Flexoelectric Engineering of Bulk Photovoltaic Photodetector.

The bulk photovoltaic effect (BPVE) offers an interesting approach to generate a steady photocurrent in a single-phase material under homogeneous illumination, and it has been extensively investigated in ferroelectrics exhibiting spontaneous polarization that breaks inversion symmetry. Flexoelectricity breaks inversion symmetry via a strain gradient in the otherwise nonpolar materials, enabling manipulation of ferroelectric order without an electric field. Combining these two effects, we demonstrate active mechanical control of BPVE in suspended 2-dimensional CuInP2S6 (CIPS) that is ferroelectric yet sensitive to electric field, which enables practical photodetection with an order of magnitude enhancement in performance. The suspended CIPS exhibits a 20-fold increase in photocurrent, which can be continuously modulated by either mechanical force or light polarization. The flexoelectrically engineered photodetection device, activated by air pressure and without any optimization, possesses a responsivity of 2.45 × 10-2 A/W and a detectivity of 1.73 × 1011 jones, which are superior to those of ferroelectric-based photodetection and comparable to those of the commercial Si photodiode.

Spatiotemporally Correlated Imaging of Interfacial Defects and Photocurrents in High Efficiency Triple-Cation Mixed-Halide Perovskites.

Triple-cation mixed-halide perovskites have attracted considerable attention due to their excellent photovoltaic properties and enhanced stability, though the power conversion efficiency (PCE) is still far below the theoretical expectation. In order to understand the microscopic mechanisms responsible for the gap, a Cs0.05 (FA0.85 MA0.15 )0.95 Pb(I0.85 Br0.15 )3 (CsFAMA)-based solar cell with respectful efficiency over 20% is examined, and distinct high- and low-current regions are observed in photoconductive atomic force microscopy (pc-AFM) mapping. Simulations attribute the difference in local photocurrents to interfacial donor defect densities at the NiO/CsFAMA interface, which is supported by electrochemical strain microscopy (ESM) mapping, revealing a negative correlation between ionic defects and photocurrents. The interfacial defects can be further manipulated by external bias upon relaxation study, resulting in reduced photocurrents accompanied by topography change when positive ions are driven toward the NiO/CsFAMA interface. It is also observed that both structure variation and photocurrent degradation upon accelerated aging test initiate at grain boundaries, which gradually expand at the expense of grain interior, suggesting that ionic defects are most active at grain boundaries. These findings render a direct correlation between interfacial defects and photocurrents while revealing degradation evolution, and if such interfacial defects heterogeneity can be mitigated, PCE toward the theoretical limit with enhanced stability can be envisioned.

Imaging Graphene Moiré Superlattices via Scanning Kelvin Probe Microscopy.

Moiré superlattices in van der Waals heterostructures are gaining increasing attention because they offer new opportunities to tailor and explore unique electronic phenomena. Using a combination of lateral piezoresponse force microscopy (LPFM) and scanning Kelvin probe microscopy (SKPM), we directly correlate ABAB and ABCA stacked graphene with local surface potential. We find that the surface potential of the ABCA domains is ∼15 mV higher (smaller work function) than that of the ABAB domains. First-principles calculations show that the different work functions between ABCA and ABAB domains arise from the stacking-dependent electronic structure. Moreover, while the moiré superlattice visualized by LPFM can change with time, imaging the surface potential distribution via SKPM appears more stable, enabling the mapping of ABAB and ABCA domains without tip-sample contact-induced effects. Our results provide a new means to visualize and probe local domain stacking in moiré superlattices along with its impact on electronic properties.

High-throughput sequential excitation for nanoscale mapping of electrochemical strain in granular ceria.

Dynamic strain based atomic force microscopy (AFM) modes often fail at the interfaces where the most interesting physics occurs because of their incapability of tracking contact resonance accurately under rough topography. To overcome this difficulty, we develop a high-throughput sequential excitation AFM that captures contact dynamics of probe-sample interactions with high fidelity and efficiency, acquiring the spectrum of data on each pixel over a range of frequencies that are excited in a sequential manner. Using electrochemically active granular ceria as an example, we map both linear and quadratic electrochemical strain accurately across grain boundaries with high spatial resolution where the conventional approach fails. The enhanced electrochemical responses point to the accumulation of small polarons in the space charge region at the grain boundaries, thought to be responsible for the enhanced electronic conductivity in nanocrystalline ceria. The spectrum of data can be processed very efficiently by physics-informed principal component analysis (PCA), speeding data processing by several orders of magnitude. This approach can be applied to a variety of AFM modes for studying a wide range of materials and structures on the nanoscale.

