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We fabricated ultrathin metal - oxide - semiconductor (MOS) nanocapacitors using atomic layer deposition. The capacitors consist of a bilayer of Al2O3 and Y2O3 with a total thickness of ~10 nm, deposited on silicon substrate. The presence of the two materials, each slab being ~5 nm thick and uniform over a large area, was confirmed with Transmission Electron Microscopy and X-ray photoelectron spectroscopy (XPS). The capacitance in accumulation varied from 1.6 nF (at 1MHz) to ~2.8 nF (at 10 kHz), which is one to two orders of magnitude higher than other nanocapacitors. This high capacitance is attributed to the synergy between the dielectric properties of ultrathin Al2O3 and Y2O3 layers. The electrical properties of the nanocapacitor are stable within a wide range of temperatures, from 25 °C to 150 °C, as indicated by capacitance-voltage (C - V). Since the thickness-to-area ratio is negligible, the nanocapacitor could be simulated as a single parallel plate capacitor in COMSOL Multiphysics, with good agreement between experimental and simulation data. As a proof-of-concept we simulated a MOSFET device with the nanocapacitor gate dielectric, whose drain current is sufficiently high for micro and nanoelectronics integrated circuits, including for applications in sensing., (Creative Commons Attribution license.)

Ferroelectricity has recently been demonstrated in germanium-based halide perovskites. We use first-principles-based simulations to study 4-18 nm CsGeBr 3 films and develop a theory for ferroelectric ultrathin films. The theory introduces (i) a local order parameter, which identifies phase transitions into both monodomain and polydomain phases, and (ii) a dipole pattern classifier, which allows efficient and reliable identification of dipole patterns. Application of the theory to both halides CsGeBr 3 and CsGeI 3 and oxide BiFeO 3 ultrathin ferroelectrics reveals two distinct scenarios. First, the films transition into a monodomain phase below the critical value of the residual depolarizing field. Above this critical value, the second scenario occurs, and the film undergoes a transition into a nanodomain phase. The two scenarios exhibit opposite responses of Curie temperature to thickness reduction. Application of a dipole pattern classifier reveals rich nanodomain phases in halide films: nanostripes, labyrinths, zig-zags, pillars, and lego domains.

Sputtering is an effective technique for producing ultrathin films with diverse applications. The review begins by providing an in-depth overview of the background, introducing the early development of sputtering and its principles. Consequently, progress in advancements made in recent decades highlights the renaissance of sputtering as a powerful technology for creating thin films with varied compositions, structures, and properties. For the first time, we have discussed a thorough overview of several sputtered thin film materials based on metal and metal oxide, metal nitride, alloys, carbon, and ceramic-based thin film along with their properties and their applicability in various fields. We further delve into the applications of sputter-coated thin films, specifically emphasizing their relevance in environmental sustainability, energy and electronics, and biomedical fields. We critically examine the recent advancements in developing sputter-coated catalysts for eliminating water pollutants andhydrogen generation. Additionally, the review sheds light on advantages, shortcomings, and future directions for developing sputter-coated thin films utilized in biodegradable metals and alloys with enhanced corrosion resistance and biocompatibility. This review is a comprehensive integration of recent literature, covering diverse sputtering thin film applications. We delve deeply into various material types and emphasize critical analysis of recent advancements, particularly in environmental, energy, and biomedical fields. By offering insights into both advancements and limitations, the review provides a nuanced understanding essential for practical utilization., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Circularly polarized luminescence (CPL) materials hold significant value in various fields, including information storage, secure communication, three-dimensional displays, biological detection, and optoelectronic devices. Using the Langmuir-Schaeffer (LS) assembly technique, we successfully construct a series of large-area flexible optical ultrathin films. Impressively, the inorganic assembled ultrathin films exhibit excellent CPL optical activity covering the visible to near-infrared (NIR) region, with the luminescence asymmetry factor g lum ranging from 0.59 to 0.72. Moreover, such ultrathin films also display outstanding mechanical flexibility, the optical activity of which even after 240 bending cycles shows almost no difference compared to the unbent samples. Owing to the ultra-broadband optical activity and ultra-stable optical activity of such full-inorganic assembled materials on flexible substrates, coupled with their excellent processability and outstanding mechanical flexibility, we anticipate they will find use in many fields such as communication technology and flexible optoelectronics., (© 2024 Wiley-VCH GmbH.)

Off-stoichiometric Ni x Fe 3-x O 4 ultrathin films (x < 2.1) with varying Ni content x and thickness 16 (±2) nm were grown on MgO(001) by reactive molecular beam epitaxy. Synchrotron-based high-resolution X-ray diffraction measurements reveal vertical compressive strain for all films, resulting from a lateral pseudomorphic adaption of the film to the substrate lattice without any strain relaxation. Complete crystallinity with smooth interfaces and surfaces is obtained independent of the Ni content x. For x < 1 an expected successive conversion from Fe 3 O 4 to NiFe 2 O 4 is observed, whereas local transformation into NiO structures is observed for films with Ni content x > 1. However, angle-resolved hard X-ray photoelectron spectroscopy measurements indicate homogeneous cationic distributions without strictly separated phases independent of the Ni content, while X-ray absorption spectroscopy shows that also for x > 1, not all Fe2+ cations are substituted by Ni2+ cations. The ferrimagnetic behavior, as observed by superconducting quantum interference device magnetometry, is characterized by decreasing saturation magnetization due to the formation of antiferromagnetic NiO parts.

Domain walls separating differently oriented polarization regions of ferroelectric materials are known to greatly impact nanoscale materials and device functionalities. Though the understanding of size effects in ferroelectric nanostructures has progressed, the effect of thickness downsizing on domain wall scaling behavior has remained unexplored. Using piezoresponse force microscopy, epitaxial BaTiO 3 film thickness size (2-90 nm) effects on the critical scaling universality of the domain wall dynamical creep and static roughness exponents including dimensionality is demonstrated. Independently estimated static roughness exponents ranging between 0.34 and 0.28 and dynamical creep exponents transition from 0.54 to 0.22 elucidate the domain wall dimensionality transition from two- to quasi-one-dimension in the thickness range of 10-25 nm, which is later validated by evaluating effective dimensionality within the paradigm of random-bond universality. The observed interdimensional transition is further credenced to the compressive strain and long-range strain-dipolar interactions, as revealed by the structural analyses and additional measurements with modified substrate-induced strain. These results provide new insights into the understanding of size effects in nanoscale ferroelectricity, paving the way toward future nanodevices., (© 2023 Wiley-VCH GmbH.)

