Broadband three-photon absorption spectra of platinum acetylide complexes

We investigate the three-photon absorption spectra of four platinum acetylides complexes employing femtosecond pulses. We observed strong three-photon absorption cross-section in the near-infrared region (from 850 nm to 1200 nm). The three-photon absorption (3PA) spectra present resonance enhancement effect as two photons of the excitation wavelength approach the lower two-photon allowed states of the molecules as well as a 3PA allowed band around 1180 nm. The 3PA cross-section spectra were interpreted using the sum-over-essential-states approach, considering a three-energy-level diagram.FAPESPCNPqCAPESAFOSR (FA9550-07-1-0374

Broadband three-photon absorption spectra of platinum acetylide complexes

We investigate the three-photon absorption spectra of four platinum acetylides complexes employing femtosecond pulses. We observed strong three-photon absorption cross-section in the near-infrared region (from 850 nm to 1200 nm). The three-photon absorption (3PA) spectra present resonance enhancement effect as two photons of the excitation wavelength approach the lower two-photon allowed states of the molecules as well as a 3PA allowed band around 1180 nm. The 3PA cross-section spectra were interpreted using the sum-over-essential-states approach, considering a three-energy-level diagram.FAPESPCNPqCAPESAFOSR (FA9550-07-1-0374

Nonlinear optical properties of organic and organometallic compounds

Nos últimos anos, a busca por materiais com altas não linearidades ópticas tem crescido rapidamente devido as suas potencias aplicações em diversas áreas das ciências, que vão de biologia até fotônica. O processo de absorção de dois fótons, por exemplo, têm sido usado em limitação óptica, micro-fabricação tridimensional, armazenamento óptico e microscopia por fluorescência. Neste trabalho, investigamos o processo de absorção de dois fótons em moléculas orgânicas e organometálicas, buscando colaborar com os esforços que vêm sendo feitos para aprofundar a compreensão dos aspectos envolvidos na absorção não linear. Os espectros de absorção de dois fótons de derivados de perilenos tetracarboxílicos, derivados de fenil-bifenilamina e complexos acetilados de platina foram determinados através da técnica de Varredura Z com pulsos ultracurtos. Para os derivados de perilenos, utilizando a técnica de Varredura Z com luz branca, observamos sutis estruturas no espectro não linear, as quais estão relacionadas a estados permitidos por dois fótons na região do ultra-violeta. A existência de tais estados foi confirmada através de cálculos usando teoria do funcional da densidade. O espectro de absorção de dois fótons para os complexos acetilados de platina apresentam bandas em torno de 600 nm, com seções de choque relativamente altas, da ordem de 640 GM. A ampla janela de transparência desses compostos na região do visível os torna interessantes candidatos para dispositivos de limitação óptica assistida por dois fótons. Por fim, as amostras da família fenil-bifenilamina mostraram uma combinação entre os efeitos não lineares do grupo fenil-bifenilamina e do grupo azoaromático, a qual pode ser explorada em dispositivos de armazenamento óptico tri-dimensional.In the last few years, the design and characterization of novel materials exhibiting high optical nonlinearities is the subject of a fast-growing interest because of their potential application in various fields, from biology to photonics. Two-photon absorption processes, for example, have been used for optical limiting, three-dimensional microfabrication, optical data storage and fluorescence imaging. In this work we investigate the two-photon absorption in organic and organometallic molecules, aiming at the understanding of aspects related to the nonlinear absorption. The two-photon absorption spectra of perylene derivatives, phenyl-diphenylamine derivatives and Platinum Acetylide Complexes were measured using the Z-scan technique with ultrashort pulses. For perylene derivatives, using the white-light continuum Z-scan, we were able to observe subtle structures in nonlinear spectra, which are related to two-photon allowed states in the UV region. Such transitions were confirmed using density functional theory. The two-photon absorption spectrum of Pt-acetylene complexes revealed bands around 600 nm, with relatively high two-photon absorption cross-section in the order of 1000 GM. The broad transparence windows exhibited by these compounds in the visible make them promising candidates for optical limiting devices assisted by two-photon absorption. Finally, the phenyl-biphenylamine samples exhibited a combination between effects from the phenyl-biphenylamine group and the azoaromatic groups, which can be explored in tri-dimensional optical storage devices

Influência da espessura nas propriedades de absorção e emissão e na morfologia de filmes automontados de poli(p-fenileno vinileno)

