Linear π-conjugated oligomers have been widely investigated, but the behavior of the corresponding cyclic oligomers is poorly understood, despite the recent synthesis of π-conjugated macrocycles such as [n]cycloparaphenylenes and cyclo[n]thiophenes. Here we present an efficient template-directed synthesis of a π-conjugated butadiyne-linked cyclic porphyrin hexamer directly from the monomer. Small-angle X-ray scattering data show that this nanoring is shape-persistent in solution, even without its template, whereas the linear porphyrin hexamer is relatively flexible. The crystal structure of the nanoring-template complex shows that most of the strain is localized in the acetylenes; the porphyrin units are slightly curved, but the zinc coordination sphere is undistorted. The electrochemistry, absorption, and fluorescence spectra indicate that the HOMO-LUMO gap of the nanoring is less than that of the linear hexamer and less than that of the corresponding polymer. The nanoring exhibits six one-electron reductions and six one-electron oxidations, most of which are well resolved. Ultrafast fluorescence anisotropy measurements show that absorption of light generates an excited state that is delocalized over the whole π-system within a time of less than 0.5 ps. The fluorescence spectrum is amazingly structured and red-shifted. A similar, but less dramatic, red-shift has been reported in the fluorescence spectra of cycloparaphenylenes and was attributed to a high exciton binding energy; however the exciton binding energy of the porphyrin nanoring is similar to those of linear oligomers. Quantum-chemical excited state calculations show that the fluorescence spectrum of the nanoring can be fully explained in terms of vibronic Herzberg-Teller (HT) intensity borrowing.

We propose a single beam method for generating optical vortices with tunable optical angular momentum without altering the intensity distribution. With the initial polarization state varying from linear to circular, we gradually control the torque transferred to the trapped non-absorbing and non-birefringent silica beads. The continuous transition from the maximum rotation speed to zero without changing the trapping potential gives a way to study the complex tribological interactions.

Vector beams, beams with a non-uniform state of polarization, have become an indispensable tool in many areas of science and technology. Harnessing topological light properties paves the way to control and manipulate light-matter interactions at different levels, from the quantum to macroscopic physics. Here we generate tabletop extreme ultraviolet (EUV) vector beams driven by high-order harmonic generation (HHG). Our experimental and theoretical results demonstrate that HHG imprints the polarization state of the fundamental (infrared) beam, ranging from radial to azimuthal, into the higher frequency radiation. Our numerical simulations also demonstrate that the generated high-order harmonic beams can be synthesized into attosecond vector beams in the EUV/soft x-ray regime. Our proposal overcomes the stateof-the-art-limitations for the generation of vector beams far from the visible domain and could be applied in fields such as diffractive imaging, EUV lithography, or ultrafast control of magnetic properties.

High-precision three-dimensional ultrafast laser direct nanostructuring of silica glass resulting in multi-layered space-variant dielectric metasurfaces embedded in volume is demonstrated. Continuous phase profiles of nearly any optical component are achieved solely by the means of geometric phase. Complex designs of half-wave retarders with 90% transmission at 532 nm and >95% transmission at >1 μm, including polarization gratings with efficiency nearing 90% and computer generated holograms with a phase gradient of ∼0.8π rad/μm, were fabricated. A vortex half-wave retarder generating a single beam optical vortex with a tunable orbital angular momentum of up to ±100ℏ is shown. The high damage threshold of silica elements enables the simultaneous optical manipulation of a large number of micro-objects using high-power laser beams. Thus, the continuous control of torque without altering the intensity distribution was implemented in optical trapping demonstration with a total of 5 W average power, which is otherwise impossible with alternate beam shaping devices. In principle, the direct-write technique can be extended to any transparent material that supports laser assisted nanostructuring and can be effectively exploited for the integration of printed optics into multi-functional optoelectronic systems.

A femto- and picosecond laser assisted periodic nanostructuring of hydrogenated amorphous silicon (a-Si:H) is demonstrated. The grating structure with the subwavelength modulation of refractive index shows form birefringence (Δn ≈ −0.6) which is two orders of magnitude higher than commonly observed in uniaxial crystals and femtosecond laser nanostructured silica glass. The laser-induced giant birefringence and dichroism in a-Si:H film introduce extra dimensions to the polarization sensitive laser writing with applications that include data storage, security marking, and flat optics.

The field of surface nanostructuring is growing rapidly with the need to search for more advanced fabrication solutions. The major challenge is the lack of appropriate combination of time/cost efficient techniques and medium possessing the advantages of both flexibility and tunable optical properties. Here we demonstrate direct-write femtosecond laser nanostructuring of indium–tin-oxide thin film where the deep-subwavelength ripples with periodicity of down to 120 nm are realized originating the form birefringence (|Δn| ≈ 0.2), which is 2 orders of magnitude higher than the commonly observed in uniaxial crystals or femtosecond laser nanostructured fused quartz. The demonstrated nanoripples with its continuously controlled space-variant orientation lead to the high density two-dimensional printing of flat optical elements. The technique can be extended to any highly transparent films that support laser-induced periodic surface structures, and can be effectively exploited for the integration of polarization sensitive modifications into multidimensional optical data storage.

Electrodes with higher transparency that can also align liquid crystals (LCs) are of high importance for improved costs and energy consumption of LC displays. Here we demonstrate for the first time alignment of liquid crystals on femtosecond laser nanostructured indium tin oxide (ITO) coated glass exhibiting also higher transparency due to the less interface reflections. The nano paterns were created by fs laser directlly on ITO films without any additional spin coating materials or lithography procces. Nine regions of laser-induced nanostructures were fabricated with different alignment orientations and various pulse energy levels on top of the ITO. The device interfacial anchoring energy was found to be 1.063 × 10 −6 2 ⁄ , comparable to the anchoring energy of nematic LC on photosensitive polymers. The device exhibits contrast of 30:1 and relaxation time of 330ms expected for thick LC devices. The measured transparency of the LC device with two ITO nanograting substrates is 10% higher than the uniform ITO film based LC devices. The alignment methodology presented here paves the way for improved LC displays and new structured LC photonic devices.

Articles you may be interested inInvestigation on the near-infrared-emitting thermal stability of Bi activated alkaline-earth aluminoborosilicate glasses J. Appl. Phys. 117, 053107 (2015); 10.1063/1.4907565In-situ characterization of femtosecond laser-induced crystallization in borosilicate glass using time-resolved surface third-harmonic generation