We report the observation of fully magnetically polarized ultrathin La 0.8 Sr 0.2 MnO 3 films by using LaMnO 3 and La 0.45 Sr 0.55 MnO 3 buffer layers grown epitaxially on SrTiO 3 (001) substrates by molecular beam epitaxy. Specifically, we show that La 0.8 Sr 0.2 MnO 3 films grown on 12-unit-cell LaMnO 3 have bulk-like magnetic moments starting from a single unit cell thickness, while for the 15-unit-cell La 0.45 Sr 0.55 MnO 3 buffer layer, the La 0.8 Sr 0.2 MnO 3 transitions from an antiferromagnetic state to a fully spin-polarized ferromagnetic state at 4 unit cells. The magnetic results are confirmed by X-ray magnetic circular dichroism, while linear dichroic measurements carried out for the La 0.8 Sr 0.2 MnO 3 /La 0.45 Sr 0.55 MnO 3 series show the presence of an orbital reorganization at the transition from the antiferromagnetic to ferromagnetic state corresponding to a change from a preferred in-plane orbital hole occupancy, characteristic of the A-type antiferromagnetic state of La 0.45 Sr 0.55 MnO 3 , to preferentially out of plane. We interpret our findings in terms of the different electronic charge transfers between the adjacent layers, confined to the unit cell in the case of insulating LaMnO 3 and extended to a few unit cells in the case of conducting La 0.45 Sr 0.55 MnO 3 . Our work demonstrates an approach to growing ultrathin mixed-valence manganite films that are fully magnetically polarized from the single unit cell, paving the way to fully exploring the unique electronic properties of this class of strongly correlated oxide materials.

Nanomaterials that can be easily processed into thin films are highly desirable for their wide range of applicability in electrical and optical devices. Currently, Te-based 2D materials are of interest because of their superior electrical properties compared to transition metal dichalcogenide materials. However, the large-scale manufacturing of these materials is challenging, impeding their commercialization. This paper reports on ultrathin, large-scale, and highly flexible Te and Te-metal nanorope films grown via low-power radiofrequency sputtering for a short period at 25 °C. Additionally, the feasibility of such films as transistor channels and flexible transparent conductive electrodes is discussed. A 20 nm thick Te-Ni-nanorope-channel-based transistor exhibits a high mobility (≈450 cm 2 V -1 s -1 ) and on/off ratio (10 5 ), while 7 nm thick Te-W nanorope electrodes exhibit an extremely low haze (1.7%) and sheet resistance (30 Ω sq -1 ), and high transmittance (86.4%), work function (≈4.9 eV), and flexibility. Blue organic light-emitting diodes with 7 nm Te-W anodes exhibit significantly higher external quantum efficiencies (15.7%), lower turn-on voltages (3.2 V), and higher and more uniform viewing angles than indium-tin-oxide-based devices. The excellent mechanical flexibility and easy coating capability offered by Te nanoropes demonstrate their superiority over conventional nanomaterials and provide an effective outlet for multifunctional devices., (© 2023 Wiley-VCH GmbH.)

Ultrathin CoxFe3-xO4 films of high structural quality and with different Co content ( x = 0.6-1.2) were prepared by reactive molecular beam epitaxy on MgO(001) substrates. Epitaxy of these ferrite films is extensively monitored by means of time-resolved (operando) X-ray diffraction recorded in out-of-plane geometry to characterize the temporal evolution of the film structure. The Co ferrite films show high crystalline ordering and smooth film interfaces independent of their Co content. All CoxFe3-xO4 films exhibit enhanced compressive out-of-plane strain during the early stages of growth, which partly releases with increasing film thickness. When the Co content of the ferrite films increases, the vertical-layer distances increase, accompanied by slightly increasing film roughnesses. The latter result is supported by surface-sensitive low-energy electron diffraction as well as X-ray reflectivity measurements on the final films. In contrast, the substrate-film interface roughness decreases with increasing Co content, which is confirmed with X-ray reflectivity measurements. In addition, the composition and electronic structure of the ferrite films is characterized by means of hard X-ray photoelectron spectroscopy performed after film growth. The experiments reveal the expected increasing Fe3+/Fe2+ cation ratios for a higher Co content.

In recent years, increased control over naturally derived structural protein formulations and their self-assembly has enabled the application of high-resolution manufacturing techniques to silk-based materials, leading to bioactive interfaces with unprecedented miniaturized formats and functionalities. Here, a hybrid biopolymer-semiconductor device, obtained by integrating nanoscale silk layers in a well-established class of inorganic field-effect transistors (silk-FETs), is presented. The devices offer two distinct modes of operation-either traditional field-effect or electrolyte-gated-enabled by the precisely controlled thickness, morphology, and biochemistry of the integrated silk layers. The different operational modes are selectively accessed by dynamically modulating the free-water content within the nanoscale protein layer from the vapor phase. The utility of these hybrid devices is illustrated in a highly sensitive and ultrafast breath sensor, highlighting the opportunities offered by the integration of nanoscale biomaterial interfaces in conjunction with traditional semiconductor devices, enabling functional outcomes at the intersection between the worlds of microelectronics and biology., (© 2023 Wiley-VCH GmbH.)

The physics of electrons, photons, and their plasmonic interactions change dramatically when one or more dimensions are reduced to atomic-level thicknesses. For example, graphene exhibits unique electrical, plasmonic, and optical properties. Likewise, atomic-thick metal films are expected to exhibit extraordinary quantum optical properties. Several methods of growing ultrathin metal films were demonstrated, but the quality of the obtained films was much worse compared to bulk films. In this work, we propose a new method of making ultrathin gold films that are close in their properties to bulk gold films. Excellent plasmonic properties are revealed by directly observing quasi-short- and quasi-long-range plasmons in such a film via scanning near-field optical microscopy. The results pave the way for the use of ultrathin gold films in flexible and transparent nanophotonics and optoelectronic applications.

The development of the new generation of non-volatile high-density ferroelectric memory requires the utilization of ultrathin ferroelectric films. The most promising candidates are polycrystalline-doped HfO 2 films because of their perfect compatibility with silicon technology and excellent ferroelectric properties. However, the remanent polarization of HfO 2 films is known to degrade when their thickness is reduced to a few nanometers. One of the reasons for this phenomenon is the wake-up effect, which is more pronounced in the thinner the film. For the ultrathin HfO 2 films, it can be so long-lasting that degradation occurs even before the wake-up procedure is completed. In this work, an approach to suppress the wake-up in ultrathin Hf 0.5 Zr 0.5 O 2 films is elucidated. By engineering internal built-in fields in an as-prepared structure, a stable ferroelectricity without a wake-up effect is induced in 4.5 nm thick Hf 0.5 Zr 0.5 O 2 film. By analysis of the functional characteristics of ferroelectric structures with a different pattern of internal built-in fields and their comparison with the results of in situ piezoresponse force microscopy and synchrotron X-ray micro-diffraction, the important role of built-in fields in ferroelectricity of ultrathin Hf 0.5 Zr 0.5 O 2 films as well as the origin of stable ferroelectric properties is revealed.

