X-ray nanodiffraction imaging reveals distinct nanoscopic dynamics of an ultrafast phase transition.

SignificancePhase transitions, the changes between states of matter with distinct electronic, magnetic, or structural properties, are at the center of condensed matter physics and underlie valuable technologies. First-order phase transitions are intrinsically heterogeneous. When driven by ultrashort excitation, nanoscale phase regions evolve rapidly, which has posed a significant experimental challenge to characterize. The newly developed laser-pumped X-ray nanodiffraction imaging technique reported here has simultaneous 100-ps temporal and 25-nm spatial resolutions. This approach reveals pathways of the nanoscale structural rearrangement upon ultrafast optical excitation, different from those transitions under slowly varying parameters. The spatiotemporally resolved structural characterization provides crucial nanoscopic insights into ultrafast phase transitions and opens opportunities for controlling nanoscale phases on ultrafast time scales.

Ultrafast Carrier-Lattice Interactions and Interlayer Modulations of Bi2Se3 by X-ray Free-Electron Laser Diffraction.

As a 3D topological insulator, bismuth selenide (Bi2Se3) has potential applications for electrically and optically controllable magnetic and optoelectronic devices. Understanding the coupling with its topological phase requires studying the interactions of carriers with the lattice on time scales down to the subpicosecond regime. Here, we investigate the ultrafast carrier-induced lattice contractions and interlayer modulations in Bi2Se3 thin films by time-resolved diffraction using an X-ray free-electron laser. The lattice contraction depends on the carrier concentration and is followed by an interlayer expansion accompanied by oscillations. Using density functional theory and the Lifshitz model, the initial contraction can be explained by van der Waals force modulation of the confined free carrier layers. Our theoretical calculations suggest that the band inversion, related to a topological phase transition, is modulated by the expansion of the interlayer distance. These results provide insights into the topological phase control by light-induced structural change on ultrafast time scales.

Dynamic Tilting of Ferroelectric Domain Walls Caused by Optically Induced Electronic Screening.

Optical excitation perturbs the balance of phenomena selecting the tilt orientation of domain walls within ferroelectric thin films. The high carrier density induced in a low-strain BaTiO_{3} thin film by an above-band-gap ultrafast optical pulse changes the tilt angle that 90° a/c domain walls form with respect to the substrate-film interface. The dynamics of the changes are apparent in time-resolved synchrotron x-ray scattering studies of the domain diffuse scattering. Tilting occurs at 298 K, a temperature at which the a/b and a/c domain phases coexist but is absent at 343 K in the better ordered single-phase a/c regime. Phase coexistence at 298 K leads to increased domain-wall charge density, and thus a larger screening effect than in the single-phase regime. The screening mechanism points to new directions for the manipulation of nanoscale ferroelectricity.

Simultaneous scanning near-field optical and X-ray diffraction microscopy for correlative nanoscale structure-property characterization.

A multimodal imaging instrument has been developed that integrates scanning near-field optical microscopy with nanofocused synchrotron X-ray diffraction imaging. The instrument allows for the simultaneous nanoscale characterization of electronic/near-field optical properties of materials together with their crystallographic structure, facilitating the investigation of local structure-property relationships. The design, implementation and operating procedures of this instrument are reported. The scientific capabilities are demonstrated in a proof-of-principle study of the insulator-metal phase transition in samarium sulfide (SmS) single crystals induced by applying mechanical pressure via a scanning tip. The multimodal imaging of an in situ tip-written region shows that the near-field optical reflectivity can be correlated with the heterogeneously transformed structure of the near-surface region of the crystal.

Micro-focused MHz pink beam for time-resolved X-ray emission spectroscopy.

The full radiation from the first harmonic of a synchrotron undulator (between 5 and 12 keV) at the Advanced Photon Source is microfocused using a stack of beryllium compound refractive lenses onto a fast-moving liquid jet and overlapped with a high-repetition-rate optical laser. This micro-focused geometry is used to perform efficient nonresonant X-ray emission spectroscopy on transient species using a dispersive spectrometer geometry. The overall usable flux achieved on target is above 1015 photons s-1 at 8 keV, enabling photoexcited systems in the liquid phase to be tracked with time resolutions from tens of picoseconds to microseconds, and using the full emission spectrum, including the weak valence-to-core signal that is sensitive to chemically relevant electronic properties.

