Recombination dynamics in polythiophene:fullerene solar cells

Organic devices based on polymer:fullerene blend films are attracting extensive interest as low cost solar cells, with power conversion efficiencies over 5%. Improvements in performance are dependent on developing a better understanding of the pertinent loss processes. This in turn requires the ability to reliably determine charge densities (n) and carrier lifetimes (τn) in real devices under standard operating conditions. In this thesis, we address the recombination dynamics in organic solar cells based on blends of poly(3-hexylthiophene) (P3HT) and methanofullerene [6,6]- phenyl C61-butyric acid methyl ester (PCBM), P3HT:PCBM devices, one of the best devices to date, using both experimental and modelling studies. Initially, a drift-diffusion model was used to study the basic principles of solar cell operation, with particular focus on investigating the ‘corrected photocurrent’, where the effects of dark injection are removed. We then have employed a series of experimental techniques – including transient photovoltage and photocurrent, transient absorption spectroscopy and charge extraction – to determine the carrier lifetimes and charge densities in standard annealed P3HT:PCBM devices under operation. The results of our studies for a device under open-circuit conditions show that the open-circuit voltage (Voc) is primarily governed by a trap dependent bimolecular recombination process. By applying charge extraction studies on devices under forward bias in the dark, we show that the dark current is also governed by the same trap dependent bimolecular recombination mechanism which determines Voc. Based on the understanding of charge carrier dynamics at Voc and the forward bias dark current, a simple model has been developed to simulate ‘light’ current-voltage (J-V) curves. Despite the simplicity of this model, remarkably good agreement was observed with experimental J-V data

Charge density dependent nongeminate recombination in organic bulk heterojunction solar cells

Apparent recombination orders exceeding the value of two expected for bimolecular recombination have been reported for organic solar cells in various publications. Two prominent explanations are bimolecular losses with a carrier concentration dependent prefactor due to a trapping limited mobility, and protection of trapped charge carriers from recombination by a donor--acceptor phase separation until reemission from these deep states. In order to clarify which mechanism is dominant we performed temperature and illumination dependent charge extraction measurements under open circuit as well as short circuit conditions at poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl-C$_{61}$butyric acid methyl ester (P3HT:PC$_{61}$BM) and PTB7:PC$_{71}$BM (Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]) solar cells in combination with current--voltage characteristics. We show that the charge carrier density $n$ dependence of the mobility $\mu$ and the recombination prefactor are different for PC$_{61}$BM at temperatures below 300K and PTB7:PC$_{71}$BM at room temperature. Therefore, in addition to $\mu(n)$ a detrapping limited recombination in systems with at least partial donor--acceptor phase separation is required to explain the high recombination orders.Comment: 7 pages, 4 figure

Polaron Recombination in Pristine and Annealed Bulk Heterojunction Solar Cells

The major loss mechanism of photogenerated polarons was investigated in P3HT:PCBM solar cells by the photo-CELIV technique. For pristine and annealed devices, we find that the experimental data can be explained by a bimolecular recombination rate reduced by a factor of about ten (pristine) and 25 (annealed) as compared to Langevin theory. Aided by a macroscopic device model, we discuss the implications of the lowered loss rate on the characteristics of polymer:fullerene solar cells.Comment: 3 pages, 4 figure

Impact of nongeminate recombination on the performance of pristine and annealed P3HT:PCBM solar cells

Transient photovoltage (TPV) and voltage dependent charge extraction (CE) measurements were applied to poly(3-hexylthiophene)(P3HT):[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) bulk heterojunction solar cells to analyze the limitations of solar cell performance in pristine and annealed devices. From the determined charge carrier decay rate under open circuit conditions and the voltage dependent charge carrier densities n(V) the nongeminate loss current jloss of the device is accessible. We found that jloss alone is sufficient to describe the j-V characteristics across the whole operational range, for annealed and, not yet shown before, also for the lower performing pristine solar cells. Even in a temperature range from 300 K to 200 K nongeminate recombination is found to be the dominant and, therefore, performance limiting loss process. Consequently, charge photogeneration is voltage independent in the voltage range studied.Comment: 3 pages, 3 figures; Rapid Research Letter 201

Validation of computational liquefaction for tailings: Tar Island slump

Finite-element analyses using critical state theory proved necessary to understand the development of static liquefaction during three recent large tailing dam failures at Fundao (in Brazil), Cadia (in Australia) and Brumadinho (in Brazil). However, the complexity of these events prevents these analyses being viewed as a complete validation of the methodology. Here the authors evaluate a far simpler case of static liquefaction: The 1974 Tar Island slump (in Canada). This upstream slump involved a rapid drop of 5 m during construction of a 12.5 m high upstream raise over loose tailings. While not a dam stability issue, the event has the attraction for validation of being load-induced, with simple geometry, and with known material properties and in situ state. The computed liquefaction develops from a prior drained condition before propagating rapidly undrained-there are similarities to the video record at Brumadinho (an animation is provided as online supplementary material to illustrate this). A range of scenarios are explored, with the base case of taking reported conditions at face value giving deformations close to those measured. An important aspect was using elastic shear moduli determined by geophysical methods. The analyses were carried out with commercial software (Plaxis) and used critical state theory with largely familiar soil properties measured by standard methods

Triplet Exciton Generation in Bulk-Heterojunction Solar Cells based on Endohedral Fullerenes

