Scalable manufacturing of flexible, fiber-shaped energy-storage devices has enabled great technological advances in wearable and portable technology. Replacing inefficient oxides with inexpensive and high-performance oxynitrides with more favorable three-dimensional (3D) structures is critical if the practical applications of these technologies are to be realized. Here, we developed a facile and controllable approach for the synthesis of 3D porous micropillars of molybdenum oxynitride (MON), which exhibit high conductivity, robust stability, and excellent energy-storage properties. Our fiber electrode, containing a 3D hierarchical MON-based anode, yields remarkable linear and areal specific capacitances of 64.8 mF cm–1 and 736.6 mF cm–2, respectively, at a scan rate of 10 mV s–1. Moreover, a wearable asymmetric supercapacitor based on TiN/MON//TiN/MnO2 demonstrates good cycling stability with a linear capacitance of 12.7 mF cm–1 at a scan rate of 10 mV s–1. These remarkable electrochemical properties are mainly attributed to the synergistic effect between the chemical composition of oxynitride and the robust 3D porous structure composed of interconnected nanocrystalline morphology. The presented strategy for the controllable design and synthesis of novel-oxide-derived functional materials offers prospects in developing portable and wearable electronic devices. We also demonstrate that these fiber supercapacitors can be combined with an organic solar cell to construct a self-powered system for broader applications.Keywords: 3D porous structure; fiber supercapacitor; high-performance; molybdenum oxynitride; self-powered system;

We report a novel small molecule acceptor (SMA) named FTTB-PDI4 obtained via ring-fusion between the thiophene and perylene diimide (PDI) units of a PDI-tetramer with a tetrathienylbezene (TTB) core. A small voltage loss of 0.53 V and a high power conversion efficiency of 10.58% were achieved, which is the highest value reported for PDI-based devices to date. By comparing the fused and nonfused SMAs, we show that the ring-fusion introduces several beneficial effects on the properties and performances of the acceptor material, including more favorable energy levels, enhanced light absorption and stronger intermolecular packing. Interestingly, morphology data reveal that the fused molecule yields higher domain purity and thus can better maintain its molecular packing and electron mobility in the blend. Theoretical calculations also demonstrate that FTTB-PDI4 exhibits a “double-decker” geometry with two pairs of mostly parallel PDI units, which is distinctively different from reported PDI-tetramers with highly twisted geometries and can explain the better performance of the material. This work highlights the promising design of PDI-based acceptors by the ring-fusion strategy.

To achieve efficient non-fullerene organic solar cells, it is important to reduce the voltage loss from the optical bandgap to the open-circuit voltage of the cell. Here we report a highly efficient non-fullerene organic solar cell with a high open-circuit voltage of 1.08 V and a small voltage loss of 0.55 V. The high performance was enabled by a novel wide-bandgap (2.05 eV) donor polymer paired with a narrow-bandgap (1.63 eV) small-molecular acceptor (SMA). Our morphology characterizations show that both the polymer and the SMA can maintain high crystallinity in the blend film, resulting in crystalline and small domains. As a result, our non-fullerene organic solar cells realize an efficiency of 11.6%, which is the best performance for a non-fullerene organic solar cell with such a small voltage loss.

The side-chain structures of conjugated molecules are well recognized to sensitively influence the crystallinity, morphology and thus carrier transport properties of organic semiconductors. Here, by varying the alkyl side-chain length in the polymer acceptors, the effect of side-chain engineering on the photovoltaic performance is systematically studied in all-polymer solar cells. Clear trends of first an increase and then a decrease in the Jsc and FF values are observed as the branched alkyl groups are extended from 4 to 8 carbons. Correspondingly, the maximum average PCE (ca. 7.40%) is attained with an acceptor bearing a branched side-chain length of seven carbon atoms.

We report a wide bandgap polymer PvBDTffBT based on a new building block: a vertical-benzodithiophene (vBDT) unit. Compared to traditional BDT based polymers, the vBDT unit in PvBDTffBT is connected via the phenyl group instead of the thiophene unit. Such modification leads to stronger torsion between the vBDT unit and the adjacent thiophene, which increases the bandgap of the polymer and introduces significant changes in the film morphology. When blended with a state-of-the-art narrow-bandgap small molecular acceptor (ITIC-Th), we find that this polymer modulation strategy significantly improves the photovoltaic performances from 3% to over 8%.

