Bond dissociation energies of organic molecules

In this Account we have compiled a list of reliable bond energies that are based on a set of critically evaluated experiments. A brief description of the three most important experimental techniques for measuring bond energies is provided. We demonstrate how these experimental data can be applied to yield the heats of formation of organic radicals and the bond enthalpies of more than 100 representative organic molecules.

Encapsulation of nanoparticles into single-crystal ZnO nanorods and microrods

One-dimensional single crystal incorporating functional nanoparticles of other materials could be an interesting platform for various applications. We studied the encapsulation of nanoparticles into single-crystal ZnO nanorods by exploiting the crystal growth of ZnO in aqueous solution. Two types of nanodiamonds with mean diameters of 10 nm and 40 nm, respectively, and polymer nanobeads with size of 200 nm have been used to study the encapsulation process. It was found that by regrowing these ZnO nanorods with nanoparticles attached to their surfaces, a full encapsulation of nanoparticles into nanorods can be achieved. We demonstrate that our low-temperature aqueous solution growth of ZnO nanorods do not affect or cause degradation of the nanoparticles of either inorganic or organic materials. This new growth method opens the way to a plethora of applications combining the properties of single crystal host and encapsulated nanoparticles. We perform micro-photoluminescence measurement on a single ZnO nanorod containing luminescent nanodiamonds and the spectrum has a different shape from that of naked nanodiamonds, revealing the cavity effect of ZnO nanorod.

Painting anatase (TiO2) nanocrystals on long nanofibers to prepare photocatalysts with large active surface for dye degradation and organic synthesis

Anatase TiO2 nanocrystals were painted on H-titanate nanofibers by using an aqueous solution of titanyl sulfate. The anatase nanocrystals were bonded solidly onto the titanate fibers through formation of coherent interfaces at which the oxygen atoms were shared by the nanocrystals and the fiber. This approach allowed us to create large anatase surfaces on the nanofibers, which are active in photocatalytic reactions. This method was also applied successfully to coat anatase nanocrystals on surfaces of fly ash and layered clay. The painted nanofibers exhibited a much higher catalytic activity for the photocatalytic degradation of sulforhodamine B and the selective oxidation of benzylamine to the corresponding imine (with a product selectivity >99%) under UV irradiation than both the parent H-titanate nanofibers and a commercial TiO2 powder, P25. We found that gold nanoparticles supported on H-titanate nanofibers showed no catalytic activity for the reduction of nitrobenzene to azoxybenzene, whereas the gold nanoparticles supported on the painted nanofibers and P25 could efficiently reduce nitrobenzene to azoxybenzene as the sole product under visible light irradiation. These results were different from those from the reduction on the gold nanoparticles photocatalyst on ZrO2, in which the azoxybenzene was the intermediate and converted to azobenzene quickly. Evidently, the support materials significantly affect the product selectivity of the nitrobenzene reduction. Finally, the new photocatalysts could be easily dispersed into and separated from a liquid because of their fibril morphology, which is an important advantage for practical applications.

Tuning of magnetization in vertical graphenes by plasma-enabled chemical conversion of organic precursors with different oxygen content

Different magnetization in vertical graphenes fabricated by plasma-enabled chemical conversion of organic precursors with various oxygen atom contents and bonding energies was achieved. The graphenes grown from fat-like precursors exhibit magnetization up to 8 emu g−1, whereas the use of sugar-containing precursors results in much lower numbers. A relatively high Curie temperature exceeding 600 K was also demonstrated.

Plasma nanoscience : setting directions, tackling grand challenges

This review paper presents historical perspectives, recent advances and future directions in the multidisciplinary research field of plasma nanoscience. The current status and future challenges are presented using a three-dimensional framework. The first and the largest dimension covers the most important classes of nanoscale objects (nanostructures, nanofeatures and nanoassemblies/nanoarchitectures) and materials systems, namely carbon nanotubes, nanofibres, graphene, graphene nanoribbons, graphene nanoflakes, nanodiamond and related carbon-based nanostructures; metal, silicon and other inorganic nanoparticles and nanostructures; soft organic nanomaterials; nano-biomaterials; biological objects and nanoscale plasma etching. In the second dimension, we discuss the most common types of plasmas and plasma reactors used in nanoscale plasma synthesis and processing. These include low-temperature non-equilibrium plasmas at low and high pressures, thermal plasmas, high-pressure microplasmas, plasmas in liquids and plasma–liquid interactions, high-energy-density plasmas, and ionized physical vapour deposition as well as some other plasma-enhanced nanofabrication techniques. In the third dimension, we outline some of the 'Grand Science Challenges' and 'Grand Socio-economic Challenges' to which significant contributions from plasma nanoscience-related research can be expected in the near future. The urgent need for a stronger focus on practical, outcome-oriented research to tackle the grand challenges is emphasized and concisely formulated as from controlled complexity to practical simplicity in solving grand challenges.

