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Ferroelectric HfO2-based thin films have attracted much interest in the utilization of ferroelectricity at the nanoscale for next-generation electronic devices. However, the structural origin and stabilization mechanism of the ferroelectric phase are not understood because the film is typically nanocrystalline with active yet stochastic ferroelectric domains. Here, electron microscopy is used to map the in-plane domain network structures of epitaxially grown ferroelectric Y:HfO2 films in atomic resolution. The ferroelectricity is confirmed in free-standing Y:HfO2 films, allowing for investigating the structural origin for their ferroelectricity by 4D-STEM, high-resolution STEM, and iDPC-STEM. At the grain boundaries of <111>-oriented Pca21 orthorhombic grains, a high-symmetry mixed-(R3m, Pnm21) phase is induced, exhibiting enhanced polarization due to in-plane compressive strain. Nanoscale Pca21 orthorhombic grains and their grain boundaries with mixed-(R3m, Pnm21) phases of higher symmetry cooperatively determine the ferroelectricity of the Y:HfO2 film. It is also found that such ferroelectric domain networks emerge when the film thickness is beyond a finite value. Furthermore, in-plane mapping of oxygen positions overlaid on ferroelectric domains discloses that polarization is suppressed at vertical domain walls, while it is active when domains are aligned horizontally with subangstrom domain walls. In addition, randomly distributed 180° charged domain walls are confined by spacer layers.
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The discovery of ferroelectricity in nanoscale hafnia-based oxide films has spurred interest in understanding their emergent properties. Investigation focuses on the size-dependent polarization behavior, which is sensitive to content and movement of oxygen vacancies. Though polarization switching and electrochemical reactions is shown to co-occur, their relationship remains unclear. This study employs X-ray photoelectron spectroscopy with depth sensitivity to examine changes in electrochemical states occurring during polarization switching. Contrasting Hf0.5Zr0.5O2 (HZO) with Hf0.88La0.04Ta0.08O2 (HLTO), a composition with an equivalent structure and comparable average ionic radius, electrochemical states are directly observed for specific polarization directions. Lower-polarization films exhibit more significant electrochemical changes upon switching, suggesting an indirect relationship between polarization and electrochemical state. This research illuminates the complex interplay between polarization and electrochemical dynamics, providing evidence for intrinsic polar states in HfO2-based ferroelectrics.
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SnSe, an environmental-friendly group-IV monochalcogenide semiconductor, demonstrates outstanding performance in various applications ranging from thermoelectric devices to solar energy harvesting. Its ultrathin films show promise in the fabrication of ferroelectric nonvolatile devices. However, the microscopic identification and manipulation of point defects in ultrathin SnSe single crystalline films, which significantly impact their electronic structure, have been inadequately studied. This study presents a comprehensive investigation of point defects in monolayer SnSe films grown via molecular beam epitaxy. By combining scanning tunneling microscopy (STM) characterization with first-principles calculations, we identified four types of atomic/molecular vacancies, four types of atomic substitutions, and three types of extrinsic defects. Notably, we have demonstrated the ability to convert a substitutional defect into a vacancy and to reposition an adsorbate by manipulating a single atom or molecule using an STM tip. We have also analyzed the local atomic displacement induced by the vacancies. This work provides a solid foundation for engineering the electronic structure of future SnSe-based nanodevices.
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In this study, the effect of annealing and substrate conditions on the ferroelectricity of undoped hafnium oxide (HfO2) was analyzed. Hafnium oxide was deposited on various substrates such as platinum, titanium nitride, and silicon (Pt, TiN, Si) through RF magnetron sputtering. Annealing was performed in a nitrogen atmosphere at temperatures ranging from 400 to 600 °C, and the process lasted anywhere from 1 to 30 min. As a result, it was confirmed that the orthorhombic phase, the main cause of ferroelectricity, was dominant after a post-anneal at 600 °C for 30 min. Additionally, it was observed that interface mixing between hafnium oxide and the substrate may degrade ferroelectricity. Accordingly, the highest remanent polarization, measured at 14.24 µC/cm2, was observed with the Pt electrode. This finding was further corroborated by piezo force microscopy and endurance tests, with the results being significant compared to previously reported values. This analysis demonstrates that optimizing substrate and annealing conditions, rather than doping, can enhance the ferroelectricity of hafnium oxide, laying the foundation for the future development of ferroelectric-based transistors.
