Origins of the open-circuit voltage in ternary organic solar cells and design rules for minimized voltage losses

The power conversion efficiency of ternary organic solar cells (TOSCs), consisting of one host binary blend and one guest component, remains limited by large voltage losses. The fundamental understanding of the open-circuit voltage (V OC) in TOSCs is controversial, limiting rational design of the guest component. In this study, we systematically investigate how the guest component affects the radiative and non-radiative related parts of V OC of a series of TOSCs using the detailed balanced principle. We highlight that the thermal population of charge-transfer and local exciton states provided by the guest binary blend (that is, the guest-component-based binary blend) has a significant influence on the non-radiative voltage losses. Ultimately, we provide two design rules for enhancing the V OC in TOSCs: high emission yield for the guest binary blend and similar charge-transfer-state energies for host/guest binary blends; high miscibility of the guest component with the low gap component in the host binary blend

Loss Mechanisms In Non-Fullerene Organic Solar Cells

Photovoltaics are one of the most important sustainable energy sources in the 21st century. Among photovoltaics, organic solar cells (OSCs) offer many advantages such as ease of processing, lightweight, the potential for flexibility, and tunable properties. Its peculiar nature and complexity present a fascinating charm, attracting many researchers. Thanks to researchers' efforts, the power conversion efficiency (PCE) of OSCs has been boosted from 1% to 19% during the last three decades. Despite the exciting PCE, some problems remain to be solved, for example, the large voltage loss and long-term stability. The aim of this thesis is to understand the fundamental physics of the state-of-the-art OSCs, especially the loss mechanism. Ultimately, properly understanding the mechanisms will sever as the basis of OSCs further improvements and commercialization. This work focuses on the loss mechanisms of OSCs, particularly the open-circuit voltage and the fill factor. The beginning of this thesis introduces basic concepts regarding semiconductors physics and donor-acceptor OSCs. This part explains how a photon is used to generate electricity and the fundamentals of organic electronics. Subsequently, the detailed balance in a solar cell is reviewed, which is the basis of voltage loss analysis. In this part, we see how the input, recombination, and output form a balance. Then, the way to determine the voltage loss is shown, and the latest understandings in reducing the loss are reviewed. The fill factor, as a measure of the quality of a solar cell, is a complex parameter, especially in OSCs.The latter part of this thesis starts from the photophysical processes in an OSC, and then relates intrinsic parameters to the fill factor. The figure of merits has been employed to express the fill factor analytically. In the end, experimental methods and basic principles for the previous analysis are introduced, including Fourier transform infrared spectroscopy, the external quantum efficiency of photovoltaics (EQEPV), spectrograph for electroluminescence or photoluminescence, transient absorption, and time-delayed collection field. Overall, the thesis combined thermal dynamics and charge dynamics to analyze voltage losses and fill factor losses. The author hopes this work can contribute to a better understanding of the loss mechanisms OSCs

Slow Relaxation of Photogenerated Charge Carriers Boosts Open-Circuit Voltage of Organic Solar Cells

Among the parameters determining the efficiency of an organic solar cell, the open-circuit voltage (V-OC) is the one with most room for improvement. Existing models for the description of V-OC assume that photogenerated charge carriers are thermalized. Here, we demonstrate that quasi-equilibrium concepts cannot fully describe V-OC of disordered organic devices. For two representative donor:acceptor blends, it is shown that V-OC is actually 0.1-0.2 V higher than it would be if the system was in thermodynamic equilibrium. Extensive numerical modeling reveals that the excess energy is mainly due to incomplete relaxation in the disorder-broadened density of states. These findings indicate that organic solar cells work as nonequilibrium devices, in which part of the photon excess energy is harvested in the form of an enhanced V-OC.Funding Agencies|Swedish Research Council (project "OPV2.0")Swedish Research Council; European Unions Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grantSKA South Africa [799801]; Carl Zeiss Foundation</p

Thermally Activated Reverse Electron Transfer Limits Carrier Generation Efficiency in PM6:Y6 Non-Fullerene Organic Solar Cells

Transient absorption and time-resolved fluorescence measurements in a wide temperature range are used to investigate the mechanism of charge carrier generation in efficient organic solar cells based on a PM6:Y6 donor-acceptor blend. The generation mechanisms differ significantly under excitation of a donor or acceptor. The investigations reveal a temperature-dependent interplay between the formation of interfacial charge transfer (CT) states and intra-moiety CT states of the acceptor, their separation into free charge carriers and carrier recombination. The efficient charge carrier generation is ensured by the carrier separation over a small energy barrier, which is easily surmountable at room temperature. However, the overall yield of charge carrier generation at room temperature is reduced by the recombination of charge carriers due to the thermally activated back transfer of electrons from the acceptor to the donor via the highest occupied molecular orbit (HOMO) levels, which is enabled by the small energy offset between HOMO levels of the donor and the acceptor

Emerging Approaches in Enhancing the Efficiency and Stability in Non-Fullerene Organic Solar Cells

