Fabrication of a quantum well heterostructure based on plasma polymerized aniline and its characterization using STM/STS

Two-dimensional electronic systems play a crucial role in modern electronics and offer a multitude of opportunities to study the fundamental phenomena at low dimensional physics. A quantum well heterostructure based on polyaniline (P) and iodine doped polyaniline (I) thin films were fabricated using radio frequency plasma polymerization on indium tin oxide coated glass plate. Scanning probe microscopy and scanning electron microscopy studies were employed to study the morphology and roughness of the polymer thin films. Local electronic density of states (LDOS) of the P–I–P heterostructures is probed using scanning tunnelling spectroscopy (STS). A step like LDOS is observed in the P–I–P heterostructure and is attributed to the quantum well confinement of electrons in the polymer heterostructure.

Piezoresistive cantilevers with an integrated bimorph actuator

Scanning Probe Microscopy (SPM) has become of fundamental importance for research in area of micro and nano-technology. The continuous progress in these fields requires ultra sensitive measurements at high speed. The imaging speed limitation of the conventional Tapping Mode SPM is due to the actuation time constant of piezotube feedback loop that keeps the tapping amplitude constant. In order to avoid this limit a deflection sensor and an actuator have to be integrated into the cantilever. In this work has been demonstrated the possibility of realisation of piezoresistive cantilever with an embedded actuator. Piezoresistive detection provides a good alternative to the usual optical laser beam deflection technique. In frames of this thesis has been investigated and modelled the piezoresistive effect in bulk silicon (3D case) for both n- and p-type silicon. Moving towards ultra-sensitive measurements it is necessary to realize ultra-thin piezoresistors, which are well localized to the surface, where the stress magnitude is maximal. New physical effects such as quantum confinement which arise due to the scaling of the piezoresistor thickness was taken into account in order to model the piezoresistive effect and its modification in case of ultra-thin piezoresistor (2D case). The two-dimension character of the electron gas in n-type piezoresistors lead up to decreasing of the piezoresistive coefficients with increasing the degree of electron localisation. Moreover for p-type piezoresistors the predicted values of the piezoresistive coefficients are higher in case of localised holes. Additionally, to the integration of the piezoresistive sensor, actuator integrated into the cantilever is considered as fundamental for realisation of fast SPM imaging. Actuation of the beam is achieved thermally by relying on differences in the coefficients of thermal expansion between aluminum and silicon. In addition the aluminum layer forms the heating micro-resistor, which is able to accept heating impulses with frequency up to one megahertz. Such direct oscillating thermally driven bimorph actuator was studied also with respect to the bimorph actuator efficiency. Higher eigenmodes of the cantilever are used in order to increase the operating frequencies. As a result the scanning speed has been increased due to the decreasing of the actuation time constant. The fundamental limits to force sensitivity that are imposed by piezoresistive deflection sensing technique have been discussed. For imaging in ambient conditions the force sensitivity is limited by the thermo-mechanical cantilever noise. Additional noise sources, connected with the piezoresistive detection are negligible.

Development of amorphous carbon protective coatings on poly(vinyl)chloride

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

Preparation and characterization of PAni-PMMA dispersions

Blends of polyaniline (PAni) and poly(methyl methacrylate) (PMMA) have been produced using core-shell particle synthesis, which is advantageous because it allows changing surface-related properties of PMMA with relatively small amounts of PAW and without the use of organic solvents. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements indicated that the deposition of pollyaniline seems to alter the regular shape of the primary acrylic latex particles. The coverage of PMMA particles by PAW was confirmed by FTIR measurements, where distinct data were obtained from the transmission and diffuse reflectance modes, since the latter is surface sensitive. The zeta potential, which is also a surface-related property, increased with the contents of PAW, as the shells probably became protonated with PAW in the emeraldine salt form. Coverage with PAW did not affect the thermal bulk properties of the PMMA shells.

Structural and surface morphology characterizations of oriented LiNbO3 thin films grown by polymeric precursor method

Polymeric precursor solution was used to deposit LiNbO3 thin films by dip coating on sapphire substrates. The effects of processing variables, such as heat treatment conditions and number of deposited layers, on crystallinity and morphology of the final films were investigated. X-ray diffraction patterns show the oriented growth of the films. The rocking curves, obtained around the (006) LiNbO3 peak, revealed that the shape peak and the FWHM value were influenced by the processing variables. According to these parameters, some films presented very homogeneous dense and smooth surfaces, as shown by the SEM and AFM studies.

Magnetoelectric coefficient in strontium ruthenate buffered lanthanum modified bismuth ferrite thin films grown by chemical method

This paper focuses on the magnetoelectric coupling (ME) at room temperature in lanthanum modified bismuth ferrite thin film (BLFO) deposited on SrRuO 3-buffered Pt/TiO 2/SiO 2/Si(100) substrates by the soft chemical method. BLFO film was coherently grown at a temperature of 500 °C. The magnetoelectric coefficient measurement was performed to evidence magnetoelectric coupling behavior. Room temperature magnetic coercive field indicates that the film is magnetically soft. The maximum magnetoelectric coefficient in the longitudinal direction was close to 12 V/cmOe. Dielectric permittivity and dielectric loss demonstrated only slight dispersion with frequency due the less two-dimensional stress in the plane of the film. Polarization reversal was investigated by applying dc voltage through a conductive tip during the area scanning. We observed that various types of domain behavior such as 71 ° and 180° domain switching, and pinned domain formation occurred. Copyright © 2009 American Scientific Publishers All rights reserved.

