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A major challenge hindering the further development of all-polymer solar cells (all-PSCs) employing polymerized small-molecule acceptors is the relatively low fill factor (FF) due to the difficulty in controlling the active-layer morphology. The issues typically arise from oversized phase separation resulting from the thermodynamically unfavorable mixing between two macromolecular species, and disordered molecular orientation/packing of highly anisotropic polymer chains. Herein, a facile top-down controlling strategy to engineer the morphology of all-polymer blends is developed by leveraging the layer-by-layer (LBL) deposition. Optimal intermixing of polymer components can be achieved in the two-step process by tuning the bottom-layer polymer swelling during top-layer deposition. Consequently, both the molecular orientation/packing of the bottom layer and the molecular ordering of the top layer can be optimized with a suitable top-layer processing solvent. A favorable morphology with gradient vertical composition distribution for efficient charge transport and extraction is therefore realized, affording a high all-PSC efficiency of 17.0% with a FF of 76.1%. The derived devices also possess excellent long-term thermal stability and can retain90% of their initial efficiencies after being annealed at 65 °C for 1300 h. These results validate the distinct advantages of employing an LBL processing protocol to fabricate high-performance all-PSCs.

A record power conversion efficiency (PCE) of over 19% is realized in planar-mixed heterojunction (PMHJ) organic solar cells (OSCs) by adopting the asymmetric selenium substitution strategy in making a pseudosymmetric electron acceptor, BS3TSe-4F. The combined molecular asymmetry with more polarizable selenium substitution increases the dielectric constant of the D18/BS3TSe-4F blend, helping lower the exciton binding energy. On the other hand, dimer packing in BS3TSe-4F is facilitated to enable free charge generation, helping more efficient exciton dissociation and lowering the radiative recombination loss (ΔE

In all-small-molecule organic solar cells (ASM-OSCs), a high short circuit current (Jsc ) usually needs a small phase separation, while a high fill factor (FF) is generally realized in a highly ordered packing system. However, small domain and ordered packing always contracted each other in ASM-OSCs, leading to a mutually restricted Jsc and FF. In this study, we propose alleviating the previous dilemma by the strategy of obtaining simultaneous good miscibility and ordered packing through modulating homo- and hetero- molecular interaction. By moving the alkyl-thiolation side chains from para- to meta-position in the small-molecule donor, the surface tension and molecular planarity are synchronously enhanced, resulting in compatible properties of good miscibility with acceptor BTP-eC9 and strong self-assemble ability. As a result, an optimized morphology with multi-length scale domains and highly ordered packing is realized. The device exhibits a long carrier lifetime (39.8 us) and fast charge collection (15.5 ns). A record efficiency of 16.2% with a high FF of 75.6% and a Jsc of 25.4 mA cm-2 in the ASM-OSCs is obtained. These results demonstrate that the strategy of simultaneously obtaining good miscibility with high crystallinity could be an efficient photovoltaic material design principle for high performance ASM-OSCs. This article is protected by copyright. All rights reserved.

International audience; The environmental impact of solution processed organic solar cells (OSCs) can be mitigated by introducing so-called green solvents during the fabrication processes. However, the effects of such green solvents on the molecular-level structures and optoelectronic properties lack in-depth characterization. Here, insights into the structure–processing–property correlation of a PPDT2FBT:PC61BM bulk-heterojunction (BHJ) system processed from a green solvent, ortho-xylene (o-XY), is investigated in comparison with the same blend processed from a traditional halogenated solvent, chlorobenzene (CB). The BHJ blends are characterized with various techniques probing at difference length scales, and an increased donor:acceptor (D:A) interfacial area as well as well-mixed features in the bulk morphologies of the active layer are observed for the o-XY processed BHJ blend. Furthermore, molecular-level differences in the D–A intermolecular interactions at the BHJ interfaces in o-XY and CB cast films are elucidated by 2-dimensional solid-state nuclear magnetic resonance (ssNMR) measurements and analysis. These results are consistent with the device properties, suggesting that the green-solvent-processed devices have longer charge carrier lifetimes and faster charge carrier extraction. The optimized PPDT2FBT:PC61BM devices processed from o-XY can achieve a noteworthy higher power conversion efficiency (PCE) owing to a higher short-circuit current density and fill factor.