Organic bulk-heterojunctions (BHJ) and solar cells containing the trimetallic nitride endohedral fullerene 1-[3-(2-ethyl)hexoxy carbonyl]propyl-1-phenyl-Lu3N@C80 (Lu3N@C80-PCBEH) show an open circuit voltage (VOC) 0.3 V higher than similar devices with [6,6]-phenyl-C[61]-butyric acid methyl ester (PC61BM). To fully exploit the potential of this acceptor molecule with respect to the power conversion efficiency (PCE) of solar cells, the short circuit current (JSC) should be improved to become competitive with the state of the art solar cells. Here, we address factors influencing the JSC in blends containing the high voltage absorber Lu3N@C80-PCBEH in view of both photogeneration but also transport and extraction of charge carriers. We apply optical, charge carrier extraction, morphology, and spin-sensitive techniques. In blends containing Lu3N@C80-PCBEH, we found 2 times weaker photoluminescence quenching, remainders of interchain excitons, and, most remarkably, triplet excitons formed on the polymer chain, which were absent in the reference P3HT:PC61BM blends. We show that electron back transfer to the triplet state along with the lower exciton dissociation yield due to intramolecular charge transfer in Lu3N@C80-PCBEH are responsible for the reduced photocurrent

Optimization of a high work function solution processed vanadium oxide hole-extracting layer for small molecule and polymer organic photovoltaic cells

We report a method of fabricating a high work function, solution processable vanadium oxide (V2Ox(sol)) hole-extracting layer. The atmospheric processing conditions of film preparation have a critical influence on the electronic structure and stoichiometry of the V2Ox(sol), with a direct impact on organic photovoltaic (OPV) cell performance. Combined Kelvin probe (KP) and ultraviolet photoemission spectroscopy (UPS) measurements reveal a high work function, n-type character for the thin films, analogous to previously reported thermally evaporated transition metal oxides. Additional states within the band gap of V2Ox(sol) are observed in the UPS spectra and are demonstrated using X-ray photoelectron spectroscopy (XPS) to be due to the substoichiometric nature of V2Ox(sol). The optimized V2Ox(sol) layer performance is compared directly to bare indium–tin oxide (ITO), poly(ethyleneoxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and thermally evaporated molybdenum oxide (MoOx) interfaces in both small molecule/fullerene and polymer/fullerene structures. OPV cells incorporating V2Ox(sol) are reported to achieve favorable initial cell performance and cell stability attributes

The Role of Secondary Airports for Today's Low-Cost Carrier Business Models: The European Case

One of the core characteristics of Low-Cost Carriers (LCCs) is their use of secondary and regional airports. However, nothing is fixed as the market constantly evolves and carriers modify their strategies in order to achieve growth. This paper uses the examples of Ryanair, easyJet and Norwegian to show how changes to LCC business models are affecting secondary airports across Europe. Using a content analysis, this paper first describes how airport choice factors for LCCs have evolved over the last 10 years. This is followed by a data analysis of historical and current airline network capacity to identify how LCC traffic at secondary airports is developing. The paper finds that cost, demand and efficiency are still the most important criteria for LCCs when choosing an airport to operate from. However, it also identifies that LCCs have become more interested in serving business passengers, which is why they are increasingly using primary airports (accounting for 58% of their recent capacity growth). Through the use of a selection of case airports it is finally concluded that the evolution of LCCs increases competition between primary and secondary gateways. In most cases, secondary airports are losing a significant amount of LCC traffic and only sustain flights to less important destinations. This research puts into question the future importance of secondary airports for LCCs. As not all airports have been impacted by the hybridisation of LCCs to the same extent, the results are not equally applicable to the whole European airport industry

Optoelectronic Studies of Methylammonium Lead Iodide Perovskite Solar Cells with Mesoporous TiO2: Separation of Electronic and Chemical Charge Storage, Understanding Two Recombination Lifetimes, and the Evolution of Band Offsets during J-V Hysteresis

Methylammonium lead iodide (MAPI) cells of the design FTO/sTiO2/ mpTiO2/MAPI/Spiro-OMeTAD/Au, where FTO is fluorine-doped tin oxide, sTiO2 indicates solid-TiO2, and mpTiO2 is mesoporous TiO2, are studied using transient photovoltage (TPV), differential capacitance, charge extraction, current interrupt, and chronophotoamperometry. We show that in mpTiO2/MAPI cells there are two kinds of extractable charge stored under operation: a capacitive electronic charge (&sim;0.2 &mu;C/ cm2) and another, larger charge (40 &mu;C/cm2), possibly related to mobile ions. Transient photovoltage decays are strongly double exponential with two time constants that differ by a factor of &sim;5, independent of bias light intensity. The fast decay (&sim;1 &mu;s at 1 sun) is assigned to the predominant charge recombination pathway in the cell. We examine and reject the possibility that the fast decay is due to ferroelectric relaxation or to the bulk photovoltaic effect. Like many MAPI solar cells, the studied cells show significant J&minus;V hysteresis. Capacitance vs open circuit voltage (Voc) data indicate that the hysteresis involves a change in internal potential gradients, likely a shift in band offset at the TiO2/MAPI interface. The TPV results show that the Voc hysteresis is not due to a change in recombination rate constant. Calculation of recombination flux at Voc suggests that the hysteresis is also not due to an increase in charge separation efficiency and that charge generation is not a function of applied bias. We also show that the J&minus;V hysteresis is not a light driven effect but is caused by exposure to electrical bias, light or dark.</div