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Organic photovoltaics (PV) is an energy-harvesting technology that offers many advantages, such as flexibility, low weight and cost, as well as environmentally benign materials and manufacturing techniques. Despite growth of power conversion efficiencies to around 19 % in the last years, organic PVs still lag behind inorganic PV technologies, mainly due to high losses in open-circuit voltage. Understanding and improving open circuit voltage in organic solar cells is challenging, as it is controlled by the properties of a donor-acceptor interface where the optical excitations are separated into charge carriers. Here, we provide an electrostatic model of a rough donor-acceptor interface and test it experimentally on small molecule PV materials systems. The model provides concise relationships between the open-circuit voltage, photovoltaic gap, charge-transfer state energy, and interfacial morphology. In particular, we show that the electrostatic bias generated across the interface reduces the photovoltaic gap. This negative influence on open-circuit voltage can, however, be circumvented by adjusting the morphology of the donor-acceptor interface.
Organic solar cells, despite their high power conversion efficiencies, suffer from open circuit voltage losses making them less appealing in terms of applications. Here, the authors, supported with experimental data on small molecule photovoltaic cells, relate open circuit voltage to photovoltaic gap, charge-transfer state energy, and donor-acceptor interfacial morphology.
Absorption Tails of Donor
(2017)
In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D A complexes occur at photon energies below the optical gaps of both the donors and the C-60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C-60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D-A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes.
Organic solar cells demonstrate external quantum efficiencies and fill factors approaching those of conventional photovoltaic technologies. However, as compared with the optical gap of the absorber materials, their open-circuit voltage is much lower, largely due to the presence of significant non-radiative recombination. Here, we study a large data set of published and new material combinations and find that non-radiative voltage losses decrease with increasing charge-transfer-state energies. This observation is explained by considering non-radiative charge-transfer-state decay as electron transfer in the Marcus inverted regime, being facilitated by a common skeletal molecular vibrational mode. Our results suggest an intrinsic link between non-radiative voltage losses and electron-vibration coupling, indicating that these losses are unavoidable. Accordingly, the theoretical upper limit for the power conversion efficiency of single-junction organic solar cells would be reduced to about 25.5% and the optimal optical gap increases to (1.45-1.65) eV, that is, (0.2-0.3) eV higher than for technologies with minimized non-radiative voltage losses.
An original set of experimental and modeling tools is used to quantify the yield of each of the physical processes leading to photocurrent generation in organic bulk heterojunction solar cells, enabling evaluation of materials and processing condition beyond the trivial comparison of device performances. Transient absorption spectroscopy, “the” technique to monitor all intermediate states over the entire relevant timescale, is combined with time-delayed collection field experiments, transfer matrix simulations, spectral deconvolution, and parametrization of the charge carrier recombination by a two-pool model, allowing quantification of densities of excitons and charges and extrapolation of their kinetics to device-relevant conditions. Photon absorption, charge transfer, charge separation, and charge extraction are all quantified for two recently developed wide-bandgap donor polymers: poly(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-difluorothiophene) (PBDT[2F]T) and its nonfluorinated counterpart poly(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-thiophene) (PBDT[2H]T) combined with PC71BM in bulk heterojunctions. The product of these yields is shown to agree well with the devices' external quantum efficiency. This methodology elucidates in the specific case studied here the origin of improved photocurrents obtained when using PBDT[2F]T instead of PBDT[2H]T as well as upon using solvent additives. Furthermore, a higher charge transfer (CT)-state energy is shown to lead to significantly lower energy losses (resulting in higher VOC) during charge generation compared to P3HT:PCBM.
We investigate the bias dependence of the hybrid charge transfer state emission at planar heterojunctions between the metal oxide acceptor ZnO and three donor molecules. The electroluminescence peak energy linearly increases with the applied bias, saturating at high fields. Variation of the organic layer thickness and deliberate change of the ZnO conductivity through controlled photodoping allow us to confirm that this bias-induced spectral shift relates to the internal electric field in the organic layer rather than the filling of states at the hybrid interface. We show that existing continuum models overestimate the hole delocalization and propose a simple electrostatic model in which the linear and quadratic Stark effects are explained by the electrostatic interaction of a strongly polarizable molecular cation with its mirror image.
Intermolecular charge-transfer states at the interface between electron donating (D) and accepting (A) materials are crucial for the operation of organic solar cells but can also be exploited for organic light-emitting diodes(1,2). Non-radiative charge-transfer state decay is dominant in state-of-the-art D-A-based organic solar cells and is responsible for large voltage losses and relatively low power-conversion efficiencies as well as electroluminescence external quantum yields in the 0.01-0.0001% range(3,4). In contrast, the electroluminescence external quantum yield reaches up to 16% in D-A-based organic light-emitting diodes(5-7). Here, we show that proper control of charge-transfer state properties allows simultaneous occurrence of a high photovoltaic and emission quantum yield within a single, visible-light-emitting D-A system. This leads to ultralow-emission turn-on voltages as well as significantly reduced voltage losses upon solar illumination. These results unify the description of the electro-optical properties of charge-transfer states in organic optoelectronic devices and foster the use of organic D-A blends in energy conversion applications involving visible and ultraviolet photons(8-11).