Femtosecond laser ultrafast photothermal exsolution

Exsolution,as an effective approach to constructing particle-decorated interfaces,is still challenging to yield interfacial films rather than isolated particles.Inspired by in vivo near-infrared laser photothermal therapy,using 3 mol%Y_(2)O_(3)stabilized tetragonal zirconia polycrystals(3Y-TZP)as host oxide matrix and iron-oxide(Fe3O4/γ-Fe_(2)O_(3)/α-Fe_(2)O_(3))materials as photothermal modulator and exsolution resource,femtosecond laser ultrafast exsolution approach is presented enabling to conquer this challenge.The key is to trigger photothermal annealing behavior via femtosecond laser ablation to initialize phase transition from monoclinic zirconia(m-ZrO_(2))to tetragonal zirconia(t-ZrO_(2))and induce t-ZrO_(2)columnar crystal growth.Fe-ions rapidly segregate along grain boundaries and diffuse towards the outmost surface,and become‘frozen’,highlighting the potential to use photothermal materials and ultrafast heating/quenching behaviors of femtosecond laser ablation for interfacial exsolution.Triggering interfacial iron-oxide coloring exsolution is composition and concentration dependent.Photothermal materials themselves and corresponding photothermal transition capacity play a crucial role,initializing at 2 wt%,3 wt%,and 5 wt%for Fe3O4/γ-Fe_(2)O_(3)/α-Fe_(2)O_(3)doped 3Y-TZP samples.Due to different photothermal effects,exsolution states of ablated 5 wt%Fe_(3)O_(4)/γ-Fe_(2)O_(3)/α-Fe_(2)O_(3)-doped 3Y-TZP samples are totally different,with whole coverage,exhaustion(ablated away)and partial exsolution(rich in the grain boundaries in subsurface),respectively.Femtosecond laser ultrafast photothermal exsolution is uniquely featured by up to now the deepest microscale(10μm from 5 wt%-Fe_(3)O_(4)-3Y-TZP sample)Fe-elemental deficient layer for exsolution and the whole coverage of exsolved materials rather than the formation of isolated exsolved particles by other methods.It is believed that this novel exsolution method may pave a good way to modulate interfacial properties for extensive applications in the fields of biology,optics/photonics,energy,catalysis,environment,etc.

Irregular LIPSS produced on metals by single linearly polarized femtosecond laser

Currently,supra-wavelength periodic surface structures(SWPSS)are only achievable on silica dielectrics and silicon by femtosecond(fs)laser ablation,while triangular and rhombic laser induced periodic surface structures(LIPSS)are achievable by circularly polarized or linear cross-polarized femtosecond laser.This is the first work to demonstrate the possibility of generating SWPSS on Sn and triangular and rhombic LIPSS on W,Mo,Ta,and Nb using a single linearly polarized femtosecond laser.We discovered,for the first time,SWPSS patches with each possessing its own orientation,which are completely independent of the light polarization direction,thus,breaking the traditional rules.Increasing the laser power enlarges SWPSS periods from 4–6μm to 15–25μm.We report a maximal period of 25μm,which is the largest period ever reported for SWPSS,~10 and~4 times the maximal periods(2.4μm/6.5μm)of SWPSS ever achieved by fs and ns laser ablation,respectively.The formation of triangular and rhombic LIPSS does not depend on the laser(power)or processing(scan interval and scan methodology)parameters but strongly depends on the material composition and is unachievable on other metals,such as Sn,Al,Ti,Zn,and Zr.This paper proposes and discusses possible mechanisms for molten droplet generation/spread/solidification,Marangoni convection flow for SWPSS formation,and linear-to-circular polarization transition for triangular and rhombic LIPSS formation.Reflectance and iridescence of as-prepared SWPSS and LIPSS are characterized.It was found that besides insufficient ablation on W,the iridescence density of Ta-,Mo-,Nb-LIPSS follows the sequence of melting temperatures:Ta>Mo>Nb,which indicates that the melting temperature of metals may affect the regularity of LIPSS.This work may inspire significant interest in further enriching the diversity of LIPSS and SWPSS.

Hierarchical microstructures with high spatial frequency laser induced periodic surface structures possessing different orientations created by femtosecond laser ablation of silicon in liquids

High spatial frequency laser induced periodic surface structures(HSFLs)on silicon substrates are often developed on flat surfaces at low fluences near ablation threshold of 0.1 J/cm2,seldom on microstructures or microgrooves at relatively higher fluences above 1 J/cm^2.This work aims to enrich the variety of HSFLs-containing hierarchical microstructures,by femtosecond laser(pulse duration:457 fs,wavelength:1045 nm,and repetition rate:100 kHz)in liquids(water and acetone)at laser fluence of 1.7 J/cm^2.The period of Si-HSFLs in the range of 110–200 nm is independent of the scanning speeds(0.1,0.5,1 and 2 mm/s),line intervals(5,15 and 20μm)of scanning lines and scanning directions(perpendicular or parallel to light polarization direction).It is interestingly found that besides normal HSFLs whose orientations are perpendicular to the direction of light polarization,both clockwise or anticlockwise randomly tilted HSFLs with a maximal deviation angle of 50°as compared to those of normal HSFLSs are found on the microstructures with height gradients.Raman spectra and SEM characterization jointly clarify that surface melting and nanocapillary waves play important roles in the formation of Si-HSFLs.The fact that no HSFLs are produced by laser ablation in air indicates that moderate melting facilitated with ultrafast liquid cooling is beneficial for the formation of HSFLs by LALs.On the basis of our findings and previous reports,a synergistic formation mechanism for HSFLs at high fluence was proposed and discussed,including thermal melting with the concomitance of ultrafast cooling in liquids,transformation of the molten layers into ripples and nanotips by surface plasmon polaritons(SPP)and second-harmonic generation(SHG),and modulation of Si-HSFLs direction by both nanocapillary waves and the localized electric field coming from the excited large Si particles.

