Dissertations / Theses on the topic 'Nanofabrication, growth and self assembly'
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Zin, Melvin T. "Self-assembly and nanofabrication approaches towards photonics and plasmonics /." Thesis, Connect to this title online; UW restricted, 2007. http://hdl.handle.net/1773/15502.
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Jung, Yeon Sik. "Templated self-assembly of siloxane block copolymers for nanofabrication." Thesis, Massachusetts Institute of Technology, 2009. http://hdl.handle.net/1721.1/52791.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2009.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Cataloged from student submitted PDF version of thesis.
Includes bibliographical references.
Monolayer patterns of block copolymer (BCP) microdomains have been pursued for applications in below sub-30 nm nanolithography. BCP selfassembly processing is scalable and low cost, and is well-suited for integration with existing semiconductor fabrication techniques. The two critical issues are how to obtain reliable long-range ordering of features with minimum defect densities and how to successfully transfer the patterns into other functional materials. Exceptionally well-ordered and robust nanoscale patterns can be made from poly(styrene-b-dimethylsiloxane) (PS-PDMS) BCPs, which have a very large Flory-Huggins interaction parameter between the blocks compared to other commonly used BCPs. Cylinder- or sphere-forming BCP films were spincoated over silicon substrates patterned with shallow steps using optical lithography or nanoscale posts made by electron-beam lithography, and solvent-annealed to induce ordering. This generates patterns with a correlation length of at least several micrometers. The annealed film was treated with plasma to obtain oxidized PDMS patterns with a lateral dimension of 14 - 18 nm. These can be used as an etch mask or an easily removable template for patterning functional materials. Solvent vapor treatments can tune the pattern dimension and morphology. Different degrees of solvent uptake in BCP films during solvent-annealing can manipulate the interfacial interaction between the two blocks, and a mixed solvent vapor can change the effective volume fraction of each block. The self-assembled patterns can be transferred into various kinds of functional materials.
(cont.) For example, arrays of parallel lines were used as a mask to pattern poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) conducting polymer thin films. The resulting PEDOT:PSS nanowire array was used as an chemiresistive-type ethanol-sensing device. Metallic films such as Ti, Pt, Ta, W, and magnetic Co and Ni were structured using a pattern-reversal process. Coercivity enhancements were observed for the fabricated ferromagnetic nanostructures such as wires, rings, and antidots. These functional nanostructures can be utilized for a variety of devices such as high-density and high performance sensor or memory devices.
by Yeon Sik Jung.
Ph.D.
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Do, Hyung Wan. "Three-dimensional nanofabrication by electron-beam lithography and directed self-assembly." Thesis, Massachusetts Institute of Technology, 2014. http://hdl.handle.net/1721.1/93778.
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Thesis: S.M., Massachusetts Institute of Technology, Department of Electrical Engineering and Computer Science, 2014.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Cataloged from student-submitted PDF version of thesis.
Includes bibliographical references.
In this thesis, we investigated three-dimensional (3D) nanofabrication using electron-beam lithography (EBL), block copolymer (BCP) self-assembly, and capillary force-induced self-assembly. We first developed new processes for fabricating 3D nanostructures using a hydrogen silsesquioxane (HSQ) and poly(methylmeth-acrylate) (PMMA) bilayer resist stack. We demonstrated self-aligned mushroom-shaped posts and freestanding supported structures. Next, we used the 3D nanostructures as topographical templates guiding the self-assembly of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) block copolymer thin films. We observed parallel cylinders, mesh-shaped structures, and bar-shaped structures in PDMS. Finally, we studied capillary force-induced self-assembly of linear nanostructures using a spin drying process. We developed a computation schema based on the pairwise collapse of nanostructures. We achieved propagation of information and built a proof of concept logic gate.
by Hyung Wan Do.
S.M.
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Perl, András. "Multivalent self-assembly at interfaces from fundamental kinetic aspects to applications in nanofabrication /." Enschede : University of Twente [Host], 2008. http://doc.utwente.nl/60316.
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Gates, Elisabeth Pound. "Self-Assembled DNA Origami Templates for the Fabrication of Electronic Nanostructures." BYU ScholarsArchive, 2013. https://scholarsarchive.byu.edu/etd/4000.
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An important goal of nanoscience is the self-assembly of nanoscale building blocks into complex nanostructures. DNA is an important and versatile building block for nanostructures because of its small size, predictable base pairing, and numerous sequence possibilities. I use DNA origami to design and fold DNA into predesigned shapes, to assemble thin, branched DNA nanostructures as templates for nanoscale metal features. Using a PCR-based scaffold strand generation procedure, several wire-like nanostructures with varying scaffold lengths were assembled. In addition, more complex prototype circuit element structures were designed and assembled, demonstrating the utility of this technique in creating complex templates. My fabrication method for DNA-templated nanodevices involves a combination of techniques, including: solution assembly of the DNA templates, surface orientation and placement, and selective nanoparticle attachment to form nanowires with designed gaps for the integration of semiconducting elements to incorporate transistor functionality. To demonstrate selective surface placement of DNA templates, DNA origami structures have been attached between gold nanospheres assembled into surface arrays. The DNA structures attached with high selectivity and density on the surfaces. In a similar base-pairing technique, 5 nm gold nanoparticles were aligned and attached to specific locations along DNA templates and then plated to form continuous metallic wires. The nanoparticles packed closely, through the use of a high density of short nucleotide attachment sequences (8 nucleotides), enabling a median gap size of 4.1 nm between neighboring nanoparticles. Several conditions, including hybridization time, magnesium ion concentration, ratio of nanoparticles to DNA origami, and age of the nanoparticle solution were explored to optimize the nanoparticle attachment process to enable thinner wires. These small, branched nanowires, along with the future addition of semiconducting elements, such as carbon nanotubes, could enable the formation of high-density self-assembled nanoscale electronic circuits.
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Pinto, Gómez Christian. "Directed self-assembly of block copolymers for the fabrication of nanomechanical structures." Doctoral thesis, Universitat Autònoma de Barcelona, 2021. http://hdl.handle.net/10803/671972.
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El principal objectiu d'aquesta tesi, titulada "autoensamblatge dirigit de copolímers de bloc per a la fabricació d'estructures nanomecàniques", és demostrar la possibilitat de fabricar estructures nanomecàniques funcionals mitjançant el autoensamblatge dirigit (DSA) de copolímers de bloc (BCPs) com a tècnica de nanoestructuració .
El DSA és una tècnica de nanolitografía bottom-up basada en la capacitat que tenen els BCPs de segregar en dominis d'escala micro / nanomètrica. Gràcies a la seva alta resolució, alt rendiment i baix cost, aquesta tècnica ha estat molt estudiada per la indústria de semiconductors per nanoelectrònica, però també ha estat aplicada en altres camps que requereixen d'una alta densitat d'elements a escala nanomètrica.
En aquesta tesi presentem un procés innovador basat en DSA que demostra ser apte per a la fabricació de sistemes nanomecànics. Vam demostrar la fabricació de membranes de silici suspeses ancorades per matrius de gran nombre de nanofils de silici emprant la grafoepitaxia de poliestirè-b-polimetilmetacrilat (PS-b-PMMA), un dels BCP més estesos. Els dispositius obtinguts poden desenvolupar-se per construir sensors de massa d'alta sensibilitat basats en ressonadors nanomecànics.El principal objetivo de esta tesis, titulada "Autoensamblaje dirigido de copolímeros de bloque para la fabricación de estructuras nanomecánicas", es demostrar la posibilidad de fabricar estructuras nanomecánicas funcionales mediante el autoensamblaje dirigido (DSA) de copolímeros de bloque (BCPs) como técnica de nanoestructuración. El DSA es una técnica de nanolitografía bottom-up basada en la capacidad que tienen los BCPs de segregarse en dominios de escala micro/nanométrica. Gracias a su alta resolución, alto rendimiento y bajo coste, esta técnica ha sido muy estudiada por la industria de semiconductores para nanoelectrónica, pero también ha sido aplicada en otros campos que requieren de una alta densidad de elementos a escala nanométrica. En esta tesis presentamos un proceso novedoso basado en DSA que demuestra ser apto para la fabricación de sistemas nanomecánicos. Demostramos la fabricación de membranas de silicio suspendidas ancladas por matrices de gran número de nanohilos de silicio empleando la grafoepitaxia de poliestireno-b-polimetilmetacrilato (PS-b-PMMA), uno de los BCP más extendidos. Los dispositivos obtenidos pueden desarrollarse para construir sensores de masa de alta sensibilidad basados en resonadores nanomecánicos.
The main goal of this dissertation, entitled "irected self-assembly of block copolymers for the fabrication of nanomechanical structures", is to demonstrate the possibility of fabricating nanomechanical functional structures by employing the directed self-assembly (DSA) of block copolymers (BCPs) as a nanopatterning tool. DSA is a bottom-up nanolithography technique based on the ability of BCPs to segregate into domains at the micro/nanoscale, and it has attracted high interest due to its inherent simplicity, high throughput, low cost and potential for sub-10 nm resolution. Thanks to these characteristics, the technique has been heavily studied by the semiconductor industry for nanoelectronics, and also applied to alternate fields that might require from the definition of high-density nanoscale features. In this thesis we present a novel fabrication route based on DSA that proves to be suitable for the fabrication of nanomechanical systems. Here, we demonstrate the fabrication of suspended silicon membranes clamped by high-density arrays of silicon nanowires by using a DSA approach based on the graphoepitaxy of polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA), a well-known diblock copolymer. Obtained devices can be further developed for building up high-sensitive mass sensors based on nanomechanical resonators.
Universitat Autònoma de Barcelona. Programa de Doctorat en Enginyeria Electrònica i de Telecomunicació
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Jespersen, Michael L. 1979. "Engineering the macro-nano interface: Designing the directed self-assembly and interfacial interactions of gold nanoparticle monolayers." Thesis, University of Oregon, 2008. http://hdl.handle.net/1794/7504.
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xviii, 192 p.Gold nanoparticles in the 1-2 mn core diameter size regime have generated a great deal of interest due to their size-dependent electronic, optical, and catalytic properties. A number of proof-of-concept experiments have demonstrated that small metal nanoparticles can be integrated into single electron transistors and optical waveguides. Still, reliable incorporation of gold nanoparticles into devices requires practical methods for their assembly on surfaces. Additionally, surface modification methods must be developed in order to control interparticle interactions and nanoparticle-environment interactions for use in sensing and catalysis. In this research, nanoparticle-substrate interactions were utilized to assemble surface-bound gold nanoparticle monolayers with interesting electronic and catalytic properties. Gold nanoparticles (1.5 nm diameter) with a thiol ligand shell containing phosphonic acid terminal functionality were synthesized and assembled selectively onto hafnium-modified silicon dioxide substrates through bonding of the terminal phosphonate to Hf(IV) surface groups. By increasing the surface coverage of Hf, it was possible to assemble monolayers of gold nanoparticles dense enough to exhibit nonlinear current-voltage properties across a 5-μm electrode gap at room temperature. Moreover, by taking advantage of the selectivity of this ligand shell for ZnO over SiO 2 , small gold nanoparticles were utilized as catalysts for selective growth of patterned, vertical ZnO nanowire arrays. In addition to engineering nanoparticle-substrate interactions, new surface modification methods were introduced to manipulate the interaction of the as-deposited gold nanoparticle monolayers with the environment. For example, thiol-thiol ligand exchange reactions were carried out on the surface-bound nanoparticle monolayers by immersion in dilute thiol solutions. Contact angle and XPS measurements indicate that the upper, surface-exposed phosphonic acid ligands are replaced by incoming thiol ligands. TEM measurements indicate that nanoparticle monolayers remain surface-bound and are stable to this exchange process, as the average particle size and surface coverage are preserved. As another example, the ligand shell can be partially removed by UV/ozone treatment to expose bare gold cores to the surrounding environment. On metal oxide substrates, this approach activates the particles for room temperature oxidation of carbon monoxide to carbon dioxide. This dissertation includes both my previously published and my co-authored materials.
