Bulk silica-based luminescent materials by sol-gel processing of non-conventional precursors

The sol-gel synthesis of bulk silica-based luminescent materials using innocuous hexaethoxydisilane and hexamethoxydisilane monomers, followed by one hour thermal annealing in an inert atmosphere at 950oC-1150oC, is reported. As-synthesized hexamethoxydisilane-derived samples exhibit an intense blue photoluminescence band, whereas thermally treated ones emit stronger photoluminescence radiation peaking below 600 nm. For hexaethoxydisilane-based material, annealed at or above 1000oC, a less intense photoluminescence band, peaking between 780 nm and 850 nm that is attributed to nanocrystalline silicon is observed. Mixtures of both precursors lead to composed spectra, thus envisaging the possibility of obtaining pre-designed spectral behaviors by varying the mixture composition.

Novel lanthanide luminescent materials based on complexes of 3-hydroxypicolinic acid and silica nanoparticles

New lanthanide complexes of 3-hydroxypicolinic acid (HpicOH) were prepared: [Ln(H2O)(picOH)(2)(mu-HpicO)].3H(2)O (Ln = Eu, Tb, Er). The complexes were characterized using photoluminescence, infrared, Raman, and H-1 NMR spectroscopy, and elemental analysis. The crystal structure of [Eu(H2O)(picOH)(2)(mu-HpicO)] . 3H(2)O 1 was determined by X-ray diffraction. Compound 1 crystallizes in a monoclinic system with space group P2(1)/c and cell parameters a = 9.105(13) Angstrom, b = 18.796(25) Angstrom, and c = 13.531(17) Angstrom, and beta = 104.86(1) deg. The 3-hydroxypicolinate ligands coordinate through both N,O- or O,O- chelation to the lanthanide ions, as shown by X-ray and spectroscopic results. Photoluminescence measurements were performed for the Eu(III) and Tb(III) complexes; the Eu(III) complex was investigated in more detail. The Eu(III) compound is highly luminescent and acts as a photoactive center in nanocomposite materials whose host matrixes are silica nanoparticles.

A highly emissive inorganic hexamolybdenum cluster complex as a handy precursor for the preparation of new luminescent materials

The synthesis and characterisation of a new, highly luminescent inorganic cluster complex, (Bu4N)2[Mo6I 8(NO3)6], are described. The complex possesses labile nitrato ligands and is therefore a useful precursor for the design of new luminescent materials. To exemplify this, functionalised polystyrene beads have been utilised as "polymeric ligands" to immobilise the molybdenum cluster complex. This journal is © the Partner Organisations 2014.

Advanced Luminescent Materials for Technological Applications

This thesis focusses on the study of several luminescent materials and investigates some related technological applications. It is made of six chapters. Chapter 1 introduces a brief history, basic principles and applications of photoluminescence. Chapter 2 presents the photophysical properties of five benzoheterodiazole dyes. These molecules were incorporated in PMMA- and PDMS-based LSC-PV devices to determine the emission quantum yields, transmission, re-absorption and IPCE properties. DFT calculations were performed to investigate the structures and energy levels of these dyes. Chapter 3 concerns the preparation of a luminescent film to calibrate an ESA satellite that will monitor the fluorescence of terrestrial vegetation. ZnPc was selected as suitable dye to make the film. Ferrocene was selected as quencher to control the emission intensity. An industrial printing technology was used to produce large-area calibration sheets coated with green pigment that simulates the NIR reflectance of green plants in which the ZnPc is embedded. Photophysical properties of a series of alkynyl gold NHC complexes containing naphthalimide chromophore were studied in Chapter 4. All the compounds were studied in solution and solid state. Further investigations were carried out by incorporating these compounds in PMMA matrix to make films. XRD and DFT calculations were made to determine the structures and energy levels of the complexes. In chapter 5 we studied the photophysical properties of star-shaped molecular systems which can operate as molecular motors when attached onto surface, along with those of their related ligands/moieties in tetrahydrofuran solution. The photophysical properties of these molecular systems can show if they are suitable to operate as light-triggered molecular machines. Finally, chapter 6 concerns the photoluminescence behavior of three NHC half-sandwich Ir/Rh metal complexes. The photophysical properties of these compounds were examined in CH2Cl2 solutions and PMMA films. These complexes may prove potential candidates for organic phosphorescent materials.

