On-chip detection of radiation guided by dielectric-loaded plasmonic waveguides.

We report a novel approach for on-chip electrical detection of the radiation guided by dielectric-loaded surface plasmon polariton waveguides (DLSPPW) and DLSPPW-based components. The detection is realized by fabricating DLSPPW components on the surface of a gold (Au) pad supported by a silicon (Si) substrate supplied with aluminum pads facilitating electrical connections, with the gold pad being perforated in a specific location below the DLSPPWs in order to allow a portion of the DLSPPW-guided radiation to leak into the Si-substrate, where it is absorbed and electrically detected. We present two-dimensional photocurrent maps obtained when the laser beam is scanning across the gold pad containing the fabricated DLSPPW components that are excited via grating couplers located at the DLSPPW tapered terminations. By comparing photocurrent signals obtained when scanning over a DLSPPW straight waveguide with those related to a DLSPPW racetrack resonator, we first determine the background signal level and then the corrected DLSPPW resonator spectral response, which is found consistent with that obtained from full wave numerical simulations. The approach developed can be extended to other plasmonic waveguide configurations and advantageously used for rapid characterization of complicated plasmonic circuits.

Van der Waals Schottky Junction Photodetector with Ultrahigh Rectifying Ratio and Switchable Photocurrent Generation.

Metal-semiconductor junctions play an important role in the development of electronic and optoelectronic devices. A Schottky junction photodetector based on two-dimensional (2D) materials is promising for self-powered photodetection with fast response speed and large signal-to-noise ratio. However, it usually suffers from an uncontrolled Schottky barrier due to the Fermi level pinning effect arising from the interface states. In this work, all-2D Schottky junctions with near-ideal Fermi level depinning are realized, attributed to the high-quality interface between 2D semimetals and semiconductors. We further demonstrate asymmetric diodes based on multilayer graphene/MoS2/PtSe2 with a current rectification ratio exceeding 105 and an ideality factor of 1.2. Scanning photocurrent mapping shows that the photocurrent generation mechanism in the heterostructure switches from photovoltaic effect to photogating effect at varying drain biases, indicating both energy conversion and optical sensing are realized in a single device. In the photovoltaic mode, the photodetector is self-powered with a response time smaller than 100 µs under the illumination of a 405 nm laser. In the photogating mode, the photodetector exhibits a high responsivity up to 460 A/W originating from a high photogain. Finally, the photodetector is employed for single-pixel imaging, demonstrating its high-contrast photodetection ability. This work provides insight into the development of high-performance self-powered photodetectors based on 2D Schottky junctions.

Two-Dimensional Cs2AgBiBr6/WS2 Heterostructure-Based Photodetector with Boosted Detectivity via Interfacial Engineering.

Two-dimensional (2D) transition metal dichalcogenide (TMDC) monolayers have been widely used for optoelectronic devices because of their ultrasensitivity to light detection acquired from their direct gap properties. However, the small cross-section of photon absorption in the atomically thin layer thickness significantly limits the generation of photocarriers, restricting their performance. Here, we integrate monolayer WS2 with 2D perovskites Cs2AgBiBr6, which serve as the light absorption layer, to greatly enhance the photosensitivity of WS2. The efficient charge transfer at the Cs2AgBiBr6/WS2 heterojunction is evidenced by the shortened photoluminescence (PL) decay time of Cs2AgBiBr6. Scanning photocurrent microscopy of Cs2AgBiBr6/WS2/graphene reveals that improved charge extraction from graphene leads to an enhanced photoresponse. The 2D Cs2AgBiBr6/WS2/graphene vertical heterostructure photodetector exhibits a high detectivity (D*) of 1.5 × 1013 Jones with a fast response time of 52.3 µs/53.6 µs and an on/off ratio of 1.02 × 104. It is worth noting that this 2D heterostructure photodetector can realize self-powered light detection behavior with an open-circuit voltage of ∼0.75 V. The results suggest that the 2D perovskites can effectively improve the TMDC layer-based photodetectors for low-power consumption photoelectrical applications.