Local electromethanical properties of the CaCu 3Ti 4O 12 ceramics

Scanning probe microscopy (SPM) was used to probe piezoelectric vibrations and local conductivity in CaCu 3Ti 4O 12 (CCTO) ceramics at room temperature. Piezoelectric contrast was observed on the polished surfaces of CCTO in both vertical (out-of-plane) and lateral (in-plane) modes and depended on the grain orientation varying in sign and amplitude. The piezoelectric contrast is shown to be controlled by the electrical bias (local poling) and displayed a ferroelectric-like reversible hysteresis accompanied with a change of the phase of piezoelectric signal. Flexoelectric effect (strain-gradient-induced polarization) due to surface relaxation was invoked to explain the observed contrast inside the grains. © 2010 Materials Research Society.

Propriedades mecânicas e tribológicas de filmes sintetizados mediante técnica de deposição e implantação iônica por imersão em plasma

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Strukturbildung in dünnen Filmen aus Mischungen statistischer Copolymere

Dünne Polymerfilme besitzen einen weiten Anwendungsbereich in vielen High-Tech Applikationen. All diese Anwendungen erfordern ein bestimmtes Anwendungsprofil des dünnen Films. Diese Anforderungen umschließen sowohl die physikalischen Eigenschaften des Films als auch seine Struktur. Um sie zu realisieren, werden oftmals Mischungsfilme aus verschiedenen Polymeren verwendet. Diese neigen jedoch in vielen Fällen zur bereits während der Präparation zu Phasenseparation.Vor diesem Hintergrund wurde untersucht welchen Einfluss die Verträglichkeit der gemischten Polymere auf die Strukturbildung des dünnen Films ausüben. Als Modellsystem hierfür dienten Mischungen statistischer Poly-styrol-stat-para brom-styrol Copolymere.Die Oberflächenstrukturen, die sich währen der Präparation der Mischungsfilme einstellten, wurden mit Rasterkraftmikroskopie untersucht. wobei die Topologie einer statistischen Analyse unterzogen wurde. Zum einen wurde hierzu die spektrale Leistungsdichte der Oberflächenkontour zum anderen die zugehörigen Minkowski-Funktionale berechnet.Neben Oberflächenstrukturen bilden sich während der Präparation auch Entmischungsstrukturen im inneren des Filmes. Zur Charakterisierung dieser Strukturen wurden die Filme durch Streuung unter streifendem Einfall untersucht. Durch eine modellfreie Interpretation der Streuexperimente gelang der Nachweis der inneren StrukturenFür nur schwach unverträglich Filme konnte auf Basis der Streuexperimente eine Replikation der Oberflächenstruktur des Substrates auf die Filmoberflächen nachgewiesen werden. Diese Replikation wurde für verschieden raue Substrate und bezueglich der Kinetik ihrer Abnahme beim Quellen der Filme untersucht.

Polymer brushes - Wetting properties and my-patterning

In this work polymer brushes on both flat and curved substrates were prepared by grafting from and grafting to techniques. The brushes on flat substrates were patterned on the µm-scale with the use of an inkjet printer. Thus it was demonstrated that chemistry with an inkjet printer is feasible. The inkjet printer was used to deposit microdroplets of acid. The saponification of surface-immobilized ATRP initiators containing an ester bond occurred in these microdroplets. The changes in the monolayer of ester molecules due to saponification were amplified by SI-ATRP. It was possible to correlate the polymer brush thickness to effectiveness of saponification. The use of an inkjet printer allowed for simultaneously screening of parameters such as type of acid, concentration of acid, and contact time between acid and surface. A dip-coater was utilized in order to test the saponification independent of droplet evaporation. The advantage of this developed process is its versatility. It can be applied to all surface-immobilized initiators containing ester bonds. The technique has additionally been used to selectively defunctionalize the initiator molecules covering a microcantilever on one side of a cantilever. An asymmetric coating of the cantilever with polymer brushes was thus generated. An asymmetric coating allows the use of a microcantilever for sensing applications. The preparation of nanocomposites comprised of polyorganosiloxane microgel particles functionalized with poly(ethyl methacrylate) (PEMA) brushes and linear, but entangled, PEMA chains is described in the second major part of this thesis. Measurement of the interparticle distance was performed using scanning probe microscopy and grazing incidence small angle X-ray scattering. The matrix molecular weight at which the nanocomposite showed microphase separation was related to abrupt changes in inter-particle distance. Microphase separation occurred once the matrix molecular exceeded the molecular weight of the brushes. The trigger for the microphase separation was a contraction of the polymer brushes, as the measurements of inter-particle distance have revealed. The brushes became impenetrable for the matrix chains upon contraction and thus behaved as hard spheres. The contraction led to a loss of anchoring between particles and matrix, as shown by nanowear tests using an atomic force microscope. Polyorganosiloxane microgel particles were functionalized with 13C enriched poly(ethyl methacrylate) brushes. New synthetic pathways were developed in order to enrich not the entire brush with 13C, but only exclusively selected regions. 13C chemical shift anisotropy, an advanced NMR technique, can thus be used in order to gather information about the extended conformations in the 13C enriched regions of the PEMA chains immobilized on the µ-gel-g-PEMA particles. The third part of this thesis deals with the grafting to of polymeric fullerene materials on silicon substrates. Active ester chemistry was employed in order to prepare the polymeric fullerene materials and graft these materials covalently on amino-functionalized silicon substrates.rn

