Silicon polymorphs with exotic electronic and optical properties have recently attracted significant attention due to their wide range of useful band gap characteristics. They are typically formed by static high-pressure techniques, which limits the crystal structures that can be made. This constitutes a major obstacle to study these polymorphs and their incorporation into existing technology. Approaches have attempted to address this shortcoming through using dynamic conditions and chemical precursor materials. Here, we report on an approach to create unusual crystal structures deep in the bulk of a silicon crystal by irradiating it with a laser pulse at ultrarelativistic intensity of up to 7 . 5 x 10 19 W/cm 2 . Laser -generated electrons with MeV energy swiftly penetrate the target with speed close to the speed of light and deposit their energy into a large volume across the whole thickness of the sample. The relativistic electron current creates, via branching propagation and ionization, high -energy -density conditions for thermodynamically nonequilibrium phase transformation paths into new crystal polymorphs. X-ray microdiffraction and synchrotron x-ray diffraction analyses indicate, along with conventional dc -Si, the presence of exotic silicon structures in the bulk of the laser intact target volume. These structures are identified as body -centered bc8-Si, rhombohedral r8 -Si, hexagonal -diamond hd-Si, and the tetragonal Si -VIII, all phases of Si that have previously been made through static techniques. Additionally, simple -tetragonal st12-Si and body -centered tetragonal bt8-Si were observed along with signatures of not yet identified diffraction spots. Both st12-Si and bt8-Si have only been observed in ultrafast laser microexplosion conditions at much lower laser intensity similar to 10 14 W/cm 2 and within a micron -thin surface layer. The findings here are supported by direct observation of nanoparticles with high -resolution transmission electron microscopy and corresponding fast Fourier transform analysis of their interatomic distances. The presented analyses of absorbed laser energy, generation of the MeV electron current, and deposition of energy across the whole target thickness provide a solid basis for drawing the conclusion that the observed silicon polymorphs were produced because of laser -generated high-energy electrons fast -penetrating deeply into the bulk of silicon. In contrast to solid -solid transformations, the plasma -solid transitions offer a paradigm for the creation of exotic, high-energy density materials inside the bulk of the sample by using laser pulses at relativistic intensities.

The laser energy per unit surface, necessary to trigger material removal, decreases with the pulse shortening, becoming pulse–time independent in the sub-picosecond range. These pulses are shorter than the electron-to-ion energy transfer time and electronic heat conduction time, minimising the energy losses. Electrons receiving an energy larger than the threshold drag the ions off the surface in the mode of electrostatic ablation. We show that a pulse shorter than the ion period (Shorter-the-Limit (StL)) ejects conduction electrons with an energy larger than the work function (from a metal), leaving the bare ions immobile in a few atomic layers. Electron emission is followed by the bare ion’s explosion, ablation, and THz radiation from the expanding plasma. We compare this phenomenon to the classic photo effect and nanocluster Coulomb explosions, and show differences and consider possibilities for detecting new modes of ablation experimentally via emitted THz radiation. We also consider the applications of high-precision nano-machining with this low intensity irradiation.

The interaction of two subsequent ultra-short sub-milli-Joule laser pulses with a thin water flow results in an emission of a strong single-cycle THz pulse associated with enhanced soft X-ray emission. In this paper, a chain of processes produced in this interaction is analyzed and compared with other THz generation studies. It is demonstrated that the enhanced THz and X-ray emissions are produced by an energetic electron beam accelerated in the interaction of a main laser pulse with liquid water ejected from the surface by the pre-pulse. This scheme thus provides an efficient laser energy conversion in a THz pulse, avoiding laser self-focusing and filamentation in air.

Controlling electronic and optical properties of semiconducting materials could substantially expand their functionality and enable new pathways for the formation of ‘smart’ materials for emerging innovative applications. An emerging new path for the synthesis of exotic silicon (Si) polymorphs is irradiation of bulk diamond-cubic Si by ultrashort laser pulses at relativistic intensity above 1019 W/cm2. Exotic polymorphs are formed due to interaction with MeV-energy electrons generated in laser-produced high-temperature plasma state. The unusual Si structures are found in the form of 5–10 nm nanoparticles confined deep in the bulk of 500-μm-thick Si samples. Raman spectroscopy, electron microscopy and X-ray diffraction studies provide an unequivocal evidence of exotic Si phase formation. A key advantage of such relativistic irradiation lies thereby in the fact that large quantities of such exotic Si is synthesised embedded within the bulk diamond-cubic Si and that further the formed Si polymorphs are stable at ambient temperature and pressure. They are thus available for further studies for electronic applications in selective band gap engineering.