Liquid vortexes and flows induced by femtosecond laser ablation in liquid governing formation of circular and crisscross LIPSS

Orientations of laser induced periodic surface structures(LIPSS)are usually considered to be governed by the laser polarization state.In this work,we unveil that fluid dynamics induced by femtosecond(fs)laser ablation in liquid(fs-LAL)can easily break this polarization restriction to produce irregular circular-LIPSS(CLIPPS)and crisscross-LIPSS(CCLIPSS).Fs laser ablation of silicon in water shows formation of diverse LIPSS depending on ablation conditions.At a high power of 700 mW(repetition rate of 100 kHz,pulse duration of 457 fs and wavelength of 1045 nm),single/twin CLIPSS are produced at the bottom of macropores of several microns in diameter due to the formation of strong liquid vortexes and occurrence of the vortex shedding effect.Theoretical simulations validate our speculation about the formation of liquid vortex with an ultrahigh static pressure,which can induce the microstructure trenches and cracks at the sidewalls for fs-LAL of Si and tungsten(W)in water,respectively.At a low power of 50 mW,weak liquid vortexes are produced,which only give birth to curved LIPSS in the valleys of grooves.Consequently,it is deduced that liquid vortex plays a crucial role in the formation of macropores.Mountain-like microstructures induce complex fluid dynamics which can cause the formation of CCLIPSS on them.It is believed that liquid vortexes and fluid dynamics presented in this work open up new possibilities to diversify the morphologies of LIPSS formed by fs-LAL.

Femtosecond laser shockwave peening ablation in liquids for hierarchical micro/nanostructuring of brittle silicon and its biological application

This paper presents a new technique,termed femtosecond laser shock peening ablation in liquids(fs-LSPAL),which can realize simultaneous crack micro/nanomanufacturing and hierarchical micro/nanolaser ablation,giving rise to the formation of diverse multiscale hierarchical structures,such as macroporous ratcheted structures and enéchelon microfringes decorated with parabolic nanoripples.Through analysis of surface morphologies,many phenomena have been confirmed to take place during fs-LSPAL,including enéchelon cracks,nanostriation,ripple densification,crack branching,and selective formation of high spatial frequency laser-induced periodic surface structures of 100–200 nm in period.At a high laser power of 700 mW,fs-LSPAL at scanning speeds of 0.2 mm s^-1 and 1 mm s^-1 enables the generation of height-fluctuated and height-homogeneous hierarchical structures,respectively.The height-fluctuated structures can be used to induce‘colony’aggregates of embryonic EB3 stem cells.At 200 mW,fs-LSPAL at 1 mm s^-1 is capable of producing homogeneous tilt macroporous structures with cracked structures interleaved among them,which are the synergistic effects of bubble-induced light refraction/reflection ablation and cracks.As shown in this paper,the conventional laser ablation technique integrated with its self-driven unconventional cracking under extreme conditions expands the horizons of extreme manufacturing and offers more opportunities for complex surface structuring,which can potentially be used for biological applications.

Underwater persistent bubble-assisted femtosecond laser ablation for hierarchical micro/nanostructuring

In this study,we demonstrate a technique termed underwater persistent bubble assisted femtosecond laser ablation in liquids(UPB-fs-LAL)that can greatly expand the boundaries of surface micro/nanostructuring through laser ablation because of its capability to create concentric circular macrostructures with millimeter-scale tails on silicon substrates.Long-tailed macrostructures are composed of layered fan-shaped(central angles of 45°–141°)hierarchical micro/nanostructures,which are produced by fan-shaped beams refracted at the mobile bubble interface(.50°light tilt,referred to as the vertical incident direction)during UPB-fs-LAL line-by-line scanning.Marangoni flow generated during UPB-fs-LAL induces bubble movements.Fast scanning(e.g.1mms−1)allows a long bubble movement(as long as 2mm),while slow scanning(e.g.0.1mms−1)prevents bubble movements.When persistent bubbles grow considerably(e.g.hundreds of microns in diameter)due to incubation effects,they become sticky and can cause both gas-phase and liquidphase laser ablation in the central and peripheral regions of the persistent bubbles.This generates low/high/ultrahigh spatial frequency laser-induced periodic surface structures(LSFLs/HSFLs/UHSFLs)with periods of 550–900,100–200,40–100 nm,which produce complex hierarchical surface structures.A period of 40 nm,less than 1/25th of the laser wavelength(1030 nm),is the finest laser-induced periodic surface structures(LIPSS)ever created on silicon.The NIR-MIR reflectance/transmittance of fan-shaped hierarchical structures obtained by UPB-fs-LAL at a small line interval(5μm versus 10μm)is extremely low,due to both their extremely high light trapping capacity and absorbance characteristics,which are results of the structures’additional layers and much finer HSFLs.In the absence of persistent bubbles,only grooves covered with HSFLs with periods larger than 100 nm are produced,illustrating the unique attenuation abilities of laser properties(e.g.repetition rate,energy,incident angle,etc)by persistent bubbles with different curvatures.This research represents a straightforward and cost-effective approach to diversifying the achievable hierarchical micro/nanostructures for a multitude of applications.

