Self-assembled carbon nanotubes on gold: polarization-modulated infrared reflection-absorption spectroscopy, high-resolution X-ray photoemission spectroscopy, and near-edge X-ray absorption fine structure spectroscopy study

Recently we reported noncovalent functionalization of nanotubes in an aqueous medium with ionic liquid-based surfactants, 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), resulting in positively charged single-wall carbon nanotube (SWNT)-1,2 composites. Thiolation of SWNTs with 2 provides their self-assembly on gold as well as templating gold nanoparticles on SWNT sidewalls via a covalent -S-Au bond. In this investigation, we studied the electronic structure, intermolecular interactions, and packing within noncovalently thiolated SWNTs and also nanotube alignment in the bulk of SWNT-2 dried droplets and self-assembled submonolayers (SAMs) on gold by high-resolution X-ray photoemission spectroscopy (HRXPS), C K-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS). HRXPS data confirmed the noncovalent nature of interactions within the nanocomposite of thiolated nanotubes. In PM-IRRAS spectra of SWNT SAMs on gold, the IR-active vibrational SWNT modes have been observed and identified. According to PM-IRRAS data, the hydrocarbon chains of 2 are oriented with less tilt angle to the bare gold normal in a SAM deposited from an SWNT-2 dispersion than those of 1 deposited from an SWNT-1 dispersion on the mercaptoethanesulfonic acid-primed gold. For both the dried SWNT-2 bulk and the SWNT-2 SAM on gold, the C K-edge NEXAFS spectra revealed the presence of CH-pi interactions between hydrocarbon chains of 2 and the pi electronic nanotube structure due to the highly resolved vibronic fine structure of carbon 1s --> R*/sigma*C-H series of states in the alkyl chain of 2. For the SWNT-2 bulk, the observed splitting and upshift of the SWNT pi* orbitals in the NEXAFS spectrum indicated the presence of pi-pi interactions. In the NEXAFS spectrum of the SWNT-2 SAM on gold, the upshifted values of the photon energy for R*/sigma*C-H transitions indicated close contact of 2 with nanotubes and with a gold surface. The angle-dependent NEXAFS for the SWNT-2 bulk showed that most of the molecules of 2 are aligned along the nanotubes, which are self-organized with orientation parallel to the substrate plane, whereas the NEXAFS for the SWNT-2 SAM revealed a more normal orientation of functionality 2 on gold compared with that in the SWNT-2 bulk.     

Photoemission studies of polythiophene and polyphenyl films produced via surface polymerization by ion-assisted deposition

Conducting polymer films are grown by mass-selected, hyperthermal thiophene ions coincident on a surface with a thermal beam of organic monomers of either alpha-terthiophene (3T) or p-terphenyl (3P) neutrals. Mass spectrometry and X-ray photoelectron spectroscopy previously verified polymerization of both 3T and 3P by 200 eV C(4)H(4)S(+) during surface polymerization by ion-assisted deposition (SPIAD). The electronic structure of these films are probed here by ultraviolet photoelectron spectroscopy (UPS) and polarized near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and compared with similar spectra of evaporated films. The conducting polymer films formed by SPIAD display new valence band features resulting from a reduction in both their band gap and barrier to hole injection, which are calculated from the occupied and unoccupied valence band states measured by UPS and NEXAFS. These changes in film electronic structure result from an increase in the electron conjugation length and other changes in film structure induced by SPIAD.     

Structure of tert-butyl carbamate-terminated thiol chemisorbed to gold

Monolayers of tert-butyl carbamate-terminated thiol were formed by adsorption of the molecules onto polycrystalline gold substrate. The adsorbates were studied using techniques as X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and infrared reflection-absorption spectroscopy (IRAS). The results provide the electronic structure, composition, characteristic fingerprint, and orientation of the molecular adsorbate. XPS verified that the thiolate group is chemically bonded to the gold surface and that a complete chemisorption of the molecule occurs. Elemental depth profiling by varying the excitation energy in XPS supports the angle-dependent XPS results. Both techniques showed that the tert-butyl group is oriented away from the gold surface. A nearly parallel orientation of the carbonyl group relative to the gold surface is deduced from the IRAS results. The main molecular axis is estimated to have an average tilt angle of about 38 degrees relative to the gold surface normal on the basis of the NEXAFS results. Cyclic voltammetry indicates a less blocking capability of the adsorbates. Overall, the molecules are oriented in an upright manner with indications of presence of pinholes and/or defects possibly due to steric hindrance of the bulky tert-butyl group. This molecular system is envisioned to be of use for surface-based organic synthesis on gold substrates.     