Nanosecond Optically Induced Phase Transformation in Compressively Strained BiFeO_{3} on LaAlO_{3}.

Above-band-gap optical illumination of compressively strained BiFeO_{3} induces a transient reversible transformation from a state of coexisting tilted tetragonal-like and rhombohedral-like phases to an untilted tetragonal-like phase. Time-resolved synchrotron x-ray diffraction reveals that the transformation is induced by an ultrafast optically induced lattice expansion that shifts the relative free energies of the tetragonal-like and rhombohedral-like phases. The transformation proceeds at interfaces between regions of the tetragonal-like phase and regions of a mixture of tilted phases, consistent with the motion of a phase boundary. The optically induced transformation demonstrates that there are new optically driven routes towards nanosecond-scale control of phase transformations in ferroelectrics and multiferroics.

Imaging ultrafast molecular dynamics with laser-induced electron diffraction.

Establishing the structure of molecules and solids has always had an essential role in physics, chemistry and biology. The methods of choice are X-ray and electron diffraction, which are routinely used to determine atomic positions with sub-ångström spatial resolution. Although both methods are currently limited to probing dynamics on timescales longer than a picosecond, the recent development of femtosecond sources of X-ray pulses and electron beams suggests that they might soon be capable of taking ultrafast snapshots of biological molecules and condensed-phase systems undergoing structural changes. The past decade has also witnessed the emergence of an alternative imaging approach based on laser-ionized bursts of coherent electron wave packets that self-interrogate the parent molecular structure. Here we show that this phenomenon can indeed be exploited for laser-induced electron diffraction (LIED), to image molecular structures with sub-ångström precision and exposure times of a few femtoseconds. We apply the method to oxygen and nitrogen molecules, which on strong-field ionization at three mid-infrared wavelengths (1.7, 2.0 and 2.3 µm) emit photoelectrons with a momentum distribution from which we extract diffraction patterns. The long wavelength is essential for achieving atomic-scale spatial resolution, and the wavelength variation is equivalent to taking snapshots at different times. We show that the method has the sensitivity to measure a 0.1 Å displacement in the oxygen bond length occurring in a time interval of ∼5 fs, which establishes LIED as a promising approach for the imaging of gas-phase molecules with unprecedented spatio-temporal resolution.

Ultrafast Three-Dimensional Integrated Imaging of Strain in Core/Shell Semiconductor/Metal Nanostructures.

Visualizing the dynamical response of material heterointerfaces is increasingly important for the design of hybrid materials and structures with tailored properties for use in functional devices. In situ characterization of nanoscale heterointerfaces such as metal-semiconductor interfaces, which exhibit a complex interplay between lattice strain, electric potential, and heat transport at subnanosecond time scales, is particularly challenging. In this work, we use a laser pump/X-ray probe form of Bragg coherent diffraction imaging (BCDI) to visualize in three-dimension the deformation of the core of a model core/shell semiconductor-metal (ZnO/Ni) nanorod following laser heating of the shell. We observe a rich interplay of radial, axial, and shear deformation modes acting at different time scales that are induced by the strain from the Ni shell. We construct experimentally informed models by directly importing the reconstructed crystal from the ultrafast experiment into a thermo-electromechanical continuum model. The model elucidates the origin of the deformation modes observed experimentally. Our integrated imaging approach represents an invaluable tool to probe strain dynamics across mixed interfaces under operando conditions.

Dynamic Optical Tuning of Interlayer Interactions in the Transition Metal Dichalcogenides.

Modulation of weak interlayer interactions between quasi-two-dimensional atomic planes in the transition metal dichalcogenides (TMDCs) provides avenues for tuning their functional properties. Here we show that above-gap optical excitation in the TMDCs leads to an unexpected large-amplitude, ultrafast compressive force between the two-dimensional layers, as probed by in situ measurements of the atomic layer spacing at femtosecond time resolution. We show that this compressive response arises from a dynamic modulation of the interlayer van der Waals interaction and that this represents the dominant light-induced stress at low excitation densities. A simple analytic model predicts the magnitude and carrier density dependence of the measured strains. This work establishes a new method for dynamic, nonequilibrium tuning of correlation-driven dispersive interactions and of the optomechanical functionality of TMDC quasi-two-dimensional materials.

