Physical Regimes and Mechanisms of Picosecond Laser Fragmentation of Gold Nanoparticles in Water from X-ray Probing and Atomistic Simulations.

Laser fragmentation in liquids has emerged as a promising green chemistry technique for changing the size, shape, structure, and phase composition of colloidal nanoparticles, thus tuning their properties to the needs of practical applications. The advancement of this technique requires a solid understanding of the mechanisms of laser-nanoparticle interactions that lead to the fragmentation. While theoretical studies have made impressive practical and mechanistic predictions, their experimental validation is required. Hence, using the picosecond laser fragmentation of Au nanoparticles in water as a model system, the transient melting and fragmentation processes are investigated with a combination of time-resolved X-ray probing and atomistic simulations. The direct comparison of the diffraction profiles predicted in the simulations and measured in experiments has revealed a sequence of several nonequilibrium processes triggered by the laser irradiation. At low laser fluences, in the regime of nanoparticle melting and resolidification, the results provide evidence of a transient superheating of crystalline nanoparticles above the melting temperature. At fluences about three times the melting threshold, the fragmentation starts with evaporation of Au atoms and their condensation into small satellite nanoparticles. As fluence increases above five times the melting threshold, a transition to a rapid (explosive) phase decomposition of superheated nanoparticles into small liquid droplets and vapor phase atoms is observed. The transition to the phase explosion fragmentation regime is signified by prominent changes in the small-angle X-ray scattering profiles measured in experiments and calculated in simulations. The good match between the experimental and computational diffraction profiles gives credence to the physical picture of the cascade of thermal fragmentation regimes revealed in the simulations and demonstrates the high promise of the joint tightly integrated computational and experimental efforts.

Kinetics of laser-induced melting of thin gold film: How slow can it get?

Melting is a common and well-studied phenomenon that still reveals new facets when triggered by laser excitation and probed with ultrafast electron diffraction. Recent experimental evidence of anomalously slow nanosecond-scale melting of thin gold films irradiated by femtosecond laser pulses motivates computational efforts aimed at revealing the underlying mechanisms of melting. Atomistic simulations reveal that a combined effect of lattice superheating and relaxation of laser-induced stresses ensures the dominance of the homogeneous melting mechanism at all energies down to the melting threshold and keeps the time scale of melting within ~100 picoseconds. The much longer melting times and the prominent contribution of heterogeneous melting inferred from the experiments cannot be reconciled with the atomistic simulations by any reasonable variation of the electron-phonon coupling strength, thus suggesting the need for further coordinated experimental and theoretical efforts aimed at addressing the mechanisms and kinetics of laser-induced melting in the vicinity of melting threshold.

Ultrashort pulse laser ablation in liquids: probing the first nanoseconds of underwater phase explosion.

The ultrafast pump-probe microscopy has shed new light on the complex dynamics of laser-induced explosive phase transformations and highlighted the importance of close integration of experimental, computational, and theoretical efforts.

Kinetics of solid-liquid interface motion in molecular dynamics and phase-field models: crystallization of chromium and silicon.

The results of molecular dynamics (MD) simulations of the crystallization process in one-component materials and solid solution alloys reveal a complex temperature dependence of the velocity of the crystal-liquid interface featuring an increase up to a maximum at 10-30% undercooling below the equilibrium melting temperature followed by a gradual decrease of the velocity at deeper levels of undercooling. At the qualitative level, such non-monotonous behaviour of the crystallization front velocity is consistent with the diffusion-controlled crystallization process described by the Wilson-Frenkel model, where the almost linear increase of the interface velocity in the vicinity of melting temperature is defined by the growth of the thermodynamic driving force for the phase transformation, while the decrease in atomic mobility with further increase of the undercooling drives the velocity through the maximum and into a gradual decrease at lower temperatures. At the quantitative level, however, the diffusional model fails to describe the results of MD simulations in the whole range of temperatures with a single set of parameters for some of the model materials. The limited ability of the existing theoretical models to adequately describe the MD results is illustrated in the present work for two materials, chromium and silicon. It is also demonstrated that the MD results can be well described by the solution following from the hodograph equation, previously found from the kinetic phase-field model (kinetic PFM) in the sharp interface limit. The ability of the hodograph equation to describe the predictions of MD simulation in the whole range of temperatures is related to the introduction of slow (phase field) and fast (gradient flow) variables into the original kinetic PFM from which the hodograph equation is obtained. The slow phase-field variable is responsible for the description of data at small undercoolings and the fast gradient flow variable accounts for local non-equilibrium effects at high undercoolings. The introduction of these two types of variables makes the solution of the hodograph equation sufficiently flexible for a reliable description of all nonlinearities of the kinetic curves predicted in MD simulations of Cr and Si. This article is part of the theme issue 'Transport phenomena in complex systems (part 1)'.

