Ion migration has been proposed as a possible cause of photovoltaic current-voltage hysteresis in hybrid perovskite solar cells. A major objection to this hypothesis is that hysteresis can be reduced ...by changing the interfacial contact materials; however, this is unlikely to significantly influence the behaviour of mobile ionic charge within the perovskite phase. Here, we show that the primary effects of ion migration can be observed regardless of whether the contacts were changed to give devices with or without significant hysteresis. Transient optoelectronic measurements combined with device simulations indicate that electric-field screening, consistent with ion migration, is similar in both high and low hysteresis CH
NH
PbI
cells. Simulation of the photovoltage and photocurrent transients shows that hysteresis requires the combination of both mobile ionic charge and recombination near the perovskite-contact interfaces. Passivating contact recombination results in higher photogenerated charge concentrations at forward bias which screen the ionic charge, reducing hysteresis.
Methylammonium lead iodide perovskite can make high-efficiency solar cells, which also show an unexplained photocurrent hysteresis dependent on the device-poling history. Here we report quasielastic ...neutron scattering measurements showing that dipolar CH3NH3(+) ions reorientate between the faces, corners or edges of the pseudo-cubic lattice cages in CH3NH3PbI3 crystals with a room temperature residence time of ∼14 ps. Free rotation, π-flips and ionic diffusion are ruled out within a 1-200-ps time window. Monte Carlo simulations of interacting CH3NH3(+) dipoles realigning within a 3D lattice suggest that the scattering measurements may be explained by the stabilization of CH3NH3(+) in either antiferroelectric or ferroelectric domains. Collective realignment of CH3NH3(+) to screen a device's built-in potential could reduce photovoltaic performance. However, we estimate the timescale for a domain wall to traverse a typical device to be ∼0.1-1 ms, faster than most observed hysteresis.
In Methyl Ammonium Lead Iodide (MAPI) perovskite solar cells, screening of the built-in field by mobile ions has been proposed as part of the cause of the large hysteresis observed in the ...current/voltage scans in many cells. We show that photocurrent transients measured immediately ( e.g. 100 μs) after a voltage step can provide direct evidence that this field screening exists. Just after a step to forward bias, the photocurrent transients are reversed in sign ( i.e. inverted), and the magnitude of the inverted transients can be used to find an upper bound on the width of the space charge layers adjacent to the electrodes. This in turn provides a lower bound on the mobile charge concentration, which we find to be ≳1 × 10 17 cm −3 . Using a new photocurrent transient experiment, we show that the space charge layer thickness remains approximately constant as a function of bias, as expected for mobile ions in a solid electrolyte. We also discuss additional characteristics of the inverted photocurrent transients that imply either an unusually stable deep trapping, or a photo effect on the mobile ion conductivity.
Tools that assess the limitations of dye sensitized solar cells (DSSCs) made with new materials are critical for progress. Measuring the transient electrical signals (voltage or current) after ...optically perturbing a DSSC is an approach which can give information about electron concentration, transport and recombination. Here we describe the theory and practice of this class of optoelectronic measurements, illustrated with numerous examples. The measurements are interpreted with the multiple trapping continuum model which describes electrons in a semiconductor with an exponential distribution of trapping states. We review standard small perturbation photocurrent and photovoltage transients, and introduce the photovoltage time of flight measurement which allows the simultaneous derivation of both effective diffusion and recombination coefficients. We then consider the utility of large perturbation measurements such as charge extraction and the current interrupt technique for finding the internal charge and voltage within a device. Combining these measurements allows differences between DSSCs to be understood in terms such as electron collection efficiency, semiconductor conduction band edge shifts and recombination kinetics.