Adviser: James E. Hutchison
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Cruz, Daniel Alejandro. "Hierarchical Self-Assembly and Substitution Rules." Scholar Commons, 2019. https://scholarcommons.usf.edu/etd/7770.
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A set of elementary building blocks undergoes self-assembly if local interactions govern how this set forms intricate structures. Self-assembly has been widely observed in nature, ranging from the field of crystallography to the study of viruses and multicellular organisms. A natural question is whether a model of self-assembly can capture the hierarchical growth seen in nature or in other fields of mathematics. In this work, we consider hierarchical growth in substitution rules; informally, a substitution rule describes the iterated process by which the polygons of a given set are individually enlarged and dissected. We develop the Polygonal Two-Handed Assembly Model (p-2HAM) where building blocks, or tiles, are polygons and growth occurs when tiles bind to one another via matching, complementary bonds on adjacent sides; the resulting assemblies can then be used to construct new, larger structures. The p-2HAM is based on a handful of well-studied models, notably the Two-Handed Assembly Model and the polygonal free-body Tile Assembly Model.
The primary focus of our work is to provide conditions which are either necessary or sufficient for the ``bordered simulation'' substitution rules. By this, we mean that a border made up of tiles is allowed to form around an assembly which then coordinates how the assembly interacts with other assemblies. In our main result, we provide a construction which gives a sufficient condition for bordered simulation. This condition is presented in graph theoretic terms and considers the adjacency of the polygons in the tilings associated to a given substitution rule. Alongside our results, we consider a collection of over one hundred substitution rules from various sources. We show that only the substitution rules in this collection which satisfy our sufficient condition admit bordered simulation. We conclude by considering open questions related to simulating substitution rules and to hierarchical growth in general.
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Gottlieb, Steven. "High-resolution guiding patterns for the directed self-assembly of block copolymers." Doctoral thesis, Universitat Autònoma de Barcelona, 2018. http://hdl.handle.net/10803/669854.
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The presented thesis entitled “High-resolution guiding patterns for the directed self-assembly of block copolymers” investigates strategies to introduce long-range order into block copolymer thin films for nanopatterning applications.
Structures defined by top-down lithography that enable the introduction of long-range order into an otherwise disordered thin film of block copolymers are referred to as guiding patterns. This thesis explores and develops different techniques that enable the fabrication of guiding patterns with a particular focus on methods capable of providing high-resolution and high-accuracy, because they are at the prospect of playing a crucial role in the directed self-assembly of very low-pitch block copolymer materials. We demonstrate the directed self-assembly of an 11.7 nm full-pitch PS-b-PMMA block copolymer with guiding patterns fabricated by means of five different top-down lithography techniques.
One strategy to fabricate guiding patterns consists in the generation of topographic structures, which is referred to as graphoepitaxy. In this case, we have used extreme-ultraviolet interference lithography to fabricate trenches with nanometer precision to study the self-assembly behavior of block copolymers under nanoconfinement with high accuracy. This system has allowed us to develop a free energy model to predict for which guiding pattern dimensions the defect-free directed self-assembly can be expected. Moreover, we have used electron beam lithography for the fabrication of sub-10 nm wide topographical guiding patterns and study the directed self-assembly of block copolymers in structures with feature sizes close to the material’s half-pitch.
Another strategy to fabricate guiding pattern consists of chemical surface modification to create areas that are selectively affine to one of the blocks. We have presented a novel approach based on thermal scanning probe lithography and adjust the patterning conditions for the fabrication of chemical guiding patterns with 10 nm line width. Due to the absence of the proximity and diffraction effects, thermal scanning probe lithography is ideal for the fabrication of dense high-resolution chemical patterns.
As a third strategy to align block copolymers, we use grain boundaries in block copolymer thin films as order-inducing surfaces. A surface modification is used to trap a grain of vertically oriented block copolymers between two grains of horizontally oriented block copolymer domains in a controlled manner. We call the developed technique “grain-boundary induced alignment”. To demonstrate its working principle we employ mechanical AFM and electron beam direct writing, and show the ordering of block copolymers on length scales of various hundreds of nanometers.
The presented thesis is complemented with the development of a probe-based imaging technique to study the thermal conductivity of polymer materials with sub-10 nm lateral resolution. The dissipation of heat into a sample is determined at each measurement point by means of an electrical circuit that is integrated into the cantilever. We study the thermal conductivity of PS-b-PMMA block copolymers with different pitches and different orientations. This technique represents an advance in the investigation of polymeric surfaces due to its high resolution and good material sensitivity.
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Molnar, G., L. Dozsa, Z. Vertesy, and Z. J. Horvath. "Thickness Dependent Growth of Epitaxial Iron Silicide Nanoobjects on Si (001)." Thesis, Sumy State University, 2013. http://essuir.sumdu.edu.ua/handle/123456789/35180.
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Strain-induced, self-assembled iron silicide nanostructures were grown on Si(001) substrate by conventional
Fe evaporation and subsequent annealing. The initial Fe thickness was in the 0.1-6.0 nm range and
the annealing temperature was 850 °C. The formed phases and structures were characterized by reflection
high energy electron diffraction, and scanning electron microscopy. The electrical characteristics were investigated
by I-V and C-V measurements, and by DLTS. The samples show silicide nanostructure formation
in the whole thickness range. The shape of the nanostructures varied from rod like to triangular
and quadratic depending on the initial Fe thickness. The size distribution of the formed iron silicide nanoobjects
was not homogeneous, but they were oriented in square directions on Si(001). Higher thickness
resulted in increased particles size.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35180
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Jiang, Feng. "Ligand Controlled Growth of Aqueous II-VI Semiconductor Nanoparticles and Their Self-Assembly." Diss., The University of Arizona, 2013. http://hdl.handle.net/10150/311311.
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Colloidal semiconductor nanoparticles (NPs) contain hundreds to thousands of atoms in a roughly spherical shape with diameters in the range of 1-10 nm. The extremely small particle size confines electron transitions and creates size tunable bandgaps, giving rise to the name quantum dots (QDs). The unique optoelectronic properties of QDs enable a broad range of applications in optical and biological sensors, solar cells, and light emitting diodes. The most common compound semiconductor combination is chalcogenide II-VI materials, such as ZnSe, CdSe, and CdTe. But III-V and group IV as well as more complicated ternary materials have been demonstrated. Coordinating organic ligands are used to cap the NP surface during the synthesis, as a mean of protecting, confining, and separating individual particles. This study investigated the impact of the ligand on particle growth and self-assembly into hierarchical structures. ZnSe QDs were synthesized using an aqueous route with four different thiol ligands, including 3-mercaptopropionic acid (MPA), thioglycolic acid (TGA), methyl thioglycolate (MTG), and thiolactic acid (TLA). The particle growth was monitored as a function of reaction time by converting the band gaps measured using UV-vis spectroscopy into particle sizes. A kinetic model based on a diffusion-reaction mechanism was developed to simulate the growth process. The growth data were fit to this model, yielding the binding strength in the order TLA < MTG ≈ TGA < MPA. This result showed the relationship between the QD growth rates and the chemical structures of the ligands. Ligands containing electron-withdrawing groups closer to the anchoring S atom and branching promoted growth, whereas longer, possibly bidendate, ligands retarded it. Removing TGA ligands from the surface of CdTe QDs in a controlled manner yielded new superstructures that were composed of either intact or fused particles. Purifying as-synthesized QDs by precipitating them using an anti-solvent removed most of the free ligand in solution. Aging this purified QD suspension for a week caused self-assembly of QDs into nanoribbons. The long time needed for self-assembly was due to the slow equilibrium between the ligands on QD surface and in solution. Accelerating the approach to equilibrium by diluting purifed CdTe QDs with organic solvents triggered rapid self-assembly of superstructures within a day, forming various nanostructures from nanoribbons to nanoflowers. The type of nanostructures that formed was determined by the solvation of TGA in the trigger solvent. Extracting the smallest portion of TGA in methanol promoted vectorial growth into ribbons consistent with dipole-dipole attractive and charge-charge repulsive interactions. Removing more of the TGA layer in IPA caused the dots to fuse into webs containing clustered ribbons and branches, and the directional nature of the superstructure was lost. Completely deprotecting the surface in acetone promoted photochemical etching and dissolved the QDs, yielding
ower-like structures composed of CdS. Nanocrystal (NC) growth mediated by a ligand was also studied in the organic synthesis of FeS₂ nanocubes. Oleylamine was used not only as the ligand but also the solvent and reductant during the reaction. A one hour reaction between iron (II) chloride and elemental sulfur in oleylamine at 200 ℃ and a S to Fe ratio of 6 yielded phase pure pyrite cubes with dimensions of 87.9±14.1 nm. X-ray diffraction (XRD) spectra and Raman peaks for pyrite at 340, 375, and 426 cm⁻¹ confirmed phase purity. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results showed that the oleylamine remained on the FeS₂ surface as a ligand. The reaction mechanism includes the production of pyrrhotite Fe₁₋ᵪS (0≤x<0.5) via reduction of S⁰ to S²⁻ by oleylamine and the oxidation of pyrrhotite to pyrite with remaining S⁰.
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Bouville, Florian. "Self-assembly of anisotropic particles driven by ice growth : Mechanisms, applications and bioinspiration." Thesis, Lyon, INSA, 2013. http://www.theses.fr/2013ISAL0155/document.