Temperature-dependent aggregation is a key property for some donor polymers to realize favorable bulk-heterojunction (BHJ) morphologies and high-efficiency (>10%) polymer solar cells. Previous studies find that an important structural feature that enables such temperature-dependent aggregation property is the 2nd position branched alkyl chains sitting between two thiophene units. In this report, we demonstrate that an optimal extent of fluorination on the polymer backbone is a second essential structural feature that enables the strong temperature-dependent aggregation property. We compare the properties of three structurally similar polymers with 0, 2 or 4 fluorine substitutions in each repeating unit through an in-depth morphological study. We show that the non-fluorinated polymer does not aggregate in solution (0.02 mg mL−1 in chlorobenzene) at room temperature, which results in poor polymer crystallinity and extremely large polymer domains. On the other hand, the polymer with four fluorine atoms in each repeating unit exhibits an excessively strong tendency to aggregate, which makes it difficult to process and causes a large domain. Only the polymer with two fluorine atoms in each repeating unit exhibits a suitable extent of temperature-dependent aggregation property. As a result, its blend film achieves a favorable morphology and high power conversion efficiency. This provides another key design rationale for developing donor polymers with suitable temperature-dependent aggregation properties and thus high performance.

A wide bandgap small molecular acceptor, SFBRCN, containing a 3D spirobifluorene core flaked with a 2,1,3-benzothiadiazole (BT) and end-capped with highly electron-deficient (3-ethylhexyl-4-oxothiazolidine-2-yl)dimalononitrile (RCN) units, has been successfully synthesized as a small molecular acceptor (SMA) for nonfullerene polymer solar cells (PSCs). This SMA exhibits a relatively wide optical bandgap of 2.03 eV, which provides a complementary absorption to commonly used low bandgap donor polymers, such as PTB7-Th. The strong electron-deficient BT and RCN units afford SFBRCN with a low-lying LUMO (lowest unoccupied molecular orbital) level, while the 3D structured spirobifluorene core can effectively suppress the self-aggregation tendency of the SMA, thus yielding a polymer:SMA blend with reasonably small domain size. As the results of such molecular design, SFBRCN enables nonfullerene PSCs with a high efficiency of 10.26%, which is the highest performance reported to date for a large bandgap nonfullerene SMA.

Four polymers based on perylenediimide co-polymerized with thiophene, bithiophene, selenophone and thieno[3,2-b]thiophene were investigated as the acceptor materials in all-polymer solar cells. Two different donor polymers, poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2,6-diyl] (PTB7-Th) and poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di(2-dodecyltetradecyl)-2,2′;5′,2″;5″,2‴-quaterthiophen-5,5‴-diyl)] (PffBT4T-2DT), with suitably complementary absorption spectra and energy levels were applied and examined. Among all different donor-acceptor pairs studied here, the combination of PTB7-Th:poly[N,N′-bis(1-hexylheptyl)-3,4,9,10-perylenediimide-1,6/1,7-diyl-alt-2,5-thiophene] (PDI-Th) exhibited the best power conversion efficiency (PCE) of 5.13%, with open-circuit voltage (Voc) = 0.79 V, short-circuit current density (Jsc = 12.35 mA·cm−2 and fill-factor (FF) = 0.52. The polymer of PDI-Th acceptor used here had a regio-irregular backbone, conveniently prepared from a mixture of 1,6- and 1,7-dibromo-PDI. It is also noteworthy that neither additive nor post-treatment is required for obtaining such a cell performance.

Benzene units are inserted into the backbone of a quaterthiophene-based polymer named PffBT4T, and the resulting polymer, PffBT4T-B, exhibits remarkably tight alkyl chain interdigitation, which can expel the ITIC-Th molecules from the polymer domains thus forming more pure and crystalline ITIC-Th domains. As a result, PffBT4T-B-based non-fullerene organic solar cells achieve a high power conversion efficiency of 9.4%.

