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We demonstrate control over the spatial and temporal properties of surface plasmon polaritons (SPPs) launched from nanohole arrays in silver. The arrays provide wave vector matching to allow the conversion of free-space photons into counter-propagating SPPs. SPPs launched from multiple arrays interfere at well-defined spatial positions, and the interference fringes form an all-SPP periodic nano-optical grating which evolves in space and time as the SPPs propagate. The spatio-temporal characteristics of the optical grating can be tuned through various nanohole array parameters such as tilt angle, separation, and array width. In addition, we examine multiperiodic arrays (MPAs) consisting of arrays with different pitches placed adjacent to one another. This platform allows the temporal interference of SPPs with different central wavelengths to be tailored through the MPA geometric and structural parameters. The temporal interference serves as an encoded signal, whereby the frequency components can be controlled by the array properties.

We demonstrate fast (0.25 s/pixel) nanoscale chemical imaging in aqueous solution via tip-enhanced Raman scattering (TERS), with sub-15 nm spatial resolution. The substrate consists of 4-mercaptobe...

Plasmonic tip-sample junctions, at which the incident and scattered optical fields are localized and optimally enhanced, are often exploited to achieve ultrasensitive and highly spatially localized tip-enhanced Raman scattering (TERS). Recent work has demonstrated that the sensitivity and spatial resolution that are required to probe single molecules are attainable in such platforms. In this work, we observe and rationalize comparable TERS from few-layer WSe(2) single crystals exfoliated onto Au- and Cr-coated Si substrates, using a plasmonic TERS probe excited with a 638 nm laser. Our experimental observations are supported by finite-difference time-domain simulations that illustrate that the attainable field enhancement factors at the Au–Au and Au–Cr tip-sample junctions are comparable in magnitude. Through a combined experimental and theoretical analysis, we propose that besides Au/Ag, several metallic substrates may be used to record bright TERS spectral images.

Directional control over surface plasmon polariton (SPP) waves is a prerequisite for the development of miniaturized optical circuitry. Here, the efficacy of single and dual component SPP steering elements is explored through photoemission electron microscopy. Our imaging scheme relies on two-color photoemission and counter-propagating SPP generation, which collectively allow SPPs to be visualized in real space. Wave-vector difference mixing between the two-dimensional nanohole array and photon momenta enables SPP steering with directionality governed by the array lattice constant and input photon direction. In our dual component configuration, separate SPP generation and Bragg diffraction based steering optics are employed. We find that array Bragg planes principally influence the SPP angles through the array band structure, which allows us to visualize both positive and negative refractory waves.

The role of surface plasmon polaritons (SPPs) in nanohole array optical extinction spectra is explored using a time-resolved technique capable of isolating the air/metal interfacial SPP contribution to the typical Fano profile in optical transmission curves. A pair of interferometrically locked broad-band femtosecond pulses is used to launch SPPs from lithographically patterned plasmonic nanohole arrays. SPPs launched in the co- and counter-propagating directions are probed using a third probe pulse in a photoemission electron microscope. Using this approach, we record interferometric SPP–SPP linear autocorrelations that selectively report on the resonances of SPPs launched from arrays of varying pitches and hole diameters. Aside from advancing an approach to selective SPP spectroscopy, we illustrate that resonant coupling in the counter-propagating direction may be exploited to control the spatial, temporal, and spectral characteristics of SPPs. For the counter-propagating direction, we show that tuning the array pitch near the fundamental plasmon resonance generates color-tuned (∼770–820 nm), narrow bandwidth SPPs, and the bandwidth may be controlled by changing the ratio of pitch to hole diameter. The SPP resonances we recover through Fourier transforms of the interferometric autocorrelations shed light on the classical problem of Fano interference in nanohole array extinction spectra.

Tip-enhanced Raman scattering (TERS) can be used to image plasmon-enhanced local electric fields on the nanoscale. This is illustrated through ambient TERS measurements recorded using silver atomic force microscope tips coated with 4-mercaptobenzonitrile molecules and used to image step edges on an Au(111) surface. The observed two-dimensional TERS images uniquely map electric fields localized at Au(111) step edges following 671 nm excitation. We establish that our measurements are not only sensitive to spatial variations in the enhanced electric fields but also to their vector components. We also experimentally demonstrate that (i) few nanometer precision is attainable in TERS nanoscopy using corrugated tips with nominal radii on the order of 100–200 nm, and (ii) TERS signals do not necessarily exhibit the expected E4 dependence. Overall, we illustrate the concept of electric field imaging via TERS and establish the connections between our observations and conventional TERS chemical imaging measurements.

Propagating surface plasmons (PSPs) launched from a protruded silver spherical cap structure are investigated using photoemission electron microscopy (PEEM) and finite difference time domain (FDTD) calculations. Our combined experimental and theoretical findings reveal that PSP coupling efficiency is comparable to conventional etched-in plasmonic coupling structures. Additionally, plasmon propagation direction can be varied by linear rotation of the driving laser polarization. A simple geometric model is proposed in which the plasmon direction selectivity is proportional to the projection of the linear laser polarization on the surface normal. A application for the spherical cap coupler as a gate device is proposed. Overall, our results indicate that protruded cap structures hold great promise as elements in emerging surface plasmon applications.

