Accomplishing High-Performance Organic Solar Sub-Modules (≈55 cm2) with >16% Efficiency by Controlling the Aggregation of an Engineered Non-Fullerene Acceptor.

The fabrication of environmentally benign, solvent-processed, efficient, organic photovoltaic sub-modules remains challenging due to the rapid aggregation of the current high performance non-fullerene acceptors (NFAs). In this regard, design of new NFAs capable of achieving optimal aggregation in large-area organic photovoltaic modules has not been realized. Here, an NFA named BTA-HD-Rh is synthesized with longer (hexyl-decyl) side chains that exhibit good solubility and optimal aggregation. Interestingly, integrating a minute amount of new NFA (BTA-HD-Rh) into the PM6:L8-BO system enables the improved solubility in halogen-free solvents (o-xylene:carbon disulfide (O-XY:CS2)) with controlled aggregation is found. Then solar sub-modules are fabricated at ambient condition (temperature at 25 ± 3 °C and humidity: 30-45%). Ultimately, the champion 55 cm2 sub-modules achieve exciting efficiency of >16% in O-XY:CS2 solvents, which is the highest PCE reported for sub-modules. Notably, the highest efficiency of BTA-HD-Rh doped PM6:L8-BO is very well correlated with high miscibility with low Flory-Huggins parameter (0.372), well-defined nanoscale morphology, and high charge transport. This study demonstrates that a careful choice of side chain engineering for an NFA offers fascinating features that control the overall aggregation of active layer, which results in superior sub-module performance with environmental-friendly solvents.

π-Conjugated Polymer with Pendant Side Chains as a Dopant-Free Hole Transport Material for High-Performance Perovskite Solar Cells.

Dopant-free polymeric hole transport materials (HTMs) have attracted considerable attention in perovskite solar cells (PSCs) due to their high carrier mobilities and excellent hydrophobicity. They are considered promising candidates for HTMs to replace commercial Spiro-OMeTAD to achieve long-term stability and high efficiency in PSCs. In this study, we developed BDT-TA-BTASi, a conjugated donor-π-acceptor polymeric HTM. The donor benzo[1,2-b:4,5-b']dithiophene (BDT) and acceptor benzotriazole (BTA) incorporated pendant siloxane, and alkyl side chains led to high hole mobility and solubility. In addition, BDT-TA-BTASi can effectively passivate the perovskite layer and markedly decrease the trap density. Based on these advantages, dopant-free BDT-TA-BTASi-based PSCs achieved an efficiency of over 21.5%. Furthermore, dopant-free BDT-TA-BTASi-based devices not only exhibited good stability in N2 (retaining 92% of the initial efficiency after 1000 h) but also showed good stability at high-temperature (60 °C) and -humidity conditions (80 ± 10%) (retaining 92 and 82% of the initial efficiency after 400 h). These results demonstrate that BDT-TA-BTASi is a promising HTM, and the study provides guidance on dopant-free polymeric HTMs to achieve high-performance PSCs.

Multifunctional Narrow Band Gap Terpolymer-Enabled High-Performance Dopant-Free Perovskite and Additive-Free Organic Solar Cells with Long-Term Stability.

The optoelectronic devices endowing multifunctionality while utilizing a single low-cost material have always been challenging. For this purpose, we adopted a random ternary copolymerization strategy for designing two terpolymers, namely TP-0.8-EG and TP-0.8-TEG comprising a benzothiadiazole (BT)-benzo[1,2-b:4,5-b']dithiophene-diketopyrrolo[3,4-c]pyrrole (A1-π-D-π-A2) backbone. The figure of merits of the narrow band gap TP-0.8-EG terpolymer include deepened frontier energy levels, high hole mobility, better film formability, enriched multifunctionality, and passivation capability. Accordingly, the suitable electronic properties of TP-0.8-EG revealed that it can function as a dopant-free hole-transporting material in perovskite solar cells (PSCs) as well as the third component in organic solar cells (OSCs). Remarkably, TP-0.8-EG outperforms by exhibiting a higher power conversion efficiency (PCE) of 20.9% over TP-0.8-TEG (PCE of 18.3%) and BT-UF (PCE of 14.6%) in dopant-free PSCs. Interestingly, TP-0.8-EG fabricated along with PM6:Y7 displayed a high PCE of 16.52% in ternary OSCs. Also, TP-0.8-EG established good device storage stabilities (85 and 83% of their initial PCEs for 1200 and 500 h) in dopant-free PSC as well as OSC devices. Notably, the devices with TP-0.8-EG showed excellent thermal and moisture stabilities. To the best of our knowledge, A1-π-D-π-A2 terpolymer performing both in PSCs and OSCs with decent efficiencies and good device stabilities is a rare scenario.

