Inverted nucleation for photoinduced nonequilibrium melting.

Ultrafast photoinduced melting provides an essential platform for studying nonequilibrium phase transitions by linking the kinetics of electron dynamics to ionic motions. Knowledge of dynamic balance in their energetics is essential to understanding how the ionic reaction is influenced by femtosecond photoexcited electrons with notable time lag depending on reaction mechanisms. Here, by directly imaging fluctuating density distributions and evaluating the ionic pressure and Gibbs free energy from two-temperature molecular dynamics that verified experimental results, we uncovered that transient ionic pressure, triggered by photoexcited electrons, controls the overall melting kinetics. In particular, ultrafast nonequilibrium melting can be described by the reverse nucleation process with voids as nucleation seeds. The strongly driven solid-to-liquid transition of metallic gold is successfully explained by void nucleation facilitated by photoexcited electron-initiated ionic pressure, establishing a solid knowledge base for understanding ultrafast nonequilibrium kinetics.

Observing femtosecond orbital dynamics in ultrafast Ge melting with time-resolved resonant X-ray scattering.

Photoinduced nonequilibrium phase transitions have stimulated interest in the dynamic interactions between electrons and crystalline ions, which have long been overlooked within the Born-Oppenheimer approximation. Ultrafast melting before lattice thermalization prompted researchers to revisit this issue to understand ultrafast photoinduced weakening of the crystal bonding. However, the absence of direct evidence demonstrating the role of orbital dynamics in lattice disorder leaves it elusive. By performing time-resolved resonant X-ray scattering with an X-ray free-electron laser, we directly monitored the ultrafast dynamics of bonding orbitals of Ge to drive photoinduced melting. Increased photoexcitation of bonding electrons amplifies the orbital disturbance to expedite the lattice disorder approaching the sub-picosecond scale of the nonthermal regime. The lattice disorder time shows strong nonlinear dependence on the laser fluence with a crossover behavior from thermal-driven to nonthermal-dominant kinetics, which is also verified by ab initio and two-temperature molecular dynamics simulations. This study elucidates the impact of bonding orbitals on lattice stability with a unifying interpretation on photoinduced melting.

Ultrafast Energy Transfer Process in Confined Gold Nanospheres Revealed by Femtosecond X-ray Imaging and Diffraction.

Femtosecond laser pulses drive nonequilibrium phase transitions via reaction paths hidden in thermal equilibrium. This stimulates interest to understand photoinduced ultrafast melting processes, which remains incomplete due to challenges in resolving accompanied kinetics at the relevant space-time resolution. Here, by newly establishing a multiplexing femtosecond X-ray probe, we have successfully revealed ultrafast energy transfer processes in confined Au nanospheres. Real-time images of electron density distributions with the corresponding lattice structures elucidate that the energy transfer begins with subpicosecond melting at the specimen boundary earlier than the lattice thermalization, and proceeds by forming voids. Two temperature molecular dynamics simulations uncovered the presence of both heterogeneous melting with the melting front propagation from surface and grain boundaries and homogeneous melting with random melting seeds and nanoscale voids. Supported by experimental and theoretical results, we provide a comprehensive atomic-scale picture that accounts for the ultrafast laser-induced melting and evaporation kinetics.

Multimodal X-ray probe station at 9C beamline of Pohang Light Source-II.

In this study, the conceptual design and performance of a multimodal X-ray probe station recently installed at the 9C coherent X-ray scattering beamline of the Pohang Light Source-II are presented. The purpose of this apparatus is to measure coherent X-ray diffraction, X-ray fluorescence and electrical properties simultaneously. A miniature vacuum probe station equipped with a four-point probe was mounted on a six-axis motion hexapod. This can be used to study the structural and chemical evolution of thin films or nanostructures, as well as device performance including electronic transport properties. This probe station also provides the capability of varying sample environments such as gas atmosphere using a mass-flow-control system and sample temperatures up to 600°C using a pyrolytic boron nitride heater. The in situ annealing of ZnO thin films and the performance of ZnO nanostructure-based X-ray photodetectors are discussed. These results demonstrate that a multimodal X-ray probe station can be used for performing in situ and operando experiments to investigate structural phase transitions involving electrical resistivity switching.

Inducing thermodynamically blocked atomic ordering via strongly driven nonequilibrium kinetics.

Ultrafast light-matter interactions enable inducing exotic material phases by promoting access to kinetic processes blocked in equilibrium. Despite potential opportunities, actively using nonequilibrium kinetics for material discovery is limited by the poor understanding on intermediate states of driven systems. Here, using single-pulse time-resolved imaging with x-ray free-electron lasers, we found intermediate states of photoexcited bismuth nanoparticles that showed kinetically reversed surface ordering during ultrafast melting. This entropy-lowering reaction was further investigated by molecular dynamics simulations to reveal that observed kinetics were thermodynamically buried in equilibrium, which emphasized the critical role of electron-mediated ultrafast free-energy modification in inducing exotic material phases. This study demonstrated that ultrafast photoexcitations of electrons provide an efficient strategy to induce hidden material phases by overcoming thermodynamic barriers via nonequilibrium reaction pathways.

