This paper provides an overview of the thermal stability of volume nanogratings (NGs) inscribed in more than 20 laboratory and commercial oxide glasses using femtosecond laser pulses. The role of glass composition and its viscosity-temperature dependence are particularly investigated. Other parameters, such as nanostructure morphology (e.g., porosity size) can play a role in it. Although it has become established that high viscosity glasses typically yield improved thermal stability, recent results highlight deviations from this trend. This is particularly pronounced in low SiO2 containing glasses with large Al2O3 content (typ. > 50 mol%), where their NGs thermal stability is comparatively higher than what is known for pure silica, which may prove useful for optical devices operating in extreme environments.
Polarization-dependent periodic nanostructures inside various materials are successfully photoinduced by ultrafast laser pulses. These periodic nanostructures in various materials can be empirically classified into the following three types: (1) structural deficiency, (2) strained structure, (3) partial phase separation. Such self-assembled nanostructures exhibit not only optical anisotropy but also intriguing electric, thermal, and magnetic properties. We demonstrate new possibilities for functionalization of common materials ranging from an eternal 5D optical storage, a polarization imaging, to a thermoelectric conversion, based on the indicated phenomena.
We have successfully observed self-assembled periodic nanostructures inside Si single crystal and GaP crystal, by the femtosecond double-pulse irradiation. These results experimentally indicate that the self-assembly of the periodic nanostructures inside semiconductors triggered by ultrashort pulses irradiation are possibly associated with a direct or an indirect band gap. More recently we have also empirically classified the photoinduced bulk nanogratings into the following three types: (1) structural deficiency, (2) compressed structure, (3) partial crystallization. We have still a big question about what material properties are involved in the bulk nanograting structure formation. In this study, to expand the selectivity of the material for bulk nanograting formation, we have employed β-Ga2O3 crystals (indirect bandgap Eg ~ 4.8 eV) as a sample for femtosecond laser irradiation. The nanograting structure inside β-Ga2O3 crystal was aligned perpendicular to the laser polarization direction. Such phenomenon is similar to the nanograting in SiO2 glass (Eg ~ 9 eV). Moreover, to clarify the band structure, we have also investigate the photoinduced structure in Sn doped β-Ga2O3 crystals, which exhibit direct bandgap according to the first principle calculation.
The polarization-dependent periodic nanostructures inside various materials are successfully induced by ultrafast laser pulses. The periodic nanostructures in various materials can be empirically classified into the following three types: (1) structural deficiency, (2) expanded structure, (3) partial phase separation. Such periodic nanostructures exhibited not only optical anisotropy but also intriguing electric, thermal, and magnetic properties. The formation mechanisms of the periodic nanostructure was interpreted in terms of the interaction between incident light field and the generated electron plasma. Furthermore, the fact that the periodic nanostructures in semiconductors could be formed empirically only if it is indirect bandgap semiconductor materials indicates the stress-dependence of bandgap structure and/or the recombination of the excited electrons are also involved to the nanostructure formation. More recently we have also confirmed that the periodic nanostructures in glass are related to whether a large amount of non-bridged oxygen is present. In the presentation, we demonstrate new possibilities for functionalization of common materials ranging from an eternal 5D optical storage, a polarization imaging, to a thermoelectric conversion, based on the indicated phenomena.
Fluorescent Carbon nanoparticles (CNPs) with tunable emission are successfully synthesized from the water
suspension of graphene oxide by the femtosecond laser irradiation. The luminescence properties were controllable
by doping nitrogen into CNPs in the presence of an ammonia molecule. We have also confirmed that CNPs with
diamond structure were directly precipitated from the solvent molecules such as cyclohexane.
Meanwhile, by the convention wire-saw technique, it is difficult to slice off a thin wafer from bulk SiC crystal without
the reserving space for cutting. In this study, we have achieved exfoliation of 4H-SiC single crystal by femtosecond laser
induced slicing method. By using this, the exfoliated surface with the root-mean-square roughness of 3 μm and the
cutting-loss thickness smaller than 30 μm was successfully demonstrated. We have also observed the nanostructure on
the exfoliated surface in SiC crystal.