Correction: The effect of pulse duration on nanoparticle generation in pulsed laser ablation in liquids: insights from large-scale atomistic simulations.

Correction for 'The effect of pulse duration on nanoparticle generation in pulsed laser ablation in liquids: insights from large-scale atomistic simulations' by Cheng-Yu Shih et al., Phys. Chem. Chem. Phys., 2020, 22, 7077-7099, DOI: .

Graphene reinforced carbon fibers.

The superlative strength-to-weight ratio of carbon fibers (CFs) can substantially reduce vehicle weight and improve energy efficiency. However, most CFs are derived from costly polyacrylonitrile (PAN), which limits their widespread adoption in the automotive industry. Extensive efforts to produce CFs from low cost, alternative precursor materials have failed to yield a commercially viable product. Here, we revisit PAN to study its conversion chemistry and microstructure evolution, which might provide clues for the design of low-cost CFs. We demonstrate that a small amount of graphene can minimize porosity/defects and reinforce PAN-based CFs. Our experimental results show that 0.075 weight % graphene-reinforced PAN/graphene composite CFs exhibits 225% increase in strength and 184% enhancement in Young's modulus compared to PAN CFs. Atomistic ReaxFF and large-scale molecular dynamics simulations jointly elucidate the ability of graphene to modify the microstructure by promoting favorable edge chemistry and polymer chain alignment.

The effect of pulse duration on nanoparticle generation in pulsed laser ablation in liquids: insights from large-scale atomistic simulations.

The generation of colloidal solutions of chemically clean nanoparticles through pulsed laser ablation in liquids (PLAL) has evolved into a thriving research field that impacts industrial applications. The complexity and multiscale nature of PLAL make it difficult to untangle the various processes involved in the generation of nanoparticles and establish the dependence of nanoparticle yield and size distribution on the irradiation parameters. Large-scale atomistic simulations have yielded important insights into the fundamental mechanisms of ultrashort (femtoseconds to tens of picoseconds) PLAL and provided a plausible explanation of the origin of the experimentally observed bimodal nanoparticle size distributions. In this paper, we extend the atomistic simulations to short (hundreds of picoseconds to nanoseconds) laser pulses and focus our attention on the effect of the pulse duration on the mechanisms responsible for the generation of nanoparticles at the initial dynamic stage of laser ablation. Three distinct nanoparticle generation mechanisms operating at different stages of the ablation process and in different parts of the emerging cavitation bubble are identified in the simulations. These mechanisms are (1) the formation of a thin transient metal layer at the interface between the ablation plume and water environment followed by its decomposition into large molten nanoparticles, (2) the nucleation, growth, and rapid cooling/solidification of small nanoparticles at the very front of the emerging cavitation bubble, above the transient interfacial metal layer, and (3) the spinodal decomposition of a part of the ablation plume located below the transient interfacial layer, leading to the formation of a large population of nanoparticles growing in a high-temperature environment through inter-particle collisions and coalescence. The coexistence of the three distinct mechanisms of the nanoparticle formation at the initial stage of the ablation process can be related to the broad nanoparticle size distributions commonly observed in nanosecond PLAL experiments. The strong dependence of the nanoparticle cooling and solidification rates on the location within the low-density metal-water mixing region has important implications for the long-term evolution of the nanoparticle size distribution, as well as for the ability to quench the nanoparticle growth or dope them by adding surface-active agents or doping elements to the liquid environment.

Effect of a liquid environment on single-pulse generation of laser induced periodic surface structures and nanoparticles.

