Fully Fused Indacenodithiophene-Centered Small-Molecule n-Type Semiconductors for High-Performance Organic Electronics.

Developing novel n-type organic semiconductors is an on-going research endeavour, given their pivotal roles in organic electronics and their relative scarcity compared to p-type counterparts. In this study, a new strategy was employed to synthesize n-type organic semiconductors featuring a fully fused conjugated backbone. By attaching two sets of adjacent amino and formyl groups to the indacenodithiophene-based central cores and triggering a tandem reaction sequence of a Knoevenagel condensation-intramolecular cyclization, DFA1 and DFA2 were realized. The solution-processed organic field effect transistors based on DFA1 exhibited unipolar n-type transport character with a decent electron mobility of ca. 0.10 cm2 V-1 s-1 (ca. 0.038 cm2 V-1 s-1 for DFA2 based devices). When employing DFA1 as a third component in organic solar cells, a high power conversion efficiency of 19.2 % can be achieved in ternary devices fabricated with PM6 : L8-BO : DFA1. This work provides a new pathway in the molecular engineering of n-type organic semiconductors, propelling relevant research forward.

Binary All-polymer Solar Cells with a Perhalogenated-Thiophene-Based Solid Additive Surpass 18 % Efficiency.

Morphological control of all-polymer blends is quintessential yet challenging in fabricating high-performance organic solar cells. Recently, solid additives (SAs) have been approved to be capable in tuning the morphology of polymer: small-molecule blends improving the performance and stability of devices. Herein, three perhalogenated thiophenes, which are 3,4-dibromo-2,5-diiodothiophene (SA-T1), 2,5-dibromo-3,4-diiodothiophene (SA-T2), and 2,3-dibromo-4,5-diiodothiophene (SA-T3), were adopted as SAs to optimize the performance of all-polymer organic solar cells (APSCs). For the blend of PM6 and PY-IT, benefitting from the intermolecular interactions between perhalogenated thiophenes and polymers, the molecular packing properties could be finely regulated after introducing these SAs. In situ UV/Vis measurement revealed that these SAs could assist morphological character evolution in the all-polymer blend, leading to their optimal morphologies. Compared to the as-cast device of PM6 : PY-IT, all SA-treated binary devices displayed enhanced power conversion efficiencies of 17.4-18.3 % with obviously elevated short-circuit current densities and fill factors. To our knowledge, the PCE of 18.3 % for SA-T1-treated binary ranks the highest among all binary APSCs to date. Meanwhile, the universality of SA-T1 in other all-polymer blends is demonstrated with unanimously improved device performance. This work provide a new pathway in realizing high-performance APSCs.

Asymmetrified Benzothiadiazole-Based Solid Additives Enable All-Polymer Solar Cells with Efficiency Over 19.

Disordered polymer chain entanglements within all-polymer blends limit the formation of optimal donor-acceptor phase separation. Therefore, developing effective methods to regulate morphology evolution is crucial for achieving optimal morphological features in all-polymer organic solar cells (APSCs). In this study, two isomers, 4,5-difluorobenzo-c-1,2,5-thiadiazole (SF-1) and 5,6-difluorobenzo-c-1,2,5-thiadiazole (SF-2), were designed as solid additives based on the widely-used electron-deficient benzothiadiazole unit in nonfullerene acceptors. The incorporation of SF-1 or SF-2 into PM6:PY-DT blend induces stronger molecular packing via molecular interaction, leading to the formation of continuous interpenetrated networks with suitable phase-separation and vertical distribution. Furthermore, after treatment with SF-1 and SF-2, the exciton diffusion lengths for PY-DT films are extended to over 40 nm, favoring exciton diffusion and charge transport. The asymmetrical SF-2, characterized by an enhanced dipole moment, increases the power conversion efficiency (PCE) of PM6:PY-DT-based device to 18.83% due to stronger electrostatic interactions. Moreover, a ternary device strategy boosts the PCE of SF-2-treated APSC to over 19%. This work not only demonstrates one of the best performances of APSCs but also offers an effective approach to manipulate the morphology of all-polymer blends using rational-designed solid additives.

Terminally Chlorinated and Thiophene-linked Acceptor-Donor-Acceptor Structured 3D Acceptors with Versatile Processability for High-efficiency Organic Solar Cells.

