The study of first-order structural transformations has been of great interest to scientists in many disciplines. Expectations from phase-transition theory are that the system fluctuates between two equilibrium structures near the transition point and that the region of transition broadens in small crystals. We report the direct observation of structural fluctuations within a single nanocrystal using transmission electron microscopy. We observed trajectories of structural transformations in individual nanocrystals with atomic resolution, which reveal details of the fluctuation dynamics, including nucleation, phase propagation, and pinning of structural domains by defects. Such observations provide crucial insight for the understanding of microscopic pathways of phase transitions.

Many ultrafast solid phase transitions are treated as chemical reactions that transform the structures between two different unit cells along a reaction coordinate, but this neglects the role of disorder. Although ultrafast diffraction provides insights into atomic dynamics during such transformations, diffraction alone probes an averaged unit cell and is less sensitive to randomness in the transition pathway. Using total scattering of femtosecond x-ray pulses, we show that atomic disordering in photoexcited vanadium dioxide (VO2) is central to the transition mechanism and that, after photoexcitation, the system explores a large volume of phase space on a time scale comparable to that of a single phonon oscillation. These results overturn the current understanding of an archetypal ultrafast phase transition and provide new microscopic insights into rapid evolution toward equilibrium in photoexcited matter.

The extreme electro-optical contrast between crystalline and amorphous states in phase-change materials is routinely exploited in optical data storage and future applications include universal memories, flexible displays, reconfigurable optical circuits, and logic devices. Optical contrast is believed to arise owing to a change in crystallinity. Here we show that the connection between optical properties and structure can be broken. Using a combination of single-shot femtosecond electron diffraction and optical spectroscopy, we simultaneously follow the lattice dynamics and dielectric function in the phase-change material Ge2Sb2Te5 during an irreversible state transformation. The dielectric function changes by 30% within 100 fs owing to a rapid depletion of electrons from resonantly bonded states. This occurs without perturbing the crystallinity of the lattice, which heats with a 2-ps time constant. The optical changes are an order of magnitude larger than those achievable with silicon and present new routes to manipulate light on an ultrafast timescale without structural changes.

Superionic materials are multi-component solids with simultaneous characteristics of both a solid and a liquid. Above a critical temperature associated with a structural phase transition, they exhibit liquid-like ionic conductivities and dynamic disorder within a rigid crystalline structure. Broad applications as electrochemical storage materials and resistive switching devices follow from this abrupt change in ionic mobility, but the microscopic pathways and speed limits associated with this switching process are largely unknown. Here we use ultrafast X-ray spectroscopy and scattering techniques to obtain an atomic-level, real-time view of the transition state in copper sulphide nanocrystals. We observe the transformation to occur on a twenty picosecond timescale and show that this is determined by the ionic hopping time.

We report time-resolved studies of hydrogen bonding in liquid H 2 O, in response to direct excitation of the O-H stretch mode at 3 µm, probed via soft x-ray absorption spectroscopy at the oxygen K-edge. This approach employs a newly developed nanofluidic cell for transient soft x-ray spectroscopy in liquid phase. Distinct changes in the near-edge spectral region (XANES) are observed, and are indicative of a transient temperature rise of 10K following transient laser excitation and rapid thermalization of vibrational energy. The rapid heating occurs at constant volume and the associated increase in internal pressure, estimated to be 8MPa, is manifest by distinct spectral changes that differ from those induced by temperature alone. We conclude that the near-edge spectral shape of the oxygen K-edge is a sensitive probe of internal pressure, opening new possibilities for testing the validity of water models and providing new insight into the nature of hydrogen bonding in water.

The functionalities of a wide range of optical and opto-electronic devices are based on resonance effects and active tuning of the amplitude and wavelength response is often essential. Plasmonic nano-structures are an efficient way to create optical resonances, a prominent example is the extraordinary optical transmission (EOT) through arrays of nano-holes patterned in a metallic film. Tuning of resonances by heating, applying electrical or optical signals has proven to be more elusive, due to the lack of materials that can induce modulation over a broad spectral range and/or at high speeds. Here we show that nano-patterned metals combined with phase change materials (PCMs) can overcome this limitation due to the large change in optical constants which can be induced thermally or on an ultrafast timescale. We demonstrate resonance wavelength shifts as large as 385 nm --an order of magnitude higher than previously reported--by combining properly designed Au EOT nanostructures with Ge2Sb2Te5 (GST). Moreover, we show, through pump-probe measurements, repeatable and reversible, large-amplitude modulations in the resonances, especially at telecommunication wavelengths, over ps time scales and at powers far below those needed to produce a permanent phase transition. Our findings open a pathway to the design of hybrid metal-PCM nanostructures with ultrafast and widely tuneable resonance responses, which hold potential impact on active nanophotonic devices such as tuneable optical filters, smart windows, bio-sensors and reconfigurable memories.* These authors made equal contribution †valerio.pruneri@icfo.eu 2 Nanophotonic devices incorporating metallic elements can support plasmons, which are collective oscillations of conduction band electrons driven by an external electromagnetic field 1 . Plasmons can confine and guide light well below the diffraction limit, and when supported by suitably engineered nanostructures, they enable the design of disruptive devices for a wide range of applications, including perfect lenses . Plasmons also play an important role in the phenomenon of extraordinary optical transmission (EOT) of visible and infrared light through periodic arrays of subwavelength nanoholes drilled in metallic films. The observation of transmission resonances in these arrays is attributed to the resonant interaction between holes mediated by surface plasmons propagating on the film surfaces 7 . More precisely, transmission peaks emerge close to the Wood anomalies 8 and are well explained in terms of geometrical resonances in the periodic lattice 9,10,11 . An important challenge in the design of plasmonic nanostructures is the precise control of their optical responses in order to meet the requirements of specific device applications. This can be accomplished by casting nanostructures with appropriate materials and geometries. However, such an approach is static and limited by material inhomogeneity and fabrication tolerances. More critically, many applications (e.g., optical switching and modulation) ...

We use resonant soft X-ray holography to image the insulator-metal phase transition in vanadium dioxide with element and polarization specificity and nanometer spatial resolution. We observe that nanoscale inhomogeneity in the film results in spatial-dependent transition pathways between the insulating and metallic states. Additional nanoscale phases form in the vicinity of defects which are not apparent in the initial or final states of the system, which would be missed in area-integrated X-ray absorption measurements. These intermediate phases are vital to understand the phase transition in VO, and our results demonstrate how resonant imaging can be used to understand the electronic properties of phase-separated correlated materials obtained by X-ray absorption.

Nanoscale dimensions in materials lead to unique electronic and structural properties with applications ranging from site-specific drug delivery to anodes for lithium-ion batteries. These functional properties often involve large-amplitude strains and structural modifications, and thus require an understanding of the dynamics of these processes. Here we use femtosecond X-ray scattering techniques to visualize, in real time and with atomic-scale resolution, light-induced anisotropic strains in nanocrystal spheres and rods. Strains at the percent level are observed in CdS and CdSe samples, associated with a rapid expansion followed by contraction along the nanosphere or nanorod radial direction driven by a transient carrierinduced stress. These morphological changes occur simultaneously with the first steps in the melting transition on hundreds of femtosecond timescales. This work represents the first direct real-time probe of the dynamics of these large-amplitude strains and shape changes in few-nanometre-scale particles.