Detailed balance theory of excitonic and bulk heterojunction solar cells

A generalized solar cell model for excitonic and classical bipolar solar cells describes the combined transport and interaction of electrons, holes, and excitons in accordance with the principle of detailed balance. Conventional inorganic solar cells, single-phase organic solar cells and bulk heterojunction solar cells, i.e., nanoscale mixtures of two organic materials, are special cases of this model. For high mobilities, the compatibility with the principle of detailed balance ensures that our model reproduces the Shockley-Queisser limit irrespective of how the energy transport is achieved. For less ideal devices distinct differences become visible between devices that are described by linear differential equations and those with nonlinear effects, such as a voltage-dependent collection in bipolar p-i-n-type devices. These differences in current-voltage characteristics are also decisive for the validity of the reciprocity theorem between photovoltaic quantum efficiency and electroluminescent emission. Finally, we discuss the effect of band offset at the heterointerface in a bulk heterojunction cell and the effect of the average distances between these heterointerfaces on the performance of a solar cell in order to show how our detailed balance model includes also these empirically important quantities.