Harnessing the influence of reactive edges and defects of graphene substrates for achieving complete cycle of room-temperature molecular sensing

Molecular doping and detection are at the forefront of graphene research, a topic of great interest in physical and materials science. Molecules adsorb strongly on graphene, leading to a change in electrical conductivity at room temperature. However, a common impediment for practical applications reported by all studies to date is the excessively slow rate of desorption of important reactive gases such as ammonia and nitrogen dioxide. Annealing at high temperatures, or exposure to strong ultraviolet light under vacuum, is employed to facilitate desorption of these gases. In this article, the molecules adsorbed on graphene nanoflakes and on chemically derived graphene-nanomesh flakes are displaced rapidly at room temperature in air by the use of gaseous polar molecules such as water and ethanol. The mechanism for desorption is proposed to arise from the electrostatic forces exerted by the polar molecules, which decouples the overlap between substrate defect states, molecule states, and graphene states near the Fermi level. Using chemiresistors prepared from water-based dispersions of single-layer graphene on mesoporous alumina membranes, the study further shows that the edges of the graphene flakes (showing p-type responses to NO2 and NH3) and the edges of graphene nanomesh structures (showing n-type responses to NO2 and NH3) have enhanced sensitivity. The measured responses towards gases are comparable to or better than those which have been obtained using devices that are more sophisticated. The higher sensitivity and rapid regeneration of the sensor at room temperature provides a clear advancement towards practical molecule detection using graphene-based materials.

Minimizing the Gibbs–Thomson effect in the low-temperature plasma synthesis of thin Si nanowires

An advanced combination of numerical models, including plasma sheath, ion- and radical-induced species creation and plasma heating effects on the surface and within a Au catalyst nanoparticle, is used to describe the catalyzed growth of Si nanowires in the sheath of a low-temperature and low-pressure plasma. These models have been used to explain the higher nanowire growth rates, low-energy barriers, much thinner Si nanowire nucleation and the less effective Gibbs–Thomson effect in reactive plasma processes, compared with those of neutral gas thermal processes. The effects of variation in the plasma sheath parameters and substrate potential on Si nanowire nucleation and growth have also been investigated. It is shown that increasing the plasma-related effects leads to decreases in the nucleation energy barrier and the critical nanoparticle radius, with the Gibbs–Thomson effect diminished, even at low temperatures. The results obtained are consistent with available experimental results and open a path toward the energy- and matter-efficient nucleation and growth of a broad range of one-dimensional quantum structures.

Heating and plasma sheath effects in low-temperature, plasma-assisted growth of carbon nanofibers

Plasma sheath, nanostructure growth, and thermal models are used to describe carbon nanofiber (CNF) growth and heating in a low-temperature plasma. It is found that when the H2 partial pressure is increased, H atom recombination and H ion neutralization are the main mechanisms responsible for energy release on the catalyst surface. Numerical results also show that process parameters such as the substrate potential, electron temperature and number density mainly affect the CNF growth rate and plasma heating at low catalyst temperatures. In contrast, gas pressure, ion temperature, and the C2H2:H2 supply ratio affect the CNF growth at all temperatures. It is shown that plasma-related processes substantially increase the catalyst particle temperature, in comparison to the substrate and the substrate-holding platform temperatures.

Plasma-controlled adatom delivery and (re)distribution: Enabling uninterrupted, low-temperature growth of ultralong vertically aligned single walled carbon nanotubes

Large-scale (∼109 atoms) numerical simulations reveal that plasma-controlled dynamic delivery and redistribution of carbon atoms between the substrate and nanotube surfaces enable the growth of ultralong single walled carbon nanotubes (SWCNTs) and explain the common experimental observation of slower growth at advanced stages. It is shown that the plasma-based processes feature up to two orders of magnitude higher growth rates than equivalent neutral-gas systems and are better suited for the SWCNT synthesis at low nanodevice friendly temperatures. © 2008 American Institute of Physics.

