16.52% Efficiency All-Polymer Solar Cells with High Tolerance of the Photoactive Layer Thickness.

All-polymer solar cells (all-PSCs) have drawn growing attention and achieved tremendous progress recently, but their power conversion efficiency (PCE) still lags behind small-molecule-acceptor (SMA)-based PSCs due to the relative difficulty on morphology control of polymer photoactive blends. Here, low-cost PTQ10 is introduced as a second polymer donor (a third component) into the PM6:PY-IT blend to finely tune the energy-level matching and microscopic morphology of the polymer blend photoactive layer. The addition of PTQ10 decreases the π-π stacking distance, and increases the π-π stacking coherence length and the ordered face-on molecular packing orientation, which improves the charge separation and transport in the photoactive layer. Moreover, the deeper highest occupied molecular orbital energy level of the PTQ10 polymer donor than PM6 leads to higher open-circuit voltage of the ternary all-PSCs. As a result, a PCE of 16.52% is achieved for ternary all-PSCs, which is one of the highest PCEs for all-PSCs. In addition, the ternary devices exhibit a high tolerance of the photoactive layer thickness with high PCEs of 15.27% and 13.91% at photoactive layer thickness of ≈205 and ≈306 nm, respectively, which are the highest PCEs so far for all-PSCs with a thick photoactive layer.

Conjugated Mesopolymer Achieving 15% Efficiency Single-Junction Organic Solar Cells.

The high-performance organic solar cells (OSCs) tend to choose the polymers with high molecular weight as donors, which easily produce good crystallinity to facilitate intermolecular charge transfer. However, these polymers usually accompanied by the low solubility and synthetic difficulty, increasing batch-to-batch variations. The proposal of conjugated mesopolymers (molar mass (Mn ) in 1-10 kDa) can overcome these problems. Herein, a new mesopolymer, MePBDFClH as donor material is designed and synthesized, and firstly applied in OSCs. As a comparison, other lower molecular weight mesopolymer of MePBDFClL and higher molecular weight polymer of PBDFCl with same structure are also prepared and investigated. Because of its appropriate phase separation and miscibility in the blend film, the MePBDFClH exhibits the highest power conversion efficiency (PCE) of 15.06% among the three materials. Meanwhile, the champion PCE is a new record for benzo[1,2-b:4,5-b']difuran-based photovoltaic materials. Importantly, comparing to the pronounced PCE decrease of polymer PBDFCl by about 12%, a slightly PCE difference for mespolymer MePBDFClL is only less than 5%, reducing the batch-to-batch variation. This work not only suggests that the benzo[1,2-b:4,5-b']difuran unit is a promising electron-donating core but also shows that the mesopolymers have great potentials to produce the low-differentiated and high-performance organic photovoltaic materials.

A Cost-Effective Alpha-Fluorinated Bithienyl Benzodithiophene Unit for High-Performance Polymer Donor Material.

To reduce synthetic cost of the classic fluorinated bithienyl benzodithiophene (BDTT-F) unit, here, an alpha-fluorinated bithienyl benzodithiophene unit, namely, α-BDTT-F (F atom in the α position of the lateral thiophene unit), is developed by the isomerization strategy of exchanging the positions of the F atom and flexible alkyl chain on the lateral thiophene unit of the BDTT-F unit. The α-BDTT-F unit was synthesized with less synthetic steps, higher synthetic yield, and less purification times from the same raw materials as those of the BDTT-F unit, thus with low synthetic cost. Theoretical calculation indicates that the α-BDTT-F unit possesses a similar twisted conformation and electronic structures as those of the BDTT-F unit. The α-BDTT-F-based polymer α-PBQ10 exhibits similar light absorption and energy levels as those of the corresponding BDTT-F-based polymer PBQ10 but marginally increased molecular aggregation and stronger hole transport than PBQ10. In consequence, the α-PBQ10:Y6-based polymer solar cell demonstrates a slightly enhanced power conversion efficiency (PCE) of 16.26% compared with that of the PBQ10:Y6-based device (PCE = 16.23%). Also, the PCE is further improved to 16.77% through subtle microscopic morphology regulation of the photoactive layer with the fullerene derivative indene-C60 bisadduct as the third component. This work provides new ideas for the design of low-cost and high-efficiency photovoltaic molecules.

Fine-Tuning Miscibility and π-π Stacking by Alkylthio Side Chains of Donor Molecules Enables High-Performance All-Small-Molecule Organic Solar Cells.

Optimization of morphology and precise control of miscibility between donors and acceptors play an important role in improving the power conversion efficiencies (PCEs) of all-small-molecule organic solar cells (SM-OSCs). Besides device optimization, methods such as additives and thermal annealing are applied for finely tuning bulk-heterojunction morphology; strategies of molecular design are also the key to achieve efficient phase separation. Here, a series of A-D-A-type small-molecule donors (SM4, SM8, and SM12) based on benzodithiophene units were synthesized with different lengths of alkylthio side chains to regulate crystallinity, and their miscibility with the acceptor (BO-4Cl) was investigated. Consequently, SM4 with a short alkylthio substituent had a high crystallization propensity, leading to the oversized molecular domains and the poor morphology of the active layer. Meanwhile, SM12 with a longer alkylthio substituent showed weak crystallinity, causing a relatively looser π-π stacking and thus adversely affecting charge-carrier transport. The SM-OSC based on the small-molecule donor SM8 with a mid-length alkylthio substituent achieved a better PCE over 13%, which was attributed to a more harmonious blend miscibility without sacrificing carrier-charge transport. Eventually, the modulation of phase separation and miscibility via controlling the lateral side chains has proven its potential in optimizing the blend morphology to aid the development of highly efficient SM-OSCs.