Carborane-stilbene dyads: influence of substituents and cluster isomers on the photoluminescence properties

Two novel styrene-containing meta-carborane derivatives substituted at the second carbon cluster atom (Cc) with either a methyl (Me), or a phenyl (Ph) group, are introduced herein alongside with a new set of stilbene-containing ortho- (o-) and meta- (m-) carborane dyads. The latter set of compounds has been prepared from styrenecontaining carborane derivatives via Heck coupling reaction. High regioselectivity has been achieved for these compounds by using a combination of palladium complexes [Pd2(dba)3]/[Pd(t-Bu3P)2] as a catalytic system, yielding exclusively E isomers. All compounds have been fully characterized and the crystal structures of seven of them analyzed by X-ray diffraction. Th…

Controlled Direct Synthesis of C-Mono- and C-Disubstituted Derivatives of [3,3′-Co(1,2-C2B9H11)2]− with Organosilane Groups: Theoretical Calculations Compared with Experimental Results

Mono- and dilithium salts of [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-), (1(-)), react with different chlorosilanes (Me(2)SiHCl, Me(2)SiCl(2), Me(3)SiCl and MeSiHCl(2)) with an accurate control of the temperature to give a set of novel C(c)-mono- (C(c) = C(cluster)) and C(c)-disubstituted cobaltabis(dicarbollide) derivatives with silyl functions: [1-SiMe(2)H-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (3(-)); [1,1'-mu-SiMe(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (4(-)); [1,1'-mu-SiMeH-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (5(-)); [1-SiMe(3)-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (6(-)) and [1,1'-(SiMe(3))(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (7(-)). In a similar way, the [8,8'-mu-(1''…

Short Photoluminescence Lifetimes Linked to Crystallite Dimensions, Connectivity, and Perovskite Crystal Phases.

Time-correlated single photon counting has been conducted to gain further insights into the short photoluminescence lifetimes (nanosecond) of lead iodide perovskite (MAPbI3) thin films (∼100 nm). We analyze three different morphologies, compact layer, isolated island, and connected large grain films, from 14 to 300 K using a laser excitation power of 370 nJ/cm2. Lifetime fittings from the Generalized Berberan-Santos decay model range from 0.5 to 6.5 ns, pointing to quasi-direct bandgap emission despite the three different sample strains. The high energy band emission for the isolated-island morphology shows fast recombination rate centers up to 4.8 ns–1, compared to the less than 2 ns–1 for…

Carboranyl Substituted Siloxanes and Octasilsesquioxanes: Synthesis, Characterization, and Reactivity

Carboranyl-containing disiloxane, cyclic-siloxane and cage-like silsesquioxane have been prepared in high yields. Two routes are compared for their preparation, a classical hydrolytic process based on hydrolysis and condensation of the freshly prepared carboranylalkylchlorosilane and ethoxysilane precursors and a nonhydrolytic route based on the specific reactivity of chorosilane toward DMSO. Based on the typical reactivity of the carboranyl group toward nucleophiles, dianionic disiloxanes and octaanionic silsesquioxanes were obtained without modification of the siloxane bond. Products are fully characterized by FTIR, NMR and MALDI-TOF methods.

Optimization of semiconductor halide perovskite layers to implement waveguide amplifiers

Semiconductor organometallic halide (CH 3 NH 3 PbX 3 , X=Cl, Br, I) perovskites (HPVK) have been emerged as a potential gain media to construct a new generation of active photonic devices. Indeed, during the last three years a significant effort has been carried out to implement HPVK-based optical amplifiers or lasers with improved quality factors. In particular, minimization of the threshold of stimulated emission has been an important concern to decrease the power consumption, and hence to enhance the performances of the device. For this purpose strategies include a suitable integration of the semiconductor in a photonic structure, or the optimization of the material. Here we propose a no…

Halide perovskite amplifiers integrated in polymer waveguides

Semiconductor organometallic halide perovskites (CH 3 NH 3 PbX 3 , X=Cl, Br, I) (HPVK) have emerged as a new promising material able to improve the optoelectronic technology performance. Although this material has mostly been applied to improve the efficiency of photovoltaic devices, it also shows amazing properties for photonic applications. In particular, HPVK exhibits high photoluminescence (PL) quantum yield (up to 70%) at room temperature together with a tunable band-gap controlled by its chemical composition. In addition, since HPVKs is deposited in solution at room conditions, it can be easily incorporated in different photonic structures to efficiently exploit its emission propertie…

Structural quality of CH3NH3PbI3 perovskites for photovoltaic applications analyzed by electron microscopy techniques