Nanoscale surface properties and interaction with fundamental biomolecules of chlorite and phlogopite

The surface properties of minerals have important implications in geology, environment, industry and biotechnology and for certain aspects in the research on the origin of life. This research project aims to widen the knowledge on the nanoscale surface properties of chlorite and phlogopite by means of advanced methodologies, and also to investigate the interaction of fundamental biomolecules, such as nucleotides, RNA, DNA and amino acid glycine with the surface of the selected phyllosilicates. Multiple advanced and complex experimental approaches based on scanning probe microscopy and spatially resolved spectroscopy were used and in some cases specifically developed. The results demonstrate that chlorite exposes at the surface atomically flat terraces with 0.5 nm steps typically generated by the fragmentation of the octahedral sheet of the interlayer (brucitic-type). This fragmentation at the nanoscale generates a high anisotropy and inhomogeneity with surface type and isomorphous cationic substitutions determining variations of the effective surface potential difference, ranging between 50-100 mV and 400-500 mV, when measured in air, between the TOT surface and the interlayer brucitic sheet. The surface potential was ascribed to be the driving force of the observed high affinity of the surface with the fundamental biomolecules, like single molecules of nucleotides, DNA, RNA and amino acids. Phlogopite was also observed to present an extended atomically flat surface, featuring negative surface potential values of some hundreds of millivolts and no significant local variations. Phlogopite surface was sometimes observed to present curvature features that may be ascribed to local substitutions of the interlayer cations or the presence of a crystal lattice mismatch or structural defects, such as stacking faults or dislocation loops. Surface chemistry was found similar to the bulk. The study of the interaction with nucleotides and glycine revealed a lower affinity with respect to the brucite-like surface of chlorite.

Caratterizzazione microscopica di un transistor organico a effetto di campo

Negli ultimi anni uno dei settori di ricerca più interessanti in ambito tecnologico è sicuramente quello dell'elettronica organica. Lo sviluppo è spinto dai vantaggi che portano i dispositivi basati su materiali organici: bassi costi di produzione, facilità di fabbricazione su grandi aree e flessibilità. In questa tesi andiamo ad esaminare un transistor organico a effetto di campo (OFET) dal punto di vista macroscopico e microscopico, cercando di mettere in relazione le sue caratteristiche morfologiche ed elettriche. Il dispositivo sottoposto ai test è un OFET realizzato con TIPS-pentacene come semiconduttore. Dai risultati ottenuti si evince che le prestazioni elettriche del transistor sono fortemente legate alla microstruttura assunta dal materiale organico durante la deposizione. I primi due capitoli illustrano i principi di funzionamento degli OFET e la tecnica SPM (scanning probe microscopy) utilizzata per l'indagine microscopica. Il terzo e quarto capitolo descrivono rispettivamente gli apparati sperimentali e i risultati ottenuti dall'indagine su due aree diverse del dispositivo.

Resolving Atomic Connectivity in Graphene Nanostructure Junctions

We report on the structural characterization of junctions between atomically well-defined graphene nanoribbons (GNRs) by means of low-temperature, noncontact scanning probe microscopy. We show that the combination of simultaneously acquired frequency shift and tunneling current maps with tight binding (TB) simulations allows a comprehensive characterization of the atomic connectivity in the GNR junctions. The proposed approach can be generally applied to the investigation of graphene nanomaterials and their interconnections and is thus expected to become an important tool in the development of graphene-based circuitry.

Deterministic Switching in Bismuth Ferrite Nanoislands

We report deterministic selection of polarization variant in bismuth BiFeO3 nanoislands via a two-step scanning probe microscopy procedure. The polarization orientation in a nanoisland is toggled to the desired variant after a reset operation by scanning a conductive atomic force probe in contact over the surface while a bias is applied. The final polarization variant is determined by the direction of the inhomogeneous in-plane trailing field associated with the moving probe tip. This work provides the framework for better control of switching in rhombohedral ferroelectrics and for a deeper under- standing of exchange coupling in multiferroic nanoscale hetero- structures toward the realization of magnetoelectric devices.

Synthesis and Characterization of Nanostructured Electro-active Materials

Thesis (Ph.D.)--University of Washington, 2016-08