While the bulk strontium titanate (STO) crystal characteristics are relatively well known, ultrathin perovskites' nanostructure, chemical composition, and crystallinity are quite complex and challenging to understand in detail. In our study, the DFT methods were used for modelling the Raman spectra of the STO bulk (space group I4/mcm) and 5-21-layer thin films (layer group p4/mbm) in tetragonal phase with different thicknesses ranging from ~0.8 to 3.9 nm. Our calculations revealed features in the Raman spectra of the films that were absent in the bulk spectra. Out of the seven Raman-active modes associated with bulk STO, the frequencies of five modes (2E g, A 1g , B 2g , and B 1g ) decreased as the film thickness increased, while the low-frequency B 2g and higher-frequency E g modes frequencies increased. The modes in the films exhibited vibrations with different amplitudes in the central or surface parts of the films compared to the bulk, resulting in frequency shifts. Some peaks related to bulk vibrations were too weak (compared to the new modes related to films) to distinguish in the Raman spectra. However, as the film thickness increased, the Raman modes approached the frequencies of the bulk, and their intensities became higher, making them more noticeable in the Raman spectrum. Our results could help to explain inconsistencies in the experimental data for thin STO films, providing insights into the behavior of Raman modes and their relationship with film thickness.

One of the unsolved problems for using high-T c superconducting cuprates for spintronic applications are the short coherence lengths of Cooper pairs in oxides (a few Å), which requires atomically sharp and defect-free interfaces. This research demonstrates the presence of high-T c superconducting La 1.84 Sr 0.16 CuO 4 in direct proximity to SrLaMnO 4 and provides evidence for the sharpness of interfaces between the cuprate and the manganite layers at the atomic scale. These findings shed light on the impact of the chemical potential at the interface of distinct materials on highly sensitive physical properties, such as superconductivity. Additionally, this results show the high stability of ultrathin layers from the same K 2 NiF 4 -type family, specifically one unit cell of Sr 2- x La x MnO 4 and three unit cells of La 1.84 Sr 0.16 CuO 4 . This work advances both the fundamental understanding of the proximity region between superconducting cuprates and manganite phases and the potential use of oxide-based materials in quantum computing., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Due to their high electromechanical coupling and energy density properties, ultrathin piezoelectric films have recently been intensively studied as key materials for the construction of miniaturized energy transducers, and in this paper we summarize the research progress. At the nanoscale, even a few atomic layers, ultrathin piezoelectric films have prominent shape anisotropic polarization, that is, in-plane polarization and out-of-plane polarization. In this review, we first introduce the in-plane and out-of-plane polarization mechanism, and then summarize the main ultrathin piezoelectric films studied at present. Secondly, we take perovskite, transition metal dichalcogenides, and Janus layers as examples to elaborate the existing scientific and engineering problems in the research of polarization, and their possible solutions. Finally, the application prospect of ultrathin piezoelectric films in miniaturized energy converters is summarized.

Ultrathin MoO 3 semiconductor nanostructures have garnered significant interest as a promising nanomaterial for transparent nano- and optoelectronics, owing to their exceptional reactivity. Due to the shortage of knowledge about the electronic and optoelectronic properties of MoO 3 / n -Si via an ALD system of few nanometers, we utilized the preparation of an ultrathin MoO 3 film at temperatures of 100, 150, 200, and 250 °C. The effect of the depositing temperatures on using bis(tbutylimido)bis(dimethylamino)molybdenum (VI) as a molybdenum source for highly stable UV photodetectors were reported. The ON-OFF and the photodetector dynamic behaviors of these samples under different applied voltages of 0, 0.5, 1, 2, 3, 4, and 5 V were collected. This study shows that the ultrasmooth and homogenous films of less than a 0.30 nm roughness deposited at 200 °C were used efficiently for high-performance UV photodetector behaviors with a high sheet carrier concentration of 7.6 × 10 10 cm -2 and external quantum efficiency of 1.72 × 10 11 . The electronic parameters were analyzed based on thermionic emission theory, where Cheung and Nord's methods were utilized to determine the photodetector electronic parameters, such as the ideality factor ( n ), barrier height (Φ 0 ), and series resistance (R s ). The n -factor values were higher in the low voltage region of the I-V diagram, potentially due to series resistance causing a voltage drop across the interfacial thin film and charge accumulation at the interface states between the MoO 3 and Si surfaces.

A potential approach to enhance the suppressed proton conductivity of nanoscale ultrathin Nafion films is to adjust the ionomer structure via regulating the catalyst-ionomer interaction. To understand the interaction between substrate surface charges and Nafion molecules, self-assembled ultrathin films (∼20 nm) were prepared on the SiO 2 model substrates, which were modified with silane coupling agents to carry either negative (COO - ) or positive (NH 3 ) charges. Specifically, the surface energy, phase separation, and proton conductivity were investigated by contact angle measurements, atomic force microscopy, and microelectrodes to illuminate the relationship between the substrate surface charge, thin-film nanostructure, and proton conduction. Compared to electrically neutral substrates, ultrathin films formed faster on the negatively charged substrate with an 83% increase in proton conductivity but formed more slowly on the positively charged substrate, with proton conductivity decreased by 35% at 50 °C. The surface charges interact with sulfonic acid groups of Nafion molecules to alter molecular orientation, resulting in different surface energies and phase separation, which are responsible for proton conductivity variation.+ ) charges. Specifically, the surface energy, phase separation, and proton conductivity were investigated by contact angle measurements, atomic force microscopy, and microelectrodes to illuminate the relationship between the substrate surface charge, thin-film nanostructure, and proton conduction. Compared to electrically neutral substrates, ultrathin films formed faster on the negatively charged substrate with an 83% increase in proton conductivity but formed more slowly on the positively charged substrate, with proton conductivity decreased by 35% at 50 °C. The surface charges interact with sulfonic acid groups of Nafion molecules to alter molecular orientation, resulting in different surface energies and phase separation, which are responsible for proton conductivity variation.

