Lanthanum zirconate nanofibers with high sintering-resistance

The PVP/lanthanum nitrate/zirconium oxychloride (PVP-precursor) nanofiber was prepared by electrospinning technique. Lanthanum zirconate (La2Zr2O7, LZ) in the nanofiber is formed after calcination at 800 degrees C and the nanofiber with pyrochlore structure and a diameter of 100-500 nm can be obtained by calcination of the above precursor fiber at 1000 degrees C for 12 h. The surface of the fiber is rough but the continuous microstructure is still maintained after calcination. LZ fibers stack randomly, resulting in a structure with a low contact area between the fibers. This special structure makes the fiber to have a high resistance to sintering at elevated temperatures. The BET (Brunauer-Emmett-Teller) specific surface areas of the LZ fiber and powder calcined at different temperatures are shown in this paper, and the fiber was characterized by TG-DTA (thermal gravimetry-differential thermal analysis), XRD (X-ray diffraction), N-2 absorption-desorption porosimetry and SEM (scanning electron microscopy).

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.

Highly sensitive surface enhanced Raman scattering (SERS) detection platforms formed by large area self-assembled Au nanorod arrays

This thesis explores a new method to fabricate SERS detection platforms formed by large area self-assembled Au nanorod arrays. For the fabrication of these new SERS platforms a new droplet deposition method for the self-assembly of Au nanorods was developed. The method, based in the controlled evaporation of organic suspensions of Au nanorods, was used for the fabrication of horizontal and vertical arrays of Au nanorods over large areas (100μm2). The fabricated nanorods arrays showed a high degree of order measured by SEM and optical microscopy over mm2 areas, but unfortunately they detached from the support when immersed in any analyte solutions. In order to improve adhesion of arrays to the support and clean off residual organic matter, we introduced an additional stamping process. The stamping process allows the immobilization of the arrays on different flexible and rigid substrates, whose feasibility as SERS platforms were tested satisfactory with the model molecule 4ABT. Following the feasibility study, the substrates were used for the detection of the food contaminant Crystal Violet and the drug analogue Benzocaine as examples of recognition of health menaces in real field applications.

Plasmonic gold nanostructures: optical properties and application in mercury detection

This thesis investigates the application of plasmonic gold nanostructures for mercury detection. Various gold and silver single nanostructures and gold nanostructure assemblies were characterised in detail by correlated single nanostructure spectroscopy and electron microscopy. Several routes for mercury detection were explored: plasmon resonance energy transfer (PRET) upon Hg2+ binding to immobilised gold nanoparticle-organic ligand hybrid structures and amalgamation of single immobilised gold nanorods upon chemical and upon electrochemical reduction of Hg2+ ions. The amalgamation approach showed large potential with extraordinary shifts of the nanorods’ scattering spectra upon exposure to reduced mercury; a result of compositional and morphological change induced in the nanorod by amalgamation with mercury. A shift of 5 nm could be recorded for a concentration as low 10 nM Hg2+. Through detailed time-dependent experiments insights into the amalgamation mechanism were gained and a model comprising 5 steps was developed. Finally, spectroelectrochemistry proved to be an excellent way to study in real time in-situ the amalgamation of mercury with gold nanorods paving the way for future work in this field.

Molecular Plasmonics with Tunable Exciton-Plasmon Coupling Strength in J-Aggregate Hybridized Au Nanorod Assemblies

Controlling coherent electromagnetic interactions in molecular systems is a problem of both fundamental interest and important applicative potential in the development of photonic and opto-electronic devices. The strength of these interactions determines both the absorption and emission properties of molecules coupled to nanostructures, effectively governing the optical properties of such a composite metamaterial. Here we report on the observation of strong coupling between a plasmon supported by an assembly of oriented gold nanorods (ANR) and a molecular exciton. We show that the coupling is easily engineered and is deterministic as both spatial and spectral overlap between the plasmonic structure and molecular aggregates are controlled. We think that these results in conjunction with the flexible geometry of the ANR are of potential significance to the development of plasmonic molecular devices.

