The interplay between molecular orientation, film morphology and luminescence properties of tetracene thin films on epitaxial AlOx/Ni3Al(1 1 1)

We report a systematic study of the interplay between molecular orientation, film morphology and luminescence properties of tetracene thin films on epitaxial alumina films on Ni₃Al(1 1 1), employing high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), and photoluminescence spectroscopy (PL). If deposited at low temperatures, tetracene forms laterally disordered and compact films in which at least the first monolayer is oriented parallel to the substrate. For thicknesses in the range of 10 Å or below, these as-deposited films show no luminescence, while thicker films exhibit weak luminescence from higher layers. On annealing to 210 K, tetracene films dewet the AlO_x/Ni₃Al(1 1 1) surface and transform into an island morphology. At the same time, molecules tend to re-orient into a more upright configuration. In this island configuration, even thin films show luminescence. We can thus conclude that in spite of the insulating nature of the surface, the interaction of flat-lying tetracene molecules with AlO_x/Ni₃Al(1 1 1) is strong enough to provide at least one efficient non-radiative decay channel.     

Determination of C60/C70 ratios in fullerene mixtures and film characterization by scanning tunneling microscopy

Fullerene powder mixtures with different C₆₀/C₇₀ ratios have been analyzed by a variety of techniques, and results have been compared. The fullerence mixtures have been characterized as solutions in n-hexane by high-pressure liquid chromatography (HPLC) and UV-VIS spectroscopy. Thin films of fullerenes on Au(111) have been prepared from the mixtures by sublimation. The sublimation process has been studied by simultaneous thermogravimetric and differential thermal analyses. Thin fullerene films on Au(111) have been investigated by scanning tunneling microscopy (STM). The STM images show primarily two types of ballshaped molecules arranged in a lattice with hexagonal symmetry (fcc(111) face, nearest neighbour distance: 1 nm). The two species differ in diameter. STM images of films made of mixtures of different C₆₀/C₇₀ ratios show that C₇₀ molecules display a larger apparent diameter (0.8 nm) and corrugation than C₆₀ molecules (0.7 nm). The C₆₀/C₇₀ ratios obtained by counting the corresponding molecular species in the STM images of the thin films are compared to the C₆₀/C₇₀ ratios determined by HPLC on hexane solutions of the mixtures. The observed differences might be explained by different rates of sublimation for the two species. The STM images reveal film defects (vacancies and boundaries) and dynamic processes (displacement of C₇₀ molecules and vacancies). In films prepared to have a C₆₀ coverage of less than one monolayer, stable structural units of the C₆₀(111) surface consisting of three or seven C₆₀ molecules are revealed by STM. Occasionally, substructure within individual fullerene molecules is observed.     

Chemical adsorption of C60 on diamond (100)(2×1) surfaces

Molecular-dynamics simulations (MDSs) and ab initiocalculations are used to investigate the adsorption behavior of C₆₀ molecules on a clean dimer-reconstructed (100)(2×1) diamond surface. C₆₀ molecules have some probability to be adsorbed on the diamond surface at low incident energy (6∼45 eV). Electron-density contours show strong chemical interaction between C₆₀ molecules and the substrate surface. The adsorption property depends strongly on the incident energy and the impacting point. An incident energy of 18 eV may be an appropriate energy to grow a sub-monolayer or monolayer C₆₀ film on a clean C(100)(2×1) surface at room temperature. Received: 5 July 2000 / Accepted: 17 October 2000 / Published online: 28 February 2001     

C60 growth on Si(100), GaSe(0001) and GeS(001)

C₆₀ films have been grown in ultra high vacuum on various crystalline substrates and the structure of the films has been investigated by low energy electron diffraction (LEED) and high resolution electron energy loss spectroscopy (HREELS). The C₆₀ films form randomly oriented nanocrystals on Si(100), mesoscopic polycrystals on GaSe(0001) and microscopic single crystals on GeS(001). The vibrational structure of the C₆₀/substrate interfaces is analyzed in detail by HREELS carried out in the dipole and impact scattering regimes. It is shown that the epitaxy of C₆₀ on GeS(001) is induced by the weak van der Waals bonding and the peculiar corrugation of the substrate surface.     