Perfect absorption and strong coupling are two highly sought-after regimes of light-matter interactions. Both regimes have been studied as separate phenomena in excitonic 2D materials, particularly in MoS 2 . However, the structures used to reach these regimes often require intricate nanofabrication. Here, we demonstrate the occurrence of perfect absorption and strong coupling in thin MoS 2 multilayers supported by a glass substrate. We measure reflection spectra of mechanically exfoliated MoS 2 flakes at various angles beyond the light-line via Fourier plane imaging and spectroscopy and find that absorption in MoS 2 monolayers increases up to 74% at the C-exciton by illuminating at the critical angle. Perfect absorption is achieved for ultrathin MoS 2 flakes (4-8 layers) with a notable angle and frequency sensitivity to the exact number of layers. By calculating zeros and poles of the scattering matrix in the complex frequency plane, we identify perfect absorption (zeros) and strong coupling (poles) conditions for thin (<10 layers) and thick (>10 layers) limits. Our findings reveal rich physics of light-matter interactions in bare MoS 2 flakes, which could be useful for nanophotonic and light harvesting applications.

Co/CoO multilayers are fabricated by means of radio-frequency magnetron sputtering. For the formation of each multilayer period, a Co layer is initially produced followed by natural oxidation. Platinum is used not only as buffer and capping layers, but also in the form of intermediate ultrathin layers to enhance perpendicular magnetic anisotropy. Three samples are compared with respect to the magnetic anisotropies and exchange bias between 4-300 K based on superconducting quantum interference device magnetometry measurements. Two of the multilayers are identical Co/CoO/Pt ones; one of them, however, is grown on a Co/Pt "magnetic substrate" to induce perpendicular magnetic anisotropy via exchange coupling through an ultrathin Pt intermediate layer. The third multilayer is of the form Co/CoO/Co/Pt. The use of a "magnetic substrate" results in the observation of loops with large remanence when the field applies perpendicular to the film plane. The CoO/Co interfaces lead to a significant exchange bias at low temperatures after field cooling. The largest exchange bias was observed in the film with double Co/CoO/Co interfaces. Consequently, significant perpendicular anisotropy coexists with large exchange bias, especially at low temperatures. Such samples can be potentially useful for applications related to spintronics and magnetic storage.

Super broadband optical absorbers with ultrathin films have been keenly pursued for a long time. Although highly lossy materials with sharp light attenuation have the potential to become super absorbers, a large percent of light from free space is inevitably reflected back for the distinct impedance mismatch. Here, a simple strategy, of which reducing the thickness of highly-lossy thin films to minish reflectance and simultaneously folding the ultrathin films to make light multiple pass through, is proposed to obtain super broadband mid-infrared absorbers with ultrathin films. Along this line, the absorbers were prepared by depositing Al-doped ZnO film on scaffolds consisted of alumina spherical shells, whose substrates were opaque. When the thickness of Al-doped ZnO is 43 nm and the layer number of scaffolds is three, a maximum average absorptance was achieved as 97.6% over the wavelength range from 3 to 15 μm. Applying this strategy on polished Al foil, excellent infrared camouflage performance on human-body background was demonstrated. Featured by the strong broadband optical absorption with ultrathin films, flexible access to multiple substrates and low-cost procedures, this approach has the potential in widespread applications of infrared thermal emitters and optoelectronic devices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Synergistic methodological strategies based on the fields of microbial biotechnology and materials science open up an enormous range of possibilities for the sustainable production of advanced materials with predictable properties. This study shows how naturally produced polyhydroxyalkanoate (PHA) particles are introduced into bacterial cellulose (BC) driven by their bacterial producers. Thanks to an extensive knowledge of the internal structure of BC, it was possible to control the colonization process, i.e. loading and localization of PHA. A subsequent acid treatment favored the PHA-BC bonding at the position reached by the bacteria. These biodegradable films showed improved mechanical and barrier properties even with respect to reference plastic films 8 times thicker, reaching a Young's modulus 4.25 times higher and an oxygen permeability 3 times lower than those of polyethylene terephthalate (PET) films. Owing to the versatility of the method, a wide variety of materials can be developed for very diverse fields of application., Competing Interests: Declaration of competing interest M Auxiliadora Prieto, Cristina Campano has patent pending to CSIC., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Superconducting nanofilms are tunable systems that can host a 3D-2D dimensional crossover leading to the Berezinskii-Kosterlitz-Thouless (BKT) superconducting transition approaching the 2D regime. Reducing the dimensionality further, from 2D to quasi-1D superconducting nanostructures with disorder, can generate quantum and thermal phase slips (PS) of the order parameter. Both BKT and PS are complex phase-fluctuation phenomena of difficult experiments. We characterized superconducting NbN nanofilms thinner than 15 nm, on different substrates, by temperature-dependent resistivity and current-voltage (I-V) characteristics. Our measurements evidence clear features related to the emergence of BKT transition and PS events. The contemporary observation in the same system of BKT transition and PS events, and their tunable evolution in temperature and thickness was explained as due to the nano-conducting paths forming in a granular NbN system. In one of the investigated samples, we were able to trace and characterize the continuous evolution in temperature from quantum to thermal PS. Our analysis established that the detected complex phase phenomena are strongly related to the interplay between the typical size of the nano-conductive paths and the superconducting coherence length.

The miniaturization of electronic devices and power systems for capacitive energy storage under harsh environments requires scalable high-quality ultrathin high-temperature dielectric films. To meet the need, ultrasonic spray-coating (USC) can be used. Novel polyimides with a dipolar group, CF 3 (F-PI), and all-organic composites with trace organic semiconductor can serve as models. These scalable high-quality ultrathin films (≈2.6 and ≈5.2 µm) are successfully fabricated via USC. The high quality of the films is evaluated from the micro-millimeter scale to the sub-millimeter and above. The high glass transition temperature T g (≈340 °C) and concurrent large bandgap E g (≈3.53 eV) induced by weak conjugation from considerable interchain distance (≈6.2 Å) enable F-PI to be an excellent matrix delivering a discharge energy density with 90% discharge efficiency U η90 of 2.85 J cm -3 at 200 °C. Further, the incorporation of a trace organic semiconductor leads to a record U η90 of ≈4.39 J cm -3 at 200 °C due to the markedly enhanced breakdown strength caused by deep charge traps of ≈2 eV. Also, a USC-fabricated multilayer F-PI foil capacitor with ≈85 nF (six layers) has good performance at 150 °C. These results confirm that USC is an excellent technology to fabricate high-quality ultrathin dielectric films and capacitors., (© 2022 Wiley-VCH GmbH.)

