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Voltage-dependent characterizations of organic solar cells with brightly-emitting charge-transfer excitons reveal excitation dynamics and trends as a function of donor molecule.

Doping has proven to be a critical tool for enhancing the performance of organic semiconductors in devices like organic light-emitting diodes. However, the challenge in working with high-ionization-energy (IE) organic semiconductors is to find p-dopants with correspondingly high electron affinity (EA) that will improve the conductivity and charge carrier transport in a film. Here, we use an oxidant that has been recently recognized to be a very strong p-type dopant, hexacyano-1,2,3-trimethylene-cyclopropane (CN6-CP). The EA of CN6-CP has been previously estimated via cyclic voltammetry to be 5.87 eV, almost 300 meV higher than other known high-EA organic molecular oxidants. We measure the frontier orbitals of CN6-CP using ultraviolet and inverse photoemission spectroscopy techniques and confirm a high EA value of 5.88 eV in the condensed phase. The introduction of CN6-CP in a film of large-band-gap, large-IE phenyldi(pyren-1-yl)phosphine oxide (POPy

Exploiting the capabilities of organic semiconductors for applications ranging from light-emitting diodes to photovoltaics to lasers relies on the creation of ordered, smooth layers for optimal charge carrier mobilities and exciton diffusion. This, in turn, creates a demand for organic small molecules that can form smooth thin film crystals

Following the 2nd release of the “Emerging PV reports,” the best achievements in the performance of emerging photovoltaic devices in diverse emerging photovoltaic research subjects are summarized, as reported in peer‐reviewed articles in academic journals since August 2021. Updated graphs, tables, and analyses are provided with several performance parameters, e.g., power conversion efficiency, open‐circuit voltage, short‐circuit current density, fill factor, light utilization efficiency, and stability test energy yield. These parameters are presented as a function of the photovoltaic bandgap energy and the average visible transmittance for each technology and application, and are put into perspective using, e.g., the detailed balance efficiency limit. The 3rd installment of the “Emerging PV reports” extends the scope toward triple junction solar cells.

High-performance inorganic-organic lead halide perovskite solar cells (PSCs) are often fabricated with a liquid additive such as dimethyl sulfoxide (DMSO), which retards crystallization and reduces roughness and pinholes in the perovskite layers. However, DMSO can be trapped during perovskite film formation and induce voids and undesired reaction byproducts upon later processing steps. Here, it is shown that the amount of residual DMSO can be reduced in as-spin-coated films significantly through use of preheated substrates, or a so-called hot-casting method. Hot casting increases the perovskite film thickness given the same concentration of solutions, which allows for reducing the perovskite solution concentration. By reducing the amount of DMSO in proportion to the concentration of perovskite precursors and using hot casting, it is possible to fabricate perovskite layers with improved perovskite-substrate interfaces by suppressing the formation of byproducts, which increase trap density and accelerate degradation of the perovskite layers. The best-performing PSCs exhibit a power conversion efficiency (PCE) of 23.4% (23.0% stabilized efficiency) under simulated solar illumination. Furthermore, encapsulated devices show considerably reduced post-burn-in decay, retaining 75% and 90% of their initial and post-burn-in efficiencies after 3000 h of operation with maximum power point tracking (MPPT) under high power of ultraviolet (UV)-containing continuous light exposure.

We illustrate the critical importance of the energetics of cation-solvent versus cation-iodoplumbate interactions in determining the stability of ABX

In addition to their attractive technological applications in photovoltaics and light emitters, the perovskite family of semiconductors has recently emerged as an excellent excitonic material for fundamental studies. Specifically, the 2D hybrid organic-inorganic perovskite (HOIP) offers the added advantage of room temperature investigations owing to their large exciton binding energy. In this work, we strongly couple excitons in 2D HOIP crystals to planar microcavity photons sustaining exciton-polaritons under ambient conditions resulting in a Rabi splitting of 290 meV. Dark excitons directly pump the polariton branch along its dispersion in resonance with the Stokes shifted emission state (radiative pumping), creating a high density of polaritons at higher in-plane momentum (k||). We further probe the nonlinear polariton dispersion dynamics at varying input laser fluence, which indicates efficient polariton-polariton scattering and decay to k|| = 0 from higher k||. The observation of Stokes shift-assisted energy exchange of dark states with lower polaritons coupled with evidence of efficient polariton-polariton scattering makes 2D HOIPs an attractive platform to study exciton-polariton many-body physics and Bose-Einstein like condensation (BEC) at room temperature.

