Air-Stable Perylene Diimide Trimer Material for N-Type Organic Electrochemical Transistors.

A new method is reported to make air-stable n-type organic mixed ionic-electronic conductor (OMIEC) films for organic electrochemical transistors (OECTs) using a solution-processable small molecule helical perylene diimide trimer, hPDI[3]-C11. Alkyl side chains are attached to the conjugated core for processability and film making, which are then cleaved via thermal annealing. After the sidechains are removed, the hPDI[3] film becomes less hydrophobic, more ordered, and has a deeper lowest unoccupied molecular orbital (LUMO). These features provide improved ionic transport, greater electronic mobility, and increased stability in air and in aqueous solution. Subsequently, hPDI[3]-H is used as the active material in OECTs and a device with a transconductance of 44 mS, volumetric capacitance of ≈250 F cm-3, µC* value of 1 F cm-1 V-1 s-1, and excellent stability (> 5 weeks) is demonstrated. As proof of their practical applications, a hPDI[3]-H-based OECTs as a glucose sensor and electrochemical inverter is utilized. The approach of side chain removal after film formation charts a path to a wide range of molecular semiconductors to be used as stable, mixed ionic-electronic conductors.

High-Performance Wearable Organic Photodetectors by Molecular Design and Green Solvent Processing for Pulse Oximetry and Photoplethysmography.

White-light detection from the visible to the near-infrared region is central to many applications such as high-speed cameras, autonomous vehicles, and wearable electronics. While organic photodetectors (OPDs) are being developed for such applications, several challenges must be overcome to produce scalable high-detectivity OPDs. This includes issues associated with low responsivity, narrow absorption range, and environmentally friendly device fabrication. Here, an OPD system processed from 2-methyltetrahydrofuran (2-MeTHF) sets a record in light detectivity, which is also comparable with commercially available silicon-based photodiodes is reported. The newly designed OPD is employed in wearable devices to monitor heart rate and blood oxygen saturation using a flexible OPD-based finger pulse oximeter. In achieving this, a framework for a detailed understanding of the structure-processing-property relationship in these OPDs is also developed. The bulk heterojunction (BHJ) thin films processed from 2-MeTHF are characterized at different length scales with advanced techniques. The BHJ morphology exhibits optimal intermixing and phase separation of donor and acceptor moieties, which facilitates the charge generation and collection process. Benefitting from high charge carrier mobilities and a low shunt leakage current, the newly developed OPD exhibits a specific detectivity of above 1012  Jones over 400-900 nm, which is higher than those of reference devices processed from chlorobenzene and ortho-xylene.

Additive-free molecular acceptor organic solar cells processed from a biorenewable solvent approaching 15% efficiency.

We report on the use of molecular acceptors (MAs) and donor polymers processed with a biomass-derived solvent (2-methyltetrahydrofuran, 2-MeTHF) to facilitate bulk heterojunction (BHJ) organic photovoltaics (OPVs) with power conversion efficiency (PCE) approaching 15%. Our approach makes use of two newly designed donor polymers with an opened ring unit in their structures along with three molecular acceptors (MAs) where the backbone and sidechain were engineered to enhance the processability of BHJ OPVs using 2-MeTHF, as evaluated by an analysis of donor-acceptor (D-A) miscibility and interaction parameters. To understand the differences in the PCE values that ranged from 9-15% as a function of composition, the surface, bulk, and interfacial BHJ morphologies were characterized at different length scales using atomic force microscopy, grazing-incidence wide-angle X-ray scattering, resonant soft X-ray scattering, X-ray photoelectron spectroscopy, and 2D solid-state nuclear magnetic resonance spectroscopy. Our results indicate that the favorable D-A intermixing that occurs in the best performing BHJ film with an average domain size of ∼25 nm, high domain purity, uniform distribution and enhanced local packing interactions - facilitates charge generation and extraction while limiting the trap-assisted recombination process in the device, leading to high effective mobility and good performance.

Interstellar photovoltaics.