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Les phénomènes d'auto-assemblage sont au premier plan de la recherche en sciences des matériaux car ils comblent le vide laissé entre les procédés d'assemblage à l'échelle macroscopique et nanoscopique. L'auto-assemblage est basé sur l'organisation spontanée de composants individuels en motifs et structures. Contrôler l’agencement de la matière peut accroître les propriétés de matériaux en introduisant une certaine anisotropie. Cet agencement, comme de nombreux matériaux naturels le prouvent, peut même sous certaines conditions faire émerger de nouvelles caractéristiques. Au cours de ces trois années, nous avons utilisé l’ « ice templating » (texturation à la glace) pour déclencher l’alignement de plaquettes de dimensions microniques, le but final étant de répliquer la microstructure de la nacre. Cette technique induit la ségrégation des constituants d’une suspension à l’échelle du micron tout en obtenant des échantillons de quelques centimètres cubes. Ce procédé a permis la création de matériaux inorganique avec une microstructure semblable à la nacre, en additionnant trois niveaux de contrôles successifs : l’alignement local des plaquettes, l’alignement à longue distance des cristaux de glaces et enfin le contrôle de l’interface entre ces-mêmes plaquettes. L’utilisation d’une modélisation par éléments discrets nous a permis d’étudier la dynamique de l’auto-assemblage des particules anisotropes. Ce modèle, parce qu’il tient compte de la dynamique du procédé, nous a révélé comment l’organisation de ces particules se produit. La tomographie par rayon X a permis de visualiser les structures finales des échantillons et d’attester de la pertinence du modèle. L’alignement local des plaquettes dans les parois générées par la solidification de la glace peuvent accroître les propriétés fonctionnelles et structurales de composites. Dans ce cadres deux applications ont été étudiées : la conduction thermique dans des composites nitrure de bore hexagonal / silicone et les propriétés mécaniques d’alumine macroporeuses. Une adaptation du procédé a permis d’obtenir l’alignement à longue distance (quelques centimètres) des cristaux de glaces. Différents outils ont été développés pour caractériser la réponse fonctionnelle de ce type de composite en fonction de leurs architectures aux deux échelles considérées (celles des macropores et parois). Enfin, après la mise en place de ces deux niveaux de contrôle sur la structure, l’addition d’une phase vitreuse inorganique et de nanoparticules aux joints de grains des plaquettes a introduit, de façon similaire à la nacre, des interfaces pouvant dévier et arrêter la propagation de fissuresSelf-assembly phenomena are of prime interest in materials science, because they fill the gap between assembly of macrostructure and processing of nanomaterials. Self-assembly is based on the spontaneous organization of individual small constituents into patterns and structures. Controlling the spatial arrangement can possibly improve materials properties by maximizing its response in a given direction. Furthermore, particular types of spatial arrangement, such as found in natural structures, can even induce new properties. During the past three years, we have used ice templating process to trigger the assembly of platelet-shaped particles to replicate the hierarchical structure of nacre. Control over this technique allowed structural customization at different length-scales: local orientation of the platelets, ice crystal long range order, and the control if the interfaces between the platelets. This hierarchical process has set the ground for the creation of a new fully mineral nacre-like alumina. The local platelet self-assembly triggered by ice growth was investigated by Discrete Element Modelling which provided new insight into the dynamic phenomenon responsible for the particles alignment. Synchrotron X-ray tomography was used to validated the model results. The different architecture observed in the final samples are not the result of a percolation threshold, as one could expect, but is instead a consequence of the delicate balance between pushing and engulfment at the solidification front. The local alignment of platelets can be beneficial for the functional and structural characteristics of composites and relevant aspects for two potential applications were investigated: the thermal properties of the hexagonal boron nitride/silicon rubber composites and the mechanical properties of macroporous alumina. Further adaptation of the process allowed for long range ordering of the ice crystals (up to the centimeter scale). Different tools have also been developed in order to characterize the response of composites as a function of the architecture at the level of the macropores and particle organisation. Once those two levels of alignment were achieved, the addition of a glassy phase and nanoparticles to the grain boundaries of the platelets introduces, just like in nacre, interfaces capable of deflect and even stopping crack propagation
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Hille, Pascal [Verfasser]. "Advanced group III-nitride nanowire heterostructures - self-assembly and position-controlled growth / Pascal Hille." Gießen : Universitätsbibliothek, 2017. http://d-nb.info/1132510511/34.
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Nardi, Elena. "Growth of organic nanostructures through on-surface reactions : from phthalocyanines self-assembly to polymeric phthalocyanines." Thesis, Aix-Marseille, 2015. http://www.theses.fr/2015AIXM4351/document.
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Le couplage covalent de précurseurs moléculaires spécialement conçus, assisté par une surface métallique, a récemment émergé comme nouvelle voie pour la création de nouvelles architectures moléculaires prometteuses pour l’électronique moléculaire. Les phtalocyanines et leurs dérivés ont attiré beaucoup d’intérêt à cause de leurs propriétés chimiques et optoélectroniques. Dans cette thèse la synthèse de composés de phtalocyanine est présentée. Les composés sont obtenus par une réaction en surface entre précurseurs fonctionnalisés avec quatre groupements carbonitriles et des atomes métalliques. L’étude expérimentale est faite par microscopie à effet tunnel et spectroscopie de photoémission X. Les précurseurs moléculaires de TCN-DBTTF et de PPCN ont été étudiés. Les TCN-DBTTF ont été déposés avec les atomes de Mn, Fe ou Cu sur Ag(111) et Au(111). La réaction de cyclotetramerization a été activée par recuits. Dans le cas le plus favorable (TCN-DBTTF avec Fe sur Ag(111)), la réaction peut être activée à 200°C et permet la synthèse de phtalocyanines individuelles. Un recuit à plus haute température permet de continuer la réaction en 1D (250°C) et en 2D (275°C). Des résultats similaires ont été obtenus pour le dépôt de PPCN avec Mn ou Cu sur Au(111). L’évolution des spectres des niveaux de coeur permet d’obtenir une preuve de la réaction. Les différents facteurs qui influencent la cyclotetramerisation ont été étudiés.L'étude démontre la versatilité de la méthode: la synthèse en surface permet la création de polymères 2D originaux connectés par des macrocycles de phtalocyanine susceptibles d’être étendus à un grand nombre de précurseurs et d’atomes métalliquesSurface-assisted covalent coupling of suitably designed molecular precursors on metal surfaces has recently emerged as a new route towards the design of novel molecular architectures promising for future applications. Phthalocyanines and their derivatives have been widely studied for their chemical and optoelectronic properties. In this thesis the synthesis of phthalocyanine compounds is presented. The compounds are obtained through an on-surface reaction between tetracarbonitrile-functionalized precursors and metals. The experimental investigation is carried out by means of scanning tunnelling microscopy and X-Ray photoemission spectroscopy. Two molecular precursors, TCN-DBTTF and PPCN, are studied. TCN-DBTTF molecules are deposited with metal atoms (Mn, Fe, or Cu) on Ag(111) and Au(111). Annealing is used to activate the reaction of cyclotetramerization between precursors and metals. In the most favourable case (TCN-DBTTF with Fe on Ag(111)) the reaction can be activated at 200°C and leads to the synthesis of individual phthalocyanines. Increasing the temperature allows the synthesis of polymeric lines, at 250°C, and small 2D domains, at 275°C. Similar results are obtained for PPCN deposition with Mn or Cu on Au(111). In this latter case, the evolution of core level spectra allows a chemical proof of the on-surface reaction. The factors affecting on-surface cyclotetramerization have also been studied. This study demonstrates the versatility of the method: on-surface cyclotetramerization allows creating original 2D polymers connected by phthalocyanine macrocycles, and may work with a wide range of tetracarbonitrile-functionalized precursors and metallic atoms
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Davey, Roger J. "The nucleation and growth of crystals from solution - molecular self assembly, materials science and process technology." Thesis, University of Manchester, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.525976.
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Dahal, Yuba Raj. "Equilibrium and kinetic factors in protein crystal growth." Diss., Kansas State University, 2017. http://hdl.handle.net/2097/36220.
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Doctor of PhilosophyDepartment of Physics
Jeremy D. Schmit
Diseases such as Alzheimer’s, Parkinson’s, eye lens cataracts, and Type 2 diabetes are the results of protein aggregation. Protein aggregation is also a problem in pharmaceutical industry for designing protein based drugs for long term stability. Disordered states such as precipitates and gels and ordered states such as crystals, micro tubules and capsids are both possible outcomes of protein–protein interaction. To understand the outcomes of protein–protein interaction and to find the ways to control forces, it is required to study both kinetic and equilibrium factors in protein–protein interactions. Salting in/salting out and Hofmeister effects are familiar terminologies used in protein science field from more than a century to represent the effects of salt on protein solubility, but they are yet to be understood theoretically. Here, we build a theory accounting both attractive and repulsive electrostatic interactions via the Poisson Boltzmann equation, ion–protein binding via grand cannonical partition function and implicit ion–water interaction using hydrated ion size, for describing salting in/salting out phenomena and Hofmeister and/or salt specific effect. Our model free energy includes Coulomb energy, salt entropy and ion–protein binding free energy. We find that the salting in behavior seen at low salt concentration near the isoelectric point of the protein is the output of Coulomb energy such that the addition of salt not only screens dipole attraction but also it enhances the monopole repulsion due to anion binding. The salting out behavior appearing after salting in at high salt concentration is due to a salt mediated depletion interaction. We also find that the salting out seen far from the isoelectric point of the protein is dominated by the salt entropy term. At low salt, the dominant effect comes from the entropic cost of confining ions within the aggregates and at high salt, the dominant effect comes from the entropy gain by ions in solution by enhancing the depletion attraction. The ion size has significant effects on the entropic term which leads to the salt specificity in the protein solubility. Crystal growth of anisotropic and fragile molecules such as proteins is a challenging task because kinetics search for a molecule having the correct binding state from a large ensemble of molecules. In the search process, crystal growth might suffer from a kinetic trap called self–poisoning. Here, we use Monte Carlo simulation to show why protein crystallization is vulnerable to the poisoning and how one can avoid such trap or recover crystal growth from such trap during crystallization. We show that self–poisoning requires only three minimal ingredients and these are related to the binding affinity of a protein molecule and its probability of occurrence. If a molecule attaches to the crystal in the crystallographic state then its binding energy will be high but in protein system this happens with very low probability (≈ 10−5). On the other hand, non–crystallographic binding is energetically weak, but it is highly probable to happen. If these things are realized, then it will not be surprising to encounter with self–poisoning during protein crystallization. The only way to recover or avoid poisoning is to alter the solution condition slightly such as by changing temperature or salt concentration or protein concentration etc.
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Yoshikawa, Taro [Verfasser], and Oliver [Akademischer Betreuer] Ambacher. "Toward ultra-thin nanocrystalline diamond film growth: electrostatic self-assembly of non-aggregated diamond nanoparticles onto substrate surfaces." Freiburg : Universität, 2017. http://d-nb.info/115294469X/34.
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Chen, Jing. "Novel H-bond donor polymers for layer-by-layer self-assembly multilayered films." Thesis, Lyon, INSA, 2013. http://www.theses.fr/2013ISAL0087/document.
