Composition-dependent structural and electronic properties of α-(Si1−xCx)3N4

The highly unusual structural and electronic properties of the α-phase of (Si1-xCx)3N4 are determined by density functional theory (DFT) calculations using the Generalized Gradient Approximation (GGA). The electronic properties of α-(Si 1-xCx)3N4 are found to be very close to those of α-C3N4. The bandgap of α-(Si 1-xCx)3N4 significantly decreases as C atoms are substituted by Si atoms (in most cases, smaller than that of either α-Si3N4 or α-C3N4) and attains a minimum when the ratio of C to Si is close to 2. On the other hand, the bulk modulus of α-(Si1-xCx)3N 4 is found to be closer to that of α-Si3N 4 than of α-C3N4. Plasma-assisted synthesis experiments of CNx and SiCN films are performed to verify the accuracy of the DFT calculations. TEM measurements confirm the calculated lattice constants, and FT-IR/XPS analysis confirms the formation and lengths of C-N and Si-N bonds. The results of DFT calculations are also in a remarkable agreement with the experiments of other authors.

3-Orders-of-magnitude density control of single-walled carbon nanotube networks by maximizing catalyst activation and dosing carbon supply

Tailoring the density of random single-walled carbon nanotube (SWCNT) networks is of paramount importance for various applications, yet it remains a major challenge due to the insufficient catalyst activation in most growth processes. Here we report on a simple and effective method to maximise the number of active catalyst nanoparticles using catalytic chemical vapor deposition (CCVD). By modulating short pulses of acetylene into a methane-based CCVD growth process, the density of SWCNTs is dramatically increased by up to three orders of magnitude without increasing the catalyst density and degrading the nanotube quality. In the framework of a vapor-liquid-solid model, we attribute the enhanced growth to the high dissociation rate of acetylene at high temperatures at the nucleation stage, which can be effective in both supersaturating the larger catalyst nanoparticles and overcoming the nanotube nucleation energy barrier of the smaller catalyst nanoparticles. These results are highly relevant to numerous applications of random SWCNT networks in next-generation energy, sensing and biomedical devices. © 2011 The Royal Society of Chemistry.

Single-step, catalyst-free plasma-assisted synthesis and growth mechanism of single-crystalline aluminum nitride nanorods

Synthesis of one-dimensional AlN nanostructures commonly requires high process temperatures (>900 °C), metal catalyst, and hazardous gas/powder precursors. We report on a simple, single-step, catalyst-free, plasma-assisted growth of dense patterns of size-uniform single-crystalline AlN nanorods at a low substrate temperature (∼650 °C) without any catalyst or hazardous precursors. This unusual growth mechanism is based on highly effective plasma dissociation of N2 molecules, localized species precipitation on AlN islands, and reduced diffusion on the nitrogen-rich surface. This approach can also be used to produce other high-aspect-ratio oxide and nitride nanostructures for applications in energy conversion, sensing, and optoelectronics. © 2010 American Institute of Physics.

Controlled-bandgap silicon nitride nanomaterials : deterministic nitrogenation in high-density plasmas

To overcome major problems associated with insufficient incorporation of nitrogen in hydrogenated amorphous silicon nitride (a-SiNx:H) nanomaterials, which in turn impedes the development of controlled-bandgap nanodevices, here we demonstrate the possibility to achieve effective bandgap control in a broad range by using high-density inductively coupled plasmas. This achievement is related to the outstanding dissociation ability of such plasmas. It is shown that the compositional, structural, optical, and morphological properties of the synthesized a-SiNx:H nanomaterials can be effectively tailored through the manipulation of the flow rate ratio of the silane to nitrogen gases X. In particular, a wide bandgap of 5.21 eV can be uniquely achieved at a low flow rate ratio of the nitrogen to silane gas of 1.0, whereas typically used values often exceed 20.0. These results are highly-relevant to the development of the next-generation nanodevices that rely on the effective control of the functional nano-layer bandgap energies.