A series of optical and electron microscopies are utilized in concert to unravel the properties of corrugated metallic tips. While the overall microscopic shapes of the tips dictate their optical resonances and plasmonic field enhancement factors, nanometric structural details govern their tip-enhanced Raman (TER) spectra and images. Using 4-thiobenzonitrile (TBN) as a molecular reporter, spatially resolved TER spectra reveal that optical rectification and molecular charging are among the prominent observables in the tip-tip TER geometry. We show the spurious appearance of anions is driven by highly localized resonances that appear as a result of surface corrugation and their manifestation throughout the course of TER nanospectroscopy complicates spectral assignments. Overall, nanoscale spatial variations in the TERS spectra suggest that the tip-tip geometry sustains junction plasmons that appear very different from what may be expected from the hybridization of the bulk tip resonances.

We record nanoscale-resolved chemical images of thiobenzonitrile (TBN)-functionalized smooth gold nanospheres on silicon via tip-enhanced Raman (TER) nanospectroscopy. The recorded images trace the nascence of the familiar doughnut-shaped scattering profile of nanoparticles on silicon at its origin (the particle surface), which appears as a horseshoe-shaped scattering pattern under our experimental conditions. The local optical field maps are in agreement with their simulated finite-difference time-domain analogues. Analysis of the recorded spectra with the aid of ab-initio-molecular-dynamics-based Raman spectral simulations further suggests that optical rectification and molecular charging take place throughout the course of atomic-force-microscopy-based TER nanoscale chemical imaging.

We deploy two-dimensional nanohole arrays as resonant surface plasmon polariton (SPP) couplers that enable counter-propagation and excitation field interference-free imaging of SPP wave packets. We monitor the spatiotemporal evolution of the resulting SPPs using two-color photoemission electron microscopy. The measurements track the electric field envelope of the SPP in real space and time and enable direct characterization of their spatiotemporal properties in a regime where the SPP wave packet is the principal observable. We provide an analysis of the observables for both the co- and counter-propagating directions via SPP trajectories that are recorded in tandem. Our results highlight the advantages of isolating SPPs through counter-propagation, where excitation field-SPP interactions are suppressed.

Overcoming the dissipative nature of propagating surface plasmons (PSPs) is a prerequisite to realizing functional plasmonic circuitry, in which large-bandwidth signals can be manipulated over length scales far below the diffraction limit of light. To this end, we report on a novel PSP-enhanced signal detection technique achieved in an all-metallic substrate. We take advantage of two strategically spatiotemporally separated phase-locked femtosecond laser pulses, incident onto lithographically patterned PSP coupling structures. We follow PSP propagation with joint femtosecond temporal and nanometer spatial resolution in a time-resolved nonlinear photoemission electron microscopy scheme. Initially, a PSP signal wave packet is launched from a hole etched into the silver surface from where it propagates through an open trench structure and is decoded through the use of a timed probe pulse. FDTD calculations demonstrate that PSP signal waves may traverse open trenches in excess of 10 μm in diameter, thereby al...

We record spectrally (400 ≤ λ ≤ 675 nm, Δλ < 4.69 nm) and spatially (diffraction-limited, sampled at 85 nm2/pixel) resolved dark field (DF) scattering from single silver nanospheres of 100 nm in diameter. Hyperspectral DF optical microscopy is achieved by coupling a hyperspectral detector to an optical microscope, whereby spectrally resolved diffraction-limited images of hundreds of silver nanoparticles can be recorded in ∼30 s. We demonstrate how the centers and edges of individual particles can be localized in two dimensions to within a single pixel (85 nm2), using a statistical method for examining texture based on a co-occurrence matrix. Subsequently, spatial averaging of the spectral response in a 3 × 3 pixel area around the particle centers affords ample signal to noise to resolve the plasmon resonance of a single silver nanosphere. A close inspection of the scattering spectra of 31 different nanospheres reveals that each particle has its unique (i) relative scattering efficiency and (ii) plasmon re...

We image 4-mercaptobenzonitrile-functionalized silver nanowires (∼20 nm diameter) through tip-enhanced Raman scattering (TERS). The enhanced local optical field-molecular interactions that govern the recorded hyperspectral TERS images are dissected through hybrid finite-difference time-domain density functional theory simulations. Our forward simulations illustrate that the recorded spatiospectral profiles of the chemically functionalized nanowires may be reproduced by accounting for the interaction between orientationally averaged molecular polarizability derivative tensors and enhanced incident/scattered local fields polarized along the tip axis. In effect, we directly map the enhanced optical fields of the nanowire in real space through TERS. The simultaneously recorded atomic force microscopy (AFM) images allow a direct comparison between our attainable spatial resolution in topographic (13 nm) and TERS (5 nm) imaging measurements performed under ambient conditions. Overall, our described protocol enables local electric field imaging with few nm precision through molecular TERS, and it is therefore generally applicable to a variety of plasmonic nanostructures.

