Epitaxial Strain Enhanced Ferroelectric Polarization toward a Giant Tunneling Electroresistance.

A substantial ferroelectric polarization is the key for designing high-performance ferroelectric nonvolatile memories. As a promising candidate system, the BaTiO3/La0.67Sr0.33MnO3 (BTO/LSMO) ferroelectric/ferromagnetic heterostructure has attracted a lot of attention thanks to the merits of high Curie temperature, large spin polarization, and low ferroelectric coercivity. Nevertheless, the BTO/LSMO heterostructure suffers from a moderate FE polarization, primarily due to the quick film-thickness-driven strain relaxation. In response to this challenge, we propose an approach for enhancing the FE properties of BTO films by using a Sr3Al2O6 (SAO) buffering layer to mitigate the interfacial strain relaxation. The continuously tunable strain allows us to illustrate the linear dependence of polarization on epitaxial strain with a large strain-sensitive coefficient of ∼27 µC/cm2 per percent strain. This results in a giant polarization of ∼80 µC/cm2 on the BTO/LSMO interface. Leveraging this large polarization, we achieved a giant tunneling electroresistance (TER) of ∼105 in SAO-buffered Pt/BTO/LSMO ferroelectric tunnel junctions (FTJs). Our research uncovers the fundamental interplay between strain, polarization magnitude, and device performance, such as on/off ratio, thereby advancing the potential of FTJs for next-generation information storage applications.

Taming heat with tiny pressure.

Heat is almost everywhere. Unlike electricity, which can be easily manipulated, the current ability to control heat is still highly limited owing to spontaneous thermal dissipation imposed by the second law of thermodynamics. Optical illumination and pressure have been used to switch endothermic/exothermic responses of materials via phase transitions; however, these strategies are less cost-effective and unscalable. Here, we spectroscopically demonstrate the glassy crystal state of 2-amino-2-methyl-1,3-propanediol (AMP) to realize an affordable, easily manageable approach for thermal energy recycling. The supercooled state of AMP is so sensitive to pressure that even several megapascals can induce crystallization to the ordered crystal, resulting in a substantial temperature increase of 48 K within 20 s. Furthermore, we demonstrate a proof-of-concept device capable of programable heating with an extremely high work-to-heat conversion efficiency of ∼383. Such delicate and efficient tuning of heat may remarkably facilitate rational utilization of waste heat.

Gradient tungsten-doped Bi3TiNbO9 ferroelectric photocatalysts with additional built-in electric field for efficient overall water splitting.

Bi3TiNbO9, a layered ferroelectric photocatalyst, exhibits great potential for overall water splitting through efficient intralayer separation of photogenerated carriers motivated by a depolarization field along the in-plane a-axis. However, the poor interlayer transport of carriers along the out-of-plane c-axis, caused by the significant potential barrier between layers, leads to a high probability of carrier recombination and consequently results in low photocatalytic activity. Here, we have developed an efficient photocatalyst consisting of Bi3TiNbO9 nanosheets with a gradient tungsten (W) doping along the c-axis. This results in the generation of an additional electric field along the c-axis and simultaneously enhances the magnitude of depolarization field within the layers along the a-axis due to strengthened structural distortion. The combination of the built-in field along the c-axis and polarization along the a-axis can effectively facilitate the anisotropic migration of photogenerated electrons and holes to the basal {001} surface and lateral {110} surface of the nanosheets, respectively, enabling desirable spatial separation of carriers. Hence, the W-doped Bi3TiNbO9 ferroelectric photocatalyst with Rh/Cr2O3 cocatalyst achieves an efficient and durable overall water splitting feature, thereby providing an effective pathway for designing excellent layered ferroelectric photocatalysts.

Schottky Barrier Control of Self-Polarization for a Colossal Ferroelectric Resistive Switching.

