Snaith group

Abstract:

Ionizing chemical dopants are widely used in organic semiconductors to enhance the charge transport properties by increasing the number of mobile charge carriers. However, together with mobile charges, chemical doping produces anion-cation pairs in the organic matrix. In this work we use experimental and computational analysis to study the influence of these ionic species on the charge transport. We show that the anion-cation pairs introduced upon doping have a detrimental, doping-level dependent effect on charge mobility. For doping levels of 0.02-0.05% molar ratio with respect to the molecular organic semiconductor, the increase in conductivity from the extra mobile charges is partially cancelled by a reduction in charge mobility from traps introduced by the anion-cation pairs. As the doping concentration increases, anion-cation pairs start to overlap, resulting in a comparatively smoother potential landscape, which increases the charge mobility to values closer to the undoped semiconductor. This result has a significant, practical impact, as it shows the need to dope at or slightly above a threshold level, which depends on the specific host-dopant combination.

Abstract:

We report the low-frequency resonant Raman spectrum of methylammonium lead-iodide, a prototypical perovskite for solar cells applications, on mesoporous Al2O3. The measured spectrum assignment is assisted by DFT simulations of the Raman spectra of suitable periodic and model systems. The bands at 62 and 94 cm-1 are assigned respectively to the bending and to the stretching of the Pb-I bonds, and are thus diagnostic modes of the inorganic cage. We also assign the librations of the organic cations at 119 and 154 cm-1. The broad, unstructured 200-400 cm-1 features are assigned to the torsional mode of the methylammonium cations, which we propose as a marker of the orientational disorder of the material. Our study provides the basis to interpret the Raman spectra of organohalide perovskites, which may allow one to further understand the properties of this important class of materials in relation to their full exploitation in solar cells. © 2013 American Chemical Society.

Abstract:

Organometal trihalide perovskite based solar cells have exhibited the highest efficiencies to-date when incorporated into mesostructured composites. However, thin solid films of a perovskite absorber should be capable of operating at the highest efficiency in a simple planar heterojunction configuration. Here, it is shown that film morphology is a critical issue in planar heterojunction CH3NH3PbI3-xCl x solar cells. The morphology is carefully controlled by varying processing conditions, and it is demonstrated that the highest photocurrents are attainable only with the highest perovskite surface coverages. With optimized solution based film formation, power conversion efficiencies of up to 11.4% are achieved, the first report of efficiencies above 10% in fully thin-film solution processed perovskite solar cells with no mesoporous layer. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Abstract:

Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI3-xClx perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9′-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr-1 m-2 at a current density of 363 mA cm-2, with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m-2 at a current density of 123 mA cm-2, giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications. © 2014 Macmillan Publishers Limited. All rights reserved.

Abstract:

Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI3-xClx perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9′-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr-1 m-2 at a current density of 363 mA cm-2, with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m-2 at a current density of 123 mA cm-2, giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications. © 2014 Macmillan Publishers Limited. All rights reserved.