A pH‐Neutral Polyelectrolyte Hole Transport Layer for Improved Energy Band Structure at the Anode/PTB7 Junction and Improved Solar Cell Performance

In organic solar cells (OSCs), interfacial properties between the donor phase and hole transport layers (HTLs) are critical factors which govern charge extraction efficiency. Many ionic and polar materials are known to function as effective interfacial layers; however, an understanding of how ionic moieties affect the electronic band structure and characteristics of OSCs is lacking. Herein, a new, pH‐neutral polyelectrolyte is introduced that resolves several problems which are encountered with the commonly used HTL, poly(3,4‐ethylenedioxythiopene):polystyrenesulfonate (PEDOT:PSS). An effective p‐type polyelectrolyte dopant is designed, comprising an anionically charged PSS backbone with easily reduced Cu²⁺ counterions (Cu:PSS), and interfacial properties for HTL/donor interfaces by photoelectron spectroscopy are analyzed. The effects of the polyelectrolyte on interfacial energy levels and charge extraction efficiency between the active layer and HTL are quantified. Using optimized processing conditions, the efficiency can be improved from 8.31% to 9.28% in conventional OSCs compared with a standard PEDOT:PSS HTL. The energy‐level alignment at the HTLs/donor interface determined by UV photoelectron spectroscopy measurements reveals the origin of distinct differences in device performances. The reduced ionization potential (IP) and hole injections barrier (Φ_h) at the HTL/donor interface play a crucial role in efficient charge extraction in conventional OSCs.