Photovoltaic effect by soft phonon excitation.

SignificanceThe quantum-mechanical geometric phase of electrons provides various phenomena such as the dissipationless photocurrent generation through the shift current mechanism. So far, the photocurrent generations are limited to above or near the band-gap photon energy, which contradicts the increasing demand of the low-energy photonic functionality. We demonstrate the photocurrent through the optical phonon excitations in ferroelectric BaTiO3 by using the terahertz light with photon energy far below the band gap. This photocurrent without electron-hole pair generation is never explained by the semiclassical treatment of electrons and only arises from the quantum-mechanical geometric phase. The observed photon-to-current conversion efficiency is as large as that for electronic excitation, which can be well accounted for by newly developed theoretical formulation of shift current.

Acousto-Drag Photovoltaic Effect by Piezoelectric Integration of Two-Dimensional Semiconductors.

Light-to-electricity conversion is crucial for energy harvesting and photodetection, requiring efficient electron-hole pair separation to prevent recombination. Traditional junction-based mechanisms using built-in electric fields fail in nonbarrier regions. Homogeneous material harvesting under a photovoltaic effect is appealing but is only realized in noncentrosymmetric systems via a bulk photovoltaic effect. Here we report the realization of a photovoltaic effect by employing surface acoustic waves (SAWs) to generate zero-bias photocurrent in the conventional layered semiconductor MoSe2. SAWs induce periodic modulation to electronic bands and drag the photoexcited pairs toward the traveling direction. The photocurrent is extracted from a local barrier. The separation of generation and extraction processes suppresses recombination and yields a large nonlocal photoresponse. We distinguish the acousto-electric drag and electron-hole pair separation effect by fabricating devices of different configurations. The acousto-drag photovoltaic effect, enabled by piezoelectric integration, offers an efficient light-to-electricity conversion method, independent of semiconductor crystal symmetry.

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.

Unique Perovskitizer N─Pb Bond Switching Induced Polar Photovoltaic Effect in Trilayered Hybrid Perovskite.

Polar photovoltaic effect (PPE) has attracted great attention in regulating desired optoelectronic properties, which can be driven by order-disorder and displacive phase transitions. Bond-switching is also a feasible method to induce PPE, but such investigation is very rare. Lead-halide hybrid perovskite (LHHP) is an outstanding photodetection material; lead atoms possess rich coordination modes to provide possibilities to construct switchable bonds. Here, a unique perovskitizer N─Pb bond-switching is disclosed to induce polar photovoltage in the emerging LHHP, PA2MHy2Pb3Br10 (1, PA = n-propylamine, MHy = methylhydrazine). Interestingly, the perovskitizer MHy+ provides 2s2 lone pair while the Pb atom affords empty d orbitals, which coordinate with each other to generate a flexible N─Pb bond. Further, the introduction of N─Pb bonds results in a high distortion of the PbBr6 octahedron to form local polarity and further orientation to induce spontaneous polarization. More importantly, such a flexible N─Pb bond switching mechanism drives a notable PPE and controllable polarized photo-response, a polarization ratio up to 9.7 at the polar phase in striking contrast with the non-polar phase (1.03). The work provides the first demonstration of bond-switching to induce polar phase transition and polar photovoltage in the photoconductive hybrid perovskites for photoelectric applications.

WS2 Nanotube Transistor for Photodetection and Optoelectronic Memory Applications.

Nanotube and nanowire transistors hold great promises for future electronic and optoelectronic devices owing to their downscaling possibilities. In this work, a single multi-walled tungsten disulfide (WS2) nanotube is utilized as the channel of a back-gated field-effect transistor. The device exhibits a p-type behavior in ambient conditions, with a hole mobility µp ≈  1.4 cm2V-1s-1 and a subthreshold swing SS ≈ 10 V dec-1. Current-voltage characterization at different temperatures reveals that the device presents two slightly different asymmetric Schottky barriers at drain and source contacts. Self-powered photoconduction driven by the photovoltaic effect is demonstrated, and a photoresponsivity R ≈ 10 mAW-1 at 2 V drain bias and room temperature. Moreover, the transistor is tested for data storage applications. A two-state memory is reported, where positive and negative gate pulses drive the switching between two different current states, separated by a window of 130%. Finally, gate and light pulses are combined to demonstrate an optoelectronic memory with four well-separated states. The results herein presented are promising for data storage, Boolean logic, and neural network applications.

