Synthesis and characterization of cyclotriphosphazenes containing silicon as single solid-state precursors for the formation of silicon/phosphorus nanostructured materials

The synthesis and characterization of new organosilicon derivatives of N3P3Cl6, N3P3[NH(CH2)3Si(OEt)3]6 (1), N3P3[NH(CH2)3Si(OEt)3]3[NCH3(CH2)3CN]3 (2), and N3P3[NH(CH2)3Si(OEt)3]3[HOC6H4(CH2)CN]3 (3) are reported. Pyrolysis of 1, 2, and 3 in air and at several temperatures results in nanostructured materials whose composition and morphology depend on the temperature of pyrolysis and the substituents of the phosphazenes ring. The products stem from the reaction of SiO2 with P2O5, leading to either crystalline Si5(PO4)6O, SiP2O7 or an amorphous phase as the glass Si5(PO4)6O/3SiO2·2P2O5, depending on the temperature and nature of the trimer precursors. From 1 at 800 °C, core−shell microspheres of SiO2 coated with Si5(PO4)6O are obtained, while in other cases, mesoporous or dense structures are observed. Atomic force microscopy examination after deposition of the materials on monocrystalline silicon wafers evidences morphology strongly dependent on the precursors. Isolated islands of size ∼9 nm are observed from 1, whereas dense nanostructures with a mean height of 13 nm are formed from 3. Brunauer−Emmett−Teller measurements show mesoporous materials with low surface areas. The proposed growth mechanism involves the formation of cross-linking structures and of vacancies by carbonization of the organic matter, where the silicon compounds nucleate. Thus, for the first time, unique silicon nanostructured materials are obtained from cyclic phosphazenes containing silicon.

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials.

Thermodynamic modeling and microcalorimetry of nanostructured materials for capacitive thermal management of electronics

Transient power dissipation profiles in handheld electronic devices alternate between high and low power states depending on usage. Capacitive thermal management based on phase change materials potentially offers a fan-less thermal management for such transient profiles. However, such capacitive management becomes feasible only if there is a significant enhancement in the enthalpy change per unit volume of the phase change material since existing bulk materials such as paraffin fall short of requirements. In this thesis I propose novel nanostructured thin-film materials that can potentially exhibit significantly enhanced volumetric enthalpy change. Using fundamental thermodynamics of phase transition, calculations regarding the enhancement resulting from superheating in such thin film systems is conducted. Furthermore design of a microfabricated calorimeter to measure such enhancements is explained in detail. This work advances the state-of-art of phase change materials for capacitive cooling of handheld devices.

Nanostructured ferroelectric materials

Nanostructured materials are central to the evolution of future electronics and information technologies. Ferroelectrics have already been established as a dominant branch in the electronics sector because of their diverse application range such as ferroelectric memories, ferroelectric tunnel junctions, etc. The on-going dimensional downscaling of materials to allow packing of increased numbers of components onto integrated circuits provides the momentum for the evolution of nanostructured ferroelectric materials and devices. Nanoscaling of ferroelectric materials can result in a modification of their functionality, such as phase transition temperature or Curie temperature (TC), domain dynamics, dielectric constant, coercive field, spontaneous polarisation and piezoelectric response. Furthermore, nanoscaling can be used to form high density arrays of monodomain ferroelectric nanostructures, which is desirable for the miniaturisation of memory devices. This thesis details the use of various types of nanostructuring approaches to fabricate arrays of ferroelectric nanostructures, particularly non-oxide based systems. The introductory chapter reviews some exemplary research breakthroughs in the synthesis, characterisation and applications of nanoscale ferroelectric materials over the last decade, with priority given to novel synthetic strategies. Chapter 2 provides an overview of the experimental methods and characterisation tools used to produce and probe the properties of nanostructured antimony sulphide (Sb2S3), antimony sulpho iodide (SbSI) and lead titanate zirconate (PZT). In particular, Chapter 2 details the general principles of piezoresponse microscopy (PFM). Chapter 3 highlights the fabrication of arrays of Sb2S3 nanowires with variable diameters using newly developed solventless template-based approach. A detailed account of domain imaging and polarisation switching of these nanowire arrays is also provided. Chapter 4 details the preparation of vertically aligned arrays of SbSI nanorods and nanowires using a surface-roughness assisted vapour-phase deposition method. The qualitative and quantitative nanoscale ferroelectric properties of these nanostructures are also discussed. Chapter 5 highlights the fabrication of highly ordered arrays of PZT nanodots using block copolymer self-assembled templates and their ferroelectric characterisation using PFM. Chapter 6 summarises the conclusions drawn from the results reported in chapters 3, 4 and 5 and the future work.

