Competing Mechanisms Determine Oxygen Redox in Doped Ni-Mn Based Layered Oxides for Na-Ion Batteries.

Cation doping is an effective strategy for improving the cyclability of layered oxide cathode materials through suppression of phase transitions in the high voltage region. In this study, Mg and Sc are chosen as dopants in P2-Na0.67Ni0.33Mn0.67O2, and both have found to positively impact the cycling stability, but influence the high voltage regime in different ways. Through a combination of synchrotron-based methods and theoretical calculations it is shown that it is more than just suppression of the P2 to O2 phase transition that is critical for promoting the favorable properties, and that the interplay between Ni and O activity is also a critical aspect that dictates the performance. With Mg doping, the Ni activity can be enhanced while simultaneously suppressing the O activity. This is surprising because it is in contrast to what has been reported in other Mn-based layered oxides where Mg is known to trigger oxygen redox. This contradiction is addressed by proposing a competing mechanism between Ni and Mg that impacts differences in O activity in Na0.67MgxNi0.33- xMn0.67O2 (x < 0 < 0.33). These findings provide a new direction in understanding the effects of cation doping on the electrochemical behavior of layered oxides.

Morphological and Surface-State Challenges in Ge Nanoparticle Applications.

The intrinsic properties of Ge in tandem with advances in its nanostructuring have resulted in its increased attention in a variety of fields as an alternative to traditional group 12-14 and 14-16 nanoparticles (NPs). The small band gap and size-dependent development of the optical properties in tandem with their good charge transport properties make Ge NPs a suitable material for optoelectronic devices. The low toxicity of Ge, together with its IR photoluminescence (PL) that overlaps with desirable biological optical windows used for tissue imaging, allows the exploitation of these materials in the field of bioimaging and as drug carriers. In addition, the ability of germanium to both exhibit high mechanical stability in its NP form and alloy with lithium and sodium metals has led to it being a highly attractive material for next-generation lithium ion and beyond-lithium batteries. While it is attracting considerable attention in a variety of areas, research on Ge NPs is still relatively nascent. Fundamental aspects of this material, such as its Bohr radius and the origin of different observed PLs, are still under debate. Moreover, the ability to produce Ge NPs with controlled dimensions and morphology is not yet as mature as for other classes of nanomaterials. In this review, the mechanisms and origins of these properties will be introduced, which we then relate to specific applications presented in the literature.

Crystallinity and Size Control of Colloidal Germanium Nanoparticles from Organogermanium Halide Reagents.

Germanium (Ge) nanoparticles are gaining increasing interest due to their properties that arise in the quantum confinement regime, such as the development of the band structure with changing size. While promising materials, significant challenges still exist related to the development of synthetic schemes allowing for good control over size and morphology in a single step. Herein, we investigate a synthetic method that combines sulfur and primary amines to promote the reduction of organometallic Ge(IV) precursors to form Ge nanoparticles at relatively low temperatures (300 °C). We propose a reaction mechanism and examine the effects of solvents, sulfur concentration, and organogermanium halide precursors. Hydrosulfuric acid (H2S) produced in situ acts as the primary reducing species, and we were able to increase the particle size more than 2-fold by tuning both the reaction time and quantity of sulfur added during the synthesis. We found that we are able to control the crystalline or amorphous nature of the resulting nanoparticles by choosing different solvents and propose a mechanism for this interaction. The reaction mechanism presented provides insight into how one can control the resulting particle size, crystallinity, and reaction kinetics. While we demonstrated the synthesis of Ge nanoparticles, this method can potentially be extended to other members of the group IV family.

End-Functionalized Semiconducting Polymers as Reagents in the Synthesis of Hybrid II-VI Nanoparticles.

The functionalization of II-VI nanocrystals with semiconducting polymers is of fundamental interest for lightweight, solution-processed optoelectronics. The direct surface functionalization of nanocrystals is useful for facilitating charge transfer across the donor/acceptor interface, in addition to promoting good mixing properties and thereby helping prevent nanoparticle aggregation. In this work, we develop a new method for the direct attachment of semiconducting polymers to II-VI inorganic nanocrystals, where the polymer plays a dual role, acting as both the desired capping agent and a chalcogenide monomer during synthesis. The success of this hybridization procedure relies on the establishment of a new polymer end-functionalization scheme, where a route toward a thio-phosphonate polymer end-group is developed; this end-group resembles many chalcogenide precursor materials used in the synthesis of II-VI nanomaterials. We show the applicability of this hybrid functionalization procedure by attaching poly(3-hexylthiophene-2,5-diyl) to CdSe and CdS. We followed the progress of the reaction by NMR and used transmission electron microscopy to determine the morphology of the resulting materials, which we found to have narrow size distributions after hybridization. Polymer attachment to the nanocrystals was confirmed by examining the steady-state and time-resolved optical properties of the hybrid materials, which also provided an insight into excited-state processes occurring across the hybrid interface.

Synthesis of Ligand-free CdS Nanoparticles within a Sulfur Copolymer Matrix.

