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Nonequilibrium chemical phenomena are known to play an important role in single molecule microscopy and spectroscopy. Herein, we explore these effects through ab initio molecular dynamics (AIMD)-based Raman spectral simulations. We target an isolated aromatic thiol (thiobenzonitrile, TBN) as a prototypical molecular system. We first show that the essential features contained in the ensemble-averaged Raman spectrum of TBN can be reproduced by averaging over 18 short AIMD trajectories spanning a total simulation time of ∼60 ps. This involved more than 90 000 polarizability calculations at the B3LYP/def2-TZVP level of theory. We then illustrate that the short trajectories (∼3.3 ps total simulation time), where the accessible phase space is not fully sampled, provide a starting point for understanding key features that are often observed in measurements targeting single molecules. Our results suggest that a complete understanding of single molecule Raman scattering needs to account for molecular conformational flexibility and nonequilibrium chemical phenomena in addition to local optical fields and modified selection rules. The former effects are well-captured using the described AIMD-based single molecule Raman spectral simulations.

Tip-enhanced Raman spectroscopy (TERS) is particularly sensitive to analytes residing at plasmonic tip-sample nanojunctions, where the incident and scattered optical fields may be localized and optimally enhanced. However, the enhanced local electric fields in this so-called gap-mode TERS configuration are nominally orthogonal to the sample plane. As such, any given Raman active vibrational eigenstate needs to have projections (of its polarizability derivative tensor elements) along the sample normal to be detectable via TERS. The faint TERS signals observed from two prototypical systems, namely, pristine graphene and graphene oxide are a classical example of the aforementioned rather restrictive TERS selection rules in this context. In this study, we demonstrate that nanoindentation, herein achieved using pulsed-force lithography with a sharp single-crystal diamond atomic force microscope probe, may be used to locally enhance TERS signals from graphene and graphene oxide flakes on gold. Nanoindentation locally perturbs the otherwise flat graphene structure and introduces out-of-plane protrusions that generate enhanced TERS. Although our approach is nominally invasive, we illustrate that the introduced nanodefects are highly localized, as evidenced by TERS nanoscale chemical mapping. As such, the described protocol may be used to extend and generalize the applicability of TERS for the rapid identification of two-dimensional material systems on the nanoscale.

We describe a unique approach to hyperspectral optical microscopy, herein achieved by coupling a hyperspectral imager to various optical microscopes. Hyperspectral fluorescence micrographs of isolated fluorescent beads are first employed to ensure spectral calibration of our detector and to gauge the attainable spatial resolution of our measurements. Different science applications of our instrument are then described. Spatially over-sampled absorption spectroscopy of a single lipid (18:1 Liss Rhod PE) layer reveals that optical densities on the order of 10−3 can be resolved by spatially averaging the recorded optical signatures. This is followed by three applications in the general areas of plasmonics and bioimaging. Notably, we deploy hyperspectral absorption microscopy to identify and image pigments within a simple biological system, namely, a single live Tisochrysis lutea cell. Overall, this work paves the way for multimodal spectral imaging measurements spanning the realms of several scientific disciplines.

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.

Recent developments in nanophotonics have paved the way for achieving significant advances in the realm of single-molecule chemical detection, imaging, and dynamics. In particular, surface-enhanced Raman scattering (SERS) is a powerful analytical technique that is now routinely used to identify the chemical identity of single molecules. Understanding how nanoscale physical and chemical processes affect single-molecule SERS spectra and selection rules is a challenging task and is still actively debated. Herein, we explore underappreciated chemical phenomena in ultrasensitive SERS. We observe a fluctuating excited electronic state manifold, governed by the conformational dynamics of a molecule (4,4′-dimercaptostilbene, DMS) interacting with a metallic cluster (Ag20). This affects our simulated single-molecule SERS spectra; the time trajectories of a molecule interacting with its unique local environment dictates the relative intensities of the observable Raman-active vibrational states. Ab initio molecular ...

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.

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...

