The contradiction between thermodynamic and kinetic effects of stress-modulated antiferroelectricity in ZrO2 thin films.

The discovery of antiferroelectricity in fluorite-structured binary oxides has opened up promising directions for next-generation electronic devices due to their excellent scalability and compatibility with silicon technology. However, understanding and improving the antiferroelectricity remain ambiguous and present considerable challenges for device applications. In this work, we discover a contradiction between the thermodynamic and kinetic effects of stress-modulated antiferroelectricity in ZrO2 thin films. On the one hand, we observe a monotonically enhanced antiferroelectricity in a ZrO2 thin film grown on the bottom electrode with a reduced coefficient of thermal expansion, i.e., ranging from Ni to TiN and W. The combined experimental characterizations and first-principle calculations show that the out-of-plane compressive stress induced by the electrode promotes the formation of the tetragonal phase, producing enhanced antiferroelectricity. On the other hand, the out-of-plane compressive stress increases the energy barrier between the tetragonal and polar orthorhombic phases, hindering the reversible phase transition between them. As a result, the antiferroelectricity of the samples annealed with top electrodes is worse compared to those without top electrodes. Our findings not only deepen the understanding of antiferroelectricity in ZrO2 thin films but also provide a strategy for improvement.

New-Style Logic Operation and Neuromorphic Computing Enabled by Optoelectronic Artificial Synapses in an MXene/Y:HfO2 Ferroelectric Memristor.

Today's computing systems, to meet the enormous demands of information processing, have driven the development of brain-inspired neuromorphic systems. However, there are relatively few optoelectronic devices in most brain-inspired neuromorphic systems that can simultaneously regulate the conductivity through both optical and electrical signals. In this work, the Au/MXene/Y:HfO2/FTO ferroelectric memristor as an optoelectronic artificial synaptic device exhibited both digital and analog resistance switching (RS) behaviors under different voltages with a good switching ratio (>103). Under optoelectronic conditions, optimal weight update parameters and an enhanced algorithm achieved 97.1% recognition accuracy in convolutional neural networks. A new logic gate circuit specifically designed for optoelectronic inputs was established. Furthermore, the device integrates the impact of relative humidity to develop an innovative three-person voting mechanism with a veto power. These results provide a feasible approach for integrating optoelectronic artificial synapses with logic-based computing devices.

A vision chip with complementary pathways for open-world sensing.

Image sensors face substantial challenges when dealing with dynamic, diverse and unpredictable scenes in open-world applications. However, the development of image sensors towards high speed, high resolution, large dynamic range and high precision is limited by power and bandwidth. Here we present a complementary sensing paradigm inspired by the human visual system that involves parsing visual information into primitive-based representations and assembling these primitives to form two complementary vision pathways: a cognition-oriented pathway for accurate cognition and an action-oriented pathway for rapid response. To realize this paradigm, a vision chip called Tianmouc is developed, incorporating a hybrid pixel array and a parallel-and-heterogeneous readout architecture. Leveraging the characteristics of the complementary vision pathway, Tianmouc achieves high-speed sensing of up to 10,000 fps, a dynamic range of 130 dB and an advanced figure of merit in terms of spatial resolution, speed and dynamic range. Furthermore, it adaptively reduces bandwidth by 90%. We demonstrate the integration of a Tianmouc chip into an autonomous driving system, showcasing its abilities to enable accurate, fast and robust perception, even in challenging corner cases on open roads. The primitive-based complementary sensing paradigm helps in overcoming fundamental limitations in developing vision systems for diverse open-world applications.

Superatomic Aromaticity in Cyclic Superatomic Molecules: Ligand-Protected Penta-Icosahedral [M@Au11]5 (M = Au, Pt) Clusters.