We study the temporal, spatial, and spectral evolution of charge carriers in hybrid perovskite thin films after optical excitation with a small laser spot. These are conditions typical of microscop...

Iodine-containing volatiles are major degradation products of halide perovskite materials under irradiation, yet iodine diffusion kinetics into and throughout organic hole transport materials (HTMs...

Solvents employed in the solution processing of metal halide perovskites are known to play a key role in defining the morphology and properties of the resulting thin film, and thus the performance of perovskite solar cell devices. Accurate metrics are needed that are capable of differentiating among candidates, finding solvents that adequately solubilize the various precursor species in solution and facilitate the nucleation and growth of these materials. Existing metrics such as the unsaturated Mayer bond order (UMBO) and the Gutmann donor number (DN) have been tested for lead iodide perovskite systems; but there has yet to be a comprehensive study on their transferability to lead-free perovskite solutions. We use ab initio methods (density functional theory) and regression analysis tools to study the usefulness of DN and BF3 affinity scales in this regard. We compared the relative effectiveness of these scales to describe interactions between solvents and BXn perovskite salts of lead (Pb2+), tin (Sn2+ and Sn4+), germanium (Ge2+), bismuth (Bi3+), and antimony (Sb3+ and Sb5+). The DN proved to be a better representation than the BF3 of such interactions, reflecting the closer similarity of these species to the “parent” SbCl5 Lewis acid than to BF3. In addition, we have uncovered the usefulness of the lithium cation affinity metric (LCA) to describe the strength of interactions between solvents and A-site cations (e.g. Na+, K+, Rb+ and Cs+) in all-inorganic metal halide perovskite solutions. We find that the coordination strengths of solvents towards species in all-inorganic metal halide perovskite solutions are best described by two different metrics with distinct modes of action: DN differentiates among BXn salt complexes, and LCA among A-site cation species. This revelation can help guide the choice of solvent to optimize processing conditions. It also emphasizes the importance of selecting solvents whose DN and LCA optimize coordination to key Lewis acid species in all-inorganic perovskite solutions.

Photocatalysis for organic synthesis is a tool capable of C–C, C–O and C–N bond transformations. This technology has the potential to transform the chemical manufacturing industry and support growing demand for chemical feedstocks. Compared to traditional catalysis, photocatalysis can access alternative reaction pathways that lower the overall energy requirement and operate at or near ambient conditions. A key challenge is the delivery of photoenergy at the scale required for rapid and efficient operation of the catalyst. The development of efficient, broad-spectrum light harvesting devices that funnel light energy to a catalyst, along with catalyst design to selectively enable high-energy reactions, are necessary steps towards solar fuels and feedstocks. This perspective highlights some recent advances in photocatalysis and advocates for expanding the scope of photocatalysis for large-scale industrial applications.

The morphology of organic semiconductors is critical to their function in optoelectronic devices and is particularly crucial in the donor-acceptor mixture that comprises the bulk heterojunction of organic solar cells. Here, energy landscapes can play integral roles in charge photogeneration, and recently have been shown to drive the accumulation of charge carriers away from the interface, resulting in the buildup of large nanoscale electric fields, much like a capacitor. In this work we combine morphological and spectroscopic data to outline the requirements for this interdomain charge accumulation, finding that this effect is driven by a three-phase morphology that creates an energetic cascade for charge carriers. By adjusting annealing conditions, we show that domain purity, but not size, is critical for an electro-absorption feature to grow-in. This demonstrates that the energy landscape around the interface shapes the movement of charges and that pure domains are required for charge carrier buildup that results in reduced recombination and large interdomain nanoscale electric fields.

Perovskite light-emitting diodes (LEDs) have experienced a rapid increase in efficiency over the last several years and are now regarded as promising low-cost devices for displays and communication systems. However, it is often challenging to employ ZnO, a well-studied electron transport material, in perovskite LEDs due to chemical instability at the ZnO/perovskite interface and charge injection imbalance caused by the relatively high conductivity of ZnO. In this work, we address these problems by depositing an ultrathin Al

The constituent ions of halide perovskite materials are mobile in the solid state and known to participate in reduction/oxidation reactions. Yet few parameters related to electrochemical processes ...