Low- and high-temperature controls in carbon nanofiber growth in reactive plasmas

A numerical growth model is used to describe the catalyzed growth of carbon nanofibers in the sheath of a low-temperature plasma. Using the model, the effects of variation in the plasma sheath parameters and substrate potential on the carbon nanofiber growth characteristics, such as the growth rate, the effective carbon flux to the catalyst surface, and surface coverages, have been investigated. It is shown that variations in the parameters, which change the sheath width, mainly affect the growth parameters at the low catalyst temperatures, whereas the other parameters such as the gas pressure, ion temperature, and percentages of the hydrocarbon and etching gases, strongly affect the carbon nanofiber growth at higher temperatures. The conditions under which the carbon nanofiber growth can still proceed under low nanodevice-friendly process temperatures have been formulated and summarized. These results are consistent with the available experimental results and can also be used for catalyzed growth of other high-aspect-ratio nanostructures in low-temperature plasmas.

Carbon saturation of arrays of Ni catalyst nanoparticles of different size and pattern uniformity on a silicon substrate

The kinetics of saturation of Ni catalyst nanoparticle patterns of the three different degrees of order, used as a model for the growth of carbon nanotips on Si, is investigated numerically using a complex model that involves surface diffusion and ion motion equations. It is revealed that Ni catalyst patterns of different degrees of order, with Ni nanoparticle sizes up to 12.5 nm, exhibit different kinetics of saturation with carbon on the Si surface. It is shown that in the cases examined (surface coverage in the range of 1-50%, highly disordered Ni patterns) the relative pattern saturation factor calculated as the ratio of average incubation times for the processes conducted in the neutral and ionized gas environments reaches 14 and 3.4 for Ni nanoparticles of 2.5 and 12.5 nm, respectively. In the highly ordered Ni patterns, the relative pattern saturation factor reaches 3 for nanoparticles of 2.5 nm and 2.1 for nanoparticles of 12.5 nm. Thus, more simultaneous saturation of Ni catalyst nanoparticles of sizes in the range up to 12.5 nm, deposited on the Si substrate, can be achieved in the low-temperature plasma environment than with the neutral gas-based process.

Growth kinetics of carbon nanowall-like structures in low-temperature plasmas

The results of a hybrid numerical simulation of the growth kinetics of carbon nanowall-like nanostructures in the plasma and neutral gas synthesis processes are presented. The low-temperature plasma-based process was found to have a significant advantage over the purely neutral flux deposition in providing the uniform size distribution of the nanostructures. It is shown that the nanowall width uniformity is the best (square deviations not exceeding 1.05) in high-density plasmas of 3.0× 1018 m-3, worsens in lower-density plasmas (up to 1.5 in 1.0× 1017 m-3 plasmas), and is the worst (up to 1.9) in the neutral gas-based process. This effect has been attributed to the focusing of ion fluxes by irregular electric field in the vicinity of plasma-grown nanostructures on substrate biased with -20 V potential, and differences in the two-dimensional adatom diffusion fluxes in the plasma and neutral gas-based processes. The results of our numerical simulations are consistent with the available experimental reports on the effect of the plasma process parameters on the sizes and shapes of relevant nanostructures.

Electrostatic nanoparticle filter for atomic scale fabrication in low-temperature plasmas

The means of reducing nanoparticle contamination in the synthesis of carbon nanostructures in reactive Ar + H2 + CH4 plasmas are studied. It is shown that by combining the electrostatic filtering and thermophoretic manipulation of nanoparticles, one can significantly improve the quality of carbon nanopatterns. By increasing the substrate heating power, one can increase the size of deposited nanoparticles and eventually achieve nanoparticle-free nanoassemblies. This approach is generic and is applicable to other reactive plasma-aided nanofabrication processes.

Self-organized ZnO nanodot arrays : effective control using SiNx interlayers and low-temperature plasmas

An advanced inductively coupled plasma (ICP)-assisted rf magnetron sputtering deposition method is developed to synthesize regular arrays of pear-shaped ZnO nanodots on a thin SiNx buffer layer pre-deposited onto a silicon substrate. It is shown that the growth of ZnO nanodots obey the cubic root-law behavior. It is also shown that the synthesized ZnO nanodots are highly-uniform, controllable by the experimental parameters, and also feature good structural and photoluminescent properties. These results suggest that this custom-designed ICP-based technique is very effective and highly-promising for the synthesis of property- and size-controllable highly-uniform ZnO nanodots suitable for next-generation light emitting diodes, energy storage, UV nanolasers, and other applications.

