EFFECT OF SURFACE-STRUCTURES UPON ULTRATHIN-FILM INTERFERENCE-FRINGES

Effect of surface structures upon ultrathin film interference fringes generated from extremely thin films or epitaxial layers grown on semiconductor wafers has been studied. Since dark regions of fringes correspond to the places where the thin films are destroyed or absent, the fringes are investigated to detect uneven surfaces with undesired structures. Therefore, surface microstructures can be detected and characterized effectively by the modification of the fringes.

Ultrathin-film growth of para-sexiphenyl (II): Formation of large-size domain and continuous thin film

The large-size domain and continuous para-sexiphenyl (p-6P) ultrathin film was fabricated successfully on silicon dioxide (SiO2) substrate and investigated by atomic force microscopy and selected area electron diffraction. At the optimal substrate temperature of 180 degrees C, the first-layer film exhibits the mode of layer growth, and the domain size approaches 100 mu m(2). Its saturated island density (0.018 mu m(-2)) is much smaller than that of the second-layer film (0.088 mu m(-2)), which begins to show the Volmer-Weber growth mode.

Ultrathin-film growth of para-sexiphenyl (I): Submonolayer thin-film growth as a function of the substrate temperature

The para-sexiphenyl (p-6P) monolayer film induces weak epitaxy growth (WEG) of disk-like organic semiconductors, and their charge mobilities are increased dramatically to the level of the corresponding single crystals [Wang et al., Adv. Mater. 2007, 19, 2168]. The growth behavior and morphology of p-6P monolayer film play decisive roles on WEG. Here, we investigated the growth behavior of p-6P submonolayer film as a function of the substrate temperature. Its growth exhibited two different mechanisms at high and low substrate temperature.

An organic-inorganic hybrid ultrathin film: preparation and characterization of copper phthalocyanine derivative-ferric oxide nanoparticles

A nanoparticulate ferric oxide-copper tris(2,4-di-tert-amylphenoxy)-8-quinolinolylphthalocyanine hybrid ultrathin film was constructed from alternate layers by the Langmuir-Blodgett technique. The composition, morphology and structure of the film were studied by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy, atomic force microscopy, small-angle X-ray diffraction, visible spectroscopy and polarized UV-Vis spectroscopy. All the above analyses suggest that the thin film is a kind of one-dimensional superlattice, composed of organic and inorganic components. The XPS data reveal that the nanoparticulate ferric oxide exists as an alpha-Fe2O3 phase in the films. Gas-sensing measurements show that the hybrid LB film has very fast response-recovery characteristics towards 2 ppm C2H5OH vapor.

Study of ferric oxide nanoparticles-tris-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine composite LB film

The ferric oxide nanoparticles-tris-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine (CuPcA(2)) composite ultrathin film was obtained by LB (Langmuir-Blodgett) technique. Structure of the composite LB film was characterized by X-ray photoelectron spectra, transmission electron microscopy, infrared spectra and visible spectra. Gas sensitivity measurements indicate that the composite LB film is sensitive to 100-200 ppm C2H5OH at room temperature. (C) 2000 Elsevier Science S.A. All rights reserved.

