Vis and NIR Diffuse Reflectance Study in Disordered Bismuth Manganate - Lead Titanate Ceramics

This work shows a correlation between light reflectance, absorption, and morphologies of series of bismuth manganate–lead titanate, (1 x) BM–x PT, (x = 0.00, 0.02, 0.04, 0.08, 0.12, 0.16, 0.24, 1.00) ceramics composite. Low reflectance in the Vis-NIR range corresponds to ‘black mirror’ features. The modified Kubelka-Munk function applied to measured visible-near infrared (Vis-NIR) diffuse reflectance enabled the estimation of the energy gaps magnitude of the order of 1.0–1.2 eV for BM-PT. Histograms of grains, obtained using a scanning electron microscope, enabled finding the correlation between grains size, reflectance magnitude, and PT content. The magnitude of energy gaps was attributed to electronic structure bands modified by crystal lattice disorder and oxygen vacancies

Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes

New stilbenoid and thiophenic compounds terminally functionalized with donor–donor, acceptor–acceptor, or donor–acceptor moieties and possessing a central [2.2]­paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]­paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]­paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both “intermolecular” excitation and charge delocalizations in [2.2]­paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors

The Two-Photon Absorption Cross-Section Studies of CsPbX3 (X = I, Br, Cl) Nanocrystals

The CsPbX3 nanocrystals (NCs) with X = I, Br, Cl, or the mixture of Br:I and Br:Cl in a 1:1 ratio were synthesized and characterized by TEM, DLS, and XRD. Recrystallization of the small luminescent NCs in the metastable cubic phase into bigger orthorhombic nanocrystals was monitored by XRD and identified as the main cause of the nanocolloid coagulation. The recrystallization also leads to a decrease in the photoluminescence quantum yield (QY) of the colloidal solution and shortening of the emission lifetime. The two-photon absorption cross-section σ2 values calculated from femtosecond Z-scan measurements were compared with those obtained based on the two-photon excited emission technique. These two techniques were shown to be equivalent with the cross-section values calculated per molar mass of CsPbX3 perovskite being in the range of 10–200 GM depending on the halide anions X−. The σ2 values recalculated for the mole of the NCs were in the range of 104–105 GM, which is in good agreement with values previously reported elsewhere and the σ2/M parameter was in the range of 0.01 to 0.33. This study shows the perovskite NCs to be a good nonlinear material with the third-order nonlinear optical susceptibility χ(3) of the NCs on the order of 10−11 esu

Optical nonlinearities of colloidal InP@ZnS core-shell quantum dots probed by Z-scan and two-photon excited emission

Spectrally resolved nonlinear optical properties of colloidal InP@ZnS core-shell quantum dots of various sizes were investigated with the Z-scan technique and two-photon fluorescence excitation method using a femtosecond laser system tunable in the range from 750 nm to 1600 nm. In principle, both techniques should provide comparable results and can be interchangeably used for determination of the nonlinear optical absorption parameters, finding maximal values of the cross sections and optimizing them. We have observed slight differences between the two-photon absorption cross sections measured by the two techniques and attributed them to the presence of non-radiative paths of absorption or relaxation. The most significant value of two-photon absorption cross section σ2 for 4.3 nm size InP@ZnS quantum dot was equal to 2200 GM, while the two-photon excitation action cross section σ2Φ was found to be 682 GM at 880 nm. The properties of these cadmium-free colloidal quantum dots can be potentially useful for nonlinear bioimaging

Third-Order Nonlinear Optical Properties of Infrared Emitting PbS and PbSe Quantum Dots

The optical properties of small band gap, colloidal quantum dots are presented, with the special emphasis put on the measurements of their nonlinear optical properties in the infrared region of spectra. In particular, two types of colloidal quantum dots (PbS and PbSe), with the first exciton absorption band maxima in the near-infrared region of spectra, were investigated using a tunable femtosecond laser system and the <i>Z</i>-scan technique. The measurements of closed- and open-aperture <i>Z</i>-scan traces allowed for the calculation of real and imaginary parts of cubic nonlinearity, which were presented as appropriate cross sections used to characterize the nonlinear refractive and absorptive properties of the studied quantum dots. The maximum two-photon absorption cross section values taken for a single quantum dot were found to be ∼2400 GM (Goeppert-Mayer units) at 1300 nm and ∼15 500 GM at 1700 nm, for PbS and PbSe QDs, respectively. PbS quantum dots showed two-photon induced emission upon infrared excitation. The obtained results demonstrate the potential of IV–VI group colloidal quantum dots for low-cost photonic devices and two-photon absorbers in the near-infrared and infrared spectral ranges

Enhancement of Two-Photon Absorption Cross Section in CdSe Quantum Rods

Nonlinear optical properties of semiconducting CdSe quantum rods (QRs), with three various aspect ratios, were examined in a wide wavelength range using femtosecond Z-scan technique. The two-photon absorption cross section σ₂ was found to be as large as 164 000 GM at the wavelength of 750 nm: about 4 times larger than that expected for CdSe quantum dots of the same mass. On the basis of the obtained dispersion of the two-photon absorption cross section, we have selected wavelength ranges for optimal excitation of two-photon-induced emission. We have also studied the luminescence kinetics using degenerate pump–probe and time-correlated single-photon counting techniques. A strong influence of semiconducting CdSe rods morphology on their steady-state and time-resolved optical properties was found

Wavelength Dependence of the Complex Third-Order Nonlinear Optical Susceptibility of Poly(3-hexylthiophene) Studied by Femtosecond <i>Z</i>‑Scan in Solution and Thin Film

Comprehensive studies of the third-order susceptibility of regioregular poly­(3-hexylthiophene) in the wavelength range from 530 to 1600 nm for both thin film (with stacked chains interactions) and dilute solution (no chains interactions) were performed with the <i>Z</i>-scan technique. Negative nonlinear refraction was observed in the whole wavelength range of the measurements. The nonlinear absorption exhibits regions of two-photon and three-photon absorption, and on approaching the linear absorption region, a saturable absorption process is seen. It was found that for thin film the effective multiphoton absorption cross-sections σ₂ and σ₃ are 1.5 and 3 times bigger than for solution, respectively. Influence of the elongated conjugation length in the stacked polythiophene chains in thin film on the red shift of the multiphoton absorption cross-section spectra in comparison with those for polythiophene in solution is discussed

Synthesis and Linear and Nonlinear Optical Properties of Three Push–Pull Oxazol-5(4<i>H</i>)‑one Compounds

Three uncharged push–pull oxazol-5­(4<i>H</i>)-ones were synthesized and thoroughly characterized. The examined molecules contained electron-donor and electron-acceptor groups interacting via a π-conjugated bridge. Spectral properties of the oxazol-5­(4<i>H</i>)-ones were studied in detail in three solvents of different polarities. The results indicate a solvatochromic shift toward lower energy for the charge-transfer state. The compounds are weakly fluorescent in polar solvents, but they have high fluorescence quantum yields in nonpolar solvents. Their two-photon absorption (2PA) properties were characterized by the open- and closed-aperture Z-scan technique, by the pump–probe technique, and by the two-photon excited fluorescence method. The dyes exhibit relatively high effective two-photon absorption cross sections ranging from 490 to 2600 GM at ∼100 GW/cm², according to the Z-scan results, which are found, however, to contain significant contribution from higher-order absorption processes. In addition, these compounds display good photostability