Mineralogy and Magnetic Properties of Basaltic Substrate Soils: Kaho'olawe and Big Island, Hawaii

Magnetic behavior of soils can seriously hamper the performance of geophysical sensors. Currently, we have little understanding of the types of minerals responsible for the magnetic behavior, as well as their distribution in space and evolution through time. This study investigated the magnetic characteristics and mineralogy of Fe-rich soils developed on basaltic substrate in Hawaii. We measured the spatial distribution of magnetic susceptibility (χlf) and frequency dependence (χfd%) across three test areas in a well-developed eroded soil on Kaho'olawe and in two young soils on the Big Island of Hawaii. X-ray diffraction spectroscopy, x-ray fluorescence spectroscopy (XFCF), chemical dissolution, thermal analysis, and temperature-dependent magnetic studies were used to characterize soil development and mineralogy for samples from soil pits on Kaho'olawe, surface samples from all three test areas, and unweathered basalt from the Big Island of Hawaii. The measurements show a general increase in magnetic properties with increasing soil development. The XRF Fe data ranged from 13% for fresh basalt and young soils on the Big Island to 58% for material from the B horizon of Kaho'olawe soils. Dithionite-extractable and oxalate-extractable Fe percentages increase with soil development and correlate with χlf-and χfd%, respectively. Results from the temperature-dependent susceptibility measurements show that the high soil magnetic properties observed in geophysical surveys in Kaho'olawe are entirely due to neoformed minerals. The results of our studies have implications for the existing soil survey of Kaho'olawe and help identify methods to characterize magnetic minerals in tropical soils.

Trace vapour detection at room temperature using Raman spectroscopy

A miniaturized flow-through system consisting of a gold coated silicon substrate based on enhanced Raman spectroscopy has been used to study the detection of vapour from model explosive compounds. The measurements show that the detectability of the vapour molecules at room temperature depends sensitively on the interaction between the molecule and the substrate. The results highlight the capability of a flow system combined with Raman spectroscopy for detecting low vapour pressure compounds with a limit of detection of 0.2 ppb as demonstrated by the detection of bis(2-ethylhexyl)phthalate, a common polymer additive emitted from a commercial polyvinyl chloride (PVC) tubing at room temperature.

Substrate, molecular structure, and solvent effects in 2D self-assembly via hydrogen and halogen bonding

Recently, halogen···halogen interactions have been demonstrated to stabilize two-dimensional supramolecular assemblies at the liquid–solid interface. Here we study the effect of changing the halogen, and report on the 2D supramolecular structures obtained by the adsorption of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TBPT) and 2,4,6-tris(4-iodophenyl)-1,3,5-triazine (TIPT) on both highly oriented pyrolytic graphite and the (111) facet of a gold single crystal. These molecular systems were investigated by combining room-temperature scanning tunneling microscopy in ambient conditions with density functional theory, and are compared to results reported in the literature for the similar molecules 1,3,5-tri(4-bromophenyl)benzene (TBPB) and 1,3,5-tri(4-iodophenyl)benzene (TIPB). We find that the substrate exerts a much stronger effect than the nature of the halogen atoms in the molecular building blocks. Our results indicate that the triazine core, which renders TBPT and TIPT stiff and planar, leads to stronger adsorption energies and hence structures that are different from those found for TBPB and TIPB. On the reconstructed Au(111) surface we find that the TBPT network is sensitive to the fcc- and hcp-stacked regions, indicating a significant substrate effect. This makes TBPT the first molecule reported to form a continuous monolayer at room temperature in which molecular packing is altered on the differently reconstructed regions of the Au(111) surface. Solvent-dependent polymorphs with solvent coadsorption were observed for TBPT on HOPG. This is the first example of a multicomponent self-assembled molecular networks involving the rare cyclic, hydrogen-bonded hexamer of carboxylic groups, R66(24) synthon.

