Ultraviolet Photoelectron Spectroscopy Spectra Research Articles

Origins of Improved Hole‐Injection Efficiency by the Deposition of MoO3 on the Polymeric Semiconductor Poly(dioctylfluorene‐alt‐benzothiadiazole)

AbstractThe electronic structure of the interfaces formed after deposition of MoO3 hole‐injection layers on top of a polymer light‐emitting material, poly(dioctylfluorene‐alt‐benzothiadiazole) (F8BT), is studied by ultraviolet photoelectron spectroscopy (UPS), X‐ray photoelectron spectroscopy and metastable atom electron spectroscopy. Significant band bending is induced in the F8BT film by MoO3 “acceptors” that spontaneously diffuse into the F8BT “host” probably driven by kinetic energy of the deposited hot MoO3. Further deposition leads to the saturation of the band bending accompanied by the formation of MoO3 overlayers. Simultaneously, a new electronic state in the vicinity of the Fermi level appears on the UPS spectra. Since this peak does not appear in the bulk MoO3 film, it can be assigned as an interface state between the MoO3 overlayer and underlying F8BT film. Both band bending and the interface state should result from charge transfer from F8BT to MoO3, and they appear to be the origin of the hole‐injection enhancement by the insertion of MoO3 layers between the F8BT light‐emitting diodes and top anodes.

Infrared and photoelectron spectroscopy study of vapor phase deposited poly (3-hexylthiophene)

Poly (3-hexylthiophene) (P3HT) was thermally evaporated and deposited in vacuum. Infrared spectroscopy was used to confirm that the thin films were indeed P3HT, and showed that in-situ thermal evaporation provides a viable route for contaminant-free surface/interface analysis of P3HT in an ultrahigh-vacuum (UHV) environment. Ultraviolet photoelectron spectroscopy (UPS) as well as X-ray photoelectron spectroscopy (XPS) experiments were carried out to examine the frontier orbitals and core energy levels of P3HT thin films vapor deposited in UHV on clean polycrystalline silver (Ag) surfaces. UPS spectra enable the determination of the vacuum shift at the polymer/metal interface, the valence band maximum (VBM), and the energy of the π-band of the overlayer film. The P3HT vacuum level decreased in contrast to that of the underlying Ag as the film thickness increased. XPS and UPS data confirmed the chemical integrity (stoichiometry) of the polymer at high coverage, as well as the shift of the C 1s and S 2p binding energy peaks and the secondary-electron edge with increasing film thickness, indicating that band bending is present at the P3HT/Ag interface and that the measured onset of the valence band is about 0.8 ± 0.05 eV relative to the Fermi level.

Valence States of One-Dimensional Molecular Assembly Formed by Ketone Molecules on the Si(100)-(2 × 1)-H Surface

The valence states of 1-D molecular assemblies of adsorbed benzophenone, acetophenone, and acetone on the Si(100)-(2 × 1)-H surface were studied with ultraviolet photoelectron spectroscopy (UPS) at room temperature. The molecular assemblies formed on the surface were checked by using in situ scanning tunneling microscopy (STM). Four major peaks at 3.8, 6.8, 9.0, and 11.2 eV relative to the Fermi level were observed in the UPS spectrum of benzophenone lines. The spectral shape of the benzophenone line is similar to that of acetophenone (except a shoulder at ∼6.8 eV instead of the intense peak) but very different from that of acetone, where the major peaks appear at 5.3, 7.6, and 9.2 eV. These suggest that the major peaks appearing for benzophenone and acetophenone lines arise from the phenyl rings of the adsorbed molecules. Comparison of the UPS spectra of benzophenone lines on the Si(100)-(2 × 1)-H surface and that of solid benzophenone clearly indicate that the electronic states of the phenyl rings assem...

