Synthesis of germanium nanocrystals from solid-state disproportionation of a chloride-derived germania glass

Germanium nanocrystals (Ge NCs) have potential to be used in several optoelectronic applications such as photodetectors and light-emitting diodes. Here, we report a solid-state route to synthesizing Ge NCs through thermal disproportionation of a germania (GeOX) glass, which was synthesized by hydrolyzing a GeCl2·dioxane complex. The GeOX glass synthesized in this manner was found to have residual Cl content. The process of nanocrystal nucleation and growth was monitored using powder X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Compared to existing solid-state routes for synthesizing colloidal Ge NCs, this approach requires fewer steps and is amenable to scaling to large-scale reactions

Silicon Nanocrystals as Signal Transducers in Ionophore-Based Fluorescent Nanosensors

Colloidal silicon crystallites in the size range of 1-12 nm, also referred to as “silicon nanocrystals” have unique optical properties that include high quantum efficiency, size-dependent emission spanning the visible to near-infrared range, and robust photostability. These features, combined with silicon’s high earth-abundance and good biocompatibility, make them an attractive option to serve as signal transduction elements in bioanalytical sensors. In this study, we combine silicon nanocrystals with a sodium-selective ionophore and a charge balancing additive in polymeric nanosensors to create a Silicon Nanocrystal NanoSensor (SiNC-NS). The SiNC-NS responded to sodium through a decrease in fluorescence intensity without the inclusion of a pH-sensitive absorbing dye which is sometimes included in analogous sensors for signal gating, leading to a sensor design with more photostable components. The SiNC-NS has a biologically relevant dynamic range of 4 – 277 mM Na+, is selective against potentially interfering cations, and its response is reversible between 0 and 2 M Na+ for at least three cycles. This work shows the first sodium-responsive silicon nanocrystal-based sensor, the first use of silicon nanocrystals in polymeric nanosensors, and demonstrates an intriguing ionophore-mediated response in silicon nanocrystals to be explored further in the future

Synthesis and optical properties of ordered-vacancy perovskite cesium bismuth halide nanocrystals

Perovskite-phase cesium bismuth halide (Cs3Bi2X9; X = Cl, Br, I) nanocrystals were synthesized using a hot-injection approach. These nanocrystals adopted ordered-vacancy perovskite crystal structures and demonstrated composition-tunable optical properties. Growth occurred by initial formation of Bi0 seeds, and morphology was controlled by precursor and seed concentration. The Cs3Bi2I9 nanocrystals demonstrated excellent stability under ambient conditions for several months. Contrary to previous reports, we find that photoluminescence originates from the precursor material as opposed to the Cs3Bi2X9 nanocrystals

Surface Chemistry of Ternary Nanocrystals: Engineering the Deposition of Conductive NaBiS2 Films

The ability to engineer the surface chemistry of complex ternary nanocrystals is critical to their successful application in photovoltaic, thermoelectric, and other energy conversion devices. For many years, several studies have shed light into the surface chemistry of unary and binary semiconductor nanocrystals, as well as their surface modification with monodentate and multidentate ligands in a variety of applications. In contrast, our understanding of the surface chemistry and ligand modification of ternary and other complex multinary nanocrystals remains relatively limited. Recently, our group reported the synthesis of colloidal NaBiS2 semiconductor nanocrystals with sizes tunable between 2–60 nm, and a light absorption edge of ca. 1.4 eV. Here, we use a combination of infrared and nuclear magnetic resonance spectroscopies to show that the as-made NaBiS2 nanocrystals are capped by oleylamine and neodecanoate ligands. We investigate biphasic liquid-liquid exchange as a means to replace these native ligands with either carboxylate-terminated lipoic acid or with small iodide ligands, leading in both cases to solubility in polar solvents—such as methanol, water, and dimethylformamide. We also investigate a layer-by-layer, biphasic solid-liquid exchange approach to prepare films of NaBiS2 nanocrystals capped with halide ligands—iodide, bromide, chloride. Upon exchange and removal of the native ligands, we show that the resistance of NaBiS2 nanocrystal films greatly decreases, with their measured conductivity being comparable to that of films made of isostructural PbS nanocrystals, which have been used in solar cells. Lastly, we report the first solar cell device made of NaBiS2 nanocrystal films with a limited power conversion efficiency (PCE) of 0.07. Further nanostructuring and ligand optimization may enable the preparation of much more efficient energy conversion devices based on NaBiS2 as well as other non-toxic and Earth-abundant, biocompatible multinary semiconductors

Optoelectronic properties of methyl-terminated germanane

Germanane is a two-dimensional, strongly confined form of germanium. It presents an interesting combination of (i) ease of integration with CMOS technology, (ii) low toxicity, and (iii) electronic confinement which transforms the indirect bandgap of the bulk material into a direct bandgap featuring photoluminescence. However, the optoelectronic properties of this material remain far less investigated than its structural properties. Here, we investigate the photoluminescence and transport properties of arrays of methyl-terminated germanane flakes. The photoluminescence appears to have two contributions, one from the band edge and the other from trap states. The dynamics of the exciton appear to be in the range of 1–100 ns. Conduction in this material appears to be p-type, while the photoconduction time response can be made as short as 100 μs

Clean thermal decomposition of tertiary-alkyl metal thiolates to metal sulfides: Environmentally-benign, non-polar inks for solution-processed chalcopyrite solar cells

We report the preparation of Cu2S, In2S3, CuInS2 and Cu(In,Ga)S2 semiconducting films via the spin coating and annealing of soluble tertiary-alkyl thiolate complexes. The thiolate compounds are readily prepared via the reaction of metal bases and tertiary-alkyl thiols. The thiolate complexes are soluble in common organic solvents and can be solution processed by spin coating to yield thin films. Upon thermal annealing in the range of 200-400 ??C, the tertiary-alkyl thiolates decompose cleanly to yield volatile dialkyl sulfides and metal sulfide films which are free of organic residue. Analysis of the reaction byproducts strongly suggests that the decomposition proceeds via an SN1 mechanism. The composition of the films can be controlled by adjusting the amount of each metal thiolate used in the precursor solution yielding bandgaps in the range of 1.2 to 3.3 eV. The films form functioning p-n junctions when deposited in contact with CdS films prepared by the same method. Functioning solar cells are observed when such p-n junctions are prepared on transparent conducting substrates and finished by depositing electrodes with appropriate work functions. This method enables the fabrication of metal chalcogenide films on a large scale via a simple and chemically clear process.ope

Solvothermal Synthesis and Characterization of Chalcopyrite CuInSe2 Nanoparticles

The ternary I-III-VI2 semiconductor of CuInSe2 nanoparticles with controllable size was synthesized via a simple solvothermal method by the reaction of elemental selenium powder and CuCl as well as InCl3 directly in the presence of anhydrous ethylenediamine as solvent. X-ray diffraction patterns and scanning electron microscopy characterization confirmed that CuInSe2 nanoparticles with high purity were obtained at different temperatures by varying solvothermal time, and the optimal temperature for preparing CuInSe2 nanoparticles was found to be between 180 and 220 °C. Indium selenide was detected as the intermediate state at the initial stage during the formation of pure ternary compound, and the formation of copper-related binary phase was completely deterred in that the more stable complex [Cu(C2H8N2)2]+ was produced by the strong N-chelation of ethylenediamine with Cu+. These CuInSe2 nanoparticles possess a band gap of 1.05 eV calculated from UV–vis spectrum, and maybe can be applicable to the solar cell devices