Mapping the intrinsic photocurrent streamlines through micromagnetic heterostructure devices.

Photocurrent in quantum materials is often collected at global contacts far away from the initial photoexcitation. This collection process is highly nonlocal. It involves an intricate spatial pattern of photocurrent flow (streamlines) away from its primary photoexcitation that depends sensitively on the configuration of current collecting contacts as well as the spatial nonuniformity and tensor structure of conductivity. Direct imaging to track photocurrent streamlines is challenging. Here, we demonstrate a microscopy method to image photocurrent streamlines through ultrathin heterostructure devices comprising platinum on yttrium iron garnet (YIG). We accomplish this by combining scanning photovoltage microscopy with a uniform rotating magnetic field. Here, local photocurrent is generated through a photo-Nernst type effect with its direction controlled by the external magnetic field. This enables the mapping of photocurrent streamlines in a variety of geometries that include conventional Hall bar-type devices, but also unconventional wing-shaped devices called electrofoils. In these, we find that photocurrent streamlines display contortion, compression, and expansion behavior depending on the shape and angle of attack of the electrofoil devices, much in the same way as tracers in a wind tunnel map the flow of air around an aerodynamic airfoil. This affords a powerful tool to visualize and characterize charge flow in optoelectronic devices.

Room-Temperature Geometrical Circular Photocurrent in Few-Layer MoS2.

Valleytronics, i.e., the manipulation of the valley degree of freedom, offers a promising path for energy-efficient electronics. One of the key milestones in this field is the room-temperature manipulation of the valley information in thick-layered material. Using scanning photocurrent microscopy, we achieve this milestone by observing a geometrically dependent circular photocurrent in a few-layer molybdenum disulfide (MoS2) under normal incidence. Such an observation shows that the system symmetry is lower than that of bulk MoS2 material, preserving the optical chirality-valley correspondence. Moreover, the circular photocurrent polarity can be reversed by applying electrical bias. We propose a model where the observed photocurrent results from the symmetry breaking and the built-in field at the electrode-sample interface. Our results show that the valley information is still retained even in thick-layered MoS2 at room temperature and opens up new opportunities for exploiting the valley index through interface engineering in multilayer valleytronics devices.

Resonant Tunneling-Enhanced Photoresponsivity in a Twisted Graphene van der Waals Heterostructure.

Leveraging its ultrahigh carrier mobility, zero-bandgap linear dispersion, and extremely short response time, graphene exhibits remarkable potential in ultrafast broad-band photodetection. Nonetheless, the inherently low responsivity of graphene photodetectors, due to the low photogenerated carrier density, significantly impedes the development of practical devices. In this study, we present an improved photoresponse within a graphene-hexagonal boron nitride-graphene vertical tunnel junction device, where the crystallographic orientation of the two graphene electrodes is aligned. Through meticulous device structure design and the adjustment of bias and gate voltages, we observe a 2 orders of magnitude increase in tunneling photocurrent, which is attributed to the momentum-conserving resonant electron tunneling. The enhanced external photoresponsivity is evident across a wide temperature and spectral range and achieves 0.7 A/W for visible light excitation. This characteristic, coupled with the device's negative differential conductance, suggests a novel avenue for highly efficient photodetection and high-frequency, logic-based optoelectronics using van der Waals heterostructures.

Chiral 3D Perovskite Formation Induced by Chiral Templates.

Chiral 3D perovskites pose challenges compared to lower-dimensional variants due to limited chiral organic cation options. Here, we present a universal and controlled method for synthesizing chiral 3D lead halide perovskites using organic amines or alcohols as chiral templates. Introducing these templates to PbCl2 in N,N-dimethylformamide (DMF) under acidic conditions induces the crystallization of R/S [DMA]PbCl3 (DMA = dimethylamine). The resulting structure aligns with the templates used, stemming from the helical Pb2Cl95- chain as verified by single-crystal X-ray diffraction. Furthermore, the chiral perovskite exhibits absorption and circular dichroism (CD) signals in the high-energy band, enabling the circularly polarized light (CPL) detection in the UV spectrum. A CPL detector constructed by this chiral perovskite demonstrates excellent performance, boasting an anisotropy factor for photocurrent (gIph) of 0.296. Our work not only introduces a novel and controllable method for crafting chiral perovskites but also opens new avenues for circularly polarized light detection.

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.