Intensity Modulated Photocurrent Microspectrosopy for Next Generation Photovoltaics.

In this report, a large-area laser beam induced current microscope that has been adapted to perform intensity modulated photocurrent spectroscopy (IMPS) in an imaging mode is described. Microscopy-based IMPS method provides a spatial resolution of the frequency domain response of the solar cell, allowing correlation of the optoelectronic response with a particular interface, bulk material, specific transport layer, or transport parameter. The system is applied to study degradation effects in back-contact perovskite cells where it is found to readily differentiate areas based on their markedly different frequency response. Using the diffusion-recombination model, the IMPS response is modeled for a sandwich structure and extended for the special case of lateral diffusion in a back-contact cell. In the low-frequency limit, the model is used to calculate spatial maps of the carrier ambipolar diffusion length. The observed frequency response of IMPS images is then discussed.

Direct observation and manipulation of hot electrons at room temperature.

In modern electronics and optoelectronics, hot electron behaviors are highly concerned, as they determine the performance limit of a device or system, like the associated thermal or power constraint of chips and the Shockley-Queisser limit for solar cell efficiency. To date, however, the manipulation of hot electrons has been mostly based on conceptual interpretations rather than a direct observation. The problem arises from a fundamental fact that energy-differential electrons are mixed up in real-space, making it hard to distinguish them from each other by standard measurements. Here we demonstrate a distinct approach to artificially (spatially) separate hot electrons from cold ones in semiconductor nanowire transistors, which thus offers a unique opportunity to observe and modulate electron occupied state, energy, mobility and even path. Such a process is accomplished through the scanning-photocurrent-microscopy measurements by activating the intervalley-scattering events and 1D charge-neutrality rule. Findings here may provide a new degree of freedom in manipulating non-equilibrium electrons for both electronic and optoelectronic applications.

Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior.

Transition metal dichalcogenide (TMD) nanoflake thin films are attractive electrode materials for photoelectrochemical (PEC) solar energy conversion and sensing applications, but their photocurrent quantum yields are generally lower than those of bulk TMD electrodes. The poor PEC performance has been primarily attributed to enhanced charge carrier recombination at exposed defect and edge sites introduced by the exfoliation process. Here, a single nanoflake PEC approach reveals how an alternative effect, doping heterogeneity, limits ensemble-level PEC performance. Photocurrent mapping and local photocurrent-potential (i-E) measurements of MoS2 nanoflakes exfoliated from naturally occurring bulk crystals revealed the presence of n- and p-type domains within the same nanoflake. Interestingly, the n- and p-type domains in the natural MoS2 nanoflakes were equally efficient for iodide oxidation and tri-iodide reduction (IQE values exceed 80%). At the single domain-level, the natural MoS2 nanoflakes were nearly as efficient as nanoflakes exfoliated from synthetic n-type MoS2 crystals. Single domain-level i-E measurements explain why natural MoS2 nanoflakes exhibit an n-type to p-type photocurrent switching effect in ensemble-level measurements: the n- and p-type diode currents from individual domains oppose each other upon illuminating the entire nanoflake, resulting in zero photocurrent at the switching potential. The doping heterogeneity effect is likely due to nonideal stoichiometry, where p-type domains are S-rich according to XPS measurements. Although this doping heterogeneity effect limits photoanode or photocathode performance, these findings open the possibility to synthesize efficient TMD nanoflake photocatalysts with well-defined lateral p- and n-type domains for enhanced charge separation.

Probing the Importance of Charge Balance and Noise Current in WSe2/WS2/MoS2 van der Waals Heterojunction Phototransistors by Selective Electrostatic Doping.