It is now possible to establish the chemical identity of a substance at the ultimate detection limit of a single molecule, i.e. the sensitivity required to probe 1.66 yoctomoles (1/NA), using surface-enhanced Raman scattering (SERS). It is also possible to image within an individual molecule, all while retaining chemical selectivity, using tip-enhanced Raman scattering (TERS). The potential applications of ultrasensitive SERS and TERS in chemical and biological detection and imaging are evident, and have attracted significant attention over the past decade. Rather than focusing on conventional single/few-molecule SERS and TERS experiments, where the objective is ultrasensitive spectroscopy and nanoscale chemical imaging, herein we consider greatly informative, yet significantly underrated, signatures of single molecules. Namely, we review recent efforts ultimately aimed at probing different aspects of a molecule’s local environment through a detailed analysis of its SERS and TERS spectra and image...

We report tip-enhanced Raman imaging experiments in which information on sample topography and local electric fields is simultaneously obtained using an all-optical detection scheme. We demonstrate how a Raman-active 4,4'-dimercaptostilbene (DMS)-coated gold tip of an atomic force microscope can be used to simultaneously map the topography and image the electric fields localized at nanometric (20 and 5 nm wide) slits lithographically etched in silver, all using optical signals. Bimodal imaging is feasible by virtue of the frequency-resolved optical response of the functionalized metal probe. Namely, the probe position-dependent signals can be subdivided into two components. The first is a 500-2250 cm(-1) Raman-shifted signal, characteristic of the tip-bound DMS molecules. The molecules report on topography through the intensity contrast observed as the tip scans across the nanoscale features. The variation in molecular Raman activity arises from the absence/formation of a plasmonic junction between the scanning probe and patterned silver surface, which translates into dimmed/enhanced Raman signatures of DMS. Using these molecular signals, we demonstrate that sub-15 nm spatial resolution is attainable using a 30 nm DMS-coated gold tip. The second response consists of two correlated sub-500 cm(-1) signals arising from mirror-like reflections of (i) the incident laser field and (ii) the Raman scattered response of an underlying glass support (at 100-500 cm(-1)) off the gold tip. We show that both the reflected low-wavenumber signals trace the local electric fields in the vicinity of the nanometric slits.

High quantum efficiency enhancement is found for hybrid metal-insulator photocathodes consisting of thin films of CsI deposited on Cu(1 0 0), Ag(1 0 0), Au(1 1 1) and Au films irradiated by 266 nm laser pulses. Low work functions (near or below 2 eV) are observed following ultraviolet laser activation. Work functions are reduced by roughly 3 eV from that of clean metal surfaces. We discuss various mechanisms of quantum efficiency enhancement for alkali halide/metal photocathode systems and conclude that the large change in work function, due to Cs accumulation of Cs metal at the metal–alkali halide interface, is the dominant mechanism for quantum efficiency enhancement.

We describe surface enhanced Raman spectroscopy (SERS) experiments in which molecular coverage is systematically varied from 3.8 × 105 to 3.8 × 102 to 0.38 molecules per μm2 using electrospray deposition of ethanolic 4,4′-dimercaptostilbene (DMS) solutions. The plasmonic SERS substrate used herein consists of a well-characterized 2-dimensional (2D) array of silver nanospheres (see El-Khoury et al., J. Chem. Phys., 2014, 141, 214308), previously shown to feature uniform topography and plasmonic response, as well as intense SERS activity. When compared to their ensemble averaged analogues, the spatially and temporally averaged spectra of a single molecule exhibit several unique features including: (i) distinct relative intensities of the observable Raman-active vibrational states, (ii) more pronounced SERS backgrounds, and (iii) broader Raman lines indicative of faster vibrational dephasing. The first observation may be understood on the basis of an intuitive physical picture in which the removal of averaging over multiple molecules exposes the tensorial nature of Raman scattering. When an oriented single molecule gives rise to the recorded SERS spectra, the relative orientation of the molecule with respect to vector components of the local electric field determines the relative intensities of the observable vibrational states. Using a single molecule SERS framework, described herein, we derive a unique molecular orientation in which a single DMS molecule is isolated at a nanojunction formed between two silver nanospheres in the 2D array. The DMS molecule is found lying nearly flat with respect to the metal. The derived orientation of a single molecule at a plasmonic nanojunction is consistent with observations (ii) and (iii). In particular, a careful inspection of the temporal spectral variations along the recorded single molecule SERS time sequences reveals that the time-averaged SERS backgrounds arise from individual molecular events, marked by broadened SERS signatures. We assign the broadened spectra along the SERS time sequence – which sum up to a SERS background in the averaged spectra – to instances in which the π-framework of the DMS molecule is parallel to the metal at a classical plasmonic nanojunction. This also accounts for Raman line broadening as a result of fast vibrational dephasing, and driven by molecular reorientation at a plasmonic nanojunction. Furthermore, we report on the molecular orientation dependence of single molecule SERS enhancement factors. We find that in the case of a single DMS molecule isolated at a plasmonic nanojunction, molecular orientation may affect the derived single molecule SERS enhancement factor by up to 5 orders of magnitude. Taking both chemical effects as well as molecular orientation into account, we were able to estimate a single molecule enhancement factor of ∼1010 in our measurements.