In this work, we investigated the influence of oxygen plasma on the growth of nickel cobaltite (NiCo 2 O 4 ) thin films compared to growth in a molecular oxygen atmosphere. The films were grown on MgO(001), MgAl 2 O 4 (001) and SrTiO 3 (001) substrates by oxygen plasma (atmosphere of activated oxygen)-assisted and reactive molecular beam epitaxy (molecular oxygen atmosphere). Soft X-ray photoelectron spectroscopy showed that only the use of oxygen plasma led to a spectrum characteristic of (NiCo 2 O 4 ). Low energy electron diffraction measurements were conducted to obtain information on the structure of the film surfaces. The results proved the formation of a spinel surface structure for films grown with oxygen plasma, while the formation of a rock salt structure was observed for growth with molecular oxygen. To determine the film thickness, X-ray reflectivity measurements were performed. If oxygen plasma were used to grow (NiCo 2 O 4 ) films, this would result in lower film thicknesses compared to growth using molecular oxygen although the cation flux was kept constant during deposition. Additional X-ray diffraction experiments delivered structural information about the bulk structure of the film. All films had a rock salt bulk structure after exposure to ambient conditions. Angle-resolved hard X-ray photoelectron spectroscopy revealed a homogeneous depth distribution of cations of the grown film, but no typical (NiCo 2 O 4 ) spectrum anymore. Thus, on the one hand, (NiCo 2 O 4 ) films with a spinel structure prepared using activated oxygen were not stable under ambient conditions. The structure of these films was transformed into NiCo oxide with a rock salt structure. On the other hand, it was not possible to form (NiCo 2 O 4 ) films using molecular oxygen. These films had a rock salt structure that was stable under ambient conditions.

The morphology of sub-monolayer sexithiophene films has been investigated in situ and ex situ as a function of the substrate temperature of deposition. In this thickness range, monolayer terraces formed of edge-on molecules, i.e. nearly upright, are typically nucleated. Herein, the terrace height is found to be correlated to both the film morphology and the substrate surface energy. In particular, the presence of a layer of variable thickness with molecules lying face-on or side-on can be identified atop the terraces when the deposition is carried out on inert substrates. This phenomenon can be evidenced thanks to accurate height measurements made with atomic force microscopy and further data obtained with advanced scanning probe microscopy techniques operating in different environments, viz. liquid, air and vacuum. An upward displacement of molecules from the substrate to the top of the terraces is considered to be responsible of this layer formation, whose molecules weakly interact with the underlying terraces., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Fabrication of ultrathin films of dielectric (with particular reference to materials with high dielectric constants) materials has significance in many advanced technological applications including hard protective coatings, sensors, and next-generation logic devices. Current state-of-the-art in microelectronics for fabricating these thin films is a combination of atomic layer deposition and photolithography. As feature size decreases and aspect ratios increase, conformality of the films becomes paramount. Here, we show a polymer brush template-assisted deposition of highly conformal, ultrathin (sub 5 nm) high-κ dielectric metal oxide films (hafnium oxide and zirconium oxide) on topographically patterned silicon nitride substrates. This technique, using hydroxyl terminated poly-4-vinyl pyridine (P4VP-OH) as the polymer brush, allows for conformal deposition with uniform thickness along the trenches and sidewalls of the substrate. Metal salts are infiltrated into the grafted monolayer polymer brush films via solution deposition. Tailoring specific polymer interfacial chemistries for ion infiltration combined with subsequent oxygen plasma treatment enabled the fabrication of high-quality sub 5 nm metal oxide films.

Piezoelectric biomaterials have attracted significant attention due to the potential effect of piezoelectricity on biological tissues and their versatile applications. However, the high cost and complexity of assembling and domain aligning biomolecules at a large scale, and the disordered arrangement of piezoelectric domains as well as the lack of ferroelectricity in natural biological tissues remain a roadblock toward practical applications. Here, utilizing the weak van der Waals interaction in the layered structure of small intestinal submucosa (SIS), a van der Waals exfoliation (vdWE) process is reported to fabricate ultrathin films down to the thickness of the effective piezoelectric domain. Based on that, the piezoelectric property is revealed of SIS stemming from the collagen fibril, with piezoelectric coefficients up to 4.1 pm V -1 and in-plane polarization orientation parallel to the fibril axis. Furthermore, a biosensor based on the vdWE-processed SIS film with an in-plane electrode is demonstrated that produces open-circuit voltages of ≈250 mV under the cantilever vibration condition. The vdWE method shows great potential in facilely fabricating ultrathin films of soft tissues and biosensors., (© 2022 Wiley-VCH GmbH.)

The formation of ultrathin films of Rh-based porous metal-organic polyhedra (Rh-MOPs) by the Langmuir-Blodgett method has been explored. Homogeneous and dense monolayer films were formed at the air-water interface either using two different coordinatively alkyl-functionalized Rh-MOPs (HRhMOP(diz) 12 and HRhMOP(oiz) 12 ) or by in situ incorporation of aliphatic chains to the axial sites of dirhodium paddlewheels of another Rh-MOP (OHRhMOP) at the air-liquid interface. All these Rh-MOP monolayers were successively deposited onto different substrates in order to obtain multilayer films with controllable thicknesses. Aliphatic chains were partially removed from HRhMOP(diz) 12 films post-synthetically by a simple acid treatment, resulting in a relevant modification of the film hydrophobicity. Moreover, the CO 2 /N 2 separation performance of Rh-MOP-supported membranes was also evaluated, proving that they can be used as selective layers for efficient CO 2 separation.

A ferromagnetic metal nanolayer with a large perpendicular magnetic anisotropy, small saturation magnetization, and small magnetic damping constant is a crucial requirement for high-speed spintronic devices. Fabrication of these devices on Si/SiO 2 amorphous substrates with polycrystalline structure is also strongly desired for the mass production industry. This study involves the investigation of sub-terahertz (THz) magnetization precessional motion in a newly developed material system consisting of Cu 2 Sb-type MnAlGe and (Mn-Cr)AlGe films by means of an all-optical pump-probe method. These materials exhibit large perpendicular magnetic anisotropy in regions of a few nanometers in size. The pseudo-2D crystal structures are clearly observed in the high-resolution transmission electron microscopy (TEM) images for the film samples grown on thermally oxidized silicon substrates. The TEM images also show a partial substitution of Cr atoms for the Mn sites in MnAlGe. A magnetization precession frequency of 0.164 THz with a relatively small effective magnetic damping constant of 0.012 is obtained for (Mn-Cr)AlGe. Theoretical calculation infers that the modification of the total density of states by Cr substitution decreases the intrinsic magnetic damping constant of (Mn-Cr)AlGe., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

In this work, we present a comprehensive study on real-time monitoring the growth of epitaxial Co x Fe 3- x O 4 thin films grown on SrTiO 3 (001) substrates via reactive molecular beam epitaxy. The growth process was monitored during evaporation by means of time resolved operando hard X-ray photoelectron spectroscopy (HAXPES). We prepared ultrathin ferrite films using different oxygen partial pressures, showing pure metallic, light oxidic, and cobalt ferrite-like growth. Additional X-ray diffraction measurements confirm HAXPES results.