Photoelectron spectroscopic studies of the interfacial reaction between glass and commercial adhesive

AbstractThe valence band and core‐level photoelectron spectroscopy [using X‐ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS)] were used to probe the interfacial reaction between glass and a commercial adhesive (Loctite). The interaction was investigated by comparing experimental valence band spectra with spectra calculated for various possible interaction schemes. The valence band spectrum for the interfacial region between the glass and the adhesive was obtained using difference spectra on a thin film of adhesive on glass. This film was sufficiently thin that the adhesion interphase could be directly probed. Chemical interaction occurs at the interface as evidenced by the fact that the spectrum for the interfacial region could not be represented by the addition of the spectrum of the glass alone and the adhesive alone. The XPS valence band spectrum and the UPS spectrum showed that the shallow top surface layer is very much enriched in acrylic acid, which is a minor component in the adhesive. When the Loctite adhesive was coated on glass, the C1s and O1s regions of the adhesion interface region showed evidences of new chemistry at the adhesive–glass interface. The possible reactions were evaluated by comparison of the experimental spectra with calculated ones based on different models using ab initio molecular orbital calculations. The experimental spectra are well represented by models where the acrylic acid of the surface region of the adhesive reacts with the glass, suggesting chemical interaction occurred at the adhesion interphase. Copyright © 2009 John Wiley & Sons, Ltd.

3s Rydberg and Cationic States of Pyrazine Studied by Photoelectron Spectroscopy

We have studied 3s(n-1 and pi-1) Rydberg states and D0(n-1) and D1(pi-1) cationic states of pyrazine [1,4-diazabenzene] by picosecond (2 + 1) resonance-enhanced multiphoton ionization (REMPI), (2 + 1) REMPI photoelectron imaging, He(I) ultraviolet photoelectron spectroscopy (UPS), and vacuum ultraviolet pulsed field ionization photoelectron spectroscopy (VUV-PFI-PE). The new He(I) photoelectron spectrum of pyrazine in a supersonic jet revealed a considerably finer vibrational structure than a previous photoelectron spectrum of pyrazine vapor. We performed Franck-Condon analysis on the observed photoelectron and REMPI spectra in combination with ab initio density functional theory and molecular orbital calculations to determine the equilibrium geometries in the D0 and 3s(n-1) states. The equilibrium geometries were found to differ slightly between the D0 and 3s states, indicating the influence of a Rydberg electron on the molecular structure. The locations of the D1-D0 and 3s(pi-1)-3s(n-1) conical intersections were estimated. From the line width in the D1 <-- S0 spectrum, we estimated the lifetime of D1 to be 12 fs for pyrazine and 15 fs for fully deuterated pyrazine. A similar lifetime was estimated for the 3s(pi-1) state of pyrazine by REMPI spectroscopy. The vibrational feature of D1 observed in the VUV-PFI-PE measurement differed dramatically from that in the UPS spectrum, which suggests that the high-n Rydberg (ZEKE) states converging to the D1 vibronic state are short-lived due to electronic autoionization to the D0 continuum.

Interfacial properties between CoO (100) andFe3O4(100)

Using molecular beam epitaxy 1\char21{}20 ML thick CoO (100) films were grown monolayer by monolayer on ${\mathrm{Fe}}_{3}{\mathrm{O}}_{4}$ (100) substrates. The stoichiometry of the films was verified by low-energy-electron diffraction and reflection-high-energy-electron diffraction patterns, as well as x-ray photoelectron spectroscopy. Auger measurements as a function of CoO film thickness indicated a layer-by-layer growth mode. Ultraviolet photoelectron spectroscopy (UPS) was used to monitor the thin film electronic properties. The evolution of the density of states in the $\mathrm{O}\phantom{\rule{0.2em}{0ex}}2p∕\mathrm{Fe}\phantom{\rule{0.2em}{0ex}}3d$ and $\mathrm{O}\phantom{\rule{0.2em}{0ex}}2p∕\mathrm{Co}\phantom{\rule{0.2em}{0ex}}3d$ bands exhibits a shift in the position of the CoO valence band for ultrathin films relative to bulklike thick films. The measured spectra (when aligned to cancel the band shift) are compared to models of the spectra that would be expected based on the bulk compounds, with and without additional interfacial electronic states. Electronic states at the ${\mathrm{Fe}}_{3}{\mathrm{O}}_{4}\text{\ensuremath{-}}\mathrm{Co}\mathrm{O}$ interface have been identified, and their UPS spectrum has been determined.

Fabrication, microstructure and UPS spectra of Co: BaTiO3/Si(100) nano-composite films

Co: BaTiO3 nano-composite films were successfully fabricated by pulsed laser deposition on single crystal Si(100) surface. The micro-structure of the Co: BaTiO3 nano-composite films with about 30 nm and 100 nm thicknesses were studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The Co: BaTiO3 nano-composition films with the above thicknesses were unidirectionally prefer-oriented and polycrystalline, respectively. The atomic force microscopic (AFM) analysis indicated that there were tetragonal crystal grains in the films of about 30 nm thickness. The valence band of the films were investigated by ultraviolet photoelectron spectroscopy (UPS) in detail. The UPS spectra showed that density of electronic states (DOS) of the films with high concentration of Co grains were obviously different from that of bulk BaTiO3 single crystal.