Mapping the frontier electronic structures of triphenylamine based organic dyes at TiO2 interfaces

The frontier electronic structures of a series of organic dye molecules containing a triphenylamine moiety, a thiophene moiety and a cyanoacrylic acid moiety have been investigated by photoelectron spectroscopy (PES), X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and resonant photoelectron spectroscopy (RPES). The experimental results were compared to electronic structure calculations on the molecules, which are used to confirm and enrich the assignment of the spectra. The approach allows us to experimentally measure and interpret the basic valence energy level structure in the dye, including the highest occupied energy level and how it depends on the interaction between the different units. Based on N 1s X-ray absorption and emission spectra we also obtain insight into the structure of the excited states, the molecular orbital composition and dynamics. Together the results provide an experimentally determined energy level map useful in the design of these types of materials. Included are also results indicating femtosecond charge redistribution at the dye/TiO(2) interface.     

Orientation of pentacene molecules on SiO2: from a monolayer to the bulk

Near edge x-ray absorption fine structure (NEXAFS) spectroscopy is used to study the orientation of pentacene molecules within thin films on SiO2 for thicknesses ranging from monolayers to the bulk (150 nm). The spectra exhibit a strong polarization dependence of the pi* orbitals for all films, which indicates that the pentacene molecules are highly oriented. At all film thicknesses the orientation varies with the rate at which pentacene molecules are deposited, with faster rates favoring a thin film phase with different tilt angles and slower rates leading to a more bulklike orientation. Our NEXAFS results extend previous structural observations to the monolayer regime and to lower deposition rates. The NEXAFS results match crystallographic data if a finite distribution of the molecular orientations is included. Damage to the molecules by hot electrons from soft x-ray irradiation eliminates the splitting between nonequivalent pi* orbitals, indicating a breakup of the pentacene molecule.     

Electronic structure of C60 on Au(887)

We present an analysis of the electronic structure of C60 adsorbed on a vicinal Au(111) surface at different fullerene coverages using photoemission, x-ray absorption, and scanning tunneling microscopy/spectroscopy (STS). STS provides a straightforward determination of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) levels with respect to the Fermi energy. At C60 coverages of 0.5 and 1 ML a 2.7 eV wide HOMO-LUMO gap is found. The near-edge x-ray absorption fine structure (NEXAFS) spectrum for the 0.5 ML C60 nanomesh structure displays a significant intensity at the low energy side of the LUMO exciton peak, which is explained as due to absorption into HOMO-LUMO gap states localized at individual C60 cluster edges. From 0.5 to 1 ML we observe a rigid shift of the HOMO-LUMO peaks in the STS spectra and an almost complete quenching of the gap states feature in NEXAFS.     

Photoemission and near-edge X-ray absorption fine structure studies of the bacterial surface protein layer of Bacillus sphaericus NCTC 9602

The electronic structure of the regular, two-dimensional bacterial surface protein layer of Bacillus sphaericus NCTC 9602 has been examined by photoemission (PE) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Both the O 1s and the N 1s core-level PE spectra show a single structure, whereas the C 1s core-level spectrum appears manifold, suggesting similar chemical states for each oxygen atom and also for each nitrogen atom, while carbon atoms exhibit a range of chemical environments in the different functional groups of the amino acids. This result is supported by the element-specific NEXAFS spectra of the unoccupied valence electronic states, which exhibit a series of characteristic NEXAFS peaks that can be assigned to particular molecular orbitals of the amino acids by applying a phenomenological building-block model. The relative contributions of the C-O, C-N, and C-C bond originating signals into the C 1s PE spectrum are in good agreement with the number ratios of the corresponding bonds calculated from the known primary structure of the bacterial surface protein. First interpretation of the PE spectrum of the occupied valence states is achieved on the basis of electronic density-of-states calculations performed for small peptides. It was found that mainly the pi clouds of the aromatic rings contribute to both the lowest unoccupied and the highest occupied molecular orbitals.     

Probing weak molecular orbital interactions in non-conjugated diene molecules by means of near-edge X-ray absorption spectroscopy

Carbon and oxygen near-edge X-ray absorption fine structure (NEXAFS) spectra of 1,4-cyclohexadiene, p-benzoquinone, norbornadiene, norbornadienone, and cis-cis-[4,4,2]propella-3,8-diene-11,12-dione were calculated by means of Hartree-Fock and hybrid density functional theory using the static-exchange (STEX) approximation. The NEXAFS spectra are used as a probe to identify weak molecular interactions between the two non-conjugated ethylenic pi* orbitals present in these molecules. We show that the X-ray absorption spectrum of 1,4-cyclohexadiene exhibits some particular spectral structures in the discrete energy region that evidence diene through-bond orbital interaction, whereas absorption peaks are identified in the norbornadiene and norbornadienone spectra that indicate effective through-space orbital interactions. The molecular structure of the cis-cis-[4,4,2]propella-3,8-diene-11,12-dione isomer is such that the indirect through-bond or through-space diene orbital interactions are too weak to be assigned by its C1s NEXAFS spectrum.     