Realization of High-Performance Self-Powered Polarized Photodetection with Large Temperature Window in a 2D Polar Perovskite.

Polarization photodetection taking advantage of the anisotropy of 2D materials shines brilliantly in optoelectronic fields owing to differentiating optical information. However, the previously reported polarization detections are mostly dependent on external power sources, which is not conducive to device integration and energy conservation. Herein, a 2D polar perovskite (CBA)2CsPb2Br7 (CCPB, CBA = 4-chlorobenzyllamine) has been successfully synthesized, which shows anticipated bulk photovoltaic effect (BPVE) with an open-circuited photovoltage up to ≈0.2 V. Devices based on CCPB monomorph fulfill a fascinating self-powered polarized photodetection with a large polarization ratio of 2.7 at room temperature. Moreover, CCPB features a high phase-transition temperature (≈475 K) which prompts such self-powered polarized photodetection in a large temperature window of device operation, since BPVE generated by spontaneous polarization can only exist in the polar structure prior to the phase transition. Further computational investigation reveals the introduction of CBA+ with a large dipole moment contributes to quite large polarization (17.5 µC cm-2) and further super high phase transition temperature of CCPB. This study will promote the application of 2D perovskite materials for self-powered polarized photodetection in high-temperature conditions.

Bulk Photovoltaic Effect in Polar 3D Perovskitoid Enables Self-Powered Polarization-Sensitive Photodetection.

The family of polar hybrid perovskites, in which bulk photovoltaic effects (BPVEs) drive steady photocurrent without bias voltage, have shown promising potentials in self-powered polarization-sensitive photodetection. However, reports of BPVEs in 3D perovskites remain scare, being mainly hindered by the limited dipole moment or lack of symmetry breaking. Herein, a polar 3D perovskitoid, (BDA)Pb2Br6 (BDA = NH3C4H8NH3), where the spontaneous polarization (Ps)-induced BPVE drives self-powered photodetection of polarized-light is reported. Emphatically, the edge-sharing Pb2Br10 dimer building unit allows the optical anisotropy and polarity in 3D (BDA)Pb2Br6, which triggers distinct optical absorption dichroism ratio of ≈2.80 and BPVE dictated photocurrent of 3.5 µA cm-2. Strikingly, these merits contribute to a polarization-sensitive photodetection with a high polarization ratio (≈4) under self-powered mode, beyond those of 2D hybrid perovskites and inorganic materials. This study highlights the potential of polar 3D perovskitoids toward intelligent optoelectronic applications.

Theory of bulk photovoltaic effect in Anderson insulator.

The localization of wavefunction by disorder makes a conductive material an insulator with vanishing conductivity at zero temperature. A similar outcome is expected for the photocurrent in semiconductor p-n junctions because the photoexcited carriers cannot drift through the device. In contrast, we here show numerically that the bulk photovoltaic effect-the photovoltaic effect in noncentrosymmetric bulk materials-occurs in a noncentrosymmetric, disordered, one-dimensional insulator where all eigenstates are localized. We find this photocurrent remains, even when the energy scale of random potential is larger than the bandwidth. On the other hand, the photocurrent decays exponentially when the excitation is local, i.e., when only a part of the device is illuminated. The photocurrent also vanishes if the relaxation occurs only by contact with the electrodes. Our result implies that the ratio of the photovoltaic current and the direct current by the variable-range hopping increases with decreasing temperature. These results suggest a route to design high-efficiency solar cells and photodetectors.

Self-Powered Programmable van der Waals Photodetectors with Nonvolatile Semifloating Gate.

