Wetting-Dewetting oscillations of liquid films during solution-mediated vacuum deposition of rubrene

We found a novel oscillating phenomenon associated with surface wetting during the vacuum deposition of an organic semiconductor (rubrene) on a liquid film (bis(2-ethylhexyl)sebacate, B2EHS). In-situ observations by an optical microscope revealed that the oscillation was associated with the growth of the rubrene crystals. The oscillation frequency was proportional to the evaporation rate of rubrene. On the basis of the contact angle measurements, it was concluded that the oscillation is probably due to the change in the contact angle of the liquid caused by the formation of ultrathin rubrene films on the liquid surface.     

Spectroscopic and microscopic investigations of organic ultrathin films: Correlation between geometrical structures and unoccupied electronic states

In this review, we summarize recent progress in experimental approaches to the investigation of the unoccupied electronic structures of organic ultrathin films, based on a combination of spectroscopic and microscopic techniques. At the molecule/substrate interface, electronic structures are greatly affected by the geometrical structures of adsorbed molecules. In addition, a delicate balance between substrate-molecule and intermolecular interactions plays an important role in the formation of complex polymorphism. In this context, we have clarified the correlation between geometric and electronic structures using a combination of two-photon photoemission (2PPE) spectroscopy, low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Organic ultrathin films of metal phthalocyanines and polycyclic aromatic hydrocarbons (naphthalene, rubrene and perylene) on graphite substrates were examined as model systems. Depending on the substrate temperature and coverage, unique morphologies, including well-ordered films, a metastable phase and a two-dimensional gas-like phase, were determined at the molecular level. The data show that variations in molecular orientation have a significant impact on the occupied/unoccupied electronic structures. In addition to static information regarding electronic states, ultrafast electron excitation and relaxation dynamics can be tracked in real time on the femtosecond scale by time-resolved 2PPE spectroscopy. The excited electron dynamics of rubrene films are discussed herein, taking into account structural information, in the presence and absence of an overlap of the wave function with the substrate. Spatial resolution at the molecular level is also obtainable via STM-based local spectroscopy and mapping, which have been utilized to elucidate the spatial extent of unoccupied orbitals in real space. Visible photon emissions from the unoccupied states of perylene monolayer films were observed using 2PPE, representing a characteristic deexcitation process from electronically excited states, depending on the surface structure. These spectroscopic and molecular level microscopic investigations provide fundamental insights into the electronic properties of organic/substrate interfaces.     

Growth of crystalline rubrene films with enhanced stability

The growth of well-oriented crystalline films of rubrene (C42H28) on SiO2 and Au111 substrates is achieved by employing "hot wall" deposition whereas organic molecular beam deposition (OMBD) only yields rather amorphous layers or poly-crystalline dendritic networks at elevated temperature. This pronounced difference in film growth is related to the conformational change of rubrene molecules involving a loss of chirality upon crystallization and the enhanced diffusion which becomes possible at high temperature and large vapor pressure. Moreover, it is demonstrated that the crystalline rubrene films reveal an enhanced thermal and chemical stability as compared to the OMBD grown films.     

Rubrenes: planar and twisted

Surprisingly, despite its very high mobility in a single crystal, rubrene shows very low mobility in vacuum-sublimed or solution-processed organic thin-film transistors. We synthesized several rubrene analogues with electron-withdrawing and electron-donating substituents and found that most of the substituted rubrenes are not planar in the solid state. Moreover, we conclude (based on experimental and calculated data) that even parent rubrene is not planar in solution and in thin films. This discovery explains why high mobility is reported in rubrene single crystals, but rubrene shows very low field-effect mobility in thin films. The substituted rubrenes obtained in this work have significantly better solubility than parent rubrene and some even form films and not crystals after evaporation of the solvent. Thus, substituted rubrenes are promising materials for organic light-emitting diode (OLED) applications.     

Roughening of gold atomic steps induced by interaction with tetrahydrofuran

Exposure of a clean gold surface to tetrahydrofuran (THF) under ambient conditions was observed to cause roughening of atomic step edges. This change was followed in situ using a scanning tunneling microscope during the exposure of a gold surface to a controlled stream of THF vapor. THF is a common solvent used in depositing molecules, self-assembled monolayers, and polymer films on surfaces, in electrochemistry, and in chemical reactions. Unlike other solvents, such as methanol, ethanol and diethyl ether, however, we found that THF itself has a profound effect on the surface morphology that needs to be taken into account when reporting on the interactions of solutes with a gold surface. At the same time, this finding may present new opportunities in catalysis or nanostructuring of surfaces.     