Chemical and bioanalytical assessment of coal seam gas associated water

A comprehensive study was undertaken involving chemical (inorganic and organic) and bioanalytical (a suite of 14 in vitro bioassays) assessments of coal seam gas (coal bed methane) associated water (CSGW) in Queensland, Australia. CSGW is a by-product of the gas extraction process and is generally considered as water of poor quality. This was done to better understand what is known about the potential biological and environmental effects associated with the organic constituents of CSGW in Australia. In Queensland, large amounts of associated water must be withdrawn from coal seams to allow extraction of the gas. CSGW is disposed of via release to surface water, reinjected to groundwater or reused for irrigation of crops or pasture, supplied for power station cooling and or reinjected specifically to augment drinking water aquifers. Groundwater samples were collected from private wells tapping into the Walloon Coal Measures, the same coal aquifer exploited for coal seam gas production in the Surat Basin, Australia. The inorganic characteristics of these water samples were almost identical to the CSGW entering the nearby gas company operated Talinga-Condabri Water Treatment Facility. The water is brackish with a pH of 8 to 9, high sodium, bicarbonate and chloride concentrations but low calcium, magnesium and negligible sulphate concentrations. Only low levels of polyaromatic hydrocarbons (PAHs) were detected in the water samples, and neither phenols nor volatile organic compounds were found. Results from the bioassays showed no genotoxicity, protein damage, or activation of hormone receptors (with the exception of the estrogen receptor). However, five of the 14 bioassays gave positive responses: an arylhydrocarbon-receptor gene activation assay (AhR-CAFLUX), estrogenic endocrine activity (ERα-CALUX), oxidative stress response (AREc32), interference with cytokine production (THP1-CPA) and non-specific toxicity (Microtox). The observed effects were benchmarked against known water sources and were similar to secondary treated wastewater effluent, stormwater and surface water. As mixture toxicity modelling demonstrated, the detected PAHs explained less than 5% of the observed biological effects.

Self-organization and dynamics of nanoparticles in chemically active plasmas for low-temperature deposition of silicon and carbon-based nanostructured films

Self-organization and dynamic processes of nano/micron-sized solid particles grown in low-temperature chemically active plasmas as well as the associated physico-chemical processes are reviewed. Three specific reactive plasma chemistries, namely, of silane (SiH4), acetylene (C 2H2), and octafluorocyclobutane (c-C4F 8) RF plasma discharges for plasma enhanced chemical vapor deposition of amorphous hydrogenated silicon, hydrogenated and fluorinated carbon films, are considered. It is shown that the particle growth mechanisms and specific self-organization processes in the complex reactive plasma systems are related to the chemical organization and size of the nanoparticles. Correlation between the nanoparticle origin and self-organization in the ionized gas phase and improved thin film properties is reported. Self-organization and dynamic phenomena in relevant reactive plasma environments are studied for equivalent model systems comprising inert buffer gas and mono-dispersed organic particulate powders. Growth kinetics and dynamic properties of the plasma-assembled nanoparticles can be critical for the process quality in microelectronics as well as a number of other industrial applications including production of fine metal or ceramic powders, nanoparticle-unit thin film deposition, nanostructuring of substrates, nucleating agents in polymer and plastics synthesis, drug delivery systems, inorganic additives for sunscreens and UV-absorbers, and several others. Several unique properties of the chemically active plasma-nanoparticle systems are discussed as well.

Colloidal semiconductor nanocrystals : controlled synthesis and surface chemistry in organic media

Colloidal semiconductor nanocrystals (CS-NCs) possess compelling benefits of low-cost, large-scale solution processing, and tunable optoelectronic properties through controlled synthesis and surface chemistry engineering. These merits make them promising candidates for a variety of applications. This review focuses on the general strategies and recent developments of the controlled synthesis of CS-NCs in terms of crystalline structure, particle size, dominant exposed facet, and their surface passivation. Highlighted are the organic-media based synthesis of metal chalcogenide (including cadmium, lead, and copper chalcogenide) and metal oxide (including titanium oxide and zinc oxide) nanocrystals. Current challenges and thus future opportunities are also pointed out in this review.

