L. Raimondo

Dielectric tensor of tetracene single crystals: the effect of anisotropy on polarized absorption and emission spectra

The full UV-visible dielectric tensor and the corresponding directions of the principal axes of triclinic tetracene crystals are reported as deduced either by polarized absorption and ellipsometry measurements or by calculations based on the molecular and crystallographic data. The results allow the attribution of the polarized bands observed in both absorption and photoluminescence emission spectra. In particular, the spectral line shape and polarization of the emission are found to depend on the sample thickness, and the effect is attributed to the modification of the state of polarization of the emitted light during its propagation inside the crystal. Indeed, the directions of polarization of the lowest optical transitions and the directions of the principal axes of the dielectric tensor are demonstrated not to coincide, in contrast to the assumptions typically made in the literature, thus causing the mixed transverse/longitudinal character of light propagation.

Reclassifying exciton-phonon coupling in molecular aggregates: Evidence of strong nonadiabatic coupling in oligothiophene crystals

Exciton-phonon (EP) coupling in molecular aggregates is reexamined in cases where extended intermolecular interactions result in low-energy excitons with high effective masses. The analysis is based on a single intramolecular vibrational mode with frequency omega0 and Huang-Rhys factor lambda2. When the curvature Jc at the exciton band bottom is much smaller than the free-exciton Davydov splitting W, the strength of the EP coupling is determined by comparing the nuclear relaxation energy lambda2omega0 with the curvature. In this way, weak (lambda2omega0<<4piJc), intermediate I (lambda2omega0 approximately 4piJc), and strong I (lambda2omega0>>4piJc) coupling regimes are introduced. The conventional intermediate (lambda2omega0 approximately W) and strong (lambda2omega0>>W) EP coupling regimes originally defined by Simpson and Peterson [J. Chem. Phys. 26, 588 (1957)] are based solely on the Davydov splitting and are referred to here as intermediate II and strong II regimes, respectively. Within the intermediate I and strong I regimes the near degeneracy of the low-energy excitons allows efficient nonadiabatic coupling, resulting in a spectral splitting between the b- and ac-polarized first replicas in the vibronic progression characterizing optical absorption. Such spectral signatures are clearly observed in OT4 thin films and crystals, where splittings for the lowest energy mode with omega0=161 cm(-1) are as large as 30 cm(-1) with a small variation due to sample disorder. Numerical calculations using a multiphonon BO basis set and a Hamiltonian including linear EP coupling yield excellent agreement with experiment.

Measured Davydov splitting in oligothiophene crystals.

The polarized absorption spectra of single crystals of oligothiophenes in a wide spectral range are reported. The experimental procedure is discussed, underlying several details which are relevant to obtain reliable spectra particularly for samples of increasing thickness. On the basis of these considerations, it has been possible to fully detect the transition to the upper Davydov exciton originating from the first molecular state. The position and shape of the main exciton peak in these materials are compared and discussed, taking into consideration the molecular arrangement and the longitudinal contribution which depends on the transition moment orientation. The Davydov splitting values as deduced from the experimental data at room temperature are also reported either for the first vibronic replica or for the electronic transition as a whole. The difference between the purely transverse and the measured Davydov splitting is discussed.

Amplified spontaneous emission in quaterthiophene single crystals

The authors demonstrate amplified spontaneous emission (ASE) from quaterthiophene single crystals and study its behavior at low temperature. The room temperature photoluminescence exhibits line narrowing (spectral width down to 10nm) at 553nm for excitation fluence larger than 1mJcm−2. At low temperature (10K), ASE is observed from two vibronic transitions at 510nm (0-1) and 553nm (0–2), with line narrowing down to 5A, for fluences larger than 100μJcm−2. The stimulated emission cross section is of the order of 10−15cm2, and the ASE is found to be strongly affected by thermally induced dynamic disorder. The emission stability under photopumping is also studied and discussed.

Effect of static and dynamic disorder on exciton mobility in oligothiophenes

The polarized optical absorption spectra of different quaterthiophene single crystals in the energy region of the exciton bands originating from the first molecular transition are reported as measured in the temperatures ranging from 7 to 140 K. The intrinsic higher mobility of the b-polarized 0-0 a(u) exciton both with respect to its replicas and to the a-polarized structures is demonstrated in high quality crystals at the lowest temperatures. The influence of structural disorder on mobility is discussed considering, for the different samples, the measured lineshape and linewidth of the absorption peaks, and the relative lineshift and intensity ratio between the 0-0 a(u) line and its first replica at the lowest temperature. The influence of dynamic disorder is discussed considering the lineshape and linewidth of the measured peaks as a function of temperature for both polarizations in the framework of the exciton-phonon coupling theory.

Polymorphism and Phonon Dynamics of α‐Quaterthiophene

Low-frequency (10-150 cm(-1)) Raman spectra of the low-temperature (LT) and high-temperature (HT) polymorphs of the organic semiconductor alpha-quaterthiophene at 300 and 10 K are reported. Polarized spectra, assisted by quasi-harmonic lattice dynamics (QHLD) calculations, allow characterization of the lattice phonon dynamics and identification of the two phases spectroscopically. The experimental data can be explained by taking into account the coupling between intermolecular (lattice) and low-frequency intramolecular modes. Finally, Raman mapping is used to investigate the phase purity.

Reflectance anisotropy spectroscopy: A probe to explore organic epitaxial growth

Reflectance anisotropy spectroscopy (RAS) is demonstrated to be particularly suitable for studying the deposition of organic epitaxial layers in ultrahigh vacuum by organic molecular beam epitaxy, thanks to its high sensitivity and applicability in situ. In the case of α-quaterthiophene, both homoepitaxy and heteroepitaxy have been monitored, demonstrating the crystallinity of the films up to tens of monolayers and the epitaxial relation to the substrate. In both cases, optical RAS data are compared to the results of ex situ characterization of the same samples by atomic force microscopy.

Optical transverse excitation in quaterthiophene crystals by ultraviolet-visible internal and attenuated total reflection

We report internal and attenuated total reflection of light at the interface between glass and a quaterthiophene crystal in the spectral region of the electronic transitions. The bands corresponding to the absorption of the a(u) and b(u) Frenkel exciton states are detected for different polarization of the incident light. In particular, the wave-normal vector being almost perpendicular to the b(u) transition dipole moment allows its transverse component to be accessed, whose excitation in conventional external reflection or transmission spectroscopies is forbidden.

Patterned Growth of Crystalline Organic Heterostructures

Organic droplet epitaxy is presented as a method for growing nanopatterned crystalline heterostructures, thanks to the transport of molecules of an amorphous first-layer on top of a crystalline second-layer, where they form an epitaxial interface. Such heterostructures may be transferred to any substrates, raising particular interest for applications (e.g., for organic photovoltaics), where crystallinity and nanopatterning constitute well recognized advantages.

Pseudomorphic growth of organic semiconductor thin films driven by incommensurate epitaxy

A stable pseudomorphic phase of α-quaterthiophene, a well known organic semiconductor, is obtained by growing films with organic molecular beam epitaxy (OMBE) on a single crystal of another organic semiconductor, namely, tetracene. The structural characteristics of the new phase are investigated by monitoring in situ the OMBE process by reflectance anisotropy spectroscopy; thus assessing that incommensurate epitaxy is in this case, the driving force for tuning the molecular packing in organic molecular films and in turn, their solid state properties.