Richard F. Haglund

Role of Defects in the Phase Transition of VO2 Nanoparticles Probed by Plasmon Resonance Spectroscopy

Defects are known to affect nanoscale phase transitions, but their specific role in the metal-to-insulator transition in VO(2) has remained elusive. By combining plasmon resonance nanospectroscopy with density functional calculations, we correlate decreased phase-transition energy with oxygen vacancies created by strain at grain boundaries. By measuring the degree of metallization in the lithographically defined VO(2) nanoparticles, we find that hysteresis width narrows with increasing size, thus illustrating the potential for domain boundary engineering in phase-changing nanostructures.

Revealing Plasmonic Gap Modes in Particle-on-Film Systems Using Dark-Field Spectroscopy

Polarization-controlled excitation of plasmonic modes in nanometric Au particle-on-film gaps is investigated experimentally using single-particle dark-field spectroscopy. Two distinct geometries are explored: nanospheres on top of and inserted in a thin gold film. Numerical simulations reveal that the three resonances arising in the scattering spectra measured for particles on top of a film originate from highly confined gap modes at the interface. These modes feature different azimuthal characteristics, which are consistent with recent theoretical transformation optics studies. On the other hand, the scattering maxima of embedded particles are linked to dipolar modes having different orientations and damping rates. Finally, the radiation properties of the particle-film gap modes are studied through the mapping of the scattered power within different solid angle ranges.

Ultrafast changes in lattice symmetry probed by coherent phonons.

The electronic and structural properties of a material are strongly determined by its symmetry. Changing the symmetry via a photoinduced phase transition offers new ways to manipulate material properties on ultrafast timescales. However, to identify when and how fast these phase transitions occur, methods that can probe the symmetry change in the time domain are required. Here we show that a time-dependent change in the coherent phonon spectrum can probe a change in symmetry of the lattice potential, thus providing an all-optical probe of structural transitions. We examine the photoinduced structural phase transition in VO(2) and show that, above the phase transition threshold, photoexcitation completely changes the lattice potential on an ultrafast timescale. The loss of the equilibrium-phase phonon modes occurs promptly, indicating a non-thermal pathway for the photoinduced phase transition, where a strong perturbation to the lattice potential changes its symmetry before ionic rearrangement has occurred.

Ultrafast Phase Transition via Catastrophic Phonon Collapse Driven by Plasmonic Hot-Electron Injection

Ultrafast photoinduced phase transitions could revolutionize data-storage and telecommunications technologies by modulating signals in integrated nanocircuits at terahertz speeds. In quantum phase-changing materials (PCMs), microscopic charge, lattice, and orbital degrees of freedom interact cooperatively to modify macroscopic electrical and optical properties. Although these interactions are well documented for bulk single crystals and thin films, little is known about the ultrafast dynamics of nanostructured PCMs when interfaced to another class of materials as in this case to active plasmonic elements. Here, we demonstrate how a mesh of gold nanoparticles, acting as a plasmonic photocathode, induces an ultrafast phase transition in nanostructured vanadium dioxide (VO2) when illuminated by a spectrally resonant femtosecond laser pulse. Hot electrons created by optical excitation of the surface-plasmon resonance in the gold nanomesh are injected ballistically across the Au/VO2 interface to induce a subpicosecond phase transformation in VO2. Density functional calculations show that a critical density of injected electrons leads to a catastrophic collapse of the 6 THz phonon mode, which has been linked in different experiments to VO2 phase transition. The demonstration of subpicosecond phase transformations that are triggered by optically induced electron injection opens the possibility of designing hybrid nanostructures with unique nonequilibrium properties as a critical step for all-optical nanophotonic devices with optimizable switching thresholds.

Plasmon-exciton hybridization in ZnO quantum-well Al nanodisc heterostructures.

