Preparation and upconversion emission properties of TiO2 :Yb, Er inverse opals

Inverse opal photonic crystals of Y b³⁺, Er³⁺ co-doped TiO₂ (TiO₂:Yb, Er) were prepared by a self-assembly technique in combination with a sol-gel method. Upconversion (UC) luminescence properties of the inverse opals were investigated. The results show that photonic bandgap has significant influence on the upconversion emission of the TiO₂:Yb, Er inverse opal photonic crystals. Significant suppression of the upconversion emission was detected if the photonic bandgap overlapped with the Er³⁺ ions emission band.     

二氧化硅人工蛋白石晶体（opal)的制备及其结构性质的研究

运用胶体化学法合成了尺寸可控的二氧化硅（SiO2）亚微米溶胶小球.透射电子显微镜（TEM）结果显示样品平均尺寸可从200nm变化至600nm，单分散性较高、平均标准偏差小于5％.通过自然沉积法，由溶胶SiO2小球自组织晶化制备了人工蛋白石晶体（opal晶体）结构.样品的剖面扫描电子显微镜（SEM）检测表明，样品为面心立方（fcc）结构.分析表明，较高的单分散性和缓慢的沉积过程是SiO2溶胶小球自组织晶化成三维有序结构的关键因素.反射谱中峰位在1320nm处的反射峰的出现，意味着样品在宏观尺度上的有序排列， 关键词： 亚微米二氧化硅溶胶小球 人工蛋白石晶体 方向带隙     

Stimulated emission at the second order stop-zone edge of the two-dimensional opal–zinc oxide photonic crystal

The fabrication of the 2D periodic structures in ZnO thin films by magnetron sputtering on the opal matrices was developed. The microstructures were characterized by AFM and SEM. The spontaneous and stimulated emissions of the ZnO layers on opal were studied at N₂ laser excitation (λ = 337 nm). The stimulated emission near 397 nm was observed at room temperature from ZnO–opal structure. The threshold of the electron–hole plasma recombination laser process was 300 kW/cm² for this structure. This threshold is two orders of magnitude smaller of that one for the flat ZnO–SiO₂ films owing to DFB resonator effect in 2D structure.     

Luminescence in the 1.54 µm region for erbium in two-dimensional and three-dimensional mesoscopic structures

We have studied the luminescence and luminescence excitation spectra of erbium in the 1.54 μm region in titanium oxide and silicon oxide xerogels, formed in the mesoscopic pores of three-dimensional synthetic opals and two-dimensional porous aluminum oxide structures. For erbium-doped titanium oxide films formed in opal, in contrast to analogous films on porous aluminum oxide, in the luminescence excitation spectra we observe an intense broad band with a maximum in the ∼360 nm region. We discuss the possible nature of this band. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 622–626, September–October, 2007.     

TMA and SEM characterization of the thermal dehydration of australian sedimentary opal

The dehydration of samples of a Coober Pedy, South Australian sedimentary white opal, displaying play of colour, was investigated using TMA by heating the samples of the specimen to a range of temperatures between room temperature and 1000 at 200°C intervals followed by cooling to room temperature. Etched fracture surfaces of the samples were then examined using SEM. The samples showed the typical expansion at low temperature up to 210°C before contraction was observed. The contraction of the opals was ascribed to both sintering, supported by morphological change observed in the SEM micrographs, and dehydroxylation of the silanol groups producing silicon-oxygen-silicon bridges resulting in a more dense silica network.     

Cell‐Friendly Inverse Opal‐Like Hydrogels for a Spatially Separated Co‐Culture System

Three‐dimensional macroporous scaffolds have extensively been studied for cell‐based tissue engineering but their use is mostly limited to mechanical support for cell adhesion and growth on the surface of macropores. Here, a templated fabrication method is described to prepare cell‐friendly inverse opal‐like hydrogels (IOHs) allowing both cell encapsulation within the hydrogel matrix and cell seeding on the surface of macropores. Ionically crosslinked alginate microbeads and photocrosslinkable biocompatible polymers are used as a sacrificial template and as a matrix, respectively. The alginate microbeads are easily removed by a chelating agent, with minimal toxicity for the encapsulated cells during template removal. The outer surface of macropores in IOHs can also provide a space for cell adherence. The cells encapsulated or attached in IOHs are able to remain viable and to proliferate over time. The elastic modulus and cell‐adhesion properties of IOHs can be easily controlled and tuned. Finally, it is demonstrated that IOH can be used to co‐culture two distinct cell populations in different spatial positions. This cell‐friendly IOH system provides a 3D scaffold for organizing different cell types in a controllable microenvironment to investigate biological processes such as stem cell niches or tumor microenvironments.

     

Inverted Opal Fluorescent Film Chemosensor for the Detection of Explosive Nitroaromatic Vapors through Fluorescence Resonance Energy Transfer

This paper reports an inverted opal fluorescence chemosensor for the ultrasensitive detection of explosive nitroaromatic vapors through resonance‐energy‐transfer‐amplified fluorescence quenching. The inverted opal silica film with amino ligands was first fabricated by the acid–base interaction between 3‐aminopropyltriethoxysilane and surface sulfonic groups on polystyrene microsphere templates. The fluorescent dye was then chemically anchored onto the interconnected porous surface to form a hybrid monolayer of amino ligands and dye molecules. The amino ligands can efficiently capture vapor molecules of nitroaromatics such as 2,4,6‐trinitrotoluene (TNT) through the charge‐transfer complexing interaction between electron‐rich amino ligands and electron‐deficient aromatic rings. Meanwhile, the resultant TNT–amine complexes can strongly suppress the fluorescence emission of the chosen dye by the fluorescent resonance energy transfer (FRET) from the dye donor to the irradiative TNT–amino acceptor through intermolecular polar–polar resonance at spatial proximity. The quenching response of the highly ordered porous films with TNT is greatly amplified by at least 10‐fold that of the amorphous silica films, due to the interconnected porous structure and large surface‐to‐volume ratio. The inverted opal film with a stable fluorescence brightness and strong analyte affinity has lead to an ultrasensitive detection of several ppb of TNT vapor in air.     

Thermal Characteristics of Australian Sedimentary Opals

Naturally occurring opals from three different regions in Australia were studied for their thermal characteristics. All the opals showed initial expansion followed by contraction in thermomechanical analysis (TMA) although the temperature at which the change from expansion to contraction occurred depended on their provenance. Thermogravimetric analysis (TG) revealed different rates and temperatures of dehydration for these opals. A general correlation between the temperature at which there was a zero thermal expansion and that of the maximum rate of dehydration was observed. A dehydration–sintering mechanism is proposed with the effect of sintering being more pronounced following total dehydration. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fabrication of BaTiO3 Inverse Opal Photonic Crystal

The colloidal crystal template or opal with a closed-packed face centered cubic (fcc) lattice, was prepared from monodisperse polystyrene (PS) spheres by gravity sedimentation. The template was used for the generation of photonic crystal. The template provided void space for infiltration of liquid precursor composed of titanium butyloxide, barium acetate, ethanol, and acetic acid. The opal composite was hydrolyzed, dried, sintered by heating for completely removing PS spheres to form BaTiO3 photonic crystals with inverse opal structure. The PS spheres were replaced by air spheres, which interconnected each other through the windows on the BaTiO3 wall.So both the BaTiO3 wall and air void constitute continuous phases.