Showing papers on "Photoemission spectroscopy published in 1998"

Molecular level alignment at organic semiconductor-metal interfaces

Abstract: In order to clarify the electronic structure of metal-molecular semiconductor contacts, we use photoemission spectroscopy to investigate the energetics of interfaces formed by vacuum deposition of four different molecular thin films on various metals. We find that the interface electron and hole barriers are not simply defined by the difference between the work functions of the metals and organic solids. The range of interface Fermi level positions is material dependent and dipole barriers are present at all these interfaces. The results demonstrate the breakdown of the vacuum level alignment rule at interfaces between these organic molecular solids and metals.

Ultraviolet Photoelectron Spectroscopy of the o-, m-, and p- Benzyne Negative Ions. Electron Affinities and Singlet−Triplet Splittings for o -, m -, and p -Benzyne

Abstract: The 351 nm photoelectron spectra of the negative ions of o-, m-, and p-benzyne (1,2-, 1,3-, and 1,4-dehydrobenzene, respectively) and their perdeuterated isotopomers have been obtained. The o-benzyne ions were generated by the reaction of benzene and benzene-d6 with O-, while the m- and p-benzyne ions were prepared by the gas-phase reaction between the corresponding 3- and 4-(trimethylsilyl)phenyl anions and molecular fluorine, F2. The photoelectron spectra of the benzyne anions each contain two features, corresponding to formation of the singlet and triplet states of the biradicals. The electron affinities of o- and p-benzyne are found to be 0.564 ± 0.007 and 1.265 ± 0.008 eV, respectively, while the electron affinities of deuterated o- and p-benzyne are found to be 8 and 5 meV lower, respectively. The electron affinity of m-benzyne could not be determined from the photoelectron spectrum because the origin peak could not be assigned unequivocally. For o- and p-benzyne, the singlet−triplet energy splittin...

Texture control of PbTiO3 and Pb(Zr,Ti)O3 thin films with TiO2 seeding

Abstract: The nature and the role of 1 to 5 nm thick TiO2 seed layers for the growth of textured PbTiO3 and Pb(Zr, Ti)O-3 thin films on textured Pt(111) thin film substrates have been studied. Under otherwise identical in situ sputter deposition process conditions, the PbTiO3 texture could be turned from (100) to (111) orientation by adding the seed layer. This is demonstrated by patterning the TiO2 film. Auger electron spectroscopy and x-ray photoemission spectroscopy showed that the seed layer was a continuous TiO2 film. X-ray photoelectron diffraction measurements revealed epitaxial ordering in the seed layer. As there is no azimutal order among the Pt grains, the reduced information of azimutally averaged polar cuts is obtained. These give strong evidence for a strained rutile (110) structure. Various deposition experiments indicated that the TiO2 is effective only when it is ordered before the PbTiO3 nucleation starts. The epitaxial relationship between PbTiO3(111) and Pt(111) is thus mediated by the intermediate, epitaxial TiO2 film, which is dissolved of transformed to PbTiO3 afterwards. The observed growth behavior is discussed in terms of surface and interface energies. (C) 1998 American Institute of Physics. [S0021-8979(98)03607-X].

Spectroscopic determination of the structure of amorphous nitrogenated carbon films

Abstract: Studies on structure and electronic properties of amorphous nitrogenated carbon films prepared in dual electron cyclotron resonance–radio frequency plasma from a mixture of methane and nitrogen are presently reported. These films are characterized by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, x-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), electrical conductivity measurement, and optical absorption spectroscopy. Symmetry breaking of aromatic rings are at a very small amount of nitrogen incorporation is understood from FTIR spectra. The relative contribution of C=N and C–N bonds is found to change with the variation of the nitrogen content in the samples, which shows a similar trend with the shift of the G peak to a higher wave number and the increase of the ID/IG ratio. From decomposition of XPS C 1s and N 1s peaks a three-phase model of CN bonds is proposed. UPS valence band spectra obtained by using a Helium II source, are decomposed into p-...