Stark Effects of Rydberg Excitons in a Monolayer WSe2 P-N Junction.

The enhanced Coulomb interaction in two-dimensional semiconductors leads to tightly bound electron-hole pairs known as excitons. The large binding energy of excitons enables the formation of Rydberg excitons with high principal quantum numbers (n), analogous to Rydberg atoms. Rydberg excitons possess strong interactions among themselves as well as sensitive responses to external stimuli. Here, we probe Rydberg exciton resonances through photocurrent spectroscopy in a monolayer WSe2 p-n junction formed by a split-gate geometry. We show that an external in-plane electric field not only induces a large Stark shift of Rydberg excitons up to quantum principal number 3 but also mixes different orbitals and brightens otherwise dark states such as 3p and 3d. Our study provides an exciting platform for engineering Rydberg excitons for new quantum states and quantum sensing.

Harnessing Persistent Photocurrent in a 2D Semiconductor-Polymer Hybrid Structure: Electron Trapping and Fermi Level Modulation for Optoelectronic Memory.

Recently, 2D semiconductor-based optoelectronic memory has been explored to overcome the limitations of conventional von Neumann architectures by integrating optical sensing and data storage into one device. Persistent photocurrent (PPC), essential for optoelectronic memory, originates from charge carrier trapping according to the Shockley-Read-Hall (SRH) model in 2D semiconductors. The quasi-Fermi level position influences the activation of charge-trapping sites. However, the correlation between quasi-Fermi level modulations and PPC in 2D semiconductors has not been extensively studied. In this study, we demonstrate optoelectronic memory based on a 2D semiconductor-polymer hybrid structure and confirm that the underlying mechanism is charge trapping, as the SRH model explains. Under light illumination, electrons transfer from polyvinylpyrrolidone to p-type tungsten diselenide, resulting in high-level injection and majority carrier-type transitions. The quasi-Fermi level shifts upward with increasing temperature, improving PPC and enabling optoelectronic memory at 433 K. Our findings offer valuable insights into optimizing 2D semiconductor-based optoelectronic memory.

Pressure-Induced Enhancement and Retainability of Optoelectronic Properties in Layered Zirconium Disulfide.

Transition metal dichalcogenides (TMDs) exhibit excellent electronic and photoelectric properties under pressure, prompting researchers to investigate their structural phase transitions, electrical transport, and photoelectric response upon compression. Herein, the structural and photoelectric properties of layered ZrS2 under pressure using in situ high-pressure photocurrent, Raman scattering spectroscopy, alternating current impedance spectroscopy, absorption spectroscopy, and theoretical calculations are studied. The experimental results show that the photocurrent of ZrS2 continuously increases with increasing pressure. At 24.6 GPa, the photocurrent of high-pressure phase P21/m is three orders of magnitude greater than that of the initial phase P 3 ¯ m 1 $P\bar{3}m1$ at ambient pressure. The minimum synthesis pressure for pure high-pressure phase P21/m of ZrS2 is 18.8 GPa, which exhibits a photocurrent that is two orders of magnitude higher than that of the initial phase P 3 ¯ m 1 $P\bar{3}m1$ and displays excellent stability. Additionally, it is discovered that the crystal structure, electrical transport properties and bandgap of layered ZrS2 can also be regulated by pressure. This work offers researchers a new direction for synthesizing high-performance TMDs photoelectric materials using high pressure, which is crucial for enhancing the performance of photoelectric devices in the future.

A New Porphyrin-based Covalent Organic Framework with High Iodine Capture Capacity and I-doping Enhanced Conductivity.

Covalent organic frameworks (COFs) are porous organic materials with well-defined and uniform structure. The material is an excellent candidate as a solid adsorbent for iodine adsorption. In the present study, we report the synthesis of COF with porphyrin moiety, TF-TA-COF, by solvothermal reaction, which was characterized by XRD, solid-state 13 C NMR, IR, TGA, and nitrogen adsorption-desorption analysis. TF-TA-COF showed a high specific surface area of 443 m2 g-1 , and exhibited good adsorption performance for iodine vapor, with an adsorption capacity of 2.74 g g-1 . XPS and Raman spectrum indicated that a hybrid of physisorption and chemisorption took place between host COF and iodine molecules. The electric properties of iodine-loaded TF-TA-COF were also studied. After doped with iodine, the conductivity of the material increased by more than 5 orders of magnitude. The photoconductivity of I2 -doped COF was also studied and TF-TA-COF showed doping-enhanced photocurrent generation.