Synthesis and Characterization of New Fluorescent Styrene-Containing Carborane Derivatives: The Singular Quenching Role of a Phenyl Substituent

A set of neutral and anionic carborane derivatives in which the styrenyl fragment is introduced as a fluorophore group has been successfully synthesized and characterized. The reaction of the monolithium salts of 1-Ph-1,2-C(2)B(10)H(11), 1-Me-1,2-C(2)B(10)H(11) and 1,2-C(2)B(10)H(12) with one equivalent of 4-vinylbenzyl chloride leads to the formation of compounds 1-3, whereas the reaction of the dilithium salt of 1,2-C(2)B(10)H(12) with two equivalents of 4-vinylbenzyl chloride gives disubstituted compound 4. The closo clusters were degraded using the classical method, KOH in EtOH, to afford the corresponding nido species, which were isolated as tetramethylammonium salts. The crystal struc…

Inhibition of light emission from the metastable tetragonal phase at low temperatures in island-like films of lead iodide perovskites

Photonic applications based on halide perovskites, namely CH3NH3PbI3 (MAPbI3), have recently attracted remarkable attention due to the high efficiencies reported for photovoltaic and light emitting devices. Despite these outstanding results, there are many temperature-, laser excitation power-, and morphology-dependent phenomena that require further research to be completely understood. In this work, we have investigated in detail the nature of exciton optical transitions and recombination dynamics below and above the orthorhombic/tetragonal ('O'-/'T'-) temperature phase transition (∼150 K) depending on the material continuity (continuous-like) or discontinuity (island-like) in MAPbI3 films…

Mechanisms of Spontaneous and Amplified Spontaneous Emission in CH3NH3PbI3 Perovskite Thin Films Integrated in an Optical Waveguide

In this paper, the physical mechanisms responsible for optical gain in ${\mathrm{CH}}_{3}{\mathrm{NH}}_{3}{\mathrm{Pb}\mathrm{I}}_{3}$ (MAPI) polycrystalline thin films are investigated experimentally and theoretically. Waveguide structures composed by a MAPI film embedded in between PMMA and silica layers are used as an efficient geometry to confine emitted light in MAPI films and minimize the energy threshold for amplified spontaneous emission (ASE). We show that photogenerated exciton density at the ASE threshold is as low as $(2.4\ensuremath{-}12)\ifmmode\times\else\texttimes\fi{}{10}^{16}\phantom{\rule{0.1em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}3}$, which is below the Mott transition den…

Structural characterization of bulk and nanoparticle lead halide perovskite thin films by (S)TEM techniques.

Lead halide (APbX3) perovskites, in polycrystalline thin films but also perovskite nanoparticles (NPs) has demonstrated excellent performance to implement a new generation of photovoltaic and photonic devices. The structural characterization of APbX3 thin films using (scanning) transmission electron microscopy ((S)TEM) techniques can provide valuable information that can be used to understand and model their optoelectronic performance and device properties. However, since APbX3 perovskites are soft materials, their characterization using (S)TEM is challenging. Here, we study and compare the structural properties of two different metal halide APbX3 perovskite thin films: bulk CH3NH3PbI3 prep…

The Role of C–H···H–B Interactions in Establishing Rotamer Configurations in Metallabis(dicarbollide) Systems

The aim of this work is to explore the self-interaction capability of the anion [3,3′-Co(1,2-C2B9H11)2]– through Ccluster–H···H–B (Cc–H···H–B) dihydrogen bonds. A set of theoretical and empirical data aiming to establish the main rules that account for the binding mode between the negatively charged borane framework made by [3,3′-Co(1,2-C2B9H11)2]– and the [NMe4]+ ions have been compiled. The interaction between cation and anion is mainly electrostatic but the covalent contribution is also proven and quantified. The existing intermolecular H···H short contacts have been studied and are compared with available data from the Cambridge Structural Database. The results show that the electronic …

Polymer/Perovskite Amplifying Waveguides for Active Hybrid Silicon Photonics

The emission properties of hybrid halide perovskites are exploited to implement a stable and very low power operation waveguide optical amplifier integrated in a silicon platform. By optimizing its design with a poly(methyl methacrylate) (PMMA) encapsulation, this novel photonic device presents a net gain of around 10 dB cm−1 and 3–4 nm linewidth with an energy threshold as low as 2 nJ pulse−1 and exhibiting no degradation after one year. This work was supported by Generalitat Valenciana (Project No. ISIC/2012/008), the Universitat Jaume I (Project No. 12I361.01/1), Spanish MINECO (Projects Nos. MAT2013-47192-C3-1-R and TEC2014-53727-C2-1-R) and EU-NAVOLCHI (Project No. 288869).