Perspective on how laser-ablated particles grow in liquids

Laser ablation in liquids has emerged as a new branch of nanoscience for developing various nanomaterials with different shapes.However, how to design and control nanomaterial growth is still a challenge due to the unique chemical-physical process chain correlated with nanomaterial nucleation and growth, including plasma phase(generation and rapid quenching), gas(bubble) phase,and liquid phase. In this review, through summarizing the literature about this topic and comparing with the well-established particle growth mechanisms of the conventional wet chemistry technique, our perspective on the possible nanoparticle growth mechanisms or routes is presented, aiming at shedding light on how laser-ablated particles grow in liquids. From the microscopic viewpoint, the nanoparticle growth contains six mechanisms, including LaMer-like growth, coalescence, Ostwald ripening, particle(oriented) attachment, adsorbate-induced growth and reaction-induced growth. For each microscopic growth mechanism, the vivid growth scenes of some representative nanomaterials recorded by TEM and SEM measurements are displayed. Afterwards,the scenes from the macroscopic viewpoint for the large submicro-and micro-scale nanospheres and anisotropic nanostructures formation and evolution from one nanostructure into another one are presented. The panorama of how diverse nanomaterials grow during and after laser ablation in liquids shown in this review is intended to offer a overview for researchers to search for the possible mechanisms correlated to their synthesized nanomaterials, and more expectation is desired to better design and tailor the morphology of the nanocrystals synthesized by LAL technique.

Femtosecond laser induced simultaneous functional nanomaterial synthesis,in situ deposition and hierarchical LIPSS nanostructuring for tunable antireflectance and iridescence applications

Femtosecond laser induced periodic surface structures(LIPSSs)are excellent biomimetic iridescent antireflective interfaces.In this work,we demonstrate the feasibility to develop tunable iridescent antireflective surfaces via simultaneous synthesis of functional metal-oxide nanomaterials,in situ deposition and hierarchical LIPSSs nanostructuring by means of femtosecond laser ablation(fs-LA)of tungsten(W)and molybdenum(Mo)in air.Adjusting the scanning interval from 1μm to 20μm allows the modulation of particle deposition rates on LIPSSs.Diminishing the scan interval enables a higher particle deposition rate,which facilitates the development of better UV-to-MIR ultrabroadband antireflective surfaces with a less pronounced iridescence.Through comparing the reflectance of hierarchical LIPSSs with different densities of loosely/tightly deposited particles,it is found that the deposited WO_(x)and MoO_(x)particle aggregates have high UV-to-MIR ultrabroadband absorbance,especially extraordinary in the MIR range.Loosely deposited particles which self-assembly into macroporous structures outperform tightly deposited particles for ultrabroadband antireflective applications.The presence of loosely deposited MoO_(x)and WO_(x)particle absorbers can cause up to 80%and 60%enhancement of antireflectance performances as compared to the tightly particle deposited LIPSSs samples.One stone of"fs-LA technique"with three birds of(particle generation,in situ deposition and LIPSS hierarchical nanostructuring)presented in this work opens up new opportunities to tune the reflectance and iridescence of metallic surfaces.

Diverse nanomaterials synthesized by laser ablation of pure metals in liquids

Diverse nanomaterials, in the forms of carbides, sulfides, oxides, metals, hydroxides, etc., have been synthesized by laser ablation in liquids(LAL) with metal targets as the dominant educts. Many advantages of LAL technique itself and its products have been revealed since 1983 when the first report about LAL was released. Different from traditional wet-chemical synthesis,one unique feature of LAL is its resultant extreme high-temperature and high-pressure local environment for the nucleation and growth of nanomaterials, despite being performed at room temperature. This extreme condition can induce the atomization and ionization of the target materials and liquid molecules to incur different chemical reactions. The laser, liquid, liquid additive, and target can significantly alter the local environment in a broad range. Thus, different phases and shapes of nanomaterials are producible even from the same target. Through directly comparing the products of LAL of 13 kinds of chosen representative metals synthesized under different conditions, this review presents and discusses current understandings, challenging issues, and perspectives related to the diversity of LAL-products, which is willing to promote a deeper investigation and discussion on a clear clarification of the chemical reactions and particle nucleation/growth processes.