The status of understanding of the operation of bulk heterojunction (BHJ) solar cells is reviewed. Because the carrier photoexcitation recombination lengths are typically 10 nm in these disordered materials, the length scale for self-assembly must be of order 10–20 nm. Experiments have verified the existence of the BHJ nanostructure, but the morphology remains complex and a limiting factor. Three steps are required for generation of electrical power: i) absorption of photons from the sun; ii) photoinduced charge separation and the generation of mobile carriers; iii) collection of electrons and holes at opposite electrodes. The ultrafast charge transfer process arises from fundamental quantum uncertainty; mobile carriers are directly generated (electrons in the acceptor domains and holes in the donor domains) by the ultrafast charge transfer (≈70%) with ≈30% generated by exciton diffusion to a charge separating heterojunction. Sweep-out of the mobile carriers by the internal field prior to recombination is essential for high performance. Bimolecular recombination dominates in materials where the donor and acceptor phases are pure. Impurities degrade performance by introducing Shockly–Read–Hall decay. The review concludes with a summary of the problems to be solved to achieve the predicted power conversion efficiencies of >20% for a single cell.

25th anniversary article: Bulk heterojunction solar cells: understanding the mechanism of operation.

Organic electronics are broadly anticipated to impact the development of flexible thin-film device technologies. Among these, solution-processable π-conjugated polymers and small molecules are proving particularly promising in field-effect transistors and bulk heterojunction solar cells. This Perspective analyzes some of the most exciting strategies recently suggested in the design and structural organization of π-functional materials for transistor and solar cell applications. Emphasis is placed on the interplay between molecular structure, self-assembling properties, nanoscale and mesoscale ordering, and device efficiency parameters. A critical look at the various approaches used to optimize both materials and device performance is provided to assist in the identification of new directions and further advances.

Molecular design and ordering effects in π-functional materials for transistor and solar cell applications.

The bulk-heterojunction blend of an electron donor and an electron acceptor material is the key component in a solution-processed organic photovoltaic device. In the past decades, a p-type conjugated polymer and an n-type fullerene derivative have been the most commonly used electron donor and electron acceptor, respectively. While most advances of the device performance come from the design of new polymer donors, fullerene derivatives have almost been exclusively used as electron acceptors in organic photovoltaics. Recently, nonfullerene acceptor materials, particularly small molecules and oligomers, have emerged as a promising alternative to replace fullerene derivatives. Compared to fullerenes, these new acceptors are generally synthesized from diversified, low-cost routes based on building block materials with extraordinary chemical, thermal, and photostability. The facile functionalization of these molecules affords excellent tunability to their optoelectronic and electrochemical properties. Within t...

Nonfullerene Acceptor Molecules for Bulk Heterojunction Organic Solar Cells

Bulk Heterojunction Solar Cells: Morphology and Performance Relationships

The authors would like to thank M. Chabinyc, H. Ade, B. Collins, R. Noriega, K. Vandewal, and D. Duong for fruitful discussions in the preparation of this review. Stanford Synchrotron Radiation Lightsource (SSRL) is a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. This publication was partially supported by the Center for Advanced Molecular Photovoltaics (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST).

Quantitative determination of organic semiconductor microstructure from the molecular to device scale.

Developing a better understanding of the evolution of morphology in plastic solar cells is the key to designing new materials and structures that achieve photoconversion efficiencies greater than 10% In the most extensively characterized system, the poly(3-hexyl thiophene) (P3HT):[6,6]-phenyl-C61-butyric-acid-methyl-ester (PCBM) bulk heterojunction, the origins and evolution of the blend morphology during processes such as thermal annealing are not well understood In this work, we use a model system, a bilayer of P3HT and PCBM, to develop a more complete understanding of the miscibility and diffusion of PCBM within P3HT during thermal annealing We find that PCBM aggregates and/or molecular species are miscible and mobile in disordered P3HT, without disrupting the ordered lamellar stacking of P3HT chains The fast diffusion of PCBM into the amorphous regions of P3HT suggests the favorability of mixing in this system, opposing the belief that phase-pure domains form in BHJs due to immiscibility of these two components

https://onlinelibrary.wiley.com/doi/pdf/10.1002/aenm.201000023

Interdiffusion of PCBM and P3HT Reveals Miscibility in a Photovoltaically Active Blend

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/aenm.201190008

Gordon Smith

Papers

Interdiffusion of PCBM and P3HT Reveals Miscibility in a Photovoltaically Active Blend

Correction: Interdiffusion of PCBM and P3HT Reveals Miscibility in a Photovoltaically Active Blend (Adv. Energy Mater. 2/2011)

Plastic Solar Cells: Interdiffusion of PCBM and P3HT Reveals Miscibility in a Photovoltaically Active Blend (Adv. Energy Mater. 1/2011)