Lignin-Modified Carbon Nanotube/Graphene Hybrid Coating as Efficient Flame Retardant.

To reduce fire hazards and expand high-value applications of lignocellulosic materials, thin films comprising graphene nanoplatelets (GnPs) and multi-wall carbon nanotubes (CNTs) pre-adsorbed with alkali lignin were deposited by a Meyer rod process. Lightweight and highly flexible papers with increased gas impermeability were obtained by coating a protective layer of carbon nanomaterials in a randomly oriented and overlapped network structure. Assessment of the thermal and flammability properties of papers containing as low as 4 wt % carbon nanomaterials exhibited self-extinguishing behavior and yielded up to 83.5% and 87.7% reduction in weight loss and burning area, respectively, compared to the blank papers. The maximum burning temperature as measured by infrared pyrometry also decreased from 834 °C to 705 °C with the presence of flame retardants. Furthermore, papers coated with composites of GnPs and CNTs pre-adsorbed with lignin showed enhanced thermal stability and superior fire resistance than samples treated with either component alone. These outstanding flame-retardant properties can be attributed to the synergistic effects between GnPs, CNTs and lignin, enhancing physical barrier characteristics, formation of char and thermal management of the material. These results provide great opportunities for the development of efficient, cost-effective and environmentally sustainable flame retardants.

Sonochemical synthesis of lignin nanoparticles and their applications in poly (vinyl) alcohol composites.

Lignin is a common and abundant byproduct of the pulp and paper industry and is generally burned to produce steam. Opportunities exist to acquire greater value from lignin by leveraging the properties of this highly conjugated biomacromolecule for applications in UV absorption and polymer reinforcement. These applications can be commercialized by producing value-added lignin nanoparticles (LNPs) using a scalable sonochemical process. In the present research, monodisperse LNPs have been synthesized by subjecting aqueous dispersions of alkali lignin to acoustic irradiation. The resulting particle size distribution and colloidal stability, as determined by dynamic light scattering, transmission electron microscopy and zeta potential analysis, of LNPs can be adjusted by varying the solution pH and ultrasonication energy. As-synthesized LNPs with a mean diameter of 204 nm were incorporated into poly (vinyl) alcohol (PVA) to prepare thin and flexible nanocomposite films using a simple solvent casting method. The addition of 2.5 wt% LNP increased the material's Sun Protection Factor up to 26 compared to 0 for neat PVA, while maintaining light transmission above 75 % in the visible spectra. In addition, the tensile strength and elastic modulus of the PVA nanocomposites improved by 47 % and 36 %, respectively. The presence of LNP also enhanced the thermal stability of the materials. Significantly, the proposed sonochemical process may be generally applicable to the synthesis of a range of naturally-derived LNPs for a variety of value-added applications.

A Robust Process to Produce Lignocellulosic Nanofibers from Corn Stover, Reed Canary Grass, and Industrial Hemp.

The use of agricultural waste biomass for nanocellulose production has gained interest due to its environmental and economic benefits compared to conventional bleached pulp feedstock. However, there is still a need to establish robust process technologies that can accommodate the variability of waste feedstocks and to understand the effects of feedstock characteristics on the final nanofiber properties. Here, lignocellulosic nanofibers with unique properties are produced from various waste biomass based on a simple and low-cost process using mild operating conditions. The process robustness is demonstrated by diversifying the feedstock, ranging from food crop waste (corn stover) to invasive grass species (reed canary grass) and industrial lignocellulosic residues (industrial hemp). This comprehensive study provides a thorough examination of the influence of the feedstocks' physico-chemical characteristics on the conversion treatment, including process yield, degree of delignification, effectiveness of nanofibrillation, fiber morphology, surface charge, and density. Results show that nanofibers have been successfully produced from all feedstocks, with minor to no adjustments to process conditions. This work provides a framework for future studies to engineer nanocellulose with specific properties by taking advantage of biomass feedstocks' intrinsic characteristics to enable versatile applications.

Dynamic Assembly of Strong and Conductive Carbon Nanotube/Nanocellulose Composite Filaments and Their Application in Resistive Liquid Sensing.

