Dynamics of wetting transitions: A time-dependent Ginzburg-Landau treatment

The dynamic behavior at wetting transitions is studied for systems with short-range forces and nonconserved order parameter. From a continuum limit of a purely relaxational lattice model in mean-field approximation, a time-dependent Ginzburg-Landau equation with a time-dependent boundary condition at the surface is derived in the long wavelength approximation. The dynamics of relaxation close to stable and metastable states is treated in linear response. A divergence of the relaxation time occurs both for critical wetting and along the surface spinodal lines (in the case of first-order wetting), although the static surface layer susceptibilities ₁, ₁₁ stay finite at the surface spinodal in the non-wet region of the phase diagram.Also the highly nonlinear relaxation that occurs when a wetting layer forms out of an initially non-wet state is considered. For late times, the thickness of the wetting layer grows proportional to the logarithm of time. A comparison with recent Monte Carlo work shows that the present mean-field theory underestimates the prefactor in this growth law. For early times and states in the metastable region a distance H ₁ away from the first order wetting transition, the formation of the wet layer starts by heterogeneous nucleation of droplets at the surface. The droplets have the shape of (approximately) caps of a sphere and involve a free energy barrier proportional to (H ₁)^–2 as H ₁0. The generalization of this phenomenological approach for the nucleation barrier to the case of long range forces is also discussed and open problems are briefly outlined.     

Dynamics of bimodal growth in pentacene thin films

Previous studies have established that pentacene films deposited on silicon oxide consist of a substrate-induced "thin-film" phase, with the bulk phase of pentacene detected in thicker films only. We show that the bulk phase nucleates as early as the first monolayer, and continues to nucleate as film growth progresses, shadowing the growth of the thin-film phase. Moreover, we find that the transition between the "thin-film" and the bulk phase is not a continuous one, as observed in heteroepitaxial systems, but rather the two phases nucleate and grow independently.     

The interplay of topography and energy dissipation in pentacene thin films

Nonlinear photoemission electron microscopy was used to study the morphology-dependent lifetime of electronic excitations in pentacene islands on Si(0 0 1) and (√3 × √3)R30°-Ag/Si(1 1 1). After an optical excitation of electrons by a λ = 400 nm femtosecond laser pulse the characteristic decay times were measured with spatial resolution in a pump-probe setup. For pentacene on Si(0 0 1), the observed lifetimes vary by a factor of two between the wetting layer and the fractal-shaped pentacene islands. The measured lifetime difference is explained by a difference in the electronic coupling of the pentacene islands and the wetting layer to the substrate. For pentacene on (√3 × √3)R30°-Ag/Si(1 1 1), similar lifetimes are found, although the orientation of the pentacene molecules in the compact islands is rotated. Our findings suggest that electronic excitations in higher layers of the pentacene islands do not diffuse to the interface before they decay.     

The effects of ambient oxygen pressure on the 1.54 μm photoluminescence of Er-doped silicon-rich silicon oxide films grown by laser ablation of a Si+Er target

We fabricated Er-doped silicon-rich silicon oxide (SRSO:Er) films by pulsed laser deposition. A Si+Er target consisting of an Er metallic strip and a silicon disk was adopted with a goal to achieve a convenient control of the Er and oxygen density in the film. We found that the photoluminescence (PL) at 1.54 m is highly dependent on the ambient oxygen pressure, which determines the relative ratio of Si-Si, SiO_x, and SiO₂ phase in the film. The PL intensity increased drastically with increase in the annealing temperature and reached the maximum intensity at 500 °C. PACS 81.15.Fg; 81.07.-b     

Features of atomic processes at the formation of a wetting layer and nucleation of three-dimensional Ge islands on Si(111) and Si(100) surfaces

The intermediate stages of the formation of a Ge wetting layer on Si(111) and Si(100) surfaces under quasiequilibrium grow conditions have been studied by means of scanning tunneling microscopy. The redistribution of Ge atoms and relaxation of mismatch stresses through the formation of surface structures of decreased density and faces different from the substrate orientation have been revealed. The sites of the nucleation of new three-dimensional Ge islands after the formation of the wetting layer have been analyzed. Both fundamental differences and common tendencies of atomic processes at the formation of wetting layers on Si(111) and Si(100) surfaces have been demonstrated. The density of three-dimensional nuclei on the Si(111) surface is determined by changed conditions for the surface diffusion of Ge adatoms after change in the surface structure. Transition to three-dimensional growth on the Si(100) surface is determined by the nucleation of single {105} faces on the rough Ge(100) surface.     

Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>x</Subscript>/Si(001) relaxed buffer layers grown by chemical vapor deposition at atmospheric pressure

Relaxed step-graded buffer layers of Si_1?xGe_x/Si(001) heterostructures with a low density of threading dislocations are grown through chemical vapor deposition at atmospheric pressure. The surface of the Si_1?xGe_x/Si(001) (x ～ 25%) buffer layers is subjected to chemical mechanical polishing. As a result, the surface roughness of the layers is decreased to values comparable to the surface roughness of the Si(001) initial substrates. It is demonstrated that Si_1?xGe_x/Si(001) buffer layers with a low density of threading dislocations and a small surface roughness can be used as artificial substrates for growing SiGe/Si heterostructures of different types through molecular-beam epitaxy.     

Structural and interfacial stabilities of epitaxial (11-20)-oriented wurtzite AlN films grown on lattice-matched MnS buffered Si(100)

Epitaxial growth of non-polar wurtzite (11-20) AlN thin films was achieved on a Si(100) substrate by inserting an MnS buffer layer. The a-plane AlN film and MnS buffer layer were fabricated by pulsed KrF excimer laser deposition, and their micro- and interfacial atomic structures were investigated by transmission electron microscopy. The epitaxial relationship between films and substrate was found to be AlN(11-20)MnS(100)Si(100) with in-plane alignment of AlN[1-101]MnS[011]Si[011]. AlN[11-20] grown on Si is perpendicular to AlN[0001] and parallel to MnS[100]. The MnS/Si interface is abrupt enough to inherit the orientation of the Si(100) surface. A sharp interface was also observed for AlN/MnS without any intermediate layer. PACS 81.05.Ea; 81.05.Zx; 81.15.Fg; 68.37.Lp     

Pressure effect on grain boundary wetting at various temperatures

Bicrystals of Fe-6 at.% Si alloy containing <001> 5 tilt grain boundaries with a deposited zinc layer have been annealed at various hydrostatic pressure at four temperatures between 700° and 905°C. After the anneals the dihedral angle of the grain boundary groove formed at the site of the grain boundary intersection with the solid-melt interphase boundary has been measured. The transition from complete to incomplete wetting of the grain boundary by the zinc-rich melt (dewetting phase transition) has been found to occur as the pressure increased at all temperatures studied. The temperature dependence of the dewetting transition pressure p _w has been determined. That dependence has a minimum at a temperature of 790°C, which is close to the peritectic temperature in the Fe–Zn system (782°C). A thermodynamic analysis of the wetting phenomena in the two-component system, based on Becker's regular solution model for the surface tension of the interphase boundary, explains the minimum in the p _w (T) dependence.     

Surface and interface properties of thin pentacene and parylene layers

To improve Organic Thin Film Transistor (OTFT) properties we study OTFT semiconductor/dielectric interfacial properties via examination of the gate dielectric using thin Parylene C layer. Structural and morphology properties of pentacene layers deposited on parylene layer and SiO₂/Si substrate structure were compared. The surface morphology was investigated using atomic force microscopy (AFM) and scanning electron microscopy (SEM). AFM topography of pentacene layer in non-contact mode confirmed the preferable pentacene grain formation on parylene surface in dependence on layer thickness. The distribution of chemical species on the surfaces and composition depth profiles were measured by secondary ion mass spectroscopy (SIMS) and surface imaging. The depth profiles of the analyzed structures show a homogenous pentacene layer, characterized with C or C₂ ions. Relatively sharp interface between pentacene and parylene layers was estimated by characteristic increased intensity of CCl ions peak. For revealing the pentacene phases in the structures the Micro-Raman spectroscopy was utilized. Conformal coatings of parylene and pentacene layers without pinholes resulted from the deposition process as was confirmed by SIMS surface imaging. For the pentacene layers thicker than 20 nm, both thin and bulk pentacene phases were detected by Micro-Raman spectroscopy, while for the pentacene layer thickness of 5 and 10 nm the preferable thin phase was detected. The complete characterisation of pentacene layers deposited on SiO₂ and parylene surface revealed that the formation of large grains suggests 3D pentacene growth at parylene layer with small voids between grains and more than one monolayer step growth. The results will be utilized for optimization of the deposition process.      