Plasmonic nanorod metamaterials for biosensing.

Label-free plasmonic biosensors rely either on surface plasmon polaritons or on localized surface plasmons on continuous or nanostructured noble-metal surfaces to detect molecular-binding events(1-4). Despite undisputed advantages, including spectral tunability(3), strong enhancement of the local electric field(5,6) and much better adaptability to modern nanobiotechnology architectures(7), localized plasmons demonstrate orders of magnitude lower sensitivity compared with their guided counterparts(3). Here, we demonstrate an improvement in biosensing technology using a plasmonic metamaterial that is capable of supporting a guided mode in a porous nanorod layer. Benefiting from a substantial overlap between the probing field and the active biological substance incorporated between the nanorods and a strong plasmon-mediated energy confinement inside the layer, this metamaterial provides an enhanced sensitivity to refractive-index variations of the medium between the rods (more than 30,000nm per refractive-index unit). We demonstrate the feasibility of our approach using a standard streptavidin-biotin affinity model and record considerable improvement in the detection limit of small analytes compared with conventional label-free plasmonic devices.

Optical transmission properties and electric field distribution of interacting 2D silver nanorod Arrays

Silver nanorods have been grown by electrodeposition into thin film porous alumina templates (AAO). Optical transmission measurements using p-polarized incident white light shows clear plasmon resonance extinction peaks. We successfully model the dependence on angle in incidence of extinction peak height and position using a multiple-multipoles (MMP) approach with the different spectral features being clearly associated with the effective electric field distribution and coupling between individual nanorods.

Wavelength Dependence of Raman Enhancement from Gold Nanorod Arrays: Quantitative Experiment and Modeling of a Hot Spot Dominated System

Surface-enhanced Raman scattering (SERS) spectra from molecules adsorbed on the surface of vertically aligned gold nanorod arrays exhibit a variation in enhancement factor (EF) as a function of excitation wavelength that displays little correlation with the elastic optical properties of the surface. The key to understanding this lack of correlation and to obtaining agreement between experimental and calculated EF spectra lies with consideration of randomly distributed, sub-10 nm gaps between nanorods forming the substrate. Intense fields in these enhancement “hot spots” make a dominant contribution to the Raman scattering and have a very different spectral profile to that of the elastic optical response. Detailed modeling of the electric field enhancement at both excitation and scattering wavelengths was used to quantitatively predict both the spectral profile and the magnitude of the observed EF.

Domain Wall Propagation in Meso and Nanoscale Ferroelectrics

As part of an ongoing programme to evaluate the extent to which external morphology alters domain wall mobility in ferroelectrics, the electrical switching characteristics of single-crystal BaTiO3 nanorods and thin film plates have been measured and compared. It was found that ferroelectric nanorods were more readily switched than thin plates; increasing the shape constraint therefore appears to enhance switchability. This observation is broadly consistent with previous work, in which local notches patterned along the length of nanorods enhanced switching (McMillen et al 2010 Appl. Phys. Lett. 96 042904), while antinotches had the opposite effect (McQuaid et al 2010 Nano Lett. 10 3566). In this prior work, local enhancement and denudation of the electric field was expected at the notch and antinotch sites, respectively, and this was thought to be the reason for the differences in switching behaviour observed. However, for the simple nanorods and plates investigated here, no differences in the electric field distributions are expected. To rationalise the functional measurements, domain development during switching was imaged directly by piezoresponse force microscopy. A two-stage process was identified, in which narrow needle-like reverse domains initially form across the entire interelectrode gap and then subsequently coarsen through domain wall propagation perpendicular to the applied electric field. To be consistent with the electrical switching data, we suggest that the initial formation of needle domains occurs more readily in the nanorods than in the plates.