The continuous flow assembly of colloidal nanoparticles from aqueous suspensions into macroscopic materials in a field-assisted double flow focusing system offers an attractive way to bridge the outstanding nanoscale characteristics of renewable cellulose nanofibrils (CNFs) at scales most common to human technologies. By incorporating single-walled carbon nanotubes (SWNTs) during the fabrication process, high-performance functional filament nanocomposites were produced. CNFs and SWNTs were first dispersed in water without any external surfactants or binding agents, and the resulting nanocolloids were aligned by means of an alternating electric field combined with extensional sheath flows. The nanoscale orientational anisotropy was then locked by a liquid-gel transition during the materials assembly into macroscopic filaments, which greatly improved their mechanical, electrical, and liquid sensing properties. Significantly, these findings pave the way toward the environmentally friendly and scalable manufacturing of a variety of multifunctional fibers for diverse applications.

Facile preparation of cellulose nanocrystals/ZnO hybrids using acidified ZnCl2 as cellulose hydrolytic media and ZnO precursor.

Hybridization of nanocellulose with zinc oxide nanoparticles can improve the dispersibility of the zinc oxide and bring new functions to the bio-based products. In this study, cellulose nanocrystal/zinc oxide (CNC/ZnO) nanohybrids with reinforcing and antibacterial properties were prepared via a facile one-pot route. Microcrystalline cellulose (MCC) was first treated with acidified zinc chloride and hydrolyzed into CNCs, which then served as a stabilizing and supporting agent for the in-situ growth of ZnO nanoparticles during subsequent chemical precipitation. The acidified ZnCl2 solution played a dual role, acting both as cellulose hydrolytic media and as ZnO precursor. By adjusting the pH of the zinc precursor solution (pH = 9-12), well-dispersed rod-like (length: 137.0-468.0 nm, width: 54.1-154.1 nm) and flower-like (average diameter: 179.6 nm) ZnO nanoparticles with hexagonal wurtzite structure were obtained. CNC/ZnO nanohybrids were incorporated into waterborne polyurethane (WPU) films. The Young's modulus and tensile strength of the nanocomposite films increased gradually from 154.8 to 509.0 MPa and from 16.5 to 29.9 MPa, respectively, with increasing CNC/ZnO nanofiller content up to 10 wt%. The 10 % CNC/ZnO composites showed inhibition rates to both E. coli and S. aureus above 88.8 %.

Laser-induced electron diffraction for probing rare gas atoms.

Recently, using midinfrared laser-induced electron diffraction (LIED), snapshots of a vibrating diatomic molecule on a femtosecond time scale have been captured [C.I. Blaga et al., Nature (London) 483, 194 (2012)]. In this Letter, a comprehensive treatment for the atomic LIED response is reported, a critical step in generalizing this imaging method. Electron-ion differential cross sections (DCSs) of rare gas atoms are extracted from measured angular-resolved, high-energy electron momentum distributions generated by intense midinfrared lasers. Following strong-field ionization, the high-energy electrons result from elastic rescattering of a field-driven wave packet with the parent ion. For recollision energies ≥100 eV, the measured DCSs are indistinguishable for the neutral atoms and ions, illustrating the close collision nature of this interaction. The extracted DCSs are found to be independent of laser parameters, in agreement with theory. This study establishes the key ingredients for applying LIED to femtosecond molecular imaging.

Chemical vapor deposition synthesis of carbon nanotube-graphene nanosheet hybrids and their application in polymer composites.

Both carbon nanotubes (CNTs) and graphene nanosheets (GNs) have potential applications in polymer composites. Combining them may induce a synergistic effect on enhancing the properties of composites. Herein, CNT-GN 3D hybrids were prepared by liquid injection chemical vapor deposition through a spray containing both carbon feedstocks and catalyst precursors. Vertically aligned CNTs were self-organized on the GNs. The morphology of hybrids could be well controlled as a function of the synthesis parameters. The unique 3D geometry of the CNT-GN hybrids provided composites with a higher electrical conductivity as compared to composites solely reinforced by CNTs or GNs. However, the thermal stability of the neat poly(vinylidene fluoride) matrix was found to decrease upon the addition of these hybrid fillers.