The term 'Solar Cell' is commonly used for Photovoltaics that convert light into electrical energy. However, light can be harvested from various sources not limited to the Sun. This work considers the possibility of harvesting photons from different star types, including our closest neighbor star Proxima Centauri. The theoretical efficiency limits of single junction photovoltaic devices are calculated for different star types at a normalized light intensity corresponding to the AM0 spectrum intensity with AM0 = 1361 W/m2. An optimal bandgap of > 12 eV for the hottest O5V star type leads to 47% Shockley-Queisser photoconversion efficiency (SQ PCE), whereas a narrower optimal bandgap of 0.7 eV leads to 23% SQ PCE for the coldest red dwarf M0, M5.5Ve, and M8V type stars. Organic Photovoltaics (OPVs) are the most lightweight solar technology and have the potential to be employed in weight-restricted space applications, including foreseeable interstellar missions. With that in mind, the Sun's G2V spectrum and Proxima Centauri's M5.5Ve spectrum are considered in further detail in combination with two extreme bandgap OPV systems: one narrow bandgap system (PM2:COTIC-4F, Eg = 1.14 eV) and one wide bandgap system (PM6:o-IDTBR, Eg = 1.62 eV). Semi-empirically modeled JV-curves reveal that the absorption characteristics of the PM2:COTIC-4F blend match well with both the G2V and the M5.5Ve spectrum, yielding theoretical PCEs of 22.6% and 12.6%, respectively. In contrast, the PM6:o-IDTBR device shows a theoretical PCE of 18.2% under G2V illumination that drops sharply to 0.9% under M5.5Ve illumination.

What We have Learnt from PM6:Y6.

Over the past three years, remarkable advancements in organic solar cells (OSCs) have emerged, propelled by the introduction of Y6-an innovative A-DA'D-A type small molecule non-fullerene acceptor (NFA). This review provides a critical discussion of the current knowledge about the structural and physical properties of the PM6:Y6 material combination in relation to its photovoltaic performance. The design principles of PM6 and Y6 are discussed, covering charge transfer, transport, and recombination mechanisms. Then, the authors delve into blend morphology and degradation mechanisms before considering commercialization. The current state of the art is presented, while also discussing unresolved contentious issues, such as the blend energetics, the pathways of free charge generation, and the role of triplet states in recombination. As such, this review aims to provide a comprehensive understanding of the PM6:Y6 material combination and its potential for further development in the field of organic solar cells. By addressing both the successes and challenges associated with this system, this review contributes to the ongoing research efforts toward achieving more efficient and stable organic solar cells.

Green-Solvent-Processed High-Performance Broadband Organic Photodetectors.

Solution-processed organic photodetectors with broadband activity have been demonstrated with an environmentally benign solvent, ortho-xylene (o-xylene), as the processing solvent. The organic photodetectors employ a wide band gap polymer donor PBDB-T and a narrow band gap small-molecule non-fullerene acceptor CO1-4F, both dissolvable in o-xylene at a controlled temperature. The o-xylene-processed devices have shown external quantum efficiency of up to 70%, surpassing the counterpart processed with chlorobenzene. With a well-suppressed dark current, the device can also present a high specific detectivity of over 1012 Jones at -2 V within practical operation frequencies and is applicable for photoplethysmography with its fast response. These results further highlight the potential of green-solvent-processed organic photodetectors as a high-performing alternative to their counterparts processed in toxic chlorinated solvents without compromising the excellent photosensing performance.

Revealing the Electrophilic-Attack Doping Mechanism for Efficient and Universal p-Doping of Organic Semiconductors.

