An overview of pulsed laser-assisted methods for nanofabrication, which are currently developed in our Institute (LP3), is presented. The methods compass a variety of possibilities for material nanostructuring offered by laser–matter interactions and imply either the nanostructuring of the laser-illuminated surface itself, as in cases of direct laser ablation or laser plasma-assisted treatment of semiconductors to form light-absorbing and light-emitting nano-architectures, as well as periodic nanoarrays, or laser-assisted production of nanoclusters and their controlled growth in gaseous or liquid medium to form nanostructured films or colloidal nanoparticles. Nanomaterials synthesized by laser-assisted methods have a variety of unique properties, not reproducible by any other route, and are of importance for photovoltaics, optoelectronics, biological sensing, imaging and therapeutics.

In a femtosecond pump-probe experiment the pump pulse injects a modest density of free carriers by multiphoton absorption. Measuring the nonlinear absorption of the probe pulse we observe exciton-seeded multiphoton ionization. The excitons self-trap in SiO2 in <300$\hskip0.3em${}fs following free-carrier injection and decay biexponentially with lifetimes of 34\ifmmode\pm\else\textpm\fi{}8 and 338\ifmmode\pm\else\textpm\fi{}67$\hskip0.3em${}ps at room temperature. The extent of the probe-pulse absorption provides a model-independent demonstration that avalanche ionization plays a significant role in free-carrier generation by laser pulses as short as 45 fs. Free-carriers injected into a dielectric from extreme-ultraviolet (XUV) sources created by high harmonic or attosecond pulse generation and then avalanched with a perfectly synchronized infrared (fundamental) probe pulse, can provide a route to nanoscale laser machining.

An important challenge in the field of three-dimensional ultrafast laser processing is to achieve permanent modifications in the bulk of silicon and narrow-gap materials. Recent attempts by increasing the energy of infrared ultrashort pulses have simply failed. Here, we establish that it is because focusing with a maximum numerical aperture of about 1.5 with conventional schemes does not allow overcoming strong nonlinear and plasma effects in the pre-focal region. We circumvent this limitation by exploiting solid-immersion focusing, in analogy to techniques applied in advanced microscopy and lithography. By creating the conditions for an interaction with an extreme numerical aperture near 3 in a perfect spherical sample, repeatable femtosecond optical breakdown and controllable refractive index modifications are achieved inside silicon. This opens the door to the direct writing of three-dimensional monolithic devices for silicon photonics. It also provides perspectives for new strong-field physics and warm-dense-matter plasma experiments.

Laser direct writing is a widely employed technique for 3D, contactless, and fast functionalization of dielectrics. Its success mainly originates from the utilization of ultrashort laser pulses, offering an incomparable degree of control on the produced material modifications. However, challenges remain for devising an equivalent technique in crystalline silicon which is the backbone material of the semiconductor industry. The physical mechanisms inhibiting sufficient energy deposition inside silicon with femtosecond laser pulses are reviewed in this article as well as the strategies established so far for bypassing these limitations. These solutions consisting of employing longer pulses (in the picosecond and nanosecond regime), femtosecond‐pulse trains, and surface‐seeded bulk modifications have allowed addressing numerous applications.

Femtosecond laser ablation of $\mathrm{Ti}$ , $\mathrm{Zr}$ , and $\mathrm{Hf}$ has been investigated by means of in situ plasma diagnostics. Fast imaging was used to characterize the plasma plume expansion on a nanosecond time scale. In addition, time- and space-resolved optical emission spectroscopy was employed to determine the plume composition and the characteristic expansion velocities of plasma species. It is shown that two plume components with different expansion velocities are generated by the interaction of ultrashort laser pulses with metals. The composition and the expansion behavior of the two components have been analyzed as a function of laser fluence and target material. The results are discussed in terms of mechanisms responsible for ablation by ultrashort laser pulses.

Using various band-gap materials and tightly focused femtosecond laser pulses with wavelengths in the range 1200\char21{}2200 nm, we show that nonlinear absorption is independent of the wavelength except for narrow gap semiconductor materials. This observation corresponds to a transition between multiphoton ionization and tunnel ionization for an adiabaticity parameter of about 3, which compares favorably with Keldysh predictions. Our results indicate that long wavelengths must open up an alternative to pulse shortening for ultraprecision optical breakdown in dielectrics.