The Impact of Spacer Size on Charge Transfer Excitons in Dion-Jacobson and Ruddlesden-Popper Layered Hybrid Perovskites.

Organic materials can tune the optical properties in layered (2D) hybrid perovskites, although their impact on photophysics is often overlooked. Here, we use transient absorption spectroscopy to probe the Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) 2D perovskite phases. We show the formation of charge transfer excitons in DJ phases, resulting in a photoinduced Stark effect which is shown to be dependent on the spacer size. By using electroabsorption spectroscopy, we quantify the strength of the photoinduced electric field, while temperature-dependent measurements demonstrate new features in the transient spectra of RP phases at low temperatures resulting from the quantum-confined Stark effect. This study reveals the impact of spacer size and perovskite phase configuration on charge transfer excitons in 2D perovskites of interest to their advanced material design.

Photogenerated charge transfer in Dion-Jacobson type layered perovskite based on naphthalene diimide.

Incorporating organic semiconducting spacer cations into layered lead halide perovskite structures provides a powerful approach to mitigate the typical strong dielectric and quantum confinement effects by inducing charge-transfer between the organic and inorganic layers. Herein we report the synthesis and characterization of thin films of novel DJ-phase organic-inorganic layered perovskite semiconductors using a naphthalene diimide (NDI) based divalent spacer cation, which is shown to accept photogenerated electrons from the inorganic layer. With alkyl chain lengths of 6 carbons, an NDI-based thin film exhibited electron mobility (based on space charge-limited current for quasi-layered 〈n〉 = 5 material) was found to be as high as 0.03 cm2 V-1 s-1 with no observable trap-filling region suggesting trap passivation by the NDI spacer cation.

Spatio-Temporal Dynamics of Free and Bound Carriers in Photovoltaic Materials.

Charge transfer and subsequent separation into free carriers are key processes that govern the efficiencies of third generation solar cell technologies based on donor-acceptor heterojunctions. As these processes typically occur on picosecond to femtosecond timescales, it is necessary to employ ultrafast spectroscopic techniques to further our understanding of these processes in order to provide vital information that can aide in furthering material design. Within the framework of the National Centre of Competence in Research "Molecular Ultrafast Science and Technology" (NCCR MUST), we have developed and utilized a suite of different ultrafast spectroscopic techniques to study charge generation, separation and recombination in a variety of small molecule based organic solar cells and lead halide perovskites. Here, we provide an overview of the main techniques used in our laboratory and the recent results obtained using these spectroscopic techniques.

Critical role of H-aggregation for high-efficiency photoinduced charge generation in pristine pentamethine cyanine salts.

The mechanism of photoinduced symmetry-breaking charge separation in solid cyanine salts at the base of organic photovoltaic and optoelectronic devices is still debated. Here, we employ femtosecond transient absorption spectroscopy (TAS) to monitor the charge transfer processes occurring in thin films of pristine pentamethine cyanine (Cy5). Oxidized dye species are observed in Cy5-hexafluorophosphate salts upon photoexcitation, resulting from electron transfer from monomer excited states to H-aggregates. The charge separation proceeds with a quantum yield of 86%, providing the first direct proof of high efficiency intrinsic charge generation in organic salt semiconductors. The impact of the size of weakly coordinating anions on charge separation and transport is studied using TAS alongside electroabsorption spectroscopy and time-of-flight techniques. The degree of H-aggregation decreases with increasing anion size, resulting in reduced charge transfer. However, there is little change in carrier mobility, as despite the interchromophore distance increasing, the decrease in energetic disorder helps to alleviate the trapping of charges by H-aggregates.

The Role of Alkyl Chain Length and Halide Counter Ion in Layered Dion-Jacobson Perovskites with Aromatic Spacers.

Layered hybrid perovskites based on Dion-Jacobson phases are of interest to various optoelectronic applications. However, the understanding of their structure-property relationships remains limited. Here, we present a systematic study of Dion-Jacobson perovskites based on (S)PbX4 (n = 1) compositions incorporating phenylene-derived aromatic spacers (S) with different anchoring alkylammonium groups and halides (X = I, Br). We focus our study on 1,4-phenylenediammonium (PDA), 1,4-phenylenedimethylammonium (PDMA), and 1,4-phenylenediethylammonium (PDEA) spacers. Systems based on PDA did not form a well-defined layered structure, showing the formation of a 1D structure instead, whereas the extension of the alkyl chains to PDMA and PDEA rendered them compatible with the formation of a layered structure, as shown by X-ray diffraction and solid-state NMR spectroscopy. In addition, the control of the spacer length affects optical properties and environmental stability, which is enhanced for longer alkyl chains and bromide compositions. This provides insights into their design for optoelectronic applications.

Semiclassical Approach to Photophysics Beyond Kasha's Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene.

Azulene is a prototypical molecule with an anomalous fluorescence from the second excited electronic state, thus violating Kasha's rule, and with an emission spectrum that cannot be understood within the Condon approximation. To better understand the photophysics and spectroscopy of azulene and other nonconventional molecules, we developed a systematic, general, and efficient computational approach combining the semiclassical dynamics of nuclei with ab initio electronic structure. First, to analyze the nonadiabatic effects, we complement the standard population dynamics by a rigorous measure of adiabaticity, estimated with the multiple-surface dephasing representation. Second, we propose a new semiclassical method for simulating non-Condon spectra, which combines the extended thawed Gaussian approximation with the efficient single-Hessian approach. S1 ← S0 and S2 ← S0 absorption and S2 → S0 emission spectra of azulene, recorded in a new set of experiments, agree very well with our calculations. We find that accuracy of the evaluated spectra requires the treatment of anharmonicity, Herzberg-Teller, and mode-mixing effects.

Toward Improved Environmental Stability of Polymer:Fullerene and Polymer:Nonfullerene Organic Solar Cells: A Common Energetic Origin of Light- and Oxygen-Induced Degradation.

With the emergence of nonfullerene electron acceptors resulting in further breakthroughs in the performance of organic solar cells, there is now an urgent need to understand their degradation mechanisms in order to improve their intrinsic stability through better material design. In this study, we present quantitative evidence for a common root cause of light-induced degradation of polymer:nonfullerene and polymer:fullerene organic solar cells in air, namely, a fast photo-oxidation process of the photoactive materials mediated by the formation of superoxide radical ions, whose yield is found to be strongly controlled by the lowest unoccupied molecular orbital (LUMO) levels of the electron acceptors used. Our results elucidate the general relevance of this degradation mechanism to both polymer:fullerene and polymer:nonfullerene blends and highlight the necessity of designing electron acceptor materials with sufficient electron affinities to overcome this challenge, thereby paving the way toward achieving long-term solar cell stability with minimal device encapsulation.