Pure or doped gold icosahedra, which can be generally viewed as superatoms, are promising candidates for cluster-assembled structures. As the first large-scale ring-like gold cluster, the report of [Au60Se2(Ph3P)10(SeR)15]+ has arisen much interest, where its Au60 core is composed of five vertex-sharing gold icosahedra in a cyclic way. From electronic characters, this Au60 core is a 40e cyclic penta-superatom network formed by five 8e closed-shell superatoms (S2P6). When more valence electrons are introduced into the penta-superatom network by atomic doping, global delocalized bonds are induced in its bonding framework. In the 42e Au60 core of the [Au60Se2Cl15]- cluster, two extra electrons occupy one delocalized π-bonding orbital formed by super D orbitals of five superatoms, resulting in superatomic π aromaticity. In the 46e [Pt@Au11]5 core of [(Pt@Au11)5Ga2Cl15] cluster, three delocalized super-π bonds are formed, which are organized in the similar way as the aromatic C5H5- molecule. The unveiling of superatomic aromaticity promotes our understanding of the stability of cyclic superatom assemblies and extends the family of superatomic bonding patterns.

Neuromorphic Computing of Optoelectronic Artificial BFCO/AZO Heterostructure Memristors Synapses.

Compared with purely electrical neuromorphic devices, those stimulated by optical signals have gained increasing attention due to their realistic sensory simulation. In this work, an optoelectronic neuromorphic device based on a photoelectric memristor with a Bi2FeCrO6/Al-doped ZnO (BFCO/AZO) heterostructure is fabricated that can respond to both electrical and optical signals and successfully simulate a variety of synaptic behaviors, such as STP, LTP, and PPF. In addition, the photomemory mechanism was identified by analyzing the energy band structures of AZO and BFCO. A convolutional neural network (CNN) architecture for pattern classification at the Mixed National Institute of Standards and Technology (MNIST) was used and improved the recognition accuracy of the MNIST and Fashion-MNIST datasets to 95.21% and 74.19%, respectively, by implementing an improved stochastic adaptive algorithm. These results provide a feasible approach for future implementation of optoelectronic synapses.

An adjustable multistage resistance switching behavior of a photoelectric artificial synaptic device with a ferroelectric diode effect for neuromorphic computing.

Neuromorphic computing, which mimics biological neural networks, is widely regarded as the optimal solution for addressing the limitations of traditional von Neumann computing architecture. In this work, an adjustable multistage resistance switching ferroelectric Bi2FeCrO6 diode artificial synaptic device was fabricated using a sol-gel method with a simple process. The device exhibits nonlinearity in its electrical characteristics, demonstrating tunable multistage resistance switching behavior and a strong ferroelectric diode effect through the manipulation of ferroelectric polarization. One of its salient advantages resides in its capacity to dynamically regulate its polarization state in response to an external electric field, thereby facilitating the fine-tuning of synaptic connection strength while maintaining synaptic stability. The device is capable of accurately simulating the fundamental properties of biological synapses, including long/short-term plasticity, paired-pulse facilitation, and spike-timing-dependent plasticity. Additionally, the device exhibits a distinctive photoelectric response and is capable of inducing synaptic plasticity by light signal activation. The utilization of a femtosecond laser for the scrutiny of carrier transport mechanisms imparts profound insights into the intricate dynamics governing the optical memory effect. Furthermore, utilizing a convolutional neural network (CNN) architecture, the recognition accuracy of the MNIST and fashion MNIST datasets was improved to 95.6% and 78%, respectively, through the implementation of improved random adaptive algorithms. These findings present a new opportunity for utilizing Bi2FeCrO6 materials in the development of artificial synapses for neuromorphic computation.

Unconventional Polarization-Switching Mechanism in (Hf, Zr)O_{2} Ferroelectrics and Its Implications.

