High-Performance Poly(3-hexyl thiophene)-Based Organic Photovoltaics with Side-Chain Engineering of Core Units of Small Molecule Acceptors.

In this study, we synthesized a series of four large-band gap small molecule acceptors with side-chain engineering of the dithieno-pyrrolo-fused pentacyclic benzotriazole (BZTTP or Y1 core) or the fused-ring dithienothiophene-pyrrolobenzothiadiazole (TPBT or Y6 core) with difluoro-indene-dione (IO2F) or dichloro-indene-dione (IO2Cl) end groups to form Y1-IO2F, Y1-IO2Cl, Y6-IO2F, and Y6-IO2Cl acceptors, respectively, for blending with poly(3-hexyl thiophene) (P3HT) for bulk heterojunction organic photovoltaics. The complementary UV-vis absorption spectra of these small molecules and P3HT along with their offset energy bands allow broad absorption and effective electron transfer. Through synchrotron wide-angle X-ray scattering (WAXS) analyses and contact angle measurements, we found that the blend of the small molecule Y6-IO2F (having a TPBT core) and P3HT achieves an optimum morphology that balances their crystallinity and miscibility, among those of these four blends, leading to a substantial enhancement in the short-circuit current density and thus power conversion efficiency (PCE) in their devices. For example, the P3HT:Y6-IO2F (w/w: 1/1.2) device exhibited a champion PCE of 10.5% with a short current density () value of 15.9 mA/cm as compared to the P3HT:Y1-IO2F device having a PCE of 2.2% with a value of 5.7 mA/cm because of the higher Y6-IO2F (with TPBT core) molecular packing that facilitated carrier transport in the devices. The enhanced thermal stability exhibited by the devices incorporating Y6-IO2F and Y6-IO2Cl, as compared to that of Y1-IO2F and Y1-IO2Cl devices, is also due to the more planar TPBT core structure, while the photostability of devices incorporating Y6-IO2Cl and Y1-IO2Cl is better than that of devices incorporating Y6-IO2F and Y1-IO2F, owing to more photostable chemical structures. These results present an outstanding performance for P3HT-based organic solar cells. Moreover, these small molecule blends are processed with an environmentally friendly solvent tetrahydrofuran, demonstrating both the sustainability and commercial viability of these types of organic photovoltaics.