Heterojunction structures using 2D materials are promising building blocks for electronic and optoelectronic devices. The limitations of conventional silicon photodetectors and energy devices are able to be overcome by exploiting quantum tunneling and adjusting charge balance in 2D p-n and n-n junctions. Enhanced photoresponsivity in 2D heterojunction devices can be obtained with WSe2 and BP as p-type semiconductors and MoS2 and WS2 as n-type semiconductors. In this study, the relationship between photocurrent and the charge balance of electrons and holes in van der Waals heterojunctions is investigated. To observe this phenomenon, a p-WSe2/n-WS2/n-MoS2 heterojunction device with both p-n and n-n junctions is fabricated. The device can modulate the charge carrier balance between heterojunction layers to generate photocurrent upon illumination by selectively applying electrostatic doping to a specific layer. Using photocurrent mapping, the operating transition zones for the device is demonstrated, allowing to accurately identify the locations where photocurrent generates. Finally, the origins of flicker and shot noise at the different semiconductor interfaces are analyzed to understand their effect on the photoresponsivity and detectivity of unit active area (2.5 µm2, λ = 405 nm) in the p-WSe2/n-WS2/n-MoS2 heterojunction device.

Laser Annealing Improves the Photoelectrochemical Activity of Ultrathin MoSe2 Photoelectrodes.

Understanding light-matter interactions in transition-metal dichalcogenides (TMDs) is critical for optoelectronic device applications. Several studies have shown that high intensity light irradiation can tune the optical and physical properties of pristine TMDs. The enhancement in optoelectronic properties has been attributed to a so-called laser annealing effect that heals chalcogen vacancies. However, it is unknown whether laser annealing improves functional properties such as photocatalytic activity. Here, we show that high intensity supra band gap illumination improves the photoelectrochemical activity of MoSe2 nanosheets for iodide oxidation in indium doped tin oxide/MoSe2/I-, I3-/Pt liquid junction solar cells. Ensemble-level photoelectrochemical measurements show that, on average, illuminating MoSe2 thin films with 1 W/cm2 532 nm excitation increases the photoelectrochemical current by 142% and shifts the photocurrent response to more favorable (negative) potentials. Scanning photoelectrochemical microscopy measurements reveal that pristine bilayer (2L)-MoSe2, trilayer (3L)-MoSe2, and multilayer-thick nanosheets are initially inactive for iodide oxidation. The light treatment activates 2L-MoSe2 and 3L-MoSe2 materials, and the activation process initiates at the edge sites. The photocurrent enhancement is more significant for 2L-MoSe2 than for 1L-MoSe2. Multilayer-thick MoSe2 remains inactive for iodide oxidation even after the laser treatment. Our microscopy measurements reveal that the laser-induced enhancement effect depends critically on MoSe2 layer thickness. X-ray photoelectron spectroscopy measurements further show that the laser treatment oxidizes Mo(IV) species that are initially associated with Se vacancies. Ambient oxygen fills the Se vacancies and removes trap states, thereby increasing the overall photogenerated carrier collection efficiency. To the best of our knowledge, this work represents the first report on using laser to enhance the photoelectrocatalytic properties of few-layer-thick TMDs. The simple and rapid laser annealing procedure is a promising strategy to tune the reactivity of TMD-based photoelectrochemical cells for electricity and chemical fuel production.

Role of Photogenerated Iodine on the Energy-Conversion Properties of MoSe2 Nanoflake Liquid Junction Photovoltaics.

Transition metal dichalcogenides (TMDs) such as MoSe2 and WSe2 are efficient materials for converting solar energy to electrical energy in photoelectrochemical photovoltaic cells. One limiting factor of these liquid junction solar cells is that photogenerated oxidation products accumulate on the electrode surface and decrease the photocurrent efficiency. However, it is unclear where the reaction products accumulate on the electrode surface and how they impact the local photoelectrochemical response. This open question is especially important for the structurally heterogeneous TMD nanoflake thin-film electrodes that are promising for large-area solar energy conversion applications. Here, we use a single-nanoflake photoelectrochemical and Raman microscopy approach to probe how the photogenerated I2/I3- products impact the photocurrent collection efficiency and the onset potential in MoSe2-nanoflake|I-/I2|Pt photoelectrochemical solar cells. We observed localized I2/I3- deposition on all types of MoSe2 nanoflake surface motifs, including basal planes, perimeter edges, and interior step edges. Illuminated nanoflake spots with the highest photocurrent collection efficiency are the first to be limited by I2/I3- formation under high-intensity illumination. Interestingly, I2/I3- formation occurs on illuminated surface spots that have the lowest photocurrent onset potential for iodide oxidation, corresponding to the highest open circuit voltage ( VOC). The VOC shifts could be attributed to variations in the surface reaction kinetics or doping density across the nanoflake. Our results highlight important limiting factors of nanoflake thin-film TMD liquid junction photovoltaics under concentrated solar illumination intensities.