Stochastic chromatin packing of 3D mitotic chromosomes revealed by coherent X-rays.

DNA molecules are atomic-scale information storage molecules that promote reliable information transfer via fault-free repetitions of replications and transcriptions. Remarkable accuracy of compacting a few-meters-long DNA into a micrometer-scale object, and the reverse, makes the chromosome one of the most intriguing structures from both physical and biological viewpoints. However, its three-dimensional (3D) structure remains elusive with challenges in observing native structures of specimens at tens-of-nanometers resolution. Here, using cryogenic coherent X-ray diffraction imaging, we succeeded in obtaining nanoscale 3D structures of metaphase chromosomes that exhibited a random distribution of electron density without characteristics of high-order folding structures. Scaling analysis of the chromosomes, compared with a model structure having the same density profile as the experimental results, has discovered the fractal nature of density distributions. Quantitative 3D density maps, corroborated by molecular dynamics simulations, reveal that internal structures of chromosomes conform to diffusion-limited aggregation behavior, which indicates that 3D chromatin packing occurs via stochastic processes.

Oxidation-induced three-dimensional morphological changes in Ni nanoparticles observed by coherent X-ray diffraction imaging.

Three-dimensional structures of Ni nanoparticles undergoing significant morphological changes on oxidation were observed non-destructively using coherent X-ray diffraction imaging. The Ni particles were oxidized into Ni1O1 while forming pores of various sizes internally. For each Ni nanoparticle, one large void was identified at a lower corner near the interface with the substrate. The porosity of the internal region of the agglomerated Ni oxide was about 38.4%. Regions of high NiO density were mostly observed at the outer crust of the oxide or at the boundary with the large voids. This research expands our understanding of general catalytic reactions with direct observation of oxidation-induced nanoscale morphological changes.

High-Throughput 3D Ensemble Characterization of Individual Core-Shell Nanoparticles with X-ray Free Electron Laser Single-Particle Imaging.

The structures as building blocks for designing functional nanomaterials have fueled the development of versatile nanoprobes to understand local structures of noncrystalline specimens. Progress in analyzing structures of individual specimens with atomic scale accuracy has been notable recently. In most cases, however, only a limited number of specimens are inspected lacking statistics to represent the systems with structural inhomogeneity. Here, by employing single-particle imaging with X-ray free electron lasers and algorithms for multiple-model 3D imaging, we succeeded in investigating several thousand specimens in a couple of hours and identified intrinsic heterogeneities with 3D structures. Quantitative analysis has unveiled 3D morphology, facet indices, and elastic strain. The 3D elastic energy distribution is further corroborated by molecular dynamics simulations to gain mechanical insight at the atomic level. This work establishes a route to high-throughput characterization of individual specimens in large ensembles, hence overcoming statistical deficiency while providing quantitative information at the nanoscale.

Nanoscale Soft Wetting Observed in Co/Sapphire during Pulsed Laser Irradiation.

Liquid drops on deformable soft substrates exhibit quite complicated wetting behavior as compared to those on rigid solid substrates. We report on a soft wetting behavior of Co nanoparticles (NPs) on a sapphire substrate during pulsed laser-induced dewetting (PLID). Co NPs produced by PLID wetted the sapphire substrate with a contact angle near 70°, which is in contrast to typical dewetting behavior of metal thin films exhibiting contact angles greater than 90°. In addition, a nanoscale γ-Al2O3 wetting ridge about 15 nm in size and a thin amorphous Al2O3 interlayer were observed around and beneath the Co NP, respectively. The observed soft wetting behavior strongly indicates that the sapphire substrate became soft and deformable during PLID. Moreover, the soft wetting was augmented under PLID in air due to the formation of a CoO shell, resulting in a smaller contact angle near 30°.

Phase separated bi-metallic PtNi nanoparticles formed by pulsed laser dewetting.

We present morphological and compositional analysis of phase-separated Pt-Ni alloy nanoparticles (NPs) formed by ns pulsed laser dewetting. The PtNi NPs obtained by the pulsed laser dewetting consist of phase-separated multiple domains including Pt3Ni, PtNi and PtNi3 phases with various crystal orientations as revealed by transmission electron microscopy, which is in contrast to thermal dewetting resulting NPs of a uniform composition. A three-dimensional (3D) electron density map of a dewetted PtNi NP obtained using the coherent x-ray diffraction microscopy elucidates the 3D morphology of Pt- and Ni-rich regions together with a nano-cavity formed during the pulsed laser irradiation.

