Unoccupied band dispersion of Si(1 1 1):√3 × √3-Ag surface studied by time- and angle-resolved two-photon photoemission spectroscopy

Band dispersion and transient population of unoccupied electronic states on Si(1 1 1):√3 × √3-Ag surface have been studied by time-resolved (TR) and angle-resolved (AR) two-photon photoemission (2PPE) spectroscopy. The band dispersions originating from unoccupied electronic states have been identified from the comparison between AR-2PPE spectra and angle-resolved one-photon photoemission spectra with synchrotron radiation. A lifetime of unoccupied surface state has been determined from the TR-2PPE spectra.     

Inhibition of copper corrosion by bis-(1,1′-benzotriazoly)-α,ω-diamide compounds in aerated sulfuric acid solution

Three kinds of novel corrosion inhibitors, bis-(1,1′-benzotriazoly)-α,ω-succinyldiamide (BSU), bis-(1,1′-benzotriazoly)-α,ω-adipoyldiamide (BAD), and bis-(1,1′-benzotriazoly)-α,ω-azelayldiamide (BAZ) were synthesized and certified by IR and ¹H NMR. Their corrosion inhibition effects for copper in 0.5 M H₂SO₄ were evaluated by weight-loss method. It shows that among the three compounds, only BSU behaves better compared with BTA. The inhibition efficiency (IE) increased with increasing BSU concentration to 85.2% at the 5 × 10⁻⁴ M level. Polarization studies showed that BSU suppressed both anodic and cathodic corrosion reactions. The minimum energy conformation of these compounds was obtained by MM2 force field program. The two benzotriazoly moieties in BSU molecule are more parallel than in other compounds. This is benefit to increase the inhibition effects of BSU.     

Structure and electronic properties of gold adsorbed on Ti(0 0 0 1)

The Au/Ti(0 0 0 1) adsorption system was studied by low energy electron diffraction (LEED) and photoemission spectroscopy with synchrotron radiation after step-wise Au evaporation onto the Ti(0 0 0 1) surface. For adsorption of Au at 300 K, no additional superstructures were observed and the (1 × 1) pattern of the clean surface simply became diffuse. Annealing of gold layers more than 1 ML thick resulted in the formation of an ordered Au-Ti surface alloy. Depending on the temperature and annealing time, three surface reconstructions were observed by LEED: (√3 × √3) R30°, (2 × 2) and a one-dimensional incommensurate (√3 × √3) rectangular pattern. The Au 4f core level and valence band photoemission spectra provided evidence of a strong chemical interaction between gold and titanium. The data indicated formation of an intermetallic interface and associated valence orbital hybridization, together with diffusion of gold into the bulk. Au core-level shifts were found to be dependent on the surface alloy stoichiometry.     

Oxygen adsorption on a Mo2C(0 0 0 1) surface: Angle-resolved photoemission study

Oxygen adsorption on a C-terminated α-Mo₂C(0 0 0 1) surface has been investigated with Auger electron spectroscopy, low-energy electron diffraction, and angle-resolved photoemission spectroscopy utilizing synchrotron radiation. It is found that the oxygen atoms adsorb on the Mo atoms in the second layer forming a (1 × 1) orthorhombic periodicity. The oxygen adsorption induces a peculiar state around the Fermi level, which is observed at 0.4 eV in the normal-emission spectra. ARPES measurements show that the state is a partially occupied metallic state. The photoionization cross section of the state shows a maximum at the photon energy of 56 eV, which is assigned as originating from the resonance of the Mo 4d photoemission involving Mo 4p → 4d photoexcitation.     

