Weak epitaxy growth affording high-mobility thin films of disk-like organic semiconductors

Thin films of phthalocyanine compounds show weak epitaxial growth on a monodomain film of a rod-like molecule (see figure). The resulting organic electronic devices exhibit high charge carrier mobilities close to those of the single-crystal devices.

Ambipolar organic field-effect transistors with air stability, high mobility, and balanced transport

Ambipolar organic field-effect transistors (OFETs) based on the organic heterojunction of copper-hexadecafluoro-phthalocyanine (F16CuPc) and 2,5-bis(4-biphenylyl) bithiophene (BP2T) were fabricated. The ambipolar OFETs eliminated the injection barrier for the electrons and holes though symmetrical Au source and drain electrodes were used, and exhibited air stability and balanced ambipolar transport behavior. High field-effect mobilities of 0.04 cm(2)/V s for the holes and 0.036 cm(2)/V s for the electrons were obtained. The capacitance-voltage characteristic of metal-oxide-semiconductor (MOS) diode confirmed that electrons and holes are transported at F16CuPc and BP2T layers, respectively. On this ground, complementary MOS-like inverters comprising two identical ambipolar OFETs were constructed.

Interfacial electronic structure of copper phthalocyanine and copper hexadecafluorophthalocyanine studied by photoemission

Electronic structures of the heterojunction between copper phthalocyanine (CuPc) and copper hexadecafluorophthalocyanine (F16CuPc) were studied with ultraviolet photoemission spectroscopy. Band bending and an interface dipole were observed at the interface due to the formation of an electron accumulation layer and a depletion layer in F16CuPc and CuPc, respectively. Such an energy level alignment leads to interesting ambipolar characteristics for application of the CuPc/F16CuPc junction in organic field-effect transistors.

Improved efficiency by a graded emissive region in organic light-emitting diodes

Electrical and optical properties of organic light-emitting diodes (OLEDs) with a stepwise graded bipolar transport emissive layer for a better control of charge transport and recombination are presented. The graded bipolar transport layer was formed by co-evaporating a hole-transporting material N,N-'-diphenyl-N,N-'-bis(1,1(')-biphenyl)-4,4(')-diamine (NPB) and an electron-transporting/emissive material tris-(8-hydroxyquinoline) aluminum (Alq(3)) in steps, where each step has a different concentration ratio of NPB to Alq(3). Compared to a conventional heterojunction OLED, electroluminescence efficiency was enhanced by a factor of more than 1.5, whereas the turn-on voltage remained unchanged in the graded structure.

Copper phthalocyanine on InSb(111)A?interface bonding, growth mode and energy band alignment

Copper phthalocyanine on InSb(111)A?interface bonding, growth mode and energy band alignment, D.A. Evans, H.J. Steiner, S. Evans, R. Middleton, T.S. Jones, S. Park, T.U. Kampen, D.R.T. Zahn, G. Cabailh and I.T. McGovern, J. Phys.: Condens. Matter, 15, S2729?S2740, (2003)

Polymer and metallodielectric based photonic crystals

The bottom-up colloidal synthesis of photonic crystals has attracted interest over top-down approaches due to their relatively simplicity, the potential to produce large areas, and the low-costs with this approach in fabricating complex 3-dimensional structures. This thesis focuses on the bottom-up approach in the fabrication of polymeric colloidal photonic crystals and their subsequent modification. Poly(methyl methacrylate) sub-micron spheres were used to produce opals, inverse opals and 3D metallodielectric photonic crystal (MDPC) structures. The fabrication of MDPCs with Au nanoparticles attached to the PMMA spheres core–shell particles is described. Various alternative procedures for the fabrication of photonic crystals and MDPCs are described and preliminary results on the use of an Au-based MDPC for surface-enhanced Raman scattering (SERS) are presented. These preliminary results suggest a threefold increase of the Raman signal with the MDPC as compared to PMMA photonic crystals. The fabrication of PMMA-gold and PMMA-nickel MDPC structures via an optimised electrodeposition process is described. This process results in the formation of a continuous dielectric-metal interface throughout a 3D inverted photonic crystal structure, which are shown to possess interesting optical properties. The fabrication of a robust 3D silica inverted structure with embedded Au nanoparticles is described by a novel co-crystallisation method which is capable of creating a SiO2/Au NP composite structure in a single step process. Although this work focuses on the creation of photonic crystals, this co-crystallisation approach has potential for the creation of other functional materials. A method for the fabrication of inverted opals containing silicon nanoparticles using aerosol assisted chemical vapour deposition is described. Silicon is a high dielectric material and nanoparticles of silicon can improve the band gap and absorption properties of the resulting structure, and therefore have the potential to be exploited in photovoltaics.

