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Substitution effect on orientation of organosilicon compounds (CH$$_{3}$$)$$_{3}$$SiX (X = F, Cl, Br, I, NCO) as studied using NEXAFS spectroscopy

NEXAFS分光を用いた有機シリコン化合物[(CH$$_{3}$$)$$_{3}$$SiX (X = F, Cl, Br, I, NCO)]の配向における置換基効果

関口 哲弘; 馬場 祐治; 下山 巖; Nath, K. G.*; Uddin, M. N.*

Sekiguchi, Tetsuhiro; Baba, Yuji; Shimoyama, Iwao; Nath, K. G.*; Uddin, M. N.*

ハロゲン置換,NCO-基置換した有機シリコン化合物について、その凝集試料のSi K吸収端近傍におけるX線吸収スペクトル(NEXAFS)測定とその偏光依存性測定を行い、その電子状態及び分子配向性、特に配向性が発生する機構を明らかにした。凝集表面において分子間の双極子-双極子相互作用により反平行配置を取りやすく、それが系全体の平均配向として現れること、正四面体型分子に近い構造の場合ほど最密充填構造をとり水平配向度が高くなる傾向があるなどのことが明らかとなった。また、スペクトルの蒸着速度依存性測定から動力学的要因によっても分子軸配向が影響を受けることを明らかにした。

The orientation nature of multilayer organosilicon compounds has been investigated by measuring the dependence of the Si K-shell near-edge X-ray absorption fine structures (NEXAFS) on the polarization angle. Two approaches helped to elucidate the orientation mechanism: the substitution effect and the deposition-rate dependence. The orientation angles of Si-X bond axes were obtained for trimethylsilyl halides, (CH$$_{3}$$)$$_{3}$$SiX (X =F Cl Br I NCO, condensed on Cu(111) at a low (82 K) temperature: the angles are 60, 73, 61, 55, and 55 degrees with respect to the surface normal, for X =F, Cl, Br, I, and NCO, respectively. Chloride (X =Cl) produces the most parallel tilt angle. The specific orientation nature of chloride is attributed to its strong dipole moment as well as the regular tetrahedron shape of the molecule. The molecular volumes calculated verify this view. Furthermore, deposition rates are found to greatly influence the growth manner: namely, high deposition rates led to a slightly perpendicular orientation of Si-X bond axis.

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パーセンタイル:92.64

分野:Physics, Condensed Matter

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