Intense THz sources are expected for further progresses in nonlinear THz science and technology. Liquids like water are durable and continuously-reusable under intense laser irradiation for THz emission though such studies on THz emission from water targets are so far limited. Polarisation fine control of THz emission is demonstrated with a tilted micro-thin water flow by the irradiation of two cross-linearly-polarised femtosecond laser pulses (800nm, 35fs, transform-limited) with spatio-temporal offsets. With an optimized horizontal offset at ∼11 μm between the ∼8 μm focal spots and time delay at 4.7ns, circularly-polarised THz emission is obtained with its intensity enhancement more than 1,500-times if compared with the single pulse irradiation. It is shown that the photon-number-based efficiency from the laser to THz at 7.1 x 10 −3 is achieved with the optimisation of the double pulse irradiation. Polarisation-resolved THz time-domain spectroscopy and time-resolved shadowgraphy imaging reveal that the circularly-polarised THz emission originates from the focal volume in front of the water flow. Coupling between a shockwave due to air-breakdown and water ablation-mediated mass transport by the pre-pulse with a laser wake-field along the optical path of the main pulse is responsible for the point-like single-cycle THz emission.

We put forward a co-axial pump(optical)-probe(X-rays) experimental concept and show performance of the optical component. A Bessel beam generator with a central 100 micrometers-diameter hole (on the optical axis) was fabricated using femtosecond (fs) laser structuring inside a silica plate. This flat-axicon optical element produces a needle-like axial intensity distribution which can be used for the optical pump pulse. The fs-X-ray free electron laser (X-FEL) beam of sub-1 micrometer diameter can be introduced through the central hole along the optical axis onto a target as a probe. Different realisations of optical pump are discussed. Such optical elements facilitate alignment of ultra-short fs-pulses in space and time and can be used in light-matter interaction experiments at extreme energy densities on the surface and in the volume of targets. Full advantage of ultra-short 10 fs X-FEL probe pulses with fs-pump(optical) opens an unexplored temporal dimension of phase transitions and the fastest laser-induced rates of material heating and quenching. A wider field of applications of fs-laser-enabled structuring of materials and design of specific optical elements for astrophotonics is presented.

Intense THz wave sources are highly expected for further progresses in nonlinear THz science and practical implementation of non-ionizing radiation in sensing and communications. Solid-based sources have inherent limits of material breakdown, while intense laser irradiation of liquids is a promising emerging technique for THz wave and hard X-ray emission. Water-based THz emission shows intensity enhancements up to 10 times when laser-pulse pairs with nanosecond delay are used. Here we show circularly-polarized THz wave emission from thin water flow irradiated by two time-separated and linearly-polarized femtosecond laser pulses. THz time-domain spectroscopy reveals the circularly-polarized THz emission dominates 4.7 ns after the first pulse irradiation. THz wave detection delay in the spectroscopy and time-resolved micrography indicate that the THz wave emission originates from the rarefied volume in front of the flow. Radial relaxation of charges in the focal volume where ponderomotive charge depletion occurred on the optical axis is the origin for the circular polarization (due to spiraling currents). Tight focusing of fs-laser pulses localized THz wave emission to the sub-wavelength (tens-of-micrometers) region.

Material states formed by high-power laser demonstrate new pathways for engineering polymorphs with novel optoelectronic properties. We present the observation of silicon phases only seen until now in laboratory experiments by ultrashort laser confined micro explosion.