Aliphatic ligands are typically used during the synthesis of nanoparticles to help mediate their growth in addition to operating as high-temperature solvents. These coordinating ligands help solubilize and stabilize the nanoparticles while in solution, and can influence the resulting size and reactivity of the nanoparticles during their formation. Despite the ubiquity of using ligands during synthesis, the presence of aliphatic ligands on the nanoparticle surface can result in a number of problems during the end use of the nanoparticles, necessitating further ligand stripping or ligand exchange procedures. We have developed a way to synthesize cadmium sulfide (CdS) nanoparticles using a unique sulfur copolymer. This sulfur copolymer is primarily composed of elemental sulfur, which is a cheap and abundant material. The sulfur copolymer has the advantages of operating both as a high temperature solvent and as a sulfur source, which can react with a cadmium precursor during nanoparticle synthesis, resulting in the generation of ligand free CdS. During the reaction, only some of the copolymer is consumed to produce CdS, while the rest remains in the polymeric state, thereby producing a nanocomposite material. Once the reaction is finished, the copolymer stabilizes the nanoparticles within a solid polymeric matrix. The copolymer can then be removed before the nanoparticles are used, which produces nanoparticles that do not have organic coordinating ligands. This nascent synthesis technique presents a method to produce metal-sulfide nanoparticles for a wide variety of applications where the presence of organic ligands is not desired.

Correction: The future of organic photovoltaics.

Correction for 'The future of organic photovoltaics' by Katherine A. Mazzio et al., Chem. Soc. Rev., 2015, 44, 78-90.

Sulfur copolymer for the direct synthesis of ligand-free CdS nanoparticles.

Organic coordinating ligands are ubiquitously used to solubilize, stabilize and functionalize colloidal nanoparticles. Aliphatic organic ligands are typically used to control size during the nanoparticle growth period and are used as a high boiling point solvent for solution-based synthesis procedures. However, these aliphatic ligands are typically not well suited for the end use of the nanoparticles, so additional ligand exchange or ligand stripping procedures must be implemented after the nanoparticle synthesis. Herein we present a ligand-free CdS nanoparticle synthesis procedure using a unique sulfur copolymer. The sulfur copolymer is derived from elemental sulfur, which is a cheap and abundant material. This copolymer is used as a sulfur source and high boiling point solvent, which produces stabilized metal-sulfide nanoparticles that are suspended within a sulfur copolymer matrix. The copolymer can then be removed, thereby yielding ligand-free metal-sulfide nanoparticles.

The future of organic photovoltaics.

Increasing global demand for energy, along with dwindling fossil fuel resources and a better understanding of the hidden costs associated with these energy sources, have spurred substantial political, academic, and industrial interest in alternative energy resources. Photovoltaics based on organic semiconductors have emerged as promising low-cost alternatives for electricity generation that relies on sunlight. In this tutorial review we discuss the relevance of these organic photovoltaics beginning with some of the economic drivers for these technologies. We then examine the basic properties of these devices, including operation and materials requirements, in addition to presenting the development of the field from a historical perspective. Potential future directions are also briefly discussed. This tutorial review is intended to be an essential overview of the progress of the field, in addition to aiding in the discussion of the future of OPV technologies.

A one pot organic/CdSe nanoparticle hybrid material synthesis with in situ π-conjugated ligand functionalization.

A one pot method for organic/colloidal CdSe nanoparticle hybrid material synthesis is presented. Relative to traditional ligand exchange processes, these materials require smaller amounts of the desired capping ligand, shorter syntheses and fewer processing steps, while maintaining nanoparticle morphology.

Surface-initiated synthesis of poly(3-methylthiophene) from indium tin oxide and its electrochemical properties.

Poly(3-methylthiophene) (P3MT) was synthesized directly from indium tin oxide (ITO) electrodes modified with a phosphonic acid initiator, using Kumada catalyst transfer polymerization (KCTP). This work represents the first time that polymer thickness has been controlled in a surface initiated KCTP reaction, highlighting the utility of KCTP in achieving controlled polymerizations. Polymer film thicknesses were regulated by the variation of the solution monomer concentration and ranged from 30 to 265 nm. Electrochemical oxidative doping of these films was used to manipulate their near surface composition and effective work function. Doped states of the P3MT film are maintained even after the sample is removed from solution and potential control confirming the robustness of the films. Such materials with controllable thicknesses and electronic properties have the potential to be useful as interlayer materials for organic electronic applications.

Oligoselenophene derivatives functionalized with a diketopyrrolopyrrole core for molecular bulk heterojunction solar cells.

Solution-processable oligoselenophenes functionalized with diketopyrrolopyrrole cores have been synthesized for use as the donor material in bulk heterojunction solar cells. The optical absorption of these materials extends to the edge of the visible spectrum. Power conversion efficiencies of 1.53 ± 0.04% for DPPS and 0.84 ± 0.04% for DPPDS were obtained under simulated 100 mW/cm(2) AM 1.5G irradiation for devices when PC(61)BM was used as an acceptor. DPPS showed hole mobilities of 4 × 10(-5) cm(2)/(V s) and a peak external quantum efficiency (EQE) of 25%, while DPPDS showed hole mobilities of 2 × 10(-5) cm(2)/(V s) and a peak EQE of 19%. To the best of our knowledge, these are the first oligoselenophenes that have been reported in molecular bulk heterojunction solar cells and this study could serve as a springboard for the design and optimization of high-performance selenophene-containing photovoltaics.