Fluorescent organic nanocrystal confined in sol–gel matrix for bio-imaging

The sol–gel chemistry combined to a spray-drying process allowed us to control the formation of original hybrid core–shell nanoparticles constituted by molecular nanocrystals of rubrene embedded in biocompatible silicate spheres. With a good management of all the physical (gas flows, temperatures) and chemical (dye, solvent and alkoxide natures, concentrations, and hydrolysis and condensation conditions) parameters, we optimized a one-step and self-assembly process allowing to obtain nanoparticles exhibiting promising optical properties such as highly fluorescent labels (two-photon excitation) for medical imaging. Moreover, the presence of Si–OH functions on the silicate shell surface make easy to functionalize these fluorescent nanoparticles by grafting biomolecules for targeting properties. The confined nucleation and growth of rubrene nanocrystals in sol–gel silicate spheres during their drying in the air laminar flows, prevents any phase segregation or particle coalescence and stabilizes mechanically and chemically the organic cores. The first particle sizes obtained in these first experiments are ranging between 80 and 600 nm, but lower diameters will be easily prepared by increasing the solvent amount. Transmission electron microscopy was used to characterize the rubrene organic cores. The electron diffraction patterns performed at 100 K, under low-dose illumination to avoid amorphization of the samples during electron irradiation, have shown the good crystallinity of the NP rubrene cores that seem to be constituted by single rubrene nanocrystals. Finally, optical confocal microscopy, used in reflection and fluorescence modes, showed that all the core–shell particles are strongly fluorescent. This high fluorescence intensity arises from the high molecule numbers of rubrene nanocrystals, which enhance the absorption and emission cross sections.     

Ultrathin monolayer of rubrene on Au(111) induced by charge transfer

An ultrathin self‐assembly monolayer of rubrene on Au(111) has been fabricated and studied by scanning tunneling microscopy. The apparent thickness of such monolayer is 0.08 nm and close to the radius of a carbon atom. Moreover, the rubrene molecules within the second layer prefer adsorbing on to the positions corresponding to the herringbone structure underneath the Au(111)–() while the Au surface is fully covered by a monolayer of rubrene. With the assistant with theoretical simulations, we reveal that small apparent height of such monolayer is due to the coupling between the molecular orbitals and the gold surface. About 0.237 electron per rubrene molecule is transferred to the surface, and as a consequence, an interfacial dipole is formed on the rubrene/Au interface. The formation of such interfacial dipole induced by charge transfer from molecules to surfaces is believed to be applied in organic molecules adsorbed on metal surfaces. Copyright © 2011 John Wiley & Sons, Ltd.     

在半金属表面上应力诱导的红荧烯晶态薄膜

报道了在Bi（001）衬底上从第一层开始形成的红荧烯晶体薄膜.随着覆盖度的增加,红荧烯薄膜的结构会发生从自组装到混合相的转变.在混合相中存在着红荧烯的晶体畴和分子自组装形成的畴壁.特别是,我们在这种晶体畴中发现了Kurdjunov-Sachs（KS）转动外延和巨大的压缩应力.随着覆盖度的增加,红荧烯薄膜会按照逐层生长的模式进行,直至第四个分子单层.我们认为,转动外延过程中所产生的巨大压缩应力是导致晶态红荧烯薄膜的形成原因.     

Molecular assembly of rubrene on a metal/metal oxide nanotemplate

We investigated the adsorption properties and self-assembly of rubrene molecules on the copper oxide nanotemplate formed by high-temperature exposure of Cu(110) to molecular oxygen. Using high-resolution scanning tunneling microscopy under ultrahigh-vacuum conditions, we observed a complex variety of self-assembled motifs, driven by competing effects such as the chemical affinity between the organic molecule and the surface, surface coverage, and spatial confinement of the rubrene molecules within the rows of the template.     

Oligomer orientation in vapor-molecular-layer-deposited alkyl-aromatic polyamide films

The surface-limited molecular-layer deposition of alkyl-aromatic polyamide films using sequential doses of 1,4-butane diamine (BDA) and terephthaloyl dichloride (TDC) is characterized using in situ quartz crystal microbalance and ex situ spectroscopy analysis. For the first time, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to offer insight into molecular orientation in films deposited via molecular-layer deposition (MLD). The results show that the oligomer units are lying nearly parallel to the surface, which differs from the linear vertical growth mode often used to illustrate film growth.     