Polar Metal Phase Induced by Oxygen Octahedral Network Relaxation in Oxide Thin Films.

ABO3 perovskite materials and their derivatives have inherent structural flexibility due to the corner sharing network of the BO6 octahedron, and the large variety of possible structural distortions and strong coupling between lattice and charge/spin degrees of freedom have led to the emergence of intriguing properties, such as high-temperature superconductivity, colossal magnetoresistance, and improper ferroelectricity. Here, an unprecedented polar ferromagnetic metal phase in SrRuO3 (SRO) thin films is presented, arising from the strain-controlled oxygen octahedral rotation (OOR) pattern. For compressively strained SRO films grown on SrTiO3 substrate, oxygen octahedral network relaxation is accompanied by structural phase separation into strained tetragonal and bulk-like orthorhombic phases, and the asymmetric OOR evolution across the phase boundary allows formation of the polar phase, while bulk metallic and ferromagnetic properties are maintained. From the results, it is expected that other oxide perovskite thin films will also yield similar structural environments with variation of OOR patterns, and thereby provide promising opportunities for atomic scale control of material properties through strain engineering.

Laser-induced metastable mixed phase of AuNi nanoparticles: a coherent X-ray diffraction imaging study.

The laser annealing process for AuNi nanoparticles has been visualized using coherent X-ray diffraction imaging (CXDI). AuNi bimetallic alloy nanoparticles, originally phase separated due to the miscibility gap, transform to metastable mixed alloy particles with rounded surface as they are irradiated by laser pulses. A three-dimensional CXDI shows that the internal part of the AuNi particles is in the mixed phase with preferred compositions at ∼29 at% of Au and ∼90 at% of Au.

Correlation between structural phase transition and surface chemical properties of thin film SrRuO3/SrTiO3 (001).

The correlation between the structural phase transition (SPT) and oxygen vacancy in SrRuO3 (SRO) thin films was investigated by in situ X-ray diffraction (XRD) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). In situ XRD shows that the SPT occurs from a monoclinic SRO phase to a tetragonal SRO phase near ∼200 °C, regardless of the pressure environment. On the other hand, significant core level shifts in both the Ru and Sr photoemission spectra are found under ultrahigh vacuum, but not under the oxygen pressure environment. The directions and behavior of the core level shift of Ru and Sr are attributed to the formation of oxygen vacancy across the SPT temperature of SRO. The analysis of in situ XRD and AP-XPS results provides an evidence for the formation of metastable surface oxide possibly due to the migration of internal oxygen atoms across the SPT temperature, indicating the close relationship between oxygen vacancy and SPT in SRO thin films.

Characterizing the intrinsic properties of individual XFEL pulses via single-particle diffraction.

With each single X-ray pulse having its own characteristics, understanding the individual property of each X-ray free-electron laser (XFEL) pulse is essential for its applications in probing and manipulating specimens as well as in diagnosing the lasing performance. Intensive research using XFEL radiation over the last several years has introduced techniques to characterize the femtosecond XFEL pulses, but a simple characterization scheme, while not requiring ad hoc assumptions, to address multiple aspects of XFEL radiation via a single data collection process is scant. Here, it is shown that single-particle diffraction patterns collected using single XFEL pulses can provide information about the incident photon flux and coherence property simultaneously, and the X-ray beam profile is inferred. The proposed scheme is highly adaptable to most experimental configurations, and will become an essential approach to understanding single X-ray pulses.

Direct observation of picosecond melting and disintegration of metallic nanoparticles.

Despite more than a century of study, the fundamental mechanisms behind solid melting remain elusive at the nanoscale. Ultrafast phenomena in materials irradiated by intense femtosecond laser pulses have revived the interest in unveiling the puzzling processes of melting transitions. However, direct experimental validation of various microscopic models is limited due to the difficulty of imaging the internal structures of materials undergoing ultrafast and irreversible transitions. Here we overcome this challenge through time-resolved single-shot diffractive imaging using X-ray free electron laser pulses. Images of single Au nanoparticles show heterogeneous melting at the surface followed by density fluctuation deep inside the particle, which is directionally correlated to the polarization of the pumping laser. Observation of this directionality links the non-thermal electronic excitation to the thermal lattice melting, which is further verified by molecular dynamics simulations. This work provides direct evidence to the understanding of irreversible melting with an unprecedented spatiotemporal resolution.

Crosslinking Effect on Thermal Conductivity of Electrospun Poly(acrylic acid) Nanofibers.