We demonstrate the formation of a hybridized plasmon-exciton state exhibiting strong exciton-plasmon coupling in ZnO/Zn(0.85)Mg(0.15)O single quantum wells capped with arrays of Al nanodiscs. Tuning the quantum-well width and the diameter and pitch of the Al nanodisc arrays facilitates a transition from the weak-coupling regime into the strong coupling regime. Finite-difference time-domain simulations substantiate the localization of the plasmonic quadrupole moment within the ZnO quantum-well layer, resulting in a hybridized plasmonexciton state demonstrating a Rabi splitting of roughly 15 meV in heterostructures that exhibit a prominent plasmon quadrupole mode. The significant tunability offered by quantum-well heterostructures like those discussed here provides a flexible system for controlling exciton plasmon coupling in a device-compatible thin-film architecture.

Tunable optical antennas enabled by the phase transition in vanadium dioxide

Optical antennas, subwavelength metallic structures resonating at visible frequencies, are a relatively new branch of antenna technology being applied in science, technology and medicine. Dynamically tuning the resonances of these antennas would increase their range of application and offer potential increases in plasmonic device efficiencies. Silver nanoantenna arrays were fabricated on a thin film of the phase change material vanadium dioxide (VO(2)) and the resonant wavelength of these arrays was modulated by increasing the temperature of the substrate above the critical temperature (approximately 68 °C). Depending on the array, wavelength modulation of up to 110 nm was observed.

Plasmonic Probe of the Semiconductor to Metal Phase Transition in Vanadium Dioxide

An array of 180 nm diameter gold nanoparticles (NPs) embedded in a thin vanadium dioxide film was used as a nanoscale probe of the thermochromic semiconductor-to-metal transition (SMT) in the VO2. The observed 30% reduction in plasmon dephasing time resulted from the interaction between the localized surface plasmon resonance of the NPs with the 1.4 eV electronic transitions in VO2. The NPs act as nanoantennas probing the SMT; homogeneous broadening of the gold plasmon resonance is observed at the temperatures where electron correlations are strongest in VO2.

Optical switching and photoluminescence in erbium-implanted vanadium dioxide thin films

Vanadium dioxide (VO2) is under intensive consideration for optical switching due to its reversible phase transition, which features a drastic and rapid shift in infrared reflectivity. Classified as an insulator–to–metal transition, the phase transition in VO2 can be induced thermally, electrically, and optically. When induced optically, the transition can occur on sub-picosecond time scales. It is interesting to dope VO2 with erbium ions (Er3+) and observe their combined properties. The first excited-state luminescence of Er3+ lies within the wavelength window of minimal transmission-loss in silicon and has been widely utilized for signal amplification and generation in silicon photonics. The incorporation of Er3+ into VO2 could therefore result in a novel photonic material capable of simultaneous optical switching and amplification. In this work, we investigate the optical switching and photoluminescence in Er-implanted VO2 thin films. Thermally driven optical switching is demonstrated in the Er-implant...

Room-Temperature Reactions for Self-Cleaning Molecular Nanosensors

New sensing techniques for detecting molecules, especially self-cleaning sensors, are in demand. Here we describe a room-temperature process in which a nanostructured substrate catalyzes the reaction of a target molecule with atmospheric oxygen and the reaction energy is absorbed by the substrate, where it can in principle be detected. Specifically, we report first-principles calculations describing a reaction between 2,4-dinitrotoluene (DNT) and atmospheric O(2) catalyzed by Fe-porphyrin at room temperature, incorporating an oxygen into the methyl group of DNT and releasing 1.9 eV per reaction. The atomic oxygen left on the Fe site can be removed by reacting with another DNT molecule, restoring the Fe catalyst.

Selective Purcell enhancement of defect emission in ZnO thin films

A zinc interstitial defect present but unobservable in ZnO thin films annealed at 500 °C in oxygen or in atmosphere was selectively detected by interaction of the film with an Ag surface-plasmon polariton. The time-dependent differential reflectivity of the ZnO near the ZnO/MgO interface exhibited a subpicosecond decay followed by a several nanosecond recovery, consistent with the Purcell-enhanced Zn interstitial luminescence seen in Ag-ZnO heterostructures. Heterostructures annealed at other temperatures showed significantly greater band-edge photoluminescence and no evidence of the Zn interstitial defect.