Sputtering of thin benzene and polystyrene overlayers by keV Ga and C60 bombardment

The mechanisms of ion-stimulated desorption of thin organic overlayers deposited on metal substrates by mono- and polyatomic projectiles are examined using molecular dynamics (MD) computer simulations. A monolayer of polystyrene tetramers (PS4) physisorbed on Ag{1 1 1} is irradiated by 15 keV Ga and C₆₀ projectiles at normal incidence. The results are compared with the data obtained for a benzene overlayer to investigate the differences in sputtering mechanisms of weakly and strongly bound organic molecules. The results indicate that the sputtering yield decreases with the increase of the binding energy and the average kinetic energy of parent molecules is shifted toward higher kinetic energy. Although the total sputtering yield of organic material is larger for 15 keV C₆₀, the impact of this projectile leads to a significant fragmentation of ejected species. As a result, the yield of the intact molecules is comparable for C₆₀ and Ga projectiles. Our data indicate that chemical analysis of the very thin organic films performed by detection of sputtered neutrals will not benefit from the use of C₆₀ projectiles.     

Electronic properties of ultrathin films based on pyrrolofullerene molecules on the surface of oxidized silicon

Results of the investigation into the interface formation during the deposition of the films based on aziridinylphenylpyrrolofullerene (APP-C₆₀) up to 8 nm thick on the surface of the oxidized silicon substrate are presented. The procedure of detecting reflection of testing low-energy electron beam from the surface implemented in the total current spectroscopy mode with a change in the incident electron energy from 0 to 25 eV is used. The structure of maxima in the total current spectra induced by the APP-C₆₀ deposited film is established, and the character of interrelation of these maxima with π* and σ* energy bands in the studied materials is determined. It is revealed due to analyzing the variation in intensities of the total current spectra of the deposited APP-C₆₀ film and the (SiO₂)n-Si substrate that the APP-C₆₀ film is formed at the early deposition stage with the coating thickness thinner than one monolayer without the formation of the intermediate modified organic layer. As the APP-C₆₀/(SiO₂)n-Si interface is formed, the work function of the surface increases by 0.7 eV, which corresponds to the transfer of the electron density from substrate (SiO₂)n-Si toward the film APP-C₆₀. The optical absorption spectra of the APP-C₆₀ films are measured and compared with the spectra of films of unsubstituted C₆₀.     

Electron-energy-loss spectroscopy of C60 monolayer films on active and inactive surfaces

The characteristics of interaction between C₆₀ molecules and Si(1 1 1)-7×7, Ag/Si(1 1 1)-√3×√3 R30° and layered material MoS₂ surfaces have been investigated using electron-energy-loss spectroscopy (EELS). The EEL spectrum of C₆₀/Si(1 1 1)-7×7 shows a new peak at loss energy of 2.7 eV. This indicates the existence of charge transfer from the substrate to C₆₀ molecules. The EEL spectrum of a C₆₀ monolayer film grown on a cleaved surface of MoS₂ is almost the same as that of bulk C₆₀. The EEL spectrum of a C₆₀ monolayer film on an Ag/Si(1 1 1) surface is quite different from that on a clean Si(1 1 1)-7×7 surface, although the films on those substrates have the same epitaxial arrangement. Furthermore, intensities of energy-loss peaks of C₆₀/Ag/Si(1 1 1) are slightly smaller than those of C₆₀/MoS₂ in spite of having the same loss-energy. This suggests that the interaction between C₆₀ molecules and the Ag/Si(1 1 1) surface is stronger than that between C₆₀ molecules and the MoS₂ surface.     

Spectroscopic and atomic force microscopy investigations of hybrid materials composed of fullerenes and 3-aminopropyltrimethoxysilane

Fullerene based materials may open a new horizon in many fields of science. In this study we fabricated thin films of the hybrid materials formed as a result of interactions between C₆₀ fullerenes and 3-aminopropyltrimethoxysilane (APTMS). The deposition technique was a combination of spin-coating and evaporation methods. Interactions within the films were investigated by means of X-ray photoelectron spectroscopy and near edge X-ray absorption fine structure spectroscopy (NEXAFS). Surface morphology was measured by atomic force microscopy (AFM). We found that there are strong chemical reactions between the nucleophilic nitrogen atoms from APTMS and electrophilic fullerene molecules. Results of NEXAFS investigations suggest that due to direct interactions between APTMS and C₆₀ the electronic structure of the fullerene molecules changes while at the same time AFM proved that the C₆₀ molecule diameter is not altered.     

