Precise Control of Phase Separation Enables 12% Efficiency in All Small Molecule Solar Cells

Compared to conjugated polymers, small-molecule organic semiconductors present negligible batch-to-batch variations, but presently provide comparatively low power conversion efficiencies (PCEs) in small-molecular organic solar cells (SM-OSCs), mainly due to suboptimal nanomorphology. Achieving precise control of the nanomorphology remains challenging. Here, two new small-molecular donors H13 and H14, created by fluorine and chlorine substitution of the original donor molecule H11, are presented that exhibit a similar or higher degree of crystallinity/aggregation and improved open-circuit voltage with IDIC-4F as acceptor. Due to kinetic and thermodynamic reasons, H13-based blend films possess relatively unfavorable molecular packing and morphology. In contrast, annealed H14-based blends exhibit favorable characteristics, i.e., the highest degree of aggregation with the smallest paracrystalline π–π distortions and a nanomorphology with relatively pure domains, all of which enable generating and collecting charges more efficiently. As a result, blends with H13 give a similar PCE (10.3%) as those made with H11 (10.4%), while annealed H14-based SM-OSCs have a significantly higher PCE (12.1%). Presently this represents the highest efficiency for SM-OSCs using IDIC-4F as acceptor. The results demonstrate that precise control of phase separation can be achieved by fine-tuning the molecular structure and film formation conditions, improving PCE and providing guidance for morphology design

Effect of main and side chain chlorination on the photovoltaic properties of benzodithiophene-: Alt -benzotriazole polymers

In developing organic semiconductor polymers for photovoltaic applications, chlorine substitution has become an effective strategy in replacing fluorine substitution to overcome the drawbacks of low yield and high cost, commonly associated with fluorination. In general, several molecular positions are available for chlorination. To obtain a clear understanding of the impact of chlorine substitution on the intrinsic polymer properties, an investigation of structure-property relationships is necessary. Herein, four donor-acceptor type polymers with the same conjugated backbone and flexible alkyl chains, but with chlorine atoms in different positions, are employed to systematically investigate the effect of the site of chlorination on the optoelectronic properties and photovoltaic performance. Substitution of fluorine by chlorine in the backbone slightly increases open circuit voltage (Voc) and fill factor (FF) of the solar cells but causes a loss of short-circuit current density (Jsc). The introduction of chlorine in the conjugated side chains, however, significantly improves Voc, FF, and power conversion efficiency, benefiting from a lower HOMO energy level, efficient and well-balanced transport properties, and superior nanoscale morphology

Synergistic Use of Pyridine and Selenophene in a Diketopyrrolopyrrole‐Based Conjugated Polymer Enhances the Electron Mobility in Organic Transistors

To achieve semiconducting materials with high electron mobility in organic field-effect transistors (OFETs), low-lying energy levels (the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)) and favorable molecular packing and ordering are two crucial factors. Here, it is reported that the incorporation of pyridine and selenophene into the backbone of a diketopyrrolopyrrole (DPP)-based copolymer produces a high-electron-mobility semiconductor, PDPPy-Se. Compared with analogous polymers based on other DPP derivatives and selenophene, PDPPy-Se features a lower LUMO that can decrease the electron transfer barrier for more effective electron injection, and simultaneously a lower HOMO that, however, can increase the hole transfer barrier to suppress the hole injection. Combined with thermal annealing at 240 °C for thin film morphology optimization to achieve large-scale crystallite domains with tight molecular packing for effective charge transport along the conducting channel, OFET devices fabricated with PDPPy-Se exhibit an n-type-dominant performance with an electron mobility (μe) as high as 2.22 cm2 V−1 s−1 and a hole/electron mobility ratio (μh/μe) of 0.26. Overall, this study demonstrates a simple yet effective approach to boost the electron mobility in organic transistors by synergistic use of pyridine and selenophene in the backbone of a DPP-based copolymer.</p

Precise Control of Phase Separation Enables 12% Efficiency in All Small Molecule Solar Cells

Compared to conjugated polymers, small-molecule organic semiconductors present negligible batch-to-batch variations, but presently provide comparatively low power conversion efficiencies (PCEs) in small-molecular organic solar cells (SM-OSCs), mainly due to suboptimal nanomorphology. Achieving precise control of the nanomorphology remains challenging. Here, two new small-molecular donors H13 and H14, created by fluorine and chlorine substitution of the original donor molecule H11, are presented that exhibit a similar or higher degree of crystallinity/aggregation and improved open-circuit voltage with IDIC-4F as acceptor. Due to kinetic and thermodynamic reasons, H13-based blend films possess relatively unfavorable molecular packing and morphology. In contrast, annealed H14-based blends exhibit favorable characteristics, i.e., the highest degree of aggregation with the smallest paracrystalline π–π distortions and a nanomorphology with relatively pure domains, all of which enable generating and collecting charges more efficiently. As a result, blends with H13 give a similar PCE (10.3%) as those made with H11 (10.4%), while annealed H14-based SM-OSCs have a significantly higher PCE (12.1%). Presently this represents the highest efficiency for SM-OSCs using IDIC-4F as acceptor. The results demonstrate that precise control of phase separation can be achieved by fine-tuning the molecular structure and film formation conditions, improving PCE and providing guidance for morphology design

