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  1. Final Report: Electron/hole selectivity in organic semiconductor contacts for solar energy conversion

    Four major and accomplishments for the project ``Electron/hole selectivity in organic semiconductor contacts for solar energy conversion.'' are reported. The first is a development of a model describing the contact-determined behavior of a solar cell. The most basic solar cell consists of an intrinsic (pure) semiconductor that acts as an absorber to which contacts are made that provide the asymmetry needed to create a driving force (voltage) for the directional flow of electrons (current), in other words, to convert sunlight into electrical energy. The asymmetry at the contacts comes from the different rate at which electrons and holes, the chargemore » carriers generated by illumination, are collected. We developed a model that describes the ideal current-voltage, and hence energy converting properties, of an ideal photovoltaic that is entirely determined by the kinetics for these charge collection processes. Second, we measured how organic semiconductor interfacial layers impact contact electron and hole transfer rates at semiconductor interfaces and described how these concepts do or do not determine the open-circuit voltage of a solar cell. The work clearly controverts common general misconceptions about the action of contact interfacial layers, such as the idea that improved selectivity for one carrier over the other results from decreased recombination, and quantitatively demonstrates how specific interfacial layer materials act to improve the efficiency of a solar cell. Third, we measured the sub-band gap external quantum efficiency (EQE) of a series of organometal halide perovskite (“perovskite”) solar cells. These measurements quantified band-tailing and revealed defect states, which can cause recombination, that correlate with composition, performance, and hysteresis. Finally, we developed a semiconductor bipolar membrane that uses light to pump ions. This structure is unique among systems that drive ion gradients using light in that it is designed to pump salt rather than one sign of ion; it is a photochemical salt pump.« less
  2. Solar cell contacts: quantifying the impact of interfacial layers on selectivity, recombination, charge transfer, and Voc

    Interfacial layers (IFLs) are ubiquitous in solar cells, but their precise impact on carrier transfer rates and the relation of these rates to performance metrics and the concepts of selectivity and recombination is lacking. We report the use of a well-defined interdigitated back-contact (IBC) silicon solar cell to determine the precise role of such IFLs. We characterize the action of the common IFL spiro-OMeTAD by making it a third contact to the IBC cell. This architecture creates three solar cells within a single structure that, with numerical simulation, provide the exchange current densities (i.e., charge transfer rates) for electrons (J0n)more » and holes (J0p) and the quasi Fermi-level splitting in the absorber, which measures the balance of generation and recombination. Further, we describe the relation of Voc to contact recombination, the asymmetry in electron/hole collection rates at a single contact (contact selectivity), and the asymmetry in collection rates of the same carrier at separate contacts (carrier selectivity). Relative to bare gold, neat spiro-OMeTAD reduces J0n and J0p (their geometric mean (J0nJ0p)0.5 decreases by 104), decreasing contact recombination. Addition of the common dopant Li-TFSI and air increase J0p/J0n by 106 with little effect on (J0nJ0p)0.5, increasing contact hole selectivity. The significant increase in Voc observed by introducing spiro-OMeTAD/Li-TFSI IFLs into the cells studied, however, is due to an increase in the carrier selectivity rather than the contact selectivity or recombination of the spiro-OMeTAD-modified contact. Operando measurements further show voltage-dependent changes in the J0s, demonstrating that spiro-OMeTAD contributes to hysteresis. Broader context: Solar cells operate by photogenerating excess charge carriers in an absorber material and, in competition with recombination, asymmetrically extracting them at so-called carrier-selective contacts, one that ideally collects only electrons and the other, only holes. Particularly in emerging photovoltaics such as perovskites, thin layers of organic semiconductors or related materials are introduced between the absorber and contact to improve power conversion efficiency. In terms of interfacial charge transfer, a prevailing view is that such interfacial layers improve performance by helping block the collection of the undesired carrier, considered a form of recombination. We use a novel platform to study the simultaneous impact of spiro-OMeTAD, a common interfacial layer, on the collection of electrons, the collection of holes, and on the recombination of electrons and holes. We quantitatively demonstrate that spiro-OMeTAD layers indeed passivate the contact toward recombination, but that larger improvements in the open-circuit voltage, a key cell metric, can come not only from this but also from increasing the asymmetry of the collection of electrons in the system. Further, operando measurements show transient changes in the properties of spiro-OMeTAD which suggest that it contributes to hysteresis phenomena commonly observed in perovskite and other solar cells.« less
  3. Semiconducting Bipolar Membranes: Photochemical Salt Pumps

