Prof Laura Herz FRS

Abstract:

Methylammonium tin triiodide (MASnI3) has been successfully employed in lead-free perovskite solar cells, but overall power-conversion efficiencies are still significantly lower than for lead-based perovskites. Here we present photoluminescence (PL) spectra and time-resolved PL from 8 to 295 K and find a marked improvement in carrier lifetime and a substantial reduction in PL line width below ∼110 K, indicating that the cause of the hindered performance is activated at the orthorhombic to tetragonal phase transition. Our measurements therefore suggest that targeted structural change may be capable of tailoring the relative energy level alignment of defects (e.g., tin vacancies) to reduce the background dopant density and improve charge extraction. In addition, we observe for the first time an above-gap emission feature that may arise from higher-lying interband transitions, raising the prospect of excess energy harvesting.

Abstract:

Controlled doping of GaAs nanowires is crucial for the development of nanowire-based electronic and optoelectronic devices. Here, we present a non-contact method based on time resolved terahertz photoconductivity for assessing n and p type doping efficiency in nanowires. Using this technique, we measure extrinsic electron and hole concentrations in excess of 10(18)cm(-3) for GaAs nanowires with n-type and p-type doped shells. Furthermore, we show that controlled doping can significantly increase the photoconductivity lifetime of GaAs nanowires by over an order of magnitude: from 0.13ns in undoped nanowires to 3.8ns and 2.5ns in n-doped and p-doped nanowires respectively. Thus, controlled doping can be used to reduce the effects of parasitic surface recombination in optoelectronic nanowire devices, which is promising for nanowire devices such as solar cells and nanowire lasers.

Abstract:

Hybrid organic-inorganic metal halide perovskites have recently emerged as exciting new light-harvesting and charge-transporting materials for efficient photovoltaic devices. Yet knowledge of the nature of the photogenerated excitations and their subsequent dynamics is only just emerging. This article reviews the current state of the field, focusing first on a description of the crystal and electronic band structure that give rise to the strong optical transitions that enable light harvesting. An overview is presented of the numerous experimental approaches toward determining values for exciton binding energies, which appear to be small (a few milli-electron volts to a few tens of milli-electron volts) and depend significantly on temperature because of associated changes in the dielectric function. Experimental evidence for charge-carrier relaxation dynamics within the first few picoseconds after excitation is discussed in terms of thermalization, cooling, and many-body effects. Charge-carrier recombination mechanisms are reviewed, encompassing trap-assisted nonradiative recombination that is highly specific to processing conditions, radiative bimolecular (electron-hole) recombination, and nonradiative many-body (Auger) mechanisms.

Abstract:

Because of their unique electronic properties, cyclic molecular structures ranging from benzene to natural light-harvesting complexes have received much attention. Rigid π-conjugated templated porphyrin nanorings serve as excellent model systems here because they possess well-defined structures that can readily be controlled and because they support highly delocalized excitations. In this study, we have deliberately modified a series of six-porphyrin nanorings to examine the impact of lowering the rotational symmetry on their photophysical properties. We reveal that as symmetry distortions increase in severity along the series of structures, spectral changes and an enhancement of radiative emission strength occur, which derive from a transfer of oscillator strength into the lowest (k = 0) state. We find that concomitantly, the degeneracy of the dipole-allowed first excited (k = ±1) state is lifted, leading to an ultrafast polarization switching effect in the emission from strongly symmetry-broken nanorings.

Abstract:

Hybrid metal-halide perovskites have emerged as a leading class of semiconductors for optoelectronic devices because of their desirable material properties and versatile fabrication methods. However, little is known about the chemical transformations that occur in the initial stages of perovskite crystal formation. Here we follow the real-time formation dynamics of MAPbI3 from a bilayer of lead iodide (PbI2) and methylammonium iodide (MAI) deposited through a two-step thermal evaporation process. By lowering the substrate temperature during deposition, we are able to initially inhibit intermixing of the two layers. We subsequently use infrared and visible light transmission, X-ray diffraction, and photoluminescence lifetime measurements to reveal the room-temperature transformations that occur in vacuum and ambient air, as MAI diffuses into the PbI2 lattice to form MAPbI3. In vacuum, the transformation to MAPbI3 is incomplete as unreacted MAI is retained in the film. However, exposure to moist air allows for conversion of the unreacted MAI to MAPbI3, demonstrating that moisture is essential in making MAI more mobile and thus aiding perovskite crystallization. These dynamic processes are reflected in the observed charge-carrier lifetimes, which strongly fluctuate during periods of large ion migration but steadily increase with improving crystallinity.