Eco-friendly luminescent hybrid materials based on EuIII and LiI co-doped chitosan

Biopolymer-based materials have been of particular interest as alternatives do synthetic polymers due to their low toxicity, biodegradability and biocompatibility. Among them, chitosan is one of the most studied ones and has recently been investigated for the application as solid state polymer electrolytes. Furthermore, it can serve as a host for luminescent species such as rare earth ions, giving rise to materials with increased functionality, of particular interest for electrochemical devices. In this study, we investigate chitosan based luminescent materials doped wit Eu3+ and Li+ triflate salts from the structural, photophysical and conductivity points of view. Because the host presents a broad emission band in the blue to green, while Eu3+ emits in the red, fine tuning of emission colour and/or generation of white light is possible by optimizing composition and excitation scheme. Europium lifetimes (5D0) are in the range 270 – 350 µs and quantum yields are as high as 2%. Although Li+ does not interfere with the luminescent properties, it grants ion-conducting properties to the material suggesting that a combination of both properties could be further explored in multifunctional device.

Luminescent Langmuir-Blodgett film of a new amphiphilic Eu(3+) beta-diketonate

This work reports on the synthesis and characterization of the ligand 3-hexadecylpentane-2,4-drone (Hhdacac) and its Eu(3+) complexes Eu(hdacac)(6) center dot 2H(2)O, Eu(hdacac)(6) center dot phen and Eu(hdacac)(6) center dot tta, where phen and tta denote 1,10-phenanthroline and thenoyltrifluoroacetone, respectively. These new compounds present long carbon chains and their expected miscibility into non-polar ambients is confirmed by the emission spectra of Eu(hdacac)6 center dot tta in hexane. Moreover, the amphiphilic properties of Eu(hdacac)6 complexes allow the obtainment of thin luminescent films by the Langmuir-Blodgett technique. In both cases (solids and films), the typical antenna effect of beta-diketonates is observed. The alluring characteristics of these compounds raise great interest in many fields of Materials Science, like photo- and electro-luminescent materials (mainly thin ""organic"" films), metal catalysts or probes in non-polar solutions, and Langmuir-Blodgett films of several compositions. For the characterization of these products, nuclear magnetic resonance spectroscopy ((1)H NMR), thermogravimetric analysis, elementary analyses (C, H), scanning electron microscopy (energy dispersive X-ray spectroscopy), absorption (UV-vis/FT-IR) and photoluminescence spectroscopies were used. (c) 2008 Elsevier B.V. All rights reserved.

The Bologna Stone: history's first persistent luminescent material

In 1603, the Italian shoemaker Vincenzo Cascariolo found that a stone (baryte) from the outskirts of Bologna emitted light in the dark without any external excitation source. However, the calcination of the baryte was needed prior to this observation. The stone later named as the Bologna Stone was among the first luminescent materials and the first documented material to show persistent luminescence. The mechanism behind the persistent emission in this material has remained a mystery ever since. In this work, the Bologna Stone (BaS) was prepared from the natural baryte (Bologna, Italy) used by Cascariolo. Its properties, e. g. impurities (dopants) and their valences, luminescence, persistent luminescence and trap structure, were compared to those of the pure BaS materials doped with different (transition) metals (Cu, Ag, Pb) known to yield strong luminescence. The work was carried out by using different methods (XANES, TL, VUV-UV-vis luminescence, TGA-DTA, XPD). A plausible mechanism for the persistent luminescence from the Bologna Stone with Cu+ as the emitting species was constructed based on the results obtained. The puzzle of the Bologna Stone can thus be considered as resolved after some 400 years of studies.

