Harunobu Koike

Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies

Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes.

Direct observation of energy band development in a one-dimensional biradical molecular chain by ultraviolet photoemission spectroscopy

We directly observed development of an energy band in a one-dimensional biradical molecular chain, which is constructed by exploiting the covalency between organic biradical molecules of a diphenyl derivative of s-indacenodiphenalene (Ph2-IDPL). The morphology and crystallinity of the Ph2-IDPL films were controlled by varying film growth conditions. Ultraviolet photoemission spectroscopy revealed the process of energy band development in the biradical molecular chain, clearly showing that the dispersion width of the π-band was extremely broad, exceeding 1 eV.

Improvement of properties of an ambipolar organic field-effect transistor by using a singlet biradicaloid film

We have improved the properties of ambipolar organic field-effect transistors by chemically treating the source and drain electrodes with a vacuum-deposited biradicaloid film. Biradicaloid was a diphenyl derivative of s-indacenodiphenalene (Ph2-IDPL). An alkane thiol self-assembled monolayer (SAM) was used as an insulator buffer layer at the Ph2-IDPL/electrode interface to prevent off-current. We confirmed the transport level alignment at the Ph2-IDPL/SAM/electrode interface by ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. Although Ph2-IDPL transistors containing the SAM showed a higher on/off ratio or mobility than a previously reported device without the buffer layer, there was a trade-off between on/off ratio and mobility. Our results suggest that biradical molecules are promising candidates for use in low-power inverters.