Motional Narrowing Effects in the Excited State Spin Populations of Mn-Doped Hybrid Perovskites.

Spin-orbit coupling in the electronic states of solution-processed hybrid metal halide perovskites forms complex spin-textures in the band structures and allows for optical manipulation of the excited state spin-polarizations. Here, we report that motional narrowing acts on the photoexcited spin-polarization in CHNHPbBr thin films, which are doped at percentage-level with Mn ions. Using ultrafast circularly polarized broadband transient absorption spectroscopy at cryogenic temperatures, we investigate the spin population dynamics in these doped hybrid perovskites and find that spin relaxation lifetimes are increased by a factor of 3 compared to those of undoped materials.

Ionic Accumulation as a Diagnostic Tool in Perovskite Solar Cells: Characterizing Band Alignment with Rapid Voltage Pulses.

Despite record-breaking devices, interfaces in perovskite solar cells are still poorly understood, inhibiting further progress. Their mixed ionic-electronic nature results in compositional variations at the interfaces, depending on the history of externally applied biases. This makes it difficult to measure the band energy alignment of charge extraction layers accurately.

Overscreening and Underscreening in Solid-Electrolyte Grain Boundary Space-Charge Layers.

Polycrystalline solids can exhibit material properties that differ significantly from those of equivalent single-crystal samples, in part, because of a spontaneous redistribution of mobile point defects into so-called space-charge regions adjacent to grain boundaries. The general analytical form of these space-charge regions is known only in the dilute limit, where defect-defect correlations can be neglected. Using kinetic Monte Carlo simulations of a three-dimensional Coulomb lattice gas, we show that grain boundary space-charge regions in nondilute solid electrolytes exhibit overscreening-damped oscillatory space-charge profiles-and underscreening-decay lengths that are longer than the corresponding Debye length and that increase with increasing defect-defect interaction strength.

3D-to-2D Transition of Anion Vacancy Mobility in CsPbBr under Hydrostatic Pressure.

Anion vacancy migration in the orthorhombic phase of the lead-halide perovskite CsPbBr under hydrostatic pressure is studied computationally. Density functional theory calculations are used to determine transition states, activation enthalpies, and attempt frequencies for vacancies to hop between nearby lattice sites, under pressure in the range 0.0-2.

Identification of recombination losses and charge collection efficiency in a perovskite solar cell by comparing impedance response to a drift-diffusion model.

Interpreting the impedance response of perovskite solar cells (PSCs) is significantly more challenging than for most other photovoltaics. This is for a variety of reasons, of which the most significant are the mixed ionic-electronic conduction properties of metal halide perovskites and the difficulty in fabricating stable, and reproducible, devices. Experimental studies, conducted on a variety of PSCs, produce a variety of impedance spectra shapes.

Putting the Squeeze on Lead Iodide Perovskites: Pressure-Induced Effects To Tune Their Structural and Optoelectronic Behavior.

Lattice compression through hydrostatic pressure has emerged as an effective means of tuning the structural and optoelectronic properties of hybrid halide perovskites. In addition to external pressure, the local strain present in solution-processed thin films also causes significant heterogeneity in their photophysical properties. However, an atomistic understanding of structural changes of hybrid perovskites under pressure and their effects on the electronic landscape is required.

Simulating morphologies of organic semiconductors by exploiting low-frequency vibrational modes.

Generating morphologies of amorphous organic materials represents a significant computational challenge and severely limits the size of systems that can be studied. Furthermore, the dynamical evolution of a film at high density occurs on time scales impractical to simulate dynamically, limiting the number of independent states that can be generated. This is a problem in glassy systems as well as protein and polymeric systems.

Utilizing Energy Transfer in Binary and Ternary Bulk Heterojunction Organic Solar Cells.

Energy transfer has been identified as an important process in ternary organic solar cells. Here, we develop kinetic Monte Carlo (KMC) models to assess the impact of energy transfer in ternary and binary bulk heterojunction systems. We used fluorescence and absorption spectroscopy to determine the energy disorder and Förster radii for poly(3-hexylthiophene-2,5-diyl), [6,6]-phenyl-C61-butyric acid methyl ester, 4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl]squaraine (DIBSq), and poly(2,5-thiophene-alt-4,9-bis(2-hexyldecyl)-4,9-dihydrodithieno[3,2-c:3',2'-h][1,5]naphthyridine-5,10-dione).

Influence of ionizing dopants on charge transport in organic semiconductors.

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.

Monte carlo studies of electronic processes in dye-sensitized solar cells.

This topic reviews random walk Monte Carlo simulation models of charge transport in DSSC. The main electron transport approaches used are covered. Monte Carlo methods and results are explained, addressing the continuous time random walk model developed for transport in disordered materials in the context of the large number of trap states present in the electron transporting material.

Simulation of loss mechanisms in organic solar cells: A description of the mesoscopic Monte Carlo technique and an evaluation of the first reaction method.