HfO_{2}-based ferroelectric thin films are promising for their application in ferroelectric devices. Predicting the ultimate magnitude of polarization and understanding its switching mechanism are critical to realize the optimal performance of these devices. Here, a generalized solid-state variable cell nudged elastic band method is employed to predict the switching pathway associated with domain-wall motion in (Hf,Zr)O_{2} ferroelectrics. It is found that the polarization reversal pathway, where threefold coordinated O atoms pass across the nominal unit-cell boundaries defined by the Hf/Zr atomic planes, is energetically more favorable than the conventional pathway where the O atoms do not pass through these planes. This finding implies that the polarization orientation in the orthorhombic Pca2_{1} phase of HfO_{2} and its derivatives is opposite to that normally assumed, predicts the spontaneous polarization magnitude of about 70 µC/cm^{2} that is nearly 50% larger than the commonly accepted value, signifies a positive intrinsic longitudinal piezoelectric coefficient, and suggests growth of ferroelectric domains, in response to an applied electric field, structurally reversed to those usually anticipated. These results provide important insights into the understanding of ferroelectricity in HfO_{2}-based ferroelectrics.

HfO2-based ferroelectric thin film and memory device applications in the post-Moore era: A review.

The rapid development of 5G, big data, and Internet of Things (IoT) technologies is urgently required for novel non-volatile memory devices with low power consumption, fast read/write speed, and high reliability, which are crucial for high-performance computing. Ferroelectric memory has undergone extensive investigation as a viable alternative for commercial applications since the post-Moore era. However, conventional perovskite-structure ferroelectrics (e.g., PbZr x Ti1- x O3) encounter severe limitations for high-density integration owing to the size effect of ferroelectricity and incompatibility with complementary metal-oxide-semiconductor technology. Since 2011, the ferroelectric field has been primarily focused on HfO2-based ferroelectric thin films owing to their exceptional scalability. Several reviews discussing the control of ferroelectricity and device applications exist. It is believed that a comprehensive understanding of mechanisms based on industrial requirements and concerns is necessary, such as the wake-up effect and fatigue mechanism. These mechanisms reflect the atomic structures of the materials as well as the device physics. Herein, a review focusing on phase stability and domain structure is presented. In addition, the recent progress in related ferroelectric memory devices and their challenges is briefly discussed.

Robustly Stable Ferroelectric Polarization States Enable Long-Term Nonvolatile Storage against Radiation in HfO2-Based Ferroelectric Field-Effect Transistors.

The ferroelectric field-effect transistors (FeFETs) with HfO2-based ferroelectric layers in the gate stacks are emerging as one of the most promising candidates for the next-generation nonvolatile memory devices due to their scalability and compatibility with conventional Si technology. Moreover, owing to the high radiation hardness of the HfO2-based ferroelectric thin films, HfO2-based FeFETs have attracted great interest in the fields of radiation-hard (rad-hard) memory. However, the reliability of their memory states under irradiation, which represents the validity of the stored information, has not been investigated. Here, we focus on the impact of the total ionizing dose (TID) on erased and programmed states of HfO2-based FeFETs. The TID radiation (X-ray) characteristics of erased and programmed HfO2-based FeFETs are characterized using an on-site read operation. Both the erased and programmed states show robust stability under irradiation at a dose rate of 90 rad(Si)/s, and even at 230 rad(Si)/s, only the erased state shows a slight variation. The possible factors contributing to memory state degradation are discussed. Through the analysis of the threshold voltage shift and subthreshold swing evolution, as well as studies of ferroelectric polarization stability under radiation, it is revealed that the erased state degradation is caused by oxide-trapped charges rather than interface degradation or polarization switching. The physical mechanism of the difference in radiation-induced oxide-trapped charges buildup in programmed and erased FeFETs is analyzed to explain different TID radiation characteristics between them. Our work suggests that the HfO2-based FeFETs have great potential in radiation environment applications.

MiR-328-5p inhibits the adipogenic differentiation of hMSCs by targeting fatty acid synthase.