Doping is of great importance to tailor the electrical properties of semiconductors. However, the present doping methodologies for organic semiconductors (OSCs) are either inefficient or can only apply to some OSCs conditionally, seriously limiting their general applications. Herein, a novel p-doping mechanism is revealed by investigating the interactions between the dopant trityl tetrakis(pentafluorophenyl) borate (TrTPFB) and poly(3-hexylthiophene) (P3HT). It is found that electrophilic attack of the trityl cations on thiophenes results in the formation of tritylated thiophenium ions, which subsequently induce electron transfer from neighboring P3HT chains to realize p-doping. This unique p-doping mechanism enables TrTPFB to p-dope various OSCs including those with high ionization energy (IE ≈ 5.8 eV). Moreover, this doping mechanism endows TrTPFB with strong doping capability, leading to doping efficiency of over 80% in P3HT. The discovery and elucidation of this novel doping mechanism not only points out that strong electrophiles are a class of efficient p-dopants for OSCs, but also provides new opportunities toward highly efficient doping of various OSCs.

Unraveling Device Physics of Dilute-Donor Narrow-Bandgap Organic Solar Cells with Highly Transparent Active Layers.

The charge generation-recombination dynamics in three narrow-bandgap near-IR absorbing nonfullerene (NFA) based organic photovoltaic (OPV) systems with varied donor concentrations of 40%, 30%, and 20% are investigated. The dilution of the polymer donor with visible-range absorption leads to highly transparent active layers with blend average visible transmittance (AVT) values of 64%, 70%, and 77%, respectively. Opaque devices in the optimized highly reproducible device configuration comprising these transparent active layers lead to photoconversion efficiencies (PCEs) of 7.0%, 6.5%, and 4.1%. The investigation of these structures yields quantitative insights into changes in the charge generation, non-geminate charge recombination, and extraction dynamics upon dilution of the donor. Lastly, this study gives an outlook for employing the highly transparent active layers in semitransparent organic photovoltaics (ST-OPVs).

Dual-Mode Organic Electrochemical Transistors Based on Self-Doped Conjugated Polyelectrolytes for Reconfigurable Electronics.

Reconfigurable organic logic devices are promising candidates for next generations of efficient computing systems and adaptive electronics. Ideally, such devices would be of simple structure and design, be power efficient, and compatible with high-throughput microfabrication techniques. This work reports an organic reconfigurable logic gate based on novel dual-mode organic electrochemical transistors (OECTs), which employ a self-doped conjugated polyelectrolyte as the active material, which then allows the transistors to operate in both depletion mode and enhancement mode. Furthermore, mode switching is accomplished by simply altering the polarity of the applied gate and drain voltages, which can be done on the fly. In contrast, achieving similar mode-switching functionality with other organic transistors typically requires complex molecular design or multi-device engineering. It in shown that dual-mode functionality is enabled by the concurrent existence of anion doping and cation dedoping of the films. A device physics model that accurately describes the behavior of these transistors is developed. Finally, the utility of these dual-mode transistors for implementing reconfigurable logic by fabricating a logic gate that may be switched between logic gates AND to NOR, and OR to NAND on the fly is demonstrated.

Efficient Fabrication of Organic Electrochemical Transistors via Wet Chemical Processing.

A wet processing method to fabricate high-performance organic electrochemical transistors (OECTs) is reported. Wet chemical processing enables a simple and reliable patterning step, substituting several complex and expensive cleanroom procedures in the fabrication of OECTs. We fabricate depletion-mode OECTs based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and enhancement-mode OECTs based on a conjugated polyelectrolyte PCPDTBT-SO3K on rigid and flexible substrates using this wet processing method. We show that the wet chemical processing step can also serve as a chemical treatment to enhance the electrical properties of the active material in OECTs. To highlight the potential of the fabrication process in applications, a transistor-based chemical sensor is demonstrated, capable of detecting methylene blue, a popular redox reporter in biodetection and immunoassays, with good detectivity. Given the tremendous potential of OECTs in emerging technologies such as biosensing and neuromorphic computing, this simple fabrication process established herein will render the OECT platform more accessible for research and applications.

Solution-Processed CsPbBr3 Quantum Dots/Organic Semiconductor Planar Heterojunctions for High-Performance Photodetectors.

