We present a high-resolution photoelectron spectroscopy investigation of condensed films of benzene, naphthalene, anthracene, tetracene, and pentacene. High spectroscopic resolution and a systematic variation of the molecular size allow a detailed analysis of the fine structures. The line shapes of the C 1s main lines are analyzed with respect to the different contributions of inhomogeneous broadening, vibronic coupling, and chemical shifts. The shake-up satellite spectra reveal trends, which give insight into the charge redistribution within the molecule upon photoexcitation. In particular, the shake-up between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) increases in intensity and moves closer toward the C 1s main line if the size of the aromatic system is increased. An explanation is given on the basis of the delocalization of the aromatic system and its capability in screening the photogenerated core hole. A comparison of the HOMO-LUMO shake-up position to the optical band gap gives additional insight into the reorganization of the electronic system upon photoexcitation.

Indium zinc oxide thin-film transistors are fabricated via a precursor in solution route on silicon substrates with silicon dioxide gate dielectric. It is found that the extracted mobility rises, peaks, and then decreases with increasing precursor concentration instead of rising and saturating. Investigation with scanning probe techniques reveals full thickness variations within the film which are assumed to adversely affect charge transport. Additional layers are coated, and the extracted mobility is observed to increase up to 19.7 cm(2) V(-1) s(-1). The reasons for this are examined in detail by direct imaging with scanning tunneling microscopy and extracting electron density profiles from X-ray reflection measurements. It is found that the optimal concentration for single layer films is suboptimal when coating multiple layers and in fact using many layers of very low concentrations of precursor in the solution, leading to a dense, defect and void free film, affording the highest mobilities. A consistent qualitative model of layer formation is developed explaining how the morphology of the film develops as the concentration of precursor in the initial solution is varied.

Abstractn‐Si/CnH2n + 1/Hg junctions (n = 12, 14, 16 and 18) can be prepared with sufficient quality to assure that the transport characteristics are not anymore dominated by defects in the molecular monolayers. With such organic monolayers we can, using electron, UV and X‐ray irradiation, alter the charge transport through the molecular junctions on n‐ as well as on p‐type Si. Remarkably, the quality of the self‐assembled molecular monolayers following irradiation remains sufficiently high to provide the same very good protection of Si from oxidation in ambient atmosphere as provided by the pristine films. Combining spectroscopic (UV photoemission spectroscopy (UPS), X‐ray photoelectron spectroscopy (XPS), Auger, near edge‐X‐ray absorption fine structure (NEXAFS)) and electrical transport measurements, we show that irradiation induces defects in the alkyl films, most likely CC bonds and CC crosslinks, and that the density of defects can be controlled by irradiation dose. These altered intra‐ and intermolecular bonds introduce new electronic states in the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the alkyl chains and, in the process, dope the organic film. We demonstrate an enhancement of 1–2 orders of magnitude in current. This change is clearly distinguishable from the previous observed difference between transport through high quality and defective monolayers. A detailed analysis of the electrical transport at different temperatures shows that the dopants modify the transport mechanism from tunnelling to hopping. This study suggests a way to extend significantly the use of monolayers in molecular electronics.

Monolayers of alkyl chains, attached through direct Si-C bonds to Si(111), via phosphonates to GaAs(100) surfaces, or deposited as alkyl-silane monolayers on SiO2, are investigated by ultraviolet and inverse photoemission spectroscopy and X-ray absorption spectroscopy. Exposure to ultraviolet radiation from a He discharge lamp, or to a beam of energetic electrons, leads to significant damage, presumably associated with radiation- or electron-induced H-abstraction leading to carbon-carbon double-bond formation in the alkyl monolayer. The damage results in an overall distortion of the valence spectrum, in the appearance of (occupied) states above the highest occupied molecular orbital of the alkyl molecule, and in a characteristic (unoccupied state) pi resonance at the edge of the carbon absorption peak. These distortions present a serious challenge for the interpretation of the electronic structure of the monolayer system. We show that extrapolation to zero damage at short exposure times eliminates extrinsic features and allows a meaningful extraction of the density of state of the pristine monolayer from spectroscopy measurements.