Simulating the spectroscopic properties of short-lived thermal and photochemical reaction intermediates and products is a challenging task, as these species often feature atypical molecular and electronic structures. The complex environments in which such species typically reside in practice add further complexity to the problem. Herein, we tackle this problem in silico using ab initio molecular dynamics (AIMD) simulations, employing iso-CHBr3, namely H(Br)C-Br-Br, as a prototypical system. This species was chosen because it features both a nonconventional C-Br-Br bonding pattern, as well as a strong dependence of its spectral features on the local environment in which it resides, as illustrated in recent experimental reports. We simulate the UV-vis and IR spectra of iso-CHBr3 in the gas phase, as well as in a Ne cluster (64 atoms) and in a methylcyclohexane cage (14 solvent molecules) representative of the previously characterized matrix isolated and solvated iso-CHBr3 species. We exclusively perform fully quantum mechanical static and dynamic simulations. By comparing our condensed phase simulations to their experimental analogues, we stress the importance of (i) conformational sampling, even at cryogenic temperatures, and (ii) using a fully quantum mechanical description of both solute and bath to properly account for the experimental observables.

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...

Carbon-hydrogen (C-H) vibration modes serve as key probes in the chemical identification of hydrocarbons and in vibrational sum-frequency generation spectroscopy of hydrocarbons at the liquid/gas interface. Their assignments pose a challenge from a theoretical viewpoint. In this work, we present a detailed study of the C-H stretching region of dimethyl sulfoxide using a new ab initio molecular dynamics (AIMD) module that we have implemented in NWChem. Through a combination of AIMD simulations and static normal mode analysis, we interpret experimental infrared and Raman spectra and explore the role of anharmonic effects in this system. Comprehensive anharmonic normal mode analysis of the C-H stretching region casts doubt upon previous experimental assignments of the shoulder on the symmetric C-H stretching peak. In addition, our AIMD simulations also show significant broadening of the in-phase symmetric C-H stretching resonance, which suggests that the experimentally observed shoulder is due to thermal broadening of the symmetric stretching resonance.

The enhanced electric field at plasmonic resonances in nanoscale antennas can lead to efficient harmonic generation, especially when the plasmonic geometry is asymmetric on either inter-particle or intra-particle levels. The planar Archimedean nanospiral offers a unique geometrical asymmetry for second-harmonic generation (SHG) because the SHG results neither from arranging centrosymmetric nanoparticles in asymmetric groupings, nor from non-centrosymmetric nanoparticles that retain a local axis of symmetry. Here, we report forward SHG from planar arrays of Archimedean nanospirals using 15 fs pulses from a Ti:sapphire oscillator tuned to 800 nm wavelength. The measured harmonic-generation efficiencies are 2.6·10−9, 8·10−9 and 1.3·10−8 for left-handed circular, linear, and right-handed circular polarizations, respectively. The uncoated nanospirals are stable under average power loading of as much as 300 μWper nanoparticle. The nanospirals also exhibit selective conversion between polarization states. These experiments show that the intrinsic asymmetry of the nanospirals results in a highly efficient, two-dimensional harmonic generator that can be incorporated into metasurface optics.

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.

Ultrathin films of barium oxide were grown on Ag(001) and Ag(111) using the evaporation of Ba metal in an O2 atmosphere by molecular beam epitaxy. Ultraviolet photoemission spectroscopy reveals that films consisting of predominantly BaO or BaO2 result in Ag(001) work function reductions of 1.74 eV and 0.64 eV, respectively. On the Ag(001) surface, Ba oxide growth is initiated by two-dimensional nucleation of epitaxial BaO, followed by a transition to three-dimensional dual-phase nucleation of epitaxial BaO and BaO2. Three-dimensional islands of primarily BaO2(111) nucleate epitaxially on the Ag(111) substrate leaving large patches of Ag uncovered. We find no indication of chemical reaction or charge transfer between the films and the Ag substrates. These data suggest that the origin of the observed work function reduction is largely due to a combination of BaO surface relaxation and an electrostatic compressive effect.

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.