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     

Effect of modifying a methyl siloxane-based dielectric by a polymer thin film for pentacene thin-film transistors

We report on the fabrication of pentacene thin-film transistors (TFTs) utilizing a spun methyl siloxane-based spin-on-glass (SOG) dielectric and show that these devices can give a similar electrical performance as achieved by using pentacene TFTs with a silicon dioxide (SiO₂) dielectric. To improve the electrical performance of pentacene TFTs with the SOG dielectric, we employed a hybrid dielectric of an SOG/cross-linked poly-4-vinylphenol (PVP) polymer. The PVP film was deposited onto the spun SOG dielectric prior to pentacene evaporation, resulting in an improvement of the saturation field effect mobility (μ_sat) from 0.01 cm²/(V s) to 0.76 cm²/(V s). The good surface morphology and the matching surface energy of the SOG dielectric that was modified with the polymer thin film allow the optimized growth of crystalline pentacene domains whose nuclei are embedded in an amorphous phase.     

Effect of surface property of polyimide substrate on the formation of pentacene thin-film

We investigated the effect of surface property of polyimide substrate on the formation of pentacene thin-film by using atomic force microscopy (AFM) and X-ray reflectivity (XRR) and diffuse scattering (XDS). Two types of polymer films were prepared: (1) polyimide (PAA-PI) from poly(amic acid) (PAA) (2) polyimide hybrid (PAA-PI-H) prepared by hybridizing the PAA and soluble polyimide (PI) with a octadecyl side chain. The hybridization ratio of PI to PAA was 2/98 in wt%. The water contact angle for PAA-PI-H and PAA-PI were around 80° and 64°, respectively. Morphology of pentacene with a ropelike structure and (1 1 0) peak around 1.4 Å in q_z was found when it was deposited on PAA-PI thin-film. Different pentacene morphology was observed when it was deposited on PAA-PI-H thin-film. The different morphology might be due to a 5-6 nm thick additional layer (∼0.95 ρ_film) at the interface between pentacene and PAA-PI-H thin-film caused by a long alkyl side chain introduced to the polymer main chain.     

Low-loss Al2O3 waveguides produced by pulsed laser deposition at room temperature

Al₂O₃ waveguides have been produced at room temperature by pulsed laser deposition on Si substrates covered by a SiO₂ buffer layer. The dependence of the refractive index and the losses on both the laser energy density and the gas used during deposition (either reactive (O₂) or inert (Ar)) are discussed in terms of densification processes, surface roughness, and oxygen-related defects. Amorphous waveguides with refractive indices >1.66 and losses below 10 dBcm^-1 were produced under a wide range of experimental conditions, the best results being achieved with low laser energy densities and gas oxygen pressures. Losses as low as 2.5 dBcm^-1, which are close to the resolution limit, were achieved under optimized conditions, even when the waveguide had a thickness inhomogeneity along the propagation direction of at least 10%. PACS 81.15.Fg; 78.20.Ci; 42.79.Gn     

Heteroepitaxial praseodymium sesquioxide films on Si(1 1 1): A new model catalyst system for praseodymium oxide based catalysts

The structure, growth and stoichiometry of heteroepitaxial Pr₂O₃ films on Si(1 1 1) were characterized by a combined RHEED, XRD, XPS and UPS study in view of future applications as a surface science model catalyst system. RHEED and XRD confirm the growth of a (0 0 0 1) oriented hexagonal Pr₂O₃ phase on Si(1 1 1), matching the surface symmetry by aligning the oxide in-plane direction along the Si azimuth. After an initial nucleation stage RHEED growth oscillation studies point to a Frank-van der Merwe growth mode up to a thickness of approximately 12 nm. XPS and UPS prove that the initial growth of the Pr₂O₃ layer on Si up to ∼1 nm thickness is characterized by an interface reaction with Si. Nevertheless stoichiometric Pr₂O₃ films of high crystalline quality form on top of these Pr-silicate containing interlayers.     

Stability and band offsets between Si and LaAlO<Subscript>3</Subscript>

The replacement of traditional SiO₂ with high-k oxides allows the physical thickness of the gate dielectric to be thinner without the tunneling problem in Si-based metal-oxide-semiconductor field-effect transistors. LaAlO₃ appears to be a promising high-k material for use in future ultra large scale integrated devices. In the present paper, the electronic properties of Si/LaAlO₃ (001) heterojunctions are investigated by first-principles calculations. We studied the initial adsorption of Si atoms on the LaAlO₃ (001) surface, and found that Si atoms preferentially adsorb on top of oxygen atoms at higher coverage. The surface phase diagrams indicate that Si atoms may substitute oxygen atoms at the LaO-terminated surface. The band offsets, electronic density of states, and atomic charges are analyzed for the various Si/LaAlO₃ heterojunctions. Our results suggest that the Si/AlO₂ interface is suitable for the design of metal oxide semiconductor devices because the valence and conduction band offsets are both larger than 1 eV.     

