Abstract
Operation mechanisms and efficiencies of organic electronic devices are principally dominated by the electronic structures of organic semiconductor solids via charge carrier behaviors inside the active materials of the devices; that is the band dispersion for high-mobility crystalline materials being desirable to e.g. organic field effect transistor application. Angle-resolved ultraviolet photoelectron spectroscopy (ARUPS) is one of the most direct and sophisticated techniques to access the valence band of the matters. Several essential physical properties, the effective mass of transport hole and intermolecular transfer integral, in direct relevance to the charge carrier mobility are accessible through accurate analyses of the ARUPS results. In this chapter, we describe technical essences of this methodology and introduce several examples of successful demonstrations of the valence band structures of crystalline organic semiconducting materials.
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Notes
- 1.
Strictly speaking, the E-k set of a photoelectron is slightly modulated during its flight from the sample toward the analyzer due to the contact potential difference. This modulation is generally sufficiently small and thus can be neglected in practice.
- 2.
This approximation is valid only for estimating a necessary condition to fulfill the sufficiently small ΔV s without any sample charging. A ‘charged’ insulating sample has to be modeled as a parallel component of a resistor and capacitor rather than a single resistor if one wants to guess the magnitude of ΔV s for a certain measurement condition.
- 3.
The UPS measurements are much more insensitive to structural imperfectness (such as impurities and lattice defects) than electric characterizations in general. Therefore the mobility estimated from the ARUPS results has to be regarded as that of a perfect crystal; the practical mobility exhibited by an actual sample is more or less reduced with respect to this ideal value. In fact, an experimentally observed hole mobility in a BTQBT single crystal was ~4 cm2V−1 s−1 [29] which is a little smaller than the expected value in Eq. (2.14).
- 4.
For systems with a clear E-K ┴ dispersion, an energy shift in the ARUPS spectra cannot always be attributed to an E-K || dispersion singly but also may be influenced by the K ┴ cosθ component.
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Acknowledgement
YN would like to thank Dr. Shin’ichi Machida, Mr. Akihiro Funakoshi, Mr. Naoki Ogawa, Mr. Yuki Uragami, and Dr. Kaveenga Rasika Koswattage of Chiba University and Prof. Kazuhiko Mase of KEK (under an approval of the PF Program Advisory Committee [2011G161]) for their help during the work presented in the last part of this article. Financial supports from a Grant-in-Aid for Young Scientists B [23750209] from the Japan Society for the Promotion of Science, and G-COE Program of Chiba University (Advanced School for Organic Electronics; G-3) are also gratefully acknowledged.
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Nakayama, Y., Duhm, S., Xin, Q., Kera, S., Ishii, H., Ueno, N. (2015). Ultraviolet Photoelectron Spectroscopy (UPS) I: Band Dispersion Measurements of “Insulating” Organic Single Crystals. In: Ishii, H., Kudo, K., Nakayama, T., Ueno, N. (eds) Electronic Processes in Organic Electronics. Springer Series in Materials Science, vol 209. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55206-2_2
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