The effect of a liquid environment on the fundamental mechanisms of surface nanostructuring and generation of nanoparticles by single pulse laser ablation is investigated in a closely integrated computational and experimental study. A large-scale molecular dynamics simulation of spatially modulated ablation of Cr in water reveals a complex picture of the dynamic interaction between the ablation plume and water. Ablation plume is found to be rapidly decelerated by the water environment, resulting the formation and prompt disintegration of a hot metal layer at the interface between the ablation and water. A major fraction of the ablation plume is laterally redistributed and redeposited back to the target, forming smooth frozen surface features. Good agreement between the shapes of the surface features predicted in the simulation and the ones generated in single pulse laser ablation experiments performed for Cr in water supports the mechanistic insights revealed in the simulation. The results of this study suggest that the presence of a liquid environment can eliminate the sharp features of the surface morphology, reduce the amount of the material removed from the target by more than an order of magnitude, and narrow down the nanoparticle size distribution as compared to laser ablation under vacuum. Moreover, the computational predictions of the effective incorporation of molecules constituting the liquid environment into the surface region of the irradiated target and the generation of high vacancy concentrations, exceeding the equilibrium levels by more than an order of magnitude, suggest a potential for hyperdoping of laser-generated surfaces by solutes present in the liquid environment.

Unveiling Carbon Ring Structure Formation Mechanisms in Polyacrylonitrile-Derived Carbon Fibers.

As the demand for electric vehicles (EVs) and autonomous vehicles (AVs) rapidly grows, lower-cost, lighter, and stronger carbon fibers (CFs) are urgently needed to respond to consumers' call for greater EV traveling range and stronger safety structures for AVs. Converting polymeric precursors to CFs requires a complex set of thermochemical processes; a systematic understanding of each parameter in fiber conversion is still, to a large extent, lacking. Here, we demonstrate the effect of carbonization temperature on carbon ring structure formation by combining atomistic/microscale simulations and experimental validation. Experimental testing, as predicted by simulations, exhibited that the strength and ductility of PAN CFs decreased, whereas the Young's modulus increased with increasing carbonization temperature. Our simulations unveiled that high carbonization temperature accelerated the kinetics of graphitic phase nucleation and growth, leading to the decrease in strength and ductility but increase in modulus. The methodology presented herein using combined atomistic/microscale simulations and experimental validation lays a firm foundation for further innovation in CF manufacturing and low-cost alternative precursor development.

Femtosecond laser generation of microbumps and nanojets on single and bilayer Cu/Ag thin films.

The formation mechanisms of microbumps and nanojets on films composed of single and double Cu/Ag layers deposited on a glass substrate and irradiated by a single 60 fs laser pulse are investigated experimentally and in atomistic simulations. The composition of the laser-modified bilayers is probed with the energy dispersive X-ray spectroscopy and used as a marker for processes responsible for the modification of the film morphology. For the bilayer with the top Ag layer facing the laser, the increase in fluence is found to result in a sequential appearance of a Ag microbump, the exposure of the Cu underlayer by removal of the Ag layer, a Cu microbump, and a frozen nanojet. The Cu on Ag bilayer exhibits a partial spallation of the top Cu film, followed by the generation of surface structures that mainly consist of Ag at higher fluences. The experimental observations are explained with atomistic simulations, which reveal that the stronger electron-phonon coupling of Cu results in the confinement of the deposited laser energy in the top Cu layer in the Cu on Ag case and channelling of the energy from the top Ag layer to the underlying Cu layer in the Ag on Cu case. This difference in the energy (re)distribution directly translates into differences in the morphology of the laser-modified bilayers. In all systems, the generation of microbumps and nanojets occurs in the molten state. It is driven by the dynamic relaxation of the laser-induced stresses and, at higher fluences, the release of vapor at the interface with the substrate. The resistance of the colder periphery of the laser spot to the ejection of spalled layers as well as the rapid solidification of the transient molten structures are largely defining the final shapes of the surface structures.

Laser-Rewriteable Ferromagnetism at Thin-Film Surfaces.