Optical and magneto-optical properties of gold core cobalt shell magnetoplasmonic nanowire arrays

In this work we present core–shell nanowire arrays of gold coated with a nanometric layer of cobalt. Despite the extremely small Co volume, these core–shell nanowires display large magneto-optical activity and plasmonic resonance determined by the geometry of the structure. Therefore, we are able to tune both the plasmonic and magneto-optical response in the visible range. Through optical and ellipsometric measurements in transmission, and applying a magnetic field to the sample, it is possible to modulate the value of the phase angle (Del {Δ}) between the S and P polarised components. It was found that the core–shell sample produced an order of magnitude larger variation in Del with changing magnetic field direction, compared with hollow cobalt tubes. The enhancement of magneto optical properties through the plasmonic nature of the gold core is complemented with the ability to induce magnetic influence over optical properties via an externally applied field. Moreover, we demonstrate for the first time the ability to use the remanent magnetisation of the Co, in conjunction with the optical properties defined by the Au, to observe remanent optical states in this uniquely designed structure. This new class of magnetoplasmonic metamaterial has great potential in a wide range of applications, from bio-sensing to data storage due to the tuneable nature of multiple resonance modes and dual functionality.

Determining the Effect of Plasma Pre-Treatment on Antimony Tin Oxide to Support Pt@Pd and the Oxygen Reduction Reaction Activity

This article reveals the effect of plasma pre-treatment on antimony tin oxide (ATO) nanoparticles. The effect is to allow Pt@Pd to be deposited homogeneously on the ATO surface with high dispersion and narrow particle size distribution. The Pt@Pd core–shell catalyst was prepared using the polyol method and shows a dramatic improvement towards ORR activity and durability.

Properties of self-assembled diluted magnetic semiconductor nanostructures

Este trabalho centra-se na investigação da possibilidade de se conseguir um semicondutor magnético diluído (SMD) baseado em ZnO. Foi levado a cabo um estudo detalhado das propriedades magnéticas e estruturais de estruturas de ZnO, nomeadamente nanofios (NFs), nanocristais (NCs) e filmes finos, dopadas com metais de transição (MTs). Foram usadas várias técnicas experimentais para caracterizar estas estruturas, designadamente difracção de raios-X, microscopia electrónica de varrimento, ressonância magnética, SQUID, e medidas de transporte. Foram incorporados substitucionalmente nos sítios do Zn iões de Mn2+ e Co2+ em ambos os NFs e NCs de ZnO. Revelou-se para ambos os iões dopantes, que a incorporação é heterogénea, uma vez que parte do sinal de ressonância paramagnética electrónica (RPE) vem de iões de MTs em ambientes distorcidos ou enriquecidos com MTs. A partir das intensidades relativas dos espectros de RPE e de modificações da superfície, demonstra-se ainda que os NCs exibem uma estrutura core-shell. Os resultados, evidenciam que, com o aumento da concentração de MTs, a dimensão dos NCs diminui e aumentam as distorções da rede. Finalmente, no caso dos NCs dopados com Mn, obteve-se o resultado singular de que a espessura da shell é da ordem de 0.3 nm e de que existe uma acumulação de Mn na mesma. Com o objectivo de esclarecer o papel dos portadores de carga na medição das interacções ferromagnéticas, foram co-dopados filmes de ZnO com Mn e Al ou com Co e Al. Os filmes dopados com Mn, revelaram-se simplesmente paramagnéticos, com os iões de Mn substitucionais nos sítios do Zn. Por outro lado, os filmes dopados com Co exibem ferromagnetismo fraco não intrínseco, provavelmente devido a decomposição spinodal. Foram ainda efectuados estudos comparativos com filmes de ligas de Zn1-xFexO. Como era de esperar, detectaram-se segundas fases de espinela e de óxido de ferro nestas ligas; todas as amostras exibiam curvas de histerese a 300 K. Estes resultados suportam a hipótese de que as segundas fases são responsáveis pelo comportamento magnético observado em muitos sistemas baseados em ZnO. Não se observou nenhuma evidência de ferromagnetismo mediado por portadores de carga. As experiências mostram que a análise de RPE permite demonstrar directamente se e onde estão incorporados os iões de MTs e evidenciam a importância dos efeitos de superfície para dimensões menores que ~15 nm, para as quais se formam estruturas core-shell. As investigações realizadas no âmbito desta tese demonstram que nenhuma das amostras de ZnO estudadas exibiram propriedades de um SMD intrínseco e que, no futuro, são necessários estudos teóricos e experimentais detalhados das interacções de troca entre os iões de MTs e os átomos do ZnO para determinar a origem das propriedades magnéticas observadas.