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Ce travail est consacré à la synthèse de nouveaux polymères donneurs de liaison Hydrogène et à leur utilisation comme partenaire dans la construction de nouveaux films multicouches préparés par le procédé d’élaboration en couche-par-couche (LbL). Plus particulièrement, une nouvelle réaction impliquant des mercaptoalcools non protégés et le poly(2,3,4,5,6-pentafluorostyrène) (PPFS) a été développé et appliquée à la synthèse de nouveaux polymères donneurs de liaisons H. Ce couplage régiosélectif et chimiosélectif de type « click » avec un thiol hétérofonctionnel peut être utilisée pour préparer une bibliothèque de polymères qui diffèrent de par leur degré de substitution (DS) et/ou leur fonctionnalité en groupements associatifs. Le contrôle de ces paramètres structuraux permet de moduler leur force d’interactions avec des partenaires accepteurs de liaison H variés, comme la poly(4-vinyl pyridine) (P4VP), le poly(acrylate de n-butyle) (PBA) et le poly(oxyde d'éthylène) (PEO), de telle façon que tous les types de mélanges binaires (mélange non miscible, partiellement ou totalement miscible, ou complexe interpolymère) peuvent être obtenus. Ensuite, les dérivés de PPFS donneurs de liaisons H ont été utilisés en partenariat avec le P4VP pour élaborer avec succès de nouveaux films multicouche dont la force motrice est l’établissement de liaisons H. L'influence de nombreux paramètres relatifs à la structure des polymères donneurs (DS, structure chimique du groupement associatif), au type de modification chimique subie par le substrat sur lequel est élaboré le film multicouche (monocouche auto-assemblée vs. polymère greffée en conformation de type brosse) ou encore des paramètres expérimentaux liés aux conditions de dépôt (concentration des solutions de dépôt, nature du partenaire adsorbé en premier) a été étudiée. Plus particulièrement, le mécanisme de croissance ainsi que les caractéristiques de surface du film ont été évaluésThis work deals with the design of novel hydrogen-bond donor polymers and their use as partner in new tailor-made multilayered films prepared by the layer-by-layer (LbL) process. In this context, a novel regioselective and chemoselective “click-type” reaction of unprotected mercaptoalcohols onto poly(2,3,4,5,6-pentafluoro-styrene) (PPFS) has been developed, and applied to the synthesis of new hydroxylated H-bond donor polymers. This coupling with heterofunctional thiol is used to prepare a library of polymers differing in the degree of substitution (DS) and/or functionality. The fine control of these parameters makes it possible to tune their interaction ability with various acceptor polymers such as poly(4-vinyl pyridine) (P4VP), poly(n-butyl acrylate) (PBA) and poly(ethylene oxide) (PEO), such that all possible scenarios (immiscible blend, partially or totally miscible blend or interpolymer complex) can be achieved. Subsequently, the resulting H-bond donor polymers (PPFS derivatives) were used to successfully build-up multilayered films with using P4VP as partner via layer-by-layer (LbL) through the dip deposition process. The influence of various parameters related to structure of the partners (DS, nature of the PPFS derivatives), the chemical structure of the surface onto which the film is built-up (self-assembled monolayer vs. polymer brush) and the deposition process (concentration of deposition solutions, nature of the first deposited partner) was in-depth evaluated, on both the growth mechanism and on the surface features of the multilayered films
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Mukherjee, Sanjoy. "Synthesis, Characterization, and Growth Mechanism of Single-Walled Metal Oxide Nanotubes." Diss., Georgia Institute of Technology, 2007. http://hdl.handle.net/1853/16176.
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Nanotubes have numerous potential applications in areas such as biotechnology, electronics, photonics, catalysis and separations. There are several challenges to be overcome in order to realize their potential, such as: (1) Synthesis of monodisperse (in diameter and in length) single-walled nanotubes; (2) Quantitative understanding of the mechanism of formation and growth of nanotubes; (3) Capability to engineer the nanotube size; (4) Low temperature synthesis process; and (5) Synthesis of impurity free nanotubes. Our investigation focuses on a class of metal oxide (aluminosilicate/germanate) nanotubes, which are; single walled nanotubes with monodisperse inner and outer diameters, can be synthesized in the laboratory by a low temperature (95ºC) process in mildly acidic aqueous solutions, and their formation timescales is hours, which makes it convenient as a model system to study the mechanisms of nanotube formation.
This work is focused on obtaining a qualitative and quantitative understanding of the mechanism of formation of aluminosilicate and aluminogermanate nanotubes. In order to achieve this overall objective, this thesis consists of the following aspects: (1) A systematic phenomenological study of the growth and structural properties of aluminosilicate and aluminogermanate nanotubes. The constant size and increasing nanotube concentration over the synthesis time strongly suggest that these nanotubular are assembled through self-assembly process. (II) Investigation of the mechanism of formation of single-walled aluminogermanate nanotubes provided the central phenomena underlying the formation of these nanostructures: (1) the generation (via pH control) of a precursor solution containing chemically bonded precursors, (2) the formation of amorphous nanoscale (~ 6 nm) condensates via temperature control, and (3) the self-assembly of short nanotubes from the amorphous nanoscale condensates. (III) Synthesis of mixed metal oxide (aluminosilicogermanate) nanotubes with precise control of elemental composition, diameter and length of the product nanotubes. (IV) Preliminary work towards generalization of the kinetic model developed for aluminogermanate nanotubes to a larger class of metal oxide nanotubes. It was found that the size of nanotubes is dependent on the amount of precursors that can be packed in a single ANP and in turn depends on the size of the ANP.
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Kleppmann, Nicola [Verfasser], Sabine [Akademischer Betreuer] Klapp, and Andreas [Akademischer Betreuer] Heuer. "Simulation of growth and self-assembly of complex molecules on surfaces / Nicola Kleppmann. Gutachter: Andreas Heuer ; Sabine Klapp. Betreuer: Sabine Klapp." Berlin : Technische Universität Berlin, 2015. http://d-nb.info/1077040156/34.
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Jones, Aleksy K. "Kinetically determined surface morphology in epitaxial growth." Thesis, University of British Columbia, 2008. http://hdl.handle.net/2429/2499.
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Molecular beam epitaxy has recently been applied to the growth and self assembly of nanostructures on crystal substrates. This highlights the importance of understanding how microscopic rules of atomic motion and assembly lead to macroscopic surface shapes. In this thesis, we present results from two computational studies of these mechanisms.
We identify a kinetic mechanism responsible for the emergence of low-angle facets in recent epitaxial regrowth experiments on patterned surfaces. Kinetic Monte Carlo simulations of vicinal surfaces show that the preferred slope of the facets matches the threshold slope for the transition between step flow and growth by island nucleation. At this crossover slope, the surface step density is minimized and the adatom density is maximized, respectively. A model is developed that predicts the temperature dependence of the crossover slope and hence the facet slope.
We also examine the "step bunching" instability thought to be present in step flow growth on surfaces with a downhill diffusion bias. One mechanism thought to produce the necessary bias is the inverse Ehrlich Schwoebel (ES) barrier. Using continuum, stochastic, and hybrid models of one dimensional step flow, we show that an inverse ES barrier to adatom migration is an insufficient condition to destabilize a surface against step bunching.
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Johnson, Tamina L. "Elastin-Like Polypeptide Fusion Tag as a Protein-Dependent Solubility Enhancer of Cysteine-Knot Growth Factors." Scholar Commons, 2018. https://scholarcommons.usf.edu/etd/7629.
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Elastin-like peptide (ELP) fusions promote therapeutic delivery and efficacy. Recombinant proteins, like neurotrophins, lack bioavailability, have short in vivo half-lives, and require high manufacturing costs. Fusing recombinant proteins with genetically encodable ELPs will increase bioavailability, enhance in vivo solubilization, as well as provide a cost-effective method for purification without the need for chromatography. During expression of neurotrophin-ELP (N-ELP) fusions, dense water-insoluble aggregates known as inclusion bodies (IBs) are formed. Inclusion bodies are partially and misfolded proteins that usually require denaturants like Urea for solubilization. Strong denaturants arrest ELPs stimuli-responsive property and increase unwanted aggregation, making purification difficult, yet possible. The current field of study exhibit issues with protein recovery due to solubility issues and aggregation. This study examines the solubility challenges of inclusion body proteins and the role ELP fusion tags play on IBs solubility. Elastin-like peptides are a class of stimuli-responsive biopolymers whose biocompatibility and limited toxicity are attractive for biological applications. ELPs are tunable polymers, which consist of peptide repeat units (VPGXG), where X is any amino acid except Proline while the guest residue or length of the sequence can be chosen. ELPs have uniquely tunable phase transitioning properties that allow the protein to undergo molecular self-assemblies into different nanostructures in response to the changes in their environment (e.g. pH or temperature). Optimizing the purification process via suppressing aggregation during the refolding process has increased protein recovery slightly however, more work is needed to attain 90 percent recovery. Usage of ELPs has increased the solubility of N-ELP fusions, specifically for brain-derived neurotrophic factor ELP fusions.
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Daher, Mansour Michel. "Transition metal nanolines on a nanopatterned silver substrate : self-organized growth and magnetic properties." Thesis, Aix-Marseille, 2019. http://www.theses.fr/2019AIXM0287.
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L'intérêt pour les propriétés magnétiques des nanostructures de métaux de transition et de lanthanides de faible dimensionnalité n’a cessé de croitre au cours des deux dernières décennies, tant pour leur intérêt en recherche fondamentale que pour la perspective d’applications technologiques. De manière remarquable, les propriétés magnétiques des nanostructures peuvent être ajustées en contrôlant leur géométrie, leur structure atomique et leur environnement chimique. Dans cette thèse, un gabarit 1D composé de nanorubans de Si auto-organisés est utilisé pour guider la croissance de nanolignes de métaux de transition dans le but d’étudier leurs propriétés magnétiques. La géométrie et la structure atomique des nanorubans de Si et des nanolignes de métaux ont été étudiées in situ par microscopie par effet tunnel. Concernant le silicium, notre étude montre qu’une température de 490 K est nécessaire pour obtenir un gabarit 1D hautement ordonné. Les résultats obtenus sur les métaux de transition ont permis de déterminer la géométrie et la structure des nanolignes. Pour accéder aux propriétés magnétiques des nanolignes de Co, des mesures par XMCD ont été effectuées en température, en utilisant différentes orientations du champ magnétique. Les résultats montrent que les deux premières couches de Co adsorbées sur les nanorubans présentent une réponse magnétique faible, tandis que les couches supérieures présentent une aimantation exaltée. Deux axes d’anisotropie dans le plan ont été mis en évidence. Les moments magnétiques et l'énergie d’anisotropie magnétique ont été déterminés quantitativement. Les études en température suggèrent un comportement superparamagnétiqueInterest in the magnetic properties of low dimensional transition metal and lanthanide nanostructures has seen an unprecedented rise in the last two decades due to both their fundamental interest and perspectives of technological applications. Remarkably, the magnetic properties of nanostructures can be tuned by controlling their geometry, atomic structure and chemical environments. In this thesis, a one-dimensional template composed of self-organized Si nanoribbons is used to grow transition metal nanolines, prior to the characterization of their magnetic properties. The geometries and the atomic structure of both the Si nanoribbons and the metal nanolines were investigated in situ by scanning tunneling microscopy. The growth mechanisms were investigated by exploring a large set of growth conditions. Regarding the Si growth, our study shows that a temperature of 490 K is necessary to obtain a long-range ordered one-dimensional template. Concerning the transition metal study, the results resolved the nanoline geometries and atomic structures.To access the magnetic properties of the Co nanolines on Si, XMCD measurements were performed using different magnetic field orientations and temperatures.The results show that the first two Co layers directly adsorbed onto the Si nanoribbons present a weak magnetic response while the upper Co layers exhibit an enhanced magnetization. Remarkably, two in-plane easy axes of magnetization were evidenced.The magnetic moments and the magnetic anisotropic energy are determined quantitatively.Temperature-dependent investigations strongly suggest a superparamagnetic behavior
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Carnevale, Santino D. "Catalyst-free III-nitride Nanowires by Plasma-assisted Molecular Beam Epitaxy: Growth, Characterization, and Applications." The Ohio State University, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=osu1374066626.
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Haubold, Danny, Annett Reichhelm, Alexander Weiz, Lars Borchardt, Christoph Ziegler, Lydia Bahrig, Stefan Kaskel, Michael Ruck, and Alexander Eychmüller. "The Formation and Morphology of Nanoparticle Supracrystals." Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2016. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-209752.
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Supracrystals are highly symmetrical ordered superstructures built up from nanoparticles via self-assembly. While the NP assembly has been intensively investigated, the formation mechanism is still not understood. To shed some light onto the formation mechanism, we are using one of the most common supracrystal morphologies, the trigonal structures, as a model system to investigate the formation process in solution. To explain the formation of the trigonal structures and determining the size of the supracrystal seeds formed in solution, we introduce the concept of substrate-affected growth. Furthermore, we show the influence of the NP concentration on the seed size and extend our investigations from Ag towards Au.
