Inverted perovskite solar cells still suffer from significant non-radiative recombination losses at the perovskite surface and across the perovskite/C60 interface, limiting the future development of perovskite-based single- and multi-junction photovoltaics. Therefore, more effective inter- or transport layers are urgently required. To tackle these recombination losses, we introduce ortho-carborane as an interlayer material that has a spherical molecular structure and a three-dimensional aromaticity. Based on a variety of experimental techniques, we show that ortho-carborane decorated with phenylamino groups effectively passivates the perovskite surface and essentially eliminates the non-radiative recombination loss across the perovskite/C60 interface with high thermal stability. We further demonstrate the potential of carborane as an electron transport material, facilitating electron extraction while blocking holes from the interface. The resulting inverted perovskite solar cells deliver a power conversion efficiency of over 23% with a low non-radiative voltage loss of 110 mV, and retain >97% of the initial efficiency after 400 h of maximum power point tracking. Overall, the designed carborane based interlayer simultaneously enables passivation, electron-transport and hole-blocking and paves the way toward more efficient and stable perovskite solar cells.

stability have taken OSC performance to new heights. The emergence of a family of nonfullerene acceptors (NFAs) have delivered a discontinuous advance in cell efficiencies, achieving the efficiency levels of first-generation silicon devices, and with the milestone of 20% now in sight. [1][2][3] Further technological challenges are related to facilitating the manufacturing process, mainly by increasing the active layer thickness, whilst preserving the device performance. [4][5][6] To this end, a straightforward and facile quantification of the charge collection performance and losses in transport-limited solar cells is required. [7][8][9] To generate an external photocurrent, free charges have to be extracted. This process is diffusive or driven by drift, where extraction (mostly) competes with nongeminate recombination of free charges. A manifestation of this competition is the fill-factor FF. Some attention has been previously focused on correlating the FF with the efficiency of charge collection in organic solar cells based on the competition between the free charge extraction and second-order bimolecular recombination. [10] The bimolecular recombination is described via a recombination coefficient which is based on the Langevin expression multiplied by a reduction factor that takes into account processes that suppress the recombination below the Langevin limit. [11] In this picture, the extraction efficiency, as characterized by the ratio of the extraction to recombination rates, Organic solar cells (OSC) nowadays match their inorganic competitors in terms of current production but lag behind with regards to their opencircuit voltage loss and fill-factor, with state-of-the-art OSCs rarely displaying fill-factor of 80% and above. The fill-factor of transport-limited solar cells, including organic photovoltaic devices, is affected by material and devicespecific parameters, whose combination is represented in terms of the established figures of merit, such as θ and α. Herein, it is demonstrated that these figures of merit are closely related to the long-range carrier drift and diffusion lengths. Further, a simple approach is presented to devise these characteristic lengths using steady-state photoconductance measurements. This yields a straightforward way of determining θ and α in complete cells and under operating conditions. This approach is applied to a variety of photovoltaic devices-including the high efficiency nonfullerene acceptor blends-and show that the diffusion length of the free carriers provides a good correlation with the fill-factor. It is, finally, concluded that most state-ofthe-art organic solar cells exhibit a sufficiently large drift length to guarantee efficient charge extraction at short circuit, but that they still suffer from too small diffusion lengths of photogenerated carriers limiting their fill factor.

A systematic spectroelectrochemical approach is presented to precisely determine frontier orbital energies of PM6:Y6 blends in device-relevant films and results are discussed regarding their impact on solar cell performance.

Morphological modification by DIO additive facilitates charge generation in the bulk of Y6, suppresses the bimolecular recombination, which results in an increased JSC and FF of single component Y6 solar cells.

The data that support the findings of this study are available from the corresponding author upon reasonable request.

The increase in the performance of organic solar cells observed over the past few years has reinvigorated the search for a deeper understanding of the loss and extraction processes in this class of device. A detailed knowledge of the density of free charge carriers under different operating conditions and illumination intensities is a prerequisite to quantify the recombination and extraction dynamics. Differential charging techniques are a promising approach to experimentally obtain the charge carrier density under the aforementioned conditions. In particular, the combination of transient photovoltage and photocurrent as well as impedance and capacitance spectroscopy have been successfully used in past studies to determine the charge carrier density of organic solar cells. In this Tutorial, these experimental techniques will be discussed in detail, highlighting fundamental principles, practical considerations, necessary corrections, advantages, drawbacks, and ultimately their limitations. Relevant references introducing more advanced concepts will be provided as well. Therefore, the present Tutorial might act as an introduction and guideline aimed at new prospective users of these techniques as well as a point of reference for more experienced researchers.

The bimolecular recombination characteristics of conjugated polymer poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2- b :2′,3′- d ]silole)-2,6-diyl-alt-(2,5-bis 3-tetradecylthiophen-2-yl thiazolo 5,4- d thiazole)-2,5diyl] (PDTSiTTz) blended with the fullerene series PC60BM, ICMA, ICBA, and ICTA have been investigated using microsecond and femtosecond transient absorption spectroscopy, in conjunction with electroluminescence measurements and ambient photoemission spectroscopy. The non-Langevin polymer PDTSiTTz allows an inspection of intrinsic bimolecular recombination rates uninhibited by diffusion, while the low oscillator strengths of fullerenes allow polymer features to dominate, and we compare our results to those of the well-known polymer Si-PCPDTBT. Using μs-TAS, we have shown that the trap-limited decay dynamics of the PDTSiTTz polaron becomes progressively slower across the fullerene series, while those of Si-PCPDTBT are invariant. Electroluminescence measurements showed an unusual double peak in pristine PDTSiTTz, attributed to a low energy intragap charge transfer state, likely interchain in nature. Furthermore, while the pristine PDTSiTTz showed a broad, low-intensity density of states, the ICBA and ICTA blends presented a virtually identical DOS to Si-PCPDTBT and its blends. This has been attributed to a shift from a delocalized, interchain highest occupied molecular orbital (HOMO) in the pristine material to a dithienosilole-centered HOMO in the blends, likely a result of the bulky fullerenes increasing interchain separation. This HOMO localization had a side effect of progressively shifting the polymer HOMO to shallower energies, which was correlated with the observed decrease in bimolecular recombination rate and increased “trap” depth. However, since the density of tail states remained the same, this suggests that the traditional viewpoint of “trapping” being dominated by tail states may not encompass the full picture and that the breadth of the DOS may also have a strong influence on bimolecular recombination.

Low-offset organic solar cell systems have attracted great interest since nonfullerene acceptors came into the picture. While numerous studies have focused on the charge generation process in these low-offset systems, only a few studies have focused on the details of each loss channel in the charge generation process and their impact on the overall device performance. Here, several nonfullerene acceptors are blended with the same polymer donor to form a series of low-offset organic solar cell systems where significant variation in device performance is observed. Through detailed analyses of loss pathways, it is found that: i) the donor:acceptor interfaces of PM6:Y6 and PM6:TPT10 are close to the optimum energetic condition, ii) energetics at the donor:acceptor interface are the most important factor to the overall device performance, iii) exciton dissociation yield can be field-dependent owing to the sufficiently small energetic offset at the donor:acceptor interface, and iv) the change in substituents in the terminal group of Y-series acceptors in this work mainly affects energetics at the donor:acceptor interface instead of the interface density in the active layer. In general, this work presents a path toward more efficient organic solar cells.