Synergistic use of pyridine and selenophene in a diketopyrrolopyrrole-based conjugated polymer enhances the electron mobility in organic transistors

To achieve semiconducting materials with high electron mobility in organic field-effect transistors (OFETs), low-lying energy levels (the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)) and favorable molecular packing and ordering are two crucial factors. Here, it is reported that the incorporation of pyridine and selenophene into the backbone of a diketopyrrolopyrrole (DPP)-based copolymer produces a high-electron-mobility semiconductor, PDPPy-Se. Compared with analogous polymers based on other DPP derivatives and selenophene, PDPPy-Se features a lower LUMO that can decrease the electron transfer barrier for more effective electron injection, and simultaneously a lower HOMO that, however, can increase the hole transfer barrier to suppress the hole injection. Combined with thermal annealing at 240 °C for thin film morphology optimization to achieve large-scale crystallite domains with tight molecular packing for effective charge transport along the conducting channel, OFET devices fabricated with PDPPy-Se exhibit an n-type-dominant performance with an electron mobility (μe) as high as 2.22 cm2 V−1 s−1 and a hole/electron mobility ratio (μh/μe) of 0.26. Overall, this study demonstrates a simple yet effective approach to boost the electron mobility in organic transistors by synergistic use of pyridine and selenophene in the backbone of a DPP-based copolymer.</p

High performance tandem organic solar cells via a strongly infrared-absorbing narrow bandgap acceptor

Tandem organic solar cells are based on the device structure monolithically connecting two solar cells to broaden overall absorption spectrum and utilize the photon energy more efficiently. Herein, we demonstrate a simple strategy of inserting a double bond between the central core and end groups of the small molecule acceptor Y6 to extend its conjugation length and absorption range. As a result, a new narrow bandgap acceptor BTPV-4F was synthesized with an optical bandgap of 1.21 eV. The single-junction devices based on BTPV-4F as acceptor achieved a power conversion efficiency of over 13.4% with a high short-circuit current density of 28.9 mA cm−2. With adopting BTPV-4F as the rear cell acceptor material, the resulting tandem devices reached a high power conversion efficiency of over 16.4% with good photostability. The results indicate that BTPV-4F is an efficient infrared-absorbing narrow bandgap acceptor and has great potential to be applied into tandem organic solar cells

Near-infrared absorbing acceptor with suppressed triplet exciton generation enabling high performance tandem organic solar cells

Reducing the energy loss of sub-cells is critical for high performance tandem organic solar cells, while it is limited by the severe non-radiative voltage loss via the formation of non-emissive triplet excitons. Herein, we develop an ultra-narrow bandgap acceptor BTPSeV-4F through replacement of terminal thiophene by selenophene in the central fused ring of BTPSV-4F, for constructing efficient tandem organic solar cells. The selenophene substitution further decrease the optical bandgap of BTPSV-4F to 1.17 eV and suppress the formation of triplet exciton in the BTPSV-4F-based devices. The organic solar cells with BTPSeV-4F as acceptor demonstrate a higher power conversion efficiency of 14.2% with a record high short-circuit current density of 30.1 mA cm(-2) and low energy loss of 0.55 eV benefitted from the low non-radiative energy loss due to the suppression of triplet exciton formation. We also develop a high-performance medium bandgap acceptor O1-Br for front cells. By integrating the PM6:O1-Br based front cells with the PTB7-Th:BTPSeV-4F based rear cells, the tandem organic solar cell demonstrates a power conversion efficiency of 19%. The results indicate that the suppression of triplet excitons formation in the near-infrared-absorbing acceptor by molecular design is an effective way to improve the photovoltaic performance of the tandem organic solar cells. Reducing energy loss of sub-cells is critical for high performance tandem organic solar cells. Here, the authors design and synthesize an ultra-narrow bandgap acceptor through replacement of terminal thiophene by selenophene in the central fused ring, achieving efficiency of 19% for tandem cells.Funding Agencies|National Key Research and Development Program of China - MOST [2019YFA0705900]; National Natural Science Foundation of China [51820105003, 21734008, 61904181, 52173188]; Basic and Applied Basic Research Major Program of Guangdong Province [2019B030302007]; ONR [N000142012155]; U.S. DOE Office of Science User Facility [DE-AC02-05CH11231]</p