Growth of crystallites consisting of C60 molecules on heated (100)Mo

The initial stages of growth of films of C₆₀ molecules on a (100)Mo surface are studied by high-resolution Auger spectroscopy and atomic force microscopy under ultrahigh vacuum conditions. It is shown that at T<750 K, after a specific coating with molecular density 1.5×310¹⁴ cm⁻², which the authors term a high-temperature (HT) monolayer, has formed on the surface, crystallites in the form of “towers” with flat tops grow on the surface. The fraction of the area occupied by towers depends strongly on the substrate temperature and the flux density of the molecules on the surface but is virtually independent of the exposure time. At temperatures _T>760 K the C₆₀ molecules making up the crystallites desorb, while the molecules making up the HT monolayer decompose, and the carbon released is dissolved in the interior of the substrate. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 12, 969–972 (25 June 1998)     

Thin PTCDA films on Si(0 0 1): 1. Growth mode

We have studied the interface and thin film formation of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA) on clean and on hydrogen passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), near edge X-ray absorption fine structure (NEXAFS), low energy electron diffraction (LEED), and atomic force microscopy (AFM). On the passivated surface the LEED pattern is somewhat diffuse but reveals that the molecules grow in several ordered domains with equivalent orientations to the substrate. NEXAFS shows that the molecules are lying flat on the substrate. The Si 2p XPS line shape is not affected when the film is deposited so it can be concluded that the interaction at the interface between PTCDA and the substrate is weak. The evolution of the film formation appears to be homogeneous for the first monolayer with a nearly complete coverage of flat lying molecules based on the XPS attenuation. For layer thickness of 0.5-2 monolayers (ML) the molecules start to form islands, attracting the molecules in between, leaving the substrate partly uncovered. For thicker films there is a Stranski-Krastanov growth mode with thick islands and a monolayer thick film in between. For the clean surface the ordering of the film is much lower and angle resolved photoelectron spectroscopy (ARPES) of the molecular orbitals have only a small dependence of the emission angle. NEXAFS shows that the molecules do not lie flat on the surface and also reveal a chemical interaction at the interface.     

X-ray pole-figure study of the epitaxial growth of C60 thin films on mica (001)

The growth of epitaxial C₆₀ thin films on mica(001) by thermal evaporation has been studied in detail by X-ray pole-figure measurements. The influence of the deposition rate, the substrate temperature and the film thickness on the in-plane epitaxial arrangements and the formation of twins has been investigated. It has been demonstrated that the C₆₀ growth is determined by two independent and equivalent C₆₀-crystal grain alignments (type-A and type-B). The nearly six-fold symmetry of the mica(001)-substrate surface offers the three-fold fcc-(111)-oriented C₆₀-crystal grains two equivalent crystal alignments. A high deposition rate of 0.5 Å/s is responsible for the formation of twins at a substrate temperature of 150°C, which diminishes by a higher substrate temperature of 200°C. By a decrease of the deposition rate down to 0.08 Å/s the twins vanish at a film thickness of 200 nm and at the substrate temperature of 150°C. Under the same sublimation conditions, in addition to the type-A and type-B crystal orientations, the growth of the thin C₆₀ films starts with a slight fibre texture which does not appear at a larger film thickness.     