Manipulation of magnetism using laser light is considered as a key to the advancement of data storage technologies. Until now, most approaches seek to optically switch the direction of magnetization rather than to reversibly manipulate the ferromagnetism itself. Here, we use ∼100 fs laser pulses to reversibly switch ferromagnetic ordering on and off by exploiting a chemical order-disorder phase transition in Fe60Al40, from the B2 to the A2 structure and vice versa. A single laser pulse above a threshold fluence causes nonferromagnetic B2 Fe60Al40 to disorder and form the ferromagnetic A2 structure. Subsequent laser pulsing below the threshold reverses the surface to B2 Fe60Al40, erasing the laser-induced ferromagnetism. Simulations reveal that the order-disorder transition is regulated by the extent of surface supercooling; above the threshold for complete melting throughout the film thickness, the liquid phase can be deeply undercooled before solidification. As a result, the vacancy diffusion in the resolidified region is limited and the region is trapped in the metastable chemically disordered state. Laser pulsing below the threshold forms a limited supercooled surface region that solidifies at sufficiently high temperatures, enabling diffusion-assisted reordering. This demonstrates that ultrafast lasers can achieve subtle atomic rearrangements in bimetallic alloys in a reversible and nonvolatile fashion.

Two mechanisms of nanoparticle generation in picosecond laser ablation in liquids: the origin of the bimodal size distribution.

The synthesis of chemically clean and environmentally friendly nanoparticles through pulsed laser ablation in liquids has shown a number of advantages over conventional chemical synthesis methods and has evolved into a thriving research field attracting laboratory and industrial applications. The fundamental understanding of processes leading to the nanoparticle generation, however, still remains elusive. In particular, the origin of bimodal nanoparticle size distributions in femto- and picosecond laser ablation in liquids, where small nanoparticles (several nanometers) with narrow size distribution are commonly observed to coexist with larger (tens to hundreds of nanometers) ones, has not been explained so far. In this paper, joint computational and experimental efforts are applied to understand the mechanisms of nanoparticle formation in picosecond laser ablation in liquids and to explain the bimodal nanoparticle size distributions. The results of a large-scale atomistic simulation reveal the critical role of the dynamic interaction between the ablation plume and the liquid environment, leading to the generation of large nanoparticles through a sequence of hydrodynamic instabilities at the plume-liquid interface and a concurrent nucleation and growth of small nanoparticles in an expanding metal-liquid mixing region. The computational predictions are supported by a series of stroboscopic videography experiments showing the emergence of small satellite bubbles surrounding the main cavitation bubble generated in single pulse experiments. Carefully timed double pulse irradiation triggers expansion of secondary cavitation bubbles indicating, in accord with the simulation results, the presence of localized sites of laser energy deposition (possibly large nanoparticles) injected into the liquid at the early stage of the bubble formation.

Generation of Subsurface Voids, Incubation Effect, and Formation of Nanoparticles in Short Pulse Laser Interactions with Bulk Metal Targets in Liquid: Molecular Dynamics Study.

The ability of short pulse laser ablation in liquids to produce clean colloidal nanoparticles and unusual surface morphology has been employed in a broad range of practical applications. In this paper, we report the results of large-scale molecular dynamics simulations aimed at revealing the key processes that control the surface morphology and nanoparticle size distributions by pulsed laser ablation in liquids. The simulations of bulk Ag targets irradiated in water are performed with an advanced computational model combining a coarse-grained representation of liquid environment and an atomistic description of laser interaction with metal targets. For the irradiation conditions that correspond to the spallation regime in vacuum, the simulations predict that the water environment can prevent the complete separation of the spalled layer from the target, leading to the formation of large subsurface voids stabilized by rapid cooling and solidification. The subsequent irradiation of the laser-modified surface is found to result in a more efficient ablation and nanoparticle generation, thus suggesting the possibility of the incubation effect in multipulse laser ablation in liquids. The simulations performed at higher laser fluences that correspond to the phase explosion regime in vacuum reveal the accumulation of the ablation plume at the interface with the water environment and the formation of a hot metal layer. The water in contact with the metal layer is brought to the supercritical state and provides an environment suitable for nucleation and growth of small metal nanoparticles from metal atoms emitted from the hot metal layer. The metal layer itself has limited stability and can readily disintegrate into large (tens of nanometers) nanoparticles. The layer disintegration is facilitated by the Rayleigh-Taylor instability of the interface between the higher density metal layer decelerated by the pressure from the lighter supercritical water. The nanoparticles emerging from the layer disintegration are rapidly cooled and solidified due to the interaction with water environment, with a cooling rate of ∼2 × 1012 K/s observed in the simulations. The computational prediction of two distinct mechanisms of nanoparticle formation yielding nanoparticles with different characteristic sizes provides a plausible explanation for the experimental observations of bimodal nanoparticle size distributions in laser ablation in liquids. The ultrahigh cooling and solidification rates suggest the possibility for generation of nanoparticles featuring metastable phases and highly nonequilibrium structures.

