In-plane charged antiphase boundary and 180° domain wall in a ferroelectric film.

The deterministic creation and modification of domain walls in ferroelectric films have attracted broad interest due to their unprecedented potential as the active element in non-volatile memory, logic computation and energy-harvesting technologies. However, the correlation between charged and antiphase states, and their hybridization into a single domain wall still remain elusive. Here we demonstrate the facile fabrication of antiphase boundaries in BiFeO3 thin films using a He-ion implantation process. Cross-sectional electron microscopy, spectroscopy and piezoresponse force measurement reveal the creation of a continuous in-plane charged antiphase boundaries around the implanted depth and a variety of atomic bonding configurations at the antiphase interface, showing the atomically sharp 180° polarization reversal across the boundary. Therefore, this work not only inspires a domain-wall fabrication strategy using He-ion implantation, which is compatible with the wafer-scale patterning, but also provides atomic-scale structural insights for its future utilization in domain-wall nanoelectronics.

Strain Tuning of Negative Capacitance in Ferroelectric KNbO3 Thin Films.

Ferroelectrics with negative capacitance effects can amplify the gate voltage in field-effect transistors to achieve low power operation beyond the limits of Boltzmann's Tyranny. The reduction of power consumption depends on the capacitance matching between the ferroelectric layer and gate dielectrics, which can be well controlled by adjusting the negative capacitance effect in ferroelectrics. However, it is a great challenge to experimentally tune the negative capacitance effect. Here, the observation of the tunable negative capacitance effect in ferroelectric KNbO3 through strain engineering is demonstrated. The magnitude of the voltage reduction and negative slope in polarization-electric field (P-E) curves as the symbol of negative capacitance effects can be controlled by imposing various epitaxial strains. The adjustment of the negative curvature region in the polarization-energy landscape under different strain states is responsible for the tunable negative capacitance. Our work paves the way for fabricating low-power devices and further reducing energy consumption in electronics.

The multi-functional system of electrochemical desalination, RhB degradation and Cr (VI) removal.

SYNOPSIS: : The single function of salt removal limits the further development of the CDI system. A multi-function CDI device is proposed to achieve electrochemical desalination, organics degradation and dichromate ion removal.

Ultrahigh Polarization Response along Large Energy Storage Properties in BiFeO3-BaTiO3-Based Relaxor Ferroelectric Ceramics under Low Electric Field.

BiFeO3-BaTiO3 (BF-BT) dielectric ceramics are receiving more and more concern for advanced energy storage devices owing to their excellent ferroelectric properties and environmental sustainability. However, the energy density and efficiency are limited in spite of the large remanent polarization. Herein, we proposed a multiscale optimization strategy via a local compositional disorder with a Birich content and nanodomain engineering by introducing the Sr0.7Bi0.2Ca0.1TiO3 (SBCT) into BF-BT ceramics. Interestingly, an extraordinary energy storage property (ESP) with a high reversible energy storage density (Wrec) of ∼3.79 J/cm3 and an ultrahigh polarization discrepancy (ΔP) of ∼58.5 µC/cm2 were obtained in the SBCT-modified BF-BT ceramics under 160 kV/cm. The boosted ESP should be attributed to the fact that the replacement of A/B-sites cations could transform the long-range ferroelectric order of the BF-BT system into polar nanoregions (PNRs) along with the refined grain size, decreased leakage current, and broadened energy band gap. Moreover, good frequency (1-103 Hz) and temperature (25-125 °C) stabilities, high fatigue resistance (× 105), large power density (∼31.1 MW/cm3), and fast discharge time (∼97 ns) were also observed for the optimized ceramics. These results illustrate a potentially effective method for creating high ESP lead-free ceramics at a low electric field.

The Preparation of High Saturation Magnetization and Low Coercivity Feco Soft Magnetic Thin Films via Controlling the Thickness and Deposition Temperature.