Influence of Environmentally Affected Hole-Transport Layers on Spatial Homogeneity and Charge-Transport Dynamics of Organic Solar Cells.

After organic photovoltaic (OPV) cells achieved efficiency of more than 10%, the control of stability and degradation mechanisms of solar cells became a prominent task. The increase of device efficiency due to incorporation of a hole-transport layer (HTL) in bulk-heterojunction solar cells has been extensively reported. However, the most widely used HTL material, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), is frequently suspected to be the dominating source for device instability under environmental conditions. Thereby, effects like photooxidation and electrode corrosion are often reported to shorten device lifetime. However, often in environmental device studies, the source of degradation, whether being from the HTL, the active layer, or the metal cathode is rather difficult to distinguish because the external diffusion of oxygen and water affects all components. In this study, different HTLs, namely, those prepared from traditional PEDOT:PSS and also two types of molybdenum trioxide (MoO3) are exposed to different environments, such as oxygen, light, or humidity, prior to device finalization under inert conditions. This allows investigating any effects within the HTL and from reactions at its interface to the indium tin oxide electrode or the active layer. The surface and bulk chemistry of the exposed HTL has been monitored and discussed in context to the observed device physics, dynamic charge transport, and spatial performance homogeneity of the corresponding OPV device. The results show that merely humidity exposure of the HTL leads to decreased device performance for PEDOT:PSS, but also for one type of the tested MoO3. The losses are related to the amount of absorbed water in the HTL, inducing loss of active area in terms of interfacial contact. The device with PEDOT:PSS HTL after humid air exposure showed seriously decreased photocurrent by microdelamination of swelling/shrinkage of the hygroscopic layer. The colloidal MoO3 with water-based precursor solution presents slight decay of solar cell performance, also here caused by swelling/shrinking reaction, but by a combination of in-plane particle contact and resistance scaling with particle expansion. However, the device with quasi-continuous and alcohol-based MoO3 showed unharmed stable electrical performance.

Short-Term Environmental Effects and Their Influence on Spatial Homogeneity of Organic Solar Cell Functionality.

In this study, we focus on the induced degradation and spatial inhomogeneity of organic photovoltaic devices under different environmental conditions, uncoupled from the influence of any auxiliary hole-transport (HT) layer. During testing of the corresponding devices comprising the standard photoactive layer of poly(3-hexylthiophene) as donor, blended with phenyl-C61-butyric acid methyl ester as acceptor, a comparison was made between the nonencapsulated devices upon exposure to argon in the dark, dry air in the dark, dry air with illumination, and humid air in the dark. The impact on the active layer's photophysics is discussed, along with the device physics in terms of integral solar cell performance and spatially resolved photocurrent distribution with point-to-point analysis of the diode characteristics to determine the origin of the observed integrated organic photovoltaic device behavior. The results show that even without the widely used hygroscopic HT layer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), humidity is still a major factor in the short-term environmental degradation of organic solar cells with this architecture, and not only oxygen or light, as is often reported. Different from previous reports where water-induced device degradation was spatially homogeneous and formation of Al2O3 islands was only seen for oxygen permeation through pinholes in aluminum, we observed insulating islands merely after humidity exposure in the present study. Further, we demonstrated with laser beam induced current mapping and point-to-point diode analysis that the water-induced performance losses are a result of the exposed device area comprising regions with entirely unaltered high output and intact diode behavior and those with severe degradation showing detrimentally lowered output and voltage-independent charge blocking, which is essentially insulating behavior. It is suggested that this is caused by transport of water through pinholes to the organic/metal interface, where they form insulating oxide or hydroxide islands, while the organic active layer stays unharmed.

