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.

Small-Molecule Acceptor with Unsymmetric Substituents and Fused Rings for High-Performance Organic Solar Cells with Enhanced Mobility and Reduced Energy Losses.

A new unsymmetric small-molecule acceptor (SMA) BTPOSe-4F was designed by unsymmetric structure modification to Y6 with an alkyl upper side chain replaced by an alkoxy side chain and a sulfur atom in its central fused ring replaced by a selenium atom, for the application as an acceptor to fabricate organic solar cells (OSCs). BTPOSe-4F exhibits a higher lowest unoccupied molecular orbital (LUMO) energy level, a reduced nonradiation energy loss, and better charge extraction properties in its binary OSCs with a higher Voc of 0.886. Furthermore, the ternary OSCs with the addition of PC71BM demonstrated a higher power conversion efficiency (PCE) of 17.33% with Voc of 0.890 V. This work reveals that the unsymmetric modification strategy can further give impetus to the photovoltaic performance promotion of OSCs for Y6-series SMAs.

Importance of Electric-Field-Independent Mobilities in Thick-Film Organic Solar Cells.

In organic solar cells (OSCs), a thick active layer usually yields a higher photocurrent with broader optical absorption than a thin active layer. In fact, a ∼300 nm thick active layer is more compatible with large-area processing methods and theoretically should be a better spot for efficiency optimization. However, the bottleneck of developing high-efficiency thick-film OSCs is the loss in fill factor (FF). The origin of the FF loss is not clearly understood, and there a direct method to identify photoactive materials for high-efficiency thick-film OSCs is lacking. Here, we demonstrate that the mobility field-dependent coefficient is an important parameter directly determining the FF loss in thick-film OSCs. Simulation results based on the drift-diffusion model reveal that a mobility field-dependent coefficient smaller than 10-3 (V/cm)-1/2 is required to maintain a good FF in thick-film devices. To confirm our simulation results, we studied the performance of two ternary bulk heterojunction (BHJ) blends, PTQ10:N3:PC71BM and PM6:N3:PC71BM. We found that the PTQ10 blend film has weaker field-dependent mobilities, giving rise to a more balanced electron-hole transport at low fields. While both the PM6 blend and PTQ10 blend yield good performance in thin-film devices (∼100 nm), only the PTQ10 blend can retain a FF = 74% with an active layer thickness of up to 300 nm. Combining the benefits of a higher JSC in thick-film devices, we achieved a PCE of 16.8% in a 300 nm thick PTQ10:N3:PC71BM OSC. Such a high FF in the thick-film PTQ10 blend is also consistent with the observation of lower charge recombination from light-intensity-dependent measurements and lower energetic disorder observed in photothermal deflection spectroscopy.

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.

Polymerized small molecular acceptor based all-polymer solar cells with an efficiency of 16.16% via tuning polymer blend morphology by molecular design.

All-polymer solar cells (all-PSCs) based on polymerized small molecular acceptors (PSMAs) have made significant progress recently. Here, we synthesize two A-DA'D-A small molecule acceptor based PSMAs of PS-Se with benzo[c][1,2,5]thiadiazole A'-core and PN-Se with benzotriazole A'-core, for the studies of the effect of molecular structure on the photovoltaic performance of the PSMAs. The two PSMAs possess broad absorption with PN-Se showing more red-shifted absorption than PS-Se and suitable electronic energy levels for the application as polymer acceptors in the all-PSCs with PBDB-T as polymer donor. Cryogenic transmission electron microscopy visualizes the aggregation behavior of the PBDB-T donor and the PSMA in their solutions. In addition, a bicontinuous-interpenetrating network in the PBDB-T:PN-Se blend film with aggregation size of 10~20 nm is clearly observed by the photoinduced force microscopy. The desirable morphology of the PBDB-T:PN-Se active layer leads its all-PSC showing higher power conversion efficiency of 16.16%.

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.

The Critical Role of Materials' Interaction in Realizing Organic Field-Effect Transistors Via High-Dilution Blending with Insulating Polymers.