Controlling the domain evolution is critical both for optimizing ferroelectric properties and for designing functional electronic devices. Here we report an approach of using the Schottky barrier formed at the metal/ferroelectric interface to tailor the self-polarization states of a model ferroelectric thin film heterostructure system SrRuO3/(Bi,Sm)FeO3. Upon complementary investigations of the piezoresponse force microscopy, electric transport measurements, X-ray photoelectron/absorption spectra, and theoretical studies, we demonstrate that Sm doping changes the concentration and spatial distribution of oxygen vacancies with the tunable host Fermi level which modulates the SrRuO3/(Bi,Sm)FeO3 Schottky barrier and the depolarization field, leading to the evolution of the system from a single domain of downward polarization to polydomain states. Accompanied by such modulation on self-polarization, we further tailor the symmetry of the resistive switching behaviors and achieve a colossal on/off ratio of ∼1.1 × 106 in the corresponding SrRuO3/BiFeO3/Pt ferroelectric diodes (FDs). In addition, the present FD also exhibits a fast operation speed of ∼30 ns with a potential for sub-nanosecond and an ultralow writing current density of ∼132 A/cm2. Our studies provide a way for engineering self-polarization and reveal its strong link to the device performance, facilitating FDs as a competitive memristor candidate used for neuromorphic computing.

Proton-mediated reversible switching of metastable ferroelectric phases with low operation voltages.

The exploration of ferroelectric phase transitions enables an in-depth understanding of ferroelectric switching and promising applications in information storage. However, controllably tuning the dynamics of ferroelectric phase transitions remains challenging owing to inaccessible hidden phases. Here, using protonic gating technology, we create a series of metastable ferroelectric phases and demonstrate their reversible transitions in layered ferroelectric α-In2Se3 transistors. By varying the gate bias, protons can be incrementally injected or extracted, achieving controllable tuning of the ferroelectric α-In2Se3 protonic dynamics across the channel and obtaining numerous intermediate phases. We unexpectedly discover that the gate tuning of α-In2Se3 protonation is volatile and the created phases remain polar. Their origin, revealed by first-principles calculations, is related to the formation of metastable hydrogen-stabilized α-In2Se3 phases. Furthermore, our approach enables ultralow gate voltage switching of different phases (below 0.4 volts). This work provides a possible avenue for accessing hidden phases in ferroelectric switching.

A Gate Programmable van der Waals Metal-Ferroelectric-Semiconductor Vertical Heterojunction Memory.

Ferroelectricity, one of the keys to realize non-volatile memories owing to the remanent electric polarization, is an emerging phenomenon in the 2D limit. Yet the demonstrations of van der Waals (vdW) memories using 2D ferroelectric materials as an ingredient are very limited. Especially, gate-tunable ferroelectric vdW memristive device, which holds promises in future multi-bit data storage applications, remains challenging. Here, a gate-programmable multi-state memory is shown by vertically assembling graphite, CuInP2 S6 , and MoS2 layers into a metal(M)-ferroelectric(FE)-semiconductor(S) architecture. The resulted devices seamlessly integrate the functionality of both FE-memristor (with ON-OFF ratios exceeding 105 and long-term retention) and metal-oxide-semiconductor field effect transistor (MOS-FET). Thus, it yields a prototype of gate tunable giant electroresistance with multi-levelled ON-states in the FE-memristor in the vertical vdW assembly. First-principles calculations further reveal that such behaviors originate from the specific band alignment between the FE-S interface. Our findings pave the way for the engineering of ferroelectricity-mediated memories in future implementations of 2D nanoelectronics.

Photocatalytic Overall Water Splitting over PbTiO3 Modulated by Oxygen Vacancy and Ferroelectric Polarization.

