Dynamics of the intermolecular transfer integral in crystalline organic semiconductors

被引:346
作者
Troisi, A [1 ]
Orlandi, G
机构
[1] Univ Warwick, Dept Chem, Coventry CV4 7AL, W Midlands, England
[2] Univ Bologna, Dipartimento Chim G Ciamician, I-40126 Bologna, Italy
关键词
D O I
10.1021/jp055432g
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In organic crystalline semiconductor molecular components are held together by very weak interactions and the transfer integrals between neighboring molecular orbitals are extremely sensitive to small nuclear displacements. We used a mixed quantum chemical and molecular dynamic methodology to assess the effect of nuclear dynamics on the modulation of the transfer integrals between close molecules. We have found that the fluctuations of the transfer integrals are of the same order of magnitude of their average value for pentacene and anthracene. Under these conditions the usual perturbative treatment of the electron-phonon coupling is invalid, the band description of the crystal breaks down and the charge carriers become localized. Organic crystals of pentacene and anthracene, even in the absence of defects, can be regarded as disordered media with respect to their charge transport properties. These results suggest that the dynamic electronic disorder can be the factor limiting the charge mobility in crystalline organic semiconductors.
引用
收藏
页码:4065 / 4070
页数:6
相关论文
共 48 条
[41]   Band structure of the four pentacene polymorphs and effect on the hole mobility at low temperature [J].
Troisi, A ;
Orlandi, G .
JOURNAL OF PHYSICAL CHEMISTRY B, 2005, 109 (05) :1849-1856
[42]   Electronic interactions and thermal disorder in molecular crystals containing cofacial pentacene units [J].
Troisi, A ;
Orlandi, G ;
Anthony, JE .
CHEMISTRY OF MATERIALS, 2005, 17 (20) :5024-5031
[43]   Dynamic nature of the intramolecular electronic coupling mediated by a solvent molecule: A computational study [J].
Troisi, A ;
Ratner, MA ;
Zimmt, MB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (07) :2215-2224
[44]   A rate constant expression for charge transfer through fluctuating bridges [J].
Troisi, A ;
Nitzan, A ;
Ratner, MA .
JOURNAL OF CHEMICAL PHYSICS, 2003, 119 (12) :5782-5788
[45]   Hole migration in DNA: a theoretical analysis of the role of structural fluctuations [J].
Troisi, A ;
Orlandi, G .
JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (08) :2093-2101
[46]   Anderson localization in two-dimensional disordered systems [J].
Unge, M ;
Stafström, S .
SYNTHETIC METALS, 2003, 139 (02) :239-244
[47]   30 nm channel length pentacene transistors [J].
Zhang, YJ ;
Petta, JR ;
Ambily, S ;
Shen, YL ;
Ralph, DC ;
Malliaras, GG .
ADVANCED MATERIALS, 2003, 15 (19) :1632-+
[48]   OPTICAL SPECTROSCOPY OF FIELD-INDUCED CHARGE IN POLY(3-HEXYL THIENYLENE) METAL-INSULATOR-SEMICONDUCTOR STRUCTURES - EVIDENCE FOR POLARONS [J].
ZIEMELIS, KE ;
HUSSAIN, AT ;
BRADLEY, DDC ;
FRIEND, RH ;
RUHE, J ;
WEGNER, G .
PHYSICAL REVIEW LETTERS, 1991, 66 (17) :2231-2234