Atomic resolution studies of oxide superlattices and ultrathin films

The ability to grow ultrathin films layer-by-layer with well-defined epitaxial relationships has allowed research groups worldwide to grow a range of artificial films and superlattices, first for semiconductors, and now with oxides. In the oxides thin film research community, there have been concerted efforts recently to develop a number of epitaxial oxide systems grown on single crystal oxide substrates that display a wide variety of novel interfacial functionality, such as enhanced ferromagnetic ordering, increased charge carrier density, increased optical absorption, etc, at interfaces. The magnitude of these novel properties is dependent upon the structure of thin films, especially interface sharpness, intermixing, defects, and strain, layering sequence in the case of superlattices and the density of interfaces relative to the film thicknesses. To understand the relationship between the interfacial thin film oxide atomic structure and its properties, atomic scale characterization is required. Transmission electron microscopy (TEM) offers the ability to study interfaces of films at high resolution. Scanning transmission electron microscopy (STEM) allows for real space imaging of materials with directly interpretable atomic number contrast. Electron energy loss spectroscopy (EELS), together with STEM, can probe the local chemical composition as well as local electronic states of transition metals and oxygen. Both techniques have been significantly improved by aberration correctors, which reduce the probe size to 1 Å, or less. Aberration correctors have thus made it possible to resolve individual atomic columns, and possibly probe the electronic structure at atomic scales. Separately, using electron probe forming lenses, structural information such as the crystal structure, strain, lattice mismatches, and superlattice ordering can be measured by nanoarea electron diffraction (NED). The combination of STEM, EELS, and NED techniques allows us to gain a fundamental understanding of the properties of oxide superlattices and ultrathin films and their relationship with the corresponding atomic and electronic structure. In this dissertation, I use the aforementioned electron microscopy techniques to investigate several oxide superlattice and ultrathin film systems. The major findings are summarized below. These results were obtained with stringent specimen preparation methods that I developed for high resolution studies, which are described in Chapter 2. The essential materials background and description of electron microscopy techniques are given in Chapter 1 and 2. In a LaMnO3-SrMnO3 superlattice, we demonstrate the interface of LaMnO3-SrMnO3 is sharper than the SrMnO3-LaMnO3 interface. Extra spectral weights in EELS are confined to the sharp interface, whereas at the rougher interface, the extra states are either not present or are not confined to the interface. Both the structural and electronic asymmetries correspond to asymmetric magnetic ordering at low temperature. In a short period LaMnO3-SrTiO3 superlattice for optical applications, we discovered a modified band structure in SrTiO3 ultrathin films relative to thick films and a SrTiO3 substrate, due to charge leakage from LaMnO3 in SrTiO3. This was measured by chemical shifts of the Ti L and O K edges using atomic scale EELS. The interfacial sharpness of LaAlO3 films grown on SrTiO3 was investigated by the STEM/EELS technique together with electron diffraction. This interface, when prepared under specific conditions, is conductive with high carrier mobility. Several suggestions for the conductive interface have been proposed, including a polar catastrophe model, where a large built-in electric field in LaAlO3 films results in electron charge transfer into the SrTiO3 substrate. Other suggested possibilities include oxygen vacancies at the interface and/or oxygen vacancies in the substrate. The abruptness of the interface as well as extent of intermixing has not been thoroughly investigated at high resolution, even though this can strongly influence the electrical transport properties. We found clear evidence for cation intermixing through the LaAlO3-SrTiO3 interface with high spatial resolution EELS and STEM, which contributes to the conduction at the interface. We also found structural defects, such as misfit dislocations, which leads to increased intermixing over coherent interfaces.