Nonresonant tip-enhanced Raman (TERS) images of 4,4′-dimercaptostilbene (DMS) molecules adsorbed on silver reveal that different vibrational resonances of the molecules are optimally enhanced at different sites of the metal surface. The recorded images map the interaction between vibrational-mode-dependent polarizability tensors of DMS and enhanced electromagnetic fields at a plasmonic tip–surface nanojunction. TERS images also provide insights into specific molecule–metal interactions. Namely, by virtue of the symmetry (C2h) of the molecular reporter specifically selected for this study, we demonstrate how non-totally symmetric vibrational modes of DMS (bu modes) map differences in vibronic coupling strength across the metal surface. In effect, each pixel in the recorded TERS images reports on the distinct local environments in which the various probed molecules reside. We illustrate the concept.

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...

We record sequences of Raman spectra at a plasmonic junction formed by a gold AFM tip in contact with a silver surface coated with 4,4'-dimercaptostilbene (DMS). A 2D correlation analysis of the recorded trajectories reveals that the observable vibrational states can be divided into subsets, by virtue of the symmetry of DMS (C2h). The first set comprises the totally symmetric vibrations of DMS (ag) that are neither correlated with each other nor with the fluctuating background, assigned to the signature of charge-transfer plasmons mediated by DMS. The second set consists of bu modes, which are correlated both with each other and with the background. Our findings are rationalized on the basis of the charge-transfer theory of Raman scattering and illustrate how current carrying plasmons modulate the vibronic coupling terms from which the intensities of the bu states are derived. In effect, this study identifies gateway molecular modes for mediating charge shuttling across a plasmonic gap.

Stability is of paramount importance in organic semiconductor devices, especially in organic solar cells (OSCs). Serious degradation in air limits wide applications of these flexible, light-weight and low-cost power-generation devices. Studying the stability of organic solar cells will help us understand degradation mechanisms and further improve the stability of these devices. There are many investigations into the efficiency and stability of OSCs. The efficiency and stability of devices even of the same photoactive materials are scattered in different papers. In particular, the extrinsic degradation that mainly occurs near the interface between the organic layer and the cathode is a major stability concern. In the past few years, researchers have developed many new cathodes and cathode buffer layers, some of which have astonishingly improved the stability of OSCs. In this review article, we discuss the recent developments of these materials and summarize recent progresses in the study of the degradation/stability of OSCs, with emphasis on the extrinsic degradation/stability that is related to the intrusion of oxygen and water. The review provides detailed insight into the current status of research on the stability of OSCs and seeks to facilitate the development of highly-efficient OSCs with enhanced stability.

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.

Using tools of density functional theory, we compute the Raman spectra of 1,3-propanedithiol (PDT) isolated in the gas phase, solvated in methanol, tethered either to the face or vertex of a tetrahedral Ag20 cluster, and bridging two Ag20 clusters. The derived molecular polarizability derivative tensors are used to simulate molecular orientation-dependent Raman scattering, achieved by rotating the polarizability tensors relative to vector components of the incident/scattered radiation fields. Our framework is weighed against SERS experiments which probe the optical response at a hotspot formed by an Ag surface coated with PDT and a single 60-nm Ag nanosphere.

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.

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.

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.

Thin films of CsBr deposited on Cu(100) have been proposed as next-generation photocathode materials for applications in particle accelerators and free-electron lasers. However, the mechanisms underlying an improved photocathode performance as well as their long-term stability remain poorly understood. We present Density Functional Theory (DFT) calculations of the work function reduction following the application of CsBr thin film coatings to Cu photocathodes. The effects of both flat and rough interface and van der Waals forces are examined. Calculations suggest that CsBr films can reduce the Cu(100) work function by about 1.5 eV, which would explain the observed increase in quantum efficiency (QE) of coated vs. uncoated photocathodes. A model explaining the experimentally observed laser activation of photocathodes is provided whereby the photo-induced creation of Br vacancies and Cs-Br di-vacancies and their subsequent diffusion to the Cu/CsBr interface lead to a further increase in QE after a period of laser irradiation.