FeCo thin films with high saturation magnetization (4 πMs) can be applied in high-frequency electronic devices such as thin film inductors and microwave noise suppressors. However, due to its large magnetocrystalline anisotropy constant and magnetostrictive coefficient of FeCo, the coercivity (Hc) of FeCo films is generally high, which is detrimental to the soft magnetic properties. Meanwhile, the thickness and deposition temperature have significant effects on the coercivity and saturation magnetization of FeCo films. In this paper, FeCo thin films with different thicknesses were prepared by magnetron sputtering at different temperatures. The effects of thickness and deposition temperature on the microstructure and magnetic properties of FeCo thin films were systematically studied. When the film thickness increases from 50 nm to 800 nm, the coercivity would decrease from 309 Oe to 160 Oe. However, the saturation magnetization decreases from 22.1 kG to 15.3 kG. After that, we try to further increase the deposition temperature from room temperature (RT) to 475 °C. It is intriguing to find that the coercivity greatly decreased from 160 Oe to 3 Oe (decreased by 98%), and the saturation magnetization increased from 15.3 kG to 23.5 kG (increased by 53%) for the film with thickness of 800 nm. For the film with thickness of 50 nm, the coercivity also greatly decreased from 309 Oe to 10 Oe (decreased by 96%), but the saturation magnetization did not change significantly. It is contributed to the increase of deposition temperature, which will lead to the increase of grain size and the decrease of the number of grain boundaries. And the coercivity decreases as the number of grain boundaries decreases. Meanwhile, for the thicker films, when increasing the deposition temperature the thermal stress increases, which changes the appearance of (200) texture, and the saturation magnetization increases. Whereas, it has a negligible effect on the orientation of thin films with small thickness (50 nm). This indicates that high-temperature deposition is beneficial to the soft magnetic properties of FeCo thin films, particularly for the films with larger thickness. This FeCo thin film with high saturation magnetization and low coercivity could be an ideal candidate for high-frequency electronic devices.

Ferroelectric photosensor network: an advanced hardware solution to real-time machine vision.

Nowadays the development of machine vision is oriented toward real-time applications such as autonomous driving. This demands a hardware solution with low latency, high energy efficiency, and good reliability. Here, we demonstrate a robust and self-powered in-sensor computing paradigm with a ferroelectric photosensor network (FE-PS-NET). The FE-PS-NET, constituted by ferroelectric photosensors (FE-PSs) with tunable photoresponsivities, is capable of simultaneously capturing and processing images. In each FE-PS, self-powered photovoltaic responses, modulated by remanent polarization of an epitaxial ferroelectric Pb(Zr0.2Ti0.8)O3 layer, show not only multiple nonvolatile levels but also sign reversibility, enabling the representation of a signed weight in a single device and hence reducing the hardware overhead for network construction. With multiple FE-PSs wired together, the FE-PS-NET acts on its own as an artificial neural network. In situ multiply-accumulate operation between an input image and a stored photoresponsivity matrix is demonstrated in the FE-PS-NET. Moreover, the FE-PS-NET is faultlessly competent for real-time image processing functionalities, including binary classification between 'X' and 'T' patterns with 100% accuracy and edge detection for an arrow sign with an F-Measure of 1 (under 365 nm ultraviolet light). This study highlights the great potential of ferroelectric photovoltaics as the hardware basis of real-time machine vision.

Nonvolatile Ferroelectric-Domain-Wall Memory Embedded in a Complex Topological Domain Structure.