Structural, electronic, and optical properties of wurtzite and rocksalt InN under pressure

Structural stability, electronic, and optical properties of InN under high pressure are studied using the first-principles calculations. The lattice constants and electronic band structure are found consistent with the available experimental and theoretical values. The pressure of the wurtzite-to-rocksalt structural transition is 13.4 GPa, which is in an excellent agreement with the most recent experimental values. The optical characteristics reproduce the experimental data thus justifying the feasibility of our theoretical predictions of the optical properties of InN at high pressures.

Mechanical model and superelastic properties of carbon microcoils with circular cross-section

Here we report on an unconventional Ni-P alloy-catalyzed, high-throughput, highly reproducible chemical vapor deposition of ultralong carbon microcoils using acetylene precursor in the temperature range 700-750 °C. Scanning electron microscopy analysis reveals that the carbon microcoils have a unique double-helix structure and a uniform circular cross-section. It is shown that double-helix carbon microcoils have outstanding superelastic properties. The microcoils can be extended up to 10-20 times of their original coil length, and quickly recover the original state after releasing the force. A mechanical model of the carbon coils with a large spring index is developed to describe their extension and contraction. Given the initial coil parameters, this mechanical model can successfully account for the geometric nonlinearity of the spring constants for carbon micro- and nanocoils, and is found in a good agreement with the experimental data in the whole stretching process.

Effects of ions and atomic hydrogen in plasma-assisted growth of single-walled carbon nanotubes

The growth of single-walled carbon nanotubes (SWCNTs) in plasma-enhanced chemical vapor deposition (PECVD) is studied using a surface diffusion model. It is shown that at low substrate temperatures (≤1000 K), the atomic hydrogen and ion fluxes from the plasma can strongly affect nanotube growth. The ion-induced hydrocarbon dissociation can be the main process that supplies carbon atoms for SWCNT growth and is responsible for the frequently reported higher (compared to thermal chemical vapor deposition) nanotube growth rates in plasma-based processes. On the other hand, excessive deposition of plasma ions and atomic hydrogen can reduce the diffusion length of the carbon-bearing species and their residence time on the nanotube lateral surfaces. This reduction can adversely affect the nanotube growth rates. The results here are in good agreement with the available experimental data and can be used for optimizing SWCNT growth in PECVD.

p-type doping of ZnO by means of high-density inductively coupled plasmas

A custom-designed inductively coupled plasma assisted radio-frequency magnetron sputtering deposition system has been used to fabricate N-doped p-type ZnO (ZnO:N) thin films on glass substrates from a sintered ZnO target in a reactive Ar + N2 gas mixture. X-ray diffraction and scanning electron microscopy analyses show that the ZnO:N films feature a hexagonal crystal structure with a preferential (002) crystallographic orientation and grow as vertical columnar structures. Hall effect and X-ray photoelectron spectroscopy analyses show that N-doped ZnO thin films are p-type with a hole concentration of 3.32 × 1018 cm- 3 and mobility of 1.31 cm2 V- 1 s- 1. The current-voltage measurement of the two-layer structured ZnO p-n homojunction clearly reveals the rectifying ability of the p-n junction. The achievement of p-type ZnO:N thin films is attributed to the high dissociation ability of the high-density inductively coupled plasma source and effective plasma-surface interactions during the growth process.

Rapid, low-temperature synthesis of nc-Si in high-density, non-equilibrium plasmas : enabling nanocrystallinity at very low hydrogen dilution

Nanocrystalline silicon thin films were deposited on single-crystal silicon and glass substrates simultaneously by inductively coupled plasma-assisted chemical vapor deposition from the reactive silane reactant gas diluted with hydrogen at a substrate temperature of 200 °C. The effect of hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen to silane gas), ranging from 1 to 20, on the structural and optical properties of the deposited films, is extensively investigated by Raman spectroscopy, X-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/VIS spectroscopy, and scanning electron microscopy. Our experimental results reveal that, with the increase of the hydrogen dilution ratio X, the deposition rate Rd and hydrogen content CH are reduced while the crystalline fraction Fc, mean grain size δ and optical bandgap ETauc are increased. In comparison with other plasma enhanced chemical vapor deposition methods of nanocrystalline silicon films where a very high hydrogen dilution ratio X is routinely required (e.g. X > 16), we have achieved nanocrystalline silicon films at a very low hydrogen dilution ratio of 1, featuring a high deposition rate of 1.57 nm/s, a high crystalline fraction of 67.1%, a very low hydrogen content of 4.4 at.%, an optical bandgap of 1.89 eV, and an almost vertically aligned columnar structure with a mean grain size of approximately 19 nm. We have also shown that a sufficient amount of atomic hydrogen on the growth surface essential for the formation of nanocrystalline silicon is obtained through highly-effective dissociation of silane and hydrogen molecules in the high-density inductively coupled plasmas. © 2009 The Royal Society of Chemistry.

