title: Comprehensive Understanding of Structure-Controlling Factors of a Zinc Tetraphenylporphyrin Thin Film Using pMAIRS and GIXD Techniques.
abstract: The performance of an organic electronic device is significantly influenced by the anisotropic molecular structure in the film, which has long been difficult to predict especially for a solution process. In the present study, a zinc tetraphenylporphyrin (ZnTPP) thin film prepared by a solution process was chosen to comprehensively explore the molecular-arrangement mechanism as a function of representative film-preparation parameters: solvent, film-preparation technique, and thermal annealing. The anisotropic structure was first analyzed by using a combination of infrared p-polarized multiple-angle incidence resolution spectrometry (pMAIRS) and grazing incidence X-ray diffraction (GIXD), which readily revealed the molecular orientation and crystal structure, respectively. As a result, the real dominant factor was found to be the evaporation time of the solvent that determines the initial two different molecular arrangements, types-I and -II, while the thermal annealing was found to play an additional role of improving the molecular order. The correlation between the molecular orientation and the crystal structure was also revealed through the individual orientation analysis of the porphyrin and phenyl rings.
authors.affiliation: Laboratory of Solution and Interface Chemistry, Division of Environmental Chemistry, Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Miyako
authors.initials: M
authors.lastname: Hada
authors.affiliation: Laboratory of Solution and Interface Chemistry, Division of Environmental Chemistry, Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Nobutaka
authors.initials: N
authors.lastname: Shioya
authors.affiliation: Laboratory of Solution and Interface Chemistry, Division of Environmental Chemistry, Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Takafumi
authors.initials: T
authors.lastname: Shimoaka
authors.affiliation: Department of Chemistry, Graduate school of Science, Kobe University, 1-1 Rokko-dai, Nada-ku, Kobe, Hyogo, 657-8501, Japan.
authors.forename: Kazuo
authors.initials: K
authors.lastname: Eda
authors.affiliation: Department of Chemistry, Division of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo, 192-0397, Japan.
authors.forename: Masahiko
authors.initials: M
authors.lastname: Hada
authors.affiliation: Laboratory of Solution and Interface Chemistry, Division of Environmental Chemistry, Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan. htakeshi@scl.kyoto-u.ac.jp.
authors.forename: Takeshi
authors.identifier: http://orcid.org/0000-0001-5574-9869
authors.initials: T
authors.lastname: Hasegawa
keywords: X-ray diffraction; molecular orientation; porphyrinoids; surface analysis; thin films