Directed self-assembly of nanorod networks: bringing the top down to the bottom up

Self-assembled electrodeposited nanorod materials have been shown to offer an exciting landscape for a wide array of research ranging from nanophotonics through to biosening and magnetics. However, until now, the scope for site-specific preparation of the nanorods on wafers is limited to local area definition. Further there is little or no lateral control of nanorod height. In this work we present a scalable method for controlling the growth of the nanorods in the vertical direction as well as their lateral position. A focused ion beam (FIB) pre-patterns the Au cathode layer prior to the creation of the Anodized Aluminium Oxide (AAO) template on top. When the pre-patterning is of the same dimension to the pore spacing of the AAO template, lines of single nanorods are successfully grown. Further, for sub-200 nm wide features a relationship between the nanorod height and distance from non-patterned cathode can be seen to follow a quadratic growth rate obeying Faradays law of electrodeposition. This facilitates lateral control of nanorod height combined with localised growth of the nanorods.

A new method for non-labeling attomolar detection of diseases based on an individual gold nanorod immunosensor

Herein, we present the use of a single gold nanorod sensor for detection of diseases on an antibody-functionalized surface, based on antibody–antigen interaction and the localized surface plasmon resonance (LSPR) ?max shifts of the resonant Rayleigh light scattering spectra. By replacing the cetyltrimethylammonium bromide (CTAB), a tightly packed self-assembled monolayer of HS(CH2)11(OCH2CH2)6OCH2COOH(OEG6) has been successfully formed on the gold nanorod surface prior to the LSPR sensing, leading to the successful fabrication of individual gold nanorod immunosensors. Using prostate specific antigen (PSA) as a protein biomarker, the lowest concentration experimentally detected was as low as 111 aM, corresponding to a 2.79 nm LSPR ?max shift. These results indicate that the detection platform is very sensitive and outperforms detection limits of commercial tests for PSA so far. Correlatively, its detection limit can be equally compared to the assays based on DNA biobarcodes. This study shows that a gold nanorod has been used as a single nanobiosensor to detect antigens for the first time; and the detection method based on the resonant Rayleigh scattering spectrum of individual gold nanorods enables a simple, label-free detection with ultrahigh sensitivity.

Tuneable magneto-optical metamaterials based on photonic resonances in nickel nanorod arrays

We investigate the magneto-optical properties of a nanostructured metamaterial comprised of arrays of nickel nanorods embedded in an anodized aluminum oxide template. The rods are grown using a self-assembly bottom-up technique that provides a uniform, quasi-hexagonal array over a large area, quickly and at low cost. The tuneability of the magneto-optic response of the material is investigated by varying the nanorod dimensions: diameter, length and inter-rod spacing as well as the overall thickness of the template. It is demonstrated that the system acts as a sub-wavelength light trap with enhanced magneto-optical properties occurring at reflectivity minima corresponding to photonic resonances of the metamaterial. Changes in dimensions of the nickel rods on the order of tens of nanometers cause a spectral blue-shift in the peak magneto-optical response of 270 nm in the visible range. A plasmonic enhancement is also observed at lower wavelengths, which becomes increasingly damped with larger diameters and increased volume fraction of nickel inclusions. This type of structure has potential applications in high density magneto-optical data storage (up to 1011–12 rods per square inch), ultrafast magneto-plasmonic switching and optical components for telecommunications.

Spin-wave modes in Ni nanorod arrays studied by Brillouin light scattering

Dynamic magnetic properties of arrays of Ni nanorods with a low aspect ratio have been investigated. It has been shown that the spectra of spin-wave resonances localized on nanorods with a low aspect ratio typically feature the presence of zones with high density of states resulting in a characteristic two-peak pattern of Stokes and anti-Stokes lines of magneto-optical (MO) Brillouin light scattering with pronounced Stokes–anti-Stokes (S-AS) asymmetry. A simple theoretical model based on the analysis of the elliptic character of the polarization of the optical wave interacting with a dipole magnetostatic wave has been proposed. It has been shown that the S-AS asymmetry is due entirely to the asymmetry of the MO interaction efficiency with respect to time reversal of the magnetic precession in a magnon.