Several applications of glass nanofibers have been proposed for the past years. We found a new method for production of nanofibers with a diameter of 100 nm order from thin glass plates by irradiation with nanoseconds pulsed UV laser (wavelength is 355 nm). Although the generation of nanofibers from the back surface of a glass plate is convenient for continuous laser irradiation and collection of fibers, the details of the mechanism have not been elucidated yet. In this paper, we focused on the dynamics of ejection of glass melts that results in the formation of nanofibers, and investigated the mechanism of nanofiber generation. Based on the observation by a high-speed camera, we found that voids inside of the glass plate propagated in the laser propagation direction shot by shot, then, the void pushed the molten glass near the back surface. We also confirmed that the molten glass was ejected from the back surface of plates at a speed of 10-100 m/s. We assumed that the driving force is "recoil pressure", and compared the estimated pressure value from this experiment with that shown in the references. The value estimated by the relationship between pressure and momentum was 1.3 MPa, which was close to that reported in the past.
Glass nanofibers are prospective material, because they have the potential to function as biomedical tissues, optical components, or catalysts. Now, precise control of synthesis method is necessary for a variety of glass nanofiber applications. We found that glass nanofibers were generated from the back surface of a substrate during a drilling experiment using a nanosecond pulsed UV laser. In this report, we investigated the generation process. To understand the process, we set up an optical system for generating nanofibers, which is capable of moving a sample linearly using an XY stage, and monitored around the laser spot using a CCD camera. A non-alkaline, thin glass substrate was irradiated with a laser beam of wavelength 355 nm and pulse width 40 ns. As a result, when the scanning speed and focusing position were favorable, glass nanofibers were generated. According to the in situ observation, microparticles were found on the tip of the nanofibers. Also, the glass substrate was modified in a wider range compared with the laser spot size. Thus, we considered that glass nanofibers were generated when the particles were ejected resulting from local heating. Additionally, glass nanofibers could be generated in combination with a galvano scanning system. The generation of glass nanofibers from the back surface of a substrate is advantageous in terms of their collection owing to the reduced interaction with the laser beam.
Local melting can be induced inside a glass by focusing femtosecond (fs) laser pulses at high repetition rate (>100kH). As the results, the spatial distributions of glass elements are modified in the molten region. Because various propertied of glasses depends on the composition of elements, the modification of spatial distribution of glass elements using fs laser will make it possible to control glass properties in three dimensional manner. The important point of the control of elemental distribution is how to control the flow of glass melt during laser irradiation. In this study, to elucidate how parallel laser irradiation affects the flow of glass melt during laser irradiation, we investigated the relationship between the flow of glass melt and various irradiation parameters by in-sites observation of flow of glass melt inside a sodalime glass during repetitive photoexcitation by 1 kHz and 250 kHz fs laser pulses at multiple spots.
Real-time acquisition of polarization distribution of light will enable us to treat new image information and give us new application of image acquisition. A polarization imaging filter, which is used to obtain a polarization distribution in realtime, is consist of two-dimensionally arrayed polarizers or waveplates of different orientations. A polarization imaging filter of waveplate-type can be fabricated by inscribing birefringent structure inside a silica glass by focused ultrashort laser pulses. Larger retardance and higher transmittance of a filter are required to acquire the polarization with a higher sensitivity. However, transmittance through inscribed birefringent structures decreases with increasing retardance. Therefore, it is necessary to elucidate the laser processing conditions to obtain larger retardance with maintaining transmittance as possible. In this study, we investigated processing characteristics such as retardance and transmittance which determine the performance of a polarization filter.
When a femtosecond laser pulse is focused tightly inside a LiF single crystal, cracks are generated in the <100<
directions from the photoexcited region. Previously, we found that cracks of different lengths are formed by
simultaneous fs laser irradiation at multiple spots. To elucidate the mechanism of modulation in crack lengths, we
observed the transient stress distributions after simultaneous fs laser irradiation at multiple spots inside a LiF single
crystal. First, we found that stress amplitude can be doubled by the interference of fs laser induced stress waves. Next,
we observed the dynamics of crack formation as well as the transient birefringence distribution. In the case in which one
crack became shorter than other cracks, the observation of the crack dynamics showed that the compressive stress by a
constrictive interference of stress waves at a crack tip prevented the crack from propagating further. However, In the case
in which the elongation of one crack occurred, we could not find any relationship between the elongation of a crack and
the interference of stress waves by the observed stress distribution. Based on the time-resolved observation, we discussed
the mechanism of the modulation of the laser induced cracks by interference of stress waves.
