On Voltage, Photovoltage, and Photocurrent in Bulk Heterojunction Organic Solar Cells

The interpretation of voltage, photovoltage, and photocurrent in polymer/fullerene bulk heterojunction (BHJ) solar cells is discussed in terms of fundamental device models and results of capacitance spectroscopy. First we establish the relationship between the applied voltage (which is the difference of Fermi levels) and the variation of electrostatic potential that governs the drift field. We then show the most common distribution of carriers and Fermi levels in the blend layer, supported on experimental results of impedance spectroscopy of P3HT:PCBM solar cells. We arrive at the conclusion that charge separation and charge transportation has very little to do with a built-in electric field between metal contacts, while kinetics plays a major role in photocurrent production. Finally, we discuss the key factors relevant to understand device properties and power conversion efficiencies of the BHJ solar cells: recombination, charge generation, and the current–potential curve, based on the suggested model that emphasizes mobile electrons and holes (that we term quasifree carriers) contributing to the respective Fermi levels

Elucidating Operating Modes of Bulk-Heterojunction Solar Cells from Impedance Spectroscopy Analysis

We discuss the progress and challenges in the application of impedance spectroscopy analysis to determine key processes and parameters in organic bulk-heterojunction solar cells. When carrier transport or outer interface extraction do not severely influence the solar cell performance, a simple method to quantify the open-circuit voltage loss caused by the kinetics of charge carrier recombination is provided, based on the determination of chemical capacitance and recombination resistance. This easily allows distinguishing between energetic and kinetic effects on photovoltage, and establishes a benchmark for the performance comparison of a set of different cells. A brief discussion of impedance analysis in the much less studied case of collection-limited solar cells is introduced

Role of ZnO Electron-Selective Layers in Regular and Inverted Bulk Heterojunction Solar Cells

Here the role of metal oxide (ZnO) electron-selective layers in the operating mechanisms of bulk-heterojunction polymer−fullerene solar cells is addressed. Inverted as well as regular structures containing ZnO layers at the cathode contact have been analyzed using capacitance methods in the dark and impedance spectroscopy under illumination. We systematically observed that the open-circuit voltage <i>V</i>_oc at 1 sun illumination results higher for inverted cells than that achieved by regular structures in Δ<i>V</i>_oc ≈ 30−50 mV. This shift correlates with the displacement of the flat-band potential <i>V</i>_fb extracted from Mott−Schottky capacitance analysis. A coherent picture is provided that states the hole Fermi level of the polymer highest occupied molecular orbital as an energy reference for both <i>V</i>_oc and <i>V</i>_fb. The study connects the position of the hole Fermi level to the <i>p</i>-doping character of the active layer that is influenced by the film morphology through vertical phase segregation

Interplay between Fullerene Surface Coverage and Contact Selectivity of Cathode Interfaces in Organic Solar Cells

Interfaces play a determining role in establishing the degree of carrier selectivity at outer contacts in organic solar cells. Considering that the bulk heterojunction consists of a blend of electron donor and acceptor materials, the specific relative surface coverage at the electrode interfaces has an impact on the carrier selectivity. This work unravels how fullerene surface coverage at cathode contacts lies behind the carrier selectivity of the electrodes. A variety of techniques such as variable-angle spectroscopic ellipsometry and capacitance–voltage measurements have been used to determine the degree of fullerene surface coverage in a set of PCPDTBT-based solar cells processed with different additives. A full screening from highly fullerene-rich to polymer-rich phases attaching the cathode interface has enabled the overall correlation between surface morphology (relative coverage) and device performance (operating parameters). The general validity of the measurements is further discussed in three additional donor/acceptor systems: PCPDTBT, P3HT, PCDTBT, and PTB7 blended with fullerene derivatives. It is demonstrated that a fullerene-rich interface at the cathode is a prerequisite to enhance contact selectivity and consequently power conversion efficiency

Molecular Electronic Coupling Controls Charge Recombination Kinetics in Organic Solar Cells of Low Bandgap Diketopyrrolopyrrole, Carbazole, and Thiophene Polymers