Organic photovoltaic (OPV) efficiencies continue to rise, raising their prospects for solar energy conversion. However, researchers have long considered how to suppress the loss of free carriers by recombination-poor diffusion and significant Coulombic attraction can cause electrons and holes to encounter each other at interfaces close to where they were photogenerated. Using femtosecond transient spectroscopies, we report the nanosecond grow-in of a large transient Stark effect, caused by nanoscale electric fields of ∼487 kV/cm between photogenerated free carriers in the device active layer. We find that particular morphologies of the active layer lead to an energetic cascade for charge carriers, suppressing pathways to recombination, which is ∼2000 times less than predicted by Langevin theory. This in turn leads to the buildup of electric charge in donor and acceptor domains-away from the interface-resistant to bimolecular recombination. Interestingly, this signal is only experimentally obvious in thick films due to the different scaling of electroabsorption and photoinduced absorption signals in transient absorption spectroscopy. Rather than inhibiting device performance, we show that devices up to 600 nm thick maintain efficiencies of >8% because domains can afford much higher carrier densities. These observations suggest that with particular nanoscale morphologies the bulk heterojunction can go beyond its established role in charge photogeneration and can act as a capacitor, where adjacent free charges are held away from the interface and can be protected from bimolecular recombination.

Fair and meaningful device per- formance comparison among luminescent solar concentrator- photovoltaic (LSC-PV) reports cannot be realized without a gen- eral consensus on reporting stan- dards in LSC-PV research. There- fore, it is imperative to adopt standardized characterization protocols for these emerging types of PV devices that are consistent with other PV devices. This commentary highlights several common limitations in LSC literature and summarizes the best practices moving for- ward to harmonize with standard PV reporting, considering the greater nuances present with LSC-PV. Based on these prac- tices, a checklist of actionable items is provided to help stan- dardize the characterization/re- porting protocols and offer a set of baseline expectations for au- thors, reviewers, and editors. The general consensus combined with the checklist will ultimately guide LSC-PV research towards reliable and meaningful ad- vances.

Charge transfer (CT) between donors and acceptors following photoexcitation of organic photovoltaics (OPVs) gives rise to bound electron–hole pairs across the donor–acceptor interface, known as CT states. While these states are essential to charge separation, they are also a source of energy loss. As a result of reduced overlap between electron and hole wavefunctions, CT states are influenced by details of the film morphology and molecular structure. Here, we describe several important strategies for tuning the energy level and dynamics of the CT state and approaches that can enhance their dissociation efficiency into free charges. Furthermore, we provide an overview of recent physical insights into the key parameters that significantly reduce the Frenkel-to-CT energy offset and recombination energy losses while preserving a high charge-generation yield. Our analysis leads to critical morphological and molecular design strategies for achieving efficient, low-energy-loss OPVs.

Atomic vibrations can inform about materials properties from hole transport in organic semiconductors to correlated disorder in metal-organic frameworks. Currently, there are several methods for predicting these vibrations using simulations, but the accuracy-efficiency tradeoffs have not been examined in depth. In this study, rubrene is used as a model system to predict atomic vibrational properties using six different simulation methods: density functional theory, density functional tight binding, density functional tight binding with a Chebyshev polynomial-based correction, a trained machine learning model, a pretrained machine learning model called ANI-1, and a classical forcefield model. The accuracy of each method is evaluated by comparison to the experimental inelastic neutron scattering spectrum. All methods discussed here show some accuracy across a wide energy region, though the Chebyshev-corrected tight-binding method showed the optimal combination of high accuracy with low expense. We then offer broad simulation guidelines to yield efficient, accurate results for inelastic neutron scattering spectrum prediction.

Characterizing the energetic disorder of the charge-transfer (CT) state is crucial to understanding organic photovoltaic devices, but is complicated by the discrepancy between temperature-dependent absorption and emission spectra. The authors show that, unlike absorption measurements, electroluminescence measurements do $n\phantom{\rule{0}{0ex}}o\phantom{\rule{0}{0ex}}t$ reveal the full extent of the CT-state distribution at low temperatures. In a highly disordered blend, CT-state filling is incomplete, and injected carriers do not reach equilibrium sites before recombining. CT disorder $c\phantom{\rule{0}{0ex}}a\phantom{\rule{0}{0ex}}n$ be reliably found from temperature-dependent measurements of external quantum efficiency, which can distinguish dynamic from static disorder.

