In iCVD, a variant of hot filament CVD, the deposition rate is enhanced and chemical functionalities of the polymers' constituents are maintained by including a thermally labile initiator in the feed stream. Due to the low energy required when using an initiator, delicate substrates can be coated. In oCVD, infusible, electrically conductive films are formed directly on the substrate of interest as the oxidant and monomer are introduced into the reactor simultaneously. This Feature Article provides an overview of the work that has been done to develop iCVD and oCVD into platform technologies. Relevant background, fundamentals, and applications will be discussed.     

Nanocrystalline Electroplated Cu–Ni: Metallic Thin Films with Enhanced Mechanical Properties and Tunable Magnetic Behavior

Nanocrystalline 3 µm thick Cu_1–xNi_x (0.45 ≤ x ≤ 0.87) films are electrodeposited galvanostatically onto Cu/Ti/Si (100) substrates, from a citrate‐ and sulphate‐based bath containing sodium lauryl sulphate and saccharine as additives. The films exhibit large values of reduced Young's modulus (173 < E_r < 192 GPa) and hardness (6.4 < H < 8.2 GPa), both of which can be tailored by varying the alloy composition. The outstanding mechanical properties of these metallic films can be ascribed to their nanocrystalline nature—as evidenced by X‐ray diffraction, transmission electron microscopy, and atomic force microscopy—along with the occurrence of stacking faults and the concomitant formation of intragranular nanotwins during film growth. Due to their nanocrystalline character, these films also show very low surface roughness (root mean square deviation of around 2 nm). Furthermore, tunable magnetic properties, including a transition from paramagnetic to ferromagnetic behavior, are observed when the Ni percentage is increased. This combination of properties, together with the simplicity of the fabrication method, makes this system attractive for widespread technological applications, including hard metallic coatings or magnetic micro/nano‐electromechanical devices.     

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.     

Effects of Annealing Temperature on Properties of ZnO Thin Films Grown by Pulsed Laser Deposition

ZnO thin films are deposited on n-Si（111） substrates by pulsed laser deposition（PLD） system. Then the samples are annealed at different temperatures in air ambient and their properties are investigated particularly as a function of annealing temperature. The microstructure, morphology and optical properties of the as-grown ZnO films are studied by X-ray diffraetion（XRD）. atomic force mieroseope（AFM）, Fourier transform infrared spectroscopy（FTIR） and photoluminescence（PL） spectra. The results show that the as- grown ZnO films have a hexagonal wurtzite structure with a preferred c-axis orientation. Moreover, the diameters of the ZnO crystallites become larger and the crystal quality of the ZnO fihns is improved with the increase of annealing temperature.     

A comparative study of pulsed laser deposition and flash evaporation of Culn0.75Ga0.25Se2 thin films

In this paper initial results are presented for the growth and characterisation of polycrystalline Culn_0.75Ga_0.25Se₂ thin films prepared by pulsed laser deposition and flash evaporation. Analogies are drawn between these two important deposition technologies. The deposited films were characterised using a veriety of analytical techniques, including energy-dispersive analysis of X-rays and Rutherford-backscattering spectroscopy for compositional evaluation, X-ray diffreaction and Raman spectroscopy for structural evaluation, scanning electron microscopy for surface examination and the four-point and hot-point probe techniques for electrical characterisation. The comparison of films produced by these two deposition methods revealed that, in terms of their stochiometry, electrical and physical characteristics, good-quality GIGS thin films could be produced by both techniques.     

脉冲激光沉积法制备氧化锌薄膜

ZnO是一种新型的Ⅱ-Ⅵ族半导体材料,具有优良的晶格、光学和电学性能,其显著的特点是在紫外波段存在受激发射。利用脉冲激光沉积法(PLD)在氧气氛中烧蚀锌靶制备了纳米晶氧化锌薄膜,衬底为石英玻璃,晶粒尺寸约为28-35 nm。X射线衍射(XRD)结果和光致发光(PL)光谱的测量表明,当衬底温度在100-250℃范围内时,所获得的ZnO薄膜具有c轴的择优取向,所有样品的强紫外发射中心均在378-385 nm范围内,深能级发射中心约518-558 nm,衬底温度为200℃时,得到了单一的紫外光发射(没有深能级发光)。这归因于其较高的结晶质量。     

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.     