Nonlinear photoemission electron microscopy of isolated nanoholes in gold thin films maps propagating surface plasmon polaritons (SPPs) launched from the lithographically patterned plasmonic structures. A damped elongated ringlike photoemission beat pattern is observed from the nanoholes, following low angle of incidence irradiation of these structures with sub-15 fs 780 nm laser pulses. A notable agreement between finite difference time domain simulations and experiment corroborates our assignment of the observed photoemission patterns to SPPs launched from isolated nanoholes and probed through nonlinear photoemission. We also demonstrate how the efficiency of coupling light waves into isolated plasmonic holes can be tuned by varying hole diameter. In this regard, a simple intuitive geometrical model, which accounts for the observed and simulated diameter dependent plasmonic response, is proposed. Overall, this study paves the way for designing nanohole assemblies where optical coupling and subsequent pl...

Here we report the structure and optical properties of a new Cu–cysteamine complex (Cu–Cy) with a formula of Cu3Cl(SR)2 (R = CH2CH2NH2). This Cu–Cy has a different structure from a previous Cu–Cy complex, in which both thio and amine groups from cysteamine bond with copper ions. Single-crystal X-ray diffraction and solid-state nuclear magnetic resonance results show that the oxidation state of copper in Cu3Cl(SR)2 is +1 rather than +2. Further, Cu3Cl(SR)2 has been observed to show intense photoluminescence and X-ray excited luminescence. More interesting is that Cu3Cl(SR)2 particles can produce singlet oxygen under irradiation by light or X-ray. This indicates that Cu3Cl(SR)2 is a new photosensitizer that can be used for deep cancer treatment as X-ray can penetrate soft tissues. All these findings mean that Cu3Cl(SR)2 is a new material with potential applications for lighting, radiation detection and cancer treatment.

We investigate desorption of Br atoms from the α-CsBr(110) and β-CsBr(100) surfaces induced by 6.4 and 7.9 eV ultraviolet laser irradiation. The mechanisms of Br-atom desorption were modeled using density functional theory (DFT) calculations. Together the experimental data and theoretical predictions demonstrate that the sub-bandgap irradiation at 6.4 eV predominantly excites the CsBr surface, leading to desorption of neutral Br atoms with a hyperthermal kinetic energy distribution. Excitation above the bandgap at 7.9 eV leads to desorption of Br atoms with both thermal and hyperthermal energies. Our theoretical modeling suggests that desorption of Br atoms with thermal velocities originates from the decay of subsurface excitons, which produces interstitial Br atoms that subsequently diffuse to the CsBr surface. Hyperthermal desorption can be explained by the surface-exciton-based desorption model. The computed maximum kinetic energy of desorbed Br atoms agrees well with the experimental observables.

The photoluminescence and X-ray luminescence of ZnS:Mn, ZnS:Mn,Eu and ZnS:Eu were investigated and it was found that the luminescence intensity of Mn2+ in ZnS:Mn,Eu co-doped phosphors is highly dependent on the doping concentration of Eu2+. At the optimized Eu2+ concentration (0.2%), the photoluminescence of Mn2+ shows about a 5.5 times enhancement and its X-ray luminescence is enhanced by a factor of 2.5. Both wurtzite and zinc blend phases are present in the samples with wurtzite phase dominant. Co-doping of Eu2+ into ZnS:Mn does not change appreciably the ratio of the two phases or the Mn2+ emission luminescence lifetime; however, the doping of Eu2+ into ZnS:Mn does change the phonon activity. Furthermore, it was found that the defect-related blue emission of ZnS:Eu overlaps with the excitation bands of Mn2+ in ZnS:Mn and there is likely energy transfer from these defect states to Mn2+ in ZnS:Mn,Eu. This energy transfer and the phonon modification are considered to be the two main reasons for the luminescence enhancement and the intensity dependence of Mn2+ emission on Eu2+ doping concentration in ZnS:Mn,Eu.

Phenomena related to the interaction of point defects and dopants with grain boundaries and interfaces have been very well documented. However, a quantitative understanding of such an interaction is still missing. In this paper we explore the correlation between radiation damage and interface structure. In doing so, Cr x Mo 1− x (0 0 1) films of thickness ∼100 nm were epitaxially grown on MgO (0 0 1) using molecular beam epitaxy. The interface dislocation density can be systematically varied by controlling the composition of the film. This system allows us to probe the response of the defects generated during the irradiation to the interface dislocation density. The microstructural features of these films before and after irradiation are carefully studied using high resolution scanning/transmission electron microscopy and electron diffraction. It has been found that the film/substrate system is very resistant to ion-induced irradiation damage. No visible point defect clusters, dislocation network or amorphization has been identified, which is contrasted with other materials of either metallic or ionic bonding. In combination with RBS analysis, we conclude that the defects in the present system appear to be very mobile and were annihilated during the irradiation process.