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Strontium aluminate, with suitable lattice parameters and environmentally friendly water solubility, has been strongly sought for use as a sacrificial layer in the preparation of freestanding perovskite oxide thin films in recent years. However, due to this material's inherent water solubility, the methods used for the preparation of epitaxial films have mainly been limited to high-vacuum techniques, which greatly limits these films' development. In this study, we prepared freestanding single-crystal perovskite oxide thin films on strontium aluminate using a simple, easy-to-develop, and low-cost chemical full-solution deposition technique. We demonstrate that a reasonable choice of solvent molecules can effectively reduce the damage to the strontium aluminate layer, allowing successful epitaxy of perovskite oxide thin films, such as 2-methoxyethanol and acetic acid. Molecular dynamics simulations further demonstrated that this is because of their stronger adsorption capacity on the strontium aluminate surface, which enables them to form an effective protective layer to inhibit the hydration reaction of strontium aluminate. Moreover, the freestanding film can still maintain stable ferroelectricity after release from the substrate, which provides an idea for the development of single-crystal perovskite oxide films and creates an opportunity for their development in the field of flexible electronic devices.
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2D sliding ferroelectric semiconductors have greatly expanded the ferroelectrics family with the flexibility of bandgap and material properties, which hold great promise for ultrathin device applications that combine ferroelectrics with optoelectronics. Besides the induced different resistance states for non-volatile memories, the switchable ferroelectric polarizations can also modulate the photogenerated carriers for potentially ultrafast optoelectronic devices. Here, it is demonstrated that the room temperature sliding ferroelectricity can be used for ultrafast switchable photovoltaic response in ε-InSe layers. By first-principles calculations and experimental characterizations, it is revealed that the ferroelectricity with out-of-plane (OOP) polarization only exists in even layer ε-InSe. The ferroelectricity is also demonstrated in ε-InSe-based vertical devices, which exhibit high on-off ratios (≈104) and non-volatile storage capabilities. Moreover, the OOP ferroelectricity enables an ultrafast (≈3 ps) bulk photovoltaic response in the near-infrared band, rendering it a promising material for self-powered reconfigurable and ultrafast photodetector. This work reveals the essential role of ferroelectric polarization on the photogenerated carrier dynamics and paves the way for hybrid multifunctional ferroelectric and optoelectronic devices.
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Metal halide perovskite ferroelectrics combining spontaneous polarization and excellent semiconducting properties is an ideal platform for enabling self-driven X-ray detection, however, achievements to date have been only based on uniaxiality, which increases the complexity of device fabrication. Multi-axial ferroelectric materials have multiple equivalent polarization directions, making them potentially amenable to multi-axial self-driven X-ray detection, but the report on these types of materials is still a huge blank. Herein, a high-quality (BA)2(EA)2Pb3I10 (1) biaxial ferroelectric single crystal was successfully grown, which exhibited significant spontaneous polarization along the c-axis and b-axis. Under X-ray irradiation, bulk photovoltaic effect (BPVE) was exhibited along both the c-axis and b-axis, with open circuit voltages (Voc) of 0.23 V and 0.22 V, respectively. Then, the BPVE revealed along the inversion of polarized direction with the polarized electric fields. Intriguingly, due to the BPVE of 1, 1 achieved multi-axial self-driven X-ray detection for the first time (c-axis and b-axis) with relatively high sensitivities and ultralow detection limits (17.2 nGyair s-1 and 19.4 nGyair s-1, respectively). This work provides a reference for the subsequent use of multi-axial ferroelectricity for multi-axial self-driven optoelectronic detection.
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Ferroelectric all-inorganic halide perovskite nanocrystals with both spontaneous polarization and visible light absorption are promising candidates for designing ferroelectric photovoltaic applications. It remains a challenge to realize ferroelectric photovoltaic devices with all-inorganic halide perovskites that can be operated in the absence of an external electric field. Here we report that a popular all-inorganic halide perovskite nanocrystal, CsPbBr3, exhibits a ferroelectricity-driven photovoltaic effect under visible light in the absence of an external electric field. Pristine CsPbBr3 nanocrystals exhibit intrinsic ferroelectric key properties with a notable saturated polarization of â¼0.15 µC/cm2 and a high Curie temperature of 462 K, driven by the stereochemical activity of the Pb(II) lone pair. Furthermore, application of an external electric field allows the photovoltaic effect to be enhanced and the spontaneous polarization to be switched with the direction of the electric field. CsPbBr3 nanocrystals exhibit a robust fatigue performance and a prolonged photoresponse under continuous illumination in the absence of an external electric field. These findings establish all-inorganic halide perovskite nanocrystals as potential candidates for designing photoferroelectric devices by coupling optical functionalities and ferroelectric responses.
