Thermally and photoinduced structural and chemical changes of a silver nanocube array on Au(111).

We have investigated the thermally and photoinduced structural and chemical changes of a polyvinylpyrrolidone (PVP)-covered silver nanocube (AgNC) array on Au(111). The Langmuir-Blodgett (LB) method was utilized to fabricate the highly ordered array of the AgNC monolayer on Au(111). In the Raman spectra obtained at room temperature, sharp vibrational peaks were observed owing to the surface-enhanced Raman scattering (SERS) effect of AgNCs. When AgNCs were annealed, their corners became rounded, followed by their height decrease and lateral expansion. Simultaneously, PVP decomposed into nanocarbons, which were eliminated from the gap between AgNCs. Further annealing AgNCs/Au(111) resulted in obvious decreases in Raman signal intensity and AgNC height due to the sintering of AgNCs. We also confirmed the photochemical transformation of PVP to nanocarbons without the deformation of AgNCs when an intense laser was irradiated on the AgNC surface.

Stress-Induced In Situ Modification of Transition Temperature in VO2 Films Capped by Chalcogenide.

We attempted to modify the monoclinic-rutile structural phase transition temperature (Ttr) of a VO2 thin film in situ through stress caused by amorphous-crystalline phase change of a chalcogenide layer on it. VO2 films on C- or R-plane Al2O3 substrates were capped by Ge2Sb2Te5 (GST) films by means of rf magnetron sputtering. Ttr of the VO2 layer was evaluated through temperature-controlled measurements of optical reflection intensity and electrical resistance. Crystallization of the GST capping layer was accompanied by a significant drop in Ttr of the VO2 layer underneath, either with or without a SiNx diffusion barrier layer between the two. The shift of Ttr was by ~30 °C for a GST/VO2 bilayered sample with thicknesses of 200/30 nm, and was by ~6 °C for a GST/SiNx/VO2 trilayered sample of 200/10/6 nm. The lowering of Ttr was most probably caused by the volume reduction in GST during the amorphous-crystalline phase change. The stress-induced in in situ modification of Ttr in VO2 films could pave the way for the application of nonvolatile changes of optical properties in optoelectronic devices.

Localized electronic structures of graphene oxide studied using scanning tunneling microscopy and spectroscopy.

We have used scanning tunneling microscopy (STM) to elucidate the nanoscale electronic structures of graphene oxide (GO). The unreduced GO layer was imaged using STM without reduction processes when deposited on a Au(111) surface covered with an octanethiolate self-assembled monolayer (C8S-SAM). The STM image of the GO sheet exhibits a grainy structure having a thickness of about 1 nm, which is in good agreement with the previous results obtained using atomic force microscopy (AFM). We found that the C8S-SAM suppresses the adsorption of water remaining on the substrate, which would be important to accomplish the nanoscale imaging of the unreduced GO by STM. Furthermore, we successfully detected the π and π* states localized in the GO sheet using scanning tunneling spectroscopy (STS). The π-π* gap energy and the gap center are not uniform within the GO sheet, indicating the existence of various sizes of the sp2 domain and evidence for the local electronic doping by the substituents.

Pump-probe STM light emission spectroscopy for detection of photo-induced semiconductor-metal phase transition of VO2.

We attempted to observe pump-probe scanning tunneling microscopy (STM)-light emission (LE) from a VO2 thin film grown on a rutile TiO2(0 0 1) substrate, with an Ag tip fixed over a semiconducting domain. Laser pulses from a Ti:sapphire laser (wavelength 920 nm; pulse width less than 1.5 ps) irradiated the tip-sample gap as pump and probe light sources. With a photon energy of 2.7 eV, suggesting phase transition from semiconducting monoclinic (M) to metallic rutile (R) phases in relation to the electronic band structure, faint LE was observed roughly 30 ps after the irradiation of the pump pulse, followed by retention for roughly 20 ps. The incident energy fluence of the pump pulse at the gap was five orders of magnitude lower than the threshold value for reported photo-induced M-R phase transition. The mechanism that makes it possible to reduce the threshold fluence is discussed.

Selective scanning tunneling microscope light emission from rutile phase of VO2.

We observed scanning tunneling microscope light emission (STM-LE) induced by a tunneling current at the gap between an Ag tip and a VO2 thin film, in parallel to scanning tunneling spectroscopy (STS) profiles. The 34 nm thick VO2 film grown on a rutile TiO2 (0 0 1) substrate consisted of both rutile (R)- and monoclinic (M)-structure phases of a few 10 nm-sized domains at room temperature. We found that STM-LE with a certain photon energy of 2.0 eV occurs selectively from R-phase domains of VO2, while no STM-LE was observed from M-phase. The mechanism of STM-LE from R-phase VO2 was determined to be an interband transition process rather than inverse photoemission or inelastic tunneling processes.

Nanoscale coupling of photons to vibrational excitation of Ag nanoparticle 2D array studied by scanning tunneling microscope light emission spectroscopy.

Scanning tunneling microscope light emission (STM-LE) spectroscopy has been utilized to elucidate the luminescence phenomena of Ag nanoparticles capped with myristate (myristate-capped AgNP) and 2-methyl-1-propanethiolate (C(4)S-capped AgNP) on the dodecanethiol-precovered Au substrate. The STM imaging revealed that myristate-capped AgNPs form an ordered hexagonal array whereas C(4)S-capped AgNPs show imperfect ordering, indicating that a shorter alkyl chain of C(4)S-capped AgNP is not sufficient to form rigid interdigitation. It should be noted that such a nanoparticle ordering affects the luminescence properties of the Ag nanoparticle. We found that the STM-LE is only detected from the Ag nanoparticles forming the two-dimensional superlattice. This indicates that the STM-LE of the Ag nanoparticle is radiated via the collective excitation of the local surface plasmon resonance (LSPR) spread over the Ag nanoparticles. Note that the STM-LE spectra of the Ag nanoparticles exhibit spike-like peaks superimposed on the broad light emission peak. Using Raman spectroscopy, we concluded that the spike-like structure appearing in the STM-LE spectra is associated with the vibrational excitation of the molecule embedded between Ag nanoparticles.

Inelastic photoemission due to scattering by surface adsorbate vibrations.

By measuring the very low energy photoemission spectra of the CO/Cu(001) surface with a high resolution, we have found the energy loss components due to inelastic scattering of electrons near the Fermi level by the CO vibrational modes. The main energy loss structure appears as a step at 254 meV below the Fermi edge for 12C16O. An isotope shift of the step to 240 meV was observed when 13C18O was adsorbed. This observation confirms that this step arises from the energy loss of photoelectrons near the Fermi level through the excitation of the C-O stretching mode.