Impact of molecular tilt angle on the absorption spectra of pentacene:perfluoropentacene blends

We investigate the relation between the optical properties and the average molecular tilt angle for blends of pentacene and perfluoropentacene, which can be considered as a prototypical donor–acceptor complex. Combining near‐edge X‐ray absorption fine‐structure spectroscopy and optical spectroscopy we study thin films of these compounds prepared at three different substrate temperatures T_sub. For T_sub =180 K we observe a larger average tilt angle than for blends prepared at higher substrate temperatures. This orientational change has significant impact on the uniaxial anisotropic optical properties of the mixed films which we measure post growth as well as in real‐time during growth. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electronic structure of the conduction band upon the formation of ultrathin fullerene films on the germanium oxide surface

The results of the investigation of the electronic structure of the conduction band in the energy range 5–25 eV above the Fermi level E_F and the interfacial potential barrier upon deposition of aziridinylphenylpyrrolofullerene (APP-C₆₀) and fullerene (C₆₀) films on the surface of the real germanium oxide ((GeO₂)Ge) have been presented. The content of the oxide on the (GeO₂)Ge surface has been determined using X-ray photoelectron spectroscopy. The electronic properties have been measured using the very low energy electron diffraction (VLEED) technique in the total current spectroscopy (TCS) mode. The regularities of the change in the fine structure of total current spectra (FSTCS) with an increase in the thickness of the APP-C₆₀ and C₆₀ coatings to 7 nm have been investigated. A comparison of the structures of the FSTCS maxima for the C₆₀ and APP-C₆₀ films has made it possible to reveal the energy range (6–10 eV above the Fermi level E_F) in which the energy states are determined by both the π* and σ* states and the FSTCS spectra have different structures of the maxima for the APP-C₆₀ and unsubstituted C₆₀ films. The formation of the interfacial potential barrier upon deposition of APP-C₆₀ and C₆₀ on the (GeO₂)Ge surface is accompanied by an increase in the work function of the surface E_vac–E_F by the value of 0.2–0.3 eV, which corresponds to the transfer of the electron density from the substrate to the organic films under investigation. The largest changes occur with an increase in the coating thickness to 3 nm, and with further deposition of APP-C₆₀ and C₆₀, the work function of the surface changes only slightly.     

Permeability of C60 films deposited on polycarbonatesyloxane to N2, O2, CH4, and He gases

In this study, we report on the gas permeability of non-polymerized and polymerized fullerene films (thickness about 0.5 μm) grown on an organic polymer substrate, polycarbonatesyloxane (PCS), using a high vacuum deposition method. The photopolymerized C₆₀ films were prepared by a simultaneous thin film deposition and UV-vis irradiation method which was reported previously [V.A. Karachevtsev, P.V. Mateichenko, N.Y. Nedbailo, A.V. Peschanskii, A.M. Plokhotnichenko, O.M. Vovk, E.N. Zubarev, A.M. Rao, Carbon 42 (2004) 2091]. Raman spectroscopy revealed that ∼90% of the C₆₀ molecules are covalently linked to neighboring C₆₀ molecules in the photopolymerized film after 20 h of film deposition/irradiation. Permeability of the resulting membranes consisting of polymer PCS base and fullerene films to the N₂, O₂, CH₄, and He gases has been investigated. Our experiments revealed that the gas permeability properties are dependent on the age of the membrane. In particular, the aged membrane exhibited an enhanced permeability for O₂ and He gases in comparison to N₂ and CH₄, respectively.     

Electronic non-equilibrium conditions at C60–pentacene heterostructures

The electronic structure of vacuum-sublimed layered organic heterostructures of pentacene (PEN) and fullerene (C₆₀) on conducting polymer substrates was investigated using ultraviolet photoelectron spectroscopy (UPS). The conditions at the PEN/C₆₀interface changed from thermodynamic non-equilibrium (i.e. the onset of the PEN highest occupied molecular orbital above the substrate Fermi-energy) for thin PEN coverages on C₆₀ to thermodynamic equilibrium for thicker PEN coverages (i.e. Fermi-level pinning of PEN). This finding is attributed to a coverage-dependent pinhole connection of PEN through the C₆₀ layer with the substrate. The experiments demonstrate the importance of organic thin film morphology for UPS measurements to assess the energy level alignment at organic/organic heterointerfaces.     