With power conversion efficiency now over 17%, a long operational lifetime is essential for the successful application of organic solar cells. However, most non-fullerene acceptors can crystallize and destroy devices, yet the fundamental underlying thermodynamic and kinetic aspects of acceptor crystallization have received limited attention. Here, room-temperature (RT) diffusion coefficients of 3.4 × 10-23 and 2.0 × 10-22 are measured for ITIC-2Cl and ITIC-2F, two state-of-the-art non-fullerene acceptors. The low coefficients are enough to provide for kinetic stabilization of the morphology against demixing at RT. Additionally profound differences in crystallization characteristics are discovered between ITIC-2F and ITIC-2Cl. The differences as observed by secondary-ion mass spectrometry, differential scanning calorimetry (DSC), grazing-incidence wide-angle X-ray scattering, and microscopy can be related directly to device degradation and are attributed to the significantly different nucleation and growth rates, with a difference in the growth rate of a factor of 12 at RT. ITIC-4F and ITIC-4Cl exhibit similar characteristics. The results reveal the importance of diffusion coefficients and melting enthalpies in controlling the growth rates, and that differences in halogenation can drastically change crystallization kinetics and device stability. It is furthermore delineated how low nucleation density and large growth rates can be inferred from DSC and microscopy experiments which could be used to guide molecular design for stability.

Solution-processed Cu(In,Ga)(S,Se)2 (CIGS) has a great potential for the production of large-area photovoltaic devices at low cost. However, CIGS solar cells processed from solution exhibit relatively lower performance compared to vacuum-processed devices because of a lack of proper composition distribution, which is mainly instigated by the limited Se uptake during chalcogenization. In this work, a unique potassium treatment method is utilized to improve the selenium uptake judiciously, enhancing grain sizes and forming a wider bandgap minimum region. Careful engineering of the bandgap grading structure also results in an enlarged space charge region, which is favorable for electron-hole separation and efficient charge carrier collection. Besides, this device processing approach has led to a linearly increasing electron diffusion length and carrier lifetime with increasing the grain size of the CIGS film, which is a critical achievement for enhancing photocurrent yield. Overall, 15% of power conversion efficiency is achieved in solar cells processed from environmentally benign solutions. This approach offers critical insights for precise device design and processing rules for solution-processed CIGS solar cells.

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.

This work was supported by the Office of Naval Research Grant N00014-17-1-2242, National Science Foundation Award CBET-1639429, and NextGen Nano.

Quasi-2D Ruddlesden-Popper halide perovskites with a large exciton binding energy, self-assembled quantum wells, and high quantum yield draw attention for optoelectronic device applications. Thin films of these quasi-2D perovskites consist of a mixture of domains having different dimensionality, allowing energy funneling from lower-dimensional nanosheets (high-bandgap domains) to 3D nanocrystals (low-bandgap domains). High-quality quasi-2D perovskite (PEA)2 (FA)3 Pb4 Br13 films are fabricated by solution engineering. Grazing-incidence wide-angle X-ray scattering measurements are conducted to study the crystal orientation, and transient absorption spectroscopy measurements are conducted to study the charge-carrier dynamics. These data show that highly oriented 2D crystal films have a faster energy transfer from the high-bandgap domains to the low-bandgap domains (

A difluorobenzoxadiazole building block is synthesized and utilized to construct a conjugated polymer leading to high-performance thick-film polymer solar cells with a V(OC) of 0.88 V and a power conversion efficiency of 9.4%. This new building block can be used in many possible polymer structures for various organic electro-nic applications.

Manipulating molecular orientation at the donor/acceptor interface is the key to boosting charge separation properties and efficiencies of anisotropic-materials-based organic photovoltaics (OPVs). By replacing the polymeric donor PBDTBDD with its 2D-conjugated polymer PBDTBDD-T, the power conversion efficiency of OPVs featuring the anisotropic polymer acceptor PNDI is drastically boosted from 2.4% up to 5.8%.

A general impact of solution shearing on molecular orientation correlation is observed in polymer:fullerene organic solar cells in which one of the components forms fi brils or aggregates. Further investigation with polarized soft X-ray scattering reveals that solution shearing induces more face-to-face orientation relative to the interface of two components compared to spincoating. This impact is shearing speed dependent, that is, slow shearing speed can induce more face-to-face orientation than a fast shearing speed. These results demonstrate that solution shearing is an effective method to control the relative molecular orientation. Solution shearing can also modify the domain size and average composition variations.

A relationship between solvent additive concentration and active layer thickness in small-molecule solar cells is investigated. Specifically, the additive concentration must scale with the amount of semiconductor material and not as absolute concentration in solution. Devices with a wide range of active layers with thickness up to 200 nm can readily achieve efficiencies close to 6% when the right concentration of additive is used.

All-polymer solar cells based on a pair of crystalline low-bandgap polymers (NT and N2200) are demonstrated to achieve a high short-circuit current density of 11.5 mA cm-2 and a power conversion efficiency of up to 5.0% under the standard AM1.5G spectrum with one sun intensity. The high performance of these NT:N2200-based cells can be attributed to the low optical bandgaps of the polymers and the reasonably high and balanced electron and hole mobilities of the NT:N2200 blends due to the crystalline nature of the two polymers.