Transparent and Highly Responsive Phototransistors Based on a Solution-Processed, Nanometers-Thick Active Layer, Embedding a High-Mobility Electron-Transporting Polymer and a Hole-Trapping Molecule.

Organic materials are suitable for light sensing devices showing unique features such as low cost, large area, and flexibility. Moreover, transparent photodetectors are interesting for smart interfaces, windows, and display-integrated electronics. The ease of depositing ultrathin organic films with simple techniques enables low light absorbing active layers, resulting in the realization of transparent devices. Here, we demonstrate a strategy to obtain high efficiency organic photodetectors and phototransistors based on transparent active layers with a visible transmittance higher than 90%. The photoactive layer is composed of two phases, each a few nanometers thick. First, an acceptor polymer, which is a good electron-transporting material, on top of which a small molecule donor material is deposited, forming noncontinuous domains. The small molecule phase acts as a trap for holes, thus inducing a high photoconductive gain, resulting in a high photoresponsivity. The organic transparent detectors proposed here can reach very high external quantum efficiency and responsivity values, which in the case of the phototransistors can be as high as ∼74000% and 340 A W-1 at 570 nm respectively, despite an absorber total thickness below 10 nm. Moreover, frequency dependent 2D photocurrent mapping allows discrimination between the contribution of a fast but inefficient and highly spatially localized photoinduced injection mechanism at the electrodes, and the onset of a slower and spatially extended photoconductive process, leading to high responsivity.

Mo1-xWxSe2-Based Schottky Junction Photovoltaic Cells.

We developed Schottky junction photovoltaic cells based on multilayer Mo1-xWxSe2 with x = 0, 0.5, and 1. To generate built-in potentials, Pd and Al were used as the source and drain electrodes in a lateral structure, and Pd and graphene were used as the bottom and top electrodes in a vertical structure. These devices exhibited gate-tunable diode-like current rectification and photovoltaic responses. Mo0.5W0.5Se2 Schottky diodes with Pd and Al electrodes exhibited higher photovoltaic efficiency than MoSe2 and WSe2 devices with Pd and Al electrodes, likely because of the greater adjusted band alignment in Mo0.5W0.5Se2 devices. Furthermore, we showed that Mo0.5W0.5Se2-based vertical Schottky diodes yield a power conversion efficiency of ∼16% under 532 nm light and ∼13% under a standard air mass 1.5 spectrum, demonstrating their remarkable potential for photovoltaic applications.

High-Performance Inverted Organic Photovoltaics Without Hole-Selective Contact.

A detailed investigation of the functionality of inverted organic photovoltaics (OPVs) using bare Ag contacts as the top electrode is presented. The inverted OPVs without a hole-transporting layer (HTL) exhibit a significant gain in hole-carrier selectivity and power-conversion efficiency (PCE) after exposure in ambient conditions. Inverted OPVs comprised of ITO-ZnO-poly(3-hexylthiophene-2,5-diyl)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM)-Ag demonstrate over 3.5% power conversion efficiency only if the devices are exposed in air for over 4 days. As concluded through a series of measurements, the oxygen presence is essential to obtaining fully operational solar cell devices without HTL. Moreover, accelerated stability tests under damp heat conditions (RH = 85% and T = 65 °C) performed to nonencapsulated OPVs demonstrate that HTL-free inverted OPVs exhibit comparable stability to the reference inverted OPVs. Importantly, it is shown that bare Ag top electrodes can be efficiently used in inverted OPVs using various high-performance polymer-fullerene bulk heterojunction material systems demonstrating 6.5% power-conversion efficiencies.