Excited state complex and electroluminescence in TPD-based single layer device

N-N′-diphenyl-N,N′-(bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine) (TPD), was used to fabricate single layer devices (ITO/TPD/Ca/Al). A near-white emission (CIE coordinate of 0.25, 0.24) is observed in electroluminescence (EL) of the single layer device with prominent emission bands at 400, 475 and 670 nm. Steady state and time-resolved emission spectra of spin-coated and annealed TPD films and TRES and TRANES analysis confirmed that emission at 400 and 475 nm are due to monomer and excimer emission, respectively. The origin of the red emission at 670 nm in EL is discussed.     

Thermal stability of thiol and silane monolayers: A comparative study

The stability of self-assembled monolayers (SAMs) at elevated temperatures is of considerable technological importance. The thermal stability of 1-octadecanethiol (ODT), 16-mercaptohexadecanoic acid (MHDA) and 1H,1H,2H,2H-perfluorodecanethiol (PFDT) SAMs on gold surfaces, and of 4-aminobutyltriethoxysilane (ABTES) and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDS) assembled on hydroxylated silicon surfaces, was studied by X-ray photoelectron spectroscopy (XPS). The samples were heated in ultrahigh vacuum to temperatures in excess of that required for SAM degradation. ODT monolayers were stable to ca. 110 °C, while MHDA and PFDT SAMs were stable to ca. 145 °C. ABTES SAMs were found to be indefinitely stable to 250 °C, while PFDS SAMs were stable to 350 °C. These studies demonstrate the advantages of using silane monolayers for moderate to high temperature applications and illustrate differences that arise due to the nature of the tail group. To demonstrate the feasibility of silanes for template-directed patterning, a hydroxylated silicon oxide surface containing microcontact-printed PFDS patterns was spin-coated with a mainly hydrophilic block copolymer. Annealing the surface at 90 °C for 2 h caused the block copolymer to dewet the hydrophobic PFDS-patterned regions and adsorb exclusively on the unpatterned regions of the surface.     

Efficient bright white organic light-emitting diode based on non-doped ultrathin 5,6,11,12-tetraphenylnaphthacene layer

High-performance undoped white organic light-emitting diode (OLED) has been fabricated using an ultrathin yellow-emitting layer of 5,6,11,12-tetraphenylnaphthacene (rubrene) inserted at two sides of interface between two N,N′-bis-(1-naphthyl)-N,N′- biphenyl-1,1′-biphenyl-4,4′- diamine (NPB) layers as a hole transporting and blue emissive layer, respectively. The results showed that a maximum luminance of the device reached to as high as 21,500 cd/m² at 15 V. The power efficiencies of 2.5 and 1.6 lm/W at a luminance of 1000 and 10000 cd/m², respectively, were obtained. The peaks of electroluminescent (EL) spectra locate at 429 and 560 nm corresponding to the Commissions Internationale De L’Eclairage (CIE) coordinates of (0.32, 0.33), which is independent of bias voltage. The performance enhancement of the device may result from direct charge carrier trapping in rubrene. Energy transfer mechanism was also found in the EL process.     

Angle resolved photoemission study of the Ce/Pd(1 1 1) interface

X-ray and UV excitation angle resolved photoemission spectroscopy of ultra-thin films of cerium deposited on a Pd(1 1 1) single-crystal surface has been carried out. Both core level and valence band spectra show a formation of a surface alloy exhibiting d- and f-electron orbital hybridization. An azimuth and polar angle mapping of X-ray excited photoemission intensities results in a surface-geometrical structure information. Mapping of ultra-violet photoelectron intensities as a function of emission angles is used for a band mapping and an electronic structure determination. The d-, f-hybridization occurs even for 0.7 ML of Ce deposited at room temperature. The surface annealing at 260 °C enhances this behavior. A shift of Pd 4d-derived states to higher binding energy in the Ce-Pd systems is observed.     