Thermal evaporation furnace with improved configuration for growing nanostructured inorganic materials

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

Nanostructured films of perylene derivatives: High performance materials for taste sensor applications

Four perylene derivatives (PTCD) have been used as transducing materials in taste sensors fabricated with nanostructured Langmuir-Blodgett (LB) films deposited onto interdigitated gold electrodes. The Langmuir monolayers of PTCDs display considerable collapse pressures, with areas per molecule indicative of an edge-on or head-on arrangement for the molecules at the air/water interface. The sensing units for the electronic tongue were produced from 5-layer LB films of the four PTCDs, whose electrical response was characterized with impedance spectroscopy. The distinct responses of the PTCDs, attributed to differences in their molecular structures, allowed one to obtain a finger printing system that was able to distinguish tastes (salty, sweet, bitter and sour) at 1 μM concentrations, which, in some cases, are three orders of magnitude below the human threshold. Using Principal Component Analysis (PCA) data analysis, the electronic tongue also detected trace amounts of a pesticide and could distinguish among samples of ultrapure, distilled and tap water, and two brands of mineral water. © 2004 by American Scientific Publishers. All rights reserved.

Organometallic derivatives of cyclotriphosphazene as precursors of nanostructured metallic materials: a new solid state method

The cyclic phosphazene trimers [N3P3(OC6H5)5OC5H4N·Ti(Cp)2Cl][PF6] (3), [N3P3(OC6H4CH2CN·Ti(Cp)2Cl)6][PF6]6 (4), [N3P3(OC6H4-But)5(OC6H4CH2CN·Ti(Cp)2Cl)][PF6] (5), [N3P3(OC6H5)5C6H4CH2CN·Ru(Cp)(PPh3)2][PF6] (6), [N3P3(OC6H5)5C6H4CH2CN·Fe(Cp)(dppe)][PF6] (7) and N3P3(OC6H5)5OC5H4N·W(CO)5 (8) were prepared and characterized. As a model, the simple compounds [HOC5H5N·Ti(Cp)2Cl]PF6 (1) and [HOC6H4CH2CN·Ti(Cp)2Cl]PF6 (2) were also prepared and characterized. Pyrolysis of the organometallic cyclic trimers in air yields metallic nanostructured materials, which according to transmission and scanning electron microscopy (TEM/SEM), energy-dispersive X-ray microanalysis (EDX), and IR data, can be formulated as either a metal oxide, metal pyrophosphate or a mixture in some cases, depending on the nature and quantity of the metal, characteristics of the organic spacer and the auxiliary substituent attached to the phosphorus cycle. Atomic force microscopy (AFM) data indicate the formation of small island and striate nanostructures. A plausible formation mechanism which involves the formation of a cyclomatrix is proposed, and the pyrolysis of the organometallic cyclic phosphazene polymer as a new and general method for obtaining metallic nanostructured materials is discussed.

Synthesis and Characterization of Nanostructured Electro-active Materials

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

Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Electrochemical fabrication of metallic nanostructured electrodes for electroanalytical applications

The use of electrodeposited metal-based nanostructures for electroanalytical applications has recently received widespread attention. There are several approaches to creating nanostructured materials through electrochemical routes that include facile electrodeposition at either untreated or modified electrodes, or through the use of physical or chemical templating methods. This allows the shape, size and composition of the nanomaterial to be readily tuned for the application of interest. The use of such materials is particularly suited to electroanalytical applications. In this mini-review an overview of recently developed nanostructured materials developed through electrochemical routes is presented as well as their electroanalytical applications in areas of biological and environmental importance.

