Polycarbonate based nonchemically amplified photoresists for extreme ultraviolet lithography

Some initial EUVL patterning results for polycarbonate based non-chemically amplified resists are presented. Without full optimization the developer a resolution of 60 nm line spaces could be obtained. With slight overexposure (1.4 × E0) 43.5 nm lines at a half pitch of 50 nm could be printed. At 2x E0 a 28.6 nm lines at a half pitch of 50 nm could be obtained with a LER that was just above expected for mask roughness. Upon being irradiated with EUV photons, these polymers undergo chain scission with the loss of carbon dioxide and carbon monoxide. The remaining photoproducts appear to be non-volatile under standard EUV irradiation conditions, but do exhibit increased solubility in developer compared to the unirradiated polymer. The sensitivity of the polymers to EUV light is related to their oxygen content and ways to increase the sensitivity of the polymers to 10 mJ cm-2 is discussed.

Controls on iron in soils and soil waters of a forested, coastal catchment in subtropical Australia

Soluble organic matter derived from exotic Pinus vegetation forms stronger complexes with iron (Fe) than the soluble organic matter derived from most native Australian species. This has lead to concern about the environmental impacts related to the establishment of extensive exotic Pinus plantations in coastal southeast Queensland, Australia. It has been suggested that the Pinus plantations may enhance the solubility of Fe in soils by increasing the amount of organically complexed Fe. While this remains inconclusive, the environmental impacts of an increased flux of dissolved, organically complexed Fe from soils to the fluvial system and then to sensitive coastal ecosystems are potentially damaging. Previous work investigated a small number of samples, was largely laboratory based and had limited application to field conditions. These assessments lacked field-based studies, including the comparison of the soil water chemistry of sites associated with Pinus vegetation and undisturbed native vegetation. In addition, the main controls on the distribution and mobilisation of Fe in soils of this subtropical coastal region have not been determined. This information is required in order to better understand the relative significance of any Pinus enhanced solubility of Fe. The main aim of this thesis is to determine the controls on Fe distribution and mobilisation in soils and soil waters of a representative coastal catchment in southeast Queensland (Poona Creek catchment, Fraser Coast) and to test the effect of Pinus vegetation on the solubility and speciation of Fe. The thesis is structured around three individual papers. The first paper identifies the main processes responsible for the distribution and mobilisation of labile Fe in the study area and takes a catchment scale approach. Physicochemical attributes of 120 soil samples distributed throughout the catchment are analysed, and a new multivariate data analysis approach (Kohonen’s self organising maps) is used to identify the conditions associated with high labile Fe. The second paper establishes whether Fe nodules play a major role as an iron source in the catchment, by determining the genetic mechanism responsible for their formation. The nodules are a major pool of Fe in much of the region and previous studies have implied that they may be involved in redox-controlled mobilisation and redistribution of Fe. This is achieved by combining a detailed study of a ferric soil profile (morphology, mineralogy and micromorphology) with the distribution of Fe nodules on a catchment scale. The third component of the thesis tests whether the concentration and speciation of Fe in soil solutions from Pinus plantations differs significantly from native vegetation soil solutions. Microlysimeters are employed to collect unaltered, in situ soil water samples. The redox speciation of Fe is determined spectrophotometrically and the interaction between Fe and dissolved organic matter (DOM) is modelled with the Stockholm Humic Model. The thesis provides a better understanding of the controls on the distribution, concentration and speciation of Fe in the soils and soil waters of southeast Queensland. Reductive dissolution is the main mechanism by which mobilisation of Fe occurs in the study area. Labile Fe concentrations are low overall, particularly in the sandy soils of the coastal plain. However, high labile Fe is common in seasonally waterlogged and clay-rich soils which are exposed to fluctuating redox conditions and in organic-rich soils adjacent to streams. Clay-rich soils are most common in the upper parts of the catchment. Fe nodules were shown to have a negligible role in the redistribution of dissolved iron in the catchment. They are formed by the erosion, colluvial transport and chemical weathering of iron-rich sandstones. The ferric horizons, in which nodules are commonly concentrated, subsequently form through differential biological mixing of the soil. Whereas dissolution/ reprecipitation of the Fe cements is an important component of nodule formation, mobilised Fe reprecipitates locally. Dissolved Fe in the soil waters is almost entirely in the ferrous form. Vegetation type does not affect the concentration and speciation of Fe in soil waters, although Pinus DOM has greater acidic functional group site densities than DOM from native vegetation. Iron concentrations are highest in the high DOM soil waters collected from sandy podosols, where they are controlled by redox potential. Iron concentrations are low in soil solutions from clay and iron oxide rich soils, in spite of similar redox potentials. This is related to stronger sorption to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for microbial metabolisation and reductive dissolution of Fe. Modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxidising conditions. Thus, inputs of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides and increase the flux of dissolved iron out of the catchment. Such inputs are most likely from the lower catchment, where podosols planted with Pinus are most widely distributed. Significant outcomes other than the main aims were also achieved. It is shown that mobilisation of Fe in podosols can occur as dissolved Fe(II) rather than as Fe(III)-organic complexes. This has implications for the large body of work which assumes that Fe(II) plays a minor role. Also, the first paper demonstrates that a data analysis approach based on Kohonen’s self organising maps can facilitate the interpretation of complex datasets and can help identify geochemical processes operating on a catchment scale.