Ultrathin, transparent, and free-standing films assembled from low-dimensional nanomaterials (LDMs) are promising for various applications, including transparent heaters and membranes. However, the intact separation of the assembled films, especially those with controlled ultrathin thickness from deposited substrates, is a tremendous challenge, particularly for fast peeling off via self-detaching. Herein, we propose a versatile method to rapidly peel off ultrathin assembled LDM films, including three types of carbon nanotubes, vermiculite, Ag nanowires, and carbon nanotube@graphene, by dissolving the MXene interlayer from the layer-by-layer filtered MXene/LDM Janus films using diluted H 2 O 2 . The MXene sacrificial interlayers play dual roles, including physical isolation of LDM films from filter membranes and the production of bubbles that buoy ultrathin LDM films, making them free-standing. The integrality and self-detaching rate of the LDM films are determined by the loading and reactivity of the MXene interlayers. The intact LDM films can self-detach in 80 s by dissolving the optimized MXene interlayer and producing bubbles. The as-made free-standing ultrathin LDM films can be transferred to arbitrary substrates and exhibit outstanding performance as transparent heaters. This scalable method provides an efficient and versatile method to produce ultrathin, transparent, and free-standing LDM films and finds new applications for the growing MXene family., (© 2021 Wiley-VCH GmbH.)

Here, we present the (element-specific) magnetic properties and cation ordering for ultrathin Co-rich cobalt ferrite films. Two Co-rich CoxFe3-xO4 films with different stoichiometry (x=1.1 and x=1.4) have been formed by reactive solid phase epitaxy due to post-deposition annealing from epitaxial CoO/Fe3O4 bilayers deposited before on Nb-doped SrTiO3(001). The electronic structure, stoichiometry and homogeneity of the cation distribution of the resulting cobalt ferrite films were verified by angle-resolved hard X-ray photoelectron spectroscopy. From X-ray magnetic circular dichroism measurements, the occupancies of the different sublattices were determined using charge-transfer multiplet calculations. For both ferrite films, a partially inverse spinel structure is found with increased amount of Co3+ cations in the low-spin state on octahedral sites for the Co1.4Fe1.6O4 film. These findings concur with the results obtained by superconducting quantum interference device measurements. Further, the latter measurements revealed the presence of an additional soft magnetic phase probably due to cobalt ferrite islands emerging from the surface, as suggested by atomic force microscope measurements.

The presence of inherently strong spin-orbit coupling in bismuth, its unique layer-dependent band topology and high carrier mobility make it an interesting system for both fundamental studies and applications. Theoretically, it has been suggested that strong quantum size effects should be present in the Bi(110) films, with the possibility of Dirac Fermion states in the odd-bilayer (BL) films, originating from dangling p z orbitals and quantum-spin hall (QSH) states in the even-bilayer films. However, the experimental verification of these claims has been lacking. Here, we study the electronic structure of Bi(110) films grown on a high- T c superconductor, Bi 2 Sr 2 CaCu 2 O 8+δ (Bi2212) using angle-resolved photoemission spectroscopy (ARPES). We observe an oscillatory behavior of electronic structure with the film thickness and identify the Dirac-states in the odd-bilayer films, consistent with the theoretical predictions. In the even-bilayer films, we find another Dirac state that was predicted to play a crucial role in the QSH effect. In the low thickness limit, we observe several extremely one-dimensional states, probably originating from the edge-states of Bi(110) islands. Our results provide a much needed experimental insight into the electronic and structural properties of Bi(110) films.

Surface termination is known to play an important role in determining the physical properties of materials. It is crucial to know how surface termination affects the metal-insulator transition (MIT) of V 2 O 3 films for both fundamental understanding and its applications. By changing growth parameters, we achieved a variety of surface terminations in V 2 O 3 films that are characterized by low-energy electron diffraction (LEED) and photoemission spectroscopy techniques. Depending upon the terminations, our results show that MIT can be partially or fully suppressed near the surface region due to the different fillings of the electrons at the surface and subsurface layers and the change of screening length compared to the bulk. Across MIT, a strong redistribution of spectral weight and its transfer from a high-to-low-binding energy regime is observed in a wide energy scale. Our results show that the total spectral weight in the low-energy regime is not conserved across MIT, indicating a breakdown of the "sum rules of spectral weight", signature of a strongly correlated system. Such a change in spectral weight is possibly linked to the change in hybridization, lattice volume ( i.e ., effective carrier density), and the spin degree of freedom in the system that occurs across MIT. We find that MIT in this system is strongly correlation-driven, where the electron-electron interactions play a pivotal role. Moreover, our results provide better insight into the understanding of the electronic structure of strongly correlated systems and highlight the importance of accounting for surface effects during interpretation of the physical property data mainly using surface-sensitive probes, such as surface resistivity.

Inversion-symmetry breaking is a ubiquitous concept in condensed-matter science: It is a prerequisite for technologically relevant effects such as piezoelectricity, nonlinear optical properties, and spin-transport phenomena. It also determines abstract properties, like the electronic topology in quantum materials. Therefore, the creation of materials where inversion symmetry can be turned on or off by design may be a versatile approach for controlling parity-related functionalities. Here, we engineer inversion symmetry on a sub-unit-cell level in ultrathin hexagonal manganite films. Although an odd number of half-unit-cell layers breaks inversion symmetry, an even number of such layers remains centrosymmetric. Optical second harmonic generation as an inversion-symmetry-sensitive functionality is thus activated and deactivated on demand and at the same time used for in situ tracking of the symmetry state of our films. Symmetry engineering on the sub-unit-cell level thus suggests a new platform for controlled activation and deactivation of symmetry-governed functionalities in oxide-electronic epitaxial thin films.

Complementary to bulk synthesis, here we propose a designer lattice with extremely high magnetic frustration and demonstrate the possible realization of a quantum spin liquid state from both experiments and theoretical calculations. In an ultrathin (111) CoCr 2 O 4 slice composed of three triangular and one kagome cation planes, the absence of a spin ordering or freezing transition is demonstrated down to 0.03 K, in the presence of strong antiferromagnetic correlations in the energy scale of 30 K between Co and Cr sublattices, leading to the frustration factor of ∼1000. Persisting spin fluctuations are observed at low temperatures via low-energy muon spin relaxation. Our calculations further demonstrate the emergence of highly degenerate magnetic ground states at the 0 K limit, due to the competition among multiply altered exchange interactions. These results collectively indicate the realization of a proximate quantum spin liquid state on the synthetic lattice.