One advantage of nonfullerene polymer solar cells (PSCs) is that they can yield high open-circuit voltage (VOC) despite their relatively low optical bandgaps. To maximize the VOC of PSCs, it is important to fine-tune the energy level offset between the donor and acceptor materials, but in a way not negatively affecting the morphology of the donor:acceptor (D:A) blends. Here, an effective material design rationale based on a family of D–A1–D–A2 terthiophene (T3) donor polymers is reported, which allows for the effective tuning of energy levels but without any negative impacts on the morphology of the blend. Based on a T3 donor unit combined with difluorobenzothiadiazole (ffBT) and difluorobenzoxadiazole (ffBX) acceptor units, three donor polymers are developed with highly similar morphological properties. This is particularly surprising considering that the corresponding quaterthiophene polymers based on ffBT and ffBX exhibit dramatic differences in their solubility and morphological properties. With the fine-tuning of energy levels, the T3 polymers yield nonfullerene PSCs with a high efficiency of 9.0% for one case and with a remarkably low energy loss (0.53 V) for another polymer. This work will facilitate the development of efficient nonfullerene PSCs with optimal energy levels and favorable morphology properties.

Non-fullerene organic solar cells (NF-OSCs) require donor polymers with different morphological properties from those used in fullerene devices to achieve optimal cell performance. In this paper, we report a random donor polymer (PTFB-M) constructed from an asymmetric donor unit (T–FB–T-M), which can effectively tune the morphology and thus enhance the performance of NF-OSCs. Compared with its analog polymer PTFB-P based on a C2 symmetric monomer, the asymmetric T–FB–T-M unit introduces some randomness in the PTFB-M polymer yielding several beneficial effects. Firstly, although the neat PTFB-M film exhibits slightly reduced crystallinity and hole mobility compared to PTFB-P, it can, to our surprise, better maintain its crystallinity when blended with non-fullerene acceptors, hence yielding NF-OSCs with higher hole mobility and fill factors (FF) compared to devices based on PTFB-P. In addition, PTFB-M also exhibits smaller and more favorable domain sizes in NF-OSCs, leading to higher external quantum efficiency (EQE) and short circuit current density (Jsc). As a result, when combined with a small molecule acceptor (SMA) ITIC-Th, PTFB-M yields a power conversion efficiency (PCE) of 10.4%, whereas the PCE is only 8.4% for PTFB-P:ITIC-Th-based cells. This provides a useful approach to tune the morphology of donor polymers and to enhance the performance of NF-OSCs.

Here a series of isoindigo (ID) and quaterthiophene (T4)-based donor–acceptor copolymers are synthesized and compared. The polymer with fluorination on the donor unit exhibits the strongest extent of temperature-dependent aggregation, which leads to a higher hole mobility of the polymer and PSCs with efficiencies up to 7.0% without using any processing additives. Our results provide important insights into how fluorination affects the aggregation properties and performance of isoindigo-based polymers.

Here we report high-performance small molecule acceptor (SMA)-based organic solar cells (OSCs) enabled by the combination of a difluorobenzothiadiazole donor polymer named PffBT4T-2DT and a SMA named SF-PDI2. It is found that SF-PDI2 matches particularly well with PffBT4T-2DT and non-fullerene OSCs with an impressive VOC of 0.98 V, and a high power conversion efficiency of 6.3% is achieved. Our study shows that PffBT4T-2DT is a promising donor material for SMA-based OSCs, and the selection of a matching SMA is also important to achieve the best OSC performance.

We report a series of difluorobenzothiadizole (ffBT) and oligothiophene-based polymers with the oligothiophene unit being quaterthiophene (T4), terthiophene (T3), and bithiophene (T2). We demonstrate that a polymer based on ffBT and T3 with an asymmetric arrangement of alkyl chains enables the fabrication of 10.7% efficiency thick-film polymer solar cells (PSCs) without using any processing additives. By decreasing the number of thiophene rings per repeating unit and thus increasing the effective density of the ffBT unit in the polymer backbone, the HOMO and LUMO levels of the T3 polymers are significantly deeper than those of the T4 polymers, and the absorption onset of the T3 polymers is also slightly red-shifted. For the three T3 polymers obtained, the positions and size of the alkyl chains play a critical role in achieving the best PSC performances. The T3 polymer with a commonly known arrangement of alkyl chains (alkyl chains sitting on the first and third thiophenes in a mirror symmetric manner) yields poor morphology and PSC efficiencies. Surprisingly, a T3 polymer with an asymmetric arrangement of alkyl chains (which is later described as having an ”asymmetric bi-repeating unit”) enables the best-performing PSCs. Morphological studies show that the optimized ffBT-T3 polymer forms a polymer:fullerene morphology that differs significantly from that obtained with T4-based polymers. The morphological changes include a reduced domain size and a reduced extent of polymer crystallinity. The change from T4 to T3 comonomer units and the novel arrangement of alkyl chains in our study provide an important tool to tune the energy levels and morphological properties of donor polymers, which has an overall beneficial effect and leads to enhanced PSC performance.