Luminophores and Carbon nanostructures: towards new functional materials

In the scenario of depleting fossil fuels, finding new energy technologies and conserving conventional energy resources have become essential to sustain modern civilization. While renewable energies are on the rise, considerable interest has been turned also to reduce energy consumption of conventional devices and appliances, which are often not yet optimized for this purpose. Modern nanotechnology provides a platform to build such devices by using nanomaterials showing exceptional physico-chemical properties. In particular, carbon materials (fullerenes, carbon nanotubes, graphene etc.), which show high thermal and electrical conductivity, aspect ratio, shear strength and chemical/mechanical resistance, are quite promising for a wide range of applications. However, the problem of solubility often hampers their handling and industrial utilization. These limitations can be mitigated by functionalizing carbon nanostructures, either covalently or non covalently, with organic or inorganic compounds. The exo- and endohedral functionalization of carbon nanotubes (CNTs) with organic/inorganic moieties to produce luminescent materials with desired properties are the main focus of this doctoral work. These hybrids have been thoroughly designed and characterized with chemical, microscopic and photophysical analyses. All the materials based on carbon nanostructures described in this thesis are innovative examples of photoactive and luminescent hybrids, and their morphological and photophysical properties help understanding the nature of interactions between the active units. This may prompt the design and fabrication of new functional materials for applications in the fields of optoelectronics and photovoltaics.

Efficient luminescent solar concentrators based on self-absorption free, Tm2+ doped halides

The optical and luminescence properties of CaI2 and NaCl doped with divalent thulium are reported for solar energy applications. These halides strongly absorb solar light from the UV up to 900 nm due to the intense Tm2+ 4f13→4f125d1 electronic transitions. Absorption is followed by emission of 1140 nm light due to the 2F5/2→2F7/2 transition of the 4f13 configuration that can be efficiently converted to electric power by thin film CuInSe2 (CIS) solar cells. Because of a negligible spectral overlap between absorption and emission spectra, a luminescent solar concentrator (LSC) based on these black luminescent materials would not suffer from self-absorption losses. The Tm2+ doped halides may therefore lead to efficient semi-transparent power generating windows that absorb solar light over the whole visible spectrum. It will be shown that the power efficiency of the Tm2+ based LSCs can be up to four times higher compared to LSCs based on organic dyes or quantum dots.

Fabrication of luminescent nanostructures by electron-beam direct writing of PMMA resist

We report on the conversion of non-luminescent conventional poly(methylmethacrylate) (PMMA)-based electron-beam resists into luminescent materials when used as negative-tone resists, that is, when exposed to high electron irradiation doses. Raman spectroscopy reveals the chemical transformation induced by electron irradiation which is responsible for the observed luminescence in the visible (blue) region. The emission intensity from exposed PMMA-based patterns can be controlled by the electron irradiation dose employed to create them.

Development of Zirconia based phosphors for application in lighting and as luminescent bioprobes

The strong progress evidenced in photonic and optoelectronic areas, accompanied by an exponential development in the nanoscience and nanotechnology, gave rise to an increasing demand for efficient luminescent materials with more and more exigent characteristics. In this field, wide band gap hosts doped with lanthanide ions represent a class of luminescent materials with a strong technological importance. Within wide band gap material, zirconia owns a combination of physical and chemical properties that potentiate it as an excellent host for the aforementioned ions, envisaging its use in different areas, including in lighting and optical sensors applications, such as pressure sensors and biosensors. Following the demand for outstanding luminescent materials, there is also a request for fast, economic and an easy scale-up process for their production. Regarding these demands, laser floating zone, solution combustion synthesis and pulsed laser ablation in liquid techniques are explored in this thesis for the production of single crystals, nanopowders and nanoparticles of lanthanides doped zirconia based hosts. Simultaneously, a detailed study of the morphological, structural and optical properties of the produced materials is made. The luminescent characteristics of zirconia and yttria stabilized zirconia (YSZ) doped with different lanthanide ions (Ce3+ (4f1), Pr3+ (4f2), Sm3+ (4f5), Eu3+ (4f6), Tb3+ (4f8), Dy3+ (4f9), Er3+ (4f11), Tm3+ (4f12), Yb3+ (4f13)) and co-doped with Er3+,Yb3+ and Tm3+,Yb3+ are analysed. Besides the Stokes luminescence, the anti- Stokes emission upon infrared excitation (upconversion and black body radiation) is also analysed and discussed. The comparison of the luminescence characteristics in materials with different dimensions allowed to analyse the effect of size in the luminescent properties of the dopant lanthanide ions. The potentialities of application of the produced luminescent materials in solid state light, biosensors and pressure sensors are explored taking into account their studied characteristics.