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Ferroelectricity has recently been demonstrated in germanium-based halide perovskites. We use first-principles-based simulations to study 4-18 nm CsGeBr3 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 CsGeBr3 and CsGeI3 and oxide BiFeO3 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.
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Piezoelectric and ferroelectric wurtzite are promising to reshape modern microelectronics because they can be easily integrated with mainstream semiconductor technology. Sc doped AlN (Al1- xScxN) has attracted much attention for its enhanced piezoelectric and emerging ferroelectric properties, yet the commonly used sputtering results in polycrystalline Al1- xScxN films with high leakage current. Here, the pulsed laser deposition of single crystalline epitaxial Al1- xScxN thin films on sapphire and 4H-SiC substrates is reported. Pure wurtzite phase is maintained up to x = 0.3 with ≤0.1 at% oxygen contamination. Polarization is estimated to be 140 µC cm-2 via atomic scale microscopy imaging and found to be switchable via a scanning probe. The piezoelectric coefficient is found to be five times of the undoped one when x = 0.3, making it desirable for high-frequency radiofrequency (RF) filters and 3D nonvolatile memories.
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Altermagnets, distinct from conventional ferromagnets or antiferromagnets, have recently attracted attention as the third category of collinear magnets, which exhibit the coexistence of zero net magnetization and spin polarization due to their unique lattice symmetries. Meanwhile, the additional layer degrees of freedom in multilayer sliding ferroelectrics offer opportunities for coupling with lattice symmetries, paving the way for an innovative approach to constructing multiferroic lattices. In this study, altermagnetic tuning in SnS2/MnPSe3/SnS2 heterostructures is achieved by breaking and restoration of lattice inversion symmetry through sliding ferroelectric switching. First-principles calculations reveal that the spin density and corresponding time-reversal symmetry of MnPSe3 can be manipulated by lattice symmetry, triggering phase transitions between antiferromagnetism and altermagnetism. This research establishes a novel form of magnetoelectric coupling mediated by lattice symmetry and provides a theoretical basis for the design of miniature information processing and memory devices based on altermagnetism.
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2D ferroelectric materials have attracted extensive research interest due to potential applications in nonvolatile memory, nanoelectronics and optoelectronics. However, the available 2D ferroelectric materials are scarce and most of them are limited by the uncontrollable preparation. Herein, a novel 2D ferroelectric material AgCrS2 is reported that are controllably synthesized in large-scale via salt-assist chemical vapor deposition growth. By tuning the growth temperature from 800 to 900 °C, the thickness of AgCrS2 nanosheets can be precisely modulated from 2.1 to 40 nm. Structural and nonlinear optical characterizations demonstrate that AgCrS2 nanosheet crystallizes in a non-centrosymmetric structure with high crystallinity and remarkable air stability. As a result, AgCrS2 of various thicknesses display robust ferroelectric polarization in both in-plane (IP) and out-of-plane (OOP) directions with strong intercorrelation and high ferroelectric phase transition temperature (682 K). Theoretical calculations suggest that the ferroelectricity in AgCrS2 originates from the displacement of Ag atoms in AgS4 tetrahedrons, which changes the dipole moment alignment. Moreover, ferroelectric switching is demonstrated in both lateral and vertical AgCrS2 devices, which exhibit exotic nonvolatile memory behavior with distinct high and low resistance states. This study expands the scope of 2D ferroelectric materials and facilitates the ferroelectric-based nonvolatile memory applications.