Ultrasensitive non-resonant detection of ultrasound with plasmonic metamaterials

Optical sensors for ultrasound detection provide high sensitivity and bandwidth, essential for photoacoustic imaging in clinical diagnostics and biomedical research. Implementing plasmonic metamaterials in a non-resonant regime facilitates sub-nanosecond, highly sensitive detectors while eliminating cumbersome optical alignment necessary for resonant sensors.

Bottom up strategies for the morphology control of BaTiO3 particulates

As propriedades funcionais dos materiais ferroeléctricos tais como a polarização reversível, piroelectricidade, piezoelectricidade, elevada actividade óptica não linear e comportamento dieléctrico não linear são fundamentais para a sua aplicação em sensores, microactuadores, detectores de infravermelhos, filtros de fase de microondas e memórias não-voláteis. Nos últimos anos, motivado pelas necessidades industriais de redução do tamanho dos dispositivos microelectrónicos, aumentando a eficiência volumétrica, tem sido feito um grande esforço ao nível da investigação para desenvolver estruturas ferroeléctricas à escala micro- e nano- métrica. É sabido que a redução de tamanho em materiais ferroeléctricos afecta significamente as suas propriedades. Neste sentido e considerando que foi previsto teoreticamente por cálculos ab initio que estruturas do tipo nanocilindros e nanodiscos apresentariam um novo tipo de ordem ferroeléctrica e, na expectativa de alcançar conhecimento para o desenvolvimento de uma nova geração de dispositivos microelectróncos, existe um grande interesse em desenvolver métodos de fabrico de nanoestruturas ferroeléctricas unidimensionais (1D) tais como nanocilindros e nanotubos. As estratégias de fabrico de nanoestruturas 1D até agora descritas na literatura indicam claramente as dificuldades inerentes à sua preparação. Existem duas grandes vias de síntese destas nanoestruturas: i) o método “topdown” que consiste na redução de tamanho de um dado material até à obtenção duma estrutura 1D; e ii) o método “bottom-up” em que átomos, iões e moléculas são agrupados para formar um material 1D. O método “top down” envolve em geral técnicas de desgaste, como o uso do feixe de electrões, que apesar de permitirem elevada precisão no posicionamento e no controlo do tamanho, falham em termos de resolução, exigem muito tempo e causam facilmente defeitos que deterioram as propriedades físicas destes materiais. Na metodologia “bottom up” a utilização de moléculas ou estruturas “molde” tem sido a mais explorada. As estructuras 1D podem também ser preparadas sem recorrer a “moldes”. Neste caso a agregação orientada é promovida pelo recurso a aditivos que controlam o crescimento dos cristais em direcções preferenciais. Neste contexto, neste trabalho utilizaram-se duas estratégias “bottom up” de baixo custo para a preparação de nanopartículas de titanato de bário (BaTiO3) com morfologia controlada: 1) síntese química (em solução e em fase vapor) com utilização de nanotubos de titanato TiNTs) como “moldes” e precursores de titânio 2) síntese química em solução com presença de aditivos. Os nanotubos de titanato de sódio foram preparados por síntese hidrotermal. Como existiam muitas dúvidas acerca da natureza estrutural e do mecanismo de formação dos NTs, a parte inicial do trabalho foi dedicada à realização de um estudo sistemático dos parâmetros intervenientes na síntese e à caracterização da sua estrutura e microestrutura. Foi demonstrado que os NTs têm a fórmula geral A2Ti2O5 (A = H+ or Na+), e não TiO2 (anátase) com defendido por vários autores na literatura, e podem ser preparados por método hidrotermal em meio fortemente alcalino usando como fonte de titânio TiO2 comercial na forma de anátase ou rútilo. A menor reactividade do rútilo exige temperaturas de síntese superiores ou tempos de reacção mais longos. A forma tubular resulta do tratamento hidrotermal e não de processos de lavagem e neutralização subsequentes. Se os NTs forem tratados após a síntese hidrotérmica em água a 200 