We combine scanning electron microscopy, atomic force microscopy, surface-enhanced Raman scattering (SERS), and tools of computational chemistry to investigate the origin of Raman scattering of 4,4’-biphenyldicarboxylic acid adsorbed as 4,4’-biphenyldicarboxylate on two different silver substrates. The first consists of a 100 nm deep cylindrical aperture embedded in an array of cylindrical nano-holes featuring an average diameter of 350 nm and a periodicity of 700 nm. The second is a nano-junction formed by a 100 nm silver nano-particle coated with the adsorbate and a flat silver surface. We find that the underlying background signal in the SERS spectra collected from the former strongly resemble the SERS spectra of the nano-sphere-featuring substrate, engineered to operate in the charge transfer plasmon limit. Our analysis of a series of SERS spectra consecutively collected from one nano-cylinder suggests that the optical response of a single molecule can be extracted, its brightest Raman active mode enhanced by a factor of 7.4 x 106.

Near-infrared (NIR) spectroscopy was applied to investigate the dissolution and chemical interaction of water dissolved into supercritical carbon dioxide (scCO2) and the influence of CaCl2 in the co-existing aqueous phase at fo empe e : 40 50 75 nd 100 C at 90 atm. Consistent with the trend of the vapor pressure of water, the solubility of pure water in scCO2 inc e ed f om 40 °C (0.32 mole%) o 100 °C (1.61 mole%). The presence of CaCl2 negatively affects the solubility of water in scCO2: at a given temperature and pressure the solubility of water decreased as the concentration of CaCl2 in the aqueous phase increased, following the trend of the activity of water. A 40 °C, the water concentration in scCO2 in contact with saturated CaCl2 aqueous solution was only 0.16 mole%, a drop of more than 50% as compared to pure water while that a 100 °C was 1.12 mole%, a drop of over 30% as compared to pure water, under otherwise the same conditions. Analysis of the spectral profiles suggested that water dissolved into scCO2 exists in the monomeric form under the evaluated temperature and pressure conditions, for both neat water and CaCl2 solutions. However,more » its rotational degrees of freedom decrease at lower temperatures due to higher fluid densities, leading to formation of weak H2O:CO2 Lewis acid-base complexes. Similarly, the nearly invariant spectral profiles of dissolved water in the presence and absence of saturated CaCl2 under the same experimental conditions was taken as evidence that CaCl2 dissolution in scCO2 was limited as the dissolved Ca2+/CaCl2 would likely be highly hydrated and would alter the overall spectra of waters in the scCO2 phase.« less

The relative intensities of propagating surface plasmons (PSPs) simultaneously launched from opposing edges of a symmetric trench structure etched into a silver thin film may be controllably varied by tuning the linear polarization of the driving field. This is demonstrated through transient multiphoton photoemission electron microscopy measurements performed using a pair of spatially separated phase-locked femtosecond pulses. Our measurements are rationalized using finite-difference time domain simulations, which reveal that the coupling efficiency into the PSP modes is inversely proportional to the magnitude of the localized surface plasmon fields excited at the trench edges. Our combined experimental and computational results allude to the interplay between localized and propagating surface plasmon modes in the trench; strong coupling to the localized modes at the edges correlates to weak coupling to the PSP modes. Polarization-directed PSP launching measurements reveal an optimal PSP contrast ratio of 4.2 using a 500 nm wide trench.

Both photons and electrons may be used to excite surface plasmon polaritons, the collective charge density fluctuations at the surface of metal nanostructures. By virtue of their nanoscopic and dissipative nature, a detailed characterization of surface plasmon (SP) eigenmodes in real space-time ultimately requires joint nanometer spatial and femtosecond temporal resolution. The latter realization has driven significant developments in the past few years, aimed at interrogating both localized and propagating SP modes. In this mini-review, we briefly highlight different techniques employed by our own groups to visualize the enhanced electric fields associated with SPs. Specifically, we discuss recent hyperspectral optical microscopy, tip-enhanced Raman nano-spectroscopy, nonlinear photoemission electron microscopy, as well as correlated scanning transmission electron microscopy-electron energy loss spectroscopy measurements targeting prototypical plasmonic nanostructures and constructs. Through selected practical examples from our own laboratories, we examine the information content in multidimensional images recorded by taking advantage of each of the aforementioned techniques. In effect, we illustrate how SPs can be visualized at the ultimate limits of space and time.

As Raman spectroscopy continues to evolve, questions arise as to the portability of Raman data: dispersive versus Fourier transform, wavelength calibration, intensity calibration, and in particular the frequency of the excitation laser. While concerns about fluorescence arise in the visible or ultraviolet, most modern (portable) systems use near-infrared excitation lasers, and many of these are relatively close in wavelength. We have investigated the possibility of porting reference data sets from one NIR wavelength system to another: We have constructed a reference library consisting of 145 spectra, including 20 explosives, as well as sundry other compounds and materials using a 1064 nm spectrometer. These data were used as a reference library to evaluate the same 145 compounds whose experimental spectra were recorded using a second 785 nm spectrometer. In 128 cases of 145 (or 88.3% including 20/20 for the explosives), the compounds were correctly identified with a mean “hit score” of 954 of 1000. Adding in criteria for when to declare a correct match versus when to declare uncertainty, the approach was able to correctly categorize 134 out of 145 spectra, giving a 92.4% accuracy. For the few that were incorrectly identified, either the matched spectra were spectroscopically similar to the target or the 785 nm signal was degraded due to fluorescence. The results indicate that imported data recorded at a different NIR wavelength can be successfully used as reference libraries, but key issues must be addressed: the reference data must be of equal or higher resolution than the resolution of the current sensor, the systems require rigorous wavelength calibration, and wavelength-dependent intensity response should be accounted for in the different systems.