The discovery and precise manipulation of atomic-size conductive ferroelectric domain walls offers new opportunities for a wide range of prospective electronic devices, and the emerging field of walltronics. Herein, a highly stable and fatigue-resistant nonvolatile memory device is demonstrated, which is based on deterministic creation and erasure of conductive domain walls that are geometrically confined in a topological domain structure. By introducing a pair of delicately designed coaxial electrodes onto the epitaxial BiFeO3  film, a center-type quadrant topological domain with conductive charged domain walls can be easily created. More importantly, reversible switching of the quadrant domain between the convergent state with highly conductive confined walls and the divergent state with insulating confined walls can be realized, resulting in an apparent resistance change with a large on/off ratio of >104  and a technically preferred readout current (up to 40 nA). Owing to restrictions from the clamped quadrant ferroelastic domain, the device exhibits excellent restoration repeatability over 108  cycles and a long retention of over 12 days (>106  s). These results provide a new pathway toward high-performance ferroelectric-domain-wall memory, which may spur extensive interest in exploring the immense potential in the emerging field of walltronics.

Breaking the Fundamental Limitations of Nanoscale Ferroelectric Characterization: Non-Contact Heterodyne Electrostrain Force Microscopy.

Perceiving nanoscale ferroelectric phenomena from real space is of great importance for elucidating underlying ferroelectric physics. During the past decades, nanoscale ferroelectric characterization has mainly relied on the Piezoresponse Force Microscopy (PFM) invented in 1992, however, the fundamental limitations of PFM have made the nanoscale ferroelectric studies encounter significant bottlenecks. In this study, a high-resolution non-contact ferroelectric measurement, named Non-Contact Heterodyne Electrostrain Force Microscopy (NC-HEsFM), is introduced. It is demonstrated that NC-HEsFM can operate on multiple eigenmodes to perform ideal high-resolution ferroelectric domain mapping, standard ferroelectric hysteresis loop measurement, and controllable domain manipulation. By using a quartz tuning fork (QTF) sensor, multi-frequency operation, and heterodyne detection schemes, NC-HEsFM achieves a real non-contact yet non-destructive ferroelectric characterization with negligible electrostatic force effect and hence breaks the fundamental limitations of the conventional PFM. It is believed that NC-HEsFM can be extensively used in various ferroelectric or piezoelectric studies with providing substantially improved characterization performance. Meanwhile, the QTF-based force detection makes NC-HEsFM highly compatible for high-vacuum and low-temperature environments, providing ideal conditions for investigating the intrinsic ferroelectric phenomena with the possibility of achieving an atomically resolved ferroelectric characterization.

Boosting Polarization Switching-Induced Current Injection by Mechanical Force in Ferroelectric Thin Films.

When scaling the lateral size of a ferroelectric random access memory (FeRAM) device down to the nanometer range, the polarization switching-induced displacement current becomes small and challenging to detect, which greatly limits the storage density of FeRAM. Here, we report the observation of significantly enhanced injection currents, much larger than typical switching currents, induced by polarization switching in BiFeO3 thin films via conductive atomic force microscopy. Interestingly, this injected current can be effectively modulated by applying mechanical force. As the loading force increases from ∼50 to ∼750 nN, the magnitude of the injected current increases and the critical voltage to trigger the current injection decreases. Notably, changing the loading force by an order of magnitude increases the peak current by 2-3 orders of magnitude. The mechanically boosted injected current could be useful for the development of high-density FeRAM devices. The mechanical modulation of the injected current may be attributed to the mechanical force-induced changes in the barrier height and interfacial layer width.

Enhancement of ferroelectricity and homogeneity of orthorhombic phase in Hf0.5Zr0.5O2thin films.

By adoption of a high permittivity ZrO2capping layer (ZOCL), enhanced ferroelectric properties were achieved in the Hf0.5Zr0.5O2(HZO) thin films. For HZO thin film with 10 Å ZOCL, the 2Prvalue can reach as high as ∼43.1µC cm-2under a sweep electric field of 3 MV cm-1. In addition, a reduced coercive field of 1.5 MV cm-1was observed, which is comparable to that of HZO with metallic CL. Furthermore, the homogeneity of ferroelectric orthorhombic phase in HZO films was observed to be clearly increased, as evidenced by nanoscale piezoelectric force microscopy measurements. These results demonstrate that ZOCL is very favorable for high performance ferroelectric HZO films and their future device applications.

