Luminescence of molecules adsorbed on surfaces of wide gap materials

We report on the photoluminescence spectra of thin films of chain-like π-conjugated molecules on well-defined surfaces of wide gap inorganic materials. The aim is to study the energy transfer processes across the organic/substrate interface which limit the luminescence of molecules in close contact to substrate surfaces. We discuss quaterthiophene (4 T) adsorbed on the c(2×2)-ZnSe(0 0 1) surface and tetracene (Tc) on the surface of a thin epitaxial Al₂O₃ film on Ni₃Al(1 1 1). For thin films vapor-deposited at low substrate temperatures, we observe no luminescence signal for both systems, which indicates the presence of fast luminescence quenching processes at the organic/inorganic interface. After annealing, luminescence spectra corresponding to those of the bulk crystals are obtained. This can be explained by the formation of 3D-crystallites, which effectively separate most molecules from the organic/inorganic interface.     

Determination of the Refractive Index of Dielectrics by Means of Light‐Induced Diffraction Gratings

Consideration is given to the possibilities of measuring the refractive index n of dielectric samples by means of spontaneous gratings produced by an spolarized laser beam in a photosensitive thin film applied to a sample in vacuum. With the specific choice of the film thickness, the value of n is determined from diffraction measurements of the period of a spontaneous grating with the error n = ±0.002. The method allows measurement of n isotropic and anisotropic samples within the range 1.32.5 on plane and cylindrical surfaces with the area determined by the section of the laser beam that induces the spontaneous grating. Examples of measurements of n on plane surfaces of glasses, a LiNbO₃ crystal, and on the cylindrical surface of a ruby rod are presented.     

Structural ripple formation in Ge/Sb multilayers induced by laser irradiation

Thin multilayer films (Ge/Sb/Ge/Sb/Si substrate) have been irradiated with single nanosecond laser pulses (=193 nm). Real-Time Reflectivity (RTR) measurements have been used to follow the transformation in situ and cross-sectional transmission electron microscope analysis was used to study both the microstructure and the composition profile before and after irradiation. Melting and mixing are both found to nucleate at preferential sites in the upper Ge/Sb interface. During this process the film surface topography changes in a way not previously seen, and rippling of the film is observed due to lateral mass flow induced in the Sb layer underneath the surface, most probably arising from volume changes upon melting. For the highest irradiation energy densities, melting of the whole multilayer configuration takes place, the ripples are no longer observed, and following cooling and solidification, a mixed amorphous GeSb film is formed.     

The reactions of acetone with the surfaces of uranium dioxide single crystal and thin film

The reaction of acetone, as an example of a carbonyl compound, is studied over UO₂ (1 1 1) single crystal and thin film surfaces. Over the stoichiometric single crystal surface, acetone is molecularly and weakly adsorbed with a computed activation energy for desorption in the range of 95-65 kJ/mol with pre-exponential factors between 10¹¹ and 10¹³ s⁻¹. On the contrary, acetone reacts very strongly on the O-defected single crystal and thin film surfaces. In addition to total decomposition evidence of aldolization and cyclization reactions were seen. The thin film of UO₂ was studied by synchrotron light, providing high resolution photoelectron spectroscopy in the core level, and high sensitivity in the both the core and valence band regions. The U5f line was considerably enhanced at grazing angle when compared to that obtained at normal angle for the O-defected surface, showing that the surface is more reduced than the next layers. The U 4f lines indicated the presence of U cations in lower oxidation states than +4 for the O-defected surface. These lines were considerably attenuated upon adsorption of acetone, due to surface oxidation by CO bond dissociation. The reaction pathway for acetone on the O-defected surface is presented, and compared to that of the previously studied acetaldehyde molecule.     

Surface states on the (100) plane of a sphalerite-type crystal

The surface states of an ideal (100) plane of a sphalerite-type crystal were studied in the one-electron approximation; both the plane formed by electronegative atoms (>0) and that consisting of electropositive atoms (<0) were investigated. The interpretation of surface states whose energy lies in the gap is the same as for the diamond-like lattice. The influence of electro-negativity or electropositivity of the surface on the position of these states in the gap was investigated and possible consequences of these states joining one of the energy bands of volume states were pointed out. The results of this paper can be used to discuss correlation effects on the (100) plane of a diamond-like crystal.     