Finely Tuned Molecular Packing Realized by a New Rhodanine-Based Acceptor Enabling Excellent Additive-Free Small- and Large-Area Organic Photovoltaic Devices Approaching 19 and 12.20% Efficiencies.

A new nonfullerene acceptor (NFA), BTA-ERh, was synthesized and integrated into a PM6:Y7:PC71BM ternary system to regulate the blend film morphology for enhanced device performance. Due to BTA-ERh's good miscibility with host active blend films, an optimized film morphology was obtained with appropriate phase separation and fine-tuning of film crystallinity, which ultimately resulted in efficient exciton dissociation, charge transport, lower recombination loss, and decreased trap-state density. The resulting additive-free quaternary devices achieved a remarkable efficiency of 18.90%, with a high voltage, fill factor, and current density of 0.87 V, 76.32%, and 28.60 mA cm-2, respectively. By adding less of a new small molecule with high crystallinity, the favorable nanomorphology shape of blend films containing NFAs might be adjusted. Consequently, this strategy can enhance photovoltaic device performance for cutting-edge NFA-based organic solar cells (OSCs). In contrast, the additive-free OSCs exhibited good operational stability. More importantly, large-area modules with the quaternary device showed a remarkable efficiency of 12.20%, with an area as high as 55 cm2 (substrate size, 100 cm2) in an air atmosphere via D-bar coating. These results highlight the enormous research potential for a multicomponent strategy for future additive-free OSC applications.

Copper laser patterning on a flexible substrate using a cost-effective 3D printer.

We studied the cost effective direct laser patterning of copper (Cu) on thin polyimide substrates (PI thickness: 12.5-50 µm) using a 405 nm laser module attached to an inexpensive 3D printer. The focal length of the laser was intentionally controlled to reduce defects on patterned Cu and surface damage of PI under predetermined process conditions. The appropriate focal length was examined at various focal distances. Focal distances of - 2.4 mm and 3 mm were found for the shorter focal length (SFL) and longer focal length (LFL), respectively, compared to the actual focal length. This resulted in clean Cu line patterns without line defects. Interestingly, the SFL case had a different Cu growth pattern to that of LFL, indicating that the small difference in the laser incident angle could affect Cu precursor sintering. Cu square patterns had a lower resistivity of 70 µΩ·cm for an LFL after three or four laser scans, while the SFL showed a resistivity below 48 µΩ·cm for a one-time laser scan. The residues of the Cu precursor on PI were easily removed with flowing water and normal surfactants. However, the resistivity of the patterns decreased after cleaning. Among the scan gaps, the Cu square pattern formed at a 70 µm scan gap had the lowest sheet resistance and the least change in resistance from around 4 to 4.4 Ω/ϒ after cleaning. This result implies that the adhesion of the patterned Cu could be improved if the coated Cu precursor was well sintered under the proper process conditions. For the application of this method to bioelectronics, including biosensors, LEDs were connected to the Cu patterns on PI attached to the arm skin and worked well, even when the substrate PI was bent during power connecting.

Facile Strategy for Third Component Optimization in Wide-Band-Gap π-Conjugated Polymer Donor-Based Efficient Ternary All-Polymer Solar Cells.

Emerging organic solar cells based on a ternary strategy is one of the most effective methods for improving the blend film morphology, absorption ability, and device performances. On the other hand, this strategy has had very limited success in all-polymer solar cells (all-PSCs) because of the scarcity of new polymers and the challenges faced during third component optimization. Herein, highly efficient ternary all-PSCs were developed from siloxane-functionalized side chains with a wide-band-gap (Eg) polymer, Si-BDT, which is blended with a medium and ultra-narrow Eg polymer donor and acceptor, PTB7-Th, and DCNBT-TPIC. An impressive power conversion efficiency (PCE) of 13.45% was achieved in the ternary all-PSCs [PTB7-Th(0.6):Si-BDT(0.4):DCNBT-TPIC(0.6)] with the addition of 0.4 wt equivalent Si-BDT into binary all-PSCs [PTB7-Th(1):DCNBT-TPIC(0.6) PCE of 10.11%]. In contrast, the binary all-PSCs with a Si-BDT(1):DCNBT-TPIC(0.6) active layer only exhibited a good PCE of 9.92%. More importantly, the siloxane-functionalized side chains increase the light-absorption ability, carrier mobility, blend miscibility, and film morphology in ternary devices compared to those of the binary devices. Hence, exciton dissociation, charge carrier transport, and suppressed recombination properties were facilitated. In the presence of Si-BDT, both binary and ternary all-PSCs PCEs are significantly improved. Indeed, 13.45% PCE is one of the best values reported for all-PSCs except for those based on polymerized small molecule acceptors. In addition, the ternary all-PSCs showed excellent environmental and thermal stabilities with 95 and 84% of the initial PCE retained after 900 and 500 h, respectively. These results offer effective device engineering, providing a new avenue for improving the device performance in ternary all-PSCs.