Femtosecond dynamics of electron localization at interfaces

Abstract: The dynamics of two-dimensional small-polaron formation at ultrathin alkane layers on a silver(111) surface have been studied with femtosecond time- and angle-resolved two-photon photoemission spectroscopy. Optical excitation creates interfacial electrons in quasi-free states for motion parallel to the interface. These initially delocalized electrons self-trap as small polarons in a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal within picoseconds by tunneling through the adlayer potential barrier. The energy dependence of the self-trapping rate has been measured and modeled with a theory analogous to electron transfer theory. This analysis determines the inter- and intramolecular vibrational modes of the overlayer responsible for self-trapping as well as the relaxation energy of the overlayer molecular lattice. These results for a model interface contribute to the fundamental picture of electron behavior in weakly bonded solids and can lead to better understanding of carrier dynamics in many different systems, including organic light-emitting diodes.

Energy level offset at organic semiconductor heterojunctions

Abstract: We present an investigation via ultraviolet photoemission spectroscopy of the electronic structure of three organic-organic heterojunctions formed between the standard electron-transport emissive material tris(8-hydroxy-quinoline)aluminum (Alq3) and two hole-transport materials, i.e., 3,4,9,10 perylenetetracarboxylic dianhydride (PTCDA), and N,N′-diphenyl-N,N′-bis(l-naphthyl)-1-1′biphenyl-4,4″diamine (α-NPD). We measure directly the energy offsets between highest occupied molecular orbitals during the formation of the interfaces. We show that the relative positions of the highest occupied and lowest unoccupied molecular orbitals across the Alq3/PTCDA and Alq3/α-NPD interfaces are qualitatively different and explain, in part, the difference in the performance of electroluminescent devices based on these heterojunctions. We demonstrate the existence of charge transfer-induced dipoles which shift the molecular levels of one organic with respect to the other and invalidate the usual assumption of vacuum level...

Photoemission spectroscopy of LiF coated Al and Pt electrodes

Abstract: Thin lithium fluoride (LiF) interlayers between the low work function electrode and the electron transport layer in organic light emitting diodes (OLED) result in improved device performance. We investigated the electronic structure of LiF coated Al and Pt electrodes by x-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS). Thin LiF films were grown in several steps onto Ar+ sputtered Al and Pt foils. After each growth step the surfaces were characterized in situ by XPS and UPS measurements. After evaluating band bending, work function and valence band offset for both samples, their band lineups were determined. Our measurements indicate that despite the insulating character of LiF in both samples, band bending is present in the LiF layer. The difference in band bending between the samples allows the conclusion that the driving force for the development of the band bending results from the contact potential between the metal and the LiF overlayer. The band bending is most...

Photoemission spectroscopy investigation of magnesium–Alq3 interfaces

Abstract: The formation of interfaces between magnesium (Mg) and the organic molecular semiconductor tris(8-hydroxy-quinoline) aluminum (Alq3) is studied via ultraviolet photoemission spectroscopy. The morphology and electronic structure of Mg-on-Alq3 and Alq3-on-Mg interfaces are compared. The energy of the Alq3 molecular levels is determined in both cases with respect to a reference Fermi level as a function of interface formation. The difference in injection characteristics between the two interfaces is examined in terms of differences in interface morphology and of electronic gap states induced by the diffusion of Mg at the Mg/Alq3 interface.

Strong hybridization in vanadium oxides: evidence from photoemission and absorption spectroscopy

Abstract: We present x-ray photoemission spectra of the vanadium oxides , and , and their analysis in terms of a simple cluster model based on the Anderson impurity Hamiltonian. The electronic structure of these materials is characterized by a strong V 3d-O 2p hybridization energy which exceeds the energy scales related to on-site Coulomb correlation and metal-ligand charge transfer. This result is at variance with the usual Mott-Hubbard picture, but agrees with recent studies of other early 3d transition metal compounds. The V 3d ground-state occupations obtained by the cluster-model analysis are considerably higher than the values derived from the formal valencies. Covalency also affects the exchange splitting observed in the V 3s core-hole spectra. X-ray absorption measurements and resonant photoemission spectroscopy at the V 2p-3d threshold provide further evidence for a strong V 3d-O 2p coupling.