Prediction of the wash-off of traffic related semi- and non-volatile organic compounds from urban roads under climate change influenced rainfall characteristics

Traffic generated semi and non volatile organic compounds (SVOCs and NVOCs) pose a serious threat to human and ecosystem health when washed off into receiving water bodies by stormwater. Climate change influenced rainfall characteristics makes the estimation of these pollutants in stormwater quite complex. The research study discussed in the paper developed a prediction framework for such pollutants under the dynamic influence of climate change on rainfall characteristics. It was established through principal component analysis (PCA) that the intensity and durations of low to moderate rain events induced by climate change mainly affect the wash-off of SVOCs and NVOCs from urban roads. The study outcomes were able to overcome the limitations of stringent laboratory preparation of calibration matrices by extracting uncorrelated underlying factors in the data matrices through systematic application of PCA and factor analysis (FA). Based on the initial findings from PCA and FA, the framework incorporated orthogonal rotatable central composite experimental design to set up calibration matrices and partial least square regression to identify significant variables in predicting the target SVOCs and NVOCs in four particulate fractions ranging from >300-1 μm and one dissolved fraction of <1 μm. For the particulate fractions range >300-1 μm, similar distributions of predicted and observed concentrations of the target compounds from minimum to 75th percentile were achieved. The inter-event coefficient of variations for particulate fractions of >300-1 μm were 5% to 25%. The limited solubility of the target compounds in stormwater restricted the predictive capacity of the proposed method for the dissolved fraction of <1 μm.

Raman spectroscopy of the borate mineral ameghinite NaB3O3(OH)4

The molecular structure of the sodium borate mineral ameghinite NaB3O3(OH)4 has been determined by the use of vibrational spectroscopy. The crystal structure consists of isolated [B3O3(OH)4]- units formed by one tetrahedron and two triangles. H bonds and Na atoms link these polyanions to form a 3-dimensional framework. The Raman spectrum is dominated by an intense band at 1027 cm-1, attributed to BO stretching vibrations of both the trigonal and tetrahedral boron. A series of Raman bands at 1213, 1245 and 1281cm-1 are ascribed to BOH in-plane bending modes. The infrared spectra are characterized by strong overlap of broad multiple bands. An intense Raman band found at 620 cm-1 is attributed to the bending modes of trigonal and tetrahedral boron. Multiple Raman bands in the OH stretching region are observed at 3206, 3249 and 3385 cm-1. Raman spectroscopy coupled with infrared spectroscopy has enabled aspects about the molecular structure of the borate mineral ameghinite to be assessed.

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe - DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe 2+) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide-rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well-drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.

Chitosan adhesive for laser tissue repair: In vitro characterization

Background and Objectives Laser tissue repair usually relies on hemoderivate protein solders, based on serum albumin. These solders have intrinsic limitations that impair their widespread use, such as limited tensile strength of repaired tissue, poor solder solubility, and brittleness prior to laser denaturation. Furthermore, the required activation temperature of albumin solders (between 65 and 70°C) can induce significant thermal damage to tissue. In this study, we report on the design of a new polysaccharide adhesive for tissue repair that overcomes some of the shortcomings of traditional solders. Study Design/Materials and Methods Flexible and insoluble strips of chitosan adhesive (elastic modulus ~6.8 Mpa, surface area ~34 mm2, thickness ~20 µm) were bonded onto rectangular sections of sheep intestine using a diode laser (continuous mode, 120 ± 10 mW, = λ 808 nm) through a multimode optical fiber with an irradiance of ~15 W/cm2. The adhesive was based on chitosan and also included indocyanin green dye (IG). The temperature between tissue and adhesive was measured using a small thermocouple (diameter ~0.25 mm) during laser irradiation. The repaired tissue was tested for tensile strength by a calibrated tensiometer. Murine fibroblasts were cultured in extracted media from chitosan adhesive to assess cytotoxicity via cell growth inhibition in a 48 hours period. Results Chitosan adhesive successfully repaired intestine tissue, achieving a tensile strength of 14.7 ± 4.7 kPa (mean ± SD, n = 30) at a temperature of 60-65°C. Media extracted from chitosan adhesive showed negligible toxicity to fibroblast cells under the culture conditions examined here. Conclusion A novel chitosan-based adhesive has been developed, which is insoluble, flexible, and adheres firmly to tissue upon infrared laser activation.