Electrochemical stability of self-assembled monolayers of biphenyl based thiols studied by cyclic voltammetry and second harmonic generation

The reductive desorption of self-assembled monolayers (SAMs) of ω-(4′-methyl-biphenyl-4-yl)-alkanethiols (CH₃-C₆H₄-C₆H₄-(CH₂)_n-SH, BPn) on Au(1 1 1) on mica was studied in 0.5 M KOH solution as a function of the length of the aliphatic spacer chain (n = 1-6 and 12) and for two different preparations temperatures (295 K and 343 K). Second harmonic generation (SHG) was applied in situ parallel to cyclic voltammetry (CV). Odd-even differences in the structure of the BPn monolayers are clearly reflected in the electrochemical stability, as well as by the charge and shape of the desorption peak. For n = 1-5 a single desorption peak is detected whereas multiple peaks occur for BP6 similar to hexadecane thiol which was also studied for comparison. An increased preparation temperature affects the shape and width of the desorption peak but not the position. BP1 exhibits a temperature dependence different from the other homologues. The relationship between coverage monitored by SHG and desorption charge determined from the CVs is found to be linear and surprisingly independent from the details of the SAMs. The combined SHG and CV experiments suggest that capacitive and faradaic current are always closely coupled even for BP6 and hexadecane thiol which exhibit multiple desorption peaks.     

Surface electronic structure of α-Mo2C(0 0 0 1)

The electronic structure of α-Mo₂C(0 0 0 1) has been investigated by angle-resolved photoemission spectroscopy utilizing synchrotron radiation. A sharp peak is observed at 3.3 eV in normal-emission spectra. Since the peak shows no dispersion as a function of photon energy and is sensitively attenuated by oxygen adsorption, the initial state of the peak is attributed to a surface state. Resonant photoemission study shows that the state includes substantial contribution of 4d orbitals of the Mo atoms in the second layer. The emissions with constant kinetic energies of 22 and 31 eV above the Fermi level (E_F) are found in normal-emission spectra, and these emissions are interpreted as originating from the Mo N₁N₂₃V and N₂₃VV Auger transitions, respectively.     

Radiation-induced decomposition of the metal-organic molecule Bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II)

The effects of vacuum ultraviolet radiation on the adsorbed copper center molecule bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (or Cu(CNdpm)₂), (C₂₄H₃₆N₂O₄Cu, Cu(II)) was studied by photoemission spectroscopy. Changes in the ultraviolet photoemission spectra (UPS) of Cu(CNdpm)₂, adsorbed on Co(1 1 1), indicate that the ultraviolet radiation leads to decomposition of Cu(CNdpm)₂ and this decomposition is initially dominated by loss of peripheral hydrogen.     

Fermi surface and band mapping of the cerium/palladium surface alloy

X-ray and UV excitation angle-resolved photoemission spectroscopy of ultra-thin films of cerium deposited on Pd(1 1 1) single-crystal surface has been carried out. Photoelectron diffraction pattern showed that deposition of 1 ML of Ce led to a formation of Ce-Pd substitutional alloy. Valence band spectra measured with high angular resolution permitted to plot valence band maps and Fermi surface scans and showed formation of surface alloy exhibiting d- and f-electron orbital hybridization. A shift of Pd 4d-derived states to higher binding energy in the Ce-Pd systems was observed.     

Exciplex or electroplex emissions from the interface between aromatic diamine and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline?

Organic light-emitting diodes (OLEDs) have been fabricated which consist of N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine) (TPD), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), and tris(8-hydroxyquinoline) aluminum (Alq₃). Four emission peaks located at about 401 nm, 425 nm, 452 nm and 480 nm have been obtained in the electroluminescence (EL) spectra of these devices. The former two emissions originate from the exciton emission of TPD molecular. The last two emissions could be attributed to local (LOC) exiplex emission and charge transfer (CT) exiplex emission at the interface between TPD and BCP layers, respectively.     