High-performance low-band-gap polymer semiconductors are visibly colored, making them unsuitable for transparent and imperceptible electronics without reducing film thickness to the nanoscale range. Herein, we demonstrate polymer/insulator blends exhibiting favorable miscibility that improves the transparency and carrier transport in an organic field-effect transistor (OFET) device. The mesoscale structures leading to more efficient charge transport in ultrathin films relevant to the realization of transparent and flexible electronic applications are explored based on thermodynamic material interaction principles in conjunction with optical and morphological studies. By blending the commodity polymer polystyrene (PS) with two high-performing polymers, PDPP3T and P (NDI2OD-T2) (known as N2200), a drastic difference in morphology and fiber network are observed due to considerable differences in the degree of thermodynamic interaction between the conjugated polymers and PS. Intrinsic material interaction behavior establishes a long-range intermolecular interaction in the PDPP3T polymer fibrillar network dispersed in the majority (80%) PS matrix resulting in a ca. 3-fold increased transistor hole mobility of 1.15 cm2 V-1 s-1 (highest = 1.5 cm2 V-1 s-1) as compared to the pristine material, while PS barely affects the electron mobility in N2200. These basic findings provide important guidelines to achieve high mobility in transparent OFETs.

High-Performance All-Polymer Solar Cells: Synthesis of Polymer Acceptor by a Random Ternary Copolymerization Strategy.

Demonstrated in this work is a simple random ternary copolymerization strategy to synthesize a series of polymer acceptors, PTPBT-ETx , by polymerizing a small-molecule acceptor unit modified from Y6 with a thiophene connecting unit and a controlled amount of an 3-ethylesterthiophene (ET) unit. Compared to PTPBT of only Y6-like units and thiophene units, PTPBT-ETx (where x represents the molar ratio of the ET unit) with an incorporated ET unit in the ternary copolymers show up-shifted LUMO energy levels, increased electron mobilities, and improved blend morphologies in the blend film with the polymer donor PBDB-T. And the all-polymer solar cell (all-PSC) based on PBDB-T:PTPBT-ET0.3 achieved a high power conversion efficiency over 12.5 %. In addition, the PTPBT-ET0.3 -based all-PSC also exhibits long-term photostability over 300 hours.

High-Efficiency All-Small-Molecule Organic Solar Cells Based on an Organic Molecule Donor with Alkylsilyl-Thienyl Conjugated Side Chains.

Two medium-bandgap p-type organic small molecules H21 and H22 with an alkylsily-thienyl conjugated side chain on benzo[1,2-b:4,5-b']dithiophene central units are synthesized and used as donors in all-small-molecule organic solar cells (SM-OSCs) with a narrow-bandgap n-type small molecule 2,2'-((2Z,2'Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (IDIC) as the acceptor. In comparison to H21 with 3-ethyl rhodanine as the terminal group, H22 with cyanoacetic acid esters as the terminal group shows blueshifted absorption, higher charge-carrier mobility and better 3D charge pathway in blend films. The power conversion efficiency (PCE) of the SM-OSCs based on H22:IDIC reaches 10.29% with a higher open-circuit voltage of 0.942 V and a higher fill factor of 71.15%. The PCE of 10.29% is among the top efficiencies of nonfullerene SM-OSCs reported in the literature to date.

Competition between exceptionally long-range alkyl sidechain ordering and backbone ordering in semiconducting polymers and its impact on electronic and optoelectronic properties.

Intra- and intermolecular ordering greatly impact the electronic and optoelectronic properties of semiconducting polymers. Despite much prior efforts regarding molecular packing, the interrelationship between ordering of alkyl sidechains and conjugated backbones has not been fully detailed. We report here the discovery of a highly ordered alkyl sidechain phase in six representative semiconducting polymers, determined from distinct spectroscopic and diffraction signatures. The sidechain ordering exhibits unusually large coherence lengths of at least 70 nm, induces torsional/twisting backbone disorder, and results in a vertically layered multilayer nanostructure with ordered sidechain layers alternating with disordered backbone layers. Calorimetry and in-situ variable temperature scattering measurements in a model system PBnDT-FTAZ clearly delineate this competition of ordering that prevents the simultaneous long-range order of both moieties. The long-range sidechain ordering can be exploited as a transient state to fabricate PBnDT-FTAZ films with an atypical edge-on texture and 2.5x improved OFET mobility. The observed influence of ordering between the moieties implies that improved molecular design could produce synergistic rather than destructive ordering effects. Given the large sidechain coherence lengths observed, such synergistic ordering should greatly improve the coherence length of backbone ordering and thereby improve electronic and optoelectronic properties such as charge transport and exciton diffusion lengths.