p-Type Conjugated Polymers Containing Electron-Deficient Pentacyclic Azepinedione.

Bisthienoazepinedione (BTA) has been reported for constructing high-performing p-type conjugated polymers in organic electronics, but the ring extended version of BTA is not well explored. In this work, we report a new synthesis of a key building block to the ring expanded electron-deficient pentacyclic azepinedione (BTTA). Three copolymers of BTAA with benzodithiophene substituted by different side chains are prepared. These polymers exhibit similar energy levels and optical absorption in solution and solid state, while significant differences are revealed in their film morphologies and behavior in transistor and photovoltaic devices. The best-performing polymers in transistor devices contained alkylthienyl side chains on the BDT unit (pBDT-BTTA-2 and pBDT-BTTA-3) and demonstrated maximum saturation hole mobilities of 0.027 and 0.017 cm2 V-1 s-1. Blends of these polymers with PC71BM exhibited a best photovoltaic efficiency of 6.78% for pBDT-BTTA-3-based devices. Changing to a low band gap non-fullerene acceptor (BTP-eC9) resulted in improved efficiency of up to 13.5%. Our results are among the best device performances for BTA and BTTA-based p-type polymers and highlight the versatile applications of this electron-deficient BTTA unit.

The Effect of the Alkyl Chains of the Alkylammonium Pesudohalide Additives on the Performance of Dion Jacobson Perovskite Solar Cells.

Dion-Jacobson perovskite (DJP) films suffer from the high structural disorder and non-compact morphology, leading to inefficient and unstable solar cells (SCs). Here, how the alkyl chains of alkylammonium pseudohalide additives including methylammonium thiocyanate (MASCN) and ethylammonium thiocyanate (EASCN), and propylammonium thiocyanate (PASCN), impact the microstructures, optoelectronic properties and the performance of the solar cells is investigated. These additives substantially improve the structural order and the morphology of the DJP films, yielding more efficient and stable solar cells than the control device. They behave quite differently in modifying the morphological features. Particularly, EASCN outstands the additives in terms of the superior morphology, which is compact and uniform and consists of the largest flaky grains. Consequently, the corresponding device delivers a power conversion efficiency (PCE) of 15.27% and maintains ≈86% of the initial PCE after aging in the air for 182 h. Conversely, MASCN as an additive produces uneven DJP film and the device maintains only 46% of the initial PCE. PASCN as an additive produces the finest grains in the DJP film, and the corresponding device yields a PCE of 11.95%. From the economical point of view, it costs 0.0025 yuan per device for the EASCN additive, allowing for cost-effective perovskite solar cells.

Modulating the Alkylation Position on Terminal Thiophene Ring of Naphtho[2,3-b:6,7-b'] Bithieno[2,3-d] Thiophene (NBTT) for High-Performance Organic Optoelectronic Devices.

Several thiophene terminated thienoacenes with high mobilities in organic thin-film transistors (OTFTs) have been reported; however, the structure-property relationship of thiophene terminated thienoacenes was unclear, especially the impact of α or ß position substitution of terminal thiophene ring on molecular packing and physicochemical properties. Here, we report the synthesis and characterization of a six-ring-fused naphtho[2,3-b:6,7-b'] bithieno[2,3-d] thiophene (NBTT) and its derivatives 2,8-dioctyl-naphtho[2,3-b:6,7-b'] bithieno [2,3-d] thiophene (2,8-C8NBTT) and 3,9-dioctyl-naphtho[2,3-b:6,7-b'] bithieno [2,3-d] thiophene (3,9-C8NBTT). It is found that the alkylation on terminal thiophene ring can effectively tune the molecular stacking from a cofacial herringbone stacking mode (NBTT) to layer-by-layer packing (2,8-C8NBTT and 3,9-C8NBTT). Impressively, a hopping to "band-like" charge transport mechanism evolution of vacuum deposited films is realized by modulating the alkylation position on the terminal thiophene rings. As a result, the OTFTs based on 2,8-C8NBTT characterized by a "band-like" transport presents the highest mobility of 3.58 cm2 V-1 s-1 together with a remarkably high current on/off ratio around 109. Furthermore, organic phototransistors (OPTs) based on 2,8-C8NBTT thin film also exhibits higher photosensitivity (P) of 2.0 × 108, photoresponsivity (R) of 3.3 × 103 A W-1, and detectivity (D*) of 1.3 × 1016 Jones than those based on NBTT and 3,9-C8NBTT.

