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Rapid, nondestructive characterization techniques for evaluating the degree of crystallinity and phase segregation of organic semiconductor blend thin films are highly desired for in-line, automated optoelectronic device fabrication facilities. Here, it is demonstrated that reflection polarized optical microscopy (POM), a simple technique capable of imaging local anisotropy of materials, is capable of determining the relative degree of crystallinity and phase segregation of thin films of polymer:fullerene blends. While previous works on POM of organic semiconductors have largely employed the transmission geometry, it is demonstrated that reflection POM provides 3× greater contrast. The optimal configuration is described to maximize contrast from POM images of polymer:fullerene films, which requires Köhler illumination and slightly uncrossed polarizers, with an uncrossing angle of ±3°. It is quantitatively demonstrated that contrast in POM images directly correlates with 1) the degree of polymer crystallinity and 2) the degree of phase segregation between polymer and fullerene domains. The origin of the bright and dark domains in POM is identified as arising from symmetry-broken liquid crystalline phases (i.e., dark conglomerates), and it is proven that they have no correlation with surface topography. The use of reflection POM as a rapid diagnostic tool for automated device fabrication facilities is discussed., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Two-dimensional (2D) in-plane heterostructures display exceptional optical and electrical properties well beyond those of their pristine components. However, they are usually produced by tedious and energy-intensive bottom-up growth approaches, not compatible with scalable solution-processing technologies. Here, we report a new stepwise microfluidic approach, based on defect engineering of liquid-phase exfoliated transition metal dichalcogenides (TMDs), to synthesize 2D hetero-networks. The healing of sulfur vacancies in MoS 2 and WS 2 is exploited to controllably bridge adjacent nanosheets of different chemical nature with dithiolated conjugated molecular linkers, yielding solution-processed nm-scale thick networks with enhanced percolation pathways for charge transport. In-plane growth and molecular-driven assembly synergistically lead to molecularly engineered heterojunctions suppressing the formation of tightly bound interlayer excitons that are typical of conventional TMD blends, promoting faster charge separation. Our strategy offers an unprecedented route to chemically assemble solution-processed heterostructures with functional complexity that can be further enhanced by exploiting stimuli-responsive molecular linkers.

Interface engineering is the core of device optimization, and this is particularly true for perovskite photovoltaics (PVs). The steady improvement in their performance has been largely driven by careful manipulation of interface chemistry to reduce unwanted recombination. Despite that, PVs devices still suffer from unavoidable open circuit voltage (V OC ) losses. Here, we propose a different approach by creating a photo-ferroelectric perovskite interface. By engineering an ultrathin ferroelectric two-dimensional perovskite (2D) which sandwiches a perovskite bulk, we exploit the electric field generated by external polarization in the 2D layer to enhance charge separation and minimize interfacial recombination. As a result, we observe a net gain in the device V OC reaching 1.21 V, the highest value reported to date for highly efficient perovskite PVs, leading to a champion efficiency of 24%. Modeling depicts a coherent matching of the crystal and electronic structure at the interface, robust to defect states and molecular reorientation. The interface physics is finely tuned by the photoferroelectric field, representing a new tool for advanced perovskite device design., (© 2024. The Author(s).)

To achieve the full potential of monolithic perovskite/silicon tandem solar cells, crystal defects and film inhomogeneities in the perovskite top cell must be minimized. We discuss the use of methylenediammonium dichloride as an additive to the perovskite precursor solution, resulting in the incorporation of in situ-formed tetrahydrotriazinium (THTZ-H + ) into the perovskite lattice upon film crystallization. The cyclic nature of the THTZ-H + cation enables a strong interaction with the lead octahedra of the perovskite lattice through the formation of hydrogen bonds with iodide in multiple directions. This structure improves the device power conversion efficiency (PCE) and phase stability of 1.68 electron volts perovskites under prolonged light and heat exposure under 1-sun illumination at 85°C. Monolithic perovskite/silicon tandems incorporating THTZ-H + in the perovskite photo absorber reached a 33.7% independently certified PCE for a device area of 1 square centimeter.