Pulsed laser deposition of c * axis oriented pentacene films

Pulsed laser desorption and film deposition behaviors have been investigated on pentacene as an organic molecule primarily due to its applications in electronics. The laser desorption time-of-flight (LDTOF) mass spectrum exhibited a single parent peak when a pressed pentacene pellet was ablated by an N₂ laser beam of its fluence lower than 100 mJ/cm², indicating that pentacene could be evaporated without an appreciable photodecomposition by the pulsed laser beam. Nd:YAG pulsed laser deposition of pentacene films was performed using such optimization parameters as laser fluences and wavelength (second, third and forth harmonic generations (SHG, THG, FHG)). The analyses with AFM, XRD and UV-Vis spectroscopy revealed the fabrication of c^* axis oriented pentacene films on quartz, silicon, and CaF₂ substrates by the SHG. The SHG films have a surface morphology superior to those of films deposited by THG and FHG. PACS 81.15.Fg; 81.05.Lg; 82.80.Rt     

“In vivo” STM studies of the growth of Germanium and Silicon on Silicon

A scanning tunneling microscope (STM) capable of imaging during crystal growth from the vapour is described. This method (MBSTM) opens the possibility to follow the growth process of semiconductor molecular beam epitaxy (MBE) in vivo. The ability of the microscope to access the evolution of specific features during growth is demonstrated by images of the Si homoepitaxy. The transition from initial multilayer to layer-by-layer growth was imaged in Si(1 1 1) homoepitaxy. In Si/Si(1 0 0) homoepitaxy the fractional coverage of non-equivalent terraces was studied as function of coverage and a theoretically predicted transient growth mode was observed. In Ge on Si(1 1 1) heteroepitaxy the nucleation of 3D Ge islands was observed. When 3D islands occurred on the surface an etching of the 2D Stranski-Krastanov layer was observed.     

Role of surface electronic structure in thin film molecular ordering

We show that the orientation of pentacene molecules is controlled by the electronic structure of the surface on which they are deposited. We suggest that the near-Fermi level density of states above the surface controls the interaction of the substrate with the pentacene pi orbitals. A reduction of this density as compared to noble metals, realized in semimetallic Bi(001) and Si(111)(5 x 2)Au surfaces, results in pentacene standing up. Interestingly, pentacene grown on Bi(001) is highly ordered, yielding the first vertically oriented epitaxial pentacene thin films observed to date.     

CEMS Investigations of Fe-Silicide Phases Formed by the Method of Concentration Controlled Phase Selection

Conversion electron Mössbauer spectroscopy (CEMS) measurements have been made on Fe-silcide samples formed using the method of concentration controlled phase selection. To prepare the samples a 10 nm layer of Fe₃₀M₇₀ (M=Cr, Ni) was evaporated onto Si(100) surfaces, followed by evaporation of a 60 nm Fe layer. Diffusion of the Fe into the Si substrate and the formation of different Fe–Si phases was achieved by subjecting the evaporated samples to a series of heating stages, which consisted of (a) a 10 min anneal at 800°C plus etch of the residual surface layer, (b) a further 3 hr anneal at 800°C, (c) a 60 mJ excimer laser anneal to an energy density of 0.8 J/cm², and (d) a final 3 hr anneal at 800°C. CEMS measurements were used to track the Fe-silicide phases formed. The CEMS spectra consisted of doublets which, based on established hyperfine parameters, could be assigned to - or -FeSi₂ or cubic FeSi. The spectra showed that -FeSi₂ had formed already at the first annealing stage. Excimer laser annealing resulted in the formation of a phase with hyperfine parameters consistent with those of -FeSi₂. A further 3 hr anneal at 800°C resulted in complete reversal to the semiconducting -FeSi₂ phase.     

内嵌CuO薄膜对并五苯薄膜晶体管性能的改善

制备了基于内嵌氧化物铜(CuO)薄膜的并五苯薄膜晶体管器件. 将3 nm CuO薄膜内嵌入到并五苯(pentacene)中, 作为空穴注入层, 降低电极与并五苯之间的空穴注入势垒. 相对于纯并五苯薄膜晶体管器件, 研制的晶体管的迁移率、阈值电压(V_TH)、电流开关比(I_on/I_off) 等参数都有明显改善. X射线光电子能谱数据表明, 这种空穴注入势垒的降低源自并五苯向CuO的电子转移.