Tunable photovoltaic photodetectors are of significant relevance in the fields of programmable and neuromorphic optoelectronics. However, their widespread adoption is hindered by intricate architectural design and energy consumption challenges. This study employs a nonvolatile MoTe2/hexagonal boron nitride/graphene semifloating photodetector to address these issues. Programed with pulsed gate voltage, the MoTe2 channel can be reconfigured from an n+-n to a p-n homojunction and the photocurrent transition changes from negative to positive values. Scanning photocurrent mapping reveals that the negative and positive photocurrents are attributed to Schottky junction and p-n homojunction, respectively. In the p-n configuration, the device demonstrates self-driven, linear, rapid response (∼3 ms), and broadband sensitivity (from 405 to 1500 nm) for photodetection, with typical performances of responsivity at ∼0.5 A/W and detectivity ∼1.6 × 1012 Jones under 635 nm illumination. These outstanding photodetection capabilities emphasize the potential of the semifloating photodetector as a pioneering approach for advancing logical and nonvolatile optoelectronics.

A Three-Dimensional Neuromorphic Photosensor Array for Nonvolatile In-Sensor Computing.

In-sensor computing hardware based on emerging reconfigurable photosensors can effectively reduce redundant data and decrease power consumption, which can greatly promote the evolution of machine vision. However, because of the complex device structures and low integration abilities, the common architectures mainly lie in two dimensions, resulting in low time and area efficiencies. Here we propose a three-dimensional (3D) neuromorphic photosensor array for parallel in-sensor image processing. It is constructed on a vertical Graphite/CuInP2S6/Graphite photosensor unit, where the directional Cu+ ion migrations after voltage pulse programming enable a reconfigurable photovoltaic effect and an in-sensor computing capability. With a memristor-like device structure, van der Waals interfaces, and a high uniformity with a low crosstalk problem, a 10 × 10 array is fabricated for intelligent image recognition. Furthermore, using a vertically stacked 3D 3 × 3 × 3 array, we demonstrate an in-sensor convolution strategy with high time and area efficiencies.

Three-Dimensional Polar Perovskites for Highly Sensitive Self-Driven X-Ray Detection.

Three-dimensional (3D) organic-inorganic hybrid perovskites (OIHPs) have achieved tremendous success in direct X-ray detection due to their high absorption coefficient and excellent carrier transport. However, owing to the centrosymmetry of classic 3D structures, these reported X-ray detectors mostly require external electrical fields to run, resulting in bulky overall circuitry, high energy consumption, and operational instability. Herein, we first report the unprecedented radiation photovoltage in 3D OIHP for efficient self-driven X-ray detection. Specifically, the 3D polar OIHP MhyPbBr3 (1, Mhy=methylhydrazine) shows an intrinsic radiation photovoltage (0.47 V) and large mobility-lifetime product (1.1×10-3  cm2 V-1 ) under X-ray irradiation. Strikingly, these excellent physical characteristics endow 1 with sensitive self-driven X-ray detection performance, showing a considerable sensitivity of 220 µC Gy-1 cm-2 , which surpasses those of most self-driven X-ray detectors. This work first explores highly sensitive self-driven X-ray detection in 3D polar OIHPs, shedding light on future practical applications.

Superior Performances of Self-Driven Near-Infrared Photodetectors Based on the SnTe:Si/Si Heterostructure Boosted by Bulk Photovoltaic Effect.

The upsurge of new materials that can be used for near-infrared (NIR) photodetectors operated without cooling is crucial. As a novel material with a small bandgap of ≈0.28 eV, the topological crystalline insulator SnTe has attracted considerable attention. Herein, this work demonstrates self-driven NIR photodetectors based on SnTe/Si and SnTe:Si/Si heterostructures. The SnTe/Si heterostructure has a high detectivity D* of 3.3 × 1012 Jones. By Si doping, the SnTe:Si/Si heterostructure reduces the dark current density and increases the photocurrent by ≈1 order of magnitude simultaneously, which improves the detectivity D* by ≈2 orders of magnitude up to 1.59 × 1014 Jones. Further theoretical analysis indicates that the improved device performance may be ascribed to the bulk photovoltaic effect (BPVE), in which doped Si atoms break the inversion symmetry and thus enable the generation of additional photocurrents beyond the heterostructure. In addition, the external quantum efficiency (EQE) measured at room temperature at 850 nm increases by a factor of 7.5 times, from 38.5% to 289%. A high responsivity of 1979 mA W-1 without bias and fast rising time of 8 µs are also observed. The significantly improved photodetection achieved by the Si doping is of great interest and may provide a novel strategy for superior photodetectors.

