Advanced Functional Materials and Devices (AFMD) Group

Abstract:

The record power conversion efficiency of solution-processed organic solar cells (OSCs) has almost doubled since non-fullerene acceptors (NFAs) replaced fullerene derivatives as the best-performing acceptor molecules. The successful transition from C60 to NFAs is still pending for vacuum-thermal evaporated (VTE) OSCs, not least because most NFAs are too large to be evaporated without breaking. Due to VTE’s relevance in terms of industrial manufacturing, discovering high-performing VTE NFAs is a major opportunity for OSCs. Here, we fabricate evaporated OSCs based on the NFA BTIC-H known from solution processing. This A–D–A molecule has an unfused bithiophene core, 1,1-dicyanomethylene-3-indanone end groups, and hexyl side chains, making it small enough to be evaporated well. We pair BTIC-H with four commonly used evaporated donors—DCV5T-Me(3,3), DTDCPB, HB194, and SubNc—in planar heterojunctions. We observe appreciable photocurrents and a voltage loss of ∼0.8 V, matching that of corresponding C60 devices. Donor:BTIC-H bulk heterojunctions likely face charge collection issues due to unfavorable microstructure. Our work demonstrates one of few NFA based evaporated OSCs with encouraging performance results and gives one potential starting point for molecule design of further NFAs suitable for VTE.

Abstract:

The advent of nonfullerene acceptors (NFAs) enabled records of organic photovoltaics (OPVs) exceeding 19% power conversion efficiency in the laboratory. However, high-efficiency NFAs have so far only been realized in solution-processed blends. Due to its proven track record in upscaled industrial production, vacuum thermal evaporation (VTE) is of prime interest for real-world OPV commercialization. Here, we combine the benchmark solution-processed NFA Y6 with three different evaporated donors in a bilayer (planar heterojunction) architecture. We find that voltage losses decrease by hundreds of millivolts when VTE donors are paired with the NFA instead of the fullerene C60, the current standard acceptor in VTE OPVs. By showing that evaporated small-molecule donors behave much like solution-processed donor polymers in terms of voltage loss when combined with NFAs, we highlight the immense potential for evaporable NFAs and the urgent need to direct synthesis efforts toward making smaller, evaporable compounds.

Abstract:

The advent of nonfullerene acceptors (NFAs) enabled records of organic photovoltaics (OPVs) exceeding 19% power conversion efficiency in the laboratory. However, high-efficiency NFAs have so far only been realized in solution-processed blends. Due to its proven track record in upscaled industrial production, vacuum thermal evaporation (VTE) is of prime interest for real-world OPV commercialization. Here, we combine the benchmark solution-processed NFA Y6 with three different evaporated donors in a bilayer (planar heterojunction) architecture. We find that voltage losses decrease by hundreds of millivolts when VTE donors are paired with the NFA instead of the fullerene C₆₀, the current standard acceptor in VTE OPVs. By showing that evaporated small-molecule donors behave much like solution-processed donor polymers in terms of voltage loss when combined with NFAs, we highlight the immense potential for evaporable NFAs and the urgent need to direct synthesis efforts toward making smaller, evaporable compounds.

Abstract:

The performance of organic solar cells is strongly governed by the properties of the photovoltaic active layer. In particular, the energetics at the donor (D)–acceptor (A) interface dictate the properties of charge transfer (CT) states and limit the open-circuit voltage. More generally, energetic landscapes in thin films are affected by intermolecular, e.g., van der Waals, dipole, and quadrupole, interactions that vary with D:A mixing ratio and impact energy levels of free charges (ionization energy, electron affinity) and excitons (singlet, CT states). Disentangling how different intermolecular interactions impact energy levels and support or hinder free charge generation is still a major challenge. In this work, we investigate interface energetics of bulk heterojunctions via sensitive external quantum efficiency measurements and by varying the D:A mixing ratios of ZnPc or its fluorinated derivatives and C60. With increasing donor fluorination, the energetic offset between FxZnPc and C60 reduces. Moving from large to low offset systems, we find qualitatively different trends in device performances with D:C60 mixing ratios. We rationalize the performance trends via changes in the energy levels that govern exciton separation and voltage losses. We do so by carefully analyzing shifts and broadening sEQE spectra on a linear and logarithmic scale. Linking this analysis with molecular properties and device performance, we comment on the impact of charge–quadrupole interactions for CT dissociation and free charge generation in our D:C60 blends. With this, our work (1) demonstrates how relatively accessible characterization techniques can be used to probe energy levels and (2) addresses ongoing discussions on future molecular design and optimal D–A pairing for efficient CT formation and dissociation.

Abstract:

Formamidinium lead triiodide (FAPbI₃) is the leading candidate for single-junction metal-halide perovskite photovoltaics, despite the metastability of this phase. To enhance its ambient-phase stability and produce world-record photovoltaic efficiencies, methylenediammonium dichloride (MDACl₂) has been used as an additive in FAPbI₃. MDA²⁺ has been reported as incorporated into the perovskite lattice alongside Cl^-. However, the precise function and role of MDA²⁺ remain uncertain. Here, we grow FAPbI₃ single crystals from a solution containing MDACl₂ (FAPbI₃-M). We demonstrate that FAPbI₃-M crystals are stable against transformation to the photoinactive δ-phase for more than one year under ambient conditions. Critically, we reveal that MDA²⁺ is not the direct cause of the enhanced material stability. Instead, MDA²⁺ degrades rapidly to produce ammonium and methaniminium, which subsequently oligomerizes to yield hexamethylenetetramine (HMTA). FAPbI₃ crystals grown from a solution containing HMTA (FAPbI₃-H) replicate the enhanced α-phase stability of FAPbI₃-M. However, we further determine that HMTA is unstable in the perovskite precursor solution, where reaction with FA⁺ is possible, leading instead to the formation of tetrahydrotriazinium (THTZ-H⁺). By a combination of liquid- and solid-state NMR techniques, we show that THTZ-H⁺ is selectively incorporated into the bulk of both FAPbI₃-M and FAPbI₃-H at ∼0.5 mol % and infer that this addition is responsible for the improved α-phase stability.