The thermal conductivity (k) of poly(acrylic acid) (PAA) nanofibers, which were electrospun at various electrospinning voltages, was measured using suspended microdevices. While the thermal conductivities of the as-spun PAA nanofibers varied depending on the electrospinning voltages, the most pronounced 3.1-fold increase in thermal conductivity in comparison to that of bulk PAA was observed at the electrospinning voltage of 14 kV. On the other hand, a reduction in the thermal conductivity of the nanofibers was observed when the as-spun nanofibers were either thermally annealed at the glass transition temperature of PAA or thermally crosslinked. It is notable that the thermal conductivity of crosslinked PAA nanofibers was comparable to that of crosslinked bulk PAA. Polarized Raman spectroscopy and Fourier transform infrared spectroscopy verified that the k enhancement via electrospinning and the k reduction by the thermal treatments could be attributed to the conformational changes between gauche and trans states, which may be further related to the orientation of molecular chains. In contrast, hydrogen bonds did not contribute significantly to the k enhancement. Additionally, the suppression of k observed for the crosslinked PAA nanofibers might result from the shortening of single molecular chains via crosslinking.

Vanadium dioxide based frequency tunable metasurface filters for realizing reconfigurable terahertz optical phase and polarization control.

Metasurfaces are two dimensional arrays of artificial subwavelength resonators, which can manipulate the amplitude and phase profile of incident electromagnetic fields. To date, limited progress has been achieved in realizing reconfigurable phase control of incident waves using metasurfaces. Here, an active metasurface is presented, whose resonance frequency can be tuned by employing insulator to metal transition in vanadium dioxide. By virtue of the phase jump accompanied by the resonance frequency tuning, the proposed metasurface acts as a phase shifter at THz frequency. It is further demonstrated that by appropriately tailoring the anisotropy of the metasurface, the observed phase shift can be used to switch the transmitted polarization from circular to approximately linear. This work thus shows potential for reconfigurable phase and polarization control at THz frequencies using vanadium dioxide based frequency tunable metasurfaces.

Nanographene oxide as a switch for CW/pulsed NIR laser triggered drug release from liposomes.

The application of pulsed and continuous wave (CW) lasers in nanomedicine has increased significantly over the last decade. Near infrared (NIR) lasers can be used for the precise control of drug release at the target site in a non-invasive manner. In this study, we have prepared nanographene oxide (nGO, size ~40nm) integrated liposomes (size ~900nm). The nGOs were not simply adsorbed onto the liposome surface but was embedded inside the liposomes as characterized by cryo-TEM, selected area electron diffraction (SAED), and fluorescence quenching studies. The embedded nGOs could act as a molecular switch for NIR light controlled drug release from the liposomes. Calcein was encapsulated into the liposome as a model drug to evaluate the efficiency of light controlled release. An on-demand pulsatile drug release was achieved by irradiation of CW/pulsed NIR lasers into the nGO-liposome suspension. Triggering with a pulsed laser resulted in larger release of calcein with a minimal temperature increase (~2°C) of the liposome solution, compared to lower release rate and a significant temperature increase (~8°C) by a CW laser with the same light energy, suggesting two separate mechanisms and different potential applications depending on the laser type.

Visualization of a Mammalian Mitochondrion by Coherent X-ray Diffractive Imaging.

We report a three dimensional (3D) quantitative visualization of a mammalian mitochondrion by coherent x-ray diffractive imaging (CXDI) using synchrotron radiation. The internal structures of a mitochondrion from a mouse embryonic fibroblast cell line (NIH3T3) were visualized by tomographic imaging at approximately 60 nm resolution without the need for sectioning or staining. The overall structure consisted of a high electron density region, composed of the outer and inner membranes and the cristae cluster, which enclosed the lower density mitochondrial matrix. The average mass density of the mitochondrion was about 1.36 g/cm3. Sectioned images of the cristae reveal that they have neither a baffle nor septa shape but were instead irregular. In addition, a high resolution, about 14 nm, 2D projection image was captured of a similar mitochondrion with the aid of strongly scattering Au reference objects. Obtaining 3D images at this improved resolution will allow CXDI to be an effective and nondestructive method for investigating the innate structure of mitochondria and other important life supporting organelles.

Depth resolved lattice-charge coupling in epitaxial BiFeO3 thin film.

For epitaxial films, a critical thickness (tc) can create a phenomenological interface between a strained bottom layer and a relaxed top layer. Here, we present an experimental report of how the tc in BiFeO3 thin films acts as a boundary to determine the crystalline phase, ferroelectricity, and piezoelectricity in 60 nm thick BiFeO3/SrRuO3/SrTiO3 substrate. We found larger Fe cation displacement of the relaxed layer than that of strained layer. In the time-resolved X-ray microdiffraction analyses, the piezoelectric response of the BiFeO3 film was resolved into a strained layer with an extremely low piezoelectric coefficient of 2.4 pm/V and a relaxed layer with a piezoelectric coefficient of 32 pm/V. The difference in the Fe displacements between the strained and relaxed layers is in good agreement with the differences in the piezoelectric coefficient due to the electromechanical coupling.