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Spin-crossover (SCO) ferroelectrics with dual-function switches have attracted great attention for significant magnetoelectric application prospects. However, the multiferroic crystals with SCO features have rarely been reported. Herein, a molecular multiferroic Fe(II) crystalline complex [FeII(C8-F-pbh)2] (1-F, C8-F-pbh = (1Z,N'E)-3-F-4-(octyloxy)-N'-(pyridin-2-ylmethylene)-benzo-hydrazonate) showing the coexistence of ferroelectricity, ferroelasticity, and SCO behavior is presented for the first time. By H/F substitution, the low phase transition temperature (270 K) of the non-fluorinated parent compound is significantly increased to 318 K in 1-F, which exhibits a spatial symmetry breaking 222F2 type ferroelectric phase transition with clear room-temperature ferroelectricity. Besides, 1-F also displays a spin transition between high- and low-spin states, accompanied by the d-orbital breaking within the t2g 4eg 2 and t2g 6eg° configuration change of octahedrally coordinated FeII center. Moreover, the 222F2 type ferroelectric phase transition is also a ferroelastic one, verified by the ferroelectric domains reversal and the evolution of ferroelastic domains. To the knowledge, 1-F is the first multiferroic SCO molecular crystal. This unprecedented finding sheds light on the exploration of molecular multistability materials for future smart devices.
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Ferroelectric Rashba semiconductors (FRS) are highly demanded for their potential capability for nonvolatile electric control of electron spins. An ideal FRS is characterized by a combination of room temperature ferroelectricity and a strong Rashba effect, which has, however, been rarely reported. Herein, we designed a room-temperature FRS by vertically stacking a Sb monolayer on a room-temperature ferroelectric In2Se3 monolayer. Our first-principles calculations reveal that the Sb/In2Se3 heterostructure exhibits a clean Rashba splitting band near the Fermi level and a strong Rashba effect coupled to the ferroelectric order. Switching the electric polarization direction enhances the Rashba effect, and the flipping is feasible with a low energy barrier of 22 meV. This Rashba-ferroelectricity coupling effect is robust against changes of the heterostructure interfacial distance and external electric fields. Such a nonvolatile electrically tunable Rashba effect at room temperature enables potential applications in next-generation data storage and logic devices operated under small electrical currents.
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Recently discovered ferroelectricity in fluorite-structure ZrO2thin film has attracted increasing and intense interest due to its lower crystallization temperature and higher content in nature in comparison to hafnium oxide. Here, the effect of HfO2interfacial layer on the ferroelectric properties of ZrO2thin films is investigated systematically by designing four types of interfacial structures. It is revealed that the ferroelectric orthorhombic phase, remanent polarization, and endurance can be improved in ZrO2thin film by inserting both a top- and bottom-HfO2interfacial layer. A maximal ferroelectric remanent polarization (2Pr) of 53.4µC cm-2and an optimal endurance performance of 3 × 107field cycles under frequency of 100 kHz are achieved in Pt/HfO2/ZrO2/HfO2/Pt capacitors, with ferroelectric stacks being crystallized at 450 °C via post-deposition annealing method. X-ray photoelectron spectroscopy analysis confirms that the HfO2bottom-layer plays a very important role in the formation of a higher ratio o-phase, thus enhancing the ferroelectricity. These results suggest that designing appropriate interfaces would help achieve excellent ferroelectric properties in ZrO2films.
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Ferroelectric materials, traditionally comprising inorganic ceramics and polymers, are commonly used in medical implantable devices. However, their nondegradable nature often necessitates secondary surgeries for removal. In contrast, ferroelectric molecular crystals have the advantages of easy solution processing, lightweight, and good biocompatibility, which are promising candidates for transient (short-term) implantable devices. Despite these benefits, the discovered biodegradable ferroelectric materials remain limited due to the absence of efficient design strategies. Here, inspired by the polar structure of polyvinylidene fluoride (PVDF), a ferroelectric molecular crystal 1H,1H,9H,9H-perfluoro-1,9-nonanediol (PFND), which undergoes a cubic-to-monoclinic ferroelectric plastic phase transition at 339 K, is discovered. This transition is facilitated by a 2D hydrogen bond network formed through O-H···O interactions among the oriented PFND molecules, which is crucial for the manifestation of ferroelectric properties. In this sense, by reducing the number of -CF2- groups from ≈5 000 in PVDF to seven in PFND, it is demonstrated that this ferroelectric compound only needs simple solution processing while maintaining excellent biosafety, biocompatibility, and biodegradability. This work illuminates the path toward the development of new biodegradable ferroelectric molecular crystals, offering promising avenues for biomedical applications.