六联苯超薄膜与弱取向外延生长

有机半导体薄膜的形态结构对器件性能具有非常重要的影响，近年来高质量有机半导体薄膜的制备成为有机半导体薄膜器件研究的核心内容之一。弱取向外延生长能够获得类单晶迁移率的高质量有机半导体薄膜。而制备出高取向、大尺寸、低缺陷、连续的高质量外延生长基底是获得类单晶外延薄膜的前提条件，这样就需要深入了解它们的生长行为、生长机理及薄膜相态特性。因此，高质量外延基底生长和弱取向外延生长行为及机理的研究就具有十分重要的理论价值和实用价值，是选择和扩展弱取向外延生长材料体系的基础。由此，本论文中工作主要分为两部分，第一部分工作是对外延基底六联苯超薄膜生长的研究：一方面生长出大尺寸、高取向、连续的超薄膜为弱取向外延生长提供高质量的外延基底，另一方面丰富和发展了有机半导体薄膜生长理论。第二部分工作是对酞菁化合物在六联苯超薄膜上弱取向外延生长行为和机理的研究，为弱取向外延材料体系的选择与扩展提供实验依据和理论指导。 首先，研究了六联苯超薄膜生长行为。研究结果表明：(1) 六联苯超薄膜在高温(＞60 oC)和低温(≤60 oC)的二氧化硅(SiO2)基底上生长具有不同的生长机理：高温时薄膜生长符合扩散受限凝聚生长(DLA)机理，低温时薄膜生长是由低有序薄膜经过亚稳分解后重组向团状岛转变。(2) 六联苯超薄膜的生长行为和相结构表明单层和双层薄膜是两种不同的相态：单层薄膜是高取向的具有液晶特性的薄膜相态，双层薄膜是长程有序的近似体相β-phase结构的结晶相。(3) 通过优化基底温度和生长参数，可以制备出高取向、大尺寸、连续的六联苯超薄膜，即可以为酞菁化合物的弱取向外延生长提供高质量的外延基底。 然后，以平面型自由酞菁(H2Pc)及酞菁锌(ZnPc)和非平面型酞菁氧钒(VOPc)为例，深入研究了酞菁化合物在六联苯超薄膜上的弱取向外延生长行为及机理。研究结果表明：(1) 弱取向外延生长的酞菁分子在六联苯超薄膜上立着生长，p-p共轭的方向平行于基底，同时酞菁分子在薄膜平面内具有规则的取向织构。这种高取向的酞菁化合物薄膜有利于载流子在薄膜平面内的传输，其迁移率达到了相应的单晶水平。(2) 由于六联苯双层及单层薄膜结构和相态的差别，平面型酞菁化合物表现出不同的外延生长行为：在六联苯双层薄膜上生长的酞菁化合物薄膜在薄膜平面内只有一种取向，对应于有公度外延生长(Commensurate Epitaxy)；在六联苯单层薄膜上生长的酞菁化合物薄膜在薄膜平面内有三种取向，同时兼具有公度外延生长和无公度外延生长(Incommensurate Epitaxy)。但非平面型VOPc由于分子排列方式及三斜晶体结构的本质，在六联苯单层及双层薄膜上都只表现出无公度外延生长。(3) 六联苯(001)晶面上突起的氢原子所形成的[110]、[1-10]和[010]沟道对酞菁分子具有强烈的预取向作用，从而形成取向的单分子柱晶核。然后在晶格匹配效应和基底沟道效应下，分别形成有公度外延生长和无公度外延生长。即晶格匹配关系和基底沟道效应为寻找弱取向外延生长有机半导体材料体系提供了理论指导依据。

Enhanced amplified spontaneous emission using layer-by-layer assembled cowpea mosaic virus

Layer-by-layer assembly technique was used to construct ultrathin film of cowpea mosaic virus (CPMV) by electrostatic interactions, and the film was employed as a precursor on which an OF8T2 film was deposited by spin coating. Amplified spontaneous emission (ASE) was observed and improved for the OF8T2 film. Compared with OF8T2 film on quartz, the introduction of CPMV nanoparticles reduced the threshold and loss, and remarkably increased the net gain. The threshold, loss, and gain reached 0.05 mJ/ pulse, 6.9 cm(-1), and 82 cm(-1), respectively. CPMV nanoparticles may enormously scatter light, resulting in a positive feedback, thus the ASE is easily obtained and improved.

A method for cathodic polymerization of aniline by in situ electrogenerated intermediate at gold surface

Polyaniline (PANI) was cathodically synthesized at an evaporated gold electrode using an in situ electrogenerated intermediate as oxidant during reduction of the dissolved oxygen. The obtained PANI layer showed an electrochemical response similar to that synthesized by the conventionally anodic polymerization, and the average rate for the growth of PANI layer at polycrystalline gold electrode was 1.59 nm h(-1), while that at the Au (111) electrode was 4.93 nm h(-1). Based on these results, the thickness of the resulted layer can be easily controlled at molecular level for potential nanodevice applications. The obtained PANI layer showed morphology from an island-like nanostructure to an ultrathin film, depending on the crystal orientation of the electrode used.

