Technological deployment of organic photovoltaic modules requires improvements in device light-conversion efficiency and stability while keeping material costs low. Here we demonstrate highly efficient and stable solar cells using a ternary approach, wherein two non-fullerene acceptors are combined with both a scalable and affordable donor polymer, poly(3-hexylthiophene) (P3HT), and a high efficiency, low band-gap polymer in a single-layer bulk-heterojunction devices. The addition of a strongly absorbing small molecule acceptor into a P3HT-based non-fullerene blend increases the device efficiency up to 7.7 ± 0.1% without any solvent additives. The improvement is assigned to changes in microstructure that reduces charge recombination and increases the photovoltage, and to improved light harvesting across the visible region. The stability of P3HT-based devices in ambient conditions is also significantly improved relative to polymer:fullerene devices. Combined with a low band gap donor polymer (PBDTTT-EFT, also known as PCE10), the two mixed acceptors also lead to solar cells with 11.0 ± 0.4% efficiency and a high open-circuit voltage of 1.03 ± 0.01V.Currently, the materials used in organic photovoltaics (OPV) are dominated by fullerene acceptors in combination with low band gap donor polymers which typically require complex and multi-step syntheses. [1][2][3][4][5] However, the commercialization of OPV requires the availability of inexpensive materials in large quantities such as poly(3-hexylthiophene) (P3HT). P3HT is readily scalable via flow or micro-reactor synthesis, even using 'green' solvents, whilst retaining a high degree of control over molecular weight and regioregularity. 6 The P3HT:60PCBM blend exhibits one of the most robust microstructures within OPV. [7][8][9] However, it has a limited open-circuit voltage (Voc) and short-circuit current (Jsc) in photovoltaic devices. 10 We have recently shown that solar cells using an alternative small molecule non-fullerene acceptor (NFA), IDTBR, when mixed with P3HT, can achieve power conversion efficiencies of up to 6.4%. 11 These results have revived interest in the use of P3HT for high performing devices and non-fullerene acceptors. [12][13][14][15][16][17][18] The combination of stability, cost and performance for P3HT:NFA devices, make them a compelling choice for commercialization of OPV compared to devices using fullerenes, for which the high costs and energy involved are prohibitive for large scale production.Recently, multi-component heterojunctions (ternary or more) have emerged as a promising strategy to overcome the power conversion efficiency (PCE) bottleneck associated with binary bulk-heterojunction (BHJ) solar cells. 3,4,[19][20][21][22][23]24 However, simultaneous increase in the Voc, Jsc and FF is a challenge in the ternary approach because of the trade-off between photocurrent and voltage. 23,25,26 Reports show ternary blends using fullerene acceptors, where the Voc is increased using a second acceptor (A2) with a higher electron affin...

Molecular doping is often used in organic semiconductors to tune their (opto)electronic properties. Despite its versatility, however, its application in organic photovoltaics (OPVs) remains limited and restricted to p‐type dopants. In an effort to control the charge transport within the bulk‐heterojunction (BHJ) of OPVs, the n‐type dopant benzyl viologen (BV) is incorporated in a BHJ composed of the donor polymer PM6 and the small‐molecule acceptor IT‐4F. The power conversion efficiency (PCE) of the cells is found to increase from 13.2% to 14.4% upon addition of 0.004 wt% BV. Analysis of the photoactive materials and devices reveals that BV acts simultaneously as n‐type dopant and microstructure modifier for the BHJ. Under optimal BV concentrations, these synergistic effects result in balanced hole and electron mobilities, higher absorption coefficients and increased charge‐carrier density within the BHJ, while significantly extending the cells' shelf‐lifetime. The n‐type doping strategy is applied to five additional BHJ systems, for which similarly remarkable performance improvements are obtained. OPVs of particular interest are based on the ternary PM6:Y6:PC71BM:BV(0.004 wt%) blend for which a maximum PCE of 17.1%, is obtained. The effectiveness of the n‐doping strategy highlights electron transport in NFA‐based OPVs as being a key issue.

Energy distributions ͓density-of-states ͑DOS͔͒ of defects in the effective band gap of organic bulk heterojunctions are determined by means of capacitance methods. The technique consists of calculating the junction capacitance derivative with respect to the angular frequency of the small voltage perturbation applied to thin film poly͑3-hexylthiophene͒ ͑P3HT͒ ͓6,6͔-phenyl C 61 -butyric acid methyl ester ͑PCBM͒ solar cells. The analysis, which was performed on blends of different composition, reveals the presence of defect bands exhibiting Gaussian shape located at E Ϸ 0.38 eV above the highest occupied molecular orbital level of the P3HT. The disorder parameter , which accounts for the broadening of the Gaussian DOS, lies within the range of 49-66 meV. The total density of defects results of order 10 16 cm −3 .

Nonfullerene solar cells have increased their efficiencies up to 13%, yet quantum efficiencies are still limited to 80%. Here we report efficient nonfullerene solar cells with quantum efficiencies approaching unity. This is achieved with overlapping absorption bands of donor and acceptor that increases the photon absorption strength in the range from about 570 to 700 nm, thus, almost all incident photons are absorbed in the active layer. The charges generated are found to dissociate with negligible geminate recombination losses resulting in a short-circuit current density of 20 mA cm−2 along with open-circuit voltages >1 V, which is remarkable for a 1.6 eV bandgap system. Most importantly, the unique nano-morphology of the donor:acceptor blend results in a substantially improved stability under illumination. Understanding the efficient charge separation in nonfullerene acceptors can pave the way to robust and recombination-free organic solar cells.

Novel p-type semiconducting polymers that can facilitate ion penetration, and operate in accumulation mode are much desired in bioelectronics. Glycol side chains have proven to be an efficient method to increase bulk electrochemical doping and optimize aqueous swelling. One early polymer which exemplifies these design approaches was p­(g2T-TT), employing a bithiophene-co-thienothiophene backbone with glycol side chains in the 3,3′ positions of the bithiophene repeat unit. In this paper, the analogous regioisomeric polymer, namely pgBTTT, was synthesized by relocating the glycol side chains position on the bithiophene unit of p­(g2T-TT) from the 3,3′ to the 4,4′ positions and compared with the original p­(g2T-TT). By changing the regio-positioning of the side chains, the planarizing effects of the S–O interactions were redistributed along the backbone, and the influence on the polymer’s microstructure organization was investigated using grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The newly designed pgBTTT exhibited lower backbone disorder, closer π-stacking, and higher scattering intensity in both the in-plane and out-of-plane GIWAXS measurements. The effect of the improved planarity of pgBTTT manifested as higher hole mobility (μ) of 3.44 ± 0.13 cm2 V–1 s–1. Scanning tunneling microscopy (STM) was in agreement with the GIWAXS measurements and demonstrated, for the first time, that glycol side chains can also facilitate intermolecular interdigitation analogous to that of pBTTT. Electrochemical quartz crystal microbalance with dissipation of energy (eQCM-D) measurements revealed that pgBTTT maintains a more rigid structure than p­(g2T-TT) during doping, minimizing molecular packing disruption and maintaining higher hole mobility in operation mode.