Interface effects on the quantum well states of Pb thin films

Using scanning tunneling spectroscopy, we have studied the interface effect on quantum well states of Pb thin films grown on various metal-terminated (Pb, Ag, and Au) n-type Si(111) surfaces and on two different p-type Si(111) surfaces. The dispersion relation E(k) of the electrons of the Pb film and the phase shift at the substrate interface were determined by applying the quantization rule to the measured energy positions of the quantum well states. Characteristic features in the phase shift versus energy curves were identified and were correlated to the directional conduction band of the silicon substrate and to the Schottky barrier formed between the metal film and the semiconductor. A model involving the band structure of the substrate, the Schottky barrier, and the effective thickness of the interface was introduced to qualitatively but comprehensively explain all the observed features of the phase shift at the substrate interface. Our physical understanding of the phase shift is critically important for using interface modification to control the quantum well states.     

P-Polarized nonlinear surface polaritons in layered structures

We found an exact solution of Maxwell's equations, which describes the propagation ofp-polarized nonlinear surface polaritons and ofp-polarized nonlinear guided wave polaritons in two cases:i) in a film of a surface active material placed on a substrate described by a diagonal dielectric tensor whose elements depend on the amplitude of the electric field according to _{1 1}=_{2 2}= + (|E ₁|² + |E ₂|²), _{3 3}=, andii) in a film described by the same dielectric tensor (optically uniaxial nonlinear crystal) placed on a substrate with dielectric constant ₃ (optically linear medium). The power carried in the surface waves has also been exactly calculated.     

Synthesis and characterization of silanized-SiO2/povidone nanocomposite as a gate insulator: The influence of Si semiconductor film type on the interface traps by deconvolution of Si2s

The polymer nanocomposite as a gate dielectric film was prepared via sol-gel method. The formation of cross-linked structure among nanofillers and polymer matrix was proved by Fourier transform infrared spectroscopy (FT-IR). Differential thermal analysis (DTA) results showed significant increase in the thermal stability of the nanocomposite with respect to that of pure polymer. The nanocomposite films deposited on the p- and n-type Si substrates formed very smooth surface with rms roughness of 0.045 and 0.058 nm respectively. Deconvoluted Si_2s spectra revealed the domination of the SiOH hydrogen bonds and SiOSi covalence bonds in the structure of the nanocomposite film deposited on the p- and n-type Si semiconductor layers respectively. The fabricated n-channel field-effect-transistor (FET) showed the low threshold voltage and leakage currents because of the stronger connection between the nanocomposite and n-type Si substrate. Whereas, dominated hydroxyl groups in the nanocomposite dielectric film deposited on the p-type Si substrate increased trap states in the interface, led to the drop of FET operation.     

Insulating properties of ultrathin KF layers on Cu(1 0 0): Resonant Auger spectroscopy

Solid-state effects in the creation and decay of K 2p core excitations in thin KF films on Cu(1 0 0) surface have been studied in resonant Auger spectra, excited using synchrotron radiation. The spectra of films of various thickness starting from a single monolayer were measured.The photoabsorption spectra reveal crystal field splitting already at film thickness of about 1 monolayer. The Auger decay spectra of the K 2p⁻¹3d core excitations in films of thickness up to 2 monolayers exhibit a band characteristic of the decay of core ionised states, showing that the excited electron delocalises into substrate before the core hole decays. In thicker films the coexistence of the decay of excited states in the bulk of the KF crystalline film and of ionised states at the KF-metal interface is observed, indicating that the charge transfer probability from the upper layers of the film into the metallic substrate is strongly reduced.     

Structure and Polarization Relaxation of Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript>/(001)Si Films

The structure and dielectric characteristics of strontium barium niobate thin films deposited on single-crystalline silicon substrates without buffer layers are studied. It is found that the c axis in these heterostructures runs largely normally to the substrate surface and the a and b axes are randomly oriented in the plane of the substrate. The polarization relaxation in such heterostructures is investigated. It is shown that the film–substrate interface in the heterostructures grown by rf cathode sputtering may contain a low amount of long-lived charged defects.     

Theory of chemisorption

We determine the electronic structure of a semiinfinite crystal with a general coverage by adatoms, if there exists a partial order described by the long-range order parameter5. The tight-binding formalism is used, the presence of the surface is included via the surface Green function method, and the effect of disorder is described by a version of the coherent potential approximation. The local densities of states at/near the surface as well as the interaction energy of adatoms are calculated as functions of the coverage, and the long-range order parameterS. The numerical examples modelling the cases of a gas adsorption on the transition metal surfaces as well as the transition metal atoms on the transition metal surfaces, are investigated.     