INTRODUCTION: Adipogenesis, a highly coordinated process regulated by numerous effectors, is largely responsible for the quantity and size of adipocytes. Attenuation of adipocyte differentiation has been proposed as a viable technique for reducing obesity and its associated diseases. MicroRNAs play an important role in human bone marrow mesenchymal stem cells (hMSCs) adipogenic differentiation. However, there is a lack of clarity regarding the role of miR-328-5p in adipogenesis. MATERIAL AND METHODS: Using the lentiviral vectors to overexpress fatty acid synthase (FASN) and miR-328-5p, RT-qPCR and Western blotting were carried out to assess RNA expression and protein levels of FASN and adipogenic marker factors. Meanwhile, Oil red O staining and lipid quantification was performed to evaluate the accumulation of intracellular lipid droplets. Additionally, the validity of FASN as a potential target gene for miR-328-5p was carried out using a luciferase reporter assay. RESULTS: Our data showed that hMSCs adipogenic differentiation was associaed with the reduced miR-328-5p expression, while an elevated expression of the underlined miRNA attenuated adipogenesis and the expression of adipogenic marker genes. Luciferase reporter assay validated FASN as a target gene of miR-328-5p, and an elevated FASN expression reversed the anti-adipogenic effects of miR-328-5p. CONCLUSIONS: The results revealed that miR-328-5p inhibits hMSCs adipogenic differentiation by targeting FASN. These findings contribute to our understanding of obesity-related disease development.

Sodium Cationization Enables Exotic Deprotonation Sites on Gaseous Mononucleotides.

We report observation and photoelectron spectroscopic characterization of sodium cationization on four doubly deprotonated mononucleotide dianions Na+·[dNMP-2H]2- (N = A, G, C, or T) in the gas phase. Multiple tautomers with distinct deprotonated sites are identified, in which Na+ enables novel double deprotonation patterns and folds the resultant mononucleotide dianions. The most stable isomer for the whole family is derived from detaching one proton from the phosphate and the other from the nucleobase (amino group for N = A, G, and C, but nitrogen atom for T), whereas high-lying isomers with protons detached separately from the phosphate and the hydroxy group of sugar coexist. Particularly, an exotic deprotomer with both protons deprived from guanosine is populated as well. This work thus displays a remarkably diverse binding landscape enabled by sodium cationization, a potentially critical element in developing a general formulism to better model metal cation and nucleotide interactions.

Conserved signalling components coordinate epidermal patterning and cuticle deposition in barley.

Faced with terrestrial threats, land plants seal their aerial surfaces with a lipid-rich cuticle. To breathe, plants interrupt their cuticles with adjustable epidermal pores, called stomata, that regulate gas exchange, and develop other specialised epidermal cells such as defensive hairs. Mechanisms coordinating epidermal features remain poorly understood. Addressing this, we studied two loci whose allelic variation causes both cuticular wax-deficiency and misarranged stomata in barley, identifying the underlying genes, Cer-g/ HvYDA1, encoding a YODA-like (YDA) MAPKKK, and Cer-s/ HvBRX-Solo, encoding a single BREVIS-RADIX (BRX) domain protein. Both genes control cuticular integrity, the spacing and identity of epidermal cells, and barley's distinctive epicuticular wax blooms, as well as stomatal patterning in elevated CO2 conditions. Genetic analyses revealed epistatic and modifying relationships between HvYDA1 and HvBRX-Solo, intimating that their products participate in interacting pathway(s) linking epidermal patterning with cuticular properties in barley. This may represent a mechanism for coordinating multiple adaptive features of the land plant epidermis in a cultivated cereal.

Superatomic Three-Center Bond in a Tri-Icosahedral Au36Ag2(SR)18 Cluster: Analogue of 3c-2e Bond in Molecules.

Probing the nature of electronic stability for ligand-protected gold clusters is important in gold chemistry. A thermally stable Au36Ag2(SR)18 nanocluster was synthesized recently. It has a D3h tri-icosahedral [Au30Ag2]12+ core with 20 valence electrons, which does not follow the magic number of gold superatoms. Herein, we propose a superatomic three-center bond to unveil its electronic stability. The [Au30Ag2]12+ core is viewed as a union of three face-fused superatoms, and chemical bonding analysis suggests a three-superatom-center two-electron (3sc-2e) bond for the octet rule of each superatom, which mimics the bonding framework of the D3h O32- molecule. Moreover, a liganded tri-icosahedral [Au27Pt3Ag2]11+ core with 18 valence electrons is predicted, and three 2sc-2e bonds are formed between each of two superatoms to satisfy the octet rule (analogue of D3h O3), indicating the flexibility of superatomic bonding. Such a superatomic three-center bond extends the community of superatomic bonding and gives a new perspective for superatom assembling.