Lignocellulosic nanomaterials production from wheat straw via peracetic acid pretreatment and their application in plastic composites.

Cellulose nanofibrils are typically prepared from high-purity bleached pulp through harsh chemical treatments (e.g., TEMPO oxidation), resulting in high costs and environmental impact. In this work, we utilize inexpensive wheat straw feedstock and alkaline peroxide pulping followed by mild peracetic acid (PAA) pretreatment to produce lignocellulosic nanomaterials (nano and microfibrils) with potential bioplastics applications. PAA was chosen due to its biodegradability, non-toxicity, and high reaction selectivity. As-synthesized lignocellulosic nanomaterials were thoroughly characterized and compared to nanofibrils produced via TEMPO oxidation pretreatment and then applied as reinforcing agents in plastic composites. A remarkable case of simultaneous strengthening and toughening of the polymer nanocomposite was achieved with high specific tensile strength (up to 59.5 MPa g-1 cm3), elastic modulus (up to 2.6 GPa g-1 cm3), and fracture strain (up to 138 %). This work is a comprehensive investigation of all process steps involved in lignocellulosic nanomaterials production, from original residue feedstock to final product application.

Simultaneous multiparameter whole blood hemostasis assessment using a carbon nanotube-paper composite capacitance sensor.

Rapid and accurate clinical assessment of hemostasis is essential for managing patients who undergo invasive procedures, experience hemorrhages, or receive antithrombotic therapies. Hemostasis encompasses an ensemble of interactions between the cellular and non-cellular blood components, but current devices assess only partial aspects of this complex process. In this work, we describe the development of a new approach to simultaneously evaluate coagulation function, platelet count or function, and hematocrit using a carbon nanotube-paper composite (CPC) capacitance sensor. CPC capacitance response to blood clotting at 1.3 MHz provided three sensing parameters with distinctive sensitivities towards multiple clotting elements. Whole blood-based hemostasis assessments were conducted to demonstrate the potential utility of the developed sensor for various hemostatic conditions, including pathological conditions, such as hemophilia and thrombocytopenia. Results showed good agreements when compared to a conventional thromboelastography. Overall, the presented CPC capacitance sensor is a promising new biomedical device for convenient non-contact whole-blood based comprehensive hemostasis evaluation.

Redshift in the optical absorption of ZnO single crystals in the presence of an intense midinfrared laser field.

We report time-resolved electroabsorption of a weak probe in a 500 µm thick zinc-oxide crystal in the presence of a strong midinfrared pump in the tunneling limit. We observe a substantial redshift in the absorption edge that scales with the cube root of intensity up to 1 TW/cm(2) (0.38 eV cm(2/3) TW(-1/3)) after which it increases more slowly to 0.4 eV at a maximum applied intensity of 5 TW/cm(2). The maximum shift corresponds to more than 10% of the band gap. The change in scaling occurs in a regime of nonperturbative high-order harmonic generation where electrons undergo periodic Bragg scattering from the Brillouin zone boundaries. It also coincides with the limit where the electric field becomes comparable to the ratio of the band gap to the lattice spacing.

Hybridization between cellulose nanofibrils and faceted silver nanoparticles used with surface enhanced Raman scattering for trace dye detection.

This research studies the surface enhanced Raman scattering (SERS) activity of cellulose nanofibrils (CNFs) hybridized with faceted silver nanoparticles (AgFNPs) for the detection of organic dyes in aqueous media. Faceted AgNPs were synthesized under environmentally benign conditions using TEMPO-oxidized CNFs as both shape-regulating, reducing and stabilizing agents. Small, zero valent, spherical AgNPs first formed on the CNF surface and transformed into larger and faceted AgNPs when reacting with H2O2 through a thermodynamically driven Ostwald ripening mechanism. The as-synthesized hybrids exhibited strong analytical enhancement in the Raman signal of methylene blue, up to 6.8 × 103 at 448 cm-1 with less than 32% spatial variations and 10% sample-to-sample variability, enabling the detection of dyes in water at the sub part-per million level. The origin of the SERS enhancement came from discrete hotspots of high silver content on the substrate, as characterized by spatially resolved laser ablation inductively coupled plasma mass spectrometry.