Computer simulation of interdiffusion in polycrystalline thin film couples

Computer simulation of superimposed lattice, grain boundary and surface diffusion, characteristic for polycrystalline thin film diffusion systems, was performed by way of discretisation of the nonlinear diffusion law. In order to give a vivid impression how such a complex process takes place under some typical conditions we have chosen pseudo three-dimensional computer plots of the spacial distribution of the concentration instead of the commonly used iso-concentration diagrams. The following cases are considered:

Electrostatic and electromagnetic surface shape resonances

The homogeneous integral equations that give the electromagnetic field in the vicinity of a protuberance or a depression on the otherwise planar interface with vacuum of a semi-infinite dielectric medium or a thin dielectric film on a semi-infinite substrate have been obtained. The Rayleigh hypothesis, the vectorial equivalent of the Kirchhoff integral, and the extinction theorem have been used for this purpose. The assumption that the perturbation of the vacuum dielectric interface has cylindrical symmetry about the normal to the nominal surface allows a significant simplification of these integral equations to be carried out. We have used Gaussian quadrature schemes to convert the resulting integral equations into matrix equations, and have obtained the frequencies of the shape resonances by equating to zero the determinants of the matrices obtained. Calculations have been carried out for Gaussian (x ₃=Aexp(–x ² /R ²)) and exponential (x ₃=Aexp(–x /R)) surface profiles, and convergent results obtained for values ofA/R of the order of unity.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

Intermolecular Electronic Energy Transfer in the Gas Phase

The kinetics of triplet-triplet energy transfer in the gas phase has been studied for various donor-acceptor pairs of aromatic hydrocarbons and ketones. For all the donor-acceptor pairs investigated the triplet-triplet energy transfer efficiencies are much lower than unity. The triplet triplet energy transfer was used to gain insight into the paths of intramolecular excitation energy degradation in benzophenone and anthraquinone vapours and to obtain sensitized anti-Stokes annihilation delayed fluorescence of vapours of anthracene and its derivatives.

The intermolecular triplet-triplet transfer (T-T transfer) of excitation energy and sensitized phosphorescence were first discovered in 1952 by Terenin and Yermolayev in organic solutions¹. Later these phenomena became known for liquid solutions², crystals³, and also for vapours^4-10. And though the nature of interactions underlying the T-T energy transfer phenomena in different aggregate states is the same, a number of specific features is observed in the vapour phase. The study of these processes makes it possible to obtain additional information on interacting molecules.     

Tailoring of the spectral–directional characteristics of rare-earth fluorescence by metal–dielectric planar structures

It is demonstrated that the spectrum, direction and polarization of rare-earth fluorescence can be tailored by embedding the impurity ions into a planar metal–dielectric structure (MDS). The latter was designed by spin coating a rare-earth-doped oxide film (TiO₂:Sm³⁺) onto a gold-covered glass substrate. For spectral–directional investigations of Sm³⁺ fluorescence, the MDS was attached to a semi-cylindrical prism and excited by UV light from the flat side. An angular scan revealed a strongly polarized and directional emission of Sm³⁺ from the convex side of the prism. The tuning of TiO₂ film thickness in the MDS allows a control of the polarization and direction of the emission bands. A theoretical modeling of the reflectivity of the MDS suggests that the observed angular resonances in the fluorescence emission are caused by its effective coupling with surface plasmons on the gold–dielectric interface or coupling with leaky modes in sufficiently thick dielectric films working as a waveguides.     

Initial growth at the F16CoPc/Ag(111) interface

An extended, combined (STM/STS)–(UPS/XPS) study was carried out towards a comprehensive understanding of the mechanism responsible for the F₁₆CoPc/Ag(111) interface formation. The evolution of the morphology and the electronic properties at the organic/metal interface is investigated for the early-stage growth of the ultrathin molecular film. Template-guided molecular structures are formed via a strong molecule–substrate interaction which leads to the formation of a new adsorption-induced interface state close to the Fermi energy (E_F). With increasing the thickness the molecular coupling to the metal surface states becomes less important while the more dominant molecule–molecule interaction governs the second layer formation. The quenching of the interface state upon increasing the molecular thickness, together with the changes observed in the Co 2p and F 1s core levels, is explained based on a charge transfer at the interface and a corresponding charge redistribution within the molecular ligand. A detailed “picture” of the energy level alignment close to E_F is achieved by correlating the high resolution UPS and highly localized STS data.     