Tri- and Tetra-superatomic Molecules in Ligand-Protected Face-Fused Icosahedral (M@Au12)n (M = Au, Pt, Ir, and Os, and n = 3 and 4) Clusters.

Cluster assembling has been one of the hottest topics in nanochemistry. In certain ligand-protected gold clusters, bi-icosahedral cores assembled from Au13 superatoms were found to be analogues of diatomic molecules F2, N2, and singlet O2, respectively, in electronic shells, depending upon the super valence bond (SVB) model. However, challenges still remain for extending the scale in cluster assembling via the SVB model. In this work, ligand-protected tri- and tetra-superatomic clusters composed of icosahedral M@Au12 (M = Au, Pt, Ir, and Os) units are theoretically predicted. These clusters are stable with reasonable highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps and proven to be analogues of simple triatomic (Cl3-, OCl2, O3, and CO2) and tetra-atomic (N≡C-C≡N, and Cl-C≡C-Cl) molecules in both geometric and electronic structures. Moreover, a stable cluster-assembling gold nanowire is predicted following the same rules. This work provides effective electronic rules for cluster assembling on a larger scale and gives references for their experimental synthesis.

Enhancement of Resistive Switching Performance in Hafnium Oxide (HfO2) Devices via Sol-Gel Method Stacking Tri-Layer HfO2/Al-ZnO/HfO2 Structures.

Resistive random-access memory (RRAM) is a promising candidate for next-generation non-volatile memory. However, due to the random formation and rupture of conductive filaments, RRMS still has disadvantages, such as small storage windows and poor stability. Therefore, the performance of RRAM can be improved by optimizing the formation and rupture of conductive filaments. In this study, a hafnium oxide-/aluminum-doped zinc oxide/hafnium oxide (HfO2/Al-ZnO/HfO2) tri-layer structure device was prepared using the sol-gel method. The oxygen-rich vacancy Al-ZnO layer was inserted into the HfO2 layers. The device had excellent RS properties, such as an excellent switch ratio of 104, retention of 104 s, and multi-level storage capability of six resistance states (one low-resistance state and five high-resistance states) and four resistance states (three low-resistance states and one high-resistance state) which were obtained by controlling stop voltage and compliance current, respectively. Mechanism analysis revealed that the device is dominated by ohmic conduction and space-charge-limited current (SCLC). We believe that the oxygen-rich vacancy concentration of the Al-ZnO insertion layer can improve the formation and rupture behaviors of conductive filaments, thereby enhancing the resistive switching (RS) performance of the device.

Multiple d-d bonds between early transition metals in TM2Lin (TM = Sc, Ti) superatomic molecule clusters.

The synthesis and application of compounds with Cr-Cr and V-V d-d quintuple bonds (σ, 2π, 2δ) have led to new thinking about whether d-d multiple bonds also exist between early transition metals such as Sc-Sc and Ti-Ti. In this study, by extensive unbiased global search at the density functional theory level, the low-energy structures of 26e and 30e TM2Lin clusters were obtained. Based on the super valence bond (SVB) theory, the prolate double-core structure of TM2Lin clusters was regarded as a superatomic molecule, of which each half was regarded as an open-shell superatom, and the electronic shell-closure was realized by forming multiple bonds between superatoms. Then, the quintuple super bonds (2δ, 2π, σ) of the Li18Ti2, Li20Sc2, [Li17V2]+, [Li17Ti2]- clusters and the triple super bonds (2π, σ) of the Li24Sc2 and Li24Y2 clusters were confirmed via chemical-bonding analysis. This way of forming multiple bonds between early transition metals through superatomic bonding has promoted the experimental synthesis and application of early transition metal multiple bond compounds.