New micro- and nanoscale devices require electrically isolating materials with specific thermal properties. One option to characterize these thermal properties is the atomic force microscopy (AFM)-based scanning thermal microscopy (SThM) technique. It enables qualitative mapping of local thermal conductivities of ultrathin films. To fully understand and correctly interpret the results of practical SThM measurements, it is essential to have detailed knowledge about the heat transfer process between the probe and the sample. However, little can be found in the literature so far. Therefore, this work focuses on theoretical SThM studies of ultrathin films with anisotropic thermal properties such as hexagonal boron nitride (h-BN) and compares the results with a bulk silicon (Si) sample. Energy fluxes from the probe to the sample between 0.6 µW and 126.8 µW are found for different cases with a tip radius of approximately 300 nm. A present thermal interface resistance (TIR) between bulk Si and ultrathin h-BN on top can fully suppress a further heat penetration. The time until heat propagation within the sample is stationary is found to be below 1 µs, which may justify higher tip velocities in practical SThM investigations of up to 20 µms -1 . It is also demonstrated that there is almost no influence of convection and radiation, whereas a possible TIR between probe and sample must be considered.

Strain engineering provides the ability to control the ground states and associated phase transition in epitaxial films. However, the systematic study of the intrinsic character and strain dependency in transition-metal nitrides remains challenging due to the difficulty in fabricating stoichiometric and high-quality films. Here the observation of an electronic state transition in highly crystalline antiferromagnetic CrN films with strain and reduced dimensionality is reported. By shrinking the film thickness to a critical value of ≈30 unit cells, a profound conductivity reduction accompanied by unexpected volume expansion is observed in CrN films. The electrical conductivity is observed surprisingly when the CrN layer is as thin as a single unit cell thick, which is far below the critical thickness of most metallic films. It is found that the metallicity of an ultrathin CrN film recovers from insulating behavior upon the removal of the as-grown strain by the fabrication of freestanding nitride films. Both first-principles calculations and linear dichroism measurements reveal that the strain-mediated orbital splitting effectively customizes the relatively small bandgap at the Fermi level, leading to an exotic phase transition in CrN. The ability to achieve highly conductive nitride ultrathin films by harnessing strain-control over competing phases can be used for utilizing their exceptional characteristics., (© 2020 Wiley-VCH GmbH.)

Graphdiyne (GDY) has been ideal candidate support for atomic catalysts (ACs) due to its unique conjugated two-dimensional (2D) structure comprising both sp- and sp 2 -hybrid carbon atoms. ACs/GDY can display excellent catalytic ability and high selectivity, emerging as a cutting-edge research area in the past few years. Recently, a growing body of work has been done in ACs/GDY, ranging from screening appropriate combinations theoretically, continuous improvement to prepare few-layered GDY to meet the critical challenge in this area, and successfully fabricating ACs/GDY in facile way. This Minireview briefly introduces recent advanced progress in this field, including the synthetic method for both thin GDY film and ACs/GDY, as well as theoretical analysis of different ACs/GDY systems, characterization, and applications. In the end, the challenges and further opportunities of ACs/GDY are summarized and proposed. It is hoped that this article brings new insights into the current study of ACs/GDY and promotes better development in this area., (© 2020 Wiley-VCH GmbH.)

We investigate THz conductivity dynamics in NdNiO 3 and EuNiO 3 ultrathin films (15 unit cells, u.c., ∼5.7 nm thick) following a photoinduced thermal quench into the metallic state and reveal a clear contrast between first- and second-order dynamics. While in EuNiO 3 the conductivity recovers exponentially, in NdNiO 3 the recovery is nonexponential and slower than a simple thermal model. Crucially, it is consistent with first-order dynamics and well-described by a 2d Avrami model, with supercooling leading to metastable phase coexistence on the nano- to mesoscopic scale. This novel observation is a fundamentally dynamic manifestation of the first-order character of the insulator-to-metal transition, which the nanoscale thickness of our films and their fast cooling rate enable us to detect. The large transients seen in our films are promising for fast electronic (and magnetic) switching applications.

Tip-enhanced Raman scattering (TERS) in ångström-scale plasmonic cavities has drawn increasing attention. However, Raman scattering at vanishing cavity distances remains unexplored. Here, we show the evolution of TERS in transition from the tunneling regime to atomic point contact (APC). A stable APC is reversibly formed in the junction between an Ag tip and ultrathin ZnO or NaCl films on the Ag(111) surface at 10 K. An abrupt increase of the TERS intensity occurs upon APC formation for ZnO, but not for NaCl. This remarkable observation is rationalized by a difference in hybridization between the Ag tip and these films, which determines the contribution of charge transfer enhancement in the fused plasmonic junction. The strong hybridization between the Ag tip and ZnO is corroborated by the appearance of a new vibrational mode upon APC formation, whereas it is not observed for the chemically inert NaCl.

While the bulk structure of vapor-deposited glasses has been extensively studied, structure at buried interfaces has received little attention, despite being important for organic electronic applications. To learn about glass structure at buried interfaces, we study the structure of vapor-deposited glasses of the organic semiconductor DSA-Ph (1,4-di-[4-( N , N -diphenyl)amino]styrylbenzene) as a function of film thickness; the structure is probed with grazing incidence X-ray scattering. We deposit on silicon and gold substrates and span a film thickness range of 10-600 nm. Our experiments demonstrate that interfacial molecular packing in vapor-deposited glasses of DSA-Ph is more disordered compared to the bulk. At a deposition temperature near room temperature, we estimate ∼8 nm near the substrate can have modified molecular packing. Molecular dynamics simulations of a coarse-grained representation of DSA-Ph reveal a similar length scale. In both the simulations and the experiments, deposition temperature controls glass structure beyond this interfacial layer of a few nanometers.