Atomistic modeling of nanoparticle generation in short pulse laser ablation of thin metal films in water.

Laser ablation in liquids is actively used for generation of clean colloidal nanoparticles with unique shapes and functionalities. The fundamental mechanisms of the laser ablation in liquids and the key processes that control the nanoparticle structure, composition, and size distribution, however, are not yet fully understood. In this paper, we report the results of first atomistic simulations of laser ablation of metal targets in liquid environment. A model combining a coarse-grained representation of the liquid environment (parameterized for water), a fully atomistic description of laser interactions with metal targets, and acoustic impedance matching boundary conditions is developed and applied for simulation of laser ablation of a thin silver film deposited on a silica substrate. The simulations, performed at two laser fluences in the regime of phase explosion, predict a rapid deceleration of the ejected ablation plume and the formation of a dense superheated molten layer at the water-plume interface. The water in contact with the hot metal layer is brought to the supercritical state and transforms into an expanding low density metal-water mixing region that serves as a precursor for the formation of a cavitation bubble. Two distinct mechanisms of the nanoparticle formation are predicted in the simulations: (1) the nucleation and growth of small (mostly ⩽10nm) nanoparticles in the metal-water mixing region and (2) the formation of larger (tens of nm) nanoparticles through the breakup of the superheated molten metal layer triggered by the emergence of complex morphological features attributed to the Rayleigh-Taylor instability of the interface between at the superheated metal layer and the supercritical water. The first mechanism is facilitated by the rapid cooling of the growing nanoparticles in the supercritical water environment, resulting in solidification of the nanoparticles located in the upper part of the mixing region on the timescale of nanoseconds. The computational prediction of the two mechanisms of nanoparticle formation yielding nanoparticles with different characteristic sizes is consistent with experimental observations of two distinct nanoparticle populations appearing at different stages of the ablation process.

Growth Twinning and Generation of High-Frequency Surface Nanostructures in Ultrafast Laser-Induced Transient Melting and Resolidification.

The structural changes generated in surface regions of single crystal Ni targets by femtosecond laser irradiation are investigated experimentally and computationally for laser fluences that, in the multipulse irradiation regime, produce sub-100 nm high spatial frequency surface structures. Detailed experimental characterization of the irradiated targets combining electron back scattered diffraction analysis with high-resolution transmission electron microscopy reveals the presence of multiple nanoscale twinned domains in the irradiated surface regions of single crystal targets with (111) surface orientation. Atomistic- and continuum-level simulations performed for experimental irradiation conditions reproduce the generation of twinned domains and establish the conditions leading to the formation of growth twin boundaries in the course of the fast transient melting and epitaxial regrowth of the surface regions of the irradiated targets. The observation of growth twins in the irradiated Ni(111) targets provides strong evidence of the role of surface melting and resolidification in the formation of high spatial frequency surface structures. This also suggests that the formation of twinned domains can be used as a sensitive measure of the levels of liquid undercooling achieved in short pulse laser processing of metals.

The minimum amount of "matrix" needed for matrix-assisted pulsed laser deposition of biomolecules.