A holographic laser machining can improve the processing efficiency. In the method, multiple light spots are generated at the processing positions by focusing a spatially phase modulated laser beam with a spatial light modulator. When this method is applied to bulk-laser machining, the accuracy of focusing positions is sometimes reduced because of the distortion of light focusing. In this paper, we present two calculation method of a phase hologram for reducing the distortion of light focusing. One method is based on the iterative Fourier transform method. In this method, the distortion of light focusing was reduced by fixing phase in light spots in the iterative process. The other is based on the optimal rotation angle method. In this method, the evaluation function was modified to make the light intensity at the positions of phase jump zero. In both two methods, we succeed to improve the quality of light spots. In addition, we show the application of these methods to writing of optical waveguides inside glasses.
Laser-induced deformation depends on the atomic structure of the material. In amorphous materials, the deformation is random or isotropic. On the other hand, in single crystals, anisotropic deformations occur in the specific directions, which is because of their regularly-arranged atomic structures. For example, when a fs laser pulse is focused inside rock-salt type crystalline materials (MgO, LiF, etc.) normal to the (001) plane, a void is formed in the photoexcited region and highly concentrated dislocation bands and cleavages are formed in the <110> and <100> directions, respectively. The directions of the dislocation bands and cleavages are often explained by the slip and cleavage planes of the crystals, however, stresses that induce these modifications have not been elucidated. In this study, we observed the dynamics of transient stress distributions after photoexcitation inside various single crystals by a pump-probe polarization microscope. After a femtosecond laser pulse was focused inside a MgO single crystal normal to the (001) plane, a void appeared in the photoexcited region and two stress waves (primary and secondary stress waves) were generated. In the primary stress wave, which propagated faster than the secondary one, the direction of the strain was identical to the propagation direction and the stress direction depended on the direction from the photoexcited region. In the secondary stress wave, there were tensile stresses normal to the (100) planes, which were identical to the cleavage planes.
Element migration in multicomponent glass is a phenomenon induced by high-repetition femtosecond laser irradiation
and enables spatially selective modification of glass composition. Since the composition of a glass affects its material
properties such as refractive index, luminescence, etching rate, viscosity, crystallization temperature, and phase-separation
property, element migration is of great interest for practical applications. However, the mechanisms
underlying migration have not been elucidated. In this study, we succeeded in identifying its driving force. In an
experimental study, we simultaneously focused two beams of femtosecond laser pulses into two spatially-separated spots
inside silicate glass. We observed the formation of characteristically shaped element distributions by electron probe
microanalysis. In addition, we performed numerical simulations in which we considered concentration- and temperature-gradient-driven diffusions. The simulation results were in excellent qualitative agreement with the experimental results,
indicating that element migration can be explained by thermodiffusion and that the driving force is the temperature
gradient. These results constitute an important advance for three-dimensional control of glass properties.
KEYWORDS: Glasses, Laser processing, Spatial light modulators, Femtosecond phenomena, Crystals, Laser crystals, Laser systems engineering, Control systems, Modulation, Chemical elements
Applications of the parallel fs laser processing system to spatial control of material properties are presented. In the
parallel laser processing system, multiple light spots are generated by modulating the spatial phase distribution of a laser
beam with a spatial light modulator. When the light spots are sufficiently separated from each other or the energies of the
excitation laser pulses are weak, there is little interaction between photoexcited regions. In many cases, no interaction
between each photoexcited regions is preferable, because thermal energies and stresses from each photoexcited regions
could influence the processing accuracy. On the other hand, we found that the interaction of thermal energies and
transient stresses in a parallel laser processing inside transparent materials can be used for controlling the spatial
distributions of material properties. In this paper, we show two applications of the interactions between multiple
photoexcited regions. One is the control of the shape of the heat modification and distributions of elements inside glasses.
Another is the modification of dislocation bands inside rock-salt crystals by the interference of stress waves generated at
multiple spots.
In this paper, micromachining inside of direct and indirect semiconductor, such as zinc oxide crystal (ZnO) and
single-crystalline silicon(c-Si) using femtosecond laser pulses is successfully demonstrated. In the case of ZnO, oxygen
vacancy or interstitial zinc was three-dimensionally induced by the near-infrared femtosecond laser pulse irradiation. The
threshold energy for oxygen defect formation increased with increasing in a pulse width. The mechanism of the pulsewidth
dependence of the damage threshold inside ZnO could be interpreted in terms of the excitonic Mott transition to
the electron-hole plasma which depends on the electron plasma density induced by the laser irradiation. We have also
successfully micromachined inside c-Si using infrared ultrashort laser pulses (λ = 1.24 μm). Optical microscope
observation under an infrared lamp illumination indicates low density material or scattering structure was formed in the
vicinity of the focal spot.
