Facile Strategy for Third Component Optimization in Wide-Band-Gap π-Conjugated Polymer Donor-Based Efficient Ternary All-Polymer Solar Cells.

Emerging organic solar cells based on a ternary strategy is one of the most effective methods for improving the blend film morphology, absorption ability, and device performances. On the other hand, this strategy has had very limited success in all-polymer solar cells (all-PSCs) because of the scarcity of new polymers and the challenges faced during third component optimization. Herein, highly efficient ternary all-PSCs were developed from siloxane-functionalized side chains with a wide-band-gap (Eg) polymer, Si-BDT, which is blended with a medium and ultra-narrow Eg polymer donor and acceptor, PTB7-Th, and DCNBT-TPIC. An impressive power conversion efficiency (PCE) of 13.45% was achieved in the ternary all-PSCs [PTB7-Th(0.6):Si-BDT(0.4):DCNBT-TPIC(0.6)] with the addition of 0.4 wt equivalent Si-BDT into binary all-PSCs [PTB7-Th(1):DCNBT-TPIC(0.6) PCE of 10.11%]. In contrast, the binary all-PSCs with a Si-BDT(1):DCNBT-TPIC(0.6) active layer only exhibited a good PCE of 9.92%. More importantly, the siloxane-functionalized side chains increase the light-absorption ability, carrier mobility, blend miscibility, and film morphology in ternary devices compared to those of the binary devices. Hence, exciton dissociation, charge carrier transport, and suppressed recombination properties were facilitated. In the presence of Si-BDT, both binary and ternary all-PSCs PCEs are significantly improved. Indeed, 13.45% PCE is one of the best values reported for all-PSCs except for those based on polymerized small molecule acceptors. In addition, the ternary all-PSCs showed excellent environmental and thermal stabilities with 95 and 84% of the initial PCE retained after 900 and 500 h, respectively. These results offer effective device engineering, providing a new avenue for improving the device performance in ternary all-PSCs.

Significantly Enhanced Molecular Stacking in Ternary Bulk Heterojunctions Enabled by an Appropriate Side Group on Donor Polymer.

Ternary strategy is a promising approach to broaden the photoresponse of polymer solar cells (PSCs) by adopting combinatory photoactive blends. However, it could lead to a more complicated situation in manipulating the bulk morphology. Achieving an ideal morphology that enhances the charge transport and light absorption simultaneously is an essential avenue to promote the device performance. Herein, two polymers with different lengths of side groups (P1 is based on phenyl side group and P2 is based on biphenyl side group) are adopted in the dual-acceptor ternary systems to evaluate the relationship between conjugated side group and crystalline behavior in the ternary system. The P1 ternary system delivers a greatly improved power conversion efficiency (PCE) of 13.06%, which could be attributed to the intense and broad photoresponse and improved charge transport originating from the improved crystallinity. Inversely, the P2 ternary device only exhibits a poor PCE of 8.97%, where the decreased device performance could mainly be ascribed to the disturbed molecular stacking of the components originating from the overlong conjugated side group. The results demonstrate a conjugated side group could greatly determine the device performance by tuning the crystallinity of components in ternary systems.

Quantum-Dot Tandem Solar Cells Based on a Solution-Processed Nanoparticle Intermediate Layer.

Tandem cells are one of the most effective ways of breaking the single junction Shockley-Queisser limit. Solution-processable phosphate-buffered saline (PbS) quantum dots are good candidates for producing multiple junction solar cells because of their size-tunable band gap. The intermediate recombination layer (RL) connecting the subcells in a tandem solar cell is crucial for device performance because it determines the charge recombination efficiency and electrical resistance. In this work, a solution-processed ultrathin NiO and Ag nanoparticle film serves as an intermediate layer to enhance the charge recombination efficiency in PbS QD dual-junction tandem solar cells. The champion devices with device architecture of indium tin oxide/S-ZnO/1.45 eV PbS-PbI2/PbS-EDT/NiO/Ag NP/ZnO NP/1.22 eV PbS-PbI2/PbS-EDT/Au deliver a 7.1% power conversion efficiency, which outperforms the optimized reference subcells. This result underscores the critical role of an appropriate nanocrystalline RL in producing high-performance solution-processed PbS QD tandem cells.

A New Wide Bandgap Donor Polymer for Efficient Nonfullerene Organic Solar Cells with a Large Open-Circuit Voltage.