The past three years have witnessed rapid growth in the field of organic solar cells (OSCs) based on non-fullerene acceptors (NFAs), with intensive efforts being devoted to material development, device engineering, and understanding of device physics. The power conversion efficiency of single-junction OSCs has now reached high values of over 18%. The boost in efficiency results from a combination of promising features in NFA OSCs, including efficient charge generation, good charge transport, and small voltage losses. In addition to efficiency, stability, which is another critical parameter for the commercialization of NFA OSCs, has also been investigated. This review summarizes recent advances in the field, highlights approaches for enhancing the efficiency and stability of NFA OSCs, and discusses possible strategies for further advances of NFA OSCs.Funding Agencies|National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [21704021, 21805288]; European Commission Marie Skodowska-Curie action [843872]; Stiftelsen for Strategisk Forskning through a Future Research Leader program [FFL18-0322]; Swedish Research Council VRSwedish Research Council [2016-06146, 2018-05484, 2018-06048]; Swedish Energy AgencySwedish Energy Agency [43691-1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]</p

Experimentally Validated Hopping-Transport Model for Energetically Disordered Organic Semiconductors

Charge transport in disordered organic semiconductors occurs by hopping of charge carriers between localized sites that are randomly distributed in a strongly energy-dependent density of states. Extracting disorder and hopping parameters from experimental data, such as temperature-dependent current-voltage characteristics, typically relies on parametrized mobility functionals that are integrated in a drift-diffusion solver. Surprisingly, the functional based on the extended Gaussian disorder model (eGDM) is extremely successful at this, despite it being based on the assumption of nearest neighbor hopping (nnH) on a regular lattice. We here propose a variable-range hopping (VRH) model that is integrated in a freeware drift-diffusion solver. The mobility model is calibrated using kinetic Monte Carlo calculations and shows good agreement with the Monte Carlo calculations over the experimentally relevant part of the parameter space. The model is applied to temperature-dependent space-charge-limited current (SCLC) measurements of different systems. In contrast to the eGDM, the VRH model provides a consistent description of both p- and n-type devices. We find a critical ratio of a(NN)/alpha (mean intersite distance:localization radius) of about three, below which hopping to non-nearest neighbors becomes important around room temperature and the eGDM cannot be used for parameter extraction. Typical (Gaussian) disorder values in the range 45-120 meV are found, without any clear correlation with photovoltaic performance, when the same active layer is used in an organic solar cell.Funding Agencies|Vetenskapsradet, project "OPV2.0"; European UnionEuropean Union (EU) [799477 - HyThermEl]</p

Carrier Mobility Dynamics under Actual Working Conditions of Organic Solar Cells

Although organic photovoltaics has made significant progress since its appearance decades ago, the underlying physics of charge transport in working cells is still under debate. Carrier mobility, determining the carrier extraction and recombination, is one of the most important but complex and still poorly understood parameters. Low-energy charge carrier states acting as traps play a particularly important role in carrier transport. Occupation of these states under real operation conditions of solar cells induces additional complexity. In this study, we use several transient methods and numerical modeling to address carrier transport under actual working conditions of bulk heterojunction organic solar cells based on fullerene and nonfullerene acceptors. We show that occupation of low-energy states strongly depends on the blend materials and the effective electric field. We define conditions when such occupation increases carrier mobility, making it less time-dependent on the microsecond time scale, and when its influence is only marginal. We also show that the initial mobility, determined by carrier relaxation within the high-energy part of the distributed density of states, strongly decreases with time independently of the low-energy state population.Funding Agencies|Vetenskapsradet, project "OPV2.0"; Carl Zeiss Foundation</p

Emerging Approaches in Enhancing the Efficiency and Stability in Non-Fullerene Organic Solar Cells

The past three years have witnessed rapid growth in the field of organic solar cells (OSCs) based on non-fullerene acceptors (NFAs), with intensive efforts being devoted to material development, device engineering, and understanding of device physics. The power conversion efficiency of single-junction OSCs has now reached high values of over 18%. The boost in efficiency results from a combination of promising features in NFA OSCs, including efficient charge generation, good charge transport, and small voltage losses. In addition to efficiency, stability, which is another critical parameter for the commercialization of NFA OSCs, has also been investigated. This review summarizes recent advances in the field, highlights approaches for enhancing the efficiency and stability of NFA OSCs, and discusses possible strategies for further advances of NFA OSCs.Funding Agencies|National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [21704021, 21805288]; European Commission Marie Skodowska-Curie action [843872]; Stiftelsen for Strategisk Forskning through a Future Research Leader program [FFL18-0322]; Swedish Research Council VRSwedish Research Council [2016-06146, 2018-05484, 2018-06048]; Swedish Energy AgencySwedish Energy Agency [43691-1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]</p

Temperature-dependent photoluminescence spectra and decay dynamics of MAPbBr3 and MAPbI3 thin films

The steady-state spectra and fluorescence lifetimes are investigated under vacuum for methylammonium lead bromide and iodide (CH3NH3PbBr3 or MAPbBr3, and CH3NH3PbI3 or MAPbI3) thin films by stably controlling the sample temperature in the range of 78 K to 320 K. The transformation of spectrum features and lifetime components are proved to be quite sensitive to the temperatures in accordance with the phase transition of structures. Our work demonstrates that the halide anions I- and Br- lead to remarkable differences on optical characteristics. Due to the distinct behaviors of excitons, electron-hole pairs and free carriers in decay channels, MAPbI3 has much longer lifetime and higher low-temperature fluorescence efficiency than those of MAPbBr3. The findings provide possible choices for certain perovskites under various ambient temperature conditions to display photovoltaic or luminescent advantage