In this letter we evaluate the accuracy of the first reaction method (FRM) as commonly used to reduce the computational complexity of mesoscale Monte Carlo simulations of geminate recombination and the performance of organic photovoltaic devices. A wide range of carrier mobilities, degrees of energetic disorder, and applied electric field are considered. For the ranges of energetic disorder relevant for most polyfluorene, polythiophene, and alkoxy poly(phenylene vinylene) materials used in organic photovoltaics, the geminate separation efficiency predicted by the FRM agrees with the exact model to better than 2%.

Bicontinuous minimal surface nanostructures for polymer blend solar cells.

This paper presents the first examination of the potential for bicontinuous structures such as the gyroid structure to produce high efficiency solar cells based on conjugated polymers. The solar cell characteristics are predicted by a simulation model that shows how the morphology influences device performance through integration of all the processes occurring in organic photocells in a specified morphology. In bicontinuous phases, the surface defining the interface between the electron and hole transporting phases divides the volume into two disjoint subvolumes.

Dynamic Monte Carlo simulation for highly efficient polymer blend photovoltaics.

We developed a model system for blend polymers with electron-donating and -accepting compounds. It is found that the optimal energy conversion efficiency can be achieved when the feature size is around 10 nm. The first reaction method is used to describe the key processes (e.

Two-dimensional simulations of bulk heterojunction solar cell characteristics.

We present a two-dimensional model of a bulk heterojunction solar cell in which we include the effects of optical interference, exciton diffusion, charge separation via the formation of polaron pairs, and charge transport in two separate interpenetrating phases. Our model shows that the current is increased by an order of magnitude with a full optical model compared to assuming that absorbed photons have a Lambertian profile, and depends much more strongly on applied bias when dissociation via polaron pairs is considered. We find a power efficiency at solar intensities of 1-3% depending on the morphology, and show that the fill factor decreases from 40% at low intensities to 20% at solar intensities because of the increase in the open circuit voltage and decreases much more rapidly at higher intensities due to the decrease in the power efficiency.

Dye-sensitized solar cells based on oriented TiO2 nanotube arrays: transport, trapping, and transfer of electrons.

Dye-sensitized solar cells fabricated using ordered arrays of titania nanotubes (tube lengths 5, 10, and 20 microm) grown on titanium have been characterized by a range of experimental methods. The collection efficiency for photoinjected electrons in the cells is close to 100% under short circuit conditions, even for a 20 microm thick nanotube array. Transport, trapping, and back transfer of electrons in the nanotube cells have been studied in detail by a range of complementary experimental techniques.

Predictive study of charge transport in disordered semiconducting polymers.

We present a theoretical study of charge transport in disordered semiconducting polymers that relates the charge mobility to the chemical structure and the physical morphology in a novel multiscale approach. Our studies, focusing on poly(9,9-dioctylfluorene) (PFO), show that the charge mobility is dominated by pathways with the highest interchain charge-transfer rates. We also find that disorder is not always detrimental to charge transport.

Analysis of photovoltage decay transients in dye-sensitized solar cells.

It is shown that application of the so-called quasi-static approximation greatly simplifies the theoretical treatment of the open circuit photovoltage decay of dye-sensitized nanostructured solar cells (DSCs), since it removes the need to treat the kinetics of trapping and detrapping explicitly and leads to a straightforward analytical solution in the case of an exponential trap distribution. To identify the conditions under which the quasi-static approach is valid, transients calculated using the quasi-static approximation are compared with the results of numerical calculations that treat trapping and detrapping of electrons explicitly. The application of the quasi-static approach to derive the rate constant for the back-reaction of electrons from experimental photovoltage decay data is illustrated for an optimized DSC.

Grain morphology and trapping effects on electron transport in dye-sensitized nanocrystalline solar cells.

We have examined the combined effects of grain morphology and electron trapping on the transient response of photoelectrons moving through the TiO2 grains in a dye-sensitized nanocrystalline solar cell using a multi-time-scale random walk Monte Carlo model. Our use of a multi-time-scale approach enables us to simulate transport for electrons moving through spherical connected grains in a three-dimensional (3D) voided network and look at the effect of the size of interparticle boundaries on carrier dynamics. We can also address similar times to those over which measurements are taken, namely, 0.

Interpretation of apparent activation energies for electron transport in dye-sensitized nanocrystalline solar cells.

Electron transport in dye-sensitized nanocrystalline solar cells appears to be a slow diffusion-controlled process. Values of the apparent electron diffusion coefficient are many orders of magnitude smaller than those reported for bulk anatase. The slow transport of electrons has been attributed to multiple trapping (MT) at energy levels distributed exponentially in the band gap of the nanocrystalline oxide.

Dynamical Monte Carlo modelling of organic solar cells: the dependence of internal quantum efficiency on morphology.

We present a dynamical Monte Carlo study of the dependence of the internal quantum efficiency (IQE) of an organic bulk heterojunction solar cell on the device morphology. The IQE is found to be strongly sensitive to the scale of phase separation in the morphology, with a peak at approximately 20 nm for the PFB/F8BT system studied. An ordered, checkered morphology exhibits a peak IQE 1.