Even though record organic semiconductor mobilities are reported for organic semiconductor single crystals, making thin film crystals remains difficult. We will show our efforts to understand crystal formation, epitaxy, and transport. In particular, we will discuss our efforts to realize pinhole free films of numerous organic semiconductors with 100s microns scale grains, and how the materials able to undergo a transition from amorphous to crystalline correlate well with thermal properties. Homoepitaxial studies uncover evidence of point and line defect formation in these films, indicating that homoepitaxy is not always strain-free. Transistors made out of large-grained films of rubrene display charge carrier mobility of up to 3.5 cm2 V–1 s–1, very close to single crystal values, highlighting their potential for practical application. Finally, we will show efforts in achieving heteroepitaxial growth of a different molecular material on top of a crystalline organic template.

While metal-halide perovskite light-emitting diodes (PeLEDs) hold the potential for a new generation of display and lighting technology, their slow operation speed and response time limit their application scope. Here, high-speed PeLEDs driven by nanosecond electrical pulses with a rise time of 1.2 ns are reported with a maximum radiance of approximately 480 kW sr-1 m-2 at 8.3 kA cm-2 , and an external quantum efficiency (EQE) of 1% at approximately 10 kA cm-2 , through improved device configuration designs and material considerations. Enabled by the fast operation of PeLEDs, the temporal response provides access to transient charge carrier dynamics under electrical excitation, revealing several new electroluminescence quenching pathways. Finally, integrated distributed feedback (DFB) gratings are explored, which facilitate more directional light emission with a maximum radiance of approximately 1200 kW sr-1 m-2 at 8.5 kA cm-2 , a more than two-fold enhancement to forward radiation output.

Online Version of Record before inclusion in an issue 2101533 Funding Information: A.G. and A.B. contributed equally to this work. The authors thank Andrey Starkov for the help with illustrations and Dr. Ivan Shuklov for providing chemical reagents. A.G., K.M., V.D. thank the late Vsevolod Gantmakher for the inspiration and support provided at the beginning of this study. The development concept was designed under financial support by Russian Science Foundation under grant 19‐73‐10154. The experiments of the model developer investigation were supported by Russian Science Foundation under grant No. 18‐72‐10135. XPS was carried out with the support of the Research Facility Center at the Institute of Solid State Physics (RAS) (R.N.M. and A.M.I). This work was performed using equipment of MIPT Shared Facilities Center. F.S.F. acknowledges Russian Foundation for Basic Research grant no. 19‐07‐00300. V.P. acknowledges support from the National Science Foundation under the grant ECCS‐1806363. B.P.R. and J.T.D. acknowledge support from the National Science Foundation Award No. ECCS‐1709222. Section on the synthesis of chitosan acetate with various molecular weights was supported by Ministry of Science and Higher Education of the Russian Federation. A.I. expresses gratitude to the Russian Foundation for Basic Research (project no. 19‐29‐03021 mk) for supporting his work. A.K.G. acknowledge RFBR grant 19‐32‐90143. A.G.N. acknowledges the Russian Science Foundation (project No 17‐19‐01787‐synthesis of carbon nanotubes and project No 21‐72‐20050‐SWCNT transistor fabrication and characterisation). Publisher Copyright: © 2021 Wiley-VCH GmbH Copyright: Copyright 2021 Elsevier B.V., All rights reserved. A variety of unconventional materials, including biological nanostructures, organic and hybrid semiconductors, as well as monolayer, and other low-dimensional systems, are actively explored. They are usually incompatible with standard lithographic techniques that use harsh organic solvents and other detrimental processing. Here, a new class of green and gentle lithographic resists, compatible with delicate materials and capable of both top-down and bottom-up fabrication routines is developed. To demonstrate the excellence of this approach, devices with sub-micron features are fabricated on organic semiconductor crystals and individual animal's brain microtubules. Such structures are created for the first time, thanks to the genuinely water-based lithography, which opens an avenue for the thorough research of unconventional delicate materials at the nanoscale.