Ferroelectric materials hold great promise in the field of photocatalytic water splitting due to their spontaneous polarization that sets up an inherent internal field for the spatial separation of photogenerated charges. The ferroelectric polarization, however, is generally accompanied by some intrinsic defects, particularly oxygen vacancies, whose impact upon photocatalysis is far from being fully understood and modulated. Here, we have studied the role of oxygen vacancies over the photocatalytic behavior of single-domain PbTiO3 through a combination of theoretical and experimental viewpoints. Our results indicate that the oxygen vacancies in the negatively polarized facet (001) are active sites for water oxidation into O2, while the defect-free sites prefer H2O2 as the oxidation product. The apparent quantum yield at 435 nm for photocatalytic overall water splitting with PbTiO3/Rh/Cr2O3 is determined to be 0.025%, which is remarkable for single undoped metal oxide-based photocatalysts. Furthermore, the strong correlation among oxygen vacancies, polarization strength, and photocatalytic activity is properly reflected by charge separation conditions in the single-domain PbTiO3. This work clarifies the crucial role of oxygen vacancies during photocatalytic reactions of PbTiO3, which provides a useful guide to the design of efficient ferroelectric photocatalysts and their water redox reaction pathways.

Regulation of Ferroelectric Polarization to Achieve Efficient Charge Separation and Transfer in Particulate RuO2 /BiFeO3 for High Photocatalytic Water Oxidation Activity.

Exploiting spontaneous polarization of ferroelectric materials to achieve high charge separation efficiency is an intriguing but challenging research topic in solar energy conversion. This work shows that loading high work function RuO2 cocatalyst on BiFeO3 (BFO) nanoparticles enhances the intrinsic ferroelectric polarization by efficient screening of charges to RuO2 via RuO2 /BFO heterojunction. This leads to enhancement of the surface photovoltage of RuO2 /BFO single nanoparticles nearly 3 times, the driving force for charge separation and transfer in photocatalytic reactions. Consequently, efficient photocatalytic water oxidation is achieved with quantum efficiency as high as 5.36 % at 560 nm, the highest activity reported so far for ferroelectric materials. This work demonstrates that, unlike low photocurrent density in film-based ferroelectric devices, high photocatalytic activity could be achieved by regulating the ferroelectric spontaneous polarization using appropriate cocatalyst to enhance driving force for efficient separation and transfer of photogenerated charges in particulate ferroelectric semiconductor materials.

Gate-Tunable and Multidirection-Switchable Memristive Phenomena in a Van Der Waals Ferroelectric.

Memristive devices have been extensively demonstrated for applications in nonvolatile memory, computer logic, and biological synapses. Precise control of the conducting paths associated with the resistance switching in memristive devices is critical for optimizing their performances including ON/OFF ratios. Here, gate tunability and multidirectional switching can be implemented in memristors for modulating the conducting paths using hexagonal α-In2 Se3 , a semiconducting van der Waals ferroelectric material. The planar memristor based on in-plane (IP) polarization of α-In2 Se3 exhibits a pronounced switchable photocurrent, as well as gate tunability of the channel conductance, ferroelectric polarization, and resistance-switching ratio. The integration of vertical α-In2 Se3 memristors based on out-of-plane (OOP) polarization is demonstrated with a device density of 7.1 × 109 in.-2 and a resistance-switching ratio of well over 103 . A multidirectionally operated α-In2 Se3 memristor is also proposed, enabling the control of the OOP (or IP) resistance state directly by an IP (or OOP) programming pulse, which has not been achieved in other reported memristors. The remarkable behavior and diverse functionalities of these ferroelectric α-In2 Se3 memristors suggest opportunities for future logic circuits and complex neuromorphic computing.

Origin of giant negative piezoelectricity in a layered van der Waals ferroelectric.

Recent research on piezoelectric materials is predominantly devoted to enhancing the piezoelectric coefficient, but overlooks its sign, largely because almost all of them exhibit positive longitudinal piezoelectricity. The only experimentally known exception is ferroelectric polymer poly(vinylidene fluoride) and its copolymers, which condense via weak van der Waals (vdW) interaction and show negative piezoelectricity. Here we report quantitative determination of giant intrinsic negative longitudinal piezoelectricity and electrostriction in another class of vdW solids-two-dimensional (2D) layered ferroelectric CuInP2S6. With the help of single crystal x-ray crystallography and density-functional theory calculations, we unravel the atomistic origin of negative piezoelectricity in this system, which arises from the large displacive instability of Cu ions coupled with its reduced lattice dimensionality. Furthermore, the sizable piezoelectric response and negligible substrate clamping effect of the 2D vdW piezoelectric materials warrant their great potential in nanoscale, flexible electromechanical devices.