Here we report a series of tetraphenyl carbon-group (tetraphenylmethane (TPC), tetraphenylsilane (TPSi) and tetraphenylgermane (TPGe)) core based 3D-structure non-fullerene electron acceptors, enabling efficient polymer solar cells with a power conversion efficiency (PCE) of up to ∼4.3%. The results show that TPC and TPSi core-based polymer solar cells (PSCs) perform significantly better than that based on TPGe. Our study provides a new approach for designing small molecular acceptor materials for polymer solar cells.

Hybrid organic/inorganic perovskite solar cells are among the most competitive emerging photovoltaic technologies. Here, we report on NiO-based inverted structure perovskite solar cells with a high power conversion efficiency of 10.68%, which is achieved by adding a small percentage (1.5 wt%) of high molecular weight polystyrene (PS) into the PCBM electron transport layer (ETL). The addition of PS facilitates the formation of a highly smooth and uniform PCBM ETL that is more effective in preventing undesirable electron–hole recombination between the perovskite layer and the top electrode. As a result, the VOC of the PCBM:PS-based cells is increased from 0.97 V to 1.07 V, which leads to significantly enhanced power conversion efficiencies of the solar cells. Our study provides a simple and low-cost approach to improving the ETL film quality and the performance of inverted perovskite solar cells.

Rational design of molecular acceptors for non-fullerene organic solar cells remains challenging. Here we show that the introduction of two simple methyl groups on a bithiophene-bridged perylene diimide dimer leads to two molecular acceptors with distinctly different properties and solar cell performance. This work contributes towards understanding the structure–performance relationship of high-performance molecular acceptors.

•A polymer PffT2-FTAZ based on fluorinated donor part is designed and synthesized.•The PffT2-FTAZ based polymer solar cell achieve 7.8% power conversion efficiency.•GIWAXS and AFM etc. are utilized to investigate the fluorination effect.•This large bandgap polymer is a potential material for highly efficient tandem cells.We report a large bandgap (1.9 eV) donor–acceptor copolymer (named PffT2-FTAZ) that enables polymer solar cells with a high power conversion efficiency of 7.8%. An important structural feature of the PffT2-FTAZ polymer is a difluorinated donor unit (3,3′-difluoro-2,2′-bithiophene, or, ffT2) that introduces several surprising and/or beneficial effects. By comparing PffT2-FTAZ with the analog polymer (PT2-FTAZ) without fluorination on the bithiophene donor unit, it is found that the ffT2 unit effectively lowers the HOMO and LUMO energy levels of the polymer and slightly reduces optical bandgap. It also introduces strong interchain aggregation for the polymer in solution, which leads to a highly crystalline polymer film and reasonably high hole transport mobility. On the other hand, the PffT2-FTAZ: fullerene blend still exhibits a reasonably small polymer domain size suitable for polymer solar cell operation. All these positive factors combined leads to dramatically enhanced performance for the polymer solar cells with the power conversion efficiency increasing from 2.8% for PT2-FTAZ to 7.8% for f PffT2-FTAZ. The high PSC performance of PffT2-FTAZ makes it a promising candidate for high efficiency tandem PSCs.