We have investigated the surface photochemical properties of Fe “doped” and (Fe,N) codoped homoepitaxial rutile TiO2(110) films grown by plasma-assisted molecular beam epitaxy. Fe does not incorporate as an electronic dopant in the rutile lattice but rather segregates to the film surface. However, codeposition of Fe with N enhances the solubility of Fe, and DFT calculations suggest that codopant complex formation is the driving force behind the enhanced solubility. The codoped films, in which a few atomic percent of Ti (O) are replaced with Fe (N), exhibit significant disorder compared to undoped films grown under the same conditions, presumably due to dopant-induced strain. Codoping redshifts the rutile bandgap into the visible. However, the film surfaces are photochemically inert with respect to hole-mediated decomposition of adsorbed trimethyl acetate. The absence of photochemical activity may result from dopant-induced trap and/or recombination sites within the film. This study indicates that enhanced...

CaZnGe 2 O 6 :Tb 3+ afterglow phosphors were prepared by solid state reaction using organic coated ZnO nanopowders and their photoluminescence, X-ray luminescence and afterglow properties were investigated. The CaZnGe 2 O 6 :Tb 3+ samples emit a green luminescence at 548 nm attributed to the 5 D 4 – 7 F 5 transition of Tb 3+ . It was observed that the replacement of bulk ZnO by ZnO nanopowder in the sample synthesis increases the luminescence intensity. By adjusting the mass ratio of bulk ZnO to nanopowder ZnO, the photoluminescence intensity, X-ray luminescence intensity, and afterglow efficiency are improved. The optimized sample made with a 0.71 ratio of nano ZnO to bulk ZnO has a factor of four enhancement in X-ray luminescence, photoluminescence and afterglow intensities in comparison with the sample made with 100% bulk ZnO.

Cr(0 0 1) films of thickness ∼100 nm were epitaxially grown on MgO(0 0 1) using molecular beam epitaxy at both room temperature and 550 °C. The structure of the films was characterized using high-resolution transmission electron microscopy, electron diffraction and electron energy-loss spectroscopy. Room temperature growth leads to highly oriented columnar structured grains in the film, while growth at 550 °C yields high-quality single-crystal Cr film, possessing a 45° rotational epitaxial relationship between the film and the substrate. For the single-crystal film, the interface exhibited coherent regions separated by equally spaced misfit dislocations. When imaged from the MgO[1 0 0]//Cr[1 1 0] direction, the dislocation spacing is 5.38 and 4.64 nm for the films grown at room temperature and 550 °C, respectively, which is slightly smaller than the expected value of 6.25 nm calculated from the differences in lattice spacing based on known lattice constants. The results presented here indicate that the lattice mismatch between the film and the substrate is accommodated mainly by interface misfit dislocations above some critical thickness. The electronic structure of the interface between the film and the substrate is also explored using electron energy-loss spectroscopy.

Green emission at around 500 nm is observed in Gd2O3:Ce3+ nanoparticles and the intensity is highly dependent on the concentration of Ce3+ in the nanoparticles. The luminescence of this emission displays both picosecond and millisecond lifetimes. The msec lifetime is over four orders of magnitude longer than typical luminescence lifetimes (10-40 ns) of Ce3+ in traditional Ce3+ doped phosphors and therefore likely originates from defect states. The picosecond lifetime is shorter than the typical Ce3+ value and is also likely due to defect or surface states. When the samples are annealed at 700 oC, this emission disappears possibly due to changes in the defect moieties or concentration. In addition, a blue emission at around 430 nm is observed in freshly-prepared Gd2O3 undoped nanoparticles which is attributed to the stabilizer, polyethylene glycol biscarboxymethyl ether. Upon aging, the undoped particles show similar emission to the doped particles with similar luminescence lifetimes. When Eu3+ ions are co-doped in Gd2O3:Ce nanoparticles, both the green emission and the emission at 612 nm from Eu3+ are observed.

We report qualitatively new highly hyperthermal (HHT) oxygen atom emission from nanostructured CaO excited by 6.4 eV nanosecond laser pulses. The kinetic energy distribution of emitted O-atoms peaks at 0.7 eV, which is over 4 times greater than previously observed. Excitation of MgO and CaO nanostructures with UV laser pulses is known to result in thermal and hyperthermal emission of oxygen atoms when photons with energies above and below the band gap, respectively, are used. The highly energetic atomic desorption we observe, following bulk excitation, challenges the conventional view that bulk excitation can only induce thermal desorption. Using density functional theory and an embedded cluster method, we propose a mechanism for this HHT feature based on the interaction of surface holes with bulk excitons. These experimental and theoretical results suggest that specific atomic desorption mechanisms in wide-bandgap materials can be controlled by selective electronic excitation of not only the surface but also the bulk of these materials.