Electronic structure of 1,3,5-trithia-2,4,6-triazapentalenyl on gold

The adsorption of 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) on a gold surface has been studied using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) under ultrahigh vacuum conditions. TTTA was deposited onto the gold substrate by gas-phase dosing. XPS and UPS spectra show that TTTA molecules strongly adsorb on the gold surface. In addition, the UPS spectrum of the TTTA monolayer is in good agreement with the gas-phase UPS spectrum of TTTA, which indicates that the molecules adsorb as a radical without electron transfer from the gold substrate.

The origin of electron injection improvement in organic light-emitting devices with an organic oxide/rubrene electron injection layer

The electronic structure of tris(8-hydroquinoline) aluminum (Alq3)/rubrene/poly(ethylene glycol) dimethyl ether (PEGDE)/Al interfaces was studied using in situ ultraviolet photoelectron spectroscopy (UPS) and x-ray photoelectron spectroscopy (XPS). The UPS and XPS spectra allowed us to evaluate the complete energy level diagrams and to analyze the chemical interactions at the interfaces. When a PEGDE/rubrene double layer was inserted between Al and Alq3, the electron injection barrier height was greatly reduced compared to the interface without PEGDE/rubrene or with a single insertion layer of either PEGDE or rubrene.

Single-Layer Model of the Hexagonal Boron Nitride Nanomesh on the Rh(111) Surface

An alternative model of the hexagonal boron nitride (h-BN) on nanomesh on the Rh(111) surface is presented. It explains the observed ultraviolet photoelectron spectroscopy spectra and reproduces experimental STM images introducing, instead of two, only one strongly corrugated layer of h-BN covering the whole Rh surface. In order to optimize the geometry of the BN layer we calculate the forces by density functional theory and analyze the interactions in the system. The final geometry is a result of a competition between BN-metal attraction or repulsion and elastic properties of the isolated h-BN layer. The calculated bonding energy is around 0.33 eV per BN molecule with a corrugation close to 0.55 A.

Apparatus for solution jet beam deposition of organic thin films andin situultraviolet photoelectron spectroscopy

We report an instrument with the combination of solution jet beam deposition method and ultraviolet photoelectron spectroscopy (UPS). The solution jet beam method is a novel technique to fabricate organic thin films in vacuum, where solution of the organic material is sprayed in vacuum. This method can be applied to organic materials which cannot be vacuum evaporated due to thermal decomposition, e.g., ionic organic solids such as cyanine dyes. The present instrument combines this method with UPS, which is a powerful method for investigating the electronic structure of solids. Using this instrument, the UPS spectra of cyanine dye films deposited by the solution jet beam method were measured without exposure to air. The observed spectra were clearer than those of spin-coated films exposed to air.

Microscopic optical and photoelectron measurements of MWO 4 (M=Mn, Fe, and Ni)

Microscopic optical (absorption and reflection) and ultraviolet photoelectron spectroscopy (UPS) measurements were performed on single microcrystals of transition-metal tungstates, MWO 4 (M=Mn, Fe, and Ni) at room temperature using Schwarzschild objectives and laboratory light sources. The diameters of the spots were 40 μm (optical) and 13 μm (UPS). From the reflectance spectra, the absorption coefficient spectra were obtained through Kramers–Kronig analyses. The weak structures of absorption spectra attributed to the d–d transitions in transition metals suggest that the M3d states contribute to the upper part of the valence band. The UPS spectra suggest that the O2p and M3d states hybridize and spread wide in the valence band. The bottom of the conduction band is attributed to the empty M3d state in NiWO 4, but the empty M4s states in FeWO 4 and MnWO 4. The contribution of the W5d state in the conduction band is located in the higher energy side.