Temperature sensitivity of soil organic matter decomposition in boreal soils

The temperature sensitivity of decomposition of different soil organic matter (SOM) fractions was studied with laboratory incubations using 13C and 14C isotopes to differentiate between SOM of different age. The quality of SOM and the functionality and composition of microbial communities in soils formed under different climatic conditions were also studied. Transferring of organic layers from a colder to a warmer climate was used to assess how changing climate, litter input and soil biology will affect soil respiration and its temperature sensitivity. Together, these studies gave a consistent picture on how warming climate will affect the decomposition of different SOM fractions in Finnish forest soils: the most labile C was least temperature sensitive, indicating that it is utilized irrespective of temperature. The decomposition of intermediate C, with mean residence times from some years to decades, was found to be highly temperature sensitive. Even older, centennially cycling C was again less temperature sensitive, indicating that different stabilizing mechanisms were limiting its decomposition even at higher temperatures. Because the highly temperature sensitive, decadally cycling C, forms a major part of SOM stock in the organic layers of the studied forest soils, these results mean that these soils could lose more carbon during the coming years and decades than estimated earlier. SOM decomposition in boreal forest soils is likely to increase more in response to climate warming, compared to temperate or tropical soils, also because the Q10 is temperature dependent. In the northern soils the warming will occur at a lower temperature range, where Q10 is higher, and a similar increase in temperature causes a higher relative increase in respiration rates. The Q10 at low temperatures was found to be inversely related to SOM quality. At higher temperatures respiration was increasingly limited by low substrate availability.

Role of Arg-401 of cytosolic serine hydroxymethyltransferase in subunit assembly and interaction with the substrate carboxy group.

In an attempt to identify the arginine residue involved in binding of the carboxylate group of serine to mammalian serine hydroxymethyltransferase, a highly conserved Arg-401 was mutated to Ala by site-directed mutagenesis. The mutant enzyme had a characteristic visible absorbance at 425 nm indicative of the presence of bound pyridoxal 5'-phosphate as an internal aldimine with a lysine residue. However, it had only 0.003% of the catalytic activity of the wild-type enzyme. It was also unable to perform reactions with glycine, beta-phenylserine or d-alanine, suggesting that the binding of these substrates to the mutant enzyme was affected. This was also evident from the interaction of amino-oxyacetic acid, which was very slow (8.4x10(-4) s-1 at 50 microM) for the R401A mutant enzyme compared with the wild-type enzyme (44.6 s-1 at 50 microM). In contrast, methoxyamine (which lacks the carboxy group) reacted with the mutant enzyme (1.72 s-1 at 250 microM) more rapidly than the wild-type enzyme (0.2 s-1 at 250 microM). Further, both wild-type and the mutant enzymes were capable of forming unique quinonoid intermediates absorbing at 440 and 464 nm on interaction with thiosemicarbazide, which also does not have a carboxy group. These results implicate Arg-401 in the binding of the substrate carboxy group. In addition, gel-filtration profiles of the apoenzyme and the reconstituted holoenzyme of R401A and the wild-type enzyme showed that the mutant enzyme remained in a tetrameric form even when the cofactor had been removed. However, the wild-type enzyme underwent partial dissociation to a dimer, suggesting that the oligomeric structure was rendered more stable by the mutation of Arg-401. The increased stability of the mutant enzyme was also reflected in the higher apparent melting temperature (Tm) (61 degrees C) than that of the wild-type enzyme (56 degrees C). The addition of serine or serinamide did not change the apparent Tm of R401A mutant enzyme. These results suggest that the mutant enzyme might be in a permanently 'open' form and the increased apparent Tm could be due to enhanced subunit interactions.

Fabrication of Fe-doped WO3 films for NO2 sensing at lower operating temperature

Fe-doped tungsten oxide thin films with different concentrations (0 to 2.6 at%) were synthesized on glass and alumina substrates at room temperature using DC reactive sputtering and subsequently annealed at 300oC for 1 hour in air. The alumina substrate has pre-printed interdigitated Pt-electrodes for gas sensing measurements. The effects of Fe-doping on the film structure and morphology, electronic and optical properties for gas sensing were investigated. The grain size of the different films on the alumina and Pt regions of the substrate vary only slightly between 43-57 nm with median size of about 50 nm. Raman spectra showed that the integrated intensity of W=O to O–W–O bands increases with increasing Fe concentrations and this indicated an increase in the number of defects. From XPS the different concentrations of the Fe-doped films were 0.03 at%, 1.33 at% and 2.6 at%. All the films deposited on glass substrate have shown similar visible transmittance (about 70%) but the optical band gap of the pure film decreased form 3.30 eV to 3.15 eV after doping with 2.6 at% Fe. The Fe-doped WO3 film with the highest Fe concentration (2.6 at% Fe) has shown an enhanced gas sensing properties to NO2 at relatively lower operating temperature (150oC) and this can be attributed to the decrease in the optical band gap and an increase in the number of defects compared to the pure WO3 film.