The ability of matrix-assisted pulsed laser evaporation (MAPLE) technique to transfer and deposit high-quality thin organic, bioorganic, and composite films with minimum chemical modification of the target material has been utilized in numerous applications. One of the outstanding problems in MAPLE film deposition, however, is the presence of residual solvent (matrix) codeposited with the polymer material and adversely affecting the quality of the deposited films. In this work, we investigate the possibility of alleviating this problem by reducing the amount of matrix in the target. A series of coarse-grained molecular dynamics simulations are performed for a model lysozyme-water system, where the water serves the role of volatile "matrix" that drives the ejection of the biomolecules. The simulations reveal a remarkable ability of a small (5-10 wt %) amount of matrix to cause the ejection of intact bioorganic molecules. The results obtained for different laser fluences and water concentrations are used to establish a "processing map" of the regimes of molecular ejection in matrix-assisted pulsed laser deposition. The computational predictions are supported by the experimental observation of the ejection of intact lysozyme molecules from pressed lysozyme targets containing small amounts of residual water. The results of this study suggest a new approach for deposition of thin films of bioorganic molecules with minimum chemical modification of the molecular structure and minimum involvement of solvent into the deposition process.

What determines MALDI ion yields? A molecular dynamics study of ion loss mechanisms.

Ion recombination in matrix-assisted laser desorption/ionization (MALDI) is as important as any ion formation process in determining the quantity of ions observed but has received comparatively little attention. Molecular dynamics simulations are used here to investigate some models for recombination, including a Langevin-type model, a soft threshold model and a tunneling model. The latter was found to be superior due to its foundations in a widespread physical phenomenon, and its lack of excessive sensitivity to parameter choice. Tunneling recombination in the Marcus inverted region may be a major reason why MALDI is a viable analytical method, by allowing ion formation to exceed ion loss on the time scale of the plume expansion. Ion velocities, photoacoustic transients and pump-probe measurements might be used to investigate the role of recombination in different MALDI matrices, and to select new matrices.

Selective ablation of Xe from silicon surfaces: molecular dynamics simulations and experimental laser patterning.

The mechanism of laser-induced removal of Xe overlayers from a Si substrate has been investigated employing MD simulations and evaluated by buffer layer assisted laser patterning experiments. Two distinct regimes of overlayer removal are identified in the simulations of a uniform heating of the Si substrate by a 5 ns laser pulse: The intensive evaporation from the surface of the Xe overlayer and the detachment of the entire Xe overlayer driven by explosive boiling in the vicinity of the hot substrate. Simulations of selective heating of only a fraction of the silicon substrate suggest that the lateral heat transfer and bonding to the unheated, colder regions of the Xe overlayer is very efficient and suppresses the separation of a fraction of the overlayer from the substrate. Interaction with surrounding cold Xe is responsible for significant increase in the substrate temperature required for achieving the spatially selective ablation of the overlayer. The predictions of the MD simulations are found to be in a qualitative agreement with the results of experimental measurements of the threshold laser power required for the removal of Xe overlayers of different thickness and the shapes of metallic stripes generated by buffer-assisted laser patterning.

Structural stability of carbon nanotube films: the role of bending buckling.

In films, mats, buckypaper, and other materials composed of carbon nanotubes (CNTs), individual CNTs are bound together by van der Waals forces and form entangled networks of bundles. Mesoscopic dynamic simulations reproduce the spontaneous self-assembly of CNTs into continuous networks of bundles and reveal that the bending buckling and the length of CNTs are the two main factors responsible for the stability of the network structures formed by defect-free CNTs. Bending buckling of CNTs reduces the bending energy of interconnections between bundles and stabilizes the interconnections by creating effective barriers for CNT sliding. The length of the nanotubes is affecting the ability of van der Waals forces of intertube interactions to counterbalance the internal straightening forces acting on curved nanotubes present in the continuous networks. The critical length for the formation of stable network structures is found to be ∼120 nm for (10,10) single-walled CNTs. In the simulations where the bending buckling is artificially switched off, the network structures are found to be unstable against disintegration into individual bundles even for micrometer-long CNTs.

Scaling laws and mesoscopic modeling of thermal conductivity in carbon nanotube materials.

The scaling laws describing the thermal conductivity in random networks of straight conducting nanofibers are derived analytically and verified in numerical simulations. The applicability of the scaling laws to more complex structures of interconnected networks of bundles in carbon nanotube (CNT) films and mats is investigated in mesoscopic simulations. The heat transfer in CNT materials is found to be strongly enhanced by self-organization of CNTs into continuous networks of bundles. The thermal conductivity of CNT films varies by orders of magnitude depending on the length of the nanotubes and their structural arrangement in the material.