Leveraging breakthroughs in Y-series nonfullerene acceptors (NFAs), organic solar cells (OSCs) have achieved impressive power conversion efficiencies (PCEs) exceeding 19%. However, progress in advancing OSCs has decelerated due to constraints in realizing the full potential of the Y-series NFAs. Herein, a simple yet effective solid additive-induced preaggregation control method employing 2-chloro-5-iodopyridine (PDCI) is reported to unlock the full potential of the Y-series NFAs. Specifically, PDCI interacts predominantly with Y-series NFAs enabling enhanced and ordered phase-aggregation in solution. This method leads to a notable improvement and a redshifted absorption of the acceptor phase during film formation, along with improved crystallinity. Moreover, the PDCI-induced preaggregation of NFAs in the solution enables ordered molecule packing during the film-formation process through delicate intermediate states transition. Consequently, the PDCI-induced preaggregated significantly improves the PCE of PM6:Y6 OSCs from 16.12% to 18.12%, among the best values reported for PM6:Y6 OSCs. Importantly, this approach is universally applicable to other Y-series NFA-based OSCs, achieving a champion PCE of 19.02% for the PM6:BTP-eC9 system. Thus, the preaggregation control strategy further unlocks the potential of Y-series NFAs, offering a promising avenue for enhancing the photovoltaic performance of Y-series NFA-based OSCs., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Conjugated polymer films, which can conduct both ionic and electronic charges, are central to building soft electronic sensors and actuators. Despite the possible interplay between light absorption and the mixed conductivity of these materials in aqueous biological media, no single polymer film has been utilized to create a solar-switchable organic bioelectronic circuit that relies on a fully reversible and redox reaction-free potentiometric photodetection and current modulation. Here we demonstrate that the absorption of light by an electron and cation-transporting polymer film reversibly modulates its electrochemical potential and conductivity in an aqueous electrolyte, which is harnessed to design an n-type photo-electrochemical transistor (n-OPECT). By controlling the intensity of light incident on the n-type polymeric gate electrode, we generate transistor output characteristics that mimic the modulation of the polymeric channel current achieved through gate voltage control. The micron-scale n-OPECT exhibits a high signal-to-noise ratio and an excellent sensitivity to low light intensities. We demonstrate three direct applications of the n-OPECT, i.e., a photoplethysmogram recorder, a light-controlled inverter circuit, and a light-gated artificial synapse, underscoring the suitability of this platform for a myriad of biomedical applications that involve light intensity changes., (© 2023. Springer Nature Limited.)

Terahertz emission from ferromagnetic/non-magnetic spintronic heterostructures had been demonstrated as pump wavelength-independent. We report, however, the pump wavelength dependence of terahertz emission from an optimized Fe/Pt spintronic bilayer on MgO substrate. Maximum terahertz generation per total pump power was observed in the 1200- to 1800-nm pump wavelength range, and a marked decrease in the terahertz emission efficiency beyond 2500 nm (pump photon energies <0.5 eV) suggests a ∼0.35-eV threshold pump photon energy for effective spintronic terahertz emission. The inferred threshold is supported by previous theoretical results on the onset energy of significant spin-filtering at the Fe-Pt interface, and confirmed by Fe/Pt electronic structure calculations in this present work. The results of terahertz time-domain emission spectroscopy show the sensitivity of spintronic terahertz emission to both the optical absorptance of the heterostructure and the energy-dependent spin transport, as dictated by the properties of the metallic thin films., Competing Interests: The authors declare no competing interests., (© 2022 The Author(s).)