Photoelectron emission microscopy (PEEM) is a versatile technique that can image a variety of materials including metals, semiconductors and even insulators. Under favorable conditions the most advanced aberration corrected instruments have a spatial resolution approaching 2 nm. Although PEEM cannot compete with transmission or scanning electron microscopies for ultimate resolution, the technique is much gentler and has the unique advantage of imaging structure as well as electronic and magnetic states on the nanoscale. Since the image contrast is derived from spatial variations in electron photoemission intensity, PEEM is ideal for interrogating both static and dynamic electronic properties of complex nanostructured materials. Here, we review the key principles and contrast mechanisms of PEEM and briefly summarize materials applications of PEEM.

When an ionic metal oxide crystal is cleaved, inhomogeneous electrical charging of the surface can be a result. Such an effect has been well documented in magnesium oxide (100). For example, recent rigorous AFM studies indicate that nanoscale charged clusters of MgO are created during cleavage, with high concentrations often located at terrace step edges (Barth and Henry in J. Phys. Chem. C 113:247, 2009). In addition, ablation processes of freshly cleaved magnesium oxide crystals may be effected by remnant surface charging and microstructures (Stoneham et al. in Appl. Phys. A 69:S81, 1999). We report here that such surface charging strongly impacts neutral atom desorption, even under conditions of extremely mild excitation of surface terrace features. In our experiments, single-crystal MgO (100) is cleaved in air and placed in an ultra-high vacuum chamber (UHV). We irradiate the crystal at 6.4 eV, photon energy resonant with five-coordinated (5-C) terrace sites and probe desorbing neutral oxygen atoms. It is found that a significant fraction of desorbed neutral oxygen atoms from the charged surface possess kinetic energies in excess of 0.7 eV. This is in contrast to uncharged samples (discharged in vacuo over 24 hours) that display a near-thermal oxygen atom distribution.

Thin film samples of CeCl3, CeBr3, and combinatorial compositions along the CeCl3–CeBr3 join were produced using thermal evaporation, which is being evaluated as a method for rapid screening of scintillator materials. The combinatorial thin films were shown to be compositionally reproducible from run-to-run within reasonable limitations. Analytical results suggest a continuous variation in the combinatorial samples in terms of their compositions, crystal structures, and luminescence characteristics.

LaF3:Ce3+-doped nanoparticles were synthesized at different temperatures in dimethyl sulfoxide (DMSO) by the chemical reaction of lanthanum nitrate hydrate and cerium nitrate hexahydrate with ammonium fluoride. The formation of Ce3+-doped LaF3 nanoparticles is confirmed by X-ray diffraction and high-resolution transmission electron microscopy. An intense emission at around 310 nm from the d−f transition of Ce3+ was observed from the LaF3:Ce3+ powder samples. However, in solution samples, the ultraviolet emission from Ce3+ is mostly absent, but intense luminescence is observed in the visible range from blue to red. The emission wavelength of the solution samples is dependent on the reaction time and temperature. More interestingly, the emission wavelength varies with the excitation wavelength. Most likely, this emission is from metal organic compounds of Ce3+ or La3+ and DMSO as similar phenomena are also observed when lanthanum nitrate hydrate or cerium nitrate hexahydrate are heated in DMSO.

Neutral magnesium atom emission from nanostructured MgO thin films is induced using two-color nanosecond laser excitation. We find that combined vis/UV excitation, for single-color pulse energies below the desorption threshold, induces neutral Mg-atom emission with hyperthermal kinetic energies in the range of 0.1–0.2 eV. The observed metal atom emission is consistent with a mechanism involving rapid electron transfer to three-coordinated Mg surface sites. The two-color Mg-atom signal is significant only for parallel laser polarizations and temporally overlapped laser pulses indicating that intermediate excited states are short-lived compared to the 5 ns laser pulse duration.

The discovery and optimization of new scintillators has traditionally been a rather slow process due to the difficulties of single crystal growth. This paper discusses the production of polycrystalline scintillator thin films which were tested in order to determine what characterizations could be made concerning a material's ultimate potential as a scintillator prior to pursuing crystal growth. Thin films of a few microns thickness of CaF2(Eu), CeF3, and CeCl3, all known scintillators, were produced by vapor deposition. The hygroscopic CeCl3 was coated with multiple polymer-aluminum oxide bi-layers. Emission wavelengths and decay times agreed with values from single crystals. The films were too thin to measure gamma photopeaks, but using alpha energy deposition peaks, one could compare the relative photon yield/MeV between materials. The values obtained appear to give a relevant indication of a material's light yield potential. The technique may also be useful for quickly indicating the proper dopant amount for a given material.