    Not provided.
  4. Exchange current density model for the contact-determined current-voltage behavior of solar cells

    An analytic expression for the current–voltage [J(V)] behavior of a solar cell as limited by equilibrium exchange current densities of both carriers at both contacts is derived. The partial currents at both contacts to a generic semiconductor absorber are assumed to be linearly proportional to the excess carrier concentration at the interface with the contacts (e.g., as with Schottky-like contacts). The assumption that the quasi-Fermi levels in the absorber are approximately flat leads to an algebraic solution for the applied voltage as a function of current, which is inverted to obtain the analytic J(V) curve. The J(V) curve reveals distinctmore » behavior associated with electrons and holes, separately, and allows for the determination of all critical performance parameters. In particular, it demonstrates how the characteristic features of the J(V) curve depend on the relative rate at which a particular carrier (electron or hole) is collected at one contact vs the other, rather than the relative rate of electron vs hole collection at a single contact. Furthermore, the model provides a unified explanation of how majority carrier extraction limitations cause nonideal J(V) behaviors such as S-shaped curves and dark/light crossover (i.e., failure of superposition). The efficacy and limitations of the model when applied to Schottky-type and doped semiconductor contacts are discussed. The work serves as a theoretical guide to scientists studying solar cells that are thought to be primarily limited by their contacts.« less
  5. Extracting electrode space charge limited current: Charge injection into conjugated polyelectrolytes with a semiconductor electrode

    Conjugated polyelectrolytes and related mixed ionic-electronic conductors (MIECs) are being explored for energy applications including solid-state lighting and photovoltaics. Fundamental models of charge injection into MIECs have been primarily developed for MIECs contacted with highly conductive or metal electrodes (MEs), despite many potential applications involving semiconductors. We theoretically and experimentally demonstrate that an appropriate semiconductor electrode (SE), n-type for electron or p-type of hole injection, can limit injection into MIECs. When the SE is the injecting electrode and is under accumulation, there is little difference from a ME. When the SE acts as the extracting electrode, however, injection into themore » MIEC can be limited because a fraction of any applied bias must support charge depletion in the semiconductor rather than charge injection into the MIEC. In a ME/MIEC/SE system, this can lead to significant asymmetry in current-voltage and injected charge-voltage behavior.« less
  6. An improved method for determining carrier densities via drive level capacitance profiling

    In this paper, we demonstrate that an analytic relationship between coefficients in the Taylor expansion of the junction capacitance can be exploited to yield more precise determinations of carrier densities in drive level capacitance profiling (DLCP). Improvements are demonstrated on data generated according to the DLCP theory and in measurements performed on a CuInxGa1–xSe2 device. We argue that the improved DLCP method is especially important for non-uniform devices, which are more susceptible to noise in the capacitance data used in DLCP because they require that the amplitude of the drive level be restricted. Importantly, the analysis does not require themore » collection of any data other than what is typically collected during a DLCP measurement while employing fewer independent parameters than the model that is typically used in DLCP. Finally and thus, we expect that it will be readily adoptable by those who perform DLCP measurements.« less
  7. Defect states in perovskite solar cells associated with hysteresis and performance

    External quantum efficiency and transient photocapacitance (TPC) spectra were obtained for perovskite solar cells with methylammonium lead triiodide perovskite absorbers formed by either dip or vapor conversion. These measurements reveal an extended band of sub-gap states in all of the devices studied. The defect band is best fit by a pair of defects, and the appearance of the defect signal in the transient photocapacitance spectra indicates that at least one of the observed defects is in the perovskite absorber. The cells with the largest density of defect states show the lowest shortcircuit current density and open-circuit voltage for slow, quasi-steady-state,more » current density-voltage sweeps and the largest hysteresis in short-circuit current density for fast sweeps. In conclusion, this suggests that defect states in the perovskite absorber limit steady-state device performance, and that these defects or associated mobile charges play a role in the hysteresis observed in current density-voltage measurements.« less

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