ºC, transformam-se em nanocilindros. Uma das partes principais desta tese consistiu na investigação do papel dos NTs de titanato no crescimento anisotrópico de BaTiO3. O potencial funcionamento dos NTs como “moldes” para além de precursores foi testado em reacção com hidróxido de bário em síntese em solução e por reacção com um precursor orgânico de bário em fase vapor. Tendo por base os estudos cinéticos realizados, bem como as alterações estruturais e morfológicas das amostras, é possível concluir que a formação do BaTiO3 a partir de NTs de titanato de sódio, ocorre por dois mecanismos dependendo da temperatura e tempo de reacção. Assim, a baixa temperatura e curto tempo de reacção verifica-se que se formam partículas dendríticas de BaTiO3 cuja superfície é bastante irregular (“wild”) e que apresentam estrutura pseudo-cúbica. Estas partículas formam-se por reacção topotáctica na fronteira dos nanotubos de titanato de sódio. A temperaturas mais altas e/ou reacções mais longas, a reacção é controlada por um mecanismo de dissolução e precipitação com formação de dendrites de BaTiO3 tetragonais com superfície mais regular (“seaweed”). A microscopia de força piezoeléctrica mostrou que as dendrites “seaweeds“ possuem actividade piezoeléctrica superior à das dendrites “wild”, o que confirma o papel desempenhado pela estrutura e pela concentração de defeitos na rede na coerência e ordem ferroeléctrica de nanoestruturas. Os nossos resultados confirmam que os NTs de titanato não actuam facilmente como “moldes” na síntese em solução de BaTiO3 já que a velocidade de dissolução dos NTs em condições alcalinas é superior à velocidade de formação do BaTiO3. Assumindo que a velocidade de reacção dos NTs com o precursor de bário é superior em fase vapor, efectuou-se a deposição de um precursor orgânico de bário por deposição química de vapor sobre um filme de NTs de titnato de sódio depositados por deposição electroforética. Estudou-se a estabilidade dos NTs nas diferentes condições do reactor. Quando os NTs são tratados a temperaturas superiores a 700 ºC, ocorre a transformação dos NTs em nanocilindros de anatase por um mecanismo de agregação orientada. Quando se faz a deposição do precursor de bário, seguida de calcinação a 700 ºC em atmosfera oxidante de O2, verifica-se que a superficie dos NTs fica coberta com nanocristais de BaTiO3 independentemente da concentração de bário. O papel dos NTs de titanato no crescimento anisotrópico de BaTiO3 em fase vapor é assim descrito pela primeira vez. Em relação à metodologias de crescimento de partículas na ausência de “moldes” mas com aditivos fez-se um estudo sistemático utilizando 5 aditivos de natureza differente. As diferenças entre aditivos foram sistematizadas tendo em conta as diferenças estruturais e morfológicas verificadas. Está provado que os aditivos podem funcionar como modificadores de crescimento cristalino por alteração do seu padrão de crescimento ou por alteração da cinética de crescimento das faces cristalográficas do cristal. Entre os aditivos testados verificou-se que o ácido poliacrilíco adsorve em faces específicas do BaTiO3 alterando a cinética de crescimento e induzindo a agregação orientada das partículas. O polivinilpirrolidona, o docecilsulfato de sódio e hidroxipropilmetilcelulose actuam mais como inibidores de crescimento do que como modificadores do tipo de crescimento. A D-frutose aumenta a energia de activação da etapa de nucleação não ocorrendo formação de BaTiO3 para as mesmas condições dos outros aditivos. Esta tese clarifica o papel dos NTs de titanato de sódio enquanto precursores e “moldes” no crescimento anisotrópico de BaTiO3 em solução e em fase vapor. É feita também a abordagem do controlo morfológico do BaTiO3 através do uso de aditivos. As estratégias de preparação de BaTiO3 propostas são de baixo custo, reprodutíveis e fáceis de efectuar. Os resultados contribuem para uma melhor compreensão da relação tamanho – morfologia – propriedade em materiais ferroeléctricos nanométricos com vista à sua potencial aplicação.