Erratum: Lattice gas study of thin-film growth scenarios and transitions between them: Role of substrate [Phys. Rev. E 103, 023302 (2021)].

This corrects the article DOI: 10.1103/PhysRevE.103.023302.

Perovskite-organic tandem solar cells with indium oxide interconnect.

Multijunction solar cells can overcome the fundamental efficiency limits of single-junction devices. The bandgap tunability of metal halide perovskite solar cells renders them attractive for multijunction architectures1. Combinations with silicon and copper indium gallium selenide (CIGS), as well as all-perovskite tandem cells, have been reported2-5. Meanwhile, narrow-gap non-fullerene acceptors have unlocked skyrocketing efficiencies for organic solar cells6,7. Organic and perovskite semiconductors are an attractive combination, sharing similar processing technologies. Currently, perovskite-organic tandems show subpar efficiencies and are limited by the low open-circuit voltage (Voc) of wide-gap perovskite cells8 and losses introduced by the interconnect between the subcells9,10. Here we demonstrate perovskite-organic tandem cells with an efficiency of 24.0 per cent (certified 23.1 per cent) and a high Voc of 2.15 volts. Optimized charge extraction layers afford perovskite subcells with an outstanding combination of high Voc and fill factor. The organic subcells provide a high external quantum efficiency in the near-infrared and, in contrast to paradigmatic concerns about limited photostability of non-fullerene cells11, show an outstanding operational stability if excitons are predominantly generated on the non-fullerene acceptor, which is the case in our tandems. The subcells are connected by an ultrathin (approximately 1.5 nanometres) metal-like indium oxide layer with unprecedented low optical/electrical losses. This work sets a milestone for perovskite-organic tandems, which outperform the best p-i-n perovskite single junctions12 and are on a par with perovskite-CIGS and all-perovskite multijunctions13.

Lattice gas study of thin-film growth scenarios and transitions between them: Role of substrate.

Thin-film growth is investigated in two types of lattice gas models where substrate and film particles are different, expressed by unequal interaction energy parameters. The first is of solid-on-solid type, whereas the second additionally incorporates desorption, diffusion in the gas phase above the film and readsorption at the film (appropriate for growth in colloidal systems). In both models, the difference between particle-substrate and particle-particle interactions plays a central role for the evolution of the film morphology at intermediate times. The models exhibit a dynamic layering transition which occurs at generally lower substrate attraction strengths than the equilibrium layering transition. A second, flattening transition is found where initial island growth transforms to layer-by-layer growth at intermediate deposition times. Combined with the known roughening behavior in such models for very large deposition times, we present four global growth scenarios, charting out the possible types of roughness evolution.

Roughness evolution in strongly interacting donor:acceptor mixtures of molecular semiconductors. An in situ, real-time growth study using x-ray reflectivity.

The evolution of surface roughness in binary mixtures of the two molecular organic semiconductors (OSCs) diindenoperylene (DIP) as electron-donor and 1, 3, 4, 5, 7, 8-hexafluoro-tetracyano naphthoquinodimethane (F6TCNNQ) as electron-acceptor is studied. We co-deposit DIP and F6TCNNQ in vacuum with varying relative molar content while keeping a molar excess of DIP in order to produce phase-heterogeneous mixtures. The excess DIP phase segregates in pristine crystallites, whereas the remaining mixed phase is constituted by DIP:F6TCNNQ co-crystallites. We calculate the surface roughness as function of film thickness by modelling x-ray reflectivity data acquired in situ and in real-time during film growth. To model the experimental data, two distinct approaches, namely the kinematic approximation and the Parratt formalism, are applied. A comparative study of surface roughness evolution as function of DIP:F6TCNNQ mixing ratio is carried out implementing the Trofimov growth model within the kinematic approximation. Depending on the thickness regime, mixing ratio-specific trends are identified and discussed. To explain them, a growth mechanism for binary heterogeneous mixtures of strongly interacting OSCs is proposed.

Robust singlet fission in pentacene thin films with tuned charge transfer interactions.

Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings.

Influence of C60 co-deposition on the growth kinetics of diindenoperylene-From rapid roughening to layer-by-layer growth in blended organic films.

We investigated the growth of the two phase-separating materials diindenoperylene (DIP) and buckminsterfullerene C60 with different mixing ratio in real-time and in situ by X-ray scattering experiments. We found that at room temperature, mixtures with an excess of DIP show a growth mode which is very close to the perfect layer-by-layer limit with DIP crystallites forming over the entire film thickness. An unexpected increase in the island size is observed for these mixtures as a function of film thickness. On the other hand, equimolar and C60 dominated mixtures grow with poor crystallinity but form very smooth films. Additionally, it is observed that higher substrate temperatures lead to an increase in the length scale of phase separation with film thickness.