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.

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.

We present a study of the lowest surface and bulk excitations of the well-studied potassium bromide (KBr) system using an embedded cluster method. The excited states of the embedded cluster are studied systematically using time-dependent density functional theory (TDDFT) and high-level equation-of-motion coupled cluster (EOMCC) methods. In particular, we have used EOMCC models with singles and doubles (EOMCCSD) and two approaches which account for the effect of triply excited configurations in non-iterative and iterative fashions. We compare and contrast the results between these theories as well as compare our results with experiment. The bulk–surface exciton shift is also calculated at the TDDFT level and compared with experiment.

Simple exposure of single-crystal ZnO to 193 nm excimer laser radiation at room temperature results in unexpected coloration. The gray to nearly black colored material, seen principally in the irradiated laser spot, is superficial. We present unambiguous evidence that this coloration is due to high densities of metallic Zn nanoparticles growing on the exposed surface of the crystal. Higher fluence laser exposure generates accumulated surface metal just outside of the irradiated spot. We suggest that the near surface bulk is photodecomposing; thermally driven diffusion leads to surface Zn metal aggregation.

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.

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.

Photoemission electron microscopy (PEEM) excited by x-ray and UV sources is used to investigate epitaxial anatase thin films embedded with rutile nanocrystals, a model system for the study of heterocatalysis on mixed-phase TiO2. Both excitation sources show distinct contrast between the two TiO2 phases, however, the contrast is reversed. Rutile nanocrystals appear darker than the anatase film in X-ray PEEM images but brighter in UV-PEEM images. Topography-induced contrast is dominant X-ray PEEM imaging, whereas work function contrast, dominates for UV-PEEM. Work function contrast results from the differences in work function and surface defect state densities between the two phases near the Fermi level. This assertion is confirmed by UPS data that shows the rutile work function to be 0.2 eV lower and a greater occupied valence band density-of-states in rutile (100) than in anatase (001). Since the boundaries between rutile nanocrystals and the anatase film are clearly resolved, these results indicate that PEEM studies of excited state dynamics and heterocatalysis are possible at chemically intriguing mixed-phase TiO2 interfaces and grain boundaries.

Thermally-induced martensitic phase transformations in polycrystalline CuZnAl and thin-film NiTiCu shape memory alloys were probed using photoemission electron microscopy (PEEM). Ultra-violet photoelectron spectroscopy shows a reversible change in the apparent work function during transformation, presumably due to the contrasting surface electronic structures of the martensite and austenite phases. In situ PEEM images provide information on the spatial distribution of these phases and the evolution of the surface microstructure during transformation. PEEM offers considerable potential for improving our understanding of martensitic transformations in shape memory alloys in real time.

The thermally-induced martensitic phase transformation in a polycrystalline NiTiCu thin film shape memory alloy was probed by photoelectron emission microscopy (PEEM). In situ PEEM images reveal distinct changes in microstructure and photoemission intensity at the phase transition temperatures. In particular, images of the low temperature, martensite phase are brighter than that of the high temperature, austenite phase, due to the relatively lower work function of the martensite. Ultra-violet photoelectron spectroscopy shows that the effective work function changes by about 0.16 eV during thermal cycling. In situ PEEM images also show that the network of trenches observed on the room temperature film disappear suddenly during heating and reappear suddenly during subsequent cooling. These trenches are also characterized by atomic force microscopy at selected temperatures. We describe implications of these observations with respect to the spatial distribution of phases during thermal cycling in this thin film shape memory alloy.

We study plasmonic nanostructures in single-crystal gold with scanning electron and femtosecond photoemission electron microscopies. We design an integrated laser coupling and nanowire waveguide structure by focused ion beam lithography in single-crystal gold flakes. The photoemission results show that the laser field is efficiently coupled into a propagating surface plasmon by a simple hole structure and propagates efficiently in an adjacent nano-bar waveguide. A strong local field is created by the propagating surface plasmon at the nano-bar tip. A similar structure, with a decreased waveguide width and thickness, displayed significantly more intense photoemission indicating enhanced local electric field at the sharper tip.