New double graded structure for enhanced performance in white organic light emitting diode

This study presents a new design that uses a combination of a graded hole transport layer (GH) structure and a gradually doped emissive layer (GE) structure as a double graded (DG) structure to improve the electrical and optical performance of white organic light-emitting diodes (WOLEDs). The proposed structure is ITO/m-MTDATA (15 nm)/NPB (15 nm)/NPB: 25% BAlq (15 nm)/NPB: 50% BAlq (15 nm)/BAlq: 0.5% Rubrene (10 nm)/BAlq: 1% Rubrene (10 nm)/BAlq: 1.5% Rubrene (10 nm)/Alq₃ (20 nm)/LiF (0.5 nm)/Al (200 nm). (m-MTDATA: 4,4′,4″ -tris(3-methylphenylphenylamino)triphenylamine; NPB: N,N′-diphenyl-N,N′-bis(1-naphthyl-phenyl)-(1,1′-biphenyl)-4,4′-diamine; BAlq: aluminum (III) bis(2-methyl-8-quinolinato) 4-phenylphenolate; Rubrene: 5,6,11,12-tetraphenylnaphthacene; Alq₃: tris-(8-hydroxyquinoline) aluminum). By using this structure, the best performance of the WOLED is obtained at a luminous efficiency at 11.8 cd/A and the turn-on voltage of 100 cd/m² at 4.6 V. The DG structure can eliminate the discrete interface, and degrade surplus holes, the electron-hole pairs are efficiently injected and balanced recombination in the emissive layer, thus the spectra are unchanged under various drive currents and quenching effects can be significantly suppressed. Those advantages can enhance efficiency and are immune to drive current density variations.     

Anchoring sulphur-headgroup organic molecules at Cu(1 0 0): Tailoring the interface electronic states

Sulphur-headgroup organic molecules have been chemisorbed on Cu(1 0 0) as self-assembled monolayers (SAMs) in highly-ordered two-fold symmetry structures, and the electronic states induced at the interface have been measured by photoemission: a close similarity of the main interface states for methane-thiolate and mercaptobenzoxazole on Cu(1 0 0) in the same p(2 × 2)-phase is observed. The bonding states for methane-thiolate/Cu(1 0 0) in the p(2 × 2) and c(2 × 2) structures have been compared to ab-initio calculation of the total density of states (DOS) for the S/Cu(1 0 0) system in the same phases. The major role of the S-Cu bonding to determine the density of state evolution at the interface is brought to light. The observed differences in the two phases depend mainly on the charge distribution associated to the different molecular packing, with a minor role of the radical group.     

Modification of the organic/La0.7Sr0.3MnO3 interface by in situ gas treatment

La_0.7Sr_0.3MnO₃ (LSMO) can act as a spin injection electrode in organic spin-valves and organic light-emitting devices. For the latter application, good control of the electronic structure of the organic/LSMO interface is a key issue to ensure sufficient current injection in the device. By exposing cleaned LSMO surfaces to activated oxygen and hydrogen, the work function of the samples can reach 5.15 and 4.3 eV, respectively, as shown by in situ photoemission measurements. The initial stage of formation of the organic/LSMO interface upon deposition of N,N′-bis-(1-naphyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) onto the oxygen-treated LSMO surface is examined. We find that the NPB molecules evenly cover the LSMO surface and that the interface barrier height is 0.8 eV, which is comparable to that at the NPB/indium tin oxide (ITO) interface with the ITO surface pretreated in situ by oxygen plasma.     

Combined EELS, LEED and SR-XPS study of ultra-thin crystalline layers of indium nitride on InP(1 0 0)—Effect of annealing at 450 °C

In this study, InP(1 0 0) surfaces were bombarded by argon ions in ultra high vacuum. Indium metallic droplets were created in well controlled quantities and played the role of precursors for the nitridation process. A glow discharge cell was used to produce a continuous plasma with a majority of N atomic species. X-ray photoelectron spectroscopy (XPS) studies indicated that the nitrogen combined with indium surface atoms to create InN thin films (two monolayers) on an In rich-InP(1 0 0) surface. This process occurred at low temperature: 250 °C. Synchrotron radiation photoemission (SR-XPS) studies of the valence band spectra, LEED and EELS measurements show an evolution of surface species and the effect of a 450 °C annealing of the InN/InP structures. The results reveal that annealing allows the crystallization of the thin InN layers, while the LEED pattern shows a (4 × 1) reconstruction. As a consequence, InN related structures in EELS and valence bands spectra are different before and after the annealing. According to SR-XPS measurements, the Fermi level is found to be pinned at 1.6 eV above the valence band maximum (VBM).     