Realization of Passive X-Ray Detection with a Low Detection Limit in Dion-Jacobson Halide Hybrid Perovskite.

Halide hybrid perovskites are a kind of intriguing contenders for X-ray detection, and their low detection limits (LoDs) have played a crucial part in X-ray safety inspection and medical examination. However, there is still a significant challenge in manufacturing perovskite X-ray detectors with low LoDs. Herein, attributed to the bulk photovoltaic effect (BPVE) of a Dion-Jacobson (DJ) type 2D halide hybrid perovskite polar structure (3-methylaminopropylamine)PbBr4 (1), self-powered X-ray detection with low detection limit is successfully realized. Specifically, the crystal-based detector of 1 exhibits a low dark current at zero bias, which reduces the noise current (0.34 pA), leading to a low detection limit (58.3 nGyair s-1 ) which is two orders of magnitude lower than that of under external voltage bias. The combination of BPVE and LoDs of halide hybrid perovskite provides an efficient strategy to achieve passive X-ray detection with low doses.

Defect tolerant zero-bias topological photocurrent in a ferroelectric semiconductor.

Lattice defect is a major cause of energy dissipation in conventional electric current due to the drift and diffusion motions of electrons. Different nature of current emerges when noncentrosymmetric materials are excited by light. This current, called the shift current, originates from the change in the Berry connection of electrons' wave functions during the interband optical transition. Here, we demonstrate the defect tolerance of shift current using single crystals of ferroelectric semiconductor antimony sulfoiodide (SbSI). Although the dark conductance spreads over several orders of magnitude in each crystal due to the difference in the density of defect levels, the observed shift current converges to an identical value. We also reveal that the shift current is scarcely disturbed by the surface defects while they drastically suppress the conventional photocurrent. The defect tolerance is a manifestation of the topological nature of shift current, which will be a crucial advantage in optoelectronic applications.

Mechanical Stress Modulation of Resistance in MoS2 Junctions.

Strain engineering is a powerful strategy to control the physical properties of material-enabling devices with enhanced functionality and improved performance. Here, we investigate a modulation of the transport behavior of the two-dimensional MoS2 junctions under the mechanical stress induced by a tip of an atomic force microscope (AFM). We show that the junction resistance can be reversibly tuned by up to 4 orders of magnitude by altering a tip-induced force. Analysis of the stress-induced evolution of the I-V characteristics indicates a combined effect of the tip-induced strain and strain gradient on the energy barrier height and profile. In addition, we show that the tip-generated flexoelectric effect leads to significant enhancement of the photovoltaic effect in the MoS2 junctions. A combination of the optical and mechanical stimuli facilitates reversible photomechanical tuning of resistance of the narrow-band 2D semiconductors and development of devices with an enhanced photovoltaic response.

Tailoring Bulk Photovoltaic Effects in Magnetic Sliding Ferroelectric Materials.

The bulk photovoltaic effect that is intimately associated with crystalline symmetry has been extensively studied in various nonmagnetic materials, especially ferroelectrics with a switchable electric polarization. In order to further engineer the symmetry, one could resort to spin-polarized systems possessing an extra magnetic degree of freedom. Here, we investigate the bulk photovoltaic effect in two-dimensional magnetic sliding ferroelectric (MSFE) systems, illustrated in VSe2, FeCl2, and CrI3 bilayers. The transition metal elements in these systems exhibit intrinsic spin polarization, and the stacking mismatch between the two layers produces a finite out-of-plane electric dipole. Through symmetry analyses and first-principles calculations, we show that photoinduced in-plane bulk photovoltaic current can be effectively tuned by their magnetic order and the out-of-plane dipole moment. The underlying mechanism is elucidated from the quantum metric dipole distribution in the reciprocal space. The ease of the fabrication and manipulation of MSFEs guarantee practical optoelectronic applications.

Bulk Photovoltaic Effect Along the Nonpolar Axis in Organic-Inorganic Hybrid Perovskites.

