Influence of Acid‐Doped Poly(ethylene imine) Interlayers on the Performance of Polymer:Nonfullerene Solar Cells

This work reports that ultrathin polymeric films doped with organic acid molecules can act as an electron‐transporting interfacial layer in polymer:nonfullerene solar cells. The polymeric interfacial layers, which consist of poly(ethylene imine) (PEI) doped with 3‐hydroxypropane‐1‐sulfonic acid (HPSA) at various HPSA molar ratios, are introduced between transparent indium‐tin oxide (ITO) electrodes and polymer:nonfullerene bulk heterojunction layers. The HPSA‐doped PEI (PEI:HPSA) films are optically translucent in the wavelength range of ≈300–800 nm, while the acidity of PEI solutions reached ≈pH = 7 at HPSA = 30 mol%. The power conversion efficiency of solar cells is improved by doping 20 mol% HPSA due to the increased short circuit current density without open circuit voltage reduction. The improvement in solar cell performances is attributed to an adequate control of HPSA doping ratios, which spares undoped amine units of PEI for making sufficient net dipole layers with ITO surfaces and makes permanent charges for high electrical conductivity in the layers. The surface morphology and doped states are characterized with atomic force microscopy and X‐ray photoelectron spectroscopy. The 3‐hydroxypropane‐1‐sulfonic acid (HPSA)‐doped poly(ethylene imine) (PEI) films are applied as an interfacial layer for polymer:nonfullerene solar cells. The power conversion efficiency of solar cells is improved by the presence of PEI:HPSA interlayers at HPSA = 20 mol% due to a balanced formation of doped and undoped units of PEI chains, leading to high electrical conductivity and sufficient formation of net dipole layers, respectively.