It was demonstrated during the past decade that an ultra-short intense laser pulse tightly-focused deep inside a transparent dielectric generates an energy density in excess of several MJ/cm3. Such an energy concentration with extremely high heating and fast quenching rates leads to unusual solid-plasma-solid transformation paths, overcoming kinetic barriers to the formation of previously unknown high-pressure material phases, which are preserved in the surrounding pristine crystal. These results were obtained with a pulse of a Gaussian shape in space and in time. Recently, it has been shown that the Bessel-shaped pulse could transform a much larger amount of material and allegedly create even higher energy density than what was achieved with the Gaussian beam (GB) pulses. Here, we present a succinct review of previous results and discuss the possible routes for achieving higher energy density employing the Bessel beam (BB) pulses and take advantage of their unique properties.

Swift excitation of transparent dielectrics by ultrashort and highly intense laser pulse leads to ultra-fast re-structuring of the electronic landscape and generates many transient material states, which are continuously reshaped in accord with the changing pulse intensity. These unconventional transient material states, which exhibit simultaneously both dielectric and metallic properties, we termed here as the 'Die-Met' states. The excited material is transparent and conductive at the same time. The real part of permittivity of the excited material changes from positive to negative values with the increase of excitation, which affects strongly the interaction process during the laser pulse. When the incident field has a component along the permittivity gradient, the amplitude of the field increases resonantly near the point of zero permittivity, which dramatically changes the interaction mode and increases absorption in a way that is similar to the resonant absorption in plasma. The complex 3D structure of the permittivity makes a transparent part of the excited dielectric (at ε0 > εre > 0) optically active. The electro-magnetic wave gets a twisted trajectory and accrues the geometric phase while passing through such a medium. Both the phase and the rotation of the polarisation plane depend on the 3D permittivity structure. Measuring the transmission, polarisation and the phase of the probe beam allows one to quantitatively identify these new transient states. We discuss the revelations of this effect in different experimental situations and their possible applications.

Understanding of material behaviour at nanoscale under intense laser excitation is becoming critical for future application of nanotechnologies. Nanograting formation by linearly polarised ultra-short laser pulses has been studied systematically in fused silica for various pulse energies at 3D laser printing/writing conditions, typically used for the industrial fabrication of optical elements. The period of the nanogratings revealed a dependence on the orientation of the scanning direction. A tilt of the nanograting wave vector at a fixed laser polarisation was also observed. The mechanism responsible for this peculiar dependency of several features of the nanogratings on the writing direction is qualitatively explained by considering the heat transport flux in the presence of a linearly polarised electric field, rather than by temporal and spatial chirp of the laser beam. The confirmed vectorial nature of the light-matter interaction opens new control of material processing with nanoscale precision.

It has been proven that the intense tightly focused Gauss beam (GB) generates pressures in excess of a few TPa creating the novel super-dense phases of Aluminium and silicon [1-5]. Recently it was demonstrated that the Bessel beam (BB) focused inside sapphire produced the cylindrical void being two orders of magnitude larger than that generated by the GB [6-8]. Analysis of the experimental data presented below allows making the remarkable conclusions based solely on the void size measurements without any ad hoc assumptions about the interaction process. First, the void size is direct evidence of strong (>40%) absorption of the pulse energy. Second, it is a direct experimental evidence of the high-energy concentration in the central spike of the focus. The unique features of the intense Bessel beam interaction then allow understanding the experimental observation. This interaction generates early in the pulse time the spatial distribution of excited permittivity changing from positive to negative values. Then the light interacts with zero-real-permittivity surface, separating plasma and dielectric areas, which leads to high energy concentration near the axis of cylindrical focus up to several MJ/cm3 (pressure range of 4-8 TPa). The effect depends on the angle between the permittivity gradient and the field polarisation. High pressure generates intense cylindrical shock/ rarefaction waves, which led to formation of void and compressed shell. We demonstrate that the Bessel beam proves to be an effective tool for producing extreme pressure/temperature conditions on the laboratory tabletop. It appears that adjusting polarisation and permittivity gradient might be a novel way for increasing the maximum pressure. This tool allows for search of novel high-pressure material phases, for the 3D laser machining and for creating Warm Dense Matter as those in star cores.