Significant progress has been made in nonfullerene small molecule acceptors (NF-SMAs) that leads to a consistent increase of power conversion efficiency (PCE) of nonfullerene organic solar cells (NF-OSCs). To achieve better compatibility with high-performance NF-SMAs, the direction of molecular design for donor polymers is toward wide bandgap (WBG), tailored properties, and preferentially ecofriendly processability for device fabrication. Here, a weak acceptor unit, methyl 2,5-dibromo-4-fluorothiophene-3-carboxylate (FE-T), is synthesized and copolymerized with benzo[1,2-b:4,5-b']dithiophene (BDT) to afford a series of nonhalogenated solvent processable WBG polymers P1-P3 with a distinct side chain on FE-T. The incorporation of FE-T leads to polymers with a deep highest occupied molecular orbital (HOMO) level of -5.60-5.70 eV, a complementary absorption to NF-SMAs, and a planar molecular conformation. When combined with the narrow bandgap acceptor ITIC-Th, the solar cell based on P1 with the shortest methyl chain on FE-T achieves a PCE of 11.39% with a large V oc of 1.01 V and a J sc of 17.89 mA cm-2. Moreover, a PCE of 12.11% is attained for ternary cells based on WBG P1, narrow bandgap PTB7-Th, and acceptor IEICO-4F. These results demonstrate that the new FE-T is a highly promising acceptor unit to construct WBG polymers for efficient NF-OSCs.

Two Well-Compatible Acceptors with Efficient Energy Transfer Enable Ternary Organic Photovoltaics Exhibiting a 13.36% Efficiency.

Organic photovoltaics (OPVs) are fabricated with PM6 as donor and T6Me, IT-2F, or their mixture as acceptor. A 13.36% power conversion efficiency (PCE) is achieved from the optimized ternary OPVs with 50 wt% IT-2F in acceptors, which is attributed to the enhanced photon harvesting of ternary active layers and improved exciton utilization efficiency through energy transfer from IT-2F to T6Me. The efficient energy transfer from IT-2F to T6Me can be confirmed from the photoluminescence spectra of neat and blend films, which may provide additional channels to enhance exciton utilization efficiency for achieving short-circuit current density (JSC ) improvement of ternary OPVs. It should be highlighted that the fill factor (FF) of ternary OPVs can be monotonously increased along with the incorporation of IT-2F, indicating the gradually optimized phase separation degree of ternary active layers. The third component IT-2F plays a key role in optimizing phase separation as a morphology regulator. Over 8% PCE improvement is achieved in the optimized ternary OPVs compared with the over 12% PCEs of the corresponding binary OPVs, respectively. This work indicates that the performance of ternary OPVs can be well optimized by carefully picking materials with good compatibility and complementary absorption spectra, as well as the appropriate energy levels.

Perfect Complementary in Absorption Spectra with Fullerene, Nonfullerene Acceptors and Medium Band Gap Donor for High-Performance Ternary Polymer Solar Cells.

Because of the mismatch between the solar irradiance spectra and the photoactive layer absorption spectra, only a part of sunlight can be utilized, which fundamentally restricting the power conversion efficiency (PCE) of the polymer solar cells (PSCs). Ternary blend PSCs, with an additional third component, have become an effective approach to extend the absorption spectra and increase the mobility of the charge carriers. Herein, we select the middle band gap PBDTBDD as an electron donor and narrow band gap ITIC and wide band gap PC60BM as electron acceptors to construct ternary blends for simultaneously enhancing the absorption intensity and expanding the absorption band. The optical properties, morphologies, and the charge-/energy-transfer behaviors of the ternary blends are investigated. By attentively adjusting the ratio of the third component, ITIC, the ternary PSCs demonstrate an expanded light-response region and greatly enhanced JSC, giving an improved overall PCE of 10.36%, much higher than that of the binary counterparts based on PBDTBDD:PC60BM (6.63%) and PBDTBDD:ITIC (9.44%). These findings indicate that proper selection of donors and acceptors to construct absorption spectra-complementary ternary blend photoactive layers is an effective way to achieve high-performance PSCs.

36% Enhanced Efficiency of Ternary Organic Solar Cells by Doping a NT-Based Polymer as an Electron-Cascade Donor.

