Small molecular weight organic thin-film photodetectors and solar cells

In this review, we discuss the physics underlying the operation of single and multiple heterojunction, vacuum-deposited organic solar cells based on small molecular weight thin films. For single heterojunction cells, we find that the need for direct contact between the deposited electrode and the active organics leads to quenching of excitons. An improved device architecture, the double heterojunction, is shown to confine excitons within the active layers, allowing substantially higher internal efficiencies to be achieved. A full optical and electrical analysis of the double heterostructure architecture leads to optimal cell design as a function of the optical properties and exciton diffusion lengths of the photoactive materials. Combining the double heterostructure with novel light trapping schemes, devices with external efficiencies approaching their internal efficiency are obtained. When applied to an organic photovoltaic cell with a power conversion efficiency of $\text{1.0\%±0.1\%}$ under 1 sun AM1.5 illumination, devices with external power conversion efficiencies of $\text{2.4\%±0.3\%}$ are reported. In addition, we show that by using materials with extended exciton diffusion lengths $L_D,$ highly efficient double heterojunction photovoltaic cells are obtained, even in the absence of a light trapping geometry. Using ${\mathrm{C}}_{60}$ as an acceptor material, double heterostructure external power conversion efficiencies of $\text{3.6\%±0.4\%}$ under 1 sun AM1.5 illumination are obtained. Stacking of single heterojunction devices leads to thin film multiple heterojunction photovoltaic and photodetector structures. Thin bilayer photovoltaic cells can be stacked with ultrathin $\text{(∼5\hspace{0.05em}Å),}$ discontinuous Ag layers between adjacent cells serving as efficient recombination sites for electrons and holes generated in the neighboring cells. Such stacked cells have open circuit voltages that are n times the open circuit voltage of a single cell, where n is the number of cells in the stack. In optimized structures, the short circuit photocurrent remains approximately constant upon stacking thin cells, leading to higher achievable power conversion efficiencies, as confirmed by modelling optical interference effects and exciton migration. A $\text{2.5\%±0.3\%}$ power efficiency under $\text{100\hspace{0.05em}}\mathrm{mW}/{\mathrm{cm}}^2$ AM1.5 illumination conditions is obtained by stacking two $\text{∼1\%}$ efficient devices. Alternatively, when the contact layers between the stacked cells are eliminated, a multilayer structure consisting of alternating films of donor and acceptor-type materials is obtained. Since the thicknesses of the individual layers $\text{(∼5\hspace{0.05em}Å)}$ can be substantially smaller than the exciton diffusion length, nearly 100% of the photogenerated excitons are dissociated, and the resulting free charges are detected. In addition, the ultrathin organic layers facilitate electron and hole transport through the multilayer stack by tunneling. When these devices are operated as photodetectors under applied fields ${\text{>10}}^6 \mathrm{V}/\mathrm{cm},$ the carrier collection efficiency reaches 80%, leading to external quantum efficiencies of $\text{75\%±1\%}$ across the visible spectrum in cells containing the thinnest layers. We find that due to the fast carrier tunneling process, the temporal response of these multilayer detectors is a direct measure of exciton dynamics. Response times of $\text{720±50\hspace{0.05em}}\mathrm{ps}$ are achieved, leading to a 3 dB bandwidth of $\text{430±30\hspace{0.05em}}\mathrm{MHz}.$ A summary of representative results obtained for both polymer and small molecule photovoltaic cells and photodetectors is included in this review. Prospects for further improvements in organic solar cells and photodetectors are considered.