Multidirection Piezoelectricity in Mono- and Multilayered Hexagonal α-In2Se3.

Piezoelectric materials have been widely used for sensors, actuators, electronics, and energy conversion. Two-dimensional (2D) ultrathin semiconductors, such as monolayer h-BN and MoS2 with their atom-level geometry, are currently emerging as new and attractive members of the piezoelectric family. However, their piezoelectric polarization is commonly limited to the in-plane direction of odd-number ultrathin layers, largely restricting their application in integrated nanoelectromechanical systems. Recently, theoretical calculations have predicted the existence of out-of-plane and in-plane piezoelectricity in monolayer α-In2Se3. Here, we experimentally report the coexistence of out-of-plane and in-plane piezoelectricity in monolayer to bulk α-In2Se3, attributed to their noncentrosymmetry originating from the hexagonal stacking. Specifically, the corresponding d33 piezoelectric coefficient of α-In2Se3 increases from 0.34 pm/V (monolayer) to 5.6 pm/V (bulk) without any odd-even effect. In addition, we also demonstrate a type of α-In2Se3-based flexible piezoelectric nanogenerator as an energy-harvesting cell and electronic skin. The out-of-plane and in-plane piezoelectricity in α-In2Se3 flakes offers an opportunity to enable both directional and nondirectional piezoelectric devices to be applicable for self-powered systems and adaptive and strain-tunable electronics/optoelectronics.

Intercorrelated In-Plane and Out-of-Plane Ferroelectricity in Ultrathin Two-Dimensional Layered Semiconductor In2Se3.

Enriching the functionality of ferroelectric materials with visible-light sensitivity and multiaxial switching capability would open up new opportunities for their applications in advanced information storage with diverse signal manipulation functions. We report experimental observations of robust intralayer ferroelectricity in two-dimensional (2D) van der Waals layered α-In2Se3 ultrathin flakes at room temperature. Distinct from other 2D and conventional ferroelectrics, In2Se3 exhibits intrinsically intercorrelated out-of-plane and in-plane polarization, where the reversal of the out-of-plane polarization by a vertical electric field also induces the rotation of the in-plane polarization. On the basis of the in-plane switchable diode effect and the narrow bandgap (∼1.3 eV) of ferroelectric In2Se3, a prototypical nonvolatile memory device, which can be manipulated both by electric field and visible light illumination, is demonstrated for advancing data storage technologies.

Effects of High Temperature and Thermal Cycling on the Performance of Perovskite Solar Cells: Acceleration of Charge Recombination and Deterioration of Charge Extraction.

In this work, we investigated the effects of high operating temperature and thermal cycling on the photovoltaic (PV) performance of perovskite solar cells (PSCs) with a typical mesostructured (m)-TiO2-CH3NH3PbI3-xClx-spiro-OMeTAD architecture. After temperature-dependent grazing-incidence wide-angle X-ray scattering, in situ X-ray diffraction, and optical absorption experiments were carried out, the thermal durability of PSCs was tested by subjecting the devices to repetitive heating to 70 °C and cooling to room temperature (20 °C). An unexpected regenerative effect was observed after the first thermal cycle; the average power conversion efficiency (PCE) increased by approximately 10% in reference to the as-prepared device. This increase of PCE was attributed to the heating-induced improvement of the crystallinity and p doping in the hole transporter, spiro-OMeTAD, which promotes the efficient extraction of photogenerated carriers. However, further thermal cycles produced a detrimental effect on the PV performance of PSCs, with the short-circuit current and fill factor degrading faster than the open-circuit voltage. Similarly, the PV performance of PSCs degraded at high operation temperatures; both the short-circuit current and open-circuit voltage decreased with increasing temperature, but the temperature-dependent trend of the fill factor was the opposite. Our impedance spectroscopy analysis revealed a monotonous increase of the charge-transfer resistance and a concurrent decrease of the charge-recombination resistance with increasing temperature, indicating a high recombination of charge carriers. Our results revealed that both thermal cycling and high temperatures produce irreversible detrimental effects on the PSC performance because of the deteriorated interfacial photocarrier extraction. The present findings suggest that the development of robust charge transporters and proper interface engineering are critical for the deployment of perovskite PVs in harsh thermal environments.

