The weathering and oxidation of mine tailings has the potential to contaminate water and soil with toxic elements. To understand the mechanisms, extent and products of the long-term weathering of complex Bolivian tailings from the Cerro Rico de Potosí, and their effects on As, Pb, P and Sb cycling, three-year long laboratory column experiments were carried out to model 20 years of dry- and wet-season conditions in the Pilcomayo basin. Chemical analysis of the leachate and column solids, optical mineralogy, X-ray diffraction, scanning electron microscopy, electron probe microanalysis, microscale X-ray absorption near edge structure spectroscopy, Bureau Commun de Référence sequential extraction and water-soluble chemical extractions, and speciation modelling have shown that the weathering of As-bearing pyrite and arsenopyrite, resulted in a loss of 13–29% of the original mass of As. By contrast, Pb and Sb showed much lower mass losses (0.1–1.1% and 0.6–1.9%, respectively) due to the formation of insoluble Pb- and Sb(V)-rich phases, which were stable at the low pH (~2) conditions that prevailed by the end of the experiment. The experiment also demonstrated a link between the cycling of As, Sb, and the oxidation of Fe(II)-bearing sphalerite, which acted as a nucleation point for an Fe-As-Sb-O phase. Phosphorus was relatively immobile in the tailings columns (up to 0.3% mass loss) but was more mobile in the soil-bearing columns (up to 10% mass loss), due to the formation of soluble P-bearing minerals or mobilization by organic matter. These results demonstrate the influence of mine tailings on the mobility of P from soils and on the potential contamination of ecosystems with As, and strongly suggest that these materials should be isolated from fluvial environments.

We study two different heat-type equations. First, global well-posedness in the energy space of some high-order semilinear heat-type equation with exponential nonlinearity is obtained for even space dimensions. Second, a finite-time blow-up result for the critical monomial focusing heat equation with the p-Laplacian is proved.

Black phosphorus (black-P) research has been the most absent for 100 years since its date of first synthesis in 1914 among all the polymorphs of phosphorus. However, recently it has been re-examined due to its specific puckered single layer geometry. Few or single atomic layer forms of black-P can be isolated using techniques such as micromechanical or liquid exfoliation. However, the exfoliation techniques limit the use of black-P, hence a method of black-P layer deposition onto a substrate is needed. Few or atomic layer deposition of black-P leads to substrate-material interactions and a possible appearance of a band gap opening at the K point. Hence, a series of experiments were conducted in order to grow black-P on different substrates. With the incorporation of doping elements, there was substantial modification in the vibrational and electrical properties. It was observed that sulfur and boron doped films exhibit improved electrical and electronic properties as compared to pristine black-P. Density functional theory predicts significant changes in the band structure and density of states as a consequence of doping. The effects of doping was also reflected in Raman A1g mode. The shift in peak position was also found to be consistent with molar mass of dopants.

The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I–V–VI chalcogenides including copper phosphide (Cu3P) and copper thiophosphate (Cu3PS4). Herein, we report a one-pot, solution-based synthesis of Cu3P nanocrystals utilizing an in situ phosphorus source: phosphorus pentasulfide (P2S5) in trioctylphosphine. By injecting this phosphorus source into a copper solution in oleylamine, uniform and size controlled Cu3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cu3P nanocrystals with decomposing thiourea forms nanoscale Cu3PS4 particles having p-type conductivity and an effective optical band gap of 2.36 eV. The synthesized Cu3PS4 produces a cathodic photocurrent during photoelectrochemical measurements, demonstrating its application as a light-absorbing material. Our process creates opportunities to explore other solution-based metal-phosphorus systems and their subsequent sulfurization for earth abundant, alternative energy materials.