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Sliding ferroelectricity in 2D materials, arising from interlayer sliding-induced interlayer hybridization and charge redistribution at the van der Waals interface, offers a means to manipulate spontaneous polarization at the atomic scale through various methods such as stacking order, interfacial contact, and electric field. However, the practical application of extending 2D sliding ferroelectricity remains challenging due to the contentious mechanisms and the complex device structures required for ferroelectric switching. Here, a sliding memristor based on a graphene/parallel-stacked hexagonal boron nitride/graphene tunneling device, featuring a stable memristive hysteresis induced by interfacial polarizations and barrier height modulations, is presented. As the tunneling current density increases, the memristive window broadens, achieving an on/off ratio of ≈103 and 2 order decrease of the trigger current density, attributed to the interlayer migration of positively charged boron ions and the formation of conductive filaments, as supported by the theoretical calculations. The findings open a path for exploring the sliding memristor via a tunneling device and bridge the gap between sliding ferroelectricity and memory applications.
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Controlling magnetism solely through electrical means is indeed a significant challenge, yet holds great potential for advancing information technology. Herein, our investigation presents a promising avenue for electrically manipulating magnetic ordering within 2D van der Waals NiCl2/GeS heterostructures. These heterostructures, characterized by their unique magnetic-ferroelectric (FE) layer stacking, demonstrate spin-constrained photoelectric memory, enabling low-power electrical writing and non-destructive optical reading. The two orientations of the polarization in the GeS FE layer bring about changes in the ground state configuration, transitioning from ferromagnetic (FM) to antiferromagnetic (AFM) orderings within the NiCl2magnetic layer. Correspondingly, the light-induced charge transfer prompts either spin-polarized or unpolarized currents from the FM or AFM states, serving as distinct '1' or '0' states, and facilitating applications in logic processing and memory devices. This transition stems from the interplay of interfacial charge transfer mechanisms and the influence of the effective electric field (Eeff), bringing a non-volatile electric enhancement in the magnetic anisotropy energy within the NiCl2/GeS heterostructure. Overall, our study highlights the NiCl2/GeS heterostructure as an optimal candidate for realizing spin-dependent photoelectric memory, offering unprecedented opportunities for seamlessly integrating memory processing capabilities into a single device through the utilization of layered multiferroic heterostructures.
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Stabilization of multiple polarization states at the atomic scale is pivotal for realizing high-density memory devices beyond prevailing bistable ferroelectric architectures. Here, we show that two-dimensional ferroelectric SnS or GeSe is able to revive and stabilize the ferroelectric order of three-dimensional ferroelectric BaTiO3, even when the latter is thinned to one unit cell in thickness. The underlying mechanism for overcoming the conventional detrimental critical thickness effect is attributed to facile interfacial inversion symmetry breaking by robust in-plane polarization of SnS or GeSe. Furthermore, when invoking interlayer sliding, we can stabilize multiple polarization states and achieve efficient interstate switching in the heterostructures, accompanied by dynamical ferroelectric skyrmionic excitations. When invoking sliding and twisting, the moiré domains exhibit nontrivial polar vortexes, which can be laterally displaced via different sliding schemes. These findings provide an intuitive avenue for simultaneously overcoming the standing critical thickness issue in bulk ferroelectrics and weak polarization issue in sliding ferroelectricity.
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At near-parallel orientation, twisted bilayers of transition metal dichalcogenides exhibit interlayer charge transfer-driven out-of-plane ferroelectricity. Here, we report detailed electrical transport in a dual-gated graphene field-effect transistor placed on a 2.1° twisted bilayer WSe2. We observe hysteretic transfer characteristics and an emergent charge inhomogeneity with multiple local Dirac points evolving with an increasing electric displacement field (D). Concomitantly, we also observe a strong nonlocal voltage signal at D â¼ 0 V/nm that decreases rapidly with increasing D. A linear scaling of the nonlocal signal with longitudinal resistance suggests edge mode transport, which we attribute to the breaking of valley symmetry of graphene due to the spatially fluctuating electric field from the underlying polarized moiré domains. A quantitative analysis suggests the emergence of finite-size domains in graphene that modulate the charge and the valley currents simultaneously. This work underlines the impact of interfacial ferroelectricity that can trigger a new generation of devices.