Molecular simulation of C60 adsorption onto a TiO2 rutile (1 1 0) surface

A Monte Carlo molecular simulation study is presented on the adsorption and growth of C₆₀ films on the surface of the (1 1 0) face of rutile. Simulations are performed for a temperature of 600 K using atomistic models both for the fullerene molecules and the TiO₂ surface. It is found in this work that C₆₀ is adsorbed preferably in an ordered arrangement along the surface depressions over the exposed undercoordinated Ti cations. At low densities adsorption occurs preferably at alternate rows, with locations in consecutive rows being occupied appreciably only at higher C₆₀ densities. At low densities, the fullerene molecules tend to aggregate into islands in the surface plane. Additional layers of C₆₀ form only as the density increases, and do so before a monolayer is completed in all consecutive rows. Full monolayer capacity obtained at the highest densities is about 0.9 C₆₀ molecules per nm², but this is only achieved by completing the packing of molecules in interstices at a slightly upper level. The fraction of the molecules that lie closest to the surface only amounts to 0.6 molecules per nm².     

Double-pulse laser ablation applied to reactive PLD method for synthesis of carbon nitride film: A second laser shot delay

Carbon nitride films were deposited using ablation of graphite target by second harmonic radiation of Nd:YAG laser in nitrogen atmosphere. To produce high hardness films, the deposited particles should have sufficient kinetic energy to provide their efficient diffusion on a substrate surface for formation of crystal structure. However, a shock wave is arisen in ambient gas as a consequence of laser plasma explosive formation. This shock wave reflected from the substrate interacts with plume particles produced by the first laser pulse and decreases their kinetic energy. This results in decrease of film crystallinity. To improve film quality, two successive laser pulses was proposed to be used. At adjusting time delay, the particles induced by the second pulse wilt serve as a piston, which will push forward both stopped particles ablated by the first pulse and arisen from chemical reactions in ambient gas. An X-ray photoelectron spectroscopy (XPS) analysis of deposited films has shown an increase of content of sp ³ carbon atoms corresponding to crystalline phase, if double-pulse configuration is employed. The luminescence of excited C₂ and CN molecules in laser plume at different distances from the target was studied to optimize the delay between laser pulses.     

Grain Boundary Diffusion in C<Subscript>60</Subscript> Thin Films

This paper focuses on the effect of grain boundaries on the diffusion processes in polycrystalline C₆₀ thin films. Electrically induced diffusion of Au was investigated by in situ measurements of the film conductivity. Electron Paramagnetic Resonance (EPR) spectroscopy was used to study diffusion of oxygen. Increase in grain sizes in polycrystalline C₆₀ thin films was found to result in the acceleration of gold and oxygen diffusion. The results are interpreted assuming that these impurities diffuse in C₆₀ films dominantly along grain boundaries.     

Epitaxial C60 thin films on Bi(0 0 0 1)

We have used the Bi(0 0 0 1)/Si(1 1 1) template to grow highly ordered C₆₀ epitaxial thin films and analyzed them using scanning tunneling microscopy and low-energy electron microscopy. The in situ low-energy electron microscope investigations show that the initial nucleation of the C₆₀ islands on the surface takes place at surface defects, such as domain boundaries and multiple steps. The in-plane lattice parameters of this C₆₀ film turns out to be the same as that of the bulk fcc(1 1 1) C₆₀. The line-on-line epitaxial structure is realized in spite of a weak interaction between the C₆₀ molecules and Bi(0 0 0 1) surface, while scanning tunneling spectroscopy indicates that there is a negligible charge transfer between the molecules and the surface.     

Structural and optical properties of electrodeposited molybdenum oxide thin films

Electrosynthesis of Mo(IV) oxide thin films on F-doped SnO₂ conducting glass (10-20/Ω/□) substrates were carried from aqueous alkaline solution of ammonium molybdate at room temperature. The physical characterization of as-deposited films carried by thermogravimetric/differential thermogravimetric analysis (TGA/DTA), infrared spectroscopy and X-ray diffraction (XRD) showed the formation of hydrous and amorphous MoO₂. Scanning electron microscopy (SEM) revealed a smooth but cracked surface with multi-layered growth. Annealing of these films in dry argon at 450 °C for 1 h resulted into polycrystalline MoO₂ with crystallites aligned perpendicular to the substrate. Optical absorption study indicated a direct band gap of 2.83 eV. The band gap variation consistent with Moss rule and band gap narrowing upon crystallization was observed.Structure tailoring of as-deposited thin films by thermal oxidation in ambient air to obtain electrochromic Mo(VI) oxide thin films was exploited for the first time by this novel route. The results of this study will be reported elsewhere.