Type-II heterostructures (HSs) are essential components of modern electronic and optoelectronic devices. Earlier studies have found that in type-II transition metal dichalcogenide (TMD) HSs, the dominating carrier relaxation pathway is the interlayer charge transfer (CT) mechanism. Here, this report shows that, in a type-II HS formed between monolayers of MoSe 2 and ReS 2 , nonradiative energy transfer (ET) from higher to lower work function material (ReS 2 to MoSe 2 ) dominates over the traditional CT process with and without a charge-blocking interlayer. Without a charge-blocking interlayer, the HS area shows 3.6 times MoSe 2 photoluminescence (PL) enhancement as compared to the MoSe 2 area alone. In a completely encapsulated sample, the HS PL emission further increases by a factor of 6.4. After completely blocking the CT process, more than 1 order of magnitude higher MoSe 2 PL emission was achieved from the HS area. This work reveals that the nature of this ET is truly a resonant effect by showing that in a similar type-II HS formed by ReS 2 and WSe 2 , CT dominates over ET, resulting in a severely quenched WSe 2 PL. This study not only provides significant insight into the competing interlayer processes but also shows an innovative way to increase the PL emission intensity of the desired TMD material using the ET process by carefully choosing the right material combination for HS.

With rapidly growing photoconversion efficiencies, hybrid perovskite solar cells have emerged as promising contenders for next generation, low-cost photovoltaic technologies. Yet, the presence of nanoscale defect clusters, that form during the fabrication process, remains critical to overall device operation, including efficiency and long-term stability. To successfully deploy hybrid perovskites, we must understand the nature of the different types of defects, assess their potentially varied roles in device performance, and understand how they respond to passivation strategies. Here, by correlating photoemission and synchrotron-based scanning probe X-ray microscopies, we unveil three different types of defect clusters in state-of-the-art triple cation mixed halide perovskite thin films. Incorporating ultrafast time-resolution into our photoemission measurements, we show that defect clusters originating at grain boundaries are the most detrimental for photocarrier trapping, while lead iodide defect clusters are relatively benign. Hexagonal polytype defect clusters are only mildly detrimental individually, but can have a significant impact overall if abundant in occurrence. We also show that passivating defects with oxygen in the presence of light, a previously used approach to improve efficiency, has a varied impact on the different types of defects. Even with just mild oxygen treatment, the grain boundary defects are completely healed, while the lead iodide defects begin to show signs of chemical alteration. Our findings highlight the need for multi-pronged strategies tailored to selectively address the detrimental impact of the different defect types in hybrid perovskite solar cells., Competing Interests: Samuel D. Stranks is a Co-Founder of Swift Solar Inc., (This journal is © The Royal Society of Chemistry.)

Strong plasmon-exciton coupling between tightly-bound excitons in organic molecular semiconductors and surface plasmons in metal nanostructures has been studied extensively for a number of technical applications, including low-threshold lasing and room-temperature Bose-Einstein condensates. Typically, excitons with narrow resonances, such as J -aggregates, are employed to achieve strong plasmon-exciton coupling. However, J -aggregates have limited applications for optoelectronic devices compared with organic conjugated polymers. Here, using numerical and analytical calculations, we demonstrate that strong plasmon-exciton coupling can be achieved for Ag-conjugated polymer core-shell nanostructures, despite the broad spectral linewidth of conjugated polymers. We show that strong plasmon-exciton coupling can be achieved through the use of thick shells, large oscillator strengths, and multiple vibronic resonances characteristic of typical conjugated polymers, and that Rabi splitting energies of over 1000 meV can be obtained using realistic material dispersive relative permittivity parameters. The results presented herein give insight into the mechanisms of plasmon-exciton coupling when broadband excitonic materials featuring strong vibrational-electronic coupling are employed and are relevant to organic optoelectronic devices and hybrid metal-organic photonic nanostructures.