Boundary layer chemistry probed by in situ infrared spectroscopy during SiO2 deposition at atmospheric pressure from tetraethylorthosilicate and ozone

The deposition of silicon dioxide films at 450 degrees C was studied in quasi real time by probing the thermally activated boundary layer region near the growing surface during atmospheric pressure chemical vapor deposition (APCVD). Potential tetraethylorthosilicate (TEOS)/O(3) reaction products have been investigated in an attempt to clarify the reaction mechanism leading to the observed silanol deposition intermediates and delineate the film formation process. The organic products formed during the TEOS/O(3) reaction are acetic acid, formic acid, formaldehyde, carbon monoxide, carbon dioxide, and water. Quantitative methods are developed using FT-IR (Fourier transform infrared) spectroscopy during ozonation of TEOS at elevated temperatures. The measurement of gaseous alcohols of silicon alkoxides by FT-IR is demonstrated by application of an in situ methodology that probes the high-temperature region within the CVD environment. Partial least squares (PLS) Beer's law absorption models are used in determining relative TEOS, ozone, and ethoxysilanol levels during the reaction. The reaction order in TEOS is measured at 1.65 +/- 0.02 over a 0.9 Torr pressure range. Similarly, the ratio of ethoxysilanol formed versus the amount of ozone consumed is ca. 1:3. A radical chain oxidative mechanism involving direct reaction of TEOS and ozone is proposed for formation of highly reactive silanol film growth intermediates.     

Growth-related properties and postgrowth phenomena in organic molecular thin films

The problem of monitoring the structural and morphological evolutions of thin films of organic molecular materials during their growth by organic molecular beam epitaxy and in the postgrowth stage is addressed here by a combination of in situ optical reflectance anisotropy measurements, ex situ optical and morphological investigations, and theoretical simulation of the material optical response. For alpha-quaterthiophene, a representative material in the class of organic molecular semiconductors, the results show that molecules crystallize in the first stage of growth in metastable structures, even when deposition is carried out at room temperature. In the postdeposition stage, the film structure evolves within a few days to the known equilibrium structure of the low temperature polymorph. When deposition is carried out at low substrate temperatures, an evolution of the film morphology is also demonstrated.     

Dynamics of vacancy defects in 2-D crystalline monolayers under chiral smectic thin films studied by scanning tunnelling microscopy

Scanning tunnelling microscopy (STM) can be used to image adsorbed organic molecules in real space and real time. The technique seems especially well suited for imaging 2-D crystalline monolayers formed under liquid crystal films. In addition to observing perfect 2-D crystals, STM provides the ability to observe crystal defects, and to observe how these defects evolve over time. In this study two different vacancy defects in 2-D lamellar monolayers of chiral liquid crystal molecules under bulk smectic films were observed in situ. Both vacancies showed dynamic behaviour and an unexpected transport anisotropy.     

Formation, structure, and reactivity of amino-terminated organic films on silicon substrates

Amino-functionalized organic films were prepared by self-assembling 3-aminopropyltriethoxysilane (APTES) on silicon wafers in either anhydrous toluene or phosphate-buffered saline (PBS) for varied deposition times. Fourier transform infrared spectroscopy (FTIR) and ellipsometry have shown that the structure and thickness of APTES films are governed by the deposition time and reaction solution. Deposition from an anhydrous toluene solution produces APTES films ranging from 10 to 144 A in thickness, depending on the reaction time. FTIR spectra indicate that film growth initially proceeds by adsorption of APTES to the silicon surface followed by siloxane condensation, and after an extended period of time APTES molecules accumulate on the underlying APTES film by either covalent or noncovalent interactions. In contrast, spectroscopically indistinguishable APTES films in thickness ranging from 8 to 13 A were formed when deposition was conducted in aqueous solutions. Measured water contact angles indicate that APTES films deposited in aqueous solutions are more hydrophilic compared to those prepared in toluene solutions. Fluorescence measurements revealed that APTES films prepared in toluene solutions contain more reactive surface amino groups by ca. 3 to 10 times than those prepared in aqueous solutions for the identical reaction time.     

Investigation of Structure and Growth of Self-Assembled Polyelectrolyte Layers by X-ray and Neutron Scattering under Grazing Angles

The structure of self-assembled polyelectrolyte thin films on float glass has been investigated by interface sensitive X-ray and neutron scattering methods. Special emphazis was given to the adsorption process of poly (ethylene imine) and polystyrole sulfonate as an important model system which is often used as a basis for subsequent multilayer buildup. From complementary X-ray and neutron reflectivity data, the vertical film density profile was derived for various growth parameters, including kinetic effects of different adsorption times. In addition to specular reflectivity, we have for the first time employed nonspecular X-ray scattering to study lateral structure parameters in self-assembled polyelectrolyte films. Furthermore, the technique of time-resolved in situ X-ray reflectivity during film growth has been demonstrated and is discussed in view of its future potential. Copyright 2000 Academic Press.     

