Robin Nicholas

Abstract:

In metal halide perovskites, the complex dielectric screening together with low energy of phonon modes leads to non-negligible Fröhlich coupling. While this feature of perovskites has already been used to explain some of the puzzling aspects of carrier transport in these materials, the possible impact of polaronic effects on the optical response, especially excitonic properties, is much less explored. Here, with the use of magneto-optical spectroscopy, we revealed the non-hydrogenic character of the excitons in metal halide perovskites, resulting from the pronounced Fröhlich coupling. Our results can be well described by the polaronic-exciton picture where electron and hole interactions are no longer described by a Coulomb potential. Furthermore, we show experimental evidence that the carrier-phonon interaction leads to the enhancement of the carrier's effective mass. Notably, our measurements reveal a pronounced temperature dependence of the carrier's effective mass, which we attribute to a band structure renormalization induced by the population of low-energy phonon modes. This interpretation finds support in our first-principles calculations.

Abstract:

Carbon nanomaterials are expected to be bright and efficient emitters, but structural disorder, intermolecular interactions and the intrinsic presence of dark states suppress their photoluminescence. Here, we study synthetically-made graphene nanoribbons with atomically precise edges and which are designed to suppress intermolecular interactions to demonstrate strong photoluminescence in both solutions and thin films. The resulting high spectral resolution reveals strong vibron-electron coupling from the radial-breathing-like mode of the ribbons. In addition, their cove-edge structure produces inter-valley mixing, which brightens conventionally-dark states to generate hitherto-unrecognised twilight states as predicted by theory. The coupling of these states to the nanoribbon phonon modes affects absorption and emission differently, suggesting a complex interaction with both Herzberg–Teller and Franck– Condon coupling present. Detailed understanding of the fundamental electronic processes governing the optical response will help the tailored chemical design of nanocarbon optical devices, via gap tuning and side-chain functionalisation.

Abstract:

The ability to characterise perovskite phases non-destructively is key on the route to ensuring their long-term stability in operando. Raman spectroscopy holds the promise to play an important role in this task. Among all perovskites, formamidinium lead iodide (FAPbI₃) has emerged as one of the most promising candidates for single-junction photovoltaic cells. However, Raman spectroscopy of FAPbI₃ remains challenging as is evidenced by conflicting reports in the literature. Here, we demonstrate that due to the vulnerability of FAPbI₃ to laser-induced degradation, the detected Raman spectrum depends strongly on the experimental conditions. This can lead to conflicting results and is revealed as the origin of discrepancies in the literature. We overcome this issue by deploying defocused Raman spectroscopy, preventing laser-induced damage to the sample and simultaneously improving the signal-to-noise ratio, allowing us to furthermore resolve much weaker Raman modes than was previously possible. We offer step-by-step instructions on how to apply this technique to a given spectrometer. Non-destructive characterisation of the FAPbI₃ phases further enables us to quantify the phase stability of pristine FAPbI₃ crystals and FAPbI₃ grown with the high-performance additive methylenediammonium chloride (MDACl₂). This shows that the neat crystals fully degrade within two weeks, whereas in samples grown with the additive only about 2% of the crystal bulk is in the δ-phase after 400 days. This establishes defocused Raman spectroscopy as a powerful tool for the characterisation of FAPbI₃ and other perovskite materials.

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.

Abstract:

We report process improvements for the fabrication of single-walled carbon nanotube ethylene-vinyl acetate transparent conductive films. CNT:EVA films demonstrate high resilience against folding and can replace the external dopant in a spiro-OMeTAD based hole selective contact of n-i-p perovskite solar cells achieving a steady-state efficiency of 16.3%. The adapted process is fully scalable, and compared to previous reports (Mazzotta et al., 2018) lowers the material cost dramatically and improves DC to optical conductivity ratio by two orders of magnitude to σdc/σop = 3.6 for pristine and σdc/σop = 15 for chemically doped films. We analyse the microstructure of our films via small angle neutron scattering and find a positive correlation between the long range packing density of the CNT:EVA films and the σdc/σop performance. Increasing monomer ratio and chain length of the EVA polymer improves resilience against bending strain, whereas no significant effect on the CNT wrapping and electrical conductivity of resulting films is found.