Prof Laura Herz FRS

Abstract:

The organic-inorganic hybrid perovskites methylammonium lead iodide (CH3NH3PbI3) and the partially chlorine-substituted mixed halide CH3NH3PbI3-xClx emit strong and broad photoluminescence (PL) around their band gap energy of ∼1.6 eV. However, the nature of the radiative decay channels behind the observed emission and, in particular, the spectral broadening mechanisms are still unclear. Here we investigate these processes for high-quality vapor-deposited films of CH3NH3PbI3-xClx using time- and excitation-energy dependent photoluminescence spectroscopy. We show that the PL spectrum is homogenously broadened with a line width of 103 meV most likely as a consequence of phonon coupling effects. Further analysis reveals that defects or trap states play a minor role in radiative decay channels. In terms of possible lasing applications, the emission spectrum of the perovskite is sufficiently broad to have potential for amplification of light pulses below 100 fs pulse duration.

Abstract:

Solid-state dye-sensitized solar cells rely on effective infiltration of a solid-state hole-transporting material into the pores of a nanoporous TiO 2 network to allow for dye regeneration and hole extraction. Using microsecond transient absorption spectroscopy and femtosecond photoluminescence upconversion spectroscopy, the hole-transfer yield from the dye to the hole-transporting material 2,2′,7,7′-tetrakis(N,N-di-p- methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) is shown to rise rapidly with higher pore-filling fractions as the dye-coated pore surface is increasingly covered with hole-transporting material. Once a pore-filling fraction of ≈30% is reached, further increases do not significantly change the hole-transfer yield. Using simple models of infiltration of spiro-OMeTAD into the TiO2 porous network, it is shown that this pore-filling fraction is less than the amount required to cover the dye surface with at least a single layer of hole-transporting material, suggesting that charge diffusion through the dye monolayer network precedes transfer to the hole-transporting material. Comparison of these results with device parameters shows that improvements of the power-conversion efficiency beyond ≈30% pore filling are not caused by a higher hole-transfer yield, but by a higher charge-collection efficiency, which is found to occur in steps. The observed sharp onsets in photocurrent and power-conversion efficiencies with increasing pore-filling fraction correlate well with percolation theory, predicting the points of cohesive pathway formation in successive spiro-OMeTAD layers adhered to the pore walls. From percolation theory it is predicted that, for standard mesoporous TiO2 with 20 nm pore size, the photocurrent should show no further improvement beyond an ≈83% pore-filling fraction. Solid-state dye-sensitized solar cells capable of complete hole transfer with pore-filling fractions as low as ∼30% are demonstrated. Improvements of device efficiencies beyond ∼30% are explained by a stepwise increase in charge-collection efficiency in agreement with percolation theory. Furthermore, it is predicted that, for a 20 nm pore size, the photocurrent reaches a maximum at ∼83% pore-filling fraction. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Abstract:

Perovskite-based solar cells have attracted significant recent interest, with power conversion efficiencies in excess of 15% already superceding a number of established thin-film solar cell technologies. Most work has focused on a methylammonium lead trihalide perovskites, with a bandgaps of ∼1.55 eV and greater. Here, we explore the effect of replacing the methylammonium cation in this perovskite, and show that with the slightly larger formamidinium cation, we can synthesise formamidinium lead trihalide perovskites with a bandgap tunable between 1.48 and 2.23 eV.We take the 1.48 eV-bandgap perovskite as most suited for single junction solar cells, and demonstrate long-range electron and hole diffusion lengths in this material, making it suitable for planar heterojunction solar cells. We fabricate such devices, and due to the reduced bandgap we achieve high short-circuit currents of >23 mA cm, resulting in power conversion efficiencies of up to 14.2%, the highest efficiency yet for solution processed planar heterojunction perovskite solar cells. Formamidinium lead triiodide is hence promising as a new candidate for this class of solar cell. © The Royal Society of Chemistry 2014.

Abstract:

We demonstrate ultrafast modulation of terahertz radiation by unaligned optically pumped single-walled carbon nanotubes. Photoexcitation by an ultrafast optical pump pulse induces transient terahertz absorption in nanowires aligned parallel to the optical pump. By controlling the polarisation of the optical pump, we show that terahertz polarisation and modulation can be tuned, allowing sub-picosecond modulation of terahertz radiation. Such speeds suggest potential for semiconductor nanowire devices in terahertz communication technologies.