Biphenyl-type sensing system in proton-rich environment by fluorescence and quantum-chemical calculations

Biphenyl derivative N-allyl-N′-(4′-nitro[1,1′-biphenyl]-4-yl)thiourea (BP1) was synthesized as a functional fluorescent sensor for protons and their photophysical properties were studied. The influence of environment protonation on photophysical properties of the biphenyls in solutions was investigated using UV absorption, steady-state and time-resolved fluorescence spectroscopy. Semi-empirical and DFT calculations and optimization of the molecular structure of the biphenyl derivatives in vacuum, in polar solvents and in a proton-rich environment were conducted using the HyperChem, Amsol and Gaussian3 software package. Fluorescence quenching with addition of acidic acid was observed and the Stern-Volmer quenching rate constant was about 3.0×10⁹ M⁻¹ s⁻¹. Intermolecular hydrogen bonds formations by the protons with the sulphur being substituted to the biphenyls generate charge movement and strong increase (×5) of the dipole moment of the fluorophore.     

Synthesis and fluorescence study of sodium-2-(4′-dimethyl-aminocinnamicacyl)-3,3-(1′,3′-alkylenedithio) acrylate

We synthesized two new compounds: Sodium 2-(4′-dimethyl-aminocinnamicacyl)-3,3-(1′,3′- ethyl- enedithio) acrylate (STAA-1) and Sodium 2-(4′-dimethyl-aminocinnamicacyl)-3, 3-(1′,3′-propylenedithio) acrylate (STAA-2). The maximum absorption of these compounds ranges from 460 to 520 nm with different molecular structures in different solvents. Meanwhile, the emission peak of these compounds arranges from yellow (510 nm) to red (605 nm). The emission spectra show red shift according to the strength of the hydrogen bonding property of the solvent. But the absorption spectra do not show clearly relationship with the strength of the hydrogen bonding property of the solvent. The Stoke shift of the compounds ranges from 42 to 102 nm. It changes in the following order, EtOH>H₂O>DMF, and STAA-1>STAA-2 in the same solvent. The fluorescent quantum yield of STAA-1 was measured to be 7.12% with quinine sulphate as the standard compound in ethanol. Furthermore, the relationship of the fluorescence of STAA-1 with pH (ranges form 4 to 14) in water (c=∼10⁻⁴) was studied to make sure that these compounds could be used as proton sensors.     

Femtosecond photoemission microscopy

We developed a novel experiment for time-resolved photoemission microscopy by combining a commercial photoemission electron microscope (PEEM) with a pulsed Ti:sapphire laser oscillator. The laser system, the setup of the delay stage for pump-probe experiments, and the interface between the PEEM and the laser system are discussed. We use self-organization of Ag islands and nanowires on Si(1 1 1) and 4° vicinal Si(0 0 1) to generate structures with a plasmon resonance that matches the photon energy of our laser (?ω = 3.1 eV after frequency doubling). In two-photon photoemission (2PPE) the photoemission yield then directly visualizes the plasmons in the nanostructures. Accordingly, the photoemission yield depends on the size and shape of the nanostructures, and on the polarization of the laser pulses as well. In Ag nanowires, we observe surface plasmon polariton (SPP) waves by a beating that is formed by interference of the SPP wave and the incident laser light. In a pump-probe experiment, we can directly visualize the propagation of the SPP on a femtosecond time scale.