A high-resolution near-edge x-ray absorption fine structure investigation of the molecular orientation in the pentacene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) pentacene/system

We present x-ray photoemission spectroscopy and highly resolved near-edge x-ray absorption fine structure spectroscopy measurements taken on pentacene thin films of different thicknesses deposited on a spin coated poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) substrate. Thin films of pentacene were prepared by using organic molecular beam deposition in situ using strictly controlled evaporation conditions. Our investigations show that pentacene thin films on PEDOT:PSS are characterized by upright standing molecules. Due to the strong dichroic behavior, the calculated values of the molecular orientation give a clear indication not only of the real molecular arrangement in the films but also of a high orientational order. This high degree of molecular orientation order is a characteristic already of the first layer. The films show the tendency to grow on the PEDOT:PSS substrate following an island-fashion mode, with a relatively narrow intermixing zone at the interface between the pentacene and the polymer blend. The peculiarity of the growth of pentacene on PEDOT:PSS is due to the fact that the substrate does not offer any template for the nucleated films and thus exerts a lateral order toward the crystal structure arrangement. Under these conditions, the upright orientation of the molecules in the films minimizes the energy required for the system stability.     

Gas-surface reactions between pentakis(dimethylamido)tantalum and surface grown hyperbranched polyglycidol films

We have investigated the growth of hyperbranched polyglycidol films, and their subsequent reaction with a transition metal coordination complex, pentakis(dimethylamido)tantalum, Ta[N(CH 3) 2] 5 using ellipsometry, contact angle measurements, atomic force microscopy and X-ray photoelectron spectroscopy (XPS). Up to thicknesses of approximately 150 A, the growth of polyglycidol is approximately linear with reaction time for growth activated using either sodium methoxide or an organic superbase. The reaction of Ta[N(CH 3) 2] 5 at room temperature with these layers depends strongly on their thickness--the amount of uptake of Ta by the surface increases with the thickness of the organic layer, and thicker films also lead to more extensive ligand exchange reactions (with the R-OH groups), with as many as 4 ligands being lost on the thicker organic films. Ta penetrates the surface of all films examined (thicknesses 30-84 A), but the average depth of the penetration is nearly independent of the thickness of the organic film, and it is approximately 15-25 A. Modification of the polyglycidol with an aminoalkoxysilane introduces a significant fraction of -NH 2 termination in the organic layer. Reactions of this layer with the Ta complex are quite different than those on an unmodified layer--now on average only a single ligand exchange reaction occurs, while on the unmodified surface as many as four ligands are exchanged.     

Stability of thin film glasses of toluene and ethylbenzene formed by vapor deposition: an in situ nanocalorimetric study

Vapor deposited thin films (~100 nm thickness) of toluene and ethylbenzene grown by physical vapor deposition show enhanced stability with respect to samples slowly cooled from the liquid at a rate of 5 K min(-1). The heat capacity is measured in situ immediately after growth from the vapor or after re-freezing from the supercooled liquid at various heating rates using quasi-adiabatic nanocalorimetry. Glasses obtained from the vapor have low enthalpies and large heat capacity overshoots that are shifted to high temperatures. The stability is maximized at growth temperatures in the vicinity of 0.8 T(g) for both molecules, although glasses of ethylbenzene show superior stabilization. Our data is consistent with previous results of larger organic molecules suggesting a generalized behavior on the stability of organic glasses grown from the vapor. In addition, we find that for the small molecules analyzed here, slowing the growth rate below 0.1 nm s(-1) does not result in increased thermodynamic stability.     

Effect of dielectric roughness on performance of pentacene TFTs and restoration of performance with a polymeric smoothing layer

The morphology, structure, and transport properties of pentacene thin film transistors (TFTs) are reported showing the influence of the gate dielectric surface roughness. Upon roughening of the amorphous SiO2 gate dielectric prior to pentacene deposition, dramatic reductions in pentacene grain size and crystallinity were observed. The TFT performance of pentacene films deposited on roughened substrates showed reduced free carrier mobility, larger transport activation energies, and larger trap distribution widths. Spin coating roughened dielectrics with polystyrene produced surfaces with 2 A root-mean-square (rms) roughness. The pentacene films deposited on these coated surfaces had grain sizes, crystallinities, mobilities, and trap distributions that were comparable to the range of values observed for pentacene films deposited on thermally grown SiO2 (roughness also approximately 2 A rms).     

Surface polymerization by ion-assisted deposition for polythiophene film growth

Cationic polymerization is induced at the gas-solid interface by hyperthermal organic cations coincident on a surface with a thermal beam of organic monomers. This process, termed surface polymerization by ion-assisted deposition (SPIAD), produces films that maintain the chemical structure of the monomer. A polythiophene film is produced here by SPIAD with 100 eV thiophene ions and terthiophene monomers coincident on Si and indium tin oxide (ITO) substrates held under vacuum. X-ray photoelectron spectroscopy observes enhancement in film growth for SPIAD compared with either thiophene ion or terthiophene exposure alone. Polythiophene films grown by both mass-selected and nonmass-selected ions with coincident terthiophene dosing both display similar fluorescence intensities at two wavelengths characteristic of emission from films of the terthiophene monomer. Raman spectra of films from nonmass-selected ions display several vibrations also observed in terthiophene films. Ions therefore play a critical role in film growth from nonmass-selected ions, in addition to any radical or photochemically driven processes that may also occur.