We review progress in the development of organic–inorganic hybrid photovoltaic materials consisting of a conjugated polymer as an electron donor and a nanocrystalline metal oxide as the electron acceptor. We distinguish two main approaches: (1) where a rigid porous metal oxide structure is filled with polymer and (2) where metal oxide nanoparticles and polymer are co-deposited from solution to form a blend film. In the case of porous structures, performance is limited by the infiltration of polymer into the pores of the metal oxide and control of the nanostructure dimensions. In the case of blends, control of the blend morphology and transport between nanoparticles are limitations. In both cases, further improvements are possible by modifying the metal oxide organic interface to optimise charge transfer, by improving both inter- and intra-particle transport within the metal oxide phase, for example by the use of single crystalline nanorods, and by optimising the choice of electrode materials. Though unlikely to achieve the highest photocurrents, the polymer–metal oxide composites provide a model system to study the effects of interface properties and film morphology on the performance of bulk heterojunction photovoltaic devices.

We focus on the preparation of hybrid polymer/zinc oxide (ZnO) solar cells, in which the metal oxide consists of ZnO columnar structures grown perpendicularly on a flat, dense “backing” layer, as a means to provide a direct and ordered path for photogenerated electrons to the collecting electrode. We used scanning electron microscopy, absorption spectroscopy and photovoltaic device measurements to study the morphology and device performance of the prepared structures. Different solution chemical routes were investigated for the synthesis of the inorganic device components, i.e. the ZnO columnar structures and the “backing” layers, which act as a seed-growth layer for the ZnO rods. The growth of the ZnO rods was dependent on the morphological and structural characteristics of the seed layer and moreover, the seed layer itself was also affected by the synthetic conditions for ZnO rod growth. Different polymers (high hole-mobility MEH-PPV based polymer and P3HT) were compared in these structures and power conversion efficiencies of 0.15 and 0.20% were achieved under 1 Sun illumination, respectively. Results are discussed in terms of the optoelectronic properties of the polymers.

We present a simple model of a molecular photovoltaic device consisting of a two-level system, connected to external contacts by chains of one or more charge transporting orbitals. Electrons may be promoted in the two-level system by photon absorption, and charge transported to the external circuit by electron transfer between neighboring orbitals. Photon absorption and emission are described by a generalized Planck equation and electron transfer is described by nonadiabatic Marcus theory. We find the steady-state current by solving the set of coupled rate equations for electron transfer in the system under illumination as a function of bias applied to the contacts. We calculate monochromatic current-voltage characteristics and power conversion efficiency as a function of the system size, orbital energy levels, and electron transfer rates, and compare with the monochromatic detailed balance limit. Using realistic values of the energy levels and charge-transfer rates, we are able to reproduce a number of commonly observed features in the current-voltage characteristics. These include a “kink” in the current-voltage curve close to open circuit when large interfacial energy steps are present or mobilities are low, and a reduction of the open-circuit voltage and crossing of the light and dark current curves when interfacial recombination is strong. We show that open-circuit voltage is dominated by the acceptor-donor energy gap when recombination is important, and by the optical gap when recombination is low. We confirm previous reports that photovoltaic energy conversion can be achieved by interfacial asymmetry alone and that a potential difference between the electrodes is unnecessary. Improved photovoltaic efficiency of molecular heterojunctions requires ohmic contacts, improved charge-carrier mobilities, and tuning of the electron-transfer rates at the heterojunction. Maximizing the rate of charge separation does not necessarily lead to maximum efficiency.

We report the effects of layer thickness, interface morphology, top contact, and polymer–metal combination on the performance of photovoltaic devices consisting of a fluorene–bithiophene copolymer and nanocrystalline ${\mathrm{TiO}}_2.$ Efficient photoinduced charge transfer is observed in this system, while charge recombination is relatively slow (∼100 μs–10 ms). External quantum efficiencies of 13% and monochromatic power conversion efficiencies of 1.4% at a wavelength of 440 nm are achieved in the best device reported here. The device produced an open-circuit voltage of 0.92 V, short-circuit current density of about 400 μA cm⁻², and a fill factor of 0.44 under simulated air mass 1.5 illumination. We find that the short-circuit current density and the fill factor increase with decreasing polymer thickness. We propose that the performance of the indium tin ${\mathrm{oxide/TiO}}_2\mathrm{/polymer/metal}$ devices is limited by the energy step at the polymer/metal interface and we investigate this situation using an alternative fluorene-based polymer and different top contact metals.