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Baltazar, Jose A. "Polycyclic aromatic hydrocarbons: exploring new processes and materials for electronics." Diss., Georgia Institute of Technology, 2013. http://hdl.handle.net/1853/51787.
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Graphene is a two-dimensional sp2 hybridized carbon lattice that is also the fundamental building block of graphite. Graphene has attracted significant interest recently due to its distinctive electrical, optical and mechanical properties. These properties have spurred research directed at modifying graphene for use in a variety of electronic, optoelectronic, and sensor technologies. However, before graphene can be used in products, it is necessary to find methods to tune, modify, grow and integrate graphene features while substantially boosting device performance and maintaining current processing compatibility and ease of integration with existing manufacturing infrastructure.
This dissertation focuses on developing techniques for controllably doping the graphene layer through scalable, industry friendly and simple chemical doping; using self-assembled monolayer compounds, photo-acid and photo-base generators, polymers and metal-organic species. We have, in fact, demonstrated simple p-n junctions fabricated in this manner. Characteristic I-V curves indicate the superposition of two separate Dirac points from the p and n regions, confirming an energy separation of neutrality points within the complementary regions; Raman studies of these methods have shown that these processes result in extremely low defect levels in the graphene. Our simple methods for producing patterned doping profiles in graphene films and devices open up a variety of new possibilities for forming complex doping profiles in a simple manner in graphene. This work can enable rapid testing, such as controlled work function tuning, complex doping profiles and simple post-fabrication tuning, of concepts for graphene that may be useful in both interconnect and transparent conductor applications.
In addition to graphene doping, we also investigated approaches to the synthesis of few-layer graphene flakes, since current techniques still produce inferior materials. Exfoliation of Graphene Sheets by an Electron Donor Surfactant was demonstrated to generate few-layers graphene flakes that rival the electrical quality of reduce graphene-oxide (rGO) flakes. Last but not least, Diels-Alder adducts on silica were explored as a controllable carbon precursor for pristine graphene; these allow for a rational direct-growth-of-graphene-on-surface reaction mediated by copper catalyst, without the use of flammable precursors, such as methane, that are used in current methods of chemical vapor deposition synthesis of graphene.
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Al-Brasi, Enteisar. "The growth and characterization of films of noble metal nanocrystals and inorganic semiconductors at the interface of two immiscible liquids." Thesis, University of Manchester, 2013. https://www.research.manchester.ac.uk/portal/en/theses/the-growth-and-characterization-of-films-of-noble-metal-nanocrystals-and-inorganic-semiconductors-at-the-interface-of-two-immiscible-liquids(5652496a-6e6d-4e91-a21b-6ae1b3f36a87).html.
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Deposition of noble metal and semiconductor nanocrystalline thin films has received much attention. CdS and CdSe are important semiconductors used in optical devices. A wet chemical route which uses the interface of two immiscible liquids to control the growth and deposition of nanocrystalline thin films forms the basis of the current study. In this method, a metal precursor dissolved in toluene or decane is held in contact with a water layer containing a reducing or sulphiding agent. The reaction proceeds at the interface of the liquids and results in deposits adhering to the interfacial region. The products of such reactions typically consist of nanocrystals forming a thin film. Stable sols of Au, Ag were found to metathesize on contact with alkylamine in oil to form monolayer films that spread across large areas at the water/oil interface. The nature and properties of interfacial thin films depend on the alkylamine. Nanocrystalline thin films consisting of CdS adhering to the interface starting with a polydispersed aqueous sol of crystallites and alkylamine were obtained. The optical band gaps of the films formed are dependent on the alkylamine chain length, with the shortest chain yielding the largest gap. A systematic increase in particle diameters following adsorption is responsible for changes in the electronic structure of films. The formation of nanocrystalline films of CdS adhering at the interface using a toluene solution of cadmium diethyldithiocarbamate and aqueous Na2S solution, in the presence of tetraoctylammonium bromide (TOAB) in the aqueous phase, was investigated under various reaction parameters, while CdSe was obtained using Na2SeSO3 solution and the influences of deposition temperature and solution concentration were studied. A ternary water/decane/2-butoxyethanol /salt system was used to grow deposits of CdSe and CdS. Nanostructured thin films were obtained at the upper interface of the ternary system, between the emulsive middle layer and oil rich top phase. The influence of deposition conditions such as precursor concentrations and temperature, as well as the nature of the medium on the properties of the deposits was studied. Deposits grown using the ternary system were compared with those obtained using water/decane and water/toluene systems. Reaction parameters such as temperature, solution concentration and the size of CdS and CdSe were controlled. A thin film of CdS and CdSe nanocrystals was formed at the interface. The grain size was found to be dependent on reaction temperature and solution concentration, with higher temperatures and solution concentration resulting in larger grains. The nature of thin films obtained at the interface of two immiscible liquids and of a water/decane/2-butoxyethanol/salt ternary system were studied using Scanning and Transmission electron microscopy, X-ray diffraction and UV-visible spectroscopy.
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Teng, Die. "Computational studies of transition metal nanoclusters on metal-supported graphene moiré." Diss., Georgia Institute of Technology, 2014. http://hdl.handle.net/1853/51830.
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The graphene moiré superstructure formed on Ru(0001) (g/Ru(0001)) has shown the potential as a template to self-assemble super-lattices of metal nanoparticles as model catalysts. To explore the possibility of rational catalyst design on g/Ru(0001), detailed density functional theory (DFT) calculations have been performed to investigate the adsorption and diffusion of Rh and Au adatoms on g/Ru(0001). The consequences of different hopping rates for cluster nucleation have been explored by performing Monte Carlo-based statistical analysis, which suggests that diffusing species other than adatoms need to be taken into account to develop an accurate description of cluster nucleation and growth on this surface. DFT calculations have also been carried out to investigate the adsorption and diffusion of 18 4d (Y-Ag) and 5d (La-Au) transition metal adatoms on g/Ru(0001). Given the necessity to study larger diffusing species than adatoms, DFT calculations have been performed to study the adsorption and diffusion of Rh and Au dimers and trimers on g/Ru(0001). It was shown that the mobility of Rh clusters decreases with the increase of cluster size, while for Au, dimers diffuse faster than monomers and trimers on the moiré surface. We then used a genetic algorithm combined with DFT calculations to predict the lowest energy structure of a Au8 cluster on g/Ru(0001). Our prediction leads us to propose that Au clusters aggregates through Oswald ripening with Au dimer being the major diffusing species. Finally, we examined the morphology of a Cu19 cluster on g/Cu(111) using MD simulations with COMB3 potential. We also studied the mobility of Cu clusters on g/Cu(111) at elevated temperatures. The analysis suggests that g/Cu(111) may not be a suitable substrate for the formation and growth of isolated Cu clusters. All these calculation results have provided us a better understanding and useful insights into the nucleation and growth mechanism of metal clusters on graphene moiré.
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Pithan, Linus. "On the role of external stimuli to tailor growth of organic thin films." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät, 2017. http://dx.doi.org/10.18452/17749.
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In dieser Arbeit werden neue Strategien zur Wachstumskontrolle funktionaler organischer Dünnschichtmaterialien aufgezeigt, mit denen sich die Eigenschaften molekularer Schichtsysteme gezielt beeinflussen lassen. Ein Fokus liegt dabei auf der Untersuchung des Einflusses von optischen Feldern auf das Wachstumsverhalten. Ein weiterer Schwerpunkt wird auf das Grundlagenverständnis von thermisch aktivierten, kinetischen Prozessen, die die Morphologie während und nach dem Schichtwachstum beeinflussen, gelegt. Zuerst wird am Beispiel des molekularen Halbleiters Sexithiophen (6T) gezeigt, wie sich Kontrolle über das Kristallphasengleichgewicht während des Wachstums auf Kaliumchlorid (KCl) erzielen lässt. Im zweiten Teil der Arbeit wird eine neue Herangehensweise zur direkten Ausrichtung von Molekülkristallen im optischen Feld während ihrer Entstehung studiert. Am Beispiel von Tetracene wird gezeigt wie sich so optische anisotrope Absorptionseigenschaften von Molekülen dazu nutzen lassen den Brechungsindex eines polykristallinen Films lokal durch ein photolitographisches Verfahren zu beeinflussen. Im dritten Teil wird der Einfluss von dynamisch variierenden Wachstumsbedingungen während des Schichtwachstums von PTCDI-C8 studiert. Es wird gezeigt, dass sich die Oberflächenrauigkeit stark reduzieren lässt, indem zu Beginn des Wachstums jeder individuellen molekularen Monolage die Nukleationsdichte stark erhöht und in den darauf folgenden Wachstumsphasen die Diffusivität gezielt gesteigert wird. Im vierten Teil wird das Diffusionsverhalten von n-Alkan Schichten unter thermischen Einflüssen betrachtet. Es wird gezeigt, dass die inhärente molekulare Anisotropie von C44H90 Molekülen (TTC) sowie die sehr geringe, stark anisotrope, Oberflächenenergie dieses Materials ein ungewöhnliches Diffusionsverhalten auslöst.The research performed in the framework of this thesis focuses on new strategies to effectively control the growth of crystalline thin films of functional organic molecules and attributes the quest for additional growth control parameters in organic molecular beam deposition (OMBD). First the influence of light on the growth process of the sexithiophene (6T) is studied. We find that 6T thin films deposited as conventional in dark environments on KCl exhibit a bimodal growth with phase coexistence of two crystal polymorphs. In contrast, films grown under illumination with 532 nm light show increased phase purity. Further, we establish light-directed molecular self-assembly (LDSA) to generate permanently aligned thin films of tetracene (C18H12) and demonstrate direct patterning with light. Polarized light illumination leads to azimuthally photoaligned films on isotropic, amorphous substrates. Thus, LDSA can be regarded as a new degree of freedom in the quest for control-parameters in organic thin film growth. Next the impact of dynamic temperature oscillations on the time scales of molecular monolayer growth during organic molecular beam deposition is discussed. We strongly increase the island density during nucleation and selectively increase interlayer diffusion at later stages of monolayer growth. We analyse the interplay between molecular interlayer transport and island sizes to understand kinetic processes during growth. In a fourth experiment we show how thermal annealing can be used to improve smoothness and to increase the lateral size of crystalline islands of n-alkane (TTC, C44H90) films. We employ real-time optical phase contrast microscopy to track the diffusion across monomolecular step edges which causes the unusual smoothing during annealing. We rationalise the smoothing behaviour with the highly anisotropic attachment energies and low surface energies of TTC.
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Zschintzsch-Dias, Manuel. "Self organized formation of Ge nanocrystals in multilayers." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2012. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-86838.
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The aim of this work is to create a process which allows the tailored growth of Ge nanocrystals for use in photovoltic applications. The multilayer systems used here provide a reliable method to control the Ge nanocrystal size after phase separation.
In this thesis, the deposition of GeOx/SiO2 and Ge:SiOx~ 2/SiO2 multilayers via reactive dc magnetron sputtering and the self-ordered Ge nanocrystal formation within the GeOx and Ge:SiOx~ 2 sublayers during subsequent annealing is investigated.