Measuring the transient current or voltage signals after optically perturbing a dye‐sensitized solar cell gives information about electron transport and recombination. These observations can be related to the internal charge concentration within a device which can be estimated using the charge extraction technique. Here the theory and practice of a wide range of these measurements is described, and illustrated with numerous examples.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
We employed transient absorption spectroscopy (TAS) to investigate the kinetic dependences of photocatalysis in anatase and rutile TiO2 films of varying morphology. In mesoporous films, anatase was ...∼30 times more efficient than rutile in the photocatalytic degradation of an intelligent ink model system. Independent of phase, up to 100 lower levels of photocatalysis were found in dense films. Charge carrier lifetimes were probed by TAS on the microsecond to second time scale. For both rutile and anatase, recombination was independent of morphology. Rutile exhibited up to 10 times slower recombination kinetics than anatase. Efficient, irreversible hole scavenging by alcohols was present in mesoporous anatase alone, resulting in the generation of long-lived electrons (τ ≈ 0.7 s) which, upon the addition of the dye reduction target resazurin, enabled efficient electron transfer (τ ≈ 3 ms). Hole scavenging by alcohols on mesoporous rutile was substantially less efficient and more reversible than anatase, resulting in only a marginal increase in electron lifetime. The lower activity of rutile was not due to differences in recombination but rather to the deficiency of rutile holes to drive efficient and irreversible alcohol oxidation.
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IJS, KILJ, NUK, PNG, UL, UM
Three organic or hybrid photovoltaic technologies are compared with respect to performance and stability under the harsh regime of concentrated light. Although all three technologies show ...surprisingly high (and linear) photocurrents, and better than expected stability, no golden apples are awarded.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
We have investigated the nature of the photocurrent generated by Photosystem II (PSII), the water oxidizing enzyme, isolated from Thermosynechococcus elongatus, when immobilized on nanostructured ...titanium dioxide on an indium tin oxide electrode (TiO2/ITO). We investigated the properties of the photocurrent from PSII when immobilized as a monolayer versus multilayers, in the presence and absence of an inhibitor that binds to the site of the exchangeable quinone (QB) and in the presence and absence of exogenous mobile electron carriers (mediators). The findings indicate that electron transfer occurs from the first quinone (QA) directly to the electrode surface but that the electron transfer through the nanostructured metal oxide is the rate-limiting step. Redox mediators enhance the photocurrent by taking electrons from the nanostructured semiconductor surface to the ITO electrode surface not from PSII. This is demonstrated by photocurrent enhancement using a mediator incapable of accepting electrons from PSII. This model for electron transfer also explains anomalies reported in the literature using similar and related systems. The slow rate of the electron transfer step in the TiO2 is due to the energy level of electron injection into the semiconducting material being below the conduction band. This limits the usefulness of the present hybrid electrode. Strategies to overcome this kinetic limitation are discussed.
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•In PSII metal oxide hybrid systems, direct electron transfer occurs from QA to the electrode surface.•Electron transfer through the nanostructured TiO2 is rate-limiting.•Redox mediators can overcome the limitation by taking electrons from the TiO2 semiconductor to the electrode surface.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
In this work we lay out design guidelines for catalytically more efficient organic photocathodes achieving stable hydrogen production in neutral pH. We propose an organic photocathode architecture ...employing a NiO hole selective layer, a PCDTBT:PCBM bulk heterojunction, a compact TiO2 electron selective contact and a RuO2 nanoparticle catalyst. The role of each layer is discussed in terms of durability and function. With this strategically designed organic photocathode we obtain stable photocurrent densities for over 5 h and discuss routes for further performance improvement.
DSSCs incorporating Co( ii / iii ) tris(bipyridine) redox couple in acetonitrile and the Z907 dye were subjected to ≥2000 hours of light soaking at 20 °C and ∼1 sun light intensity from white LEDs ...(∼no UV component). Initial energy efficiencies were near 6.3%. After 2000 hours, the best acetonitrile based cells maintained ∼66% of the initial efficiency. Both J SC and fill factor (FF) declined, while the V OC remained highly stable. In comparison, the best Z907/cobalt cells with 3-methoxypropionitrile (MPN) as a solvent, maintained 91% of the initial efficiency after 2000 hour light soaking. Only FF declined in MPN based cells. In follow up testing of similar ACN cells at the maximum power point, at 30 °C, the best cells maintained ∼100% of the initial efficiency after 1000 hours. Impedance, J SC vs. intensity and charge extraction data are consistent with a decrease in the Co( iii ) concentration, or a restriction in Co( iii ) diffusion, during light soaking.
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