In recent years, ternary organic photovoltaic cells (OPVs) have been dedicated to improving power conversion efficiency (PCE) by broadening optical absorption spectra. Ternary OPVs with different poly[thieno[3,2-b]thiophene-2,5-diyl-alt-4,9-bis(4-(2-decyltetradecyl)thien-2-yl)naphtho[1,2-c:5,6-c']bis[1,2,5]thiadiazole-5,5'-diyl] (PTT-DTNT-DT) doping concentrations were designed and the effect of PTT-DTNT-DT as a complementary electron donor on the performance of OPVs was investigated. The optimized PCE of OPVs was increased from 3.42% to 4.66% by doping 20 wt % PTT-DTNT-DT. The remarkable improvement in the performance of the ternary device is mainly attributed to the sharp increase in the short-circuit current density and fill-factor. The major reasons have been systematically studied from atomic force microscopy, electrochemical impedance spectroscopy, surface energy, space charge limited current and photocurrent behavior. It has been found that the separation of excitons and the transportation of charge are enhanced while light absorption is increased, and the charge recombination also decreases due to the optimization of the cascade energy level and the morphology of the ternary active layer. The results show that it is feasible to improve the performance of ternary OPVs by their complementary absorption.

Ternary Nonfullerene Polymer Solar Cells with 12.16% Efficiency by Introducing One Acceptor with Cascading Energy Level and Complementary Absorption.

A novel small-molecule acceptor, (2,2'-((5E,5'E)-5,5'-((5,5'-(4,4,9,9-tetrakis(5-hexylthiophen-2-yl)-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(4-(2-ethylhexyl)thiophene-5,2-diyl))bis(methanylylidene)) bis(3-hexyl-4-oxothiazolidine-5,2-diylidene))dimalononitrile (ITCN), end-capped with electron-deficient 2-(3-hexyl-4-oxothiazolidin-2-ylidene)malononitrile groups, is designed, synthesized, and used as the third component in fullerene-free ternary polymer solar cells (PSCs). The cascaded energy-level structure enabled by the newly designed acceptor is beneficial to the carrier transport and separation. Meanwhile, the three materials show a complementary absorption in the visible region, resulting in efficient light harvesting. Hence, the PBDB-T:ITCN:IT-M ternary PSCs possess a high short-circuit current density (Jsc ) under an optimal weight ratio of donors and acceptors. Moreover, the open-circuit voltage (Voc ) of the ternary PSCs is enhanced with an increase of the third acceptor ITCN content, which is attributed to the higher lowest unoccupied molecular orbital energy level of ITCN than that of IT-M, thus exhibits a higher Voc in PBDB-T:ITCN binary system. Ultimately, the ternary PSCs achieve a power conversion efficiency of 12.16%, which is higher than the PBDB-T:ITM-based PSCs (10.89%) and PBDB-T:ITCN-based ones (2.21%). This work provides an effective strategy to improve the photovoltaic performance of PSCs.

Efficient Energy Transfer (EnT) in Pyrene- and Porphyrin-Based Mixed-Ligand Metal-Organic Frameworks.

Designing and synthesizing the ordered light-harvesting systems, possessing complementary absorption and energy-transfer process between the chromophores, are essential steps to accomplish successful mimicking of the natural photosynthetic systems. Metal-organic frameworks (MOFs) can be considered as an ideal system to achieve this due to their highly ordered structure, superior synthetic versatility, and tailorable functionality. Herein, we have synthesized the new light-harvesting mixed-ligand MOFs (MLMs, MLM-1-3) via solvothermal reactions between a Zr6 cluster and a mixture of appropriate ratio of 1,3,6,8-tetrakis(p-benzoic acid)pyrene and [5,10,15,20-tetrakis(4-carboxy-phenyl)porphyrinato]-Zn(II) ligands. The identical symmetry and connectivity of the two ligands of the MLMs was the key parameter of successful synthesis as a single MOF form, and the ample overlap between the emission spectrum of pyrene and the absorption spectrum of porphyrin provided the ideal platform to design an efficient-energy transfer (EnT) process within the MLMs. We obtained the nanoscale maps of the fluorescence intensities and lifetimes of microsize MLM grains for unambiguous visualization of EnT phenomena occurring between two ligands in MLMs. Moreover, due to complementary absorption and energy transfer between the two ligands in the MLMs, our MLMs performed as superior photoinduced singlet-oxygen generators, verifying the enhanced light-harvesting properties of the pyrene- and porphyrin-based MLMs.

Fullerene-Free Organic Solar Cells with an Efficiency of 10.2% and an Energy Loss of 0.59 eV Based on a Thieno[3,4-c]Pyrrole-4,6-dione-Containing Wide Band Gap Polymer Donor.

