Electronic properties of oligoacenes from first principles

We present the electronic band structures and dielectric tensors for a series of crystalline linear oligoacenes—i.e., naphthalene, anthracene, tetracene, and pentacene—calculated within the density functional framework. The band dispersions, the effective charge carrier masses, and the optical response are discussed as a function of the oligomer length compared to previously reported calculations. The total band dispersions of the two topmost valence and lowest conduction bands are between 0.14 and 0.52 eV, which, however, are strongly anisotropic. Regarding the charge transport properties, the band dispersions are large enough for bandlike transport only along crystalline directions within the herringbone plane. Except for naphthalene, the conduction bands are more dispersive than the valence bands. This indicates that the electron transport is favored compared to hole migration. The revised stable pentacene single-crystal structure exhibits the largest conduction-band dispersions among the series. Consequently the effective electron masses in pentacene are only 0.8m0, whereas the hole masses are in the order of 1.3m0. The electronic and optical gaps and thus the onset of the optical response decrease almost linearly, when going from naphthalene to pentacene.

[1]  Claudia Ambrosch-Draxl,et al.  Oligoacene exciton binding energies: Their dependence on molecular size , 2005 .

[2]  Claudia Ambrosch-Draxl,et al.  Lowest optical excitations in molecular crystals: bound excitons versus free electron-hole pairs in anthracene. , 2004, Physical review letters.

[3]  Georg Kresse,et al.  Theory of polaron bandwidth narrowing in organic molecular crystals , 2004 .

[4]  Pa Peter Bobbert,et al.  Anisotropy effects in phonon-assisted charge-carrier transport in organic molecular crystals , 2004 .

[5]  C. Ambrosch-Draxl,et al.  Electronic, optical, and structural properties of oligophenylene molecular crystals under high pressure: An ab initio investigation , 2003 .

[6]  C. Ambrosch-Draxl,et al.  Ab initio study of anthracene under high pressure , 2003 .

[7]  Steven G. Louie,et al.  Ab initio calculation of the electronic and optical properties of solid pentacene , 2003 .

[8]  N. Karl,et al.  Charge carrier transport in organic semiconductors , 2003 .

[9]  Yuan-Chung Cheng,et al.  Three-dimensional band structure and bandlike mobility in oligoacene single crystals: A theoretical investigation , 2003 .

[10]  G. Wijs,et al.  Anisotropy of the mobility of pentacene from frustration , 2003, cond-mat/0301078.

[11]  Lin H. Yang,et al.  Structural and electronic properties of pentacene molecule and molecular pentacene solid , 2002, cond-mat/0211420.

[12]  C. C. Mattheus,et al.  Identification of polymorphs of pentacene , 2002, cond-mat/0210228.

[13]  Claudia Ambrosch-Draxl,et al.  Suppression of electron-hole correlations in 3D polymer materials. , 2002, Physical review letters.

[14]  J. P. Calbert,et al.  Organic semiconductors: A theoretical characterization of the basic parameters governing charge transport , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[15]  G. Bussi,et al.  Solid state effects on exciton states and optical properties of PPV. , 2002, Physical review letters.

[16]  Z. Rang,et al.  Hydrostatic-pressure dependence of the photoconductivity of single-crystal pentacene and tetracene , 2001 .

[17]  C. C. Mattheus,et al.  Polymorphism in pentacene. , 2001, Acta crystallographica. Section C, Crystal structure communications.

[18]  Nicola Cioffi,et al.  Organic thin film transistors: from active materials to novel applications , 2001 .

[19]  R. Haddon,et al.  Enhanced Physical Properties in a Pentacene Polymorph. , 2001, Angewandte Chemie.

[20]  N. Karl,et al.  Electron and Hole Mobilities in High Purity Anthracene Single Crystals , 2001 .

[21]  Debra J. Mascaro,et al.  Organic thin-film transistors: A review of recent advances , 2001, IBM J. Res. Dev..

[22]  David J. Singh,et al.  An alternative way of linearizing the augmented-plane-wave method , 2000 .

[23]  K. Peter C. Vollhardt,et al.  On the Nature of Nonplanarity in the [N]Phenylenes , 1999 .

[24]  Dept. of Physics,et al.  Ab initio calculation of the electronic and optical excitations in polythiophene: Effects of intra- and interchain screening , 1999, cond-mat/9909412.

[25]  C. Ambrosch-Draxl,et al.  Density-functional study for the oligomers of poly(para-phenylene): Band structures and dielectric tensors , 1999 .

[26]  C. Dimitrakopoulos,et al.  Low-voltage organic transistors on plastic comprising high-dielectric constant gate insulators , 1999, Science.

[27]  Thomas N. Jackson,et al.  Temperature-independent transport in high-mobility pentacene transistors , 1998 .

[28]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[29]  Christos D. Dimitrakopoulos,et al.  Molecular beam deposited thin films of pentacene for organic field effect transistor applications , 1996 .

[30]  P. Vogl,et al.  Optical absorbance of oriented thin films , 1996 .

[31]  Blöchl,et al.  Improved tetrahedron method for Brillouin-zone integrations. , 1994, Physical review. B, Condensed matter.

[32]  M. Schlüter,et al.  Self-energy operators and exchange-correlation potentials in semiconductors. , 1988, Physical review. B, Condensed matter.

[33]  E. Morikawa,et al.  Two-color pulsed photoconductivity study of naphthalene single crystal: photoionization of singlet exciton , 1986 .

[34]  H. Bässler,et al.  Charge-transfer transitions in crystalline anthracene and their role in photoconductivity , 1983 .

[35]  H. Bässler,et al.  Charge transfer transitions in solid tetracene and pentacene studied by electroabsorption , 1981 .

[36]  E. A. Silinsh,et al.  Organic Molecular Crystals , 1980 .

[37]  A. Belkind,et al.  Energy levels of polyacene crystals , 1974 .

[38]  H. Baessler,et al.  Bandgap-Determination from Autoionization Data in Molecular Crystals , 1973 .

[39]  H. Baessler,et al.  Hot Carrier Injection into Molecular Crystals and Its Relevance to the Field Dependence of Photocurrents , 1972 .

[40]  C. Braun,et al.  Intrinsic Photoconductivity in Naphthalene Single Crystals , 1970 .

[41]  M. Pope,et al.  Low‐Lying Valence Band States and Intrinsic Photoconductivity in Crystalline Anthracene and Tetracene , 1969 .

[42]  S. Rice,et al.  On the Electronic States of Crystalline Naphthalene , 1965 .

[43]  R. Mason.  The crystallography of anthracene at 95°K and 290°K , 1964 .

[44]  R. B. Campbell,et al.  The crystal structure of hexacene, and a revision of the crystallographic data for tetracene , 1962 .

[45]  R. B. Campbell,et al.  The crystal and molecular structure of pentacene , 1961 .

[46]  J. Robertson,et al.  The crystal and molecular structure of tetracene , 1961 .

[47]  H. Ehrenreich,et al.  Self-Consistent Field Approach to the Many-Electron Problem , 1959 .

[48]  D. Cruickshank,et al.  A detailed refinement of the crystal and molecular structure of naphthalene , 1957 .