Adsorption of 4,4 '-thiobisbenzenethiol on silver surfaces: surface-enhanced Raman scattering study

Adsorption of 4,4'-thiobisbenzenethiol (4,4'-TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface-enhanced Raman scattering (SERS) for the first time, which indicates that 4,4'-TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H-atoms of the S-H bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4'-TBBT in the two systems.

Probing structural changes of spin-coated polystyrene film after swelling and precipitation by synchrotron GIUSAXS and AFM

Polystyrenc film of about 50 nm in thickness on silicon wafer was obtained by spin-coating in tetrahydrofuran solution.The film exhibits a rough surface as shown by atomic force microscopy images and ellipsometry data.

Stimuli-responsive polyelectrolyte block copolymer brushes synthesized from the si wafer via atom-transfer radical polymerization

Surface-tethered oppositely charged weak polyelectrolyte block copolymer brushes composed of poly(2-vinyl pyridine) (P2VP) and poly(acrylic acid) (PAA) were grown from the Si wafer by atom-transfer radical polymerization. The P2VP-b-PAA brushes were prepared through hydrolysis of the second PtBA block to the corresponding acrylic acid. The P2VP-b-PAA brushes with different PAA block length were obtained. The P2VP-b-PAA brushes revealed a unique reversible wetting behavior with pH. The difference between the solubility parameters for P2VP and PAA, the changes of surface chemical composition and surface roughness, and the reversible wetting behavior illustrated that the surface rearrangement occurred during treatment of the P2VP-b-PAA brushes by aqueous solution with different pH value. The reversible properties of the P2VP-b-PAA brushes can be used to regulate the adsorption of the sulfonated PS nanoparticles.

Interfacial supramolecular self-assembled monolayers of C-60 by thiolated beta-cyclodextrin on gold surfaces via monoanionic C-60

The supramolecular self-assembled monolayers (SAMs) of C-60 by thiolated beta-cyclodextrin (CD) on gold surfaces were constructed for the first time using C-60 monoanion. The results indicate that monoanionic C-60 plays a crucial role in the formation of the C-60-containing self-assembled monolayers. The generation of C-60 monoanion and the formation process of C-60 SAMs were monitored in-situ by UV-visible and near-IR spectroscopy. The resulting C-60 SAMs were fully characterized by spectroscopic ellipsometry (SE), cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and water contact angle measurements. After the immobilization of C-60 by the SAMs of thiolated beta-CD, the film thickness increased by approximately 1 nm from 0.8 to 1.8 nm as determined by SE, demonstrating the formation of the supramolecular self-assembled monolayers of thiolated beta-CD/C-60. The new C-60 SAMs exhibited one quasi-reversible redox couple at half wave potential of -0.57 V vs SCE in aqueous solution containing 0.1 M KCl. The surface coverage of C-60 on the gold surfaces was estimated to be 1.1 x 10(-10) mol cm(-2). The XPS showed the assembly of C-60 over the thiolated beta-CD SAMs.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

Layer-by-layer multilayer films self-assembled from a rare-earth-containing poly-oxometalate Na-9[Eu(W5O18)(2)] and poly (allylamine hydrochloride) and their photoluminescent properties

Ultrathin multilayer films of a rare-earth-containing polyoxometalate Na-9[Eu(W5O18)(2)] (EW) and Poly (allyamine hydrochloride) (PAH) have been prepared by layer-by-layer self-assembly from dilute aqueous solutions. The fabrication process of the EW/PAH multilayer films was followed by UV-vis spectroscopy and ellipsometry, which show that the deposition process is linear and highly reproducible from layer to layer. An average EW/PAH bilayer thickness of ca. 2.1 nm was determine,by ellipsometry. In addition, the scanning electron microscopy (SEM) image of the EW/PAH film indicates that the film sufface is relatively uniform and smooth. The photoluminescent properties of these films were also investigated by fluoresence spectroscopy.