Oriented polyoxometalate-polycation multilayers on a carbon substrate

In this paper, a new method of fabricating multilayers on a carbon substrate is presented. First, a uniformly charged carbon surface was prepared through molecular design. Then an ultrathin film consisting of layer-pairs of oppositely charged polymeric cationic poly(diallyldimethylammonium chloride) (PDDA) and silicotungstate, SiW12O404- (SiW12), was grown layer-by-layer onto the grafted carbon substrate using a molecular self-assembly technique and an electrochemical method. The technique allows one to prepare highly adherent, dense and smooth films of polyoxometalates with special properties. By combining cyclic voltammetry (CV) and X-ray (XR) reflectometry, it was determined that the average surface density of SiW12 was 2.10 x 10(-10) mol cm(-2), and the thickness increase per adsorption of PDDA-SiW12 was 1.7 +/- 0.2 nm, indicating that the amount of SiW12 anion per one layer adsorption corresponded to a monolayer coverage. Atomic force microscopy (AFM) was also used to examine the surface morphology and determine the grain size distribution and roughness for multilayer films. An increase in root-mean-square (RMS) surface roughness from 7 to 9 Angstrom was observed as the number of layer-pairs in the film increased from 2 to 6. FTIR results showed that the good stability of the multilayer films was due to Coulomb interactions between the SiW12 anion and the polymeric cations PDDA. Moreover, the multilayer films, in acidic aqueous solution, showed good electrocatalytic activity toward the reduction of NO2-, and the catalytic currents increased with increasing the layer numbers of SiW12 adsorption. These characteristics of the multilayer films might find potential applications in the field of sensors and microelectronics devices.

Preparation and characterization of DBSA doped polyaniline thin films

Stable monolayer of the polyaniline(PAn) doped with dodecyl benzenesulfonic acid(DBSA) can form on the pure water surface. The multilayer ultrathin film can be successfully deposited by Langmuir-Blodgett(LB) technique onto CaF2 substrate. The limiting mean molecular area and collapse pressure observed are 0.066 nm(2) and 35 mN m(-1), respectively. The multilayer LB film and casting film were all characterized by TR and UV-Vis-NIR spectroscopies.

Dynamic in situ optical and magneto-optical monitoring of the growth of Co-Pd multilayers

In situ ellipsometry and Kerr polarimetry have been used to follow the continuous evolution of the optical and magneto- optical properties of multiple layers of Co and Pd during their growth. Films were sputter deposited onto a Pd buffer layer on glass substrates up to a maximum of N = 10 bi-layer periods according to the scheme glass/Pd(10)Ar x (0.3Co/3Pd) (nm). Magnetic hysteresis measurements taken during the deposition consistently showed strong perpendicular anisotropy at all stages of film growth following the deposition of a single monolayer of Co. Magneto-optic signals associated with the normal-incidence polar Kerr effect indicated strong polarization of Pd atoms at both Co-Pd and Pd-Co interfaces and that the magnitude of the complex magneto-optic Voigt parameter and the magnetic moment of the Pd decrease exponentially with distance from the interface with a decay constant of 1.1 nm(- 1). Theoretical simulations have provided an understanding of the observations and allow the determination of the ultrathin- film values of the elements of the skew-symmetric permittivity tensor that describe the optical and magneto-optical properties for both CO and Pd. Detailed structure in the observed Kerr ellipticity shows distinct Pd-thickness-dependent oscillations with a spatial period of about 1.6 nm that are believed to be associated with quantum well levels in the growing Pd layer.

Nanostructures de surface obtenues par dépôt de films minces à base d'assemblage supramoléculaire de copolymères blocs

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Pt monolayer electrocatalysts for O-2 reduction: PdCo/C substrate-induced activity in alkaline media

We measured the activity of electrocatalysts, comprising Pt monolayers deposited on PdCo/C substrates with several Pd/Co atomic ratios, in the oxygen reduction reaction in alkaline solutions. The PdCo/C substrates have a core-shell structure wherein the Pd atoms are segregated at the particle`s surface. The electrochemical measurements were carried out using an ultrathin film rotating disk-ring electrode. Electrocatalytic activity for the O-2 reduction evaluated from the Tafel plots or mass activities was higher for Pt monolayers on PdCo/C compared to Pt/C for all atomic Pd/Co ratios we used. We ascribed the enhanced activity of these Pt monolayers to a lowering of the bond strength of oxygenated intermediates on Pt atoms facilitated by changes in the 5d-band reactivity of Pt. Density functional theory calculations also revealed a decline in the strength of PtOH adsorption due to electronic interaction between the Pt and Pd atoms. We demonstrated that very active O-2 reduction electrocatalysts can be devised containing only a monolayer Pt and a very small amount of Pd alloyed with Co in the substrate.

Estudo da estabilização da fase perovskita PMN em filmes ultrafinos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)