Correlation between XPS, Raman and TEM measurements and the gas sensitivity of Pt and Pd doped SnO2 based gas sensors

Abstract: Nanocrystalline thick-film SnO2 sensors with different dopants were fabricated by an optimized screen printing process and subsequent annealing. Powders were used as starting materials which were prepared by a wet chemical process from SnCl4. Microanalysis was performed of both, the precursors and the final sensor materials with their different annealing conditions. Gas sensing tests with CO, CH4 and NO2 in air with controlled humidity were correlated with results from X-ray photoemission spectroscopy (XPS), Raman spectroscopy and transmission electron microscopy (TEM). As an interesting result, the distribution of the transition metal dopants Pd and Pt (as deduced from TEM and XPS data) rules out the existence of metallic clusters or even atoms in the metallic state at the surface. This finding does not allow to explain the sensor effects on SnO2 based materials as usually done by means of spill-over effects or Fermi energy control.

Electronic structures of organic molecular materials for organic electroluminescent devices studied by ultraviolet photoemission spectroscopy

Abstract: Electronic structures of evaporated films of five organic light-emitting and carrier-injecting materials for organic electroluminescent devices were studied by ultraviolet photoemission spectroscopy. The compounds examined were (i) light-emitting materials tris(8-hydroxyquinolino) aluminum (Alq3) and 1,2,3,4,5-pentaphenylcyclopentadiene, (ii) a hole-injecting material N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine, and (iii) electron-injecting materials N,N′-diphenyl-1,4,5,8-naphthyletracarboxyldiimide and 1,3,5-tris(5-phenyl-1,3,4-oxadiazol-2-yl)benzene. The spectral features corresponding to the top parts of the valence states, which dominate the electric properties of the materials, were assigned by the comparison with the simulated density of states obtained from PM3 molecular orbital calculations. Using these calculations, the evolution of the electronic structure of each molecule from those of constituent parts was discussed. The characters of the unoccupied states obtained by t...

GaN (0001)-(1×1) surfaces: Composition and electronic properties

Abstract: We use low energy electron diffraction, Auger electron spectroscopy, and ultraviolet and x-ray photoemission spectroscopy to study the surface structure, stoichiometry, and electronic properties of n- and p-type GaN (0001) grown by metal-organic chemical vapor deposition. Ordered (1×1) surfaces with nearly stoichiometric composition are prepared by nitrogen sputtering and annealing. The band bending is found to be 0.75±0.1 eV up and 0.75±0.1 eV down for n- and p-type samples, respectively. The work function, electron affinity, and Ga 3d core level binding energy are also determined.

Energy-level alignment at model interfaces of organic electroluminescent devices studied by UV photoemission: trend in the deviation from the traditional way of estimating the interfacial electronic structures