Planar heterojunctions (PHJs) are fundamental building blocks for construction of semiconductor devices. However, fabricating PHJs with solution-processable semiconductors such as organic semiconductors (OSCs) is a challenge. Herein, utilizing the orthogonal solubility and good wettability between CsPbBr3 perovskite quantum dots (PQDs) and OSCs, fabrication of solution-processed PQD/OSC PHJs are reported. The phototransistors based on bilayer PQD/PDVT-10 PHJs show responsivity up to 1.64 × 104 A W-1 , specific detectivity of 3.17 × 1012 Jones, and photosensitivity of 5.33 × 106 when illuminated by 450 nm light. Such high photodetection performance is attributed to efficient charge dissociation and transport, as well as the photogating effect in the PHJs. Furthermore, the tri-layer PDVT-10/PQD/Y6 PHJs are used to construct photodiodes working in self-powered mode, which exhibit broad range photoresponse from ultraviolet to near-infrared, with responsivity approaching 10-1 A W-1 and detectivity over 106 Jones. These results present a convenient and scalable production processes for solution-processed PHJs and show their great potential for optoelectronic applications.

Structural insights into Lewis acid- and F4TCNQ-doped conjugated polymers by solid-state magnetic resonance spectroscopy.

Molecular doping strategies facilitate orders of magnitude enhancement in the charge carrier mobility of organic semiconductors (OSCs). Understanding the different doping mechanisms and molecular-level constraints on doping efficiency related to the material energy levels is crucial to develop versatile dopants for OSCs. Given the compositional and structural heterogeneities associated with OSC thin films, insight into dopant-polymer interactions by long-range techniques such as X-ray scattering and electron microscopy is exceedingly challenging to obtain. This study employs short-range probes, solid-state (ss)NMR and EPR spectroscopy, to resolve local structures and intermolecular interactions between dopants such as F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), Lewis acid BCF (tris[pentafluorophenyl] borane) and Lewis base conjugated polymer, PCPDTBT (P4) (poly[2,6-(4,4-bis(2-hexadecyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]). Analysis of 1H and 13C ssNMR spectra of P4, P4 : F4TCNQ and P4 : BCF blends indicates that the addition of dopants induces local structural changes in the P4 polymer, and causes paramagnetism-induced signal broadening and intensity losses. The hyperfine interactions in P4 : BCF and P4 : F4TCNQ are characterized by two-dimensional pulsed EPR spectroscopy. For P4 : F4TCNQ, 19F ssNMR analysis indicates that the F4TCNQ molecules are distributed and aggregated into different local chemical environments. By comparison, BCF molecules are intermixed with the P4 polymer and interact with traces of water molecules to form BCF-water complexes that serve as Brønsted acid sites, as revealed by 11B ssNMR spectroscopy. These results indicate that the P4-dopant blends exhibit complex morphology with different distributions of dopants, whereby the combined use of ssNMR and EPR provides essential insights into how higher doping efficiency is observed with BCF and a mediocre efficiency is associated with F4TCNQ molecules.

Current Progress of Interfacing Organic Semiconducting Materials with Bacteria.

Microbial bioelectronics require interfacing microorganisms with electrodes. The resulting abiotic/biotic platforms provide the basis of a range of technologies, including energy conversion and diagnostic assays. Organic semiconductors (OSCs) provide a unique strategy to modulate the interfaces between microbial systems and external electrodes, thereby improving the performance of these incipient technologies. In this review, we explore recent progress in the field on how OSCs, and related materials capable of charge transport, are being used within the context of microbial systems, and more specifically bacteria. We begin by examining the electrochemical communication modes in bacteria and the biological basis for charge transport. Different types of synthetic organic materials that have been designed and synthesized for interfacing and interrogating bacteria are discussed next, followed by the most commonly used characterization techniques for evaluating transport in microbial, synthetic, and hybrid systems. A range of applications is subsequently examined, including biological sensors and energy conversion systems. The review concludes by summarizing what has been accomplished so far and suggests future design approaches for OSC bioelectronics materials and technologies that hybridize characteristic properties of microbial and OSC systems.

Efficiency of Thermally Activated Delayed Fluorescence Sensitized Triplet Upconversion Doubled in Three-Component System.