Solution-processed organic–inorganic hybrid perovskites have recently emerged as promising low-cost materials for optoelectronic applications. However, exposure to light or applied bias causes phas...

Rubrene is a promising and archetypal organic semiconductor owing to its high reported hole mobility. However, this high mobility only exists in its crystalline state, with orders of magnitude reduction in disordered films. Thus, as it pertains to thin film polycrystalline rubrene, it is important to understand structure and the presence of disordered regions at grain boundaries. Here, we use scanning transmission X-ray microscopy (STXM) to investigate polycrystalline rubrene thin films with either platelet or spherulite morphology. The STXM images allow us to distinguish and quantify the arrangement of the local structure in the crystal. The analysis suggests that the platelet film has more oriented molecules in the crystal than in the spherulite phase. Also, at spherulite grain boundaries, we reveal a high number of misaligned molecules compared to the smooth boundary in the platelet case, with grain boundary sinuosity of 0.045 ± 0.002 and 0.139 ± 0.002 μm for the platelet and spherulite cases, respectively, which help to explain the higher mobility in the former case.

International audience; In this work, we demonstrate several organic amorphous donor−acceptor systems that exhibit sub-bandgap features over a more than 2 eV spectral range. An in-depth study of one of these systems, NPB:HAT-CN (NPB is N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine and HAT-CN is 1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile), reveals that the broad sub-bandgap features are attributed to multiple electronic charge transfer (CT) state transitions, broadened by energetic disorder sourcing from the fluctuations of intramolecular conformations and by the disordered intermolecular environment. These unique CT features originate from an unconventional donor and acceptor selection that reveals new insight about photocurrent generation and nonradiative recombination. Unlike materials employed in high performing organic solar cells, the materials studied here feature large optical energy gaps with very large frontier orbital energy level offsets, creating high bandgap devices with low open-circuit voltage. In addition to multiple electronic CT levels, we reveal that the internal quantum efficiency of these multiple CT transitions is not constant but photon energy dependent and with photoluminescence that originates primarily from the second lowest electronic CT state implying slow (relative to radiative and nonradiative rates) internal conversion within the CT manifold. Overall, this class of donor−acceptor pairs provides an opportunity to probe CT states in unique ways to potentially unravel their role in carrier generation−recombination and energy loss mechanisms. ■ INTRODUCTION With more than 15% power conversion efficiency recently achieved 1 and coupled with the ability to be grown on flexible substrates on a large scale with low-cost fabrication techniques, organic solar cells are making a strong case for energy conversion applications. Most advances in power conversion efficiency are the result of impressive material and interface engineering and innovation. However, due to the lack of a complete understanding and consensus of carrier generation and recombination processes as well as loss mechanisms at charge generating donor−acceptor (D-A) interfaces, 2 the actual limits of organic solar cell performance remain unknown. In this context, intermolecular charge transfer (CT) excitations at D−A interfaces play an important role in the photophysical processes and energy losses of organic solar cells. 3−6 In order to understand how carrier generation and recombination are affected by CT states, a better comprehension of their origin and energetic distribution is crucial. More specifically, some key issues that are currently under inquiry include whether the carrier dissociation efficiency Special Issue: Jean-Luc Bredas Festschrift

We show that tin-doped indium oxide (ITO) can be thermally etched by the Bronsted acid salts methylammonium iodide (MAI), methylammonium lead triiodide (MAPbI3), and formamidinium lead triiodide (FAPbI3) in solid-state films and devices at common processing temperatures. More importantly, a series of reactions within an ITO/hybrid perovskite/Au device can be electrochemically induced near room temperature by applied cathodic voltages as low as −1.2 V. Cyclic voltammetry in this range leads to eventual In3+ leaching into the perovskite layer in the form of InI3, unambiguously identified by a binding energy signature of 445.9–446.3 eV measured by X-ray photoelectron spectroscopy. Furthermore, the etching is exacerbated by defects generated by O2-plasma treatment of the ITO compared to UV-ozone cleaning, lowering the reaction potential and the electrochemical stability window of an ITO/MAPbI3/Au device. Low-temperature, electrochemical reactivity at this interface has implications on operational stability, f...