Electronic transport properties of hot-pressed B6Si

Measurements of the electrical conductivity, Seebeck coefficient and Hall mobility from -300K to -1300K have been carried out on multiphase hotpressed samples of the nominal composition B6Si. In all samples the conductivity and the p-type Seebeck coefficient both increase smoothly with increasing temperature. By themselves, these facts suggest small-polaronic hopping between inequivalent sites. The measured Hall mobilities are always low, but vary in sign. A possible explanation is offered for this anomalous behavior.

Assessment of the molecular structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O using vibrational spectroscopy

The structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O, a borate–carbonate of calcium and magnesium has been assessed using vibrational spectroscopy. Assignment of bands is undertaken by comparison with the data from other published results. Intense Raman band at 1134 cm−1 with a shoulder at 1123 cm−1 is assigned to the symmetric stretching mode. The Raman spectrum displays bands at 1479, 1524 and 1560 cm−1 which are assigned to the antisymmetric stretching vibrations. The observation of multiple carbonate stretching bands supports the concept that the carbonate units are non-equivalent. The Raman band at 968 cm−1 with a shoulder at 950 cm−1 is assigned to the symmetric stretching mode of trigonal boron. Raman bands at 627 and 651 cm−1 are assigned to the out-of-plane bending modes of trigonal and tetrahedral boron. Raman spectroscopy coupled with infrared spectroscopy enables the molecular structure of the mineral sakhaite to be assessed.

The borate mineral jeremejevite Al6(BO3)5(F,OH)3 – A vibrational spectroscopic study

Jeremejevite is a borate mineral of aluminium and is of variable colour, making the mineral and important inexpensive jewel. The mineral contains variable amounts of F and OH, depending on origin. A comparison of the vibrational spectroscopic data is made with the published data of borate minerals. Raman spectra were averaged over a range of crystal orientations. Two intense Raman bands observed at 961 and 1067 cm−1 are assigned to the symmetric stretching and antisymmetric stretching modes of trigonal boron. Infrared spectrum, bands observed at 1229, 1304, 1350, 1388 and 1448 cm−1 are attributed to BOH in-plane bending modes. Intense Raman band found at 372 cm−1 with other bands of significant intensity at 327 and 417 cm−1 is assigned to trigonal borate bending modes. A quite intense Raman band is found at 3673 cm−1 with other sharp Raman bands found at 3521, 3625 and 3703 cm−1 are assigned to the stretching modes of OH. Raman and infrared spectroscopy has been used to assess the molecular structure of the mineral jeremejevite. Such research is important in the study of borate based nanomaterials.

Assessment of the molecular structure of the borate mineral boracite Mg3B7O13Cl using vibrational spectroscopy

Boracite is a magnesium borate mineral with formula: Mg3B7O13Cl and occurs as blue green, colorless, gray, yellow to white crystals in the orthorhombic – pyramidal crystal system. An intense Raman band at 1009 cm−1 was assigned to the BO stretching vibration of the B7O13 units. Raman bands at 1121, 1136, 1143 cm−1 are attributed to the in-plane bending vibrations of trigonal boron. Four sharp Raman bands observed at 415, 494, 621 and 671 cm−1 are simply defined as trigonal and tetrahedral borate bending modes. The Raman spectrum clearly shows intense Raman bands at 3405 and 3494 cm−1, thus indicating that some Cl anions have been replaced with OH units. The molecular structure of a natural boracite has been assessed by using vibrational spectroscopy.