For the blend film of PBDTTT-C-T:PC71 BM, the use of 1,8-diiodooctane as the solvent additive enriches the polymer at the top surface, so that a power conversion efficiency of 9.13% is recorded in the inverted polymer solar cell based on the blend, which is much higher than that of the device with conventional structure.

Acknowledge support from the Office of Naval Research (N00014-14-1-0142), KAUST Center for Advanced Molecular Photovoltaics at Stanford and the Stanford Global Climate and Energy Program, NSF DMR-1303742 and the National Natural Science Foundation of China (Projects 21174004 and 21222403). Soft X-ray characterization and analysis by NCSU supported by the U.S. Department of Energy, Office of Science, Basic Energy Science, Division of Materials Science and Engineering under Contract DE-FG02-98ER45737. Soft X-ray data was acquired at beamlines 11.0.1.2 at the Advanced Light Source, which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U. S. Department of Energy under Contract No. DE-AC02-05CH11231. We thank Professor Michael D. McGehee, Dr. George F. Burkhard and Dr. Eric T. Hoke for their help in discussion of the recombination mechanism.

The field dependence and yield of free charge carrier generation in polymer:fullerene blends with varying energetic offsets is not affected when the excitation energy is varied from above band-gap to direct CT state excitation. Instead, the ability of the CT state to split is dictated by the energetic offset between the relaxed CT state and the charge separated (CS) state.

Author(s): Rosenthal, Katie Danielle | Advisor(s): Nguyen, Thuc-Quyen | Abstract: Open-circuit voltage (VOC) losses in organic photovoltaics (OPVs) inhibit devices from reaching VOC values comparable to the bandgap of the donor-acceptor blend. Specifically, nonradiative recombination losses (∆Vnr) are much greater in OPVs than in silicon or perovskite solar cells, yet the origins of this are not fully understood. To understand what makes a system have high or low loss, an investigation of the nonradiative recombination losses in a total of nine blend systems was carried out. An apparent relationship was observed between the relative domain purity of six blends and the degree of nonradiative recombination loss, where films exhibiting relatively less pure domains show lower ∆Vnr than films with higher domain purity. Additionally, it is shown that when paired with a fullerene acceptor, polymer donors which have bulky backbone units to inhibit close π-π stacking exhibit lower nonradiative recombination losses than in blends where the polymer can pack more closely. This work reports a strategy that ensures ∆Vnr can be measured accurately and reports key observations on the relationship between ∆Vnr and properties of the donor/acceptor interface.

Attaching meta-alkoxy-phenyl groups as conjugated side chains is an easy and effective way to modulate the molecular energy level of D-A polymer for photovoltaic application, and the polymer solar cells based on the polymer consisting meta-alkoxy-phenyl groups as conjugated side chain, PBT-OP, shows an enhanced open circuit voltage and thus higher efficiency of 7.50%, under the illumination of AM 1.5G, 100 mW/cm(2) .

The correlation among molecular conformation, the crystallinity of the morphology, propensity for π-π stacking, J- versus H-aggregation, and photovoltaic performance have been studied based on two newly designed polymers, PBDTTT-S-T and PDT-S-T. The results show that more linear backbone structure is helpful to improve photovoltaic properties of the polymer, and therefore, molecular conformation should be considered for molecular design of photovoltaic polymers.

Domain purity and interface structure are known to be critical for fullerene-based bulk heterojunction (BHJ) solar cells, yet have been very difficult to study. Using novel soft X-ray tools, we delineate the importance of these parameters by comparing high performance cells based on a novel naphtha[1,2-c:5,6-c]bis[1,2,5]thiadiazole (NT) material to cells based on a 2,1,3-benzothiadiazole (BT) analogue. BT-based devices exhibit ∼15 nm, mixed domains that differ in composition by at most 22%, causing substantial bimolecular recombination. In contrast, NT-based devices have more pure domains that are >80 nm in size, yet the polymer-rich phase still contains at least 22% fullerene. Power conversion efficiency >6% is achieved for NT devices despite a domain size much larger than the nominal exciton diffusion length due to a favourable trade-off in the mixed domain between exciton harvesting, charge transport, and bimolecular recombination. The miscibility of the fullerene with the NT and BT polymer is measured and correlated to the purity in devices. Importantly, polarized x-ray scattering reveals preferential face-on orientation of the NT polymer relative to the PCBM-rich domains. Such ordering has previously not been observed in fullerene-based solar cells and is shown here to be possibly a controlling or contributing factor to high performance.