Photoluminescent organic-inorganic composite films layer-by-layer self-assembled from the rare-earth-containing polyoxometalate Na-9[EuW10O36] and poly(allylamine hydrochloride)

Photoluminescent organic-inorganic composite films incorporating the rare-earth-containing polyoxometalate Na-9[EuW10O36] (EW) and poly(allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer self-assembly method. UV-vis spectroscopy and ellipsometry were used to follow the fabrication process of the EW/PAH composite films. The experimental results show that the deposition process is linear and highly reproducible from layer to layer. An average EW/PAH bilayer thickness of ca. 2.1 nm was determined by ellipsometry. In addition, scanning electron microscopy and atomic force microscopy images of the EW/PAH composite films indicate that the film surface is relatively uniform and smooth. The photoluminescent properties of these films were investigated by fluorescence spectroscopy.

Preparation and characterization of self-assembled monolayers of trichlorogermanyl propanoic acid and its derivatives

Self-assembled monolayers(SAMs) of trichlorogermanyl propanoic acid derivatives on hydroxylated silicon substrates are prepared for the first time. Contact angle measurement, ellipsometry and X-ray photoelectron spectrometry(XPS) are used to characterize these SAMs, It is demonstrated that a quasi-2D network is formed on the surface of the substrate after molecules adsorbed on it. The molecular chains have certain tilt angles to the substrate surface, The wettabilities of the SAMs are various,because the molecules adsorbed and liquids used in the experiments are different. It can be concluded that trichlorogermanes have similar self-assembly behavior as trichlorosilanes, Four SAMs are studied together: they are acid, ethyl, butyl and hexyl surfaces whose results are of good consistency.

Inhibition Effect of 2,3,5-Triphenyl-2H-tetrazolium Chloride and 2,4,6-Tri(2-pyridyl)-s-triazine on the Corrosion of Mild Steel in 1 mol/L HCl and Mechanism Study (II)

The inhibitory effect of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 2,4,6-tri(2-pyridyl)-s-triazine (TPT) molecules on the corrosion of mild steel in 1 mol/L HCl and microcosmic inhibitory mechanism were investigated by X-ray photoelectron spectroscopy and ellipsometry. XPS results showed that C Is and N Is peaks of TTC, C Is and N Is peaks of TPT and their integral areas were obtained, which suggested the layer of the inhibitors (TTC or TPT) should have effectively protected the mild steel surface from the corrosion; and the depression from the inhibitors for the corrosion of mild steel surface was studied using ellipsometry combined with potentiodynamic polarization and the phasic difference was gained, which displayed the inhibitory coverage of the inhibitors formed.

Optical and ion-scattering study of SiO2 layers thermally grown on 4H-SiC

Jenkins, Tudor; Hayton, D.J.; Bailey, P.; Noakes, T.C.Q., (2002) 'Optical and ion-scattering study of SiO2 layers thermally grown on 4H-SiC', Semiconductor Science and Technology 17 pp.L29-L32 RAE2008

Synthesis and characterization of oxide materials

Nanostructured materials are central to the evolution of future electronics and biomedical applications amongst other applications. This thesis is focused on developing novel methods to prepare a number of nanostructured metal oxide particles and films by a number of different routes. Part of the aim was to see how techniques used in nanoparticle science could be applied to thin film methods to develop functional surfaces. Wet-chemical methods were employed to synthesize and modify the metal oxide nanostructures (CeO2 and SiO2) and their structural properties were characterized through advanced X-ray diffraction, electron microscopy, photoelectron spectroscopy and other techniques. Whilst particulates have uses in many applications, their attachment to surfaces is of importance and this is frequently challenging. We examined the use of block copolymer methods to form very well defined metal oxide particulate-like structures on the surface of a number of substrates. Chapter 2 describes a robust method to synthesize various sized silica nanoparticles. As-synthesized silica nanoparticles were further functionalized with IR-820 and FITC dyes. The ability to create size controlled nanoparticles with associated (optical) functionality may have significant importance in bio-medical imaging. Thesis further describes how non-organic modified fluorescent particles might be prepared using inorganic oxides. A study of the concentrations and distributions of europium dopants within the CeO2 nanoparticles was undertaken and investigated by different microscopic and spectroscopic techniques. The luminescent properties were enhanced by doping and detailed explanations are reported. Additionally, the morphological and structural evolution and optical properties were correlated as a function of concentrations of europium doping as well as with further annealing. Further work using positron annihilation spectroscopy allowed the study of vacancy type defects formed due to europium doping in CeO2 crystallites and this was supported by complimentary UV-Vis spectra and XRD work. During the last few years the interest in mesoporous silica materials has increased due to their typical characteristics such as potential ultra-low dielectric constant materials, large surface area and pore volume, well-ordered and uniform pores with adjustable pores between 2 and 50 nm. A simple, generic and cost-effective route was used to demonstrate the synthesis of 2D mesoporous silica thin films over wafer scale dimensions in chapter 5. Lithographic resist and in situ hard mask block copolymer followed by ICP dry etching were used to fabricate mesoporous silica nanostructures. The width of mesoporous silica channels can be varied by using a variety of commercially available lithographic resists whereas depth of the mesoporous silica channels can be varied by altering the etch time. The crystal structure, morphology, pore arrangement, pore diameters, thickness of films and channels were determined by XRD, SEM, ellipsometry and the results reported. This project also extended work towards the study of the antimicrobial study of nanopatterned silver nanodot arrays formed using the block copolymer approach defined above. Silver nanodot arrays were successfully tested for antimicrobial activity over S. aureus and P. aeruginosa biofilms and results shows silver nanodots has good antimicrobial activity for both S. aureus and P. aeruginosa biofilms. Thus, these silver nanodot arrays shows a potential to be used as a substitute for the resolution of infection complications in many areas.