Vibrational spectroscopy of the borate mineral henmilite Ca2Cu[B(OH)4]2(OH)4

Henmilite is a triclinic mineral with the crystal structure consisting of isolated B(OH)4 tetrahedra, planar Cu(OH)4 groups and Ca(OH)3 polyhedra. The structure can also be viewed as having dimers of Ca polyhedra connected to each other through 2B(OH) tetrahedra to form chains parallel to the C axis. The structure of the mineral has been assessed by the combination of Raman and infrared spectra. Raman bands at 902, 922, 951, and 984 cm−1 and infrared bands at 912, 955 and 998 cm−1 are assigned to stretching vibrations of tetragonal boron. The Raman band at 758 cm−1 is assigned to the symmetric stretching mode of tetrahedral boron. The series of bands in the 400–600 cm−1 region are due to the out-of-plane bending modes of tetrahedral boron. Two very sharp Raman bands are observed at 3559 and 3609 cm−1. Two infrared bands are found at 3558 and 3607 cm−1. These bands are assigned to the OH stretching vibrations of the OH units in henmilite. A series of Raman bands are observed at 3195, 3269, 3328, 3396, 3424 and 3501 cm−1 are assigned to water stretching modes. Infrared spectroscopy also identified water and OH units in the henmilite structure. It is proposed that water is involved in the structure of henmilite. Hydrogen bond distances based upon the OH stretching vibrations using a Libowitzky equation were calculated. The number and variation of water hydrogen bond distances are important for the stability off the mineral.

Vibrational spectroscopy of the borate mineral kotoite Mg3(BO3)2

Vibrational spectroscopy has been used to assess the structure of kotoite a borate mineral of magnesium which is isostructural with jimboite. The mineral is orthorhombic with point group: 2/m 2/m 2/m. The mineral has the potential as a new memory insulator material. The mineral has been characterised by a combination of Raman and infrared spectroscopy. The Raman spectrum is dominated by a very intense band at 835 cm−1, assigned to the symmetric stretching mode of tetrahedral boron. Raman bands at 919, 985 and 1015 cm−1 are attributed to the antisymmetric stretching modes of tetrahedral boron. Kotoite is strictly an hydrous borate mineral. An intense Raman band observed at 3559 cm−1 is attributed to the stretching vibration of hydroxyl units, more likely to be associated with the borate mineral hydroxyborate. The lack of observation of water bending modes proves the absence of water in the kotoite structure.

Hybrid graphene and graphitic carbon nitride nanocomposite : gap opening, electron–hole puddle, interfacial charge transfer, and enhanced visible light response

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C3N4) and electronically active graphene. We find an inhomogeneous planar substrate (g-C3N4) promotes electronrich and hole-rich regions, i.e., forming a well-defined electron−hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C3N4 substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C3N4 interface opens a 70 meV gap in g-C3N4-supported graphene, a feature that can potentially allow overcoming the graphene’s band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C3N4 is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C3N4 monolayer, the hybrid graphene/g-C3N4 complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

How to achieve maximum charge carrier loading on heteroatom-substituted graphene nanoribbon edges: density functional theory study

The practical number of charge carriers loaded is crucial to the evaluation of the capacity performance of carbon-based electrodes in service, and cannot be easily addressed experimentally. In this paper, we report a density functional theory study of charge carrier adsorption onto zigzag edge-shaped graphene nanoribbons (ZGNRs), both pristine and incorporating edge substitution with boron, nitrogen or oxygen atoms. All edge substitutions are found to be energetically favorable, especially in oxidized environments. The maximal loading of protons onto the substituted ZGNR edges obeys a rule of [8-n-1], where n is the number of valence electrons of the edge-site atom constituting the adsorption site. Hence, a maximum charge loading is achieved with boron substitution. This result correlates in a transparent manner with the electronic structure characteristics of the edge atom. The boron edge atom, characterized by the most empty p band, facilitates more than the other substitutional cases the accommodation of valence electrons transferred from the ribbon, induced by adsorption of protons. This result not only further confirms the possibility of enhancing charge storage performance of carbon-based electrochemical devices through chemical functionalization but also, more importantly, provides the physical rationale for further design strategies.

Charge carrier exchange at chemically modified graphene edges: A density functional theory study

Heteroatom doping on the edge of graphene may serve as an effective way to tune chemical activity of carbon-based electrodes with respect to charge carrier transfer in an aqueous environment. In a step towards developing mechanistic understanding of this phenomenon, we explore herein mechanisms of proton transfer from aqueous solution to pristine and doped graphene edges utilizing density functional theory. Atomic B-, N-, and O- doped edges as well as the native graphene are examined, displaying varying proton affinities and effective interaction ranges with the H3O+ charge carrier. Our study shows that the doped edges characterized by more dispersive orbitals, namely boron and nitrogen, demonstrate more energetically favourable charge carrier exchange compared with oxygen, which features more localized orbitals. Extended calculations are carried out to examine proton transfer from the hydronium ion in the presence of explicit water, with results indicating that the basic mechanistic features of the simpler model are unchanged.