Preparation of epitaxial compositionally graded (Ba1-xSrx)TiO3 thin films with enhanced dielectric properties

Epitaxial compositionally graded (Ba_1-xSr_x)TiO₃ (BST) (0.0x0.25) thin films were deposited on (100) LaAlO₃ substrates by pulsed laser ablation, the substrates having bottom electrodes made of 100-nm-thick conductive La_0.5Sr_0.5CoO₃ (LSCO). Extensive X-ray diffraction, rocking-curve, and -scan studies indicate that the graded films are (100)-oriented and exhibit good in-plane relationships of [010]_BST//[010]_LAO and [001]_BST//[001]_LAO. For the up-graded films with barium concentration (1-x) increasing across the film thickness in the direction from the film/substrate interface to the film surface, the full width at half maximum of the BST film (200) rocking curve and the surface roughness, examined by atomic force microscopy, were larger than those of the down-graded films with barium concentration decreasing from the film/substrate interface to the film surface. The dielectric properties of the graded films, measured using vertical structures, show that at room temperature, the dielectric constant (_r) and dissipation factor (cos) at 100 kHz were 380 and 0.013 for the up-graded films, and 650 and 0.010 for the down-graded films, respectively. The dielectric behavior was enhanced in the down-graded films, which was attributed to the fact that the pure BaTiO₃ layer in the down-graded BST films not only serves as a bottom layer but also acts as an excellent seeding layer for enhancing subsequent film growth, leading to better film crystallinity and larger grain sizes in the down-graded films. The graded BST films undergo a diffuse phase transition, giving a broad, flat capacitance-versus-temperature profile. With such a graded structure, it is possible to build a dielectric thin-film capacitor having a capacitance which has a low temperature dependence over a broad temperature regime. PACS 77.55.+f; 68.55.Jk; 81.15.Fg     

Electronic properties of the surface of perylene tetracarboxylic acid dianhydride film upon deposition of the ultrathin conjugated layers of Pyronine B

Ultrathin conjugated layers of Pyronine B were thermally deposited in UHV on the surface of perylene tetracarboxylic acid dianhydride (PTCDA) film. The structure of unoccupied electron states located 5-20 eV above the Fermi level (E_F) and the surface potential were monitored during the Pyronine B overlayer deposition, using an incident beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. Electronic work function of the PTCDA surface changed from 4.9 ± 0.1 eV, during the Pyronine B deposition due to the change of the contents of the surface layer, until it reached a stable value 4.6 ± 0.1 eV at the Pyronine B film thickness 8-10 nm. The interface dipole corresponds to electron transfer from the Pyronine B overlayer to the PTCDA surface and the polarization in the Pyronine B overlayer was found confined within approximately 1 nm near the interfaces. The edges of major bands of density of unoccupied electronic states (DOUS) of PTCDA substrate and of the Pyronine B overlayer were unaffected by the process of the interface formation. The major TCS spectral features of the Pyronine B film corresponding to the DOUS band edges were identified and the assignment of the π^*, σ^*(C-C) and σ^*(CC) character was suggested.     

Laser-induced fabrication of randomly distributed nanostructures in fused silica surfaces

The nanostructuring of dielectrics is a big challenge for laser patterning methods. In this study a novel laser structuring method for the fabrication of randomly distributed nanostructures, called laser-induced front side etching using in situ pre-structured metal layers (IPSM-LIFE), is presented. The pulsed laser irradiation of a thin metal film deposited onto a dielectric substrate with fluences below the ablation threshold results in the formation of randomly distributed metal structures by self-assembly processes. Further pulsed laser irradiation of these metal structures with higher or equal laser fluences causes the formation of complex patterns at the surface of the dielectric due to localized ablation and melting processes of the dielectric surface induced by the absorption of the laser energy by the metal structures and the local energy transfer into the dielectric surface. The pattern formation observed in the film and the dielectrics substrate after irradiation of 10 nm chromium layers on fused silica, with laser pulses (Δt _p =25 ns, λ=248 nm), was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Different features with a lateral size down to a few tens of nanometers, like concentric ring patterns, donut-like structures, and bar patterns were observed at the dielectric.     

Effect of substrates on the morphology of Ba<Subscript>x</Subscript>Sr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>TiO<Subscript>3</Subscript> nanometer-scale films

The initial stages in the growth of Ba_xSr_1?xTiO₃ films on various dielectric substrates were studied using the middle-energy ion scattering spectroscopy, and the results obtained were used to analyze microdefects in the film. The character of film growth was found to depend on the shape, size, and electrostatic state of crystallographic unit cells of the substrate surface. The growth was epitaxial on an SrTiO₃ substrate. The film prepared on an LaAlO₃ substrate consists of slightly disordered crystallites. Films on MgO substrates demonstrated island-type growth up to a thickness of 20 nm, with foreign phases observed to form; as the film thickness increased, the growth acquired an epitaxial pattern. The film grown on the \(\alpha - Al_2 O_3 (1\bar 102)\) surface was polycrystalline and contained textured blocks.