To exploit the potential of our newly developed three-dimensional (3D) dimerized acceptors, a series of chlorinated 3D acceptors (namely CH8-3/4/5) were reported by precisely tuning the position of chlorine (Cl) atom. The introduction of Cl atom in central unit affects the molecular conformation. Whereas, by replacing fluorinated terminal groups (CH8-3) with chlorinated terminal groups (CH8-4 and CH8-5), the red-shift absorption and enhanced crystallization are achieved. Benefiting from these, all devices received promising power conversion efficiencies (PCEs) over 16 % as well as decent thermal/photo-stabilities. Among them, PM6:CH8-4 based device yielded a best PCE of 17.58 %. Besides, the 3D merits with multi alkyl chains enable their versatile processability during the device preparation. Impressive PCEs of 17.27 % and 16.23 % could be achieved for non-halogen solvent processable devices prepared in glovebox and ambient, respectively. 2.88 cm2 modules also obtained PCEs over 13 % via spin-coating and blade-coating methods, respectively. These results are among the best performance of dimerized acceptors. The decent performance of CH8-4 on small-area devices, modules and non-halogen solvent-processed devices highlights the versatile processing capability of our 3D acceptors, as well as their potential applications in the future.

Electronic Configuration Tuning of Centrally Extended Non-Fullerene Acceptors Enabling Organic Solar Cells with Efficiency Approaching 19 .

In the molecular optimizations of non-fullerene acceptors (NFAs), extending the central core can tune the energy levels, reduce nonradiative energy loss, enhance the intramolecular (donor-acceptor and acceptor-acceptor) packing, facilitate the charge transport, and improve device performance. In this study, a new strategy was employed to synthesize acceptors featuring conjugation-extended electron-deficient cores. Among these, the acceptor CH-BBQ, embedded with benzobisthiadiazole, exhibited an optimal fibrillar network morphology, enhanced crystallinity, and improved charge generation/transport in blend films, leading to a power conversion efficiency of 18.94 % for CH-BBQ-based ternary organic solar cells (OSCs; 18.19 % for binary OSCs) owing to its delicate structure design and electronic configuration tuning. Both experimental and theoretical approaches were used to systematically investigate the influence of the central electron-deficient core on the properties of the acceptor and device performance. The electron-deficient core modulation paves a new pathway in the molecular engineering of NFAs, propelling relevant research forward.

High Sensitivity of Non-Fullerene Organic Solar Cells Morphology and Performance to a Processing Additive.

Although solvent additives are used to optimize device performance in many novel non-fullerene acceptor (NFA) organic solar cells (OSCs), the effect of processing additives on OSC structures and functionalities can be difficult to predict. Here, two polymer-NFA OSCs with highly sensitive device performance and morphology to the most prevalent solvent additive chloronaphthalene (CN) are presented. Devices with 1% CN additive are found to nearly double device efficiencies to 10%. However, additive concentrations even slightly above optimum significantly hinder device performance due to formation of undesirable morphologies. A comprehensive analysis of device nanostructure shows that CN is critical to increasing crystallinity and optimizing phase separation up to the optimal concentration for suppressing charge recombination and maximizing performance. Here, domain purity and crystallinity are highly correlated with photocurrent and fill factors. However, this effect is in competition with uncontrolled crystallization of NFAs that occur at CN concentrations slightly above optimal. This study highlights how slight variations of solvent additives can impart detrimental effects to morphology and device performance of NFA OSCs. Therefore, successful scale-up processing of NFA-based OSCs will require extreme formulation control, a tuned NFA structure that resists runaway crystallization, or alternative methods such as additive-free fabrication.

4,4',5,5'-Tetracarboxy-2,2'-bipyridine Ru(II) sensitizers for dye-sensitized solar cells.

Two Ru(II) sensitizers TCR-1 and TCR-2 bearing four carboxy anchoring groups were prepared using 4,4',5,5'-tetraethoxycarbonyl-2,2'-bipyridine chelate and 4-(5-hexylthien-2-yl)-2-(3-trifluoromethyl-1H-pyrazol-5-yl)pyridine and 6-t-butyl-1-(3-trifluoromethyl-1H-pyrazol-5-yl)isoquinoline, respectively. Dissolution of these sensitizers in DMF solution afforded a light green solution up to 10(-5) M, for which their color gradually turned red upon further dilution and deposition on the surface of a TiO2 photoanode due to the spontaneous deprotonation of carboxylic acid groups. These sensitizers were characterized using electrochemical means and structural analysis time-dependent density functional theory (TDDFT) simulation and were also subjected to actual device fabrication. The as-fabricated DSC devices showed overall efficiencies η = 6.16% and 6.23% versus their 4,4'-dicarboxy counterparts TFRS-2 and TFRS-52 with higher efficiencies of 7.57% and 8.09%, using electrolyte with 0.2 M LiI additive. Their inferior efficiencies are possibly caused by the combination of blue-shifted absorption on TiO2, inadequate dye loading, and the perpendicularly oriented central carboxy groups.