Tailoring the Cu(100) work function by substituted benzenethiolate self-assembled monolayers

The structure and electronic interface properties of five differently substituted benzenethiol based self-assembled monolayers (SAMs) on Cu(100) have been studied by means of low energy electron diffraction, thermal desorption spectroscopy, X-ray absorption spectroscopy (NEXAFS), and UV photoelectron spectroscopy. Because highly ordered SAMs are formed of which lateral density had been precisely determined, effective molecular dipole moments were derived from the measured work function shifts. These values are compared with gas phase dipole moments computed by quantum chemical calculations for the individual thiol molecules considering the molecular orientation determined from NEXAFS data. Furthermore, this comparison yields clear evidence for a coverage dependent depolarization effect of the adsorbed molecules within the SAMs.     

Near edge X-ray absorption fine structure spectroscopy of bacterial hydroxamate siderophores in aqueous solutions

X-ray absorption spectroscopy (XAS) is widely used to explore the coordination environments and structures of metal complexes in aqueous solutions and disordered phases. Although soft-XAS studies on gaseous phases, solid phases and their interfaces have shown that XAS is a versatile tool in studying the functional group composition of organic molecules, the application of XAS to studying aqueous solutions is seriously limited because of experimental difficulties. In this report, using a modified synchrotron endstation geometry, we show how soft-XAS was used to study the changes in electronic states of reactive functional groups in a bacterial macromolecule, desferrioxamine B (desB, a hydroxamate siderophore) and its structural analogue (acetohydroxamic acid (aHa)). We collected C, N, and O near edge X-ray absorption fine structure (NEXAFS) spectra of these molecules in aqueous solutions and complemented their spectral interpretation with calculated X-ray spectra of "hydrated" aHa. The experimental spectra of desB are similar to those for aHa at the C, N, and O K-edges. In addition, the electronic transitions of amide and hydroxamate functional groups in the macromolecule can be distinguished from the N spectra. Small energy differences in the pi*(C=O)NO and the transitions at the C- and N-edges of aHa and desB indicate that the substituent attached to N in desB ((CH2)n) determines the electron density in the (C=O)NO core. As the solution pH increased, the pi*(C=O)NO transition of the hydroxamate group of these two molecules exhibit energy shifts at the C-, N-, and O-edges, which are consistent with increased electron delocalization in the (C=O)NO core of aHa (and desB), predicted from the calculations. The spectra of the aHa(H2O)3- anion also provide evidence for partial N-deprotonation at pH values usually attributed to an O-acid. These results indicate that soft-XAS is well suited for studying the electronic states of different functional groups in aqueous organic macromolecules.     

Direct observation of defect levels in InN by soft X-ray absorption spectroscopy

We have used synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to study the electronic structure of nitrogen-related defects in InN(0001). Several defect levels within the band gap or the conduction band of InN were clearly resolved in NEXAFS spectra around the nitrogen K-edge. We attribute the level observed at 0.3 eV below the conduction band minimum (CBM) to interstitial nitrogen, the level at 1.7 eV above the CBM to antisite nitrogen, and a sharp resonance at 3.2 eV above the CBM to molecular nitrogen, in full agreement with theoretical simulations.     

Near edge X-ray absorption fine structure spectroscopy as a tool to probe electronic and structural properties of thin organic films and liquids

Synchrotron-based spectroscopic techniques have contributed significantly to a better understanding of the properties of materials on the macroscopic and microscopic scale over the last decades. They can be applied to samples from a diversity of fields, including Biology, Life Sciences, Chemistry and Materials. One of these techniques is Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy, revealing electronic structure and information on the orientation of adsorbed molecules. The present article describes the basics of the technique and the progress it has made over the last three decades, and summarizes some of its more recent developments and applications. This tutorial review article should be accessible for novices to the field from Physics, Chemistry, Biology, Materials, and the Life Sciences, interested in thin organic films and liquid systems.     

Selective adsorption of atomic hydrogen on a h-BN thin film

The adsorption of atomic hydrogen on hexagonal boron nitride (h-BN) is studied using two element-specific spectroscopies, i.e., near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS). B K-edge NEXAFS spectra show a clear change in the energy region of the π* band before and after reaction with atomic deuterium. On the other hand, N K-edge NEXAFS spectra show only a little change. B 1s XPS spectra show a distinct component at the low binding energy side of a main component, while N 1s XPS spectra show peak broadening at the high binding energy side. These experimental results are analyzed by the discrete variational Xα method with a core-hole effect and are explained by a model in which hydrogen atoms are preferentially adsorbed on the B sites of h-BN. Based on the experimental and theoretical results, we propose a site-selective property of BN material on adsorption of atomic hydrogen.     