Near-Infrared Acceptors with Imide-Containing End Groups for Organic Solar Cells.

Near-infrared electron acceptors for organic solar cells (OSCs) mostly contain electron-withdrawing 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC) end groups, which can be modified by but limited to phenyl, thienyl, and naphthyl units with halogenated, methyl, and methyloxy substitution. In this work, we employed an imide-containing unit to construct a new IC end group, based on which a series of new electron acceptors were synthesized. The strong electron-deficient nature of imide units enables the new acceptors to show efficient intramolecular charge transfer and hence red-shifted absorption spectra compared to their IC counterparts. These new electron acceptors were applied to OSCs, providing efficiencies of over 17% with a low voltage loss of 0.52 eV. These results demonstrate that the new imide-containing end groups are promising fragments for the construction of near-infrared electron acceptors for high-performance OSCs.

Observing the On-Site Generation of Excitons and Charges by Low-Temperature Spectroscopy.

Understanding the relation between phase morphology and physical processes in polymer blends is the key to the fabrication of reproducible and reliable polymer optoelectronic devices. In this work, taking the advantage of low-temperature spectroscopy, we have observed the on-site generation of excitons and long-lived charges in different phase morphology polymer/fullerene blends. Probing at 10K, the photo-generated species are localized to where they are generated. We found that the generation of excitons and long-lived charges is highly influenced by the local molecular phase morphology. We further demonstrated that although the influence of phase morphology is localized to the place that excitons and long-lived charges are generated, this influence can persist over sub-millisecond timescales. Thus, we believe that the fate of excitons and long-lived charges is determined by the location at which they are generated, which can in turn be controlled precisely by molecular phase morphology.

Reconciling models of interfacial state kinetics and device performance in organic solar cells: impact of the energy offsets on the power conversion efficiency.

Achieving the simultaneous increases in the open circuit voltage (V oc), short circuit current (J sc) and fill factor (FF) necessary to further increase the power conversion efficiency (PCE) of organic photovoltaics (OPV) requires a unified understanding of how molecular and device parameters affect all three characteristics. In this contribution, we introduce a framework that for the first time combines different models that have been used separately to describe the different steps of the charge generation and collection processes in OPV devices: a semi-classical rate model for charge recombination processes in OPV devices, zero-dimensional kinetic models for the photogeneration process and exciton dissociation and one-dimensional semiconductor device models. Using this unified multi-scale model in conjunction with experimental techniques (time-resolved absorption spectroscopy, steady-state and transient optoelectronic measurements) that probe the various steps involved in charge generation we can shed light on how the energy offsets in a series of polymer: non-fullerene devices affect the charge carrier generation, collection, and recombination properties of the devices. We find that changing the energy levels of the donor significantly affects not only the transition rates between local-exciton (LE) and charge-transfer (CT) states, but also significantly changes the transition rates between CT and charge-separated (CS) states, challenging the commonly accepted picture of charge generation and recombination. These results show that in order to obtain an accurate picture of charge generation in OPV devices, a variety of different experimental techniques under different conditions in conjunction with a comprehensive model of processes occurring at different time-scales are required.

Multibranched aliphatic side chains for π-conjugated polymers with a high density of 'unshielded' aromatics.

The synthesis of strongly solubilising multibranched aliphatic side chains for π-conjugated polymers is reported. The solubilising capability of the side chains and their effect on the polymer properties are studied on the example of copolymers composed of up to six unsubstituted, 'unshielded' thiophene units per side chain-substituted naphthalene diimide unit.

Publisher Correction: Deciphering photocarrier dynamics for tuneable high-performance perovskite-organic semiconductor heterojunction phototransistors.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Tunable Control of the Hydrophilicity and Wettability of Conjugated Polymers by a Postpolymerization Modification Approach.