Subunit cell-level measurement of polarization in an individual polar vortex.

Recently, several captivating topological structures of electric dipole moments (e.g., vortex, flux closure) have been reported in ferroelectrics with reduced size/dimensions. However, accurate polarization distribution of these topological ferroelectric structures has never been experimentally obtained. We precisely measure the polarization distribution of an individual ferroelectric vortex in PbTiO3/SrTiO3 superlattices at the subunit cell level by using the atomically resolved integrated differential phase contrast imaging in an aberration-corrected scanning transmission electron microscope. We find, in vortices, that out-of-plane polarization is larger than in-plane polarization, and that downward polarization is larger than upward polarization. The polarization magnitude is closely related to tetragonality. Moreover, the contribution of the Pb─O bond to total polarization is highly inhomogeneous in vortices. Our precise measurement at the subunit cell scale provides a sound foundation for mechanistic understanding of the structure and properties of a ferroelectric vortex and lattice-charge coupling phenomena in these topological ferroelectric structures.

Enhanced electromagnon excitations in Nd-doped BiFeO3 nanoparticles near morphotropic phase boundaries.

In multiferroics, electromagnons have been recognized as a noticeable topic due to their indispensable role in magnetoelectric, magnetodielectric, and magnetocapacitance effects. Here, the electromagnons of Bi1-xNdxFeO3 (x = 0-0.2) nanoparticles are studied via terahertz time-domain spectroscopy, and the impacts of doping concentrations on electromagnons have been discussed. We found that the electromagnons in Bi1-xNdxFeO3 nanoparticles are associated with their phase transition. The total coupling weight of electromagnons is gradually increased in polar R3c structures and then reduces in the antipolar Pbam phase, and the weight in the antipolar phase is less than that of the pure R3c phase. Interestingly, a colossal electromagnon is observed at polar-antipolar and antiferromagnetic-ferromagnetic phase boundaries. Our work offers an avenue for designing and choosing materials with better magnetodielectric and magnetocapacitance properties.

Memory Window and Endurance Improvement of Hf0.5Zr0.5O2-Based FeFETs with ZrO2 Seed Layers Characterized by Fast Voltage Pulse Measurements.

The HfO2-based ferroelectric field effect transistor (FeFET) with a metal/ferroelectric/insulator/semiconductor (MFIS) gate stack is currently being considered as a possible candidate for high-density and fast write speed non-volatile memory. Although the retention performance of the HfO2-based FeFET with a MFIS gate stack could satisfy the requirements for practical applications, its memory window (MW) and reliability with respect to endurance should be further improved. This work investigates the advantage of employing ZrO2 seed layers on the MW, retention, and endurance of the Hf0.5Zr0.5O2 (HZO)-based FeFETs with MFIS gate stacks, by using fast voltage pulse measurements. It is found that the HZO-based FeFET with a ZrO2 seed layer shows a larger initial and 10-year extrapolated MW, as well as improved endurance performance compared with the HZO-based FeFET without the ZrO2 seed layer. The results indicate that employing of a direct crystalline high-k/Si gate stack would further improve the MW and reliability of the HfO2-based FeFETs.

Self-Assembled Ferroelectric Nanoarray.

Self-assembled heteroepitaxial nanostructures have played an important role for miniaturization of electronic devices, e.g., the ultrahigh density ferroelectric memories, and cause for great concern. Our first principle calculations predict that the materials with low formation energy of the interface ( Ef) tend to form matrix structure in self-assembled heteroepitaxial nanostructures, whereas those with high Ef form nanopillars. Under the guidance of the theoretical modeling, perovskite BiFeO3 (BFO) nanopillars are swimmingly grown into CeO2 matrix on single-crystal (001)-SrTiO3 (STO) substrates by pulsed laser deposition, where CeO2 has a lower formation energy of the interface ( Ef) than BFO. This work provides a good paradigm for controlling self-assembled nanostructures as well as the application of self-assembled ferroelectric nanoscale memory.