Halide perovskite materials have promising performance characteristics for low-cost optoelectronic applications. Photovoltaic devices fabricated from perovskite absorbers have reached power conversion efficiencies above 25 per cent in single-junction devices and 28 per cent in tandem devices 1,2 . This strong performance (albeit below the practical limits of about 30 per cent and 35 per cent, respectively 3 ) is surprising in thin films processed from solution at low-temperature, a method that generally produces abundant crystalline defects 4 . Although point defects often induce only shallow electronic states in the perovskite bandgap that do not affect performance 5 , perovskite devices still have many states deep within the bandgap that trap charge carriers and cause them to recombine non-radiatively. These deep trap states thus induce local variations in photoluminescence and limit the device performance 6 . The origin and distribution of these trap states are unknown, but they have been associated with light-induced halide segregation in mixed-halide perovskite compositions 7 and with local strain 8 , both of which make devices less stable 9 . Here we use photoemission electron microscopy to image the trap distribution in state-of-the-art halide perovskite films. Instead of a relatively uniform distribution within regions of poor photoluminescence efficiency, we observe discrete, nanoscale trap clusters. By correlating microscopy measurements with scanning electron analytical techniques, we find that these trap clusters appear at the interfaces between crystallographically and compositionally distinct entities. Finally, by generating time-resolved photoemission sequences of the photo-excited carrier trapping process 10,11 , we reveal a hole-trapping character with the kinetics limited by diffusion of holes to the local trap clusters. Our approach shows that managing structure and composition on the nanoscale will be essential for optimal performance of halide perovskite devices.

Integration of organic/inorganic hybrid perovskites with metallic or semiconducting phases of 2D MoS 2 nanosheets via solution processing is demonstrated. The results show that the collection of charge carriers is strongly dependent on the electronic properties of the 2D MoS 2 with metallic MoS 2 showing high responsivity and the semiconducting phase exhibiting high on/off ratios., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hybrid organic-inorganic heterostructures are attracting tremendous attention for optoelectronic applications due to their low-cost processing and high performance in devices. In particular, van der Waals p-n heterojunctions formed between inorganic two-dimensional (2D) materials and organic semiconductors are of interest due to the quantum confinement effects of 2D materials and the synthetic control of the physical properties of organic semiconductors, enabling a high degree of tunable optoelectronic properties for the heterostructure. However, for photovoltaic applications, hybrid 2D-organic heterojunctions have demonstrated low power conversion efficiencies due to the limited absorption from constraints on the physical thickness of each layer. Here, we investigate the ultrafast charge transfer dynamics between an organic polymer:fullerene blend and 2D n-type MoS 2 using transient pump-probe reflectometry. We employ plasmonic metasurfaces to enhance the absorption and charge photogeneration within the physically thin hybrid MoS 2 -organic heterojunction. For the hybrid MoS 2 -organic heterojunction in the presence of the plasmonic metasurface, the charge generation within the polymer is enhanced 6-fold, and the total active layer absorption bandwidth is increased by 90 nm relative to the polymer:fullerene blend alone. We demonstrate that MoS 2 -organic heterojunctions can serve as hybrid solar cells, and their efficiencies can be improved using plasmonic metasurfaces.

Van der Waals materials, existing in a range of thicknesses from monolayer to bulk, allow for interplay between surface and bulk nonlinearities, which otherwise dominate only at atomically-thin or bulk extremes, respectively. Here, we observe an unexpected peak in intensity of the generated second harmonic signal versus the thickness of Indium Selenide crystals, in contrast to the quadratic increase expected from thin crystals. We explain this by interference effects between surface and bulk nonlinearities, which offer a new handle on engineering the nonlinear optical response of 2D materials and their heterostructures.

Interactions between absorbers and plasmonic metasurfaces can give rise to unique optical properties not present for either of the individual materials and can influence the performance of a host of optical sensing and thin-film optoelectronic applications. Here we identify three distinct mode types of absorber-coated plasmonic metasurfaces: localized and propagating surface plasmons and a previously unidentified optical mode type called absorption-induced scattering. The extinction of the latter mode type can be tuned by controlling the morphology of the absorber coating and the spectral overlap of the absorber with the plasmonic modes. Furthermore, we show that surface plasmons are backscattered when the crystallinity of the absorber is low but are absorbed for more crystalline absorber coatings. This work furthers our understanding of light-matter interactions between absorbers and surface plasmons to enable practical optoelectronic applications of metasurfaces.