The addition of pulsed lasers to atom probe tomography (APT) extends its high spatial and mass resolution capability to nonconducting materials, such as oxides. For a prototypical metal oxide, MgO, the measured stoichiometry depends strongly on the laser pulse energy and applied voltage. Very low laser energies (0.02 pJ) and high electric fields yield optimal stoichiometric accuracy. Correlated APT and aberration-corrected transmission electron microscopy (TEM) are used to establish the high density of corner and terrace sites on MgO sample surfaces before and after APT. For MgO, long-lifetime photoexcited holes localized at oxygen corner sites can assist in the creation of oxygen neutrals that may spontaneously desorb either as atomic O or as molecular O2. The observed trends are best explained by the relative field-dependent ionization of photodesorbed O or O2 neutrals. These results emphasize the importance of considering electronic excitations in APT analysis of oxide materials.

Nonlinear photoemission electron microscopy (PEEM) of nanohole arrays in gold films is used to map propagating surface plasmons (PSPs) launched from lithographically patterned structures. Strong near-field photoemission patterns are observed in the PEEM images, recorded following low angle of incidence irradiation of nanohole arrays with sub-15 fs laser pulses centered at 780 nm. The recorded photoemission patterns are attributed to constructive and destructive interference between PSPs launched from the individual nanoholes which comprise the array. By exploiting the wave nature of PSPs, we demonstrate how varying the array geometry (hole diameter, pitch, and number of rows/columns) ultimately yields intense localized photoemission. Through a combination of PEEM experiments and finite-difference time-domain simulations, we identify the optimal array geometry for efficient light coupling and interferometric plasmonic lensing. We show a preliminary application of inteferometric plasmonic lensing by enhancing the photoemission from the vertex of a gold triangle using a nanohole array.

The electronic structure, geometry, diffusion barriers and optical properties of fundamental defects of CsBr are calculated using hybrid functional DFT and TD-DFT methods. The B3LYP functional with a modified exchange contribution has been used in an embedded cluster scheme to model the structure and spectroscopic properties of the self-trapped triplet exciton, interstitial Br atoms and ions, self-trapped holes and Br vacancies. The calculated migration barriers and positions of maxima of optical absorption bands are in good agreement with experiment, justifying the obtained defect geometries. The off-center triplet exciton luminescence energy is also accurately calculated.

We record time-resolved nonlinear photoemission electron microscopy (tr-PEEM) images of propagating surface plasmons (PSPs) launched from a lithographically patterned rectangular trench on a flat gold surface. Our tr-PEEM scheme involves a pair of identical, spatially separated, and interferometrically locked femtosecond laser pulses. Power-dependent PEEM images provide experimental evidence for a sequential coherent nonlinear photoemission process, in which one laser source launches a PSP through a linear interaction, and the second subsequently probes the PSP via two-photon photoemission. The recorded time-resolved movies of a PSP allow us to directly measure various properties of the surface-bound wave packet, including its carrier wavelength (783 nm) and group velocity (0.95c). In addition, tr-PEEM images reveal that the launched PSP may be detected at least 250 μm away from the coupling trench structure.

Subwavelength Archimedean spirals have no inversion symmetry, and efficiently generate second-harmonic light when pumped by femtosecond laser pulses, especially in the circularly polarized mode that focuses the optical near field in the nanospiral center.

Photoemission electron microscopy is used to probe photon-induced oxygen vacancies generated on TiO2 (110)-(1×2) surfaces. An increased oxygen vacancy concentration within the irradiated region leads to an increase of local photoelectron emission. The local oxygen deficient region can be compensated by exposing the surface to molecular oxygen at 1×10-5 Torr, or via surface diffusion at 450 K in vacuum. The surface diffusion coefficient was estimated to be on the order of 10-12 m2/s. Photoemission electron microscopy allows in situ studies of surface electronic defect formation and removal.