Organic solar cells (OSCs) have been dominated by donor:acceptor blends based on fullerene acceptors for over two decades. This situation has changed recently, with non-fullerene (NF) OSCs developing very quickly. The power conversion efficiencies of NF OSCs have now reached a value of over 13%, which is higher than the best fullerene-based OSCs. NF acceptors show great tunability in absorption spectra and electron energy levels, providing a wide range of new opportunities. The coexistence of low voltage losses and high current generation indicates that new regimes of device physics and photophysics are reached in these systems. This Review highlights these opportunities made possible by NF acceptors, and also discuss the challenges facing the development of NF OSCs for practical applications.

A nonfullerene-based polymer solar cell (PSC) that significantly outperforms fullerene-based PSCs with respect to the power-conversion efficiency is demonstrated for the first time. An efficiency of >11%, which is among the top values in the PSC field, and excellent thermal stability is obtained using PBDB-T and ITIC as donor and acceptor, respectively.

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We have modeled experimental short-circuit photocurrent action spectra of poly(3-(4′-(1″,4″,7″-trioxaoctyl)phenyl)thiophene) (PEOPT)/fullerene (C60) thin film heterojunction photovoltaic devices. Modeling was based on the assumption that the photocurrent generation process is the result of the creation and diffusion of photogenerated species (excitons), which are dissociated by charge transfer at the PEOPT/C60 interface. The internal optical electric field distribution inside the devices was calculated with the use of complex indices of refraction and layer thickness of the materials as determined by spectroscopic ellipsometry. Contributions to the photocurrent from optical absorption in polymer and fullerene layers were both necessary to model the experimental photocurrent action spectra. We obtained values for the exciton diffusion range of 4.7 and 7.7 nm for PEOPT and C60, respectively. The calculated internal optical electric field distribution and resulting photocurrent action spectra were used in order to study the influence of the geometrical structure with respect to the efficiency of the thin film devices. In this way the photocurrent was optimized.

The open-circuit voltage of organic solar cells is usually lower than the values achieved in inorganic or perovskite photovoltaic devices with comparable bandgaps. Energy losses during charge separation at the donor-acceptor interface and non-radiative recombination are among the main causes of such voltage losses. Here we combine spectroscopic and quantum-chemistry approaches to identify key rules for minimizing voltage losses: (1) a low energy offset between donor and acceptor molecular states and (2) high photoluminescence yield of the low-gap material in the blend. Following these rules, we present a range of existing and new donor-acceptor systems that combine efficient photocurrent generation with electroluminescence yield up to 0.03%, leading to non-radiative voltage losses as small as 0.21 V. This study provides a rationale to explain and further improve the performance of recently demonstrated high-open-circuit-voltage organic solar cells.