The electronic structure and adsorption geometry of L-histidine on Cu(110)

The adsorption of L-histidine on clean and oxygen-covered Cu(110) surfaces has been studied by soft X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The valence band spectra, carbon, nitrogen and oxygen 1 s XPS and N K edge absorption spectra were measured for submonolayer, monolayer, and multilayer films. The spectra provide a detailed picture of the electronic structure and adsorption geometry at each coverage. In the monolayer, the histidine molecules are randomly oriented, in contrast to the submonolayer regime, where the molecules are coordinated to the copper surface with the imidazole functional group nearly parallel to, and strongly interacting with, the surface. The pi*/sigma* intensity ratio in NEXAFS spectra at the nitrogen edge varies strongly with angle, showing the imidazole ring is oriented. Adsorption models are proposed.     

Core excitations of naphthalene: vibrational structure versus chemical shifts

High-resolution x-ray photoelectron emission (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectra of naphthalene are analyzed in terms of the initial state chemical shifts and the vibrational fine structure of the excitations. Carbon atoms located at peripheral sites experience only a small chemical shift and exhibit rather similar charge-vibrational coupling, while the atoms in the bridging positions differ substantially. In the XPS spectra, C-H stretching modes provide important contributions to the overall shape of the spectrum. In contrast, the NEXAFS spectrum contains only vibrational progressions from particular C-C stretching modes. The accuracy of ab initio calculations of absolute electronic transition energies is discussed in the context of minute chemical shifts, the vibrational fine structure, and the state multiplicity.     

Molecular orientation of evaporated pentacene films on gold: alignment effect of self-assembled monolayer

Pentacene films deposited on self-assembled monolayers (SAMs) bearing different terminal functional groups have been studied by reflection-absorption IR, grazing angle XRD, NEXAFS, AFM, and SEM analyses. A film with pentacene molecules nearly perpendicularly oriented was observed on Au surfaces covered with an SAM of alkanethiol derivative of X-(CH2)(n)-SH, with X = -CH(3), -COOH, -OH, -CN, -NH(2), C(60), or an aromatic thiol p-terphenylmethanethiol. On the other hand, a film with the pentacene molecular plane nearly parallel to the substrate surface was found on bare Au surface. A similar molecular orientation was found in thinner ( approximately 5 nm) and thicker (100 nm) deposited films. Films deposited on different surfaces exhibit distinct morphologies: with apparently smaller and rod-shaped grains on clean bare Au surface but larger and islandlike crystals on SAM-modified surfaces. X-ray photoemission electron microscopy (X-PEEM) was used to analyze the orientation of pentacene molecules deposited on a SAM-patterned Au surface. With the micro-NEXAFS spectra and PEEM image analysis, the microarea-selective orientation control on Au was characterized. The ability to control the packing orientation in organic molecular crystals is of great interest in fabricating organic field effect transistors because of the anisotropic nature of charge transport in organic semiconducting materials.     

Near-edge X-ray absorption fine structure spectroscopy of diamondoid thiol monolayers on gold

Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 +/- 0.05 and 0.16 +/- 0.04 eV, respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different degrees of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond nanoparticles.     

Thin film structure of tetraceno[2,3-b]thiophene characterized by grazing incidence X-ray scattering and near-edge X-ray absorption fine structure analysis

Understanding the structure-property relationship for organic semiconductors is crucial in rational molecular design and organic thin film process control. Charge carrier transport in organic field-effect transistors predominantly occurs in a few semiconductor layers close to the interface in contact with the dielectric layer, and the transport properties depend sensitively on the precise molecular packing. Therefore, a better understanding of the impact of molecular packing and thin film morphology in the first few monolayers above the dielectric layer on charge transport is needed to improve the transistor performance. In this Article, we show that the detailed molecular packing in thin organic semiconductor films can be solved through a combination of grazing incidence X-ray diffraction (GIXD), near-edge X-ray absorption spectra fine structure (NEXAFS) spectroscopy, energy minimization packing calculations, and structure refinement of the diffraction data. We solve the thin film structure for 2 and 20 nm thick films of tetraceno[2,3-b]thiophene and detect only a single phase for these thicknesses. The GIXD yields accurate unit cell dimensions, while the precise molecular arrangement in the unit cell was found from the energy minimization and structure refinement; the NEXAFS yields a consistent molecular tilt. For the 20 nm film, the unit cell is triclinic with a = 5.96 A, b = 7.71 A, c = 15.16 A, alpha = 97.30 degrees, beta = 95.63 degrees, gamma = 90 degrees; there are two molecules per unit cell with herringbone packing (49-59 degree angle) and tilted about 7 degrees from the substrate normal. The thin film structure is significantly different from the bulk single-crystal structure, indicating the importance of characterizing thin film to correlate with thin film device performance. The results are compared to the corresponding data for the chemically similar and widely used pentacene. Possible effects of the observed thin film structure and morphology on charge carrier mobility are discussed.