Impact of Aryl End Group Engineering of Donor Polymers on the Morphology and Efficiency of Halogen-Free Solvent-Processed Nonfullerene Organic Solar Cells.

End group engineering on the side chain of π-conjugated donor polymers is explored as an effective way to develop efficient photovoltaic devices. In this work, we designed and synthesized three new π-conjugated polymers (PBDT-BZ-1, PBDT-S-BZ, and PBDT-BZ-F) with terminal aryl end groups on the side chain of chlorine-substituted benzo[1,2-b:4,5b']dithiophene (BDT). End group modifications showed notable changes in energy levels, dipole moments, exciton lifetimes, energy losses, and charge transport properties. Remarkably, the three new polymers paired with IT-4F (halogen-free solvent processed/toluene:DPE) displayed high power conversion efficiencies (PCEs) compared to a polymer (PBDT-Al-5) without a terminal end group (PCE of 7.32%). Interestingly, PBDT-S-BZ:IT-4F (PCE of 13.73%) showed a higher PCE than the benchmark PM7:IT-4F. The improved performance of PBDT-S-BZ well correlates with its improved charge mobility, well-interdigitated surface morphology, and high miscibility with a low Flory-Huggins interaction parameter (1.253). Thus, we successfully established a correlation between the end group engineering and bulk properties of the new polymers for realizing the high performance of halogen-free nonfullerene organic solar cells.

All-Polymer Solar Cells Approaching 12% Efficiency with a New π-Conjugated Polymer Donor Enabled by a Nonhalogenated Solvent Process.

High efficiency and nonhalogenated solvent processing are important issues for commercial application of all-polymer solar cells (all-PSCs). In this regard, we increased the photovoltaic performance of all-PSCs to a benchmark power conversion efficiency (PCE) of 11.66% by manipulating the pre-aggregation of a new π-conjugated polymer donor (Nap-SiBTz) using toluene as a solvent. This use of Nap-SiBTz enhanced the absorption coefficient (λmax = 9.30 × 104 cm-1), increased charge carrier mobility, suppressed trap-assisted recombination, improved bulk heterojunction morphology, and resulted in high PCEs of all-PSCs with an active layer thickness of 200 nm. To overcome severe charge recombination and energy losses, a 1-phenylnapthalene additive was used to achieve a well-ordered microstructure and molecular packing that inherently improved the device performances. The resulting encapsulation-free devices exhibited good ambient and thermal stabilities. The results of this study augur well for the future of the roll-to-roll production of all-PSCs.

Super Stretchable and Durable Electroluminescent Devices Based on Double-Network Ionogels.

Ionogels are good candidates for flexible electronics owing to their excellent mechanical and electrical properties, including stretchability, high conductivity, and stability. In this study, conducting ionogels comprising a double network (DN) of poly(N-isopropylacrylamide-co-N,N'-diethylacrylamide)/chitosan which are further reinforced by the ionic and covalent crosslinking of the chitosan network by tripolyphosphate and glutaraldehyde, respectively, are prepared. Based on their excellent mechanical properties and high conductivity, the developed DN ionogels are envisioned as stretchable ionic conductors for extremely stretchable alternating-current electroluminescent (ACEL) devices. The ACEL device fabricated with the developed ionogel exhibits stable working operation under an ultrahigh elongation of over 1200% as well as severe mechanical deformations such as bending, rolling, and twisting. Furthermore, the developed ACEL devices also display stable luminescence over 1000 stretch/release cycles or at temperatures as harsh as 200 °C.

External Quantum Efficiency Exceeding 24% with CIEy Value of 0.08 using a Novel Carbene-Based Iridium Complex in Deep-Blue Phosphorescent Organic Light-Emitting Diodes.