Abstract: The electronic structures of model interfaces of organic electroluminescent (EL) devices were investigated with UV photoemission spectroscopy (UPS). Interfaces of TTN (tetrathianaphthacene) and TCNQ (tetracyanoquinodimethane) were also studied as extreme cases for hole transport and electron transport material, respectively. For all organic/metal interfaces studied, the work function of metal electrode was changed by deposition of organic layer, i.e., the vacuum level was shifted at the interface, indicating the invalidity of the traditional energy level alignment model where a common vacuum level was assumed at organic/metal interface. At TCNQ/Au, DP-NTCI/Al, which are acceptor/metal interfaces, upward shift of the vacuum level of organic layer relative to that of metal was observed, suggesting the formation of interfacial dipole due to electron-transfer from metal to acceptor. At other organic/metal interfaces, TPD(N, N'-diphenyl-N, N'-(3-methylphenyl)-1, 1'-biphenyl-4, 4'-diamine)/Au or ITO (indium tin oxide), ALq/sub 3/ (tris(8-hydroxyquinolino) aluminum)/Al, DP-NTCl(N, N'-diphenyl-1,4,5,8- naphthyltetracarboxylimide)/Al or Au, downward shift of the vacuum level was observed. Such downward shift has been also observed in our previous study for porphyrin/metal interfaces, and seems to be a trend for organic/metal interfaces at which no electron-transfer from metal to organic layer occurs. This trend suggests that the traditional model tends to underestimate (overestimate) the barrier height for hole (electron) injection. On the other hand, the vacuum level shift at ALq/sub 3//TPD interface was less than 0.1 eV, leading to an apparent applicability of the traditional model. However, it is not always the case for organic/organic interfaces: finite shift of 0.2 eV was observed at TTN/TCNQ interface due to electron-transfer from TTN to TCNQ. Possible origins of vacuum level shift at organic/metal interfaces were also discussed.

Energy-level alignment at interfaces between metals and the organic semiconductor 4,4′-N,N′-dicarbazolyl-biphenyl

Abstract: We have used ultraviolet photoemission spectroscopy to study the formation of interfaces between the organic semiconductor, 4,4′-N,N′-dicarbazolyl-biphenyl (CBP), and the metals Au, Ag, and Mg. Each interface was studied by depositing the organic on the metal, and by depositing the metal on the organic. The two methods produced inequivalent interfaces, except in the case of Au/CBP. The position of the highest occupied molecular orbital relative to the Fermi level and the magnitude of the interface dipole were measured for each interface. The barrier to electron injection from each metal was estimated using the magnitude of the measured optical gap. An interface dipole, of magnitude nearly independent of the metal work function, was formed when CBP was deposited on a metal surface. The position of the Fermi level within the CBP gap was found to vary strongly with the metal work function.

Electronic Structures and Chemical Bonding of Fluorinated Fullerenes Studied by NEXAFS, UPS, and Vacuum-UV Absorption Spectroscopies

Abstract: The chemical bonding and the electronic structures of C60Fx and C70Fx were investigated by near edge X-ray absorption fine structure (NEXAFS) spectroscopy and UV photoemission spectroscopy (UPS), which are useful methods for examining the unoccupied and the occupied states, respectively. With these results and XPS measurements, we derived the electronic energy diagram of C60Fx and discussed the change of the electronic structure from that of C60 by fluorination. The energies of the LUMO and the Fermi level of solid C60F48 were estimated to be −5.0 and −5.4 eV below the vacuum level, indicating that highly doped C60Fx is a strong electron acceptor. The electronic absorption spectra of C60Fx solutions deep into the vacuum-ultraviolet region were also measured, and the isomerism of C60Fx was discussed by comparing the observed results with theoretical simulations.

Surface charge neutralization of insulating samples in x-ray photoemission spectroscopy

Abstract: Obtaining high resolution x-ray photoemission spectroscopy (XPS) spectra of insulating samples has long been a problem because of difficulty controlling sample surface potentials. A flood of low energy electrons has traditionally been used to control surface potential, but as monochromatized instruments with small, intense x-ray beams have become available, control has become much more difficult, particularly on larger samples. Increasing the current or energy from the flood gun does not improve the control appreciably. To understand the charging effect in a quantitative way, we have conducted some experiments with a test sample, configured to approximate the geometry present in several commercial XPS instruments using focused x-ray sources. These results show that, because of the energy spread of the flooding electrons, a negative potential is induced by the flood gun in the region surrounding the x-ray beam. This negative potential repels electrons, inhibiting the adequate neutralization of many samples...