In this report, we studied the thickness effect on the optical and morphological properties of self-assembled (SA) poly(p-phenylenevinylene) (PPV) films, wich were processed with 5 and 75 layers from a PPV precursor polymer and dodecylbenzenesulfonate, and then, thermally converted at 230 °C. The increase of the film thickness yielded more intense peaks in the vibrational spectral range. The electron-phonon coupling was quantified by the Huang - Rhys factor, that shows the effects on the polymer chain mobility in the interface substrate/polymer. A strong emission anisotropy r=0.57 was observed for the film with 5 layers of thickness decreasing to 0.34 for the film with 75 layers. Finally, the surface topology of the films was measured using Atomic Force Microscopy

Influência da espessura nas propriedades de absorção e emissão e na morfologia de filmes automontados de poli(p-fenileno vinileno

In this report, we studied the thickness effect on the optical and morphological properties of self-assembled (SA) poly(p-phenylenevinylene) (PPV) films, wich were processed with 5 and 75 layers from a PPV precursor polymer and dodecylbenzenesulfonate, and then, thermally converted at 230 degreesC. The increase of the film thickness yielded more intense peaks in the vibrational spectral range. The electron-phonon coupling was quantified by the Huang - Rhys factor, that shows the effects on the polymer chain mobility in the interface substrate/polymer. A strong emission anisotropy r=0.57 was observed for the film with 5 layers of thickness decreasing to 0.34 for the film with 75 layers. Finally, the surface topology of the films was measured using Atomic Force Microscopy

Thickness and Annealing Temperature Effects on the Optical Properties and Surface Morphology of Layer-by-Layer Poly(p-phenyline vinylene) plus Dodecylbenzenesulfonate Films

The fabrication of controlled molecular architectures is essential for organic devices, as is the case of emission of polarized light for the information industry. In this study, we show that optimized conditions can be established to allow layer-by-layer (LbL) films of poly(p-phenylene vinylene) (PPV)+dodecylbenzenesulfonate (DBS) to be obtained with anisotropic properties. Films with five layers and converted at 110 degrees C had a dichroic ratio delta = 2.3 and order parameter r = 34%, as indicated in optical spectroscopy and emission ellipsometry data. This anisotropy was decreased with the number of layers deposited, with delta = 1.0 for a 75-layer LbL PPV + DBS film. The analysis with atomic force microscopy showed the formation of polymer clusters in a random growth process with the normalized height distribution being represented by a Gaussian function. In spite of this randomness in film growth, the self-covariance function pointed to a correlation between clusters, especially for thick films. In summary, the LbL method may be exploited to obtain both anisotropic films with polarized emission and regular, nanostructured surfaces. (c) 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 206-213, 2011Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)CAPESFAPEMIGFundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG)CNPqConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)FAPESPINEO (Brazil)INEO (Brazil

Substrate/semiconductor interface effects on the emission efficiency of luminescent polymers

The importance of interface effects for organic devices has long been recognized, but getting detailed knowledge of the extent of such effects remains a major challenge because of the difficulty in distinguishing from bulk effects. This paper addresses the interface effects on the emission efficiency of poly(p-phenylene vinylene) (PPV), by producing layer-by-layer (LBL) films of PPV alternated with dodecylbenzenesulfonate. Films with thickness varying from similar to 15 to 225 nm had the structural defects controlled empirically by converting the films at two temperatures, 110 and 230 degrees C, while the optical properties were characterized by using optical absorption, photoluminescence (PL), and photoluminescence excitation spectra. Blueshifts in the absorption and PL spectra for LBL films with less than 25 bilayers (<40-50 nm) pointed to a larger number of PPV segments with low conjugation degree, regardless of the conversion temperature. For these thin films, the mean free-path for diffusion of photoexcited carriers decreased, and energy transfer may have been hampered owing to the low mobility of the excited carriers. The emission efficiency was then found to depend on the concentration of structural defects, i.e., on the conversion temperature. For thick films with more than 25 bilayers, on the other hand, the PL signal did not depend on the PPV conversion temperature. We also checked that the interface effects were not caused by waveguiding properties of the excited light. Overall, the electronic states at the interface were more localized, and this applied to film thickness of up to 40-50 nm. Because this is a typical film thickness in devices, the implication from the findings here is that interface phenomena should be a primary concern for the design of any organic device. (C) 2011 American Institute of Physics. [doi:10.1063/1.3622143]CNPqCoordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)FAPEMIGINEO/MCT Ministério de Ciência e Tecnologia (Brazil