Structural evolution of nanocrystalline silicon thin films synthesized in high-density, low-temperature reactive plasmas

Silicon thin films with a variable content of nanocrystalline phase were deposited on single-crystal silicon and glass substrates by inductively coupled plasma-assisted chemical vapor deposition using a silane precursor without any hydrogen dilution in the low substrate temperature range from 100 to 300 °C. The structural and optical properties of the deposited films are systematically investigated by Raman spectroscopy, x-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/vis spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy. It is shown that the structure of the silicon thin films evolves from the purely amorphous phase to the nanocrystalline phase when the substrate temperature is increased from 100 to 150 °C. It is found that the variations of the crystalline fraction fc, bonded hydrogen content CH, optical bandgap ETauc, film microstructure and growth rate Rd are closely related to the substrate temperature. In particular, at a substrate temperature of 300 °C, the nanocrystalline Si thin films of our interest feature a high growth rate of 1.63nms-1, a low hydrogen content of 4.0at.%, a high crystalline fraction of 69.1%, a low optical bandgap of 1.55eV and an almost vertically aligned columnar structure with a mean grain size of approximately 10nm. It is also shown that the low-temperature synthesis of nanocrystalline Si thin films without any hydrogen dilution is attributed to the outstanding dissociation ability of the high-density inductively coupled plasmas and effective plasma-surface interactions during the growth process. Our results offer a highly effective yet simple and environmentally friendly technique to synthesize high-quality nanocrystalline Si films, vitally needed for the development of new-generation solar cells and other emerging nanotechnologies.

Cortical organization of environmental sounds by attribute

Semantic knowledge is supported by a widely distributed neuronal network, with differential patterns of activation depending upon experimental stimulus or task demands. Despite a wide body of knowledge on semantic object processing from the visual modality, the response of this semantic network to environmental sounds remains relatively unknown. Here, we used fMRI to investigate how access to different conceptual attributes from environmental sound input modulates this semantic network. Using a range of living and manmade sounds, we scanned participants whilst they carried out an object attribute verification task. Specifically, we tested visual perceptual, encyclopedic, and categorical attributes about living and manmade objects relative to a high-level auditory perceptual baseline to investigate the differential patterns of response to these contrasting types of object-related attributes, whilst keeping stimulus input constant across conditions. Within the bilateral distributed network engaged for processing environmental sounds across all conditions, we report here a highly significant dissociation within the left hemisphere between the processing of visual perceptual and encyclopedic attributes of objects.

Excited-state dynamics in diketopyrrolopyrrole-based copolymer for organic photovoltaics investigated by transient optical spectroscopy

We investigate the photoexcited state dynamics in a donor-acceptor copolymer, poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]- pyrrole-1,4-dione-alt-naphthalene} (pDPP-TNT), by picosecond fluorescence and femtosecond transient absorption spectroscopies. Timeresolved fluorescence lifetime measurements of pDPP-TNT thin films reveal that the lifetime of the singlet excited state is 185 ± 5 ps and that singlet-singlet annihilation occurs at excitation photon densities above 6 × 1017 photons/cm3. From the results of singlet-singlet annihilation analysis, we estimate that the single-singlet annihilation rate constant is (6.0 ± 0.2) × 109cm3 s-1 and the singlet diffusion length is -7 nm. From the comparison of femtosecond transient absorption measurements and picosecond fluorescence measurements, it is found that the time profile of the photobleaching signal in the charge-transfer (CT) absorption band coincides with that of the fluorescence intensity and there is no indication of long-lived species, which clearly suggests that charged species, such as polaron pairs and triplet excitons, are not effectively photogenerated in the neat pDPP-TNT polymer.

