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Novel boron(III) subphthalocyanines (SubPcs) soluble in organic solvents containing a variety of donor and acceptor substituent groups have been synthesized by boron trihalide-induced cyclotrimerization of adequately substituted derivatives of phthalonitrile in 1-chloronaphthalene. The choice of the substituents on the 1,2-dicyanobenzene derivatives has been made taking into account the high reactivity of the Lewis acid BCl3 toward many functional groups. Considering this limitation, we set out to synthesize phthalodinitriles equipped with iodo, nitro, alkyl- or arylthio, alkyl- or arylsulfonyl groups that are sufficiently stable under the required reaction conditions and also provide an easily accessible set of acceptor/donor substituents. The quadratic and cubic hyperpolarizabilities of these compounds as well as their linear optical and electrochemical properties have been measured by several techniques, including EFISH (at two wavelengths), HRS, and THG, steady-state and time-resolved absorption and fluorescence, laser-induced optoacoustic calorimetry, time-resolved near-infrared emission spectroscopy, and cyclic voltammetry. βHRS has been measured at 1.46 μm, where the contamination from the multiphoton-induced fluorescence can be ruled out. βHRS reachs high values that markedly depend on substitution. It shows a clear enhancement with the acceptor character of the substituents, the highest values being obtained for the compounds bearing the strongest acceptor groups. They are comparable or even superior to many efficient second-order compounds. A main outcome of these results is that an adequate choice of the substituents offers a promising route for optimization of the quadratic response of the SubPcs. This kind of compounds is less prone to aggregation than their expanded analogues, the phthalocyanines, fluoresces with quantum yields ca. 0.25, lower than those typical for phthalocyanines, and has larger triplet quantum yields. The triplet-state lifetime is in the 100-μs time range, long enough for efficient oxygen quenching. Indeed, subphthalocyanines sensitize singlet molecular oxygen, O2(1Δg), with quantum yields ranging from 0.23 to 0.75. The ground-state oxidation potentials are similar to those of phthalocyanines, while the reduction potentials are clearly more negative; i.e., they are more difficult to reduce. In contrast, electronically excited subphthalocyanines are more easily oxidized than the corresponding phthalocyanines by ca. 500 mV which results in lower photostability, especially in polar solvents.

We demonstrate a swift ion-beam irradiation procedure based on electronic (not nuclear) excitation to generate a large index jump step-like optical waveguide (Δn0≈0.2,Δne≈0.1) in LiNbO3. The method uses medium-mass ions with a kinetic energy high enough to assure that their electronic stopping power Se(z) reaches a maximum value close to the amorphous (latent) track threshold inside the crystal. Fluorine ions of 20 and 22MeV and fluences in the range (1–30)×1014 are used for this work. A buried amorphous layer having a low refractive index (2.10 at a wavelength of 633nm) is then generated at a controlled depth in LiNbO3, whose thickness is also tuned by irradiation fluence. The layer left at the surface remains crystalline and constitutes the core of the optical waveguide which, moreover, is several microns far from the end of the ion range. The waveguides show, after annealing at 300°C, low propagation losses (≈1dB∕cm) and a high second-harmonic generation coefficient (50%–80% of that for bulk unirradiated LiNbO3, depending on the fluence). The formation and structure of the amorphous layer has been monitored by additional Rutherford backscattering/channeling experiments.

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The operation of photovoltaic (PV) tweezers, using the evanescent light-induced PV fields to trap and pattern nano- and micro-meter particles on a LiNbO(3) crystal surface, is discussed. The case of a periodic light pattern is addressed in detail, including the role of particle shape and the modulation index of the light pattern. The use of a single Gaussian light beam is also considered. Illustrative experiments for the two situations are presented. The performance of such PV tweezers in comparison to the best established case of optical tweezers, using optical forces, is considered. Differential features between the two trapping approaches are remarked.

The application of evanescent photovoltaic (PV) fields, generated by visible illumination of Fe:LiNbO 3 substrates, for parallel massive trapping and manipulation of micro-and nano-objects is critically reviewed. The technique has been often referred to as photovoltaic or photorefractive tweezers. The main advantage of the new method is that the involved electrophoretic and/or dielectrophoretic forces do not require any electrodes and large scale manipulation of nano-objects can be easily achieved using the patterning capabilities of light. The paper describes the experimental techniques for particle trapping and the main reported experimental results obtained with a variety of micro-and nano-particles (dielectric and conductive) and different illumination configurations (single beam, holographic geometry, and spatial light modulator projection). The report also pays attention to the physical basis of the method, namely, the coupling of the evanescent photorefractive fields to the dielectric response of the nano-particles. The role of a number of physical parameters such as the contrast and spatial periodicities of the illumination pattern or the particle deposition method is discussed. Moreover, the main properties of the obtained particle patterns in relation to potential applications are summarized, and first demonstrations reviewed. Finally, the PV method is discussed in comparison to other patterning strategies, such as those based on the pyroelectric response and the electric fields associated to domain poling of ferroelectric materials.