Quasi-one-dimensional metallic conduction channels in exotic ferroelectric topological defects.

Ferroelectric topological objects provide a fertile ground for exploring emerging physical properties that could potentially be utilized in future nanoelectronic devices. Here, we demonstrate quasi-one-dimensional metallic high conduction channels associated with the topological cores of quadrant vortex domain and center domain (monopole-like) states confined in high quality BiFeO3 nanoislands, abbreviated as the vortex core and the center core. We unveil via the phase-field simulation that the superfine metallic conduction channels along the center cores arise from the screening charge carriers confined at the core region, whereas the high conductance of vortex cores results from a field-induced twisted state. These conducting channels can be reversibly created and deleted by manipulating the two topological states via electric field, leading to an apparent electroresistance effect with an on/off ratio higher than 103. These results open up the possibility of utilizing these functional one-dimensional topological objects in high-density nanoelectronic devices, e.g. nonvolatile memory.

Enhanced Ferroelectric Properties and Insulator-Metal Transition-Induced Shift of Polarization-Voltage Hysteresis Loop in VOx-Capped Hf0.5Zr0.5O2 Thin Films.

A capping layer is known to be critical for stabilizing the ferroelectric (FE) orthorhombic phase (o-phase) in a HfO2-based thin film. Here, vanadium oxide (VOx), a functional oxide exhibiting the insulator-metal transition, is used as a novel type of a capping layer for the Hf0.5Zr0.5O2 (HZO) thin film. It is demonstrated that the VOx capping layer (VCL) can enhance the FE properties of the HZO thin film comprehensively. Specifically, the HZO thin film with a VCL shows large remanent polarization (2Pr ≈36.9 µC/cm2), relatively small coercive field (Ec ≈1.09 MV/cm), high endurance (up to 109 cycles), and long retention (>105 seconds). The enhanced FE properties may be attributed to the VCL-induced stabilization of the FE o-phase and suppression of oxygen vacancies at the interface. Furthermore, the HZO thin film with a VCL exhibits a successive rightward shift of polarization-voltage (P-V) hysteresis loop as the temperature increases. This is well correlated with the insulator-metal transition in a VCL, which can modulate the interfacial built-in field and thus cause the P-V loop shift. It is therefore demonstrated that a VCL not only enhances the FE properties of HZO thin films but also provides a temperature degree of freedom to modulate the FE properties, which may open up a new pathway to develop HfO2-based FE memories with high performance and novel functionalities.

Discovery of a Silicon-Containing Pan-Genotype Hepatitis C Virus NS5A Inhibitor.

We describe a study leading to the discovery of compound 11, a pan-genotypic hepatitis C virus (HCV) nonstructural protein 5A (NS5A) inhibitor with excellent potency, metabolic stability, and pharmacokinetics (PK). Compound 11 incorporating a 4-silapiperidine group was discovered by further optimizing our previous lead with a triethylsilyl moiety. It displayed great potency against genotype 1 subtype a (GT1a), -1b, -2a, -3a, -4a, -5a, and -6a with an EC50 range of 0.33-17 pM and improved potency against the resistance-associated variant GT1a_M28T. Pharmacokinetics (PK) study indicated that compound 11 has reasonable PK exposures with a high liver distribution in preclinical animal species (mouse, rat, and dog). The results of a 14 day repeat-dose toxicity study identified the safety of compound 11.

Large-scale multiferroic complex oxide epitaxy with magnetically switched polarization enabled by solution processing.