Electrospun Contrast Agent-Loaded Fibers for Colon-Targeted MRI

Magnetic resonance imaging is a diagnostic tool used for detecting abnormal organs and tissues, often using Gd(III) complexes as contrast-enhancing agents. In this work, core–shell polymer fibers have been prepared using coaxial electrospinning, with the intent of delivering gadolinium (III) diethylenetriaminepentaacetate hydrate (Gd(DTPA)) selectively to the colon. The fibers comprise a poly(ethylene oxide) (PEO) core loaded with Gd(DTPA), and a Eudragit S100 shell. They are homogeneous, with distinct core–shell phases. The components in the fibers are dispersed in an amorphous fashion. The proton relaxivities of Gd(DTPA) are preserved after electrospinning. To permit easy visualization of the release of the active ingredient from the fibers, analogous materials are prepared loaded with the dye rhodamine B. Very little release is seen in a pH 1.0 buffer, while sustained release is seen at pH 7.4. The fibers thus have the potential to selectively deliver Gd(DTPA) to the colon. Mucoadhesion studies reveal there are strong adhesive forces between porcine colon mucosa and PEO from the core, and the dye-loaded fibers can be successfully used to image the porcine colon wall. The electrospun core–shell fibers prepared in this work can thus be developed as advanced functional materials for effective imaging of colonic abnormalities.

Novos compostos orgânicos reticuláveis para aplicações em células fotovoltaicas

Trabalho Final de Mestrado para obtenção do grau de mestre em Engenharia Química e Biológica

Demux devices based on A-SiC:H

In this paper we present results about the functioning of a multilayered a-SiC:H heterostructure as a device for wavelength-division demultiplexing of optical signals. The device is composed of two stacked p-i-n photodiodes, both optimized for the selective collection of photogenerated carriers. Band gap engineering was used to adjust the photogeneration and recombination rates profiles of the intrinsic absorber regions of each photodiode to short and long wavelength absorption and carrier collection in the visible spectrum. The photocurrent signal using different input optical channels was analyzed at reverse and forward bias and under steady state illumination. This photocurrent is used as an input for a demux algorithm based on the voltage controlled sensitivity of the device. The device functioning is explained with results obtained by numerical simulation of the device, which permit an insight to the internal electric configuration of the double heterojunction.These results address the explanation of the device functioning in the frequency domain to a wavelength tunable photocapacitance due to the accumulation of space charge localized at the internal junction. The existence of a direct relation between the experimentally observed capacitive effects of the double diode and the quality of the semiconductor materials used to form the internal junction is highlighted.