Síntese e estudo de ortossilicatos de zinco luminescentes com aplicação da técnica sol-gel

Usually, the concepts of the Sol-Gel technique are not applied in experimental chemistry courses. This work presents a feasible experiment for chemistry instruction, which involves the synthesis of luminescent materials - Zn2SiO4, with and without Mn2+ as a dopant - by the Sol-Gel technique. The obtained materials were analyzed by scanning electron microscopy, X-Ray diffraction, IR spectroscopy and luminescence measures by UV-vis spectroscopy. The results allow the students to confirm the luminescent properties of the zinc orthosilicate luminophores as well as the structural features expected from literature data.

Re-Design of ribbon for new applications

O conceito de qualidade de vida surge pela primeira vez em 1920, através do economista inglês Arthur Cecil Pigou, que utiliza este termo para descrever o impacto governamental sobre a vida das pessoas mais desfavorecidas. Com a instalação de uma era industrializada e com o fim da 2º Guerra Mundial, a sociedade mudou de paradigma e iniciou uma procura incessante de formas para melhorar a sua qualidade de vida. Este conceito desenvolve-se juntamente com o desenvolvimento do conceito de educação, saúde, habitação, transporte, trabalho e lazer, bem como indicadores do aumento da esperança de vida, a diminuição da mortalidade infantil e dos níveis de poluição. O avanço da tecnologia teve um papel fundamental para a evolução desses conceitos, bem como o Design na procura de soluções para aplicação dessas mesmas tecnologias. No caso concreto da indústria tèxtil, a tendência é o desenvolvimento de têxteis inteligentes envolvendo a engenharia electrónica no seu processo de conceptualização e de fabrico. A chamada tecnologia wearable abre novos horizontes para a criação de soluções inovadoras, abrindo novos nichos de mercado com elevado valor acrescentado. Existem atualmente vários produtos no mercado cuja funcionalidade e utilidade lhes conferiu um estatuto imutável ao longo dos anos, onde a evolução não avançou na tendência atual. Esse é o caso dos tecidos estreitos, cuja funcionalidade poderá adquirir novas capacidades e ser utilizada em diferentes componentes têxteis nas mais variadas áreas. Essas capacidades poderão ser acrescentadas pela incorporação de materiais com luminosidade (Led’s e L-Wire) nas suas estruturas. Neste estudo realizado o design de produtos com novas funcionalidades, adaptando as tecnologias até agora desenvolvidas em novas soluções e/ou novas recriações de produto.

Propriedades fotofísicas de Eu3+ e Tb3+ imobilizados em sílica gel funcionalizada com beta-Dicetonas

Synthetic procedures, characterization and luminescent properties of Eu3+ and Tb3+ ions supported on silica gel functionalized with beta-diketones are presented. The functionalization with propyl benzoyltrifluoroacetone (BPG), dibenzoylmethane (DBM) and hexafluoroacetone (HPG), leads to new luminescent materials which photophysical properties depend on the group substituent in the beta-diketone. These systems were evaluated in terms of luminescence and lifetime of the Eu3+ and Tb3+ ions. Silica functionalization was confirmed by TGA and Elemental Analysis. The sample contents of ions were from 0,2 to 0,3 % (w/w).

Filmes de titânio-silício preparados por "spin" e "dip-coating"

The conditions for the preparation of luminescent materials, consisting of Eu3+ ions entrapped in a titanium matrix, in the forma of a thin film, using the sol-gel process, are described. The films were obtained from sols prepared with TEOS and TEOT, in the presence of acetylacetone as the hidrolysis-retarding agent, using the dip-coating and spin-coating techniques. The influence of these techniques on the films based on titanium and silicon are presented. The Eu3+ was used as a luminescent probe. The films have been characterized by luminescence, reflection and transmittance. The thickness of the films could be related to the preparation procedure. Transparent thin films have been prepared by dip-coating technique.