Charge transfer state energy in ternary bulk-heterojuncton polymer-fullerene solar cells

In ternary bulk heterojunction solar cells based on a semiconducting biphenyl-dithienyldiketopyrrolopyrrole copolymer donor and two different fullerene acceptors that distinctly differ in electron affinity, the open-circuit voltage is found to depend in a slightly sublinear fashion on the relative ratio of the two fullerenes in the blend. Similar effects have previously been observed and have been attributed to the formation of an alloyed fullerene phase possessing electronic levels that are the weighted average of the two components. By analyzing the contribution of the charge transfer (CT)-state absorption to the external quantum efficiency of the ternary blend solar cells as a function of composition, we find no evidence for a CT state formed between the polymer and an alloyed fullerene phase. Rather, the results are consistent with the presence of two distinct CT states, one for each polymer–fullerene combination. The two-state CT model does not, however, explain the sublinear behavior of the open-circuit voltage as a function of the blend composition

Origin of Work Function Modification by Ionic and Amine-Based Interface Layers

Work function modification by polyelectrolytes and tertiary aliphatic amines is found to be due to the formation of a net dipole at the electrode interface, induced by interaction with its own image dipole in the electrode. In polyelectrolytes differences in size and side groups between the moving ions lead to differences in approach distance towards the surface. These differences determine magnitude and direction of the resulting dipole. In tertiary aliphatic amines the lone pairs of electrons are anticipated to shift towards their image when close to the interface rather than the nitrogen nuclei, which are sterically hindered by the alkyl side chains. Data supporting this model is from scanning Kelvin probe microscopy, used to determine the work function modification by thin layers of such materials on different substrates. Both reductions and increases in work function by different materials are found to follow a general mechanism. Work function modification is found to only take place when the work function modification layer (WML) is deposited on conductors or semiconductors. On insulators no effect is observed. Additionally, the work function modification is independent of the WML thickness or the substrate work function in the range of 3 to 5 eV. Based on these results charge transfer, doping, and spontaneous dipole orientation are excluded as possible mechanisms. This understanding of the work function modification by polyelectrolytes and amines facilitates design of new air-stable and solution-processable WMLs for organic electronics.Funding Agencies|Dutch program NanoNextNL; Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO); Hyet Solar; Ministry of Education, Culture and Science [024.001.035]; Solliance Organic Photovoltaics Programme</p

Depositing fullerenes in swollen polymer layers via sequential processing of organic solar cells

Polymer solar cells are conventionally processed by coating a multicomponent mixture containing polymer, fullerene, solvent, and cosolvent. The photovoltaic performance strongly depends on the nanoscale morphology of the blend, which is largely determined by the precise nature of the solvent composition and drying conditions. Here, an alternative processing route is investigated in which the two active layer components are deposited sequentially via spin coating or doctor blading. Spin coating the fullerene from o-dichlorobenzene on top of the polymer provides virtually identical morphologies and photovoltaic performance. Using blade coating, the influence of the second-layer solvent for the fullerene derivative is investigated in further detail. Different aromatic solvents are compared regarding swelling of the polymer layer, fullerene solubility, and evaporation rate. It is found that while swelling of the polymer by the second-layer solvent is a necessity for sequential processing, the solubility of the fullerene derivative in this solvent has the strongest influence on solar cell performance. Homogeneous layers in which a sufficient amount of fullerene can infiltrate the polymer film can only be achieved when solvents are used that have a very high solubility for the fullerene and swell the polymer layer.\u3cbr/\u3