Nonlinear nanoelectrodynamics of a Weyl metal.

Chiral Weyl fermions with linear energy-momentum dispersion in the bulk accompanied by Fermi-arc states on the surfaces prompt a host of enticing optical effects. While new Weyl semimetal materials keep emerging, the available optical probes are limited. In particular, isolating bulk and surface electrodynamics in Weyl conductors remains a challenge. We devised an approach to the problem based on near-field photocurrent imaging at the nanoscale and applied this technique to a prototypical Weyl semimetal TaIrTe4 As a first step, we visualized nano-photocurrent patterns in real space and demonstrated their connection to bulk nonlinear conductivity tensors through extensive modeling augmented with density functional theory calculations. Notably, our nanoscale probe gives access to not only the in-plane but also the out-of-plane electric fields so that it is feasible to interrogate all allowed nonlinear tensors including those that remained dormant in conventional far-field optics. Surface- and bulk-related nonlinear contributions are distinguished through their "symmetry fingerprints" in the photocurrent maps. Robust photocurrents also appear at mirror-symmetry breaking edges of TaIrTe4 single crystals that we assign to nonlinear conductivity tensors forbidden in the bulk. Nano-photocurrent spectroscopy at the boundary reveals a strong resonance structure absent in the interior of the sample, providing evidence for elusive surface states.

THz Generation by Two-Color Plasma: Time Shaping and Ultra-Broadband Polarimetry.

The generation of terahertz radiation via laser-induced plasma from two-color femtosecond pulses in air has been extensively studied due to its broad emission spectrum and significant pulse energy. However, precise control over the temporal properties of these ultra-broadband terahertz pulses, as well as the measurement of their polarization state, remain challenging. In this study, we review our latest findings on these topics and present additional results not previously reported in our earlier works. First, we investigate the impact of chirping on the fundamental wave and the effect of manipulating the phase difference between the fundamental wave and the second-harmonic wave on the properties of generated terahertz pulses. We demonstrate that we can tune the time shape of terahertz pulses, causing them to reverse polarity or become bipolar by carefully selecting the correct combination of chirp and phase. Additionally, we introduce a novel technique for polarization characterization, termed terahertz unipolar polarimetry, which utilizes a weak probe beam and avoids the systematic errors associated with traditional methods. This technique is effective for detecting polarization-structured terahertz beams and the longitudinal component of focused terahertz beams. Our findings contribute to the improved control and characterization of terahertz radiation, enhancing its application in fields such as nonlinear optics, spectroscopy, and microscopy.

Transition from Diffusive to Superdiffusive Transport in Carbon Nanotube Networks via Nematic Order Control.

The one-dimensional confinement of quasiparticles in individual carbon nanotubes (CNTs) leads to extremely anisotropic electronic and optical properties. In a macroscopic ensemble of randomly oriented CNTs, this anisotropy disappears together with other properties that make them attractive for certain device applications. The question however remains if not only anisotropy but also other types of behaviors are suppressed by disorder. Here, we compare the dynamics of quasiparticles under strong electric fields in aligned and random CNT networks using a combination of terahertz emission and photocurrent experiments and out-of-equilibrium numerical simulations. We find that the degree of alignment strongly influences the excited quasiparticles' dynamics, rerouting the thermalization pathways. This is, in particular, evidenced in the high-energy, high-momentum electronic population (probed through the formation of low energy excitons via exciton impact ionization) and the transport regime evolving from diffusive to superdiffusive.

A Simple-Structured Perovskite Wavelength Sensor for Full-Color Imaging Application.

In this study, simple-structured wavelength sensors were developed by depositing two back-to-back Au/MAPbI3/Au photodetectors on an MAPbI3 single crystal. This sensor could quantitatively distinguish wavelengths. Further device analysis showed that both photodetectors possess entirely disparate optoelectronic properties. Consequently, the as-developed wavelength sensor could accurately distinguish incident-light wavelengths ranging from 265 to 860 nm with a resolution of less than 1.5 nm based on the relation between the photocurrent ratios of both photodetectors and the incident light wavelengths. Notably, a high resolution and wide detection range are among the optimum reported values for such sensors and enable full-color imaging. Furthermore, technology computer-aided design (TCAD) simulations showed that a mechanism involved in distinguishing wavelengths is attributed to the wavelength-dependent photon generation rate in MAPbI3 single crystals. The high-performance MAPbI3 wavelength sensor can potentially drive the research progress of perovskites in wavelength recognition and full-color imaging.