The anti-correlation effect of alkyl chain size on the photovoltaic performance of centrally extended non-fullerene acceptors.

Contrary to previous results, a unique anti-correlation effect of the alkyl chain size on the photovoltaic performance of acceptors was observed. For a centrally-extended acceptor, replacing linear alkyl chains (n-undecyl for CH-BBQ) on the thienothiophene unit with branched ones (2-butyloctyl for CH-BO) leads to a plunge in the power conversion efficiency of organic solar cells (18.12% vs. 11.34% for binary devices), while the largely shortened ones (n-heptyl for CH-HP) bring a surge in performance (18.74%/19.44% for binary/ternary devices). Compared with CH-BO, the more compact intermolecular packing of CH-HP facilitates carrier transport. The characterization of organic field effect transistors and carrier dynamics also echoes the above results. Molecular dynamics simulations indicate that the encounter of the branched alkyl chains and the extended central core hinders the effective interfacial interaction of polymer donors and acceptors, thus deteriorating the device performance. This work suggests that the conventional strategy for alkyl chain engineering of Y-series acceptors might need to be reconsidered in other molecular systems.

An asymmetric end-capping strategy enables a new non-fullerene acceptor for organic solar cells with efficiency over 10.

Two different terminal groups, rhodanine-flanked benzo[c][1,2,5]thiadiazole (BR) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IM2F), were connected to an indaceno[1,2-b:5,6-b']dithiophene (IDT) core to construct a new non-fullerene acceptor (IDTBF). Solar cells based on this acceptor exhibited promising photovoltaic performances with a power conversion efficiency (PCE) of up to 10.43%.

A "σ-Hole"-Containing Volatile Solid Additive Enabling 16.5% Efficiency Organic Solar Cells.

Here we introduce a σ-hole-containing volatile solid additive, 1, 4-diiodotetrafluorobenzene (A3), in PM6:Y6-based OSCs. Aside from the appropriate volatility of A3 additive, the synergetic halogen interactions between A3 and photoactive matrix contribute to more condensed and ordered molecular arrangement in the favorable interpenetrating donor/acceptor domains. As a result, greatly accelerated charge transport process with suppressed charge recombination possibility is observed and ultimately a champion PCE value of 16.5% is achieved. Notably, the A3 treated OSCs can maintain a high efficiency of over 16.0% in a wide concentration range of A3 additive between 10 and 35 mg/mL. The A3-treated device shows excellent stability with an efficiency of 15.9% after 360-h storage. This work demonstrates that the σ-hole interaction can be applied to enhance the OSC performance and highlights the importance of non-covalent interactions in the optoelectronic materials.

Effects of Fluorination on Fused Ring Electron Acceptor for Active Layer Morphology, Exciton Dissociation, and Charge Recombination in Organic Solar Cells.

Fluorination is one of the effective approaches to alter the organic semiconductor properties that impact the performance of the organic solar cells (OSCs). Positive effects of fluorination are also revealed in the application of fused ring electron acceptors (FREAs). However, in comparison with the efforts allocated to the material designs and power conversion efficiency enhancement, understanding on the excitons and charge carriers' behaviors in high-performing OSCs containing FREAs is limited. Herein, the impact of fluorine substituents on the active layer morphology, and therefore exciton dissociation, charge separation, and charge carriers' recombination processes are examined by fabricating OSCs with PTO2 as the donor and two FREAs, O-IDTT-IC and its fluorinated analogue O-IDTT-4FIC, as the acceptors. With the presence of O-IDTT-4FIC in the devices, it is found that the excitons dissociate more efficiently, and the activation energy required to split the excitons to free charge carriers is much lower; the charge carriers live longer and suffer less extent of trap-assisted recombination; the trap density is 1 order of magnitude lower than that of the nonfluorinated counterpart. Overall, these findings provide information about the complex impacts of FREA fluorination on efficiently performed OSCs.