As in many fields, the most exciting endeavors in photon upconversion research focus on increasing the efficiency (upconversion quantum yield) and performance (anti-Stokes shift) while diminishing the cost of production. In this vein, studies employing metal-free thermally activated delayed fluorescence (TADF) sensitizers have garnered increased interest. Here, for the first time, the strategy of ternary photon upconversion is utilized with the TADF sensitizer 2,4,5,6-tetrakis(carbazol-9-yl)isophthalonitrile (4CzIPN), resulting in a doubling of the upconversion quantum yield in comparison to the binary system employing p-terphenyl as the emitter. In this ternary blend, the sensitizer 4CzIPN is paired with an intermediate acceptor, 1-methylnaphthalene, in addition to the emitter molecule, p-terphenyl, yielding a normalized upconversion quantum yield of 7.6% while maintaining the 0.83 eV anti-Stokes shift. These results illustrate the potential benefits of utilizing this strategy of energy-funneling, previously used only with heavy-metal based sensitizers, to increase the performance of these photon upconversion systems.

Resolving Atomic-Scale Interactions in Nonfullerene Acceptor Organic Solar Cells with Solid-State NMR Spectroscopy, Crystallographic Modelling, and Molecular Dynamics Simulations.

Fused-ring core nonfullerene acceptors (NFAs), designated "Y-series," have enabled high-performance organic solar cells (OSCs) achieving over 18% power conversion efficiency (PCE). Since the introduction of these NFAs, much effort has been expended to understand the reasons for their exceptional performance. While several studies have identified key optoelectronic properties that govern high PCEs, little is known about the molecular level origins of large variations in performance, spanning from 5% to 18% PCE, for example, in the case of PM6:Y6 OSCs. Here, a combined solid-state NMR, crystallography, and molecular modeling approach to elucidate the atomic-scale interactions in Y6 crystals, thin films, and PM6:Y6 bulk heterojunction (BHJ) blends is introduced. It is shown that the Y6 morphologies in BHJ blends are not governed by the morphology in neat films or single crystals. Notably, PM6:Y6 blends processed from different solvents self-assemble into different structures and morphologies, whereby the relative orientations of the sidechains and end groups of the Y6 molecules to their fused-ring cores play a crucial role in determining the resulting morphology and overall performance of the solar cells. The molecular-level understanding of BHJs enabled by this approach will guide the engineering of next-generation NFAs for stable and efficient OSCs.

The role of charge recombination to triplet excitons in organic solar cells.

The use of non-fullerene acceptors (NFAs) in organic solar cells has led to power conversion efficiencies as high as 18%1. However, organic solar cells are still less efficient than inorganic solar cells, which typically have power conversion efficiencies of more than 20%2. A key reason for this difference is that organic solar cells have low open-circuit voltages relative to their optical bandgaps3, owing to non-radiative recombination4. For organic solar cells to compete with inorganic solar cells in terms of efficiency, non-radiative loss pathways must be identified and suppressed. Here we show that in most organic solar cells that use NFAs, the majority of charge recombination under open-circuit conditions proceeds via the formation of non-emissive NFA triplet excitons; in the benchmark PM6:Y6 blend5, this fraction reaches 90%, reducing the open-circuit voltage by 60 mV. We prevent recombination via this non-radiative channel by engineering substantial hybridization between the NFA triplet excitons and the spin-triplet charge-transfer excitons. Modelling suggests that the rate of back charge transfer from spin-triplet charge-transfer excitons to molecular triplet excitons may be reduced by an order of magnitude, enabling re-dissociation of the spin-triplet charge-transfer exciton. We demonstrate NFA systems in which the formation of triplet excitons is suppressed. This work thus provides a design pathway for organic solar cells with power conversion efficiencies of 20% or more.

Optical Expediency of Back Electrode Materials for Organic Near-Infrared Photodiodes.