Powerful short laser pulse focused on a surface swiftly transforms the solid into the thermally and electrically inhomogeneous conductive plasma with the large temperature and dielectric permeability gradients across the focal spot. The laser-affected spot becomes thermally inhomogeneous with where temperature has maximum in the centre and gradually decreasing to the boundaries of the spot in accord to the spatial intensity distribution of the Gaussian pulse. Here we study the influence of laser polarisation on ionization and absorption of laser radiation in the focal spot. In this paper we would like to discuss new effect in thermally inhomogeneous plasma under the action of imposed high frequency electric field. We demonstrate that high-frequency (HF) electric field is coupled with the temperature gradient generating the additional contribution to the conventional electronic heat flow. The additional heat flow strongly depends on the polarisation of the external field. It appears that effect has maximum when the imposed electric field is collinear to the thermal gradient directed along the radius of a circular focal spot. Therefore, the linear polarised field converts the circular laser affected spot into an oval with the larger oval’s axis parallel to the field direction. We compare the developed theory to the available experiments, discuss the results and future directions.

We demonstrate how the coupling between (i) polarization of the writing laser beam, (ii) tight focusing and (iii) heat conduction affects the size, shape and absorption in the laser-affected area and therefore the polymerization process. It is possible to control the sizes of 3D laser-produced structure at the scale of several nanometers. Specifically we were able to tune the aspect ratio of 3D suspended line up to 20% in hybrid SZ2080 resist. The focal spot of tightly focused linearly polarized beam has an elliptical form with the long axis in the field direction. It is shown here that this effect is enhanced by increase in the electronic heat conduction when polarization coincide with temperature gradient along with the absorption. Overlapping of three effects (iiii) results in the difference of several tens of nanometers between two axes of the focal ellipse. Narrow line appears when polarization and scan direction coincide, while the wide line is produced when these directions are perpendicular to each other. The effect scales with the laser intensity giving a possibility to control the width of the structure on nanometer scale as demonstrated experimentally in this work. These effects are of general nature and can be observed in any laser-matter interaction experiments where plasma produced by using tight focusing of linear-polarized light.

A systematic analysis of polarization effects in a direct write femtosecond laser 3D lithography is presented. It is newly shown that coupling between linear polarization of the writing light electric field and temperature gradient can be used to fine-tune feature sizes in structuring of photoresists at a nanoscale. The vectorial Debye focusing is used to simulate polarization effects and a controlled variation up to 20 experimentally for the identical axial extent of the polymerised features. The revealed mechanisms are relevant for a wide range of phenomena of light-matter interaction at tight focusing in laser-tweezers and in plasmonic or dielectric sub-wavelength focusing where strong light intensity and thermal gradients coexist.

Tilt between the orientation of the beam scan direction and nanogratings formed by linearly polarized ultra-short laser pulses was systematically studied in fused silica. The dependence of period of nanogratings on the scanning direction is also observed.

Femtosecond Bessel pulses with a needle-like intensity distribution were focused inside sapphire crystal to create voids and the shock-wave affected volume which is by more than two orders of magnitude larger as compared with that made by the Gaussian pulse.

New material phases formed under non-equilibrium conditions at pressures above 100 GPa and temperatures exceeding 10(4)K, the conditions of the warm dense matter (WDM), have become accessible using micro-explosions triggered by ultra-short sub-1 ps pulses tightly focused into micro-volume with cross sections comparable with the wavelength of light. Laser-induced micro-explosions convert a material in a focal volume into a non-equilibrium disordered plasma state confined inside the bulk of pristine crystal. Ultra-high quenching rates overcome kinetic barriers to the formation of new metastable high pressure phases, which are preserved in the surrounding pristine crystal for following recovery and exploitation. Direct laser writing was used to pattern large areas by closely packed arrays of the microexplosion modified sites for structural characterisation of the minute volumes of nano-materials with transmission electron microscopy, diffraction and synchrotron X-ray diffraction. The method of ultrafast-laser induced confined microexplosion is demonstrated for modification and creation of new phases in case of bcc-Al inside sapphire, valence change of Fe-ions in olivine, formation of new tetragonal bt8 and st12 phases of silicon, Ge and O separation in GeO2 glass and molecular oxygen formation inside voids at the site of microexplosion inside glasses.