Femtosecond photoemission study of ultrafast electron dynamics in single-crystal au(111) films

Abstract: The energy-dependent relaxation of photoexcited electrons has been measured by time-resolved two-photon photoemission spectroscopy on single-crystal Au~111! films with thickness ranging from 150 to 3000 A. It is found that the energy-dependent relaxation does not show any significant thickness dependence, which indicates that electron transport is a much slower dynamical process in the near-surface region than expected from bulk properties. Furthermore, lifetimes of the photoexcited electrons can be fitted well by the Fermi-liquid theory with a scaling factor plus an effective upper lifetime. This observation enables separation of electronelectron scattering, and to a lesser extent electron-phonon scattering, processes from electron-transport effects on the surface dynamics. @S0163-1829~98!04840-1#

Ballistic electron emission microscopy study of barrier height inhomogeneities introduced in au/n-si schottky contacts by a hf pretreatment

Abstract: The distribution of Schottky barrier heights over the contact area in Au/n-Si diodes was determined by ballistic electron emission microscopy. For samples on which an aqueous HF pretreatment of the Si substrate was applied, the histogram contains several high barrier Gaussian distribution components. After a short rinse, in de-ionized water or methanol, it was mainly the most important lower Gaussian component which was left. Using additional x-ray photoemission spectroscopy and atomic force microscopy measurements allowed us to propose a model, wherein negatively charged species containing F at the interface, are thought to be responsible for the high barrier Gaussian components.

A photoabsorption, photodissociation and photoelectron spectroscopy study of C6H6 and C6D6

Abstract: The absolute photoabsorption, photoionisation and photodissociation cross-sections and the photoionisation quantum efficiency of benzene and hexadeuterobenzene have been measured from the ionisation threshold to 350 A using a double ion chamber and monochromated synchrotron radiation. The HeI excited photoelectron spectrum of C 6 D 6 has been recorded and the vibrational structure exhibited in the X 2 E 1g , A 2 E 2g , E 2 B 1u and F 2 A 1g bands has been analysed with the aid of theoretical predictions and by analogy with the recently reported high-resolution photoelectron spectrum of C 6 H 6 . The photoabsorption spectrum displays extensive vibrational structure extending from the ionisation threshold to ∼730 A, and many of these absorption features have been arranged into Rydberg series. A detailed assignment of the vibrational progressions associated with some Rydberg states has been accomplished by making use of the corresponding photoelectron spectrum. A sum rule analysis has been carried out by combining the present absolute photoabsorption measurements with similar data covering the remaining wavelength regions.

Zinc oxide and its anion: A negative ion photoelectron spectroscopic study

Abstract: We have recorded, assigned, and analyzed the photoelectron spectrum of ZnO−. The adiabatic electron affinity (E.A.a) of ZnO and the vibrational frequencies of both ZnO and ZnO− were determined directly from the spectrum, with a Franck–Condon analysis of its vibrational profile providing additional refinements to these parameters along with structural information. As a result, we found that E.A.a(ZnO)=2.088±0.010 eV, ωe(ZnO)=805±40 cm−1, ωe(ZnO−)=625±40 cm−1, and that re(ZnO−)>re(ZnO) by 0.07 A. Since our measured value of E.A.a(ZnO) is 0.63 eV larger than the literature value of E.A.(O), it was also evident, through a thermochemical cycle, that D0(ZnO−)>D0(ZnO) by 0.63 eV. This, together with the literature value of D0(ZnO), gives a value for D0(ZnO−) of 2.24 eV. Since the extra electron in ZnO− is expected to occupy an antibonding orbital, the combination of D0(ZnO−)>D0(ZnO), ωe(ZnO−) re(ZnO) was initially puzzling. An explanation was provided by the calculations of Bauschlicher and...