Properties of InAlN/GaN Heterostructures Prepared by Molecular Beam Epitaxy

InAlN thin films and InAlN/GaN heterostructures have been intensively studied over recent years due to their applications in a variety of devices, including high electron mobility transistors (HEMTs). However, the quality of InAlN remains relatively poor with basic material and structural characteristics remain unclear.

Molecular beam epitaxy (MBE) is used to synthesize the materials for this research, as MBE is a widely used tool for semiconductor growth but has rarely been explored for InAlN growth. X-ray photoelectron spectroscopy (XPS) is used to determine the electronic and chemical characteristics of InAlN surfaces. This tool is used for the first time in application to MBE-grown InAlN and heterostructures for the characterization of surface oxides, the bare surface barrier height (BSBH), and valence band offsets (VBOs).

The surface properties of InAlN are studied in relation to surface oxide characteristics and formation. First, the native oxide compositions are studied. Then, methods enabling the effective removal of the native oxides are found. Finally, annealing is explored for the reliable growth of surface thermal oxides.

The bulk properties of InAlN films are studied. The unintentional compositional grading in InAlN during MBE growth is discovered and found to be affected by strain and relaxation. The optical characterization of InAlN using spectroscopy ellipsometry (SE) is also developed and reveals that a two-phase InAlN model applies to MBE-grown InAlN due to its natural formation of a nanocolumnar microstructure. The insertion of an AlN interlayer is found to mitigate the formation of this microstructure and increases mobility of whole structure by fivefold.

Finally, the synthesis and characterization of InAlN/GaN HEMT device structures are explored. The density and energy distribution of surface states are studied with relationships to surface chemical composition and surface oxide. The determination of the VBOs of InAlN/GaN structures with different In compositions are discussed at last.

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.

Dynamic, in situ optical, magnetic and magneto-optical monitoring of the growth of Co/Au and Pd/Co/Au multilayer systems

The growth of magnetron sputtered Co/Au and Pd/Co/Au superlattices on Au and Pd buffer layers, deposited onto glass substrates, has been monitored optically and magneto-optically in real time, using rotating analyser ellipsometry and Kerr polarimetry, at a wavelength of 633 nm. The magneto-optical traces, combined with ex situ and in situ hysteresis loops, provide a detailed and informative fingerprint of the optical and magnetic properties of the films as they evolve during growth. For Co/Au, oscillations in the polar magneto-optical effect developed during the deposition of An overlayers on Co and these may be attributed to quantum well states. However, the hysteresis measurements show that the magnetic field required to maintain saturation magnetization throughout the experiment was larger than available in situ, introducing a degree of confusion concerning the interpretation of the data. This problem was overcome by the incorporation of Pd layers into the Co/Au structure, thereby eliminating variation in magnetic orientation during growth of the Au layers as a contributory factor to the observations.

Étude de films de nanotubes de carbone dans le domaine de fréquences térahertz : propriété antiréfléchissante

Les expériences de spectroscopie ont été réalisées en collaboration avec Jean-François Allard du groupe de Denis Morris de l'Université de Sherbrooke.