When femtosecond laser pulses are focused inside a single crystal, anisotropic structural changes such as dislocation and
cleavage occur along specific orientations. It can be interpreted that the anisotropic structural changes should be induced
by transient stress after photoexcitation, such as a thermal stress and stress wave. To elucidate the mechanism of the laser
induced structural changes inside crystals, we developed a novel time-resolved polarization imaging system, in which
circularly polarized laser pulse was used as a probe light. The system enabled us to observe laser-induced transient stress
distribution as well as the orientation after focusing fs laser pulses inside MgO and LiF single crystals. Based on the
observation, we elucidated the relation between laser-induced transient stress distribution and anisotropic structural change
inside the crystals.
Localized phase separation was induced inside a glass, the composition of which is not immiscible, by femtosecond
laser-induced compositional modification. The glass composition was changed locally from a miscible composition to an
immiscible one with high-repetition femtosecond laser irradiation. The phase separation was confirmed by analyzing the
composition of the irradiated area with confocal Raman spectroscopy and by observing the co-continuous structure due
to phase separation with scanning electron microscopy. The compositional change seems to be related to
thermomigration, which is the migration of atoms or ions by the temperature gradient, because the sharp temperature
gradient is caused with a high-repetition femtosecond laser. With this method, we can obtain nanoscale co-continuous
structure, which would have high surface area, on a glass surface. Moreover, we can control the morphology of the
structure by heat treatment while avoiding phase separation in the entire glass because the composition of the non-modified
region is not immiscible.
A femtosecond laser processing system with a spatial light modulator (SLM) and its application are presented. Three-dimensional
refractive index structures can be fabricated inside glasses by focusing femtosecond laser pulses. When a
three-dimensional structure is created, number of processing time is necessary. In addition, fast scanning cannot be
applied to shorten the processing time, because long exposure time of laser pulses is necessary to avoid a formation of
cracks in the photoexcited region. Therefore, fabrication efficiency is a critical problem. Our laser processing system
with an SLM can improve the fabrication efficiency, because multiple light spots can be generated by modulating the
spatial phase distribution of laser beam with an SLM. In this paper, we will present the principle of the laser machining
system as well as the applications for parallel writing of 3D optical waveguides, diffractive gratings, and optical data
storage.
Recently a remarkable phenomenon in ultrafast laser processing of transparent materials has been reported manifesting
itself as a change in material modification by reversing the writing direction. It has been experimentally demonstrated
that the pulse front tilt is responsible for the occurrence of directional dependence. Additionally, an anisotropic
cavitation was observed in the vicinity of the focus at high fluences. The bubbles, formed in the bulk of the glass, can be
trapped and manipulated in the plane perpendicular to the light propagation direction by controlling the laser writing
direction relative to the tilt of the pulse front. Another intriguing effect recently discovered occurs when the direction of
the femtosecond laser beam is reversed from +Z to - Z directions, the structures written in a lithium niobate crystal are
mirror images when translating the beam along the +Y and -Y directions. In contrast to glass, the directional dependence
of writing in lithium niobate depends on the orientation of the crystal with respect to the direction of the beam movement
and the light propagation direction. A theoretical model was created to demonstrate how in the lithium niobate, the
nonreciprocal photosensitivity manifests itself as a changing the sign of the light-induced current when the light
propagation direction is reversed. Therefore, in a non-centrosymmetric medium, modification of the material can be
different when light propagates in opposite directions.
Various structures can be produced at the focal point inside a transparent material by using pulsed laser operating at the
non-resonant wavelength with pulse widths of the order of femtoseconds. We have succeeded in the three-dimensional
structural-phase transformation from diamond to amorphous structures which have high electrically conductive
properties by the femtosecond laser pulses irradiation. The spatially periodic conductive structures indicate photonic
crystal properties in terahertz region. We have also demonstrated the three-dimensional nanostructuring inside a glass
material by the single femtosecond laser beam irradiation. The self-organized sub-wavelength periodic nanostructures
are created by a pattern of interference between the incident light field and the electric field of the bulk electron plasma
wave excited via two plasmon parametric decay. More recently, we have observed metallic Cu nanowires with a length
of 1.0 μm and a diameter of 85 nm which were successfully photo-converted from commercial scale-like Cu particles,
dispersed in a methanol solution, by using femtosecond laser irradiation. The growth mechanism of Cu nanowires under
laser irradiation was suggested to be a nucleation growth process.