Donor Derivative Incorporation: An Effective Strategy toward High Performance All-Small-Molecule Ternary Organic Solar Cells.

Thick-film all-small-molecule (ASM) organic solar cells (OSCs) are preferred for large-scale fabrication with printing techniques due to the distinct advantages of monodispersion, easy purification, and negligible batch-to-batch variation. However, ASM OSCs are typically constrained by the morphology aspect to achieve high efficiency and maintain thick film simultaneously. Specifically, synchronously manipulating crystallinity, domain size, and phase segregation to a suitable level are extremely challenging. Herein, a derivative of benzodithiophene terthiophene rhodanine (BTR) (a successful small molecule donor for thick-film OSCs), namely, BTR-OH, is synthesized with similar chemical structure and absorption but less crystallinity relative to BTR, and is employed as a third component to construct BTR:BTR-OH:PC71BM ternary devices. The power conversion efficiency (PCE) of 10.14% and fill factor (FF) of 74.2% are successfully obtained in ≈300 nm OSC, which outperforms BTR:PC71BM (9.05% and 69.6%) and BTR-OH:PC71BM (8.00% and 65.3%) counterparts, and stands among the top values for thick-film ASM OSCs. The performance enhancement results from the enhanced absorption, suppressed bimolecular/trap-assisted recombination, improved charge extraction, optimized domain size, and suitable crystallinity. These findings demonstrate that the donor derivative featuring similar chemical structure but different crystallinity provides a promising third component guideline for high-performance ternary ASM OSCs.

Simple near-Infrared Nonfullerene Acceptors Enable Organic Solar Cells with >9% Efficiency.

Nonfullerene acceptors (NFAs) based on calamitic-shaped small molecules are being developed rapidly to improve the photoelectron conversion efficiencies (PCEs) of organic solar cells. NFAs with light absorption extended to the near-infrared (NIR) region are of interest because they play a pivotal role in both organic tandem cells and semitransparent devices. In this work, two simple acceptor-donor-acceptor-structured NFAs (CPDT-4Cl and CPDT-4F) have been designed and synthesized. Featured with dimerized 4H-cyclopenta[1,2-b:5,4-b']dithiophene (CPDT) as the electron-donating core and Cl- or F-substituted 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile as the electron-accepting unit, the absorption spectra of two NFAs are extended to the NIR region with an absorption edge at approximately 910 nm. In conjunction with the polymer donor material PBDB-T, a PCE of 9.47% was achieved by using a CPDT-4F-based device with a short-circuit current density of up to 20.1 mA/cm2, which slightly outperforms its counterpart CPDT-4Cl (PCE = 9.28%) under the same condition. This work broadens the scope of developing new NIR NFAs with both high efficiency and easy accessibility.

Blue-emitting heteroleptic Ir(III) phosphors with functional 2,3'-bipyridine or 2-(pyrimidin-5-yl)pyridine cyclometalates.

We have synthesized four Ir(iii) metal complexes () bearing dual fluorine-free cyclometalates that are derived from 2',6'-dimethoxy-4-t-butyl-2,3'-bipyridine (pypy)H or 2-(2,4-dimethoxypyrimidin-5-yl)-4-t-butylpyridine (pmpy)H and a third ancillary, e.g. 5-pyridin-2-yl-pyrazolate (Pz) or 5-pyridin-2-yl-pyrrolide (Pr), respectively. The Ir(iii) complexes and were examined by X-ray diffraction studies for providing the structural proofs. Photophysical properties were next measured in CH2Cl2 at RT, among which the pypy complexes and showed an identical structured emission with an E0-0 peak located at 458 nm, while the corresponding pmpy derivative displayed the most blue-shifted E0-0 peak at 444 nm. Organic light-emitting diodes (OLEDs) were fabricated using multiple layered architecture and the aforementioned phosphor at 8 wt% doping level. The associated OLED performances, cf. max. E.Q.E. = 9.0%, 14.3%, 5.8% and 9.4% and CIEx,y coordinates at (0.16, 0.22), (0.16, 0.24), (0.16, 0.17) and (0.16, 0.20) at 100 cd m(-2) for phosphors in sequence, confirmed their potential to act as blue dopants for phosphorescent OLEDs.