A facile method to prepare hydrophilic polymers by a postpolymerization nucleophillic aromatic substitution reaction of fluoride on an emissive conjugated polymer (CP) backbone is reported. Quantitative functionalization by a series of monofunctionalized ethylene glycol oligomers, from dimer to hexamer, as well as with high molecular weight polyethylene glycol is demonstrated. The length of the ethylene glycol sidechains is shown to have a direct impact on the surface wettability of the polymer, as well as its solubility in polar solvents. However, the energetics and band gap of the CPs remain essentially constant. This method therefore allows an easy way to modulate the wettability and solubility of CP materials for a diverse series of applications.

Crucial Role of Fluorine in Fully Alkylated Ladder-Type Carbazole-Based Nonfullerene Organic Solar Cells.

Two fused ladder-type nonfullerene acceptors, DTCCIC and DTCCIC-4F, based on an electron-donating alkylated dithienocyclopentacarbazole core flanked by electron-withdrawing nonfluorinated or fluorinated 1,1-dicyanomethylene-3-indanone (IC or IC-4F), are prepared and utilized in organic solar cells (OSCs). The two new molecules reveal planar structures and strong aggregation behavior, and fluorination is shown to red-shift the optical band gap and downshift energy levels. OSCs based on DTCCIC-4F exhibit a power conversion efficiency of 12.6%, much higher than that of DTCCIC-based devices (6.2%). Microstructural studies reveal that while both acceptors are highly crystalline, bulk heterojunction blends based on the nonfluorinated DTCCIC result in overly coarse domains, while blends based on the fluorinated DTCCIC-4F exhibit a more optimal nanoscale morphology. These results highlight the importance of end group fluorination in controlling molecular aggregation and miscibility.

Deciphering photocarrier dynamics for tuneable high-performance perovskite-organic semiconductor heterojunction phototransistors.

Looking beyond energy harvesting, metal-halide perovskites offer great opportunities to revolutionise large-area photodetection technologies due to their high absorption coefficients, long diffusion lengths, low trap densities and simple processability. However, successful extraction of photocarriers from perovskites and their conversion to electrical signals remain challenging due to the interdependency of photogain and dark current density. Here we report hybrid hetero-phototransistors by integrating perovskites with organic semiconductor transistor channels to form either "straddling-gap" type-I or "staggered-gap" type-II heterojunctions. Our results show that gradual transforming from type-II to type-I heterojunctions leads to increasing and tuneable photoresponsivity with high photogain. Importantly, with a preferential edge-on molecular orientation, the type-I heterostructure results in efficient photocarrier cycling through the channel. Additionally, we propose the use of a photo-inverter circuitry to assess the phototransistors' functionality and amplification. Our study provides important insights into photocarrier dynamics and can help realise advanced device designs with "on-demand" optoelectronic properties.

Erratum: Diseleno[3,2-b:2',3'-d]selenophene-Containing High-Mobility Conjugated Polymer for Organic Field-Effect Transistors.

[This corrects the article DOI: 10.1002/advs.201900245.].

Addition of the Lewis Acid Zn(C6 F5 )2 Enables Organic Transistors with a Maximum Hole Mobility in Excess of 20 cm2 V-1 s-1.

Incorporating the molecular organic Lewis acid tris(pentafluorophenyl)borane [B(C6 F5 )3 ] into organic semiconductors has shown remarkable promise in recent years for controlling the operating characteristics and performance of various opto/electronic devices, including, light-emitting diodes, solar cells, and organic thin-film transistors (OTFTs). Despite the demonstrated potential, however, to date most of the work has been limited to B(C6 F5 )3 with the latter serving as the prototypical air-stable molecular Lewis acid system. Herein, the use of bis(pentafluorophenyl)zinc [Zn(C6 F5 )2 ] is reported as an alternative Lewis acid additive in high-hole-mobility OTFTs based on small-molecule:polymer blends comprising 2,7-dioctyl[1]benzothieno [3,2-b][1]benzothiophene and indacenodithiophene-benzothiadiazole. Systematic analysis of the materials and device characteristics supports the hypothesis that Zn(C6 F5 )2 acts simultaneously as a p-dopant and a microstructure modifier. It is proposed that it is the combination of these synergistic effects that leads to OTFTs with a maximum hole mobility value of 21.5 cm2 V-1 s-1 . The work not only highlights Zn(C6 F5 )2 as a promising new additive for next-generation optoelectronic devices, but also opens up new avenues in the search for high-mobility organic semiconductors.

