Dye sensitized solar cells as optically random photovoltaic media

n order to enhance optical absorption, light trapping by multiple scattering is commonly achieved in dye sensitized solar cells by adding particles of a different sort. Herein we propose a theoretical method to find the structural parameters (particle number density and size) that optimize the conversion efficiency of electrodes of different thicknesses containing spherical inclusions of diverse composition. Our work provides a theoretical framework in which the response of solar cells containing diffuse scattering particles can be rationalized. Optical simulations are performed by combining a Monte Carlo approach with Mie theory, in which the angular distribution of scattered light is accounted for. Several types of scattering centers, such as anatase, gold and silver particles, as well as cavities, are considered and their effect compared. Estimates of photovoltaic performance, insight into the physical mechanisms responsible for the observed enhancements, and guidelines to improve the cell design are provided. We discuss the results in terms of light transport in weakly disordered optical media and find that the observed variations between the optimum scattering configurations attained for different electrode thicknesses can be understood as the result of the randomization of the light propagation direction at different depths within the active layer. A primary conclusion of our study is that photovoltaic performance is optimised when the scattering properties of the film are adjusted so that the distance over which incident photons are randomized is comparable to the thickness of the film. This simple relationship could also be used as a design rule to attain the optimum optical design in other photovoltaic materials.European Union 307081Ministerio de Economía y Competitividad MAT2011-23593, CSD2007-00007Junta de Andalucía FQM3579, FQM524

Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal and cubic phases of methylammonium lead iodide

The hybrid halide perovskite CH3NH3PbI3 exhibits a complex structural behaviour, with successive transitions between orthorhombic, tetragonal and cubic polymorphs at ca. 165 K and 327 K. Herein we report first-principles lattice dynamics (phonon spectrum) for each phase of CH3NH3PbI3. The equilibrium structures compare well to solutions of temperature-dependent powder neutron diffraction. By following the normal modes we calculate infrared and Raman intensities of the vibrations, and compare them to the measurement of a single crystal where the Raman laser is controlled to avoid degradation of the sample. Despite a clear separation in energy between low frequency modes associated with the inorganic PbI3 network and high-frequency modes of the organic CH3NH3+ cation, significant coupling between them is found, which emphasises the interplay between molecular orientation and the corner-sharing octahedral networks in the structural transformations. Soft modes are found at the boundary of the Brillouin zone of the cubic phase, consistent with displacive instabilities and anharmonicity involving tilting of the PbI6 octahedra around room temperature.Comment: 9 pages, 4 figure

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films

Charge recombination between oxidized dyes attached to mesoporous TiO2 and electrons in the TiO2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts

The role of hole transport between dyes in solid-state dye-sensitized solar cells

In dye-sensitized solar cells (DSSCs) photogenerated positive charges are normally considered to be carried away from the dyes by a separate phase of hole-transporting material (HTM). We show that there can also be significant transport within the dye monolayer itself before the hole reaches the HTM. We quantify the fraction of dye regeneration in solid-state DSSCs that can be attributed to this process. By using cyclic voltammetry and transient anisotropy spectroscopy, we demonstrate that the rate of interdye hole transport is prevented both on micrometer and nanometer length scales by reducing the dye loading on the TiO₂ surface. The dye regeneration yield is quantified for films with high and low dye loadings (with and without hole percolation in the dye monolayer) infiltrated with varying levels of HTM. Interdye hole transport can account for >50% of the overall dye regeneration with low HTM pore filling. This is reduced to about 5% when the infiltration of the HTM in the pores is optimized in 2 μm thick films. Finally, we use hole transport in the dye monolayer to characterize the spatial distribution of the HTM phase in the pores of the dyed mesoporous TiO₂

Experimental and theoretical optical properties of methylammonium lead halide perovskites

The optical constants from the ellipsometry of single crystals of CH3NH3PbX3(X = I, Br, Cl) are interpreted with high levelab initioQSGW calculations.</p

Identifying Dominant Recombination Mechanisms in Perovskite Solar Cells by Measuring the Transient Ideality Factor

The light ideality factor determined by measuring the open-circuit voltage (V) as a function of light intensity is often used to identify the dominant recombination mechanism in solar cells. Applying this “Suns-V” technique to perovskite cells is problematic since the V evolves with time in a way that depends on the previously applied bias (V), bias light intensity, device architecture and processing route. Here, we show that the dominant recombination mechanism in two structurally similar CH3NH3PbI3 devices containing either mesoporous Al2O3 or TiO2 layers can be identified from the signature of the transient ideality factor following application of a forward bias, V, to the device in the dark. The transient ideality factor is measured by monitoring the evolution of V as a function of time at different light intensities. The initial values of ideality found using this technique are consistent with estimates of the ideality factor obtained from measurements of photoluminescence vs light intensity and electroluminescence vs current density. Time-dependent simulations of the measurement on modeled devices, which include the effects of mobile ionic charge, reveal that this initial value can be correlated to an existing zero-dimensional model while steady-state values must be analyzed taking into account the homogeneity of carrier populations throughout the absorber layer. The analysis shows that Shockley-Read-Hall (SRH) recombination through deep traps at the charge-collection interfaces is dominant in both architectures of measured device. Using transient photovoltage measurements directly following illumination on bifacial devices, we further show that the perovskite–electron-transport-layer interface extends throughout the mesoporous TiO2 layer, consistent with a transient ideality signature corresponding to SRH recombination in the bulk of the film. This method will be useful for identifying performance bottlenecks in alternative variants of perovskite and other mixed ionic-electronic conducting absorber-based solar cells