Signature optique d’effet Stark dans une bicouche de CuPc:C60

Les hétérojonctions formées de deux matériaux, un donneur et un accepteur (D/A), sont la base de la majorité des mélanges photovoltaïques organiques. Les mécanismes de séparation des charges dans ces systèmes représentent aujourd'hui l'un des sujets les plus chauds et les plus débattus dans ce domaine. Nous entrons au coeur de ce débat en choisissant un système D/A à base de phtalocyanine de cuivre (CuPc) et de fullerène (C60). Pour sonder les états excités de nos molécules et obtenir de l'information sur les phénomènes à l'interface D/A, nous réalisons une expérience pompe-sonde, appelée absorption photoinduite (PIA). Nous y mesurons le changement fractionnaire de transmission au travers de l'échantillon. Les mesures de PIA sont réalisées à l'état de quasi équilibre, à T=10K. Nous observons une modulation prononcée dans la région du photoblanchiment de l'état fondamental qui nous indique que la pompe induit un décalage du spectre d'absorption de l'état fondamental. Ce décalage peut être expliqué par deux processus : soit l'échantillon est chauffé par la pompe (effet thermique) ou bien des charges sont créées à l'interface entre les deux matériaux (effet Stark). La dépendance en température du spectre d'absorption entre 10K et 290K montre une signature thermique pour un changement de température de 80K. Grâce au ratio des raies Raman anti-Stokes et Stokes, nous démontrons que la pompe chauffe l'échantillon de 34 K, température insuffisante pour attribuer notre signal à un effet thermique. Nous évaporons ensuite la bicouche CuPc/C60 sur de l'ITO et du saphir, substrats qui possèdent des conductivités thermiques différentes et nous observons le même signal de PIA, excluant par le fait même l'hypothèse de l'effet thermique. Puisque notre étude est comparable à la spectroscopie à effet Stark, nous procédons à une analyse similaire en comparant notre signal de PIA au spectre de la transmittance et à ses dérivés première et seconde. Nous observons alors que notre signal reproduit presque parfaitement la dérivée seconde de la transmittance. Ces résultats sont conformes à une signature optique d'effet Stark due à la création de charges à l'interface D/A.

Preparation and characterisation of certain II-VI, I-III-VI2 semiconductor thin films and transparent conducting oxides

There is an increasing demand for renewable energies due to the limited availability of fossil and nuclear fuels and due to growing environmental problems. Photovoltaic (PV) energy conversion has the potential to contribute significantly to the electrical energy generation in the future. Currently, the cost for photovoltaic systems is one of the main obstacles preventing production and application on a large scale. The photovoltaic research is now focused on the development of materials that will allow mass production without compromising on the conversion efficiencies. Among important selection criteria of PV material and in particular for thin films, are a suitable band gap, high absorption coefficient and reproducible deposition processes capable of large-volume and low cost production. The chalcopyrite semiconductor thin films such as Copper indium selenide and Copper indium sulphide are the materials that are being intensively investigated for lowering the cost of solar cells. Conversion efficiencies of 19 % have been reported for laboratory scale solar cell based on CuInSe2 and its alloys. The main objective of this thesis work is to optimise the growth conditions of materials suitable for the fabrication of solar cell, employing cost effective techniques. A typical heterojunction thin film solar cell consists of an absorber layer, buffer layer and transparent conducting contacts. The most appropriate techniques have been used for depositing these different layers, viz; chemical bath deposition for the window layer, flash evaporation and two-stage process for the absorber layer, and RF magnetron sputtering for the transparent conducting layer. Low cost experimental setups were fabricated for selenisation and sulphurisation experiments, and the magnetron gun for the RF sputtering was indigenously fabricated. The films thus grown were characterised using different tools. A powder X-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive X-ray analysis (EDX) and scanning electron microscopy i (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UV-Vis-NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using the two probe and four probe electrical measurements. Nature of conductivity of the films was determined by thermoprobe and thermopower measurements. The deposition conditions and the process parameters were optimised based on these characterisations.