激光重复频率对ZnO薄膜发光特性的影响

在不同激光重复频率下用脉冲激光沉积方法(PLD)在Si (111)衬底上生长了ZnO薄膜, 以325 nm He-Cd激光器为激发源获得了薄膜的荧光光谱以研究其发光特性, 用X射线衍射仪(XRD)和原子力显微镜(AFM)研究了薄膜的晶体结构和表面形貌, 结果表明, 在激光重复频率为5 Hz时薄膜不仅具有良好的结晶质量, 同时也具有优异的紫外发光特性。对于相同的生长时间, 通过分析薄膜的厚度和激光脉冲频率的关系发现：每一个激光脉冲并不对应于薄膜的一个生长瞬间, 而是能够在较长的时间内维持薄膜生长的必要成分和分压。     

脉冲激光双光束沉积掺Mg的GaN薄膜的研究

采用脉冲激光双光束沉积系统在Si(111)衬底上生长了掺Mg的GaN薄膜和未掺杂GaN薄膜。利用X射线衍射(XRD)、原子力显微镜(AFM)、室温范德堡霍尔测量及光致发光(PL)光谱对两类薄膜进行对比分析，结果显示，所生长的GaN薄膜均为六方纤锌矿晶体结构，掺Mg可细化所生长的GaN薄膜晶粒。随着掺Mg量的增加，GaN薄膜无需后处理即可由”型导电转化为p型导电，GaN薄膜的光学性能随p型载流子浓度增大而提高；然而掺Mg却导致GaN薄膜结晶质量下降，掺镁量过大的GaN薄膜中p型载流子浓度反而减少，光致发光中黄发射峰增强较大。研究表明通过优化脉冲激光双光束沉积参数无需任何后处理可直接获得高空穴载流子浓度的p型GaN薄膜。     

Probing the Effects of Nanoscale Architecture on the Mechanical Properties of Hexagonal Silica/Polymer Composite Thin Films

We examine the effects of controlling nanoscale architecture on the tensile properties of honeycomb‐structured silica/polymer composite films. The hexagonal films are produced using evaporation‐induced self‐assembly and uniaxially strained using a home‐built tensile testing apparatus. Significant differences in the yield strain, failure strain, and tensile moduli between the axes parallel and perpendicular to the film‐deposition direction are observed for the thinnest films examined and are attributed to anisotropy in the film nanostructure that is further characterized with transmission electron microscopy and atomic force microscopy. For properly oriented composites, these films have tensile moduli comparable to the Young's modulus of bulk silica but exhibit failure strains that are about an order of magnitude larger than those seen in typical bulk‐silica systems. The yielding and failure processes are explored using X‐ray diffraction and optical microscopy and are characterized by irreversible changes in the nanoscale architecture. We show that tuning the nanoscale architecture can provide control over the tensile properties of composites, allowing for materials with combinations of stiffness and elasticity unachievable in the analogous bulk systems.     

温度对飞秒激光沉积ZnO/Si薄膜的结构和性能的影响

通过飞秒脉冲激光(50 fs,800 nm,1 kHz,2 mJ)沉积技术在n型Si(100)单晶基片上制备了ZnO薄膜.详细研究了基片温度变化以及退火处理对ZnO薄膜的结构、表面形貌及光学性质的影响.X射线衍射(XRD)结果表明,不同温度下(20~350℃)生长的ZnO薄膜具有纤锌矿结构,并且呈c轴择优取向;当基片温度为80℃时,薄膜沿(002)晶面高度择优生长;当基片温度为500℃时薄膜沿(103)晶面择优生长,场发射扫描电子显微镜(FEEM)结果表明薄膜呈纳米晶结构,并观察到了ZnO的六方结构.进一步通过透射光谱的测量讨论了基片温度及退火处理对ZnO薄膜光学透射率的影响,结果表明退火后薄膜的透射率增大.