Mostly the focus of this work is on the determination of the proper deposition conditions for tuning the composition of the systems investigated. For the GeOx/SiO2 multilayers this involves changing the GeOx composition between elemental Ge (x = 0) and GeO2 (x = 2), whereas for the Ge:SiOx~ 2/SiO2 multilayers this involves changing the stoichiometry of the Ge:SiOx~ 2 sublayers in the vicinity of stochiometric silica (x = 2). The deposition conditions are controlled by the variation of the deposition rate, the deposition temperature and the oxygen partial pressure.
A convenient process window has been found which allows the sequential deposition of GeOx/SiO2 or Ge:SiOx ~2/SiO2 without changing the oxygen partial pressure during deposition. For stoichiometry determination Rutherford back-scattering spectrometry has been applied extensively.
The phase separation in the spatially confined GeOx and Ge:SiOx ~2 sublayers was investigated by X-ray absorption spectroscopy at the Ge K-edge. The Ge sub-oxides content of the as-deposited multilayers diminishes with increasing annealing temperature, showing complete phase separation at approximately 450° C for both systems (using inert N2 at ambient pressure). With the use of chemical reducing H2 in the annealing atmosphere, the temperature regime where the GeOx phase separation occurs is lowered by approximately 100 °C. At temperatures above 400° C the sublayer composition, and thus the density of the Ge nanocrystals, can be altered by making use of the reduction of GeO2 by H2.
The Ge nanocrystal formation after subsequent annealing was investigated with X-ray scattering, Raman spectroscopy and electron microscopy. By these methods the existence of 2 - 5 nm Ge nanocrystals at annealing temperatures of 550 (GeOx) - 700° C (Ge:SiOx ~2) has been confirmed which is within the multilayer stability range.
The technique used allows the production of extended multilayer stacks (50 periods ~ 300 nm) with very smooth interfaces (roughness ~ 0.5 nm). Thus it was possible to produce Ge nanocrystal layers with ultra-thin SiO2 separation layers (thickness ~ 1 nm) which offers interesting possibilities for charge transport via direct tunneling.
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Ourdjini, Oualid. "Etude par microscopie à effet tunnel de la croissance de polymères 2D sur des surfaces métalliques." Thesis, Aix-Marseille, 2012. http://www.theses.fr/2012AIXM4315/document.
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La croissance de polymères bidimensionnels a été étudiée sous ultra-haut vide sur des surfaces métalliques par microscopie à effet tunnel (STM). La première étude concerne la croissance de réseaux nanoporeux covalents bidimensionnels obtenus par réaction de déshydratation des molécules d'acide 1.4 diboronique (BDBA). Les meilleurs réseaux sont obtenus pour les dépôts à flux élevés sur des substrats d'Argent chauffés à 150°C. La deuxième étude concerne la réaction chimique entre les molécules de 1,2,4,5 tétracyanobenzène (TCNB) et les atomes de Fer. La formation de liaison covalente entre les molécules et les atomes de Fer est thermiquement activée par des recuits à 200°C et permet la formation d'octacyanophtalocyanine de Fer. Ce travail ouvre de nouvelles perspectives pour la fabrication de matériaux 2D originaux obtenus par des réactions chimiques de surfaceThe growth of two dimensional polymers has been studied under ultra-high vacuum on metallic surfaces by scanning tunnelling microscopy (STM). The first study relates on the growth of two dimensional covalent nanoporous networks obtained after dehydratation reaction of the 1,4 diboronic acid benzene molecule (BDBA). The best networks have been obtained with high molecular flux on silver metallic substrates maintained at 150°C during deposition. The second study relates on chemical reaction between the 1, 2, 4, 5 tetracyanobenzene molecule (TCNB) and iron atoms. The reaction takes place after an annealing at 200°C. In that case some iron octacyanophthalocyanine have been successfully synthesised at surfaces. This work opens new perspectives for the fabrication of 2D original materials by chemical reactions on surfaces
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Diebold, Morgane. "Systèmes composites organogélateurs/polymères semi-conducteurs : de la preuve conceptuelle aux matériaux nanostructurés pour l'électronique plastique." Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAE002.
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L’amélioration des performances des dispositifs photovoltaïques organiques passe par le contrôle de la morphologie de leurs couches actives. Nous avons cherché à préparer une hétérojonction volumique donneur-accepteur nanostructurée en utilisant la nucléation hétérogène du poly (3-hexylthiophène) (P3HT, donneur) par des fibres d’organogélateurs à base de naphthalène diimide (NDI, accepteur). La première partie de ce travail présente l’étude des propriétés d’auto-assemblage d’organogélateurs à cœur NDI substitué par des groupements amides et des dendrons trialkoxyphényles. Nous avons évalué l’influence de la longueur de la chaîne flexible entre le cœur naphthalène et les groupements amides (2 liaisons C-C pour NDI2 et 4 pour NDI4) sur les propriétés physico-chimiques des organogélateurs. La seconde partie de ce travail met en évidence le polymorphisme du composé NDI2 en identifiant 4 polymorphes ainsi que leurs signatures optiques, spectroscopiques et structurales. Un diagramme de phase de l’état solide du NDI2 est proposé. La dernière partie de la thèse concerne l’élaboration de nano-composites donneur-accepteur entre les organogélateurs à cœur NDI et le P3HT. Le processus de formation en solution de ces nano-composites est analysé en suivant les cinétiques de cristallisation du P3HT par spectroscopie d’absorption UV-Visible et les morphologies obtenues (structures shish-kebab) par microscopie électronique en transmission. L’effet nucléant des organogélateurs sur le P3HT a été montré. Les études en cellules solaires des composés P3HT:PCBM : organogélateur ont prouvé que le rendement de conversion énergétique peut être augmenté en présence d’organogélateursImproving the performances of organic photovoltaic devices requires morphology control of the active layers. Highly nanostructured donor-acceptor bulk heterojunctions were prepared by heterogeneous nucleation of poly (3-hexylthiophene) (P3HT, donor) on naphthalene diimide organogelators fibers (NDI, acceptor). The first part of this work was dedicated to the self-assembly of NDI-core organogelators substituted by amide groups and trialkoxyphenyls dendrons. We evaluated the influence of the flexible chain between the naphthalene core and the amide groups (2 C-C bonds for NDI2 and 4 for NDI4) on the physico-chemical properties of the organogelators.The second part of this work focused on the polymorphism of NDI2 with identification of four different polymorphs with their optical, spectroscopic and structural signatures. A phase diagram of NDI2 in the solid state was determined. The last part of this manuscript concerns the fabrication of donor-acceptor nano-composites between NDI organogelators and P3HT. The formation process in solution of these nano-composites was analyzed by following the crystallization kinetics of P3HT by UV-Vis absorption spectroscopy and the thin film morphology (shish-kebab structures) by transmission electron microscopy. The nucleating effect of various organogelators on P3HT was demonstrated. Solar cells were made from the composites P3HT:PCBM : organogelator and their energetic conversion yield was shown to be increased in the presence of organogelators
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Varghai, Daniel. "Tubular Tissue Engineered Scaffold-Free High-Cell-Density Mesenchymal Condensations For Femoral Defect Regeneration." Case Western Reserve University School of Graduate Studies / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=case1497222797338966.
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De, Vet Christiaan J. F. "Auto-assemblage d'un anthacène fluorescent aux échelles nano- et micrométriques par photoréaction contrôlée." Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0333/document.
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Le contrôle spatial et temporel de l'auto-assemblage de molécules fluorescentes en nano-objets organisés et en matériaux mous a été réalisé par photochimie.La photodécarbonylation quantitative du progélifiant dkDDOA sous irradiation génère le super gélifiant 2,3-didécyloxyanthracène (DDOA) à température ambiante et simultanément gélifie le DMSO. DkDDOA est réactif sous excitation avec de la lumière bleue en raison de la fonction alpha-dicétone sensible à la lumière qui est ajoutée au noyau aromatique. De plus,l’ajustement de la couleur de l'émission du gel du bleu au vert a été obtenu en ajoutant un dérivé 1,2-dicétone-5,12-diphényltétracène photo réactif qui donne un 5,12-diphényltétracène émissif vert sensibilisé par un transfert d'énergie efficace.Sous un microscope, l'irradiation laser focalisée permet la structuration de nanofibres émissives sur une surface de verre. Bien que la surface de verre soit non traitée, on peut obtenir des micropattern de nanofibres de DDOA hautement alignées. Ces surfaces émettent une lumière bleue polarisée linéairement, comme le prouve la microscopie de polarisation. L'anisotropie élevée et l'orientation des fibres ont été obtenues en contrôlant la densité de nucléation et la direction de balayage du laser focalisé. Des micropattern orientés perpendiculairement peuvent ainsi être juxtaposés sur la même surfaceThe spatial and temporal control of the self-assembly of fluorescent molecules into organized nano-objects and into soft materials was achieved by photochemistry. The quantitative photodecarbonylation of the progelator dkDDOA under irradiation generates the supergelator 2,3-didecyloxyanthracene (DDOA) at room temperature and simultaneously gelates DMSO. dkDDOA is reactive under excitation withblue light due to the light sensitive alpha-diketone moiety that is added to the aromatic core.Additional colour-tuning from blue to green emission from the gel was achieved by adding a similar photoreactive 1,2-diketone-5,12-diphenyltetracene that yields a green emissive 5,12-diphenyltetracene sensitized through an efficient energy transfer. Under a microscope, focused laser irradiation enables the patterning of blue-emissive nanofibers on to a glass surface. Although the surface is non-treated, micropatterns of highly aligned DDOA nanofibers can be obtained. These surfaces emit linearly polarized blue light,as proven with polarization microscopy. The high anisotropy and the orientation of the fibers was achieved by controlling the nucleation density and the direction of scanning of the focused laser. Perpendicularly oriented micropatterns can thereby be juxtaposed on the same surface
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Chomette, Cyril. "Design et fabrication de meta-atomes plasmoniques à partir de nanoparticules à patchs." Thesis, Bordeaux, 2015. http://www.theses.fr/2015BORD0232/document.