Substrate Lattice-Guided Seed Formation Controls the Orientation of 2D Transition-Metal Dichalcogenides.

Two-dimensional (2D) transition-metal dichalcogenide (TMDC) semiconductors are important for next-generation electronics and optoelectronics. Given the difficulty in growing large single crystals of 2D TMDC materials, understanding the factors affecting the seed formation and orientation becomes an important issue for controlling the growth. Here, we systematically study the growth of molybdenum disulfide (MoS2) monolayer on c-plane sapphire with chemical vapor deposition to discover the factors controlling their orientation. We show that the concentration of precursors, that is, the ratio between sulfur and molybdenum oxide (MoO3), plays a key role in the size and orientation of seeds, subsequently controlling the orientation of MoS2 monolayers. High S/MoO3 ratio is needed in the early stage of growth to form small seeds that can align easily to the substrate lattice structures, while the ratio should be decreased to enlarge the size of the monolayer at the next stage of the lateral growth. Moreover, we show that the seeds are actually crystalline MoS2 layers as revealed by high-resolution transmission electron microscopy. There exist two preferred orientations (0° or 60°) registered on sapphire, confirmed by our density functional theory simulation. This report offers a facile technique to grow highly aligned 2D TMDCs and contributes to knowledge advancement in growth mechanism.

Heterostructured WS2 /CH3 NH3 PbI3 Photoconductors with Suppressed Dark Current and Enhanced Photodetectivity.

Heterostructured photoconductors based on hybrid perovskites and 2D transition-metal dichalcogenides are fabricated and characterized. Due to the superior properties of CH3 NH3 PbI3 and WS2 , as well as the efficient interfacial charge transfer, such photoconductors show high performance with on/off ratio of ≈10(5) and responsivity of ≈17 A W(-1) . Furthermore, the response times of the heterostructured photoconductors are four orders of magnitude faster compared to the counterpart of a perovskite single layer.

Ambipolar solution-processed hybrid perovskite phototransistors.

Organolead halide perovskites have attracted substantial attention because of their excellent physical properties, which enable them to serve as the active material in emerging hybrid solid-state solar cells. Here we investigate the phototransistors based on hybrid perovskite films and provide direct evidence for their superior carrier transport property with ambipolar characteristics. The field-effect mobilities for triiodide perovskites at room temperature are measured as 0.18 (0.17) cm(2) V(-1) s(-1) for holes (electrons), which increase to 1.24 (1.01) cm(2) V(-1) s(-1) for mixed-halide perovskites. The photoresponsivity of our hybrid perovskite devices reaches 320 A W(-1), which is among the largest values reported for phototransistors. Importantly, the phototransistors exhibit an ultrafast photoresponse speed of less than 10 µs. The solution-based process and excellent device performance strongly underscore hybrid perovskites as promising material candidates for photoelectronic applications.

Space-charge-mediated anomalous ferroelectric switching in P(VDF-TrEE) polymer films.

We report on the switching dynamics of P(VDF-TrEE) copolymer devices and the realization of additional substable ferroelectric states via modulation of the coupling between polarizations and space charges. The space-charge-limited current is revealed to be the dominant leakage mechanism in such organic ferroelectric devices, and electrostatic interactions due to space charges lead to the emergence of anomalous ferroelectric loops. The reliable control of ferroelectric switching in P(VDF-TrEE) copolymers opens doors toward engineering advanced organic memories with tailored switching characteristics.