Probing the Formation of Dark Interlayer Excitons via Ultrafast Photocurrent.

Optically dark excitons determine a wide range of properties of photoexcited semiconductors yet are hard to access via conventional time-resolved spectroscopies. Here, we develop a time-resolved ultrafast photocurrent technique (trPC) to probe the formation dynamics of optically dark excitons. The nonlinear nature of the trPC makes it particularly sensitive to the formation of excitons occurring at the femtosecond time scale after the excitation. As a proof of principle, we extract the interlayer exciton formation time of 0.4 ps at 160 µJ/cm2 fluence in a MoS2/MoSe2 heterostructure and show that this time decreases with fluence. In addition, our approach provides access to the dynamics of carriers and their interlayer transport. Overall, our work establishes trPC as a technique to study dark excitons in various systems that are hard to probe by other approaches.

Stable Radical Isoporphyrin Copolymer Prepared with Di(phenylphosphane).

Two diphosphanes with variable-length ligands tested as nucleophiles to prepare isoporphyrin copolymers in the presence of ditolylporphyrin of zinc (ZnT2P) prevented the oxidation of the diphosphine ligand. This paper demonstrates the power of this approach and describes the photoelectrocatalytic properties. The obtained copolymers were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy, atomic force micrograph (AFM), EQCM (Electrochemical Quartz Cristal Microbalance) and electrochemistry. Their impedance properties (EIS) were studied and their photovoltaic performances were also investigated by photocurrent transient measurements under visible light irradiation.

Hot or Not? Reassessing Mechanisms of Photocurrent Generation in Plasmon-Enhanced Electrocatalysis.

It is now widely accepted that certain effects arising from localised surface plasmon resonance, such as enhanced electromagnetic fields, hot carriers, and thermal effects, can facilitate electrocatalytic processes. This newly emerging field of research is commonly referred to as plasmon-enhanced electrocatalysis (PEEC) and is attracting increasing interest from the research community, particularly regarding harnessing the high energy of hot carriers. However, this has led to a lack of critical analysis in the literature, where the participation of hot carriers is routinely claimed due to their perceived desirability, while the contribution of other effects is often not sufficiently investigated. As a result, correctly differentiating between the possible mechanisms at play has become a key point of contention. In this review, we specifically focus on the mechanisms behind photocurrents observed in PEEC and critically evaluate the possibility of alternative sources of current enhancement in the reported PEEC systems. Furthermore, we present guidelines for the best experimental practices and methods to distinguish between the various enhancement mechanisms in PEEC.

Pressure-Tuning Localized Excitons Toward Enhanced Emission, Photocurrent Enhancement and Piezochromism in Unconventional ACI-Type 2D Hybrid Perovskites.

Simultaneous enhancement of free excitons (FEs) emission and self-trapped excitons (STEs) emission remains greatly challenging because of the radiative pathway competition. Here, a significant fluorescence improvement, associated with the radiative recombination of both FEs and STEs is firstly achieved in an unconventional ACI-type hybrid perovskite, (ACA)(MA)PbI4 (ACA=acetamidinium) crystals with {PbI6} octahedron units, through hydrostatic pressure processing. Note that (ACA)(MA)PbI4 exhibits a 91.5-fold emission enhancement and considerable piezochromism from green to red in a mild pressure interval of 1 atm to 2.5 GPa. The substantial distortion of both individual halide octahedron and the Pb-I-Pb angles between two halide octahedra under high pressure indeed determines the pressure-tuning localized excitons behavior. Upon higher pressure, photocurrent enhancement is also observed, which is attributed to the promoted electronic connectivity in (ACA)(MA)PbI4. The anisotropic compaction reduces the distance between neighboring organic molecules and {PbI6} octahedra, leading to the enhancement of hydrogen bonding interactions. This work not only offers a deep understanding of the structure-optical relationships of ACI-type perovskites, but also presents insights into breaking the limits of luminescent efficiency by pressure-suppressed nonradiative recombination.

The Retinal Basis of Light Aversion in Neonatal Mice.