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Les méta-matériaux sont une nouvelle classe de matériaux composites artificiels quiprésentent des propriétés inédites. Ils sont typiquement sous divisés en unité appelées méta-atomes.Un design approprié de ces méta-atomes, architecturés à l’échelle nanométrique, permet d’induire despropriétés aussi extraordinaires qu’un indice de réfraction négatif. Dans ce contexte, nous avonsdéveloppé des particules à patchs, capable de développer des interactions selon des directionsprédéterminées. Des clusters multipodiques fait de ces particules (diélectrique) entourées d’un nombrecontrôlé de satellites plasmoniques (or) ont été développés. Nous nous sommes focalisés sur desclusters isotropes, dérivant de géométries tétraédriques, octaédriques et icosaédriques (trois des cinqsolides de Platon). Pour cela, nous avons utilisé des clusters silice/polystyrène, obtenus parpolymérisation ensemencée en émulsion, qui ont servi de préformes. Ils ont ainsi permis d’obtenir desparticules dont les patchs sont en fait des fossettes au fond desquelles subsiste un résidu de chaînespolystyrène greffées. En modifiant chimiquement ces chaînes, nous avons permis soit l’accrochage aufond de ces fossettes de colloïdes d’or puis leur croissance, soit l’accostage de satellites de silice surlesquels nous avons ensuite fait croître une coquille d’or. La seconde voie à offert un meilleur contrôlede la morphologie des clusters et notamment de la distance entre les satellites d’or (quelquesnanomètres) qui est primordiale pour assurer un couplage plasmonique optimal. Les propriétés desclusters obtenus ont été modélisées et mesuréesMetamaterials are a novel class of artificial composite materials, typically made of subunit called meta-atoms and exhibiting unusual properties. Such meta-atoms, have to be architecturedat the nanometric level, to induce as extraordinary properties as a negative refractive index. In thiscontext, we developed patchy particles, capable to create interactions along predetermined directions.Multipodic clusters made of those (dielectric) particles surrounded by a controlled number ofplasmonic satellites (gold) were developed. We focused on isotropic clusters deriving fromtetrahedral, octahedral and icosahedral geometry (three of the fifth Platonic solids). For that purpose,we used silica/polystyrene clusters, obtained from seeded emulsion polymerization, as template. Byderiving those clusters, patchy particles bearing dimples containing grafted residual polystyrene chainswere obtained. By chemically deriving those chains, we explored two synthetic pathways, thedecoration of the dimples with gold colloids subsequently grown or the anchoring of silica satellitesonto which gold shells were subsequently grown. The second one was prove to offer a better controlover the cluster morphology as well as the inter-satellites gap (few nanometer) which is pivotal toensure an optimal plasmonic coupling. Then, the optical properties of the as obtained clusters weresimulated and measured
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Jubert, Pierre-Olivier. "Croissance et propriétés magnétiques de nanostructures épitaxiées auto-assemblées : le système Fe/Mo(110)." Phd thesis, Université Joseph Fourier (Grenoble), 2001. http://tel.archives-ouvertes.fr/tel-00004054.
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L'objectif de cette thèse était l'élaboration par croissance auto-assemblée et l'étude des processus de retournement d'aimantation de particules magnétiques modèles de Fer épitaxiées sur une surface (110) de Molybdène. Une étude systématique de la croissance de Fe sur Mo(110)/Al2O3(11-20) sous ultra-vide par Dépôt Laser Pulsé est présentée. Cette étude a permis d'affiner les connaissances de la littérature concernant la croissance de couches continues grâce à des observations STM in-situ, et d'étudier en détail les différentes méthodes permettant d'auto-assembler des nanostructures (plots, bandes). A haute température (Ts>600K), la croissance de Fe sur Mo(110) conduit à la formation d'îlots 3D compacts auto-assemblés qui, comme démontré par un calcul énergétique, présentent la forme facettée et les rapports d'aspect de cristaux de Fe à l'équilibre thermodynamique. A température modérée (300K< Ts< 600k), la croissance de Fe sur Mo(110)est affectée par des limitations cinétiques. Un dépôt à 500K, ou le recuit d'une couche continue déposée à 300K ou à 400K, conduit à la formation de bandes nanométriques de Fe auto-organisées le long des marches de la surface faiblement vicinale de Mo(110). Dans le cadre de cette thèse, nous avons étudié particulièrement les propriétés magnétiques d'îlots 3D compacts de taille sub-micronique. En combinant des mesures macroscopiques, des mesures sur des particules individuelles, et des simulations micromagnétiques, nous arrivons à décrire de façon détaillée la configuration en domaines et les processus de retournement d'une particule individuelle en fonction de ses caractéristiques morphologiques et structurales. Par ailleurs, les propriétés magnétiques de particules qui présentent une rémanence non nulle (petits îlots compacts, bandes auto-organisées de Fer) ont été étudiées à partir des cycles d'hystérésis macroscopiques à l'aide d'une méthode de séparation des contributions réversible et irréversible à la variation d'aimantation.
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Xiao, Qijun. "Hierarchical multiple bit clusters and patterned media enabled by novel nanofabrication techniques – High resolution electron beam lithography and block polymer self assembly." 2010. https://scholarworks.umass.edu/dissertations/AAI3397756.
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This thesis discusses the full scope of a project exploring the physics of hierarchical clusters of interacting nanomagnets. These clusters may be relevant for novel applications such as multilevel data storage devices. The work can be grouped into three main activities: micromagnetic simulation, fabrication and characterization of proof-of-concept prototype devices, and efforts to scale down the structures by creating the hierarchical structures with the aid of diblock copolymer self assembly. Theoretical micromagnetic studies and simulations based on Landau-Lifshitz-Gilbert (LLG) equation were conducted on nanoscale single domain magnetic entities. For the simulated nanomagnet clusters with perpendicular uniaxial anisotropy, the simulation showed the switching field distributions, the stability of the magnetostatic states with distinctive total cluster perpendicular moments, and the stepwise magnetic switching curves. For simulated nanomagnet clusters with in-plane shape anisotropy, the simulation showed the stepwise switching behaviors governed by thermal agitation and cluster configurations. Proof-of-concept cluster devices with three interacting Co nanomagnets were fabricated by e-beam lithography (EBL) and pulse-reverse electrochemical deposition (PRECD). EBL patterning on a suspended 100 nm SiN membrane showed improved lateral lithography resolution to 30 nm. The Co nanomagnets deposited using the PRECD method showed perpendicular anisotropy. The switching experiments with external applied fields were able to switch the Co nanomagnets through the four magnetostatic states with distinctive total perpendicular cluster magnetization, and proved the feasibility of multilevel data storage devices based on the cluster concept. Shrinking the structures size was experimented by the aid of diblock copolymer. Thick poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer templates aligned with external electrical field were used to fabricate long Ni/Fe magnetic nanowire array, dominant shape anisotropy was observed and compared to the result from previously reported Co nanowire array with strong crystalline anisotropy. Guided diblock copolymer poly(styrene)-b-poly(4-vinyl pyridine) (PS- b-P4VP) self assembly was performed to generate clustered microdomains. Direct e-beam patterning on PS-b-P4VP thin film showed precise and arbitrary patterning on the lateral ordering of the self assembly. Graphoepitaxy of self-assembled PS-b-P4VP copolymers on isolated SiN triangular plateaus successfully resulted in the exact clusters of three microdomains. Theoretical consideration and system modeling based on the micellar configuration of the microdomains were done, and the distribution of the cluster’s size and number of elements were explained qualitatively.
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Wei-CheTang and 唐偉哲. "Catalyst-assisted Growth of InGaN Nanowires and Chlorine-assisted Growth of Self-assembly GaN Nanorods for Optoelectronic Device." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/07931298472155093208.
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博士國立成功大學
化學工程學系
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This research is involving of two parts. First part is that Au-assisted growths of InGaN nanowires by VLS growth mechanism at 700℃. GaN nanowires with a mount of planar defects were synthesized as low indium vapor pressure in the gas phase. As the high indium vapor pressure in the gas phase, there are InGaN nanowires with 14% atomic indium and high-intensity wavelength emission at 410 nm grown on Si(100). According to Le Chatelier's Principle, in order to enhance the thermal stability of InN material at the high temperature, the high nitrogen plasma concentration has used. Therefore, the indium content in InGaN nanowires with 460 nm emission light increases to 24% atomic. Other part is the single crystal GaN nanorods grown for Optoelectronic devices. In advance, at 960℃ growth temperature, high-quality Si-doped n-GaN nanorods were synthesized. Cl2-assisted InGaN and p-GaN epitaxial films were respectively grown on n-GaN nanorods at 600℃ to form p-i-n GaN for Optoelectronic structure.
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Qian, Jieshu. "Factors Affecting the Growth and Fragmentation of Polyferrocenylsilane Diblock Copolymer Micelles." Thesis, 2013. http://hdl.handle.net/1807/65522.
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Polyferrocenylsilane (PFS) diblock copolymers self-assemble in selective solvents to form one-dimensional micelles for a broad range of polymer compositions and experimental conditions, driven by the crystallization of the PFS block that forms the micelle core. The most striking feature of these micelles is that they remain active for further growth. They can be extended in length when additional polymer, dissolved in a good solvent, is added to a solution of the pre-existing micelles. This thesis describes several studies investigating the factors that affect the growth and fragmentation of PFS diblock copolymer micelles in solution, with a particular emphasis on polyisoprene-PFS (PI-PFS) diblock copolymers. The goal of my research was trying to provide deeper understanding of this crystallization-driven self-assembly (CDSA) process.
In an attempt to understand the growth kinetics of the PI-PFS cylindrical micelles, I added tiny amount of short micelle seeds into supersaturated solution of the same polymer, and followed the micelle growth by light scattering. The data analysis showed that the increase of micelle length could be described by an expression with two exponential decay terms. In another attempt to examine the factors that may affect the growth behavior of the PI-PFS micelles, I found that PI-PFS long micelles underwent fragmentation when they were subjected to external stimuli, e.g. addition of polar solvent, or heating. During the course of studying the effect of heating on the micelles, I developed a new approach to generate cylindrical micelles with controllable and uniform length, a one-dimensional analogue of self-seeding of crystalline polymers. I carried out a systematic study to investigate the self-seeding behavior of PFS block copolymers.
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Chung, Siyon. "Microfluidic Modeling of Cell Flow & Self-assembly of Gold Nanorods with Different Lengths." Thesis, 2012. http://hdl.handle.net/1807/35514.
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The thesis is divided into two parts: (1) microfluidic modeling of blood cell flow in constricted microvasculature and (2) the kinetic study of self-assembly of Au nanorods with different lengths.
The passive mechanism of the flow of neutrophils was studied by using poly(dimethyl siloxane) microchannels with circular cross-sections as model blood vessels and agarose microgels as model cells. Their velocity and pressure profiles at various locations inside the microchannel with constrictions were studied as functions of (a) the initial velocity of the microgels, (b) the degree at which the channel-at-large tapered into the constriction, and (c) the size of microgels.
Previously, our group proposed that the kinetics of self-assembly of Au nanorods resembles that of the reaction-controlled step-growth polymerization. To investigate factors that affect the reactivity of functional groups, self-assembly experiments were performed for nanorods with different lengths and their kinetics was analyzed.
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Swain, Monalisa. "Study Of Structure, Dynamics & Self-Assembly Of Human Insulin-Like Growth Factor Binding Protein-2 By Novel NMR And Biophysical Methods." Thesis, 2011. http://etd.iisc.ernet.in/handle/2005/2357.
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My research work for PhD has focused on: (i) the development and application of new NMR methodologies to solve challenging problems in structural biology and (ii) studying important biological systems to correlate their structural and functional aspects. I have worked on diverse research projects ranging from NMR methodology development to the study of structure and dynamics of protein-based nanotubes.
Chapter 1 of my thesis gives brief introduction to bio-molecular NMR spectroscopy and the different biological systems that I have studied. In recent years, several new methods have emerged for rapid NMR data collection. One class of methods is G-matrix Fourier transform (GFT) projection NMR spectroscopy. GFT NMR spectroscopy involves phase sensitive joint sampling of two or more chemical shifts in an indirect dimension of a multidimensional NMR experiment. Chapter 2 describes a new method based on the principle of GFT NMR for increasing further the speed of data collection. In the current implementations of the GFT method, cosine/sine modulation of all chemical shifts involved in the joint sampling are collected and stored as separate FIDs. A post-acquisition data processing step (application of G-matrix) then separates the different inter-modulations of chemical shifts. Thus, joint sampling of K+1 spins results in 2K combination of chemical shifts (also representing 2K projection angles). One limitation of this approach is that even if only a few of the 2K components of the multiplet (or projection angles) is desired, an entire data set containing information for all 2K shift combinations is collected. We have proposed a simple method which releases this restriction and allows one to selectively detect only the desired linear combination of chemical shifts/projection angles out of 2K combinations in a phase sensitive manner. The method involves selecting the appropriate cosine/sine modulations of chemical shifts and forming the desired linear combination by phase cycling of the radiofrequency pulses and receiver. This will benefit applications where only certain linear combination of shifts are desired or/and are sufficient. Further, G-matrix transformation required for forming the linear combination is performed within the pulse sequence. This avoids the need for any post-acquisition data processing. Taken together, this mode of data acquisition will foster new applications in projection NMR spectroscopy for rapid resonance assignment and structure determination.