Sequential Deposition of Organic Films with Eco-Compatible Solvents Improves Performance and Enables Over 12%-Efficiency Nonfullerene Solar Cells.

Casting of a donor:acceptor bulk-heterojunction structure from a single ink has been the predominant fabrication method of organic photovoltaics (OPVs). Despite the success of such bulk heterojunctions, the task ofcontrolling the microstructure in a single casting process has been arduous and alternative approaches are desired. To achieve OPVs with a desirable microstructure, a facile and eco-compatible sequential deposition approach is demonstrated for polymer/small-molecule pairs. Using a nominally amorphous polymer as the model material, the profound influence of casting solvent is shown on the molecular ordering of the film, and thus the device performance and mesoscale morphology of sequentially deposited OPVs can be tuned. Static and in situ X-ray scattering indicate that applying (R)-(+)-limonene is able to greatly promote the molecular order of weakly crystalline polymers and form the largest domain spacing exclusively, which correlates well with the best efficiency of 12.5% in sequentially deposited devices. The sequentially cast device generally outperforms its control device based on traditional single-ink bulk-heterojunction structure. More crucially, a simple polymer:solvent interaction parameter χ is positively correlated with domain spacing in these sequentially deposited devices. These findings shed light on innovative approaches to rationally create environmentally friendly and highly efficient electronics.

Hybridization of Local Exciton and Charge-Transfer States Reduces Nonradiative Voltage Losses in Organic Solar Cells.

A number of recent studies have shown that the nonradiative voltage losses in organic solar cells can be suppressed in systems with low energetic offsets between donor and acceptor molecular states, but the physical reasons underpinning this remain unclear. Here, we present a systematic study of 18 different donor/acceptor blends to determine the effect that energetic offset has on both radiative and nonradiative recombination of the charge-transfer (CT) state. We find that, for certain blends, low offsets result in hybridization between charge-transfer and lowest donor or acceptor exciton states, which leads to a strong suppression in the nonradiative voltage loss to values as low as 0.23 V associated with an increase in the luminescence of the CT state. Further, we extend a two-state CT-state recombination model to include the interaction between CT and first excited states, which allows us to explain the low nonradiative voltage losses as an increase in the effective CT to ground state oscillator strength due to the intensity borrowing mechanism. We show that low nonradiative voltage losses can be achieved in material combinations with a strong electronic coupling between CT and first excited states and where the lower band gap material has a high oscillator strength for transitions from the excited state to the ground state. Finally, from our model we propose that achieving very low nonradiative voltage losses may come at a cost of higher overall recombination rates, which may help to explain the generally lower FF and EQE of highly hybridized systems.

Post-polymerisation functionalisation of conjugated polymer backbones and its application in multi-functional emissive nanoparticles.

Backbone functionalisation of conjugated polymers is crucial to their performance in many applications, from electronic displays to nanoparticle biosensors, yet there are limited approaches to introduce functionality. To address this challenge we have developed a method for the direct modification of the aromatic backbone of a conjugated polymer, post-polymerisation. This is achieved via a quantitative nucleophilic aromatic substitution (SNAr) reaction on a range of fluorinated electron-deficient comonomers. The method allows for facile tuning of the physical and optoelectronic properties within a batch of consistent molecular weight and dispersity. It also enables the introduction of multiple different functional groups onto the polymer backbone in a controlled manner. To demonstrate the versatility of this reaction, we designed and synthesised a range of emissive poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT)-based polymers for the creation of mono and multifunctional semiconducting polymer nanoparticles (SPNs) capable of two orthogonal bioconjugation reactions on the same surface.

An Alkylated Indacenodithieno[3,2-b]thiophene-Based Nonfullerene Acceptor with High Crystallinity Exhibiting Single Junction Solar Cell Efficiencies Greater than 13% with Low Voltage Losses.