Deep-blue triplet emitters remain far inferior to standard red and green triplet emitters in terms of exhibiting high-color-purity Commission International de l'Éclairage (CIE) y values of ≤0.1, external quantum efficiencies (EQEs), and high electroluminescent brightnesses in phosphorescent organic light-emitting diodes. In fact, no deep-blue triplet emitter with color purity and high device performance has previously been reported. In this study, a deep-blue triplet emitter, mer-tris(N-phenyl, N-benzyl-pyridoimidazol-2-yl)iridium(III) (mer-Ir1) is developed, which meets the requirements of the National Television System Committee (NTSC) CIE(x, y) coordinates of (0.149, 0.085) with an extremely high EQE of 24.8% and maximum brightness (Lmax ) of 6453 cd m-2 , by a device with a 40 vol% doping ratio. Moreover, another device demonstrates an EQEmax of 21.3%, an Lmax of 5247 cd m-2 , and CIE(x, y) coordinates of (0.151, 0.086) at a 30 vol% doping ratio. This is the first report of a high-performance, deep-blue phosphor, carbene-based Ir(III) complex device with outstanding CIE(x, y) color coordinates and a high EQE. The results of this study indicate that the novel dopant mer-Ir1 is a promising candidate for reducing power consumption in display applications.

An Efficient Amphiphilic-Type Triphenylamine-Based Organic Hole Transport Material for High-Performance and Ambient-Stable Dopant-Free Perovskite and Organic Solar Cells.

A new set of simply structured triphenylamine-based small molecules are synthesized and evaluated as dopant-free hole transporting materials (HTMs) for high-performance perovskite solar cells (PSCs) and bulk heterojunction inverted organic solar cells (BHJ IOSCs). Surprisingly, the new amphiphilic-type HTM-1 (with internal hydrophilic groups and peripheral hydrophobic alkyl tails) showed better compatibility and performance than the actual target molecule, that is, HTM-2 in PSCs and BHJ IOSCs. Importantly, the HTM-1-based dopant-free PSCs and BHJ IOSCs exhibited high power conversion efficiencies (PCEs) of 11.45 % and 8.34 %, respectively. These performances are superior and comparable to those of standard HTMs Spiro-OMeTAD (2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene) and PEDOT:PSS (poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate) in PSCs and BHJ IOSCs, respectively. The enhanced device performance of the HTM-1-based PSCs is ascribed to its strong affinity towards the perovskite, properly aligned energy levels with respect to the perovskite valence band, and excellent hole transporting behavior. In addition, the well-organized energy levels of the HTMs showed excellent compatibility in BHJ IOSCs. The new amphiphilic-type HTM-based photovoltaic devices also showed long-term air stability over 700 h. These promising results offer new and unexpected prospects for engineering the interface between the photoactive material and HTMs in PSCs and BHJ IOSCs.

Triazine-based Polyelectrolyte as an Efficient Cathode Interfacial Material for Polymer Solar Cells.

A novel polyelectrolyte containing triazine (TAZ) and benzodithiophene (BDT) scaffolds with polar phosphine oxide (P═O) and quaternary ammonium ions as pendant groups, respectively, in the polymer backbone (PBTAZPOBr) was synthesized to use it as a cathode interfacial layer (CIL) for polymer solar cell (PSC) application. Owing to the high electron affinity of the TAZ unit and P═O group, PBTAZPOBr could behave as an effective electron transport material. Due to the polar quaternary ammonium and P═O groups, the interfacial dipole moment created by PBTAZPOBr substantially reduced the work function of the metal cathode to afford better energy alignment in the device, thus enabling electron extraction and reducing recombination of excitons at the photoactive layer/cathode interface. Consequently, the PSC devices based on the poly[4,8-bis(2-ethylhexyloxyl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-ethylhexyl-3-fluorothithieno[3,4-b]thiophene-2-carboxylate-4,6-diyl]:[6,6]-phenyl-C71-butyric acid methyl ester (PTB7:PC71BM) system with PBTAZPOBr as CIL displayed simultaneously enhanced open-circuit voltage, short-circuit current density, and fill factor, whereas the power conversion efficiency increased from 5.42% to 8.04% compared to that of the pristine Al device. The outstanding performance of PBTAZPOBr is attributed not only to the polar pendant groups of BDT unit but also to the TAZ unit linked with the P═O group of PBTAZPOBr, demonstrating that functionalized TAZ building blocks are very promising cathode interfacial materials (CIMs). The design strategy proposed in this work will be helpful to develop more efficient CIMs for high performance PSCs in the future.

Wafer-Scale Single-Crystalline AB-Stacked Bilayer Graphene.

Single-crystalline artificial AB-stacked bilayer graphene is formed by aligned transfer of two single-crystalline monolayers on a wafer-scale. The obtained bilayer has a well-defined interface and is electronically equivalent to exfoliated or direct-grown AB-stacked bilayers.