A cross-linkable water/alcohol soluble conjugated polymer (WSCP) material poly[9,9-bis(6′-(N,N-diethylamino)propyl)-fluorene-alt-9,9-bis(3-ethyl(oxetane-3-ethyloxy)-hexyl) fluorene] (PFN-OX) was designed. The cross-linkable nature of PFN-OX is good for fabricating inverted polymer solar cells (PSCs) with well-defined interface and investigating the detailed working mechanism of high-efficiency inverted PSCs based on poly[4,8-bis(2-ethylhexyloxyl)benzo[1,2-b:4,5-b′]dithio-phene-2,6-diyl-alt-ethylhexyl-3-fluorothithieno[3,4-b]thiophene-2-carboxylate-4,6-diyl] (PTB7) and (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) blend active layer. The detailed working mechanism of WSCP materials in high-efficiency PSCs were studied and can be summarized into the following three effects: a) PFN-OX tunes cathode work function to enhance open-circuit voltage (Voc); b) PFN-OX dopes PC71BM at interface to facilitate electron extraction; and c) PFN-OX extracts electrons and blocks holes to enhance fill factor (FF). On the basis of this understanding, the hole-blocking function of the PFN-OX interlayer was further improved with addition of a ZnO layer between ITO and PFN-OX, which led to inverted PSCs with a power conversion efficiency of 9.28% and fill factor high up to 74.4%.

Hybrid organic/inorganic perovskite solar cells are among the most competitive emerging photovoltaic technologies. Here, we report on NiO-based inverted structure perovskite solar cells with a high power conversion efficiency of 10.68%, which is achieved by adding a small percentage (1.5 wt%) of high molecular weight polystyrene (PS) into the PCBM electron transport layer (ETL). The addition of PS facilitates the formation of a highly smooth and uniform PCBM ETL that is more effective in preventing undesirable electron–hole recombination between the perovskite layer and the top electrode. As a result, the VOC of the PCBM:PS-based cells is increased from 0.97 V to 1.07 V, which leads to significantly enhanced power conversion efficiencies of the solar cells. Our study provides a simple and low-cost approach to improving the ETL film quality and the performance of inverted perovskite solar cells.

Here we report a series of tetraphenyl carbon-group (tetraphenylmethane (TPC), tetraphenylsilane (TPSi) and tetraphenylgermane (TPGe)) core based 3D-structure non-fullerene electron acceptors, enabling efficient polymer solar cells with a power conversion efficiency (PCE) of up to ∼4.3%. The results show that TPC and TPSi core-based polymer solar cells (PSCs) perform significantly better than that based on TPGe. Our study provides a new approach for designing small molecular acceptor materials for polymer solar cells.

Rational design of molecular acceptors for non-fullerene organic solar cells remains challenging. Here we show that the introduction of two simple methyl groups on a bithiophene-bridged perylene diimide dimer leads to two molecular acceptors with distinctly different properties and solar cell performance. This work contributes towards understanding the structure–performance relationship of high-performance molecular acceptors.

Here a series of isoindigo (ID) and quaterthiophene (T4)-based donor–acceptor copolymers are synthesized and compared. The polymer with fluorination on the donor unit exhibits the strongest extent of temperature-dependent aggregation, which leads to a higher hole mobility of the polymer and PSCs with efficiencies up to 7.0% without using any processing additives. Our results provide important insights into how fluorination affects the aggregation properties and performance of isoindigo-based polymers.

The side-chain structures of conjugated molecules are well recognized to sensitively influence the crystallinity, morphology and thus carrier transport properties of organic semiconductors. Here, by varying the alkyl side-chain length in the polymer acceptors, the effect of side-chain engineering on the photovoltaic performance is systematically studied in all-polymer solar cells. Clear trends of first an increase and then a decrease in the Jsc and FF values are observed as the branched alkyl groups are extended from 4 to 8 carbons. Correspondingly, the maximum average PCE (ca. 7.40%) is attained with an acceptor bearing a branched side-chain length of seven carbon atoms.

We report a wide bandgap polymer PvBDTffBT based on a new building block: a vertical-benzodithiophene (vBDT) unit. Compared to traditional BDT based polymers, the vBDT unit in PvBDTffBT is connected via the phenyl group instead of the thiophene unit. Such modification leads to stronger torsion between the vBDT unit and the adjacent thiophene, which increases the bandgap of the polymer and introduces significant changes in the film morphology. When blended with a state-of-the-art narrow-bandgap small molecular acceptor (ITIC-Th), we find that this polymer modulation strategy significantly improves the photovoltaic performances from 3% to over 8%.