A new synthetic route, to prepare an alkylated indacenodithieno[3,2-b]thiophene-based nonfullerene acceptor (C8-ITIC), is reported. Compared to the reported ITIC with phenylalkyl side chains, the new acceptor C8-ITIC exhibits a reduction in the optical band gap, higher absorptivity, and an increased propensity to crystallize. Accordingly, blends with the donor polymer PBDB-T exhibit a power conversion efficiency (PCE) up to 12.4%. Further improvements in efficiency are found upon backbone fluorination of the donor polymer to afford the novel material PFBDB-T. The resulting blend with C8-ITIC shows an impressive PCE up to 13.2% as a result of the higher open-circuit voltage. Electroluminescence studies demonstrate that backbone fluorination reduces the energy loss of the blends, with PFBDB-T/C8-ITIC-based cells exhibiting a small energy loss of 0.6 eV combined with a high JSC of 19.6 mA cm-2 .

Remarkable Enhancement of the Hole Mobility in Several Organic Small-Molecules, Polymers, and Small-Molecule:Polymer Blend Transistors by Simple Admixing of the Lewis Acid p-Dopant B(C6F5)3.

Improving the charge carrier mobility of solution-processable organic semiconductors is critical for the development of advanced organic thin-film transistors and their application in the emerging sector of printed electronics. Here, a simple method is reported for enhancing the hole mobility in a wide range of organic semiconductors, including small-molecules, polymers, and small-molecule:polymer blends, with the latter systems exhibiting the highest mobility. The method is simple and relies on admixing of the molecular Lewis acid B(C6F5)3 in the semiconductor formulation prior to solution deposition. Two prototypical semiconductors where B(C6F5)3 is shown to have a remarkable impact are the blends of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene:poly(triarylamine) (diF-TESADT:PTAA) and 2,7-dioctyl[1]-benzothieno[3,2-b][1]benzothiophene:poly(indacenodithiophene-co-benzothiadiazole) (C8-BTBT:C16-IDTBT), for which hole mobilities of 8 and 11 cm2 V-1 s-1, respectively, are obtained. Doping of the 6,13-bis(triisopropylsilylethynyl)pentacene:PTAA blend with B(C6F5)3 is also shown to increase the maximum hole mobility to 3.7 cm2 V-1 s-1. Analysis of the single and multicomponent materials reveals that B(C6F5)3 plays a dual role, first acting as an efficient p-dopant, and secondly as a microstructure modifier. Semiconductors that undergo simultaneous p-doping and dopant-induced long-range crystallization are found to consistently outperform transistors based on the pristine materials. Our work underscores Lewis acid doping as a generic strategy towards high performance printed organic microelectronics.

Measurement of Cohesion and Adhesion of Semiconducting Polymers by Scratch Testing: Effect of Side-Chain Length and Degree of Polymerization.

Most advantages of organic electronic materials are enabled by mechanical deformability, as flexible (and stretchable) devices made from these materials must be able to withstand roll-to-roll printing and survive mechanical insults from the external environment. Cohesion and adhesion are two properties that dictate the mechanical reliability of a flexible organic electronic device. In this paper, progressive-load scratch tests are used for the first time to correlate the cohesive and adhesive behavior of poly(3-alkylthiophenes) (P3ATs) with respect to two molecular parameters: length of the alkyl side chain and molecular weight. In contrast to metrological techniques based on buckling or pull testing of pseudofreestanding films, scratch tests reveal information about both the cohesive and adhesive properties of thin polymeric films from a single procedure. Our data show a decrease in cohesion and adhesion, that is, a decrease in overall mechanical robustness, with increasing length of the side chain. This behavior is likely due to increases in free volume and concomitant decreases in the glass transition temperature. In contrast, we observe increases in both the cohesion and adhesion with increasing molecular weight. This behavior is attributed to an increased density of entanglements with high molecular weight, which manifests as increased extensibility. These observations are consistent with the results of molecular dynamics simulations. Interestingly, the normal (applied) forces associated with cohesive and adhesive failure are directly proportional to the average degree of polymerization, as opposed to simply the molecular weight, as the length of the alkyl side chain increases the molecular weight without increasing the degree of polymerization.