The Electronic Structure and the Energy Level Alignment at the Interface Between Organic Molecules and Metals

ABSTRACTWe investigated the electronic structure and the energy level alignment at the interfaces between perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) and metals (Au, Cu and Co) by ultraviolet photoelectron spectroscopy (UPS). In the case of PTCDA/Au interface, the apparent interface states and charge transfer (CT) states were not observed in its UPS spectra. In the case of PTCDA/Cu and Co interfaces, however, we found that the CT from metal to PTCDA occurred, and that the apparent CT states were observed at PTCDA/Cu interface.

Energy Level Alignment at Metal−Octaethylporphyrin Interfaces

We studied the electronic structure of copper-octaethylporphyrin (CuEOP) adsorbed on three metal surfaces--Ag(001), Ag(111), and Cu(111)--by means of ultraviolet photoelectron spectroscopy (UPS). The adsorption-induced work function shifts saturate roughly beyond two monolayers. The saturation values are substrate dependent, negative, and range from -1.30 to -0.85 eV. This shift is larger than that for tetraphenylporphyrins. The two highest occupied molecular orbitals (HOMO and HOMO-1) of the organic are clearly resolved in the UPS spectra. The origin of the negative work function shift is discussed.

Surface State and Composition of a Disperse Pd Catalyst after Its Exposure to Ethylene

Pd black was exposed to ethylene alone or in its mixture with hydrogen at 300 and 573 K. The samples were investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). Room temperature introduction of C(2)H(4) (also in the presence of H(2)) induced a binding-energy (BE) shift in the Pd 3d doublet and changed its full width at half-maximum (fwhm). The UPS features indicate shifting of electrons from the Pd d-band to Pd-H, Pd-C, and even Pd-OH species. Vinylidene (BE approximately 284.1 eV) may be the most abundant individual surface species on disperse Pd black, along with carbon in various stages of polymerization: "disordered C" (BE approximately 284 eV), graphite (approximately 284.6 eV), and ethylene polymer (approximately 286 eV), and also some "atomic" C (BE approximately 283.5 eV). Introduction of H(2) followed by ethylene brought about stronger changes in the state of Pd than exposure in the reverse sequence. This may indicate that the presence of some surface C may hinder the decomposition of bulk PdH. Formation of Pd hydride was blocked when ethylene was introduced prior to H(2). The C 1s intensity increased, the low-binding-energy C components disappeared, and graphitic carbon (BE approximately equal to 284.6 eV) prevailed after ethylene treatment at 573 K. The loss of the Pd surface state and "PdH" signal were observed in the corresponding valence band and UPS spectra. Hydrogen treatment at 540 K was not able to decrease the concentration of surface carbon and re-establish the near-surface H-rich state. UPS showed overlayer-type C in these samples. The interaction of Pd with components from the feed gas modified its electronic structure that is consistent with lattice strain induced by dissolution of carbon and hydrogen into Pd, as indicated by the d-band shift and the dilution of the electron density at E(F).

Alkyl Chain Conformation and the Electronic Structure of Octyl Heavy Chalcogenolate Monolayers Adsorbed on Au(111)

Adsorption states of dioctyl dichalcogenides (dioctyl disulfide, dioctyl diselenide, and dioctyl ditelluride) arranged on Au(111) have been studied by X-ray photoelectron spectroscopy (XPS), infrared-visible sum-frequency generation (SFG), and ultraviolet photoelectron spectroscopy (UPS). XPS measurements suggest that dioctyl dichalcogenides dissociatively adsorbed on Au(111) surfaces to form the corresponding monolayers having chalcogen-gold covalent bonds. The elemental compositions of octanechalcogenolates on Au(111) indicate that the saturation coverages of the octyl heavy chalcogenolate (OcSe, OcTe) monolayers are lower than that of the octanethiolate (OcS) self-assembled monolayers (SAMs). The SFG observations of the CH(2) vibrational bands for the heavy chalcogenolate monolayers strongly suggest that a discernible amount of gauche conformation exists in the monolayers, while OcS SAMs adopt highly ordered all-trans conformation. The intensity ratio of the symmetric and asymmetric CH(3) stretching vibration modes measured by SFG shows that the average tilt angle of the methyl group of the OcSe monolayers is greater than that of the OcS SAMs. The larger tilt angle of the methyl group and the existence of a discernible amount of gauche conformation in the OcSe monolayers are due to the lower surface coverage of the OcSe monolayers compared with the OcS SAMs. The smaller polarization dependence in the angle-resolved UPS (ARUPS) spectra of the OcSe monolayers than that of the OcS SAMs is caused by the more disordered structures of the alkyl chain in the former. XPS, SFG, and ARUPS measurements indicate a similar tendency for the OcTe monolayers. The density of states (DOS) observed by UPS at around 1.3 eV for OcS adsorbed on Au(111) is considered to be the antibonding state of the Au-sulfur bond. Similar DOS is also observed by UPS at around 1.0 eV for the OcSe monolayers and at approximately 1.6 eV for the OcTe monolayers on Au(111).