Sepiolite/CNT/S@PANI composite with stable network structure for high performance lithium sulfur batteries.

Composite materials with a stable network structure consisting of natural sepiolite (Sep) powders, carbon nanotubes (CNTs) and conductive polymer (PANI) have been successfully synthesized using a simple vacuum heat treatment and chemical oxidation method, and they have been used as cathode materials for lithium sulfur batteries. It is found that Sep/CNT/S@PANI composites possess high initial discharge capacity, good cyclic stability and good rate performance. The initial discharge capacity of the Sep/CNT/S@PANI-II composite is about 1100 mA h g-1 at 2C, and remained at 650 mA h g-1 after 300 cycles, and the corresponding coulombic efficiency is above 93%. Such performance is attributed to specific porous structure, outstanding adsorption characteristics, and excellent ion exchange capability of sepiolite, as well as excellent conductivity of CNT. Furthermore, the PANI coating has a pinning effect for sulfur, which enhances the utilization of the active mass and improves the cycling stability and the coulombic efficiency of the composites at high current rates.

Deterministic, Reversible, and Nonvolatile Low-Voltage Writing of Magnetic Domains in Epitaxial BaTiO3/Fe3O4 Heterostructure.

The ability to electrically write magnetic bits is highly desirable for future magnetic memories and spintronic devices, though fully deterministic, reversible, and nonvolatile switching of magnetic moments by electric field remains elusive despite extensive research. In this work, we develop a concept to electrically switch magnetization via polarization modulated oxygen vacancies, and we demonstrate the idea in a multiferroic epitaxial heterostructure of BaTiO3/Fe3O4 fabricated by pulsed laser deposition. The piezoelectricity and ferroelectricity of BaTiO3 have been confirmed by macro- and microscale measurements, for which Fe3O4 serves as the top electrode for switching the polarization. X-ray absorption spectroscopy and X-ray magnetic circular dichroism spectra indicate a mixture of Fe2+ and Fe3+ at O h sites and Fe3+ at T d sites in Fe3O4, while the room-temperature magnetic domains of Fe3O4 are revealed by microscopic magnetic force microscopy measurements. It is demonstrated that the magnetic domains of Fe3O4 can be switched by not only magnetic fields but also electric fields in a deterministic, reversible, and nonvolatile manner, wherein polarization reversal by electric field modulates the oxygen vacancy distribution in Fe3O4, and thus its magnetic state, making it attractive for electrically written magnetic memories.

Multifield Control of Domains in a Room-Temperature Multiferroic 0.85BiTi0.1Fe0.8Mg0.1O3-0.15CaTiO3 Thin Film.

Single-phase materials that combine electric polarization and magnetization are promising for applications in multifunctional sensors, information storage, spintronic devices, etc. Following the idea of a percolating network of magnetic ions (e.g., Fe) with strong superexchange interactions within a structural scaffold with a polar lattice, a solid solution thin film with perovskite structure at a morphotropic phase boundary with a high level of Fe atoms on the B site of perovskite structure is deposited to combine both ferroelectric and ferromagnetic ordering at room temperature with magnetoelectric coupling. In this work, a 0.85BiTi0.1Fe0.8Mg0.1O3-0.15CaTiO3 thin film has been deposited by pulsed laser deposition (PLD). Both the ferroelectricity and the magnetism were characterized at room temperature. Large polarization and a large piezoelectric effective coefficient d33 were obtained. Multifield coupling of the thin film has been characterized by scanning force microscopy. Ferroelectric domains and magnetic domains could be switched by magnetic field ( H), electric field ( E), mechanical force ( F), and, indicating that complex cross-coupling exists among the electric polarization, magnetic ordering and elastic deformation in 0.85BiTi0.1Fe0.8Mg0.1O3-0.15CaTiO3 thin film at room temperature. This work also shows the possibility of writing information with electric field, magnetic field, and mechanical force and then reading data by magnetic field. We expect that this work will benefit information applications.