Complex oxides with tunable structures have many fascinating properties, though high-quality complex oxide epitaxy with precisely controlled composition is still out of reach. Here we have successfully developed solution-based single-crystalline epitaxy for multiferroic (1-x)BiTi(1-y)/2Fe y Mg(1-y)/2O3-(x)CaTiO3 (BTFM-CTO) solid solution in large area, confirming its ferroelectricity at the atomic scale with strong spontaneous polarization. Careful compositional tuning leads to a bulk magnetization of 0.07 ± 0.035 µB/Fe at room temperature, enabling magnetically induced polarization switching exhibiting a large magnetoelectric coefficient of 2.7-3.0 × 10-7 s/m. This work demonstrates the great potential of solution processing in large-scale complex oxide epitaxy and establishes novel room-temperature magnetoelectric coupling in epitaxial BTFM-CTO film, making it possible to explore a much wider space of composition, phase, and structure that can be easily scaled up for industrial applications.

Alkyl and aromatic nitrates in atmospheric particles determined by gas chromatography tandem mass spectrometry.

Organic nitrates in the atmosphere are associated with photochemical pollution and are the main components of secondary organic aerosols, which are related to haze. An efficient method for determining organic nitrates in atmospheric fine particles (PM2.5) was established using synthesized standards. Four alkyl (C7-C10) nitrates and three aromatic nitrates (tolyl nitrate, phenethyl nitrate, and p-xylyl nitrate) were synthesized and characterized by 1H and 13C nuclear magnetic resonance spectroscopy. The optimal ions for quantifying and confirming the identities of the analytes were identified by analyzing the standards by gas chromatography tandem mass spectrometry. The tandem mass spectrometer was a triple quadrupole instrument. This method can obtain more accurate information of organic nitrates than on-line methods. Spiked recovery tests were performed using three spike concentrations, and the recoveries were 61.0-111.4 %, and the relative standard deviations were < 8.2% for all of the analytes. Limits of detection and quantification were determined, and the linearity of the method for each analyte was assessed. The applicability of the method was demonstrated by analyzing six PM2.5 samples. Overall, 87% of the analytes were detected in the samples. Phenethyl nitrate, heptyl nitrate, and octyl nitrate were detected in every sample. Phenethyl nitrate was found at a higher mean concentration (3.23 ng/m3) than the other analytes.

All-Inorganic Flexible Ba0.67Sr0.33TiO3 Thin Films with Excellent Dielectric Properties over a Wide Range of Frequencies.

With rapid advances in flexible electronics and communication devices, flexible dielectric capacitors exhibiting high permittivity, low loss, and large electric-field tunability over a wide frequency range have attracted increasing attention. Here, a large-scale Ba0.67Sr0.33TiO3 (BST) dielectric thin film sandwiched between SrRuO3 (SRO) bottom electrode and Pt top electrode is fabricated on a flexible mica substrate. The mica/SRO/BST/Pt capacitor exhibits a dielectric constant (εr') of more than 1200, a loss tangent [tan(δ)] as low as 0.16, and a tunability of 67% at low frequencies around 10 kHz. Simultaneously, the capacitor can retain an εr' of 540 and a tan(δ) of 0.07 at microwave frequencies, e.g., 18.6 GHz. Moreover, even when the capacitor is bent to a small radius of 5 mm or undergoes 12 000 bending cycles (at 5 mm radius), almost no deterioration in εr', tan(δ), and tunability is observed. The excellent dielectricity and mechanical flexibility and durability endow the mica/SRO/BST/Pt capacitor with huge potential for flexible electronic and microwave applications.

Controllable defect driven symmetry change and domain structure evolution in BiFeO3 with enhanced tetragonality.

