Reactivity Manipulation of Ionic Liquid Based on Alkyl Primary Ammonium: Protonation Control Using 4‐ <i>tert</i> ‐Butylpyridine Additive for Effective Spontaneous Passivation of Perovskite via Hole Transport Material Deposition
Naoyuki Nishimura, Hiroaki Tachibana, Ryuzi Katoh, Hiroyuki Kanda, Takurou N. Murakami
Abstract
Alkyl‐primary‐ammonium‐based room‐temperature ionic liquids (RTILs) designed to exhibit specific reactivities allowing functions that cannot be achieved by other RTILs have recently emerged. The archetype of the reactive RTILs is n ‐octylammonium bis(trifluoromethanesulfonyl)imide (OA‐TFSI), which has promising functions as an additive for hole transport materials (HTMs) in perovskite solar cells (PSCs); the high reactivity of the OA cations on the perovskite surface allows spontaneous perovskite passivation via HTM deposition, effectively improving the photovoltaic (PV) performance. However, although the reactivity manipulation of the reactive RTILs is instrumental for exploiting their potential functions and exploring their application scope, methods for reactivity control have not been developed. Herein, it is proposed that the coaddition of a pyridine derivative (4‐ tert ‐butylpridine: TBP) can effectively manipulate the reactivity of OA‐TFSI by controlling the protonation between OA and the 2,2′,7,7′‐tetrakis‐( N,N ‐di‐4‐methoxyphenylamino)‐9,9′‐spirobifluorene (Spiro‐OMeTAD) HTM. The TBP prevents OA deprotonation presumably via stabilization of the OA cation, thus retaining its ammonium form, which allows efficient spontaneous perovskite passivation, effectively enhancing the PV performance. This reveals the protonation preference in the OA‐TFSI system, which is opposite to that in conventional RTILs. This first proposal of a method in manipulating reactivity of the reactive RTILs will contribute to the development of materials science.