Upconversion (UC) phosphors emit high-energy photons when they are excited by low-energy photons. This property is attractive for flat-panel displays, [1,2] optical storage, [3] biolabels, [4] solid-state lasers, [5] and light-emitting diodes.[6] High UC luminescence efficiency is typically generated by bulk materials [1] and colloidal nanocrystals [7] of hexagonal-phase lanthanide-doped rare-earth fluorides, but nanoarrays of single crystals are more desirable for solid-state lasers. The UC luminescence efficiency can be enhanced if the nanoarrays are aligned with photonic-crystal microstructures, and the faceted end planes of well-shaped crystals serve as good laser-cavity mirrors.[8]Herein, we report a general solution-based approach for the preparation of uniform nanostructured arrays of the sodium rare-earth (M) fluorides NaMF 4 . The arrays can be prepared with well-controlled morphologies (tubes, disks, or rods), phases (cubic or hexagonal), sizes (80-900 nm), and compositions. This approach avoids the assistance of templates, applied fields, and undercoating on substrates, [9,10] and is industrially feasible, owing to its ease and low cost. Multicolor UC fluorescence is also generated when the nanoarrays are pumped in the near-infrared (NIR) region; for example, green or blue fluorescence is produced for nanoarrays of NaYF 4 codoped with Yb 3+ and Er 3+ , or Yb 3+and Tm 3+

Highly ordered mesoporous carbons and silicas with ultralarge accessible pores have been successfully synthesized by using laboratory-made poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymers as templates via the evaporation-induced self-assembly (EISA) approach. Resols and tetraethyl orthosilicate (TEOS) serve as carbon and silica precursors, respectively. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) measurements show that the mesoporous carbons (denoted as C-FDU-18) possess face centered cubic closed-packing (fcc) mesostructure (Fm3m) with large-domain ordering. N2 sorption isotherms reveal a large mesopore at the mean value of 22.6 nm with a narrow pore-size distribution. Mesoporous silicas (Si-FDU-18) also display a highly ordered fcc closed-packing mesostructure with an ultralarge unit cell (a = 54.6 nm). A hydrothermal recrystallization was introduced for the first time to produce micropores in thick silica walls (approximately 7.7 nm) and thus to generate ultralarge accessible mesopores (30.8 nm). Notably, the amphiphilic diblock copolymer with high molecular weight (PEO125-PS230, 29700 g mol-1) in this report was prepared via a simple method of atom transfer radical polymerization (ATRP). It can be easily available for chemists even without any experience in polymer synthesis.

The knowledge of the quantum dot (QD) concentration in a colloidal suspension and the quantitative understanding of the size-dependence of the band gap of QDs are of crucial importance from both applied and fundamental viewpoints. In this work, we investigate the size-dependence of the optical properties of nearly spherical wurtzite (wz) CuInS2 (CIS) QDs in the 2.7 to 6.1 nm diameter range (polydispersity ≤10%). The QDs are synthesized by partial Cu+ for In3+ cation exchange in template Cu2–xS nanocrystals, which yields CIS QDs with very small composition variations (In/Cu = 0.91 ± 0.11), regardless of their sizes. These well-defined QDs are used to investigate the size-dependence of the band gap of wz CIS QDs. A sizing curve is also constructed for chalcopyrite CIS QDs by collecting and reanalyzing literature data. We observe that both sizing curves follow primarily a 1/d dependence. Moreover, the molar absorption coefficients and the absorption cross-section per CIS formula unit, both at 3.1 eV and at the band gap, are analyzed. The results demonstrate that the molar absorption coefficients of CIS QDs follow a power law at the first exciton transition energy (εE1 = 5208d2.45) and scale with the QD volume at 3.1 eV. This latter observation implies that the absorption cross-section per unit cell at 3.1 eV is size-independent and therefore can be estimated from bulk optical constants. These results also demonstrate that the molar absorption coefficients at 3.1 eV are more reliable for analytical purposes, since they are less sensitive to size and shape dispersion.

A facile dual-templating approach is demonstrated to prepare hierarchically ordered macro-/mesoporous carbons. Monodispersed silica colloidal crystals are used as a hard template, amphiphilic triblock copolymer PEO-PPO-PEO as a soft template, and soluble resols as a carbon source. The procedure involves packing and aging of silica microspheres, evaporation-induced organic-organic assembly of mesostructures in the void of microspheres, thermosetting and carbonization of phenolic formaldehyde (PF), and removal of silica scaffolds by HF. The obtained porous carbons have a highly ordered face-centered cubic macrostructure with tunable pore sizes of 230-430 nm and interconnected windows with a size of 30-65 nm. The rigid silica hard templates can prevent the shrinkage of the mesostructure during the thermosetting and carbonization process, resulting in large cell parameters (∼18 nm) and pore sizes (∼11 nm). The bimodal porous carbon materials have large BET surface areas (up to 760 m 2 /g), large pore volumes (∼1.25 cm 3 /g), and partially graphitized frameworks. With the increase in the silica sphere diameter, the BET surface areas and the window sizes increase. The hierarchically ordered carbon structures show strong diffraction at wavelengths of 500-690 nm depending on the treatment used.

The pore variations of ordered cage-type mesoporous silica FDU-12s have been analyzed in detail by PXRD, SAXS, nitrogen sorption, and electron crystallography. FDU-12s with a cubic symmetry (space group, Fmm) were templated by amphiphilic triblock copolymer F127 with the addition of 1,3,5-trimethylbenzene and KCl under an acidic condition. Three typical samples with different unit cell sizes, pore cage diameters, and entrance sizes were obtained from different synthesis and hydrothermal treatment temperatures, as indicated by the differences in the PXRD and SAXS patterns. The pore structure changes in the three materials were observed by nitrogen adsorption/desorption and 3-D reconstruction of HRTEM images taken from different crystal orientations. The approximate pore structures of FDU-12s can be regarded as a face-centered cubic (fcc) close-packing of spherical cages, each connected to 12 nearest neighboring cages. However, the ideal spherical model is only valid for the FDU-12s prepared at a low temperature (L-FDU-12-100). The cage shape of the FDU-12s synthesized at a high temperature deviates from perfect spheres and is accompanied by an entrance enlargement. The temperature-dependent behavior of the PEO block is discussed with regard to its influence on the micelles and hence the cage configuration. The better understanding of the formation mechanism via the combined characterization techniques and modeling may lead to a more rational approach for tuning the pore cages and entrances of the mesoporous FDU-12 materials.