A femtosecond laser machining has been utilized to fabricate various optical devices inside transparent material. To
elucidate the mechanism of the femtosecond laser induced structural change inside a glass, we have observed the
dynamics of the structural change and detected pressure wave propagation by a Transient Lens (TrL) method. Although
the pressure wave generation has been already observed in our previous study, the analysis to obtain the temporal
evolution of the refractive index distribution change was rather complex. In this study, we show alternative analysis
method for TrL signals of bulk modification inside glass by femtosecond laser. From the analysis, the dynamics of the
structural change including refractive index change at the center and shape of pressure wave becomes clear.
Femtosecond laser has been widely used in a light source for materials processing when high accuracy and small
structure size are required. When a transparent material e.g. glass is irradiated by a tightly focused femtosecond laser, the
photo-induced reaction is expected to occur only near the focused part of the laser beam inside the glass due to the
multiphoton processes based on the ultrashort interaction time and the ultrahigh light intensity. We proposed a research
idea of "induced structure" which means spatially modified micro- and nanostructures in a transparent material by the
femtosecond laser irradiation. In this paper, we review our recent investigations on the three-dimensional nanostructure
self-organization composed of oxygen deficiencies inside fused silica, the space-selective silicon structures formation in
silicate glass based on thermite reaction triggered by femtosecond laser pulses, and diffusion of elements constituting
glass based on thermal accumulation by high repetition rate femtosecond laser pulses. We also discuss the mechanisms
and possible applications of the observed phenomena.
We have fabricated silicon structure in silicate glass prepared with metallic aluminum in the starting material, using femtosecond laser irradiation and subsequent annealing. Small Si-rich structures such as oxygen-deficiency (O-deficiency) defects or Si clusters transform into nano-sized Si particles by the focusing irradiation of the laser. Then the Si-rich structures grow into micro-size particles due to the thermite reaction promoted by heat treatment. We determine the effect of focused laser pulse on the Si deposition process by using a time-resolved transient lens method with a sub-picosecond laser pulse. Localized high-temperature, high-pressure, and the generation of shock waves appear to be very important in forming the Si-rich structures that ultimately grow into Si particles. The diffusion of oxygen by shock waves and the existence of Al-rich structures help form Si-rich structures as Si-O bonds continuously break under high temperature. The focusing irradiation of femtosecond lasers is very useful for fabricating Si structures inside glass.
Femtosecond laser has been widely used in microscopic modifications to materials due to its ultra-short laser pulse and ultrahigh light intensity. When a transparent material e.g. glass is irradiated by a tightly focused femtosecond laser, the photo-induced reaction is expected to occur only near the focused part of the laser beam inside the glass due to the multiphoton processes. We observed various induced localized microstructures e.g. color center defects, refractive index change, micro-void and micro-crack, in glasses after the femtosecond laser irradiation, and discussed the possible applications of the microstructures in the fabrication of various micro-optical components, e.g. optical waveguide, micro-grating, micro-lens, fiber attenuator, 3-dimensional optical memory. In this paper, we review our recent investigations on single femtosecond laser-beam induced nanostructures. We introduce the space-selective nanoscale valence state manipulation of active ions, precipitation and control of metal nanoparticles and observation of polarization-dependent permanent nanostructures, and discuss the mechanisms and possible applications of the observed phenomena.
Femtosecond laser is under intense study as a new laser processing tool which can induce refractive index change and color center, etc. inside of transparent materials. Here, we report on the first observation of the formation of polarization-dependent nano-grating by irradiation of only single femtosecond laser beam inside silica glasses. This nano-grating was formed by the self-organization at intervals of 200 nm of generated oxygen defect in the laser focal point. The direction of nano-grating was controllable by laser polarization direction. Additionally, the periodicity was variable according to the irradiation laser light of energy and pulse number. We proposed a mechanism of this novel phenomenon containing the interference between the laser light (photon) and the generated plasma wave on the focal point.
New phenomena of anisotropic light scattering, anisotropic Cherenkov third-harmonic generation, photoinduced birefringence and anisotropic reflection from femtosecond direct-write structure are reviewed. The phenomena and recent direct observation reveal the smallest embedded structures ever created by light and new mechanism of light-matter interaction.
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