Chapter 3 describes another GFT NMR-based method for rapid estimation of secondary structure in proteins. This involves the detection of specific linear combination of backbone chemical shifts and facilitates a clear separation and estimation of residues in different secondary structures of a given protein. This methodology named as CSSI-PRO (Combination of Shifts for Secondary structure Identification in PROteins), involves detection of specific linear combination of backbone 1Hα and 13C’ chemical shifts in a two dimensional (2D) NMR experiment. Such linear combination of shifts facilitates editing of residue belonging to α-helical/ β-strand regions into distinct spectral regions nearly independent of the amino acid type. This helps in the estimation of overall secondary structure content of the protein. Comparison of the estimated secondary structure content with those obtained from the respective 3D structures and/or the method of Chemical Shift Index (CSI) was carried out for 254 proteins and gives a correlation of more than 90% and an overall RMSD of 6.5%. The method has high sensitivity and data can be acquired in a few minutes. This methodology has several applications such as for high-throughput screening of proteins in structural proteomics and for monitoring conformational changes during protein folding and/or ligand-binding events.
Chapter 4 (Part-A and Part-B) describes an area of my research which involves the study of structure and function in the Insulin-like Growth Factor Binding Protein (IGFBP) family. IGFBPs (six in number; IGFBP1-6) belong to the IGF-system, which plays an important role in growth and development of the human body. This system is comprised of the following components: (i) Two peptide hormones, IGF-1 and -2, (ii) type 1 and type 2 IGF receptors, (iii) six IGF-binding proteins (IGFBP; numbered 1-6) and (iv) IGFBP proteases. IGF-1 and -2 are small signalling peptides (~7.5 kDa) that stimulate action by binding to specific cell surface receptors (IGF-1R) evoking subsequent response inside the cell. Six soluble IGF binding proteins, the IGFBPs, which range in 22-31 kDa in size and share overall sequence and structural homology with each other, regulate the activity of the IGFs. IGFBPs bind strongly to IGFs (KD ~ 300-700 pM) to ensure that all the circulating IGF in the blood stream is sequestered and inhibit the action of IGFs by blocking their access to the receptors. Proteolysis of the IGFBPs dissociates IGFs from the complex, enabling them to bind and activate the cell surface receptors. IGFBPs have been recently implicated in different cancers and HIV/AIDS. However, the nature of their interaction with the ligand: IGF-1 or IGF-2 at a molecular level poorly understood. This is due to the difficulty in over-expressing these proteins in large scale and in soluble amounts which is required for structural studies. We have for the first time developed an efficient method for bacterial expression of full-length human IGFBP-2, a 33 kDa system, in soluble (upto 30 mg/ml) and folded form. Using a single step purification protocol, hIGFBP-2 was obtained with >95% purity and structurally characterized using NMR spectroscopy. The protein was found to exist as a monomer at the high concentrations required for structural studies and to exist in a single conformation exhibiting a unique intra-molecular disulfide-bonding pattern. The protein retained full biologic activity as evident from its strong binding to IGF-1 and IGF-2 detected using surface plasmon resonance (SPR). This study represents the first high-yield expression of wild-type recombinant human IGFBP-2 in E. coli and first structural characterization by NMR. Using different NMR methods, we are now in the process of elucidating the 3D structure of this molecule.
Chapter 5 (Part-A and Part-B) describes our discovery of nanotubular structures formed by spontaneous self-assembly of a small fragment from the C-terminal domain of hIGFBP-2. The nanotubular structures are several micrometers long and have a uniform outer diameter of ~35 nm. These structures were studied extensively by NMR and other techniques such as TEM, fluorescence and circular dichroism (CD). The water soluble nanotubes form through intermolecular disulphide bonds due to the presence of three cysteines in the polypeptide chain and exhibit enhanced tyrosine fluorescence. Based on different experimental evidences we have proposed a mechanism for the formation of the nanotubes. This was considered as a breakthrough by the journal ChemComm and featured on the cover-page of the journal. An article highlighting the discovery was also published in RSC news.
In recent years, a number of novel polypeptide and DNA based nanotubes have been reported. Our study reveals intrinsically fluorescent self-assembling nanotubes made up of disulphide bonds having the following novel properties: (i) their formation/dissociation can be controlled by tuning the redox conditions, (ii) they do not require the support of any additional chemical agent for self-assembly, (iii) they have high stability due to the involvement of covalent interactions, (iv) the monomer is a small polypeptide chain which can be chemically synthesized or produced using simple recombinant methods and (v) they possess high inherent fluorescence and can thus be easily detected against a background of other proteins. In addition, the presence of an RGD motif in this polypeptide fragment offers avenues for novel biomedical applications. The RGD motif is known to be recognized by integrins. The design of such self-assembling polypeptide fragments containing an RGD motif can be utilized to enhance the efficacy of cancer therapeutics. Towards this end, we have investigated the structural basis of formation of these nanotubular structures by NMR spectroscopy and proposed its application for cancer cell imaging.
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Thirupathi, Ravula. "Design, Synthesis and Characterization of Novel Nanomaterials." Thesis, 2014. http://hdl.handle.net/2005/3177.
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The present thesis entitled “Design, Synthesis and Characterization of Novel Nanomaterials” is divided into five chapters, staring with a general introduction. The remaining chapters focus on four different areas/projects that I have worked on.
Chapter 1: Introduction to nanomaterials
This chapter reviews the basic concepts of nanomaterials and their fabrication methods. Nanomaterials are defined as materials whose dimensions (at least one) are below 100 nm. One of the most exciting aspects of nanomaterials is that their properties may differ significantly from those of the corresponding bulk materials. Nanomaterials fabrication methods can be broadly classified according to whether the assembly follows either i) the bottom-up approach or ii) the top-down approach. These methods have been discussed with various examples including the self-assembly of proteins, peptides and small molecules. In the top-down approach synthetic procedures for Graphene Oxide and its application are discussed. All characterization techniques that are used for characterizing the nanomaterials are also described briefly.
Chapter 2 Section A: Self-assembly of 1-Hydroxy benzotriazole (HOBT) in water
The studies presented in Chapter 2 identifies HOBT as the smallest non-peptide building block that spontaneously self-assembles into hollow micro tubular structures upon evaporation of water. The tubes form under ambient conditions by rolling over of crystalline sheets of HOBT. The packing of HOBT in the tubes seem to be predominantly driven by intermolecular π-stacking interactions between the aromatic rings of HOBT. These structural and packing patterns are similar to those found in nanotubes formed by the self-assembly of peptides and other larger molecules. The cavities of these thermolabile microtubes act as molds for casting gold nanoparticles for the synthesis of gold microrods with monodisperse dimensions. The non-reacting inner surfaces of the cavities have been used to uniquely synthesize R6G-functionalized gold microrods. With these features, HOBT is an important novel non-peptide building block for accessing micro and nanometric materials for their applications in medicine, biology and molecular biotechnology.
Section B: Controlling the orientation of self-assembly of HOBT microtubes
The studies presented in this chapter address the self-assembly of HOBT into microtubular structures in different solvents of varying polarities (H2O and DCM:MeOH) to understand the role of solvent volatility and its direction on the orientation of the HOBT microtubes. HOBT self-assembles from DCM:MeOH mixtures in its bipolar canonical form and is coordinated with its water of hydration, similar to its crystals obtained from water. FTIR and TGA data shows that MeOH is also integrated with the microtubes. We observe for the first time that the orientation of microtubular self-assembly is controlled in the direction of evaporation of the solvent. We demonstrate further this feature by controlling the orientation of HOBT self-assembly in exclusively vertical direction through controlled vertical evaporation of the solvent mixture DCM:MeOH (9:1). Additionally, the unique transition between vertical and horizontal orientations for self-assembled HOBT microtubes is achieved by simple change of solvation between aqueous and organic solvents. These results reveal a dynamic relationship between the rate of evaporation of solvent and the rates of formation of different self-assembled morphologies. The rate of evaporation of the solvent primarily governs the rate of formation of the tubes, rather than their orientations in three dimensions.
Chapter 3: Chemical origins of debris in Graphene Oxide (GO)
This chapter is focused on the investigation of the carbonyl rich fragments arising from GO and provides an understanding of its formation. The fragments are expelled from GO due to an uncontrolled nucleophile driven reaction in aqueous medium leaving the holes on the sheet. These fragments are carbonyl rich small (5 ± 2 nm) nonaromatic molecules that form as by-products of oxidative chemical reactions that occur at the sp3 clusters on the basal surface of GO sheets when they are treated with nucleophilic bases under aqueous conditions. The structure and size of the debris, and hence that of the hole, depend on the size of the sp3 cluster on the sheet. These debris fall out of the GO sheet surface, leading to formation of nanometer sized holes. Formation of debris and hence the holes can be avoided by using anhydrous polar solvents. This work sheds new light on the fundamental structure of GO and the prevention of debris from it during redox reactions enabling better control over functionalization of the GO surface.
Chapter 4: Measurement of mechanical properties of polypeptide fragment from Insulin like growth factor binding protein nanotubes by the Peak Force QNM method
This chapter describes the discovery of Polypeptide fragment from an IGFBP-2. This fragment self-assembles spontaneously and reversibly into nanotubular structures under oxidizing conditions. These nanotubes were characterized by using Transmission electron microscopy. Notably as compared to the monomer, an increase in intrinsic fluorescence upon self-assembly. The thermal stability of these nanotubes is realized form the fluorescence studies. Peak Force Quantitative Nanomechanical Mapping method of AFM was used to measure the Young’s modulus of the nanotubes. These nanotubes were found to have Young’s modulus value of ~10 Gpa, which is comparable to those of bones presumably due to intermolecular disulphide bonds. These nanotubes will have potential applications in tissue engineering.
Chapter 5: Probing the pathways of n→π* interaction in peptides
This chapter deals with the theoretical study of n→π* interaction in designed peptidomimetics. The n→π* interaction involves the delocalization of the lone pair of the donor group into the antibonding orbital (π*) of a carbonyl group. However despite beeing extensively studied there exists a debate over the validation of these n→π* interaction which is reminiscent to Bürgi and Dunitz trajectory. This chapter present our findings that peptidomimetics containing the 5,6-dihydro-4H-1,3-oxazine (Oxa) and 5,6-dihydro-4H-1,3-thiazine (Thi) functional groups at the C-terminus of Pro selectively stabilizes the cis conformer by reverse n→πi-1* interaction. These systems have been used to study the n→πi1* interaction using Natural Bond Orbital (NBO) method. Our study reveals that the energetically most favorable trajectory of a nucleophile for a favorable n→π* interaction presumably to facilitate the overlap between the lonepair of the nucleophile and the antibonding orbital of the carbonyl group. The geometrical requirements for the optimum n→π* interaction depends on the relative orientations of the orbitals that are involved. This study has implications for more accurately identifying long distant n→π* interaction.