Organic semiconductor devices, including organic photodetectors (OPDs) and organic photovoltaics (OPVs), have undergone vast improvements, thanks to the development of non-fullerene acceptors. The absorption range of such NFA-based systems is typically shifted toward the near-infrared (near-IR) region compared to early-generation fullerene-based systems, rendering organic semiconductor devices suitable for near-IR sensing applications. While most efforts are concentrated on the photoactive materials, less attention is paid to the impact of the back electrodes on the device performance. Therefore, this work focuses on the optical expediency of gold (Au), silver (Ag), aluminum (Al), and graphite as back electrode materials in organic optoelectronics. This work shows that the "one size fits all" methodology is not a valid approach for choosing the back electrode material. Instead, considering the active layer absorption, the active layer thickness, and the intended application is necessary. A traditional polymer/fullerene-based system, poly(3-hexylthiophene) with [6,6]-phenyl C61 butyric acid methyl ester (P3HT:PC60BM), and a state-of-the-art narrow-band gap non-fullerene-based system, poly[4,8bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b; 4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethy-lhexyl)3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-(2-6-diyl)] and 2,2'-((2Z,2'Z)-((5,5'-(4,4-bis(2-ethylhexyl)4H-cyclopenta[1,2-b:5,4-b']dithiophene-2,6-diyl)bis(4-((2ethylhexyl)oxy)thiophene-5,2-diyl))bis(methanylylidene)) bis(5,6-difluoro3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (PCE10:COTIC-4F), are investigated by combining optical transfer matrix modeling simulations with experimentally determined recombination and extraction losses. We find that the narrow-band gap system shows performance gains when employing Au as the back electrode. Furthermore, we show that these performance gains are dependent on active layer thickness, yielding the most significance for thin active layers (<100 nm). Such thin, ultra-narrow-band gap devices are the focus of near-IR sensing applications, highlighting the importance of methodically choosing the back electrode. Lastly, the impact of the back electrode on the OPV device performance is outlined.

Understanding how Lewis acids dope organic semiconductors: a "complex" story.

We report on computational studies of the potential of three borane Lewis acids (LAs) (B(C6F5)3 (BCF), BF3, and BBr3) to form stable adducts and/or to generate positive polarons with three different semiconducting π-conjugated polymers (PFPT, PCPDTPT and PCPDTBT). Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations based on range-separated hybrid (RSH) functionals provide insight into changes in the electronic structure and optical properties upon adduct formation between LAs and the two polymers containing pyridine moieties, PFPT and PCPDTPT, unravelling the complex interplay between partial hybridization, charge transfer and changes in the polymer backbone conformation. We then assess the potential of BCF to induce p-doping in PCPDTBT, which does not contain pyridine groups, by computing the energetics of various reaction mechanisms proposed in the literature. We find that reaction of BCF(OH2) to form protonated PCPDTBT and [BCF(OH)]-, followed by electron transfer from a pristine to a protonated PCPDTBT chain is highly endergonic, and thus unlikely at low doping concentration. The theoretical and experimental data can, however, be reconciled if one considers the formation of [BCF(OH)BCF]- or [BCF(OH)(OH2)BCF]- counterions rather than [BCF(OH)]- and invokes subsequent reactions resulting in the elimination of H2.

Understanding and Countering Illumination-Sensitive Dark Current: Toward Organic Photodetectors with Reliable High Detectivity.

Continuously enhanced photoresponsivity and suppressed dark/noise current combinatorially lead to the recent development of high-detectivity organic photodetectors with broadband sensing competence. Despite the achievements, reliable photosensing enabled by organic photodetectors (OPDs) still faces challenges. Herein, we call for heed over a universal phenomenon of detrimental sensitivity of dark current to illumination history in high-performance inverted OPDs. The phenomenon, unfavorable to the attainment of high sensitivity and consistent figures-of-merit, is shown to arise from exposure of the commonly used electron transport layer in OPDs to high-energy photons and its consequent loss of charge selectivity via systematic studies. To solve this universal problem, "double" layer tin oxide as an alternative electron transport layer is demonstrated, which not only eliminates the inconsistency between the initial and after-illumination dark current characteristics but also preserves the low magnitude of dark current, good external quantum efficiency, and rapid transient response.