Structure formation in perfluoropentacene:diindenoperylene blends and its impact on transient effects in the optical properties studied in real-time during growth.

We discuss the result of the competing effects of favourable intermolecular interactions and steric incompatibilities due to the size mismatch of perfluoropentacene (PFP) and diindenoperylene (DIP) on the structure formation and associated optical properties in mixed films. Using real-time grazing incidence X-ray diffraction we investigate the size of coherently scattering islands l(s) as a function of film thickness and mixing ratio. We find that for PFP:DIP 1:2 blends l(s) is by a factor of ~4 smaller than in pure DIP films, while l(s) of the PFP:DIP 2:1 blends is not significantly reduced compared with pure PFP. Yet, we observe an increase in l(s) with film thickness for all of the samples, independent on the mixing ratio. In parallel with the structural characterization we investigate the evolution of the absorption spectra in the visible spectral range and its dependence on l(s) in situ during film growth using differential reflectance spectroscopy. We observe a surprisingly strong effect of changes in the structural order on the shape of ε(2, xy)(E), evident by a pronounced evolution of characteristic peaks in the thickness range from 1.6 nm to 9.6 nm. The combined results of the real-time experiments allow to identify the thickness dependent crystal grain size as the origin of the observed transient effects in the absorption spectra.

Evidence for kinetically limited thickness dependent phase separation in organic thin film blends.

We present depth-resolved grazing incidence x-ray diffraction, grazing incidence small angle scattering and x-ray reflectivity studies on the structure of mixed C(60) and diindinoperylene (DIP) films as a function of the mixing ratio. We observe enhanced out-of-plane order and smoothing of the mixed films compared to pure films upon coevaporation of DIP:C(60) thin films (in different mixing ratio) which otherwise phase separate. The mixing ratio of molecules can be tuned to alter the in-plane crystallite size as well as the interisland distances of the mixing molecules. Real-time in situ grazing incidence x-ray diffraction measurements show the kinetics and thickness dependence of phase separation, which appears to proceed only after a certain thickness. The crystallite grain size of the individual phase separated components is significantly larger at the top of the film than at the bottom with implications for the understanding of devices.

Mixing-induced anisotropic correlations in molecular crystalline systems.

We investigate the structure of mixed thin films composed of pentacene and diindenoperylene using x-ray reflectivity and grazing incidence x-ray diffraction. For equimolar mixtures we observe vanishing in-plane order coexisting with an excellent out-of-plane order, a yet unreported disordering behavior in binary mixtures of organic semiconductors, which are crystalline in their pure form. One approach to rationalize our findings is to introduce an anisotropic interaction parameter in the framework of a mean field model. By comparing the structural properties with those of other mixed systems, we discuss the effects of sterical compatibility and chemical composition on the mixing behavior, which adds to the general understanding of interactions in molecular mixtures.

Structure and morphology of coevaporated pentacene-perfluoropentacene thin films.

The structural properties of coevaporated thin films of pentacene (PEN) and perfluoropentacene (PFP) on SiO(2) were studied using x-ray reflectivity and grazing incidence x-ray diffraction. Reciprocal space maps of the coevaporated thin films with different volume fractions reveal the coexistence of two different molecular mixed PEN-PFP phases together with the pure PEN and PFP crystallites. The crystal structure of PEN:PFP blends does not change continuously with volume fraction, instead the proportion of the appropriate phases changes, as seen from the diffraction analysis. Additional temperature dependent experiments reveal that the fraction of the two mixed PEN-PFP phases varies with growth temperature. The λ-phase (molecular plane parallel to the substrate) is metastable and induced by low growth temperature. The σ-phase (molecular plane nearly perpendicular to the substrate) is thermally stable and nucleates predominantly at high growth temperatures.

Real-time changes in the optical spectrum of organic semiconducting films and their thickness regimes during growth.

We present real-time in situ studies of optical spectra during thin film growth of several prototype organic semiconductors (pentacene, perfluoropentacene, and diindenoperylene) on SiO2. These data provide insight into surface and interface effects that are of fundamental importance and of relevance for applications in organic electronics. With respect to the bulk, the different molecular environment and structural changes within the first few monolayers can give rise to significant optical changes. Similar to interface-driven phenomena in, e.g., magnetism, spectral changes as a function of thickness d are a very general effect, decaying as 1/d in the simplest approximation. We observe energy shifts of 50-100 meV, rather small changes of the exciton-phonon coupling, and new transitions in specific systems, which should be considered as general features of the growth of organics.