Cathodic corrosion of Cu substrates as a route to nanostructured Cu/M (M = Ag, Au, Pd) surfaces

The electrochemical formation of nanostructured materials is generally achieved by reduction of a metal salt onto a substrate that does not influence the composition of the deposit. In this work we report that Ag, Au and Pd electrodeposited onto Cu under conditions where galvanic replacement is not viable and hydrogen gas is evolved results in the formation of nanostructured surfaces that unexpectedly incorporate a high concentration of Cu in the final material. Under cathodic polarization conditions the electrodissolution/corrosion of Cu occurs which provides a source of ionic copper that is reduced at the surface-electrolyte interface. The nanostructured Cu/M (M = Ag, Au and Pd) surfaces are investigated for their catalytic activity for the reduction of 4 nitrophenol by NaBH4 where Cu/Ag was found to be extremely active. This work indicates that a substrate electrode can be utilized in an interesting manner t make bimetallic nanostructures with enhanced catalytic activity.

Combustion synthesis and properties of nanostructured ceria-zirconia solid solutions

Nanostructured ceria-zirconia solid solutions (Ce1 − xZrxO2, X = 0 to 0.9) have been synthesized by a single step solution combustion process using cerous nitrate, zirconyl nitrate and oxalyl dihydrazide (ODH) / carbohydrazide (CH). The as-synthesized powders show extensive XRD line broadening and the crystallite sizes calculated from the XRD line broadening are in the nanometer range (6–11 nm). The combustion derived ceria zirconia solid solutions have high surface area in the range of 36–120 m2/g. Calcination of Ce1 −xZrxO2 at 1350 °C showed three distinct solid solution regions: single phase cubic (x ≤ 0.2), biphasic cubic-tetragonal (0.2 < x Image .8) and tetragonal (x > 0.8). When x ≥ 0.9, the metastable tetragonal phase formed transforms to monoclinic phase on cooling after calcination above 1100 °C. The homogeneity of Ce1 − xZrxO2 has been confirmed by EDAX analysis. The Temperature Programmed Reduction (TPR) measurement of Ce0.5Zr0.5O2 was carried out with H2 and the TPR profile showed two water formation peaks corresponding to the utilization of surface and bulk oxygen.

Synthesis of nanostructured titanium alloys

The synthesis of nanostructured materials is a critical step in the development elf these novel materials. The basic principles involved in the production of nanocrystals and nanocomposites by rapid solidification are dealt with. An analysis of the various factors influencing the final grain size of the nanocrystals achieved during mechanical alloying has been presented. The devitrification of amorphous phase formed during rapid solidification processing and mechanical alloying provides an alternative and attractive route. Examples of the synthesis of nanostructured materials using these three different routes are drawn from our work on titanium alloys.

Synthesis of mesoporous materials based on titanium(IV)oxide and titanium nitride

Nanoparticles of titania were obtained by the controlled hydrolysis of Ti(i-OC3H7)(4) in the reverse micelles of dodecylamine derived from dodecylamine-isopropanol-water solution (water/oil microemulsion). The mesolamellar phase based on titanium nitride (TiN) was obtained by first decomposing TiN atleast partially using the 1:1 solution of acid mixture (HF and HNO3 in the ratio of 9:1) in water and then templating onto the cationic surfactant namely, cetyltrimethylammaniumbromide (abbreviated as CTAB) at 80 degrees C. The synthesis of mesolamellar phase based on TiN involves the charge matched templating approach following the counter-ion mediated pathway. The samples thus obtained were characterized by small angle x-ray diffraction using Cuk(a) radiation, scanning electron microscopy and transmission electron microscopy, which indicated some satisfactory results. (C) 1999 Acta Metallurgica Inc.