Nanoparticles of wide band gap materials MgO and CaO, subjected to low-intensity ultraviolet irradiation with 266 nm (4.66 eV) photons, emit hyperthermal oxygen atoms with kinetic energies of up to ∼0.4 eV. We use an ab initio embedded cluster method to study theoretically a variety of elementary photoinduced processes at both ideal and defect-containing surfaces of these nanoparticles and to develop a mechanism for the desorption process. The proposed mechanism includes multiple local photoexcitations resulting in sequential formation of localized excitons, their ionization, and further excitations. It is suggested that judicious choice of sub-band gap photon energies can be used to selectively modify surfaces of nanomaterials.

Many methods have been reported for the formation of sulfide nanoparticles by the reaction of metallic salts with sulfide chemical sources in aqueous solutions or organic solvents. Here, we report the formation of sulfide nanoparticles in dimethylsulfoxide (DMSO) by boiling metallic salts without sulfide sources. The sulfide sources are generated from the boiling of DMSO and react with metallic salts to form sulfide nanoparticles. In this method DMSO functions as a solvent and a sulfide source as well as a stabilizer for the formation of the nanoparticles. The recipe is simple and economical making sulfide nanoparticles formed in this way readily available for many potential applications.

Water-soluble ZnO nanoparticles coated with polyethylene glycol biscarboxymethyl (PEG(COOH)2) were prepared in ethanol/water solutions. The ZnO nanoparticles have a hexagonal structure with an average size of 10 nm. Three different luminescence bands are observed from the nanoparticle solutions: green emission at 530 nm from surface states or defects, UV emission at 380 nm from the ZnO exciton, and an emission band at around 338 nm from the PEG(COOH)2. The fresh as-prepared samples have very strong green emission at 530 nm from surface states or defects but very weak excitonic emission at 380 nm. After dilution with ethanol, the green emission decreases in intensity and the excitonic emission increases. In the diluted samples, the excitonic luminescence intensity increases with storage time. This intensity increase is attributed to surface passivation by CH3COO− ligands resulting from precursor reactions in the ethanol solvent.

Phase transformation of thin film (∼30 nm)In2Se3/Si(111) (amorphous→crystalline) was performed by resistive annealing and the reverse transformation (crystalline→amorphous) was performed by nanosecond laser annealing. As an intrinsic-vacancy, binary chalcogenide semiconductor, In2Se3 is of interest for non-volatile phase-change memory. Amorphous In x Se y was deposited at room temperature on Si(111) after pre-deposition of a crystalline In2Se3 buffer layer (0.64 nm). Upon resistive annealing to 380°C, the film was transformed into a γ-In2Se3 single crystal with its {0001} planes parallel to the Si(111) substrate and $(11\bar{2}0)$ parallel to Si $(1\bar{1}0)$ , as evidenced by scanning tunneling microscopy, low energy electron diffraction, and X-ray diffraction. Laser annealing with 20-ns pulses (0.1 millijoules/pulse, fluence≤50 mJ/cm2) re-amorphized the region exposed to the laser beam, as observed with photoemission electron microscopy (PEEM). The amorphous phase in PEEM appears dark, likely due to abundant defect levels inhibiting electron emission from the amorphous In x Se y film.

International audience; We excite low-coordinated surface sites of nanostructured MgO samples using 4.7 eV UV laser pulses and observe dominant hyperthermal O-atom emission. Excitation of the same samples with 7.9 eV photons results in thermal O-atom desorption. These results are analyzed in the context of laser desorption models developed previously for alkali halide crystals and MgO. We detail two multi-step mechanisms for hyperthermal O-atom, desorption, under surface selective excitation, based on exciton and hole trapping at three-coordinated (corner) O-atom sites, and evaluate the validity of each based on available experimental data and calculated results. The proposed models are significantly different from and more complex than the surface exciton desorption model established for alkali halides. Nonetheless, the principles of site-specific photo-excitation and exciton and hole localization induced atomic desorption are clearly extendable to a prototypical metal oxide. (c) 2008 Elsevier B.V. All rights reserved.

Upconversion luminescence is observed from colloidal CdS and CdZnS quantum dots dispersed in hexanes. These binary and ternary nanocrystals were synthesized via noninjection approaches and at relatively low temperature and exhibit cubic crystal structures and narrow size distributions. The upconversion luminescence of these nanocrystal ensembles is similar to their corresponding photoluminescence emission, regarding peak shape, position, and dynamics. The upconversion luminescence yield exhibits a near-quadratic laser power dependence. Accordingly, our study indicates that the upconversion luminescence is due to two-photon excitation.

We have used plasma-assisted molecular beam epitaxy to synthesize structurally near-perfect crystalline films of TiO 2− x N x rutile for the first time. These materials allow the properties of TiO 2− x N x to be elucidated without the interfering effects of bulk substoichiometric defects that have characterized previous investigations. In the absence of such defects, the extent of N incorporation in the lattice is limited to ∼2 ± 1 at.% of the anions. Substitutional N (N O ) exhibits a −3 formal charge due to charge transfer from shallow-donor interstitial Ti(III), which forms during epitaxial growth. Hybridization between N O and adjacent lattice Ti ions occurs, resulting in new states at the top of the rutile valence band and an apparent band gap reduction of ∼0.6 eV.