Determination of frontier orbital alignment and band bending at an organic semiconductor heterointerface by combined x-ray and ultraviolet photoemission measurements

Abstract: The alignment of the highest occupied molecular orbitals (HOMO) at the tris (8-hydroxy quinoline) aluminum (Alq3)/N,N′-di-(3-methylphenyl)-N,N′diphenyl-4,4′-diaminobiphenyl (TPD) heterojunction, used in organic light-emitting diodes (OLED), was determined by growing a TPD layer in several steps on a thick Alq3 substrate layer After each growth step the sample was characterized in situ by x-ray and ultraviolet photoemission spectroscopy The offset of the HOMO maxima at the interface was determined to be −013 eV from Alq3 to TPD By including the known HOMO–lowest occupied molecular orbital (LUMO) gaps for both molecules into the evaluation, the offset of the LUMO minima was determined to be −033 eV from Alq3 to TPD These values are consistent with previous assumptions that this interface represents a higher barrier for electron injection from Alq3 to TPD than for hole injection from TPD to Alq3

Negative electron affinity of cesiated p-GaN(0001) surfaces

Abstract: The adsorption of cesium on clean n- and p-GaN(0001)-1×1 surfaces at 150 K was investigated using x-ray photoemission spectroscopy, photoemission spectroscopy with monochromatized He I radiation ultraviolet photoelectron spectroscopy (UPS) and a Kelvin probe (contact potential difference, CPD). The CPD measurements gave work functions of 3.88±0.15 and 3.6±0.15 eV for clean n- and p-GaN(0001) surfaces, respectively. The widths of UPS energy distribution curves yield an ionization energy of 6.8±0.15 eV. Thus, depletion and inversion layers exist at clean surfaces of n- and p-GaN(0001) surfaces, respectively. As a function of Cs coverage, the work function displays the well-known behavior in that it first decreases, passes through a minimum, and eventually reaches a value of 2.1 eV, the work function of metallic cesium. In the submonolayer coverage regime, the ionization energy decreases by 2.3±0.15 eV. At clean p-GaN(0001) surfaces the vacuum level lies by only 0.3 eV above the conduction-band minimum in th...

Surface Chemistry of SO2 on Zn and ZnO: Photoemission and Molecular Orbital Studies

Abstract: The reaction of SO2 with polycrystalline Zn and ZnO surfaces has been investigated using synchrotron-based high-resolution photoemission spectroscopy and ab initio self-consistent-field calculations. The chemistry of SO2 on Zn surfaces is quite complex and depends on both the temperature of adsorption and the SO2 exposure. At 300 K, SO2 dissociates on a clean Zn surface to form atomic sulfur and atomic oxygen (SO2,gas → Sa + 2Oa; SO2,gas → SOgas + Oa). The Zn ↔ SO2 bonding interactions induce a significant weakening of the S−O bonds. The theoretical calculations suggest the η2-O,O and η2-S,O bonding conformations of SO2 as the two possible precursors for the dissociation of the molecule. The dissociation reactions are much more exothermic than the formation of SO3 or SO4: SO2,gas + nOa → SOx, where x = 3 or 4. At high SO2 exposures (300 K), when most surface sites are blocked and dissociation of SO2 cannot occur, SO3 and SO4 are formed on the Zn surface. Adsorption at 100 K suppresses the SO2 dissociatio...

Laser-produced lithium plasma as a narrow-band extended ultraviolet radiation source for photoelectron spectroscopy

Abstract: Extended ultraviolet (EUV) emission characteristics of a laser-produced lithium plasma are determined with regard to the requirements of x-ray photoelectron spectroscopy. The main features of interest are spectral distribution, photon flux, bandwidth, source size, and emission duration. Laser-produced lithium plasmas are characterized as emitters of intense narrow-band EUV radiation. It can be estimated that the lithium Lyman-α line emission in combination with an ellipsoidal silicon/molybdenum multilayer mirror is a suitable EUV source for an x-ray photoelectron spectroscopy microscope with a 50-meV energy resolution and a 10-μm lateral resolution.