Low-bandgap diketopyrrolopyrrole- and carbazole-based polymer bulk-heterojunction solar cells exhibit much faster charge carrier recombination kinetics than that encountered for less-recombining poly­(3-hexylthiophene). Solar cells comprising these polymers exhibit energy losses caused by carrier recombination of approximately 100 mV, expressed as reduction in open-circuit voltage, and consequently photovoltaic conversion efficiency lowers in more than 20%. The analysis presented here unravels the origin of that energy loss by connecting the limiting mechanism governing recombination dynamics to the electronic coupling occurring at the donor polymer and acceptor fullerene interfaces. Previous approaches correlate carrier transport properties and recombination kinetics by means of Langevin-like mechanisms. However, neither carrier mobility nor polymer ionization energy helps understanding the variation of the recombination coefficient among the studied polymers. In the framework of the charge transfer Marcus theory, it is proposed that recombination time scale is linked with charge transfer molecular mechanisms at the polymer/fullerene interfaces. As expected for efficient organic solar cells, small electronic coupling existing between donor polymers and acceptor fullerene (<i>V</i>_if < 1 meV) and large reorganization energy (λ ≈ 0.7 eV) are encountered. Differences in the electronic coupling among polymer/fullerene blends suffice to explain the slowest recombination exhibited by poly­(3-hexylthiophene)-based solar cells. Our approach reveals how to directly connect photovoltaic parameters as open-circuit voltage to molecular properties of blended materials

How the Charge-Neutrality Level of Interface States Controls Energy Level Alignment in Cathode Contacts of Organic Bulk-Heterojunction Solar Cells

Electronic equilibration at the metal–organic interface, leading to equalization of the Fermi levels, is a key process in organic optoelectronic devices. How the energy levels are set across the interface determines carrier extraction at the contact and also limits the achievable open-circuit voltage under illumination. Here, we report an extensive investigation of the cathode energy equilibration of organic bulk-heterojunction solar cells. We show that the potential to balance the mismatch between the cathode metal and the organic layer Fermi levels is divided into two contributions: spatially extended band bending in the organic bulk and voltage drop at the interface dipole layer caused by a net charge transfer. We scan the operation of the cathode under a varied set of conditions, using metals of different work functions in the range of ∼2 eV, different fullerene acceptors, and several cathode interlayers. The measurements allow us to locate the charge-neutrality level within the interface density of sates and calculate the corresponding dipole layer strength. The dipole layer withstands a large part of the total Fermi level mismatch when the polymer:fullerene blend ratio approaches ∼1:1, producing the practical alignment between the metal Fermi level and the charge-neutrality level. Origin of the interface states is linked with fullerene reduced molecules covering the metal contact. The dipole contribution, and consequently the band bending, is highly sensitive to the nature and amount of fullerene molecules forming the interface density of states. Our analysis provides a detailed picture of the evolution of the <i>potentials</i> in the bulk and the interface of the solar cell when forward <i>voltage</i> is applied or when photogeneration takes place

Operating Mechanisms of Mesoscopic Perovskite Solar Cells through Impedance Spectroscopy and <i>J</i>–<i>V</i> Modeling

The performance of perovskite solar cell (PSC) is highly sensitive to deposition conditions, the substrate, humidity, and the efficiency of solvent extraction. However, the physical mechanism involved in the observed changes of efficiency with different deposition conditions has not been elucidated yet. In this work, PSCs were fabricated by the antisolvent deposition (AD) and recently proposed air-extraction antisolvent (AAD) process. Impedance analysis and <i>J</i>–<i>V</i> curve fitting were used to analyze the photogeneration, charge transportation, recombination, and leakage properties of PSCs. It can be elucidated that the improvement in morphology of perovskite film promoted by AAD method leads to increase in light absorption, reduction in recombination sites, and interstitial defects, thus enhancing the short-circuit current density, open-circuit voltage, and fill factor. This study will open up doors for further improvement of device and help in understanding its physical mechanism and its relation to the deposition methods

Amorphous Iron Oxyhydroxide Nanosheets: Synthesis, Li Storage, and Conversion Reaction Kinetics

We present a facile approach to synthesize amorphous iron oxyhydroxide nanosheet from the surfactant-assisted oxidation of iron sulfide nanosheet. The amorphous iron oxyhydroxide nanosheet is porous and has a high surface area of 223 m² g^–1. The lithium storage properties of the amorphous iron oxyhydroxide are characterized: it is a conversion-reaction electrode material, and it demonstrates superior rate capabilities (e.g., discharge capacities as high as 642 mAh g^–1 are delivered at a current density of 2 C). The impedance spectroscopy analysis identifies a <i>RC</i> series subcircuit originated by the conversion-reaction process. Investigation of the conversion-reaction kinetics through the <i>RC</i> subcircuit time constant reproduces the hysteresis in the discharge/charge voltage profile. Hysteresis is then connected to underlying thermodynamics of the conversion reaction rather than to a kinetic limitation