Aversive responses to bright light (photoaversion) require signaling from the eye to the brain. Melanopsin-expressing intrinsically photosensitive retinal ganglion cells (ipRGCs) encode absolute light intensity and are thought to provide the light signals for photoaversion. Consistent with this, neonatal mice exhibit photoaversion before the developmental onset of image vision, and melanopsin deletion abolishes photoaversion in neonates. It is not well understood how the population of ipRGCs, which constitutes multiple physiologically distinct types (denoted M1-M6 in mouse), encodes light stimuli to produce an aversive response. Here, we provide several lines of evidence that M1 ipRGCs that lack the Brn3b transcription factor drive photoaversion in neonatal mice. First, neonatal mice lacking TRPC6 and TRPC7 ion channels failed to turn away from bright light, while two photon Ca2+ imaging of their acutely isolated retinas revealed reduced photosensitivity in M1 ipRGCs, but not other ipRGC types. Second, mice in which all ipRGC types except for Brn3b-negative M1 ipRGCs are ablated exhibited normal photoaversion. Third, pharmacological blockade or genetic knockout of gap junction channels expressed by ipRGCs, which reduces the light sensitivity of M2-M6 ipRGCs in the neonatal retina, had small effects on photoaversion only at the brightest light intensities. Finally, M1s were not strongly depolarized by spontaneous retinal waves, a robust source of activity in the developing retina that depolarizes all other ipRGC types. M1s therefore constitute a separate information channel between the neonatal retina and brain that could ensure behavioral responses to light but not spontaneous retinal waves.SIGNIFICANCE STATEMENT At an early stage of development, before the maturation of photoreceptor input to the retina, neonatal mice exhibit photoaversion. On exposure to bright light, they turn away and emit ultrasonic vocalizations, a cue to their parents to return them to the nest. Neonatal photoaversion is mediated by intrinsically photosensitive retinal ganglion cells (ipRGCs), a small percentage of the retinal ganglion cell population that express the photopigment melanopsin and depolarize directly in response to light. This study shows that photoaversion is mediated by a subset of ipRGCs, called M1-ipRGCs. Moreover, M1-ipRGCs have reduced responses to retinal waves, providing a mechanism by which the mouse distinguishes light stimulation from developmental patterns of spontaneous activity.

Titanium dioxide nanoparticles enhance photocurrent generation of cyanobacteria.

Photosynthetic microorganisms such as cyanobacteria can convert photons into electrons, providing ideal eco-friendly materials for converting solar energy into electricity. However, the electrons are hardly transported outside the cyanobacterial cells due to the insulation feature of the cell wall/membrane. Various nanomaterials have been reported to enhance extracellular electron transfer of heterotrophic electroactive microorganisms, but its effect on intact photosynthetic microorganisms remains unclear. In this study, we investigated the effect of six different nanomaterials on the photocurrent generation of cyanobacterium Synechocystis sp. PCC 6803. Among the nanomaterials tested, titanium dioxide (TiO2) nanoparticles increased the photocurrent generation of Synechocystis sp. PCC 6803 up to four-fold at the optimum concentration of 2 mg/mL. Transmission electron microscopy and scanning electron microscopy showed that TiO2 bound to cyanobacterial cells and likely penetrated inside of cell membrane. Photochemical analyses for photosystems showed that TiO2 blocked the electrons transfer downstream in PS I, implying a possible extracellular electron pathway mediated by TiO2. This study provides an alternative approach for enhancing the photocurrent generation of cyanobacteria, showing the potential of photosynthetic-nanomaterial hybrids.

Optoelectronic and Optomechanical Properties of Few-Atomic-Layer Black Phosphorus Nanoflakes as Revealed by In Situ TEM.

The optoelectronic signatures of free-standing few-atomic-layer black phosphorus nanoflakes are analyzed by in situ transmission electron microscopy (TEM). As compared to other 2D materials, the band gap of black phosphorus (BP) is related directly to multiple thicknesses and can be tuned by nanoflake thickness and strain. The photocurrent measurements with the TEM show a stable response to infrared light illumination and change of nanoflakes band gap with deformation while pressing them between two electrodes assembled in the microscope. The photocurrent spectra of an 8- and a 6-layer BP nanoflake samples are comparatively measured. Density functional theory (DFT) calculations are performed to identify the band structure changes of BP during deformations. The results should help to find the best pathways for BP smart band gap engineering via tuning the number of material atomic layers and programmed deformations to promote future optoelectronic applications.