Although the combination of wide band gap polymer donors and narrow band gap small-molecule acceptors achieved state-of-the-art performance as bulk heterojunction (BHJ) active layers for organic solar cells, there have been only several of the wide band gap polymers that actually realized high-efficiency devices over >10%. Herein, we developed high-efficiency, low-energy-loss fullerene-free organic solar cells using a weakly crystalline wide band gap polymer donor, PBDTTPD-HT, and a nonfullerene small-molecule acceptor, ITIC. The excessive intermolecular stacking of ITIC is efficiently suppressed by the miscibility with PBDTTPD-HT, which led to a well-balanced nanomorphology in the PBDTTPD-HT/ITIC BHJ active films. The favorable optical, electronic, and energetic properties of PBDTTPD-HT with respect to ITIC achieved panchromatic photon-to-current conversion with a remarkably low energy loss (0.59 eV).

High Efficiency Nonfullerene Polymer Solar Cells with Thick Active Layer and Large Area.

In this work, high-efficiency nonfullerene polymer solar cells (PSCs) are developed based on a thiazolothiazole-containing wide bandgap polymer PTZ1 as donor and a planar IDT-based narrow bandgap small molecule with four side chains (IDIC) as acceptor. Through thermal annealing treatment, a power conversion efficiency (PCE) of up to 11.5% with an open circuit voltage (Voc ) of 0.92 V, a short-circuit current density (Jsc ) of 16.4 mA cm-2 , and a fill factor of 76.2% is achieved. Furthermore, the PSCs based on PTZ1:IDIC still exhibit a relatively high PCE of 9.6% with the active layer thickness of 210 nm and a superior PCE of 10.5% with the device area of up to 0.81 cm2 . These results indicate that PTZ1 is a promising polymer donor material for highly efficient fullerene-free PSCs and large-scale devices fabrication.

High-Performance Nonfullerene Polymer Solar Cells based on Imide-Functionalized Wide-Bandgap Polymers.

High-performance nonfullerene polymer solar cells (PSCs) are developed by integrating the nonfullerene electron-accepting material 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophne) (ITIC) with a wide-bandgap electron-donating polymer PTzBI or PTzBI-DT, which consists of an imide functionalized benzotriazole (TzBI) building block. Detailed investigations reveal that the extension of conjugation can affect the optical and electronic properties, molecular aggregation properties, charge separation in the bulk-heterojunction films, and thus the overall photovoltaic performances. Single-junction PSCs based on PTzBI:ITIC and PTzBI-DT:ITIC exhibit remarkable power conversion efficiencies (PCEs) of 10.24% and 9.43%, respectively. To our knowledge, these PCEs are the highest efficiency values obtained based on electron-donating conjugated polymers consisting of imide-functionalized electron-withdrawing building blocks. Of particular interest is that the resulting device based on PTzBI exhibits remarkable PCE of 7% with the thickness of active layer of 300 nm, which is among the highest values of nonfullerene PSCs utilizing thick photoactive layer. Additionally, the device based on PTzBI:ITIC exhibits prominent stability, for which the PCE remains as 9.34% after thermal annealing at 130 °C for 120 min. These findings demonstrate the great promise of using this series of wide-bandgap conjugated polymers as electron-donating materials for high-performance nonfullerene solar cells toward high-throughput roll-to-roll processing technology.

Efficient Nonfullerene Polymer Solar Cells Enabled by a Novel Wide Bandgap Small Molecular Acceptor.

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.

High-Performance Non-Fullerene Polymer Solar Cells Based on a Pair of Donor-Acceptor Materials with Complementary Absorption Properties.

A 7.3% efficiency non-fullerene polymer solar cell is realized by combining a large-bandgap polymer PffT2-FTAZ-2DT with a small-bandgap acceptor IEIC. The complementary absorption of donor polymer and small-molecule acceptor is responsible for the high-performance of the solar-cell device. This work provides important guidance to improve the performance of non-fullerene polymer solar cells.

Performance Enhancement of Polymer Solar Cells by Using Two Polymer Donors with Complementary Absorption Spectra.

Performance enhancement of polymer solar cells (PSCs) is achieved by expanding the absorption of the active layer of devices. To better match the spectrum of solar radiation, two polymers with different band gaps are used as the donor material to fabricate ternary polymer cells. Ternary blend PSCs exhibit an enhanced short-circuit current density and open-circuit voltage in comparison with the corresponding HD-PDFC-DTBT (HD)- and DT-PDPPTPT (DPP)-based binary polymer solar cells, respectively. Ternary PSCs show a power conversion efficiency (PCE) of 6.71%, surpassing the corresponding binary PSCs. This work demonstrates that the fabrication of ternary PSCs by using two polymers with complementary absorption is an effective way to improve the device performance.