Nanoscale phase domain structure and associated device performance of organic solar cells based on a diketopyrrolopyrrole polymer

We investigate the blend morphology and performance of bulk heterojunction organic photovoltaic devices comprising the donor polymer, pDPP-TNT (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) and the fullerene acceptor, [70]PCBM ([6,6]-phenyl C71-butyric acid methyl ester). The blend morphology is heavily dependent upon the solvent system used in the fabrication of thin films. Thin films spin-coated from chloroform possess a cobblestone-like morphology, consisting of thick, round-shaped [70]PCBM-rich mounds separated by thin polymer-rich valleys. The size of the [70]PCBM domains is found to depend on the overall film thickness. Thin films spin-coated from a chloroform:dichlorobenzene mixed solvent system are smooth and consist of a network of pDPP-TNT nanofibers embedded in a [70]PCBM-rich matrix. Rinsing the films in hexane selectively removes [70]PCBM and allows for analysis of domain size and purity. It also provides a means for investigating exciton dissociation efficiency through relative photoluminescence yield measurements. Devices fabricated from chloroform solutions show much poorer performance than the devices fabricated from the mixed solvent system; this disparity in performance is seen to be more pronounced with increasing film thickness. The primary cause for the improved performance of devices fabricated from mixed solvents is attributed to the greater donor-acceptor interfacial area and resulting greater capacity for charge carrier generation.

Experimental evidence for competitive N–O and O–C bond homolysis in gasphase alkoxyamines

The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO–R3) and a stable nitroxyl radical (R1R2NO•) via homolysis of the labile O–C bond. Competing homolysis of the alkoxyamine N–O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O–C and N–O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N–O and O–C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC–R1R2NO–R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M – H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O–C and/or N–O bonds. The relative efficacy of N–O and O–C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O–C bond are observed and product ions resulting from cleavage of the N–O bond are minor or absent. A limited number of examples were encountered however, where N–O homolysis is a competitive dissociation pathway because the O–C bond is stabilised by adjacent heteroatom(s) (e.g., R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O–C homolysis pathway.

Hydrolysis of genotoxic methyl-substituted oxiranes : Experimental kinetic and semiempirical studies

The kinetics of acid-catalyzed hydrolysis of seven methylated aliphatic epoxides - R1R2C(O)CR3R4 (A: R1=R2=R3=R4=H; B: R1=R2=R3=H, R4=Me; C: R1=R2=H, R3=R4=Me; D: R1=R3=H, R2=R4=Me(trans); E: R1=R3=H, R2=R4=Me(cis); F: R1=R3=R4=Me, R2=H; G: R1=R2=R3=R4=Me) - has been studied at 36 ± 1.5°C. Compounds with two methyl groups at the same carbon atom of the oxirane ring exhibit highest rate constants (k(eff) in reciprocal molar concentration per second: 11.0 ± 1.3 for C, 10.7 ± 2.1 for F, and 8.7 ± 0.7 for G as opposed to 0.124 ± 0.003 for B, 0.305 ± 0.003 for D, and 0.635 ± 0.036 for E). Ethylene oxide (A) displays the lowest rate of hydrolysis (0.027 M-1 s-1). The results are consistent with literature data available for compounds A, B, and C. To model the reactivities we have employed quantum chemical calculations (MNDO, AM1, PM3, and MINDO/3) of the main reaction species. There is a correlation of the logarithm k(eff) with the total energy of epoxide ring opening. The best correlation coefficients (r) were obtained using the AM1 and MNDO methods (0.966 and 0.957, respectively). However, unlike MNDO, AM1 predicts approximately zero energy barriers for the oxirane ring opening of compounds B, C, E and G, which is not consistent with published kinetic data. Thus, the MNDO method provides a preferential means of modeling the acidic hydrolysis of the series of methylated oxiranes. The general ranking of mutagenicity in vitro, A > B > C, is in line with the concept that this sequence also gradually leaves the expoxide reactivity optimal for genotoxicity toward reactivities leading to higher biological detoxifications.