Nanomorphology influence on the light conversion mechanisms in highly efficient diketopyrrolopyrrole based organic solar cells

In this work, diketopyrrolopyrrole-based polymer bulk heterojunction solar cells with inverted and regular architecture have been investigated. The influence of the polymer:fullerene ratio on the photoactive film nanomorphology has been studied in detail. Transmission Electron Microscopy and Atomic Force Microscopy reveal that the resulting film morphology strongly depends on the fullerene ratio. This fact determines the photocurrent generation and governs the transport of free charge carriers. Slight variations on the PCBM ratio respect to the polymer show great differences on the electrical behavior of the solar cell. Once the polymer:fullerene ratio is accurately adjusted, power conversion efficiencies of 4.7% and 4.9% are obtained for inverted and regular architectures respectively. Furthermore, by correlating the optical and morphological characterization of the polymer:fullerene films and the electrical behavior of solar cells, an ad hoc interpretation is proposed to explain the photovoltaic performance as a function of this polymer:blend composition.

Cubic silsesquioxanes for use in solution processable organic light emitting diodes (OLED)

Commercial products using organic light emitting diode (OLED) display technology have begun to appear in cell phones, mp3 players and even televisions. One key area that has allowed and will allow for this technology to continue its ascension into the flat panel display and lighting markets is materials R and D. From this perspective, recent progress in cubic silsesquioxane (SSQ) based materials may provide some new advantageous properties well suited for OLEDs. In this feature article we provide an overview of recent progress in the synthesis, characterization and implementation of SSQ-based materials with properties well suited for application in solution processable organic/polymer electronics, specifically OLEDs.

Band gap tunable N-type molecules for organic field effect transistors

A series of four novel n-type molecules has been synthesized. Unlike previous approaches, the end group of these molecules was fixed and the molecular core was varied. The resulting materials were thoroughly analyzed. Electronic properties were derived from photoemission spectroscopy, optical properties were derived with the help of optical spectroscopy, and the structure of thin films on Au(111) was derived by scanning tunneling microscopy (STM). In addition, prototypical organic field-effect transistors (OFETs) (forming n-channels in OFETs) have been fabricated and tested. The correlation between the device performance of the respective OFETs (i.e., electron mobility) and their electronic as well as structural properties was investigated. It turned out that a combination of beneficial electronic and structural properties provides the best results. These findings are important for the design of new materials for future device applications.

Charge transport and density of trap states in balanced high mobility ambipolar organic thin-film transistors

We report on charge transport and density of trap states (trap DOS) in ambipolar diketopyrrolopyrrole-benzothiadiazole copolymer thin-film transistors. This semiconductor possesses high electron and hole field-effect mobilities of up to 0.6 cm 2/V-s. Temperature and gate-bias dependent field-effect mobility measurements are employed to extract the activation energies and trap DOS to understand its unique high mobility balanced ambipolar charge transport properties. The symmetry between the electron and hole transport characteristics, parameters and activation energies is remarkable. We believe that our work is the first charge transport study of an ambipolar organic/polymer based field-effect transistor with room temperature mobility higher than 0.1 cm 2/V-s in both electrons and holes.

Characteristics of high-performance ambipolar organic field-effect transistors based on a diketopyrrolopyrrole-benzothiadiazole copolymer

In this paper, we report the device characteristics of ambipolar thin-film transistors (TFTs) based on a diketopyrrolopyrrole-benzothiadiazole copolymer. This polymer semiconductor exhibits the largest comparable electron and hole mobility values in a single organic semiconductor. The key to realizing such high mobility values, which are $0.5&cm}{2}/\hbox{V}̇\hbox{s, is molecular design, i.e., the use of suitable surface treatments of the source/drain contact electrodes and device architectures, particularly top-gate configurations. The subthreshold characteristics of the TFT devices are greatly improved by the use of dual-gate device geometry. We also report the first measurement of the velocity distribution of electron and hole velocities in an ambipolar organic semiconductor.

Synthesis, thin-film morphology, and comparative study of bulk and bilayer heterojunction organic photovoltaic devices using soluble diketopyrrolopyrrole molecules

Diketopyrrolopyrrole (DPP)-based organic semiconductors EH-DPP-TFP and EH-DPP-TFPV with branched ethyl-hexyl solubilizing alkyl chains and end capped with trifluoromethyl phenyl groups were designed and synthesized via Suzuki coupling. These compounds show intense absorptions up to 700 nm, and thin film-forming characteristics that sensitively depend on the solvent and coating conditions. Both materials have been used as electron donors in bulk heterojunction and bilayer organic photovoltaic (OPV) devices with fullerenes as acceptors and their performance has been studied in detail. The best power conversion efficiency of 3.3% under AM1.5G illumination (100 mW cm -2) was achieved for bilayer solar cells when EH-DPP-TFPV was used with C 60, after a thermal annealing step to induce dye aggregation and interdiffusion of C 60 with the donor material. To date, this is one of the highest efficiencies reported for simple bilayer OPV devices.