Defect engineering has been a powerful tool to enable the creation of exotic phases and the discovery of intriguing phenomena in ferroelectric oxides. However, the accurate control of the concentration of defects remains a big challenge. In this work, ion implantation, which can provide controllable point defects, allows us to produce a controlled defect driven true super-tetragonal (T) phase with a single-domain-state in ferroelectric BiFeO3 thin films. This point-defect engineering is found to drive the phase transition from the as-grown mixed rhombohedral-like (R) and tetragonal-like (MC) phase to true tetragonal (T) symmetry and induce the stripe multi-nanodomains to a single domain state. By further increasing the injected dose of the He ion, we demonstrate an enhanced tetragonality super-tetragonal (super-T) phase with the largest c/a ratio of ∼1.3 that has ever been experimentally achieved in BiFeO3. A combination of the morphology change and domain evolution further confirms that the mixed R/MC phase structure transforms to the single-domain-state true tetragonal phase. Moreover, the re-emergence of the R phase and in-plane nanoscale multi-domains after heat treatment reveal the memory effect and reversible phase transition and domain evolution. Our findings demonstrate the reversible control of R-Mc-T-super T symmetry changes (leading to the creation of true T phase BiFeO3 with enhanced tetragonality) and multidomain-single domain structure evolution through controllable defect engineering. This work also provides a pathway to generate large tetragonality (or c/a ratio) that could be extended to other ferroelectric material systems (such as PbTiO3, BaTiO3 and HfO2) which might lead to strong polarization enhancement.

Electric field driven multi-state magnetization switching in triangular nanomagnets on piezoelectric substrate.

Electric field control of magnetic state switching mediated by magneto-elastic coupling in multiferroic heterostructures consisting of shape anisotropic magnetostrictive nanomagnets elastically coupled with a piezoelectric substrate has a promising potential for next generation magneto-elastic memory and logic devices. In this work, by using micromagnetic simulation, we showed that localized strain-induced magnetic anisotropy caused by the electric field-induced piezostrain combined with strong multifold shape anisotropy effect can be used for achieving a multistate switching of magnetization in a triangular soft magnetic nano-island on a piezoelectric substrate. A piezostrain-induced uniaxial magnetic anisotropy pulse applied in specific directions switches the magnetization within the triangular nanomagnet by an angle of 60° from the initial state. The relation between critical magnitude of the strain pulse for the switching of the magnetization states and geometric parameters (thickness and lateral size) within the triangular nanomagnets has been worked out. Complete cycles of clockwise as well as counter-clockwise switching of the magnetization states of the triangular nanomagnet have been achieved by a series of sequential switching with different directions of applied strain-induced magnetic anisotropy. This local gating scheme-based multistate switching can be used for electric field-induced ultra-fast, deterministic and reversible magnetization switching which are the key challenges in designing of the magnetoelastic and/or magnetoelectric memory and logic devices.

Topological domain states and magnetoelectric properties in multiferroic nanostructures.

Multiferroic nanostructures have been attracting tremendous attention over the past decade, due to their rich cross-coupling effects and prospective electronic applications. In particular, the emergence of some exotic phenomena in size-confined multiferroic systems, including topological domain states such as vortices, center domains, and skyrmion bubble domains, has opened a new avenue to a number of intriguing physical properties and functionalities, and thus underpins a wide range of applications in future nanoelectronic devices. It is also highly appreciated that nano-domain engineering provides a pathway to control the magnetoelectric properties, which is promising for future energy-efficient spintronic devices. In recent years, this field, still in its infancy, has witnessed a rapid development and a number of challenges too. In this article, we shall review the recent advances in the emergent domain-related exotic phenomena in multiferroic nanostructures. Specific attention is paid to the topological domain structures and related novel physical behaviors as well as the electric-field-driven magnetic switching via domain engineering. This review will end with a discussion of future challenges and potential directions.

Defect-Induced Exchange Bias in a Single SrRuO3 Layer.

Exchange bias stems from the interaction between different magnetic phases, and therefore, it generally occurs in magnetic multilayers. Here, we present a large exchange bias in a single SrRuO3 layer induced by helium ion irradiation. When the fluence increases, the induced defects not only suppress the magnetization and the Curie temperature but also drive a metal-insulator transition at a low temperature. In particular, a large exchange bias field up to ∼0.36 T can be created by the irradiation. This large exchange bias is related to the coexistence of different magnetic and structural phases that are introduced by embedded defects. Our work demonstrates that spintronic properties in complex oxides can be created and enhanced by applying ion irradiation.