The origin of the bulk photovoltaic effect (BPVE) was considered as a built-in electric field formed by the macroscopic polarization of materials. Alternatively, the "shift current mechanism" has been gradually accepted as the more appropriate description of the BPVE. This mechanism implies that the photocurrent generated by the BPVE is a topological current featuring an ultrafast response and dissipation-less nature, which is very attractive for photodetector applications. Meanwhile, the origin of the BPVE in organic-inorganic hybrid perovskites (OIHPs) has not been discussed and is still widely accepted as the classical mechanism without any experimental evidence. Herein, we observed the BPVE along the nonpolar axis in OIHPs, which is inconsistent with the classical explanation. Furthermore, based on the nonlinear optical tensor correlation, we substantiated that the BPVE in OIHPs is originated in the shift current mechanism.

Rashba Band Splitting and Bulk Photovoltaic Effect Induced by Halogen Bonds in Hybrid Layered Perovskites.

Non-covalent interactions play an essential role in directing the self-assembly of hybrid organic-inorganic crystals. In hybrid halide perovskites, hydrogen bonding has been the paramount non-covalent interaction. Here, we show another non-covalent interaction, namely, the halogen bond interaction, that directs a symmetry-breaking assembly in a new series of two-dimensional (2D) perovskites (ICH2 CH2 NH3 )2 (CH3 NH3 )n-1 Pbn I3n+1 (n is the layer thickness, n=1-4). Structural analysis shows that the halogen bond strength varies with the layer thickness. For the odd number (n=1, 3) layered perovskites, stronger halogen interaction leads to centrosymmetric structures, whereas for the n=2 layered perovskites, weaker halogen bonds result in non-centrosymmetric structures. Transient reflection spectroscopy shows a suppressed radiative recombination rate (k2 ≈0) and prolonged spin lifetime for n=2 structure, suggesting an enhanced Rashba band splitting effect. The structural asymmetry is further confirmed with a reversible bulk photovoltaic effect. Our work provides a new design strategy to enable hybrid perovskites with emerging properties and functionalities associated with structural asymmetry.

High-Sensitivity Infrared Photoelectric Detection Based on WS2 /Si Structure Tuned by Ferroelectrics.

As one of the typical transition-metal dichalcogenides with distinct optical and electrical properties, WS2 exhibits tremendous potential for optoelectronic devices. However, its inherent band gap range limits the application in the infrared region. To overcome this draw-back and improve the sensitivity, P(VDF-CTFE) is used as a ferroelectric gate to control the states of WS2 /Si junctions and achieve an enhanced infrared photodetection. The polarization electric field not only broadens the range of absorption wavelength (405-1550 nm) but also greatly promotes the sensitivity of lateral photovoltaic effect (LPE) (from 198.6 to 503.2 mV mm-1 ). This phenomenon is attributed to the reduction of WS2 band gap and the change of potential barrier at the interface of the junction. Meanwhile, the response speed is improved significantly due to the increase of carrier initial kinetic energy. This new scheme for ferroelectric tuned LPE opens up a way to realize high-sensitivity, ultrafast, and stable infrared photodetection.

Self-Powered Lithium Niobate Thin-Film Photodetectors.

Thin-film lithium niobate platform, namely lithium-niobate-on-insulator (LNOI), brings new opportunities for integrated photonics, taking advantages from both outstanding crystalline properties and special structural features. The excellent properties of LNOI have triggered development of a variety of on-chip photonic devices for light generation and manipulation. However, as an indispensable component for photonic circuit with full functionalities, the thin-film photodetector lacks in portfolios of LNOI-based devices due to standing obstacles of low electrical conductivity and poor photoelectric conversion ability. Here, a self-powered broadband LNOI photodetector based on enhanced photovoltaic effect, benefitting from encapsulated plasmonic nanoparticles and doped silver ions, is reported. Maximum responsivity of 0.25 A W-1 and detectivity (1.56 × 1014 Jones) are achieved. First-principle calculations and electric-field simulation reveal intrinsic mechanisms and crucial roles of plasmonic nanoparticles and silver ions on photocurrent generation and collection. This work opens an avenue to develop high-performance on-chip LNOI photodetectors, offering a conceivable means toward multiple-functional photonic circuits.