Neuromorphic computing consisting of artificial synapses and neural network algorithms provides a promising approach for overcoming the inherent limitations of current computing architecture. Developments in electronic devices that can accurately mimic the synaptic plasticity of biological synapses, have promoted the research boom of neuromorphic computing. It is reported that robust ferroelectric tunnel junctions can be employed to design high-performance electronic synapses. These devices show an excellent memristor function with many reproducible states (≈200) through gradual ferroelectric domain switching. Both short- and long-term plasticity can be emulated by finely tuning the applied pulse parameters in the electronic synapse. The analog conductance switching exhibits high linearity and symmetry with small switching variations. A simulated artificial neural network with supervised learning built from these synaptic devices exhibited high classification accuracy (96.4%) for the Mixed National Institute of Standards and Technology (MNIST) handwritten recognition data set., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ceramic oxide electrolytes are outstanding due to their excellent thermostability, wide electrochemical stable windows, superior Li-ion conductivity, and high elastic modulus compared to other electrolytes. To achieve high energy density, all-solid-state batteries require thin solid-state electrolytes that are dozens of micrometers thick due to the high density of ceramic electrolytes. Perovskite-type Li 0.34 La 0.56 TiO 3 (LLTO) freestanding ceramic electrolyte film with a thickness of 25 µm is prepared by tape-casting. Compared to a thick electrolyte (>200 µm) obtained by cold-pressing, the total Li ionic conductivity of this LLTO film improves from 9.6 × 10 -6 to 2.0 × 10 -5 S cm -1 . In addition, the LLTO film with a thickness of 25 µm exhibits a flexural strength of 264 MPa. An all-solid-state Li-metal battery assembled with a 41 µm thick LLTO exhibits an initial discharge capacity of 145 mAh g -1 and a high capacity retention ratio of 86.2% after 50 cycles. Reducing the thickness of oxide ceramic electrolytes is crucial to reduce the resistance of electrolytes and improve the energy density of Li-metal batteries., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Heat transfer processes in micro- and nanoscale devices have become more and more important during the last decades. Scanning thermal microscopy (SThM) is an atomic force microscopy (AFM) based method for analyzing local thermal conductivities of layers with thicknesses in the range of several nm to µm. In this work, we investigate ultrathin films of hexagonal boron nitride (h-BN), copper iodide in zincblende structure (γ-CuI) and some test sample structures fabricated of silicon (Si) and silicon dioxide (SiO 2 ) using SThM. Specifically, we analyze and discuss the influence of the sample topography, the touching angle between probe tip and sample, and the probe tip temperature on the acquired results. In essence, our findings indicate that SThM measurements include artefacts that are not associated with the thermal properties of the film under investigation. We discuss possible ways of influence, as well as the magnitudes involved. Furthermore, we suggest necessary measuring conditions that make qualitative SThM measurements of ultrathin films of h-BN with thicknesses at or below 23 nm possible., Competing Interests: The authors declare no conflict of interest.

We report on the emergent magnetic state of (111)-oriented CoCr 2 O 4 ultrathin films sandwiched between Al 2 O 3 spacer layers in a quantum confined geometry. At the two-dimensional crossover, polarized neutron reflectometry reveals an anomalous enhancement of the total magnetization compared to the bulk value. Synchrotron X-ray magnetic circular dichroism measurements demonstrate the appearance of a long-range ferromagnetic ordering of spins on both Co and Cr sublattices. Brillouin function analyses and ab-initio density functional theory calculations further corroborate that the observed phenomena are due to the strongly altered magnetic frustration invoked by quantum confinement effects, manifested by the onset of a Yafet-Kittel-type ordering as the magnetic ground state in the ultrathin limit, which is unattainable in the bulk.

The deformation behavior of neat, glassy polymer-grafted nanoparticle (PGN) monolayer films is studied using coarse-grained molecular dynamics simulations and experiments on polystyrene-grafted silica. In both the simulations and experiments, apparent crazing behavior is observed during deformation. The PGN systems show a relatively more uniform, perforated sheet craze structure and significantly higher strain at break than reference homopolymers of the same length. Short chain, unentangled PGN monolayers are also simulated for comparison; these are brittle and break apart without crazing. The entangled PGN simulations are analyzed in detail for systems at both high and moderate graft density. Stress-strain curves show three distinct regions: yielding and strain localization, craze widening, and strain hardening preceding catastrophic failure. The PGN stress-strain behavior appears more similar to that of longer chain, highly entangled homopolymer films than to the reference homopolymer films of the same length as the graft chains, suggesting that the particles effectively add additional entanglement points. The moderate graft density particles have higher strain-to-failure and maximum stress than the high graft density particles. We suggest this increased robustness for lower graft density systems is due to their increased interpenetration of graft chains between neighboring particles, which leads to increased interparticle entanglements per chain.

Ferroelectric heterostructures, with capability of storing data at ultrahigh densities, could act as the platform for next-generation memories. The development of new device paradigms has been hampered by the long-standing notion of inevitable ferroelectricity suppression under reduced dimensions. Despite recent experimental observation of stable polarized states in ferroelectric ultrathin films, the out-of-plane polarization components in these films are strongly attenuated compared to thicker films, implying a degradation of device performance in electronic miniaturization processes. Here, in a model system of BiFeO 3 /La 0.7 Sr 0.3 MnO 3 , we report observation of a dramatic out-of-plane polarization enhancement that occurs with decreasing film thickness. Our electron microscopy analysis coupled with phase-field simulations reveals a polarization-enhancement mechanism that is dominated by the accumulation of oxygen vacancies at interfacial layers. The results shed light on the interplay between polarization and defects in nanoscale ferroelectrics and suggest a route to enhance functionality in oxide devices.

Atomically thin oxychalcogenides have been attracting intensive attention for their fascinating fundamental properties and application prospects. Bi 2 O 2 Se, a representative of layered oxychalcogenides, has emerged as an air-stable high-mobility 2D semiconductor that holds great promise for next-generation electronics. The preparation and device fabrication of high-quality Bi 2 O 2 Se crystals down to a few atomic layers remains a great challenge at present. Here, molecular beam epitaxy (MBE) of atomically thin Bi 2 O 2 Se films down to monolayer on SrTiO 3 (001) substrate is achieved by co-evaporating Bi and Se precursors in oxygen atmosphere. The interfacial atomic arrangements of MBE-grown Bi 2 O 2 Se/SrTiO 3 are unambiguously revealed, showing an atomically sharp interface and atom-to-atom alignment. Importantly, the electronic band structures of one-unit-cell (1-UC) thick Bi 2 O 2 Se films are observed by angle-resolved photoemission spectroscopy (ARPES), showing low effective mass of ≈0.15 m 0 and bandgap of ≈0.8 eV. These results may be constructive to the synthesis of other 2D oxychalcogenides and investigation of novel physical properties., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

On account of unique characteristics, the integration of metal-organic frameworks as active materials in electronic devices attracts more and more attention. The film thickness, uniformity, area, and roughness are all fatal factors limiting the development of electrical and optoelectronic applications. However, research focused on ultrathin free-standing films is in its infancy. Herein, a new method, vapor-induced method, is designed to construct centimeter-sized Ni 3 (HITP) 2 films with well-controlled thickness (7, 40, and 92 nm) and conductivity (0.85, 2.23, and 22.83 S m -1 ). Further, traditional transfer methods are tactfully applied to metal-organic graphene analogue (MOGA) films. In order to maintain the integrity of films, substrates are raised up from bottom of water to hold up films. The stripping method greatly improves the surface roughness R q (root mean square roughness) without loss of conductivity and endows the film with excellent elasticity and flexibility. After 1000 buckling cycles, the conductance shows no obvious decrease. Therefore, the work may open up a new avenue for flexible electronic and magnetic devices based on MOGA., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)