Excited-state Absorption

We report here the studies on third-order nonlinear optical properties of two novel polythiophene composite films investigated using the Z-scan technique. The measurements were carried out using a Q-switched, frequency doubled Nd:YAG laser producing 7 nanosecond laser pulses at 532 nm. Z-scan results reveal that the composite films exhibit self-defocusing nonlinearity. The real and imaginary parts of the third-order nonlinear optical susceptibility were of the order 10−12 esu. The effective excited-state absorption cross section was found to be larger than the ground state absorption cross section, indicating that the operating nonlinear mechanism is reverse saturable absorption (RSA). The polythiophene composite films also exhibit good optical power limiting of the nanosecond laser pulses. The nonlinear optical parameters are found to increase on increasing the strength of the electron-donor group, indicating the dependence of χ (3) on the electron-donor/acceptor units of polythiophenes.

Intense red upconversion emission around 650nm in PbGeO3–PbF2–CdF2 transparent glass ceramic containing β-PbF2:Ho3+ nanocrystals, is presented. The holmium-doped vitroceramic samples were excited by a 980nm diode laser source. The 650nm upconversion signal was assigned to the 5F5→5I8 transition of holmium ions. Very low intensity signals around 490 and 540nm corresponding to the 5F2,3→5I8 and 4S2,5F4→5I8 transitions, respectively, were also detected.

An experimental investigation of the third-order nonlinear optical properties of new poly{2-{5-[3,4-ditetradecyloxy-5-(1,3,4-oxadiazol-2-yl)thiophen-2-yl]-1,3,4-oxadiazol-2-yl}pyridine} (P) in tetrahydrofuran (THF) solution and in solid poly(methylmethacrylate) (PMMA) matrix, by Z-scan technique is reported. The Z-scan traces reveal that the composite films exhibit large negative nonlinear refractive index of the order 10−10 esu. The excited-state absorption cross-section was found to be larger than the ground-state absorption indicating that the operating nonlinear process is reverse saturable absorption (RSA). The new polymer P exhibits good optical power limiting properties in the nanosecond regime in solution and as well in solid PMMA matrix.

The effect of ytterbium ions upon energy transfer (ET) excited upconversion emission in Nd3+/Pr3+-codoped PbGeO3–PbF2–CdF2 glass under 810nm diode laser excitation is investigated. The results revealed that the presence of Yb3+ ions in the Nd3+/Pr3+-doped sample yields a fourfold enhancement in the visible and near infrared upconversion luminescence. The dependence of the upconversion process upon the excitation power, Nd3+, and

Within a rigid-band correlated electron model for oligomers of poly-(paraphenylene) (PPP) and poly-(paraphenylenevinylene) (PPV), we show that there exist two fundamentally different classes of two-photon A$_g$ states in these systems to which photoinduced absorption (PA) can occur. At relatively lower energies there occur A$_g$ states which are superpositions of one electron - one hole (1e--1h) and two electron -- two hole (2e--2h) excitations, that are both comprised of the highest delocalized valence band and the lowest delocalized conduction band states only. The dominant PA is to one specific member of this class of states (the mA$_g$). In addition to the above class of A$_g$ states, PA can also occur to a higher energy kA$_g$ state whose 2e--2h component is {\em different} and has significant contributions from excitations involving both delocalized and localized bands. Our calculated scaled energies of the mA$_g$ and the kA$_g$ agree reasonably well to the experimentally observed low and high energy PAs in PPV. The calculated relative intensities of the two PAs are also in qualitative agreement with experiment. In the case of ladder-type PPP and its oligomers, we predict from our theoretical work a new intense PA at an energy considerably lower than the region where PA have been observed currently. Based on earlier work that showed that efficient charge--carrier generation occurs upon excitation to odd--parity states that involve both delocalized and localized bands, we speculate that it is the characteristic electronic nature of the kA$_g$ that leads to charge generation subsequent to excitation to this state, as found experimentally.

We present a photophysical and device-based investigation of a new bipyridyl-NCS ruthenium complex sensitizer with an extended π system, in both sensitized TiO2 and incorporated into solid-state dye-sensitized solar cells. We compare this new sensitizer to an analog dye without the extended π system. We observe very similar excited-state absorption spectra and charge recombination kinetics for the two systems. However,

We have investigated the nonlinear optical mechanisms responsible for optical limiting of both picosecond and nanosecond 532-nm optical pulses in the organometallic compound cyclopentadienyliron carbonyl tetramer (King's complex). For fluences below approximately 200 mJ/cm2, picosecond pump-probe measurements in solutions of the King's complex reveal a prompt reverse saturable absorption (RSA) that recovers with a time constant of 120 ps. We attribute this RSA to excited-state absorption within the singlet system of the King's complex, and we demonstrate that the RSA is completely characterized by a simple three-level model. We find, however, that the material parameters extracted from these picosecond measurements cannot account for the strong optical limiting previously observed in identical solutions of this compound using nanosecond excitation at higher fluences. Picosecond measurements at fluences greater than 200 mJ/cm2 reveal the onset of an additional loss mechanism that appears approximately 1 ns after excitation. The magnitude of this loss depends on both the laser repetition rate and the solvent, indicating that the loss is not directly related to the intrinsic properties of the King's complex but is most likely thermal in origin. Using nanosecond excitation pulses, we have performed angularly resolved transmission and reflection measurements, which reveal strong forward- and backward-induced scattering at these fluences. Furthermore, when the King's complex is incorporated in a solid host, we observe negligible induced scatter and the response is completely described by the singlet parameters extracted from the picosecond measurements. These observations indicate that the nanosecond optical limiter response of solutions of King's complex is dominated by thermally induced scattering.

We report direct measurements of the excited singlet state absorption cross section and the associated nonlinear refractive cross section using picosecond pulses at 532 nm in solutions of phthalocyanine and naphthalocyanine dyes. By monitoring the transmittance and far field spatial beam distortion for different pulsewidths in the picosecond regime, we determine that both the nonlinear absorption and refraction are fluence (energy per unit area) rather than irradiance dependent. Thus, excited state absorption (ESA) is the dominant nonlinear absorption process, and the observed nonlinear refraction is also due to real population excitation.