NanoESCA: imaging UPS and XPS with high energy resolution

A novel imaging electron spectrometer has been used for laterally resolved ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) in the soft X-ray range. The instrument is based on a high-resolution emission microscope optics using a cathode lens and an imaging dispersive analyser. The analyser is corrected for the leading aberration term ( α 2-term) by means of two hemispherical analysers in antisymmetric configuration with an appropriate transfer lens. Small-area spectra as well as energy-filtered images have been taken in the soft X-ray range for a meteorite sample and in the range of the d-band of a Cu polycrystal. An energy resolution of 106 meV along with a high spatial resolution allows a detailed analysis of trace elements in the meteorite sample as well as local UPS spectra of the surface of the Cu sample.

Studies of the electronic structure at the Fe3O4–NiO interface

The interfacial electronic structure between the metallic ferrimagnet Fe3O4 and the insulating antiferromagnet NiO is investigated in the lattice matched heteroepitaxial system Fe3O4 (100)–NiO (100) by growing ultrathin NiO films on single-crystal Fe3O4 (100) substrates. The Fe3O4 (√2×√2)R45° surface is characterized prior to growth by low-energy electron diffraction, reflection high-energy diffraction, scanning tunneling microscopy, ultraviolet photoelectron spectroscopy (UPS), x-ray photoemission spectroscopy (XPS) and Auger electron spectroscopy. UPS and XPS, which sample several monolayers in the substrate–overlayer structure, are used to monitor near-surface electronic properties versus NiO overlayer thickness. Comparison of experimental He II UPS spectra of the valence band electronic structure with a simple model of substrate–overlayer emission indicates that the electronic transition from Fe3O4 to NiO is nearly atomically sharp.

Electronic couplings in organic mixed-valence compounds: the contribution of photoelectron spectroscopy.

We show that the electronic coupling in strongly coupled organic mixed-valence systems can be effectively probed by means of gas-phase ultraviolet photoelectron spectroscopy (UPS). Taking six diamines as examples, the UPS estimates for the electronic couplings H(ab) are compared with the corresponding values determined from the intervalence charge-transfer absorption bands and from electronic structure calculations. Similar trends are observed for the H(ab) values estimated from UPS and optical spectra; this provides support for the applicability of Hush theory to strongly coupled organic mixed-valence systems. The UPS electronic couplings are found to be somewhat smaller than those from optical spectroscopy, which is attributed to the role of vibronic coupling to symmetrical modes; when corrected for this vibronic coupling, the UPS H(ab) estimates confirm that triarylamine-based mixed-valence systems are close to the class-II/class-III borderline.

Chemical states and electronic properties of the interface between aluminium and a photoluminescent conjugated copolymer containing europium complex

The chemical states and electronic properties of the interface between thermally evaporated aluminium and a photoluminescent conjugated copolymer containing 9,9′-dihexylfluorene and europium complex-chelated benzoate units in the main chain (PF6-Eu(dbm)2phen) were studied in situ by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The changes in C 1s, Eu 3d, N 1s, and Al 2p core-level lineshapes with progressive deposition of aluminium atoms were carefully monitored. Aluminium was found to interact with the conjugated backbone of the copolymer to form the Al carbide, Al–O–C complex, and Al(III)–N chelate at the interface. In addition, the europium ions were reduced to the metallic state by the deposited aluminium atoms, which were oxidized and chelated by the 1,10-phenanthroline ligands (phen). The changes in chemical states at the interface suggest that the intramolecular energy transfer process in this copolymer had been affected. Moreover, aluminium also interacted with the bulk-adsorbed oxygen, which migrates to the surface in response to the deposition of aluminium atoms, to form a layer of metal oxides. On the other hand, the evolution of the UPS spectra suggests that the π-states of the conjugated system were affected and an unfavorable dipole layer was induced by the deposited aluminium atoms.