Researchers at the Georgia Institute of Technology and colleagues from three other institutions, have developed a technique that provides a new way of inducing p-type electrical doping in organic semiconductor films. The process involves briefly immersing the films in a solution at room temperature, and would replace a more complex technique that requires vacuum processing.
The researchers said that the simple solution-based electrical doping technique could help reduce the cost of polymer solar cells and organic electronic devices, potentially expanding the applications for these technologies. By enabling production of efficient single-layer solar cells, the new process could help move organic photovoltaics into a new generation of wearable devices and enable small-scale distributed power generation.
The technique consists of immersing thin films of organic semiconductors and their blends in polyoxometalate (PMA and PTA) solutions in nitromethane for a brief time—on the order of minutes. The diffusion of the dopant molecules into the films during immersion leads to efficient p-type electrical doping over a limited depth of 10 to 20 nm from the surface of the film.
The p-doped regions show increased electrical conductivity and high work function, reduced solubility in the processing solvent, and improved photo-oxidation stability in air.
This new method provides a simpler alternative to air-sensitive molybdenum oxide layers used in the most efficient polymer solar cells that are generally processed using expensive vacuum equipment. When applied to polymer solar cells, the new doping method provided efficient hole collection.
For the first time, single-layer polymer solar cells were demonstrated by combining this new method with spontaneous vertical phase separation of amine-containing polymers that leads to efficient electron collection at the opposing electrode. The geometry of these new devices is unique as the functions of hole and electron collection are built into the light-absorbing active layer, resulting in the simplest single-layer geometry with few interfaces.
Organic solar cells have been studied in many academic and industrial laboratories for several decades, and have experienced a continuous and steady improvement in their power conversion efficiency with laboratory values reaching 13 percent - compared to around 20 percent for commercial silicon-based cells. Though polymer-based cells are currently less efficient, they require less energy to produce than silicon cells and can be more easily recycled at the end of their lifetime.
Source: Georgia Tech's Center for Organic Photonics and Electronics
Bernard Kippelen, director of Georgia Tech's Center for Organic Photonics and Electronics and a professor in the School of Electrical and Computer Engineering, said, "Our hope is that this will be a game-changer for organic photovoltaics by further simplifying the process for fabricating polymer-based solar cells." Bernard added, "We believe this technique is likely to impact many other device platforms in areas such as organic printed electronics, sensors, photodetectors and light-emitting diodes."
Canek Fuentes-Hernandez, a senior research scientist in Kippelen's research group, said, "The realization of single-layer photovoltaics with our approach enables both electrodes in the device to be made out of low-cost conductive materials." Canek added, "This offers a dramatic simplification of a device geometry, and it improves the photo-oxidation stability of the donor polymer. Although lifetime and cost analysis studies are needed to assess the full impact of these innovations, they are certainly very exciting developments on the road to transform organic photovoltaics into a commercial technology."
Felipe Larrain, a Ph.D. student in Kippelen's lab, said, "By simplifying the production of organic solar cells, the new processing technique could allow fabrication of solar cells in areas of Africa and Latin America that lack capital-intensive manufacturing capabilities." Felipe added, "Our goal is to further simplify the fabrication of organic solar cells to the point at which every material required to fabricate them may be included in a single kit that is offered to the public." Filipe concluded "The solar cell product may be different if you are able to provide people with a solution that would allow them to make their own solar cells. It could one day enable people to power themselves and be independent of the grid."
Vladimir Kolesov, a Ph.D. researcher and the paper's lead author, said, "Being able to process solar cells entirely at room temperature using this simple solution-based technique could pave the way for a scalable and vacuum-free method of device fabrication, while significantly reducing the time and cost associated with it."
Wen-Fang Chou, Ph.D. researcher said, "Beyond solar cells, the doping technique could be more broadly used in other areas of organic electronics." Wen-Feng added, "With its simplicity, this is truly a promising technology offering adjustable conductivity of semiconductors that could be applied to various organic electronics, and could have huge impact on the industry for mass production."
Sponsored by the Office of Naval Research, the work was reported December 5 in the journal Nature Materials. The research also involved scientists from the University of California at Santa Barbara, Kyushu University in Japan, and the Eindhoven University of Technology in The Netherlands.
Solution-based electrical doping of semiconducting polymer films over a limited depth
Vladimir A. Kolesov | Canek Fuentes-Hernandez | Wen-Fang Chou | Naoya Aizawa | Felipe A. Larrain | Ming Wang, Alberto Perrotta | Sangmoo Choi | Samuel Graham | Guillermo C. Bazan | Thuc-Quyen Nguyen | Seth R. Marder | Bernard Kippelen
Nature Materials (2016) | doi:10.1038/nmat4818
Received 23 May 2016 | Accepted 02 November 2016 | Published online 05 December 2016
Abstract
Solution-based electrical doping protocols may allow more versatility in the design of organic electronic devices; yet, controlling the diffusion of dopants in organic semiconductors and their stability has proven challenging. Here we present a solution-based approach for electrical p-doping of films of donor conjugated organic semiconductors and their blends with acceptors over a limited depth with a decay constant of 10–20 nm by post-process immersion into a polyoxometalate solution (phosphomolybdic acid, PMA) in nitromethane. PMA-doped films show increased electrical conductivity and work function, reduced solubility in the processing solvent, and improved photo-oxidative stability in air. This approach is applicable to a variety of organic semiconductors used in photovoltaics and field-effect transistors. PMA doping over a limited depth of bulk heterojunction polymeric films, in which amine-containing polymers were mixed in the solution used for film formation, enables single-layer organic photovoltaic devices, processed at room temperature, with power conversion efficiencies up to 5.9 ± 0.2% and stable performance on shelf-lifetime studies at 60 °C for at least 280 h.