Background: Previous studies suggest that brain serotonin neurotransmission may mediate the actions of lithium carbonate. Acute tryptophan depletion (ATD) reduces brain serotonin and allows the study of this neurotransmitter in patient groups. Serotonin modulates electroencephalographic (EEG) activity, which is abnormal in bipolar disorder, and EEG abnormalities persist in euthymic bipolar patients. The EEG may therefore be a sensitive marker of 5-HT function in bipolar disorder.

Aims: This study examined the effects of ATD on mood, suicidal ideation and EEG activity in bipolar patients who were symptomatically stable on lithium.

Methods: 19 subjects satisfying DSM-IV criteria for bipolar I disorder participated in a within-subject, double-blind, placebo-controlled random-order crossover study. Following acute tryptophan depletion (induced by a 100g amino acid drink following an overnight fast) symptoms were evaluated, quantitative power spectrum brain mapping and measurement of auditory evoked potentials were carried out.

Results: ATD produced a significant fall in the amplitude of N1P2 and P300 components of the auditory evoked potential, but no significant changes in the power spectrum. There was an 83% reduction in plasma tryptophan (p<0.05, paired t-test) after the depleting but not the control drink. No significant changes in mood or suicidally scores were recorded after ATD.

Conclusions: ATD attenuates auditory evoked potentials in bipolar disorder but does not reverse lithium's effects on mood and suicidally in bipolar disorder.

Phosphorus (P) doped ultra thin n+-layer is formed on crystalline silicon (c-Si) at low substrate temperatures of 80 – 350 °C using radicals generated by the catalytic reaction of phosphine (PH3) with a tungsten catalyzer heated at 1300 °C. The sheet carrier concentration obtained by Hall effect is in the range between 3×1012cm-2 and 8×1012cm-2. The distribution of P atoms obtained by secondary ion mass spectrometry (SIMS) indicates that P atoms locate within the depth of 4 nm from surface and the profile has almost the same distribution independent of any doping conditions such as substrate temperature or radical exposure time. The sheet carrier concentration is 1.15 – 2.12% of the amount of P atoms incorporated through the radical doping. The ratio of activated donors increases with substrate temperature during the radical doping, suggesting that P-related species bonded on the c-Si surface require thermal energy for their activation. Using the n+-layer formed by radical doping, the reduction of surface recombination velocity for n-type c-Si wafer is attempted. The effective minority carrier lifetime of the n-type c-Si sample covered with 6-nm-thick intrinsic amorphous Si (i-a-Si) layers on both side increases from 32 μs to1576 μs by the radical doping of P atoms to n-type c-Si surface, suggesting that the radical doping can be utilized for the formation of passivation layers on a-Si/ n-c-Si hetero-interface.

The Si–P system at high temperatures up to 6 wt%P was investigated. Silicon–phosphorus alloys were prepared through the melting of silicon–phosphorus mixtures in closed silica tubes. Microstructural studies indicated two phases in the alloys, i.e., a solid solution of P in Si and the intermediate compound SiP. Thermal analysis technique was applied to study the phase transformations in the alloys at elevated temperatures. It was observed that SiP is melted at 1139 ± 2 °C. A eutectic reaction in the system, in which liquid Si–P alloy is transformed to SiP and a solid solution of P in Si was observed at 1129 ± 2 °C. Moreover, the liquidus and solidus on the silicon-rich part of the phase diagram were determined as:

Solidus: TS = −75.03 CP + 1414 (°C) 0.35 < CP < 1 wt%P

Liquidus: TL = −6.74 CP + 1414 (°C) CP < 6 wt%P

The distribution coefficient of P in Si was calculated as k0 = 0.09 using the obtained solidus and liquidus at low concentrations.

We propose a new technique to fabricate 4H-SiC metal–oxide–semiconductor field-effect transistors (MOSFETs) with high inversion channel mobility. P atoms were incorporated into the SiO2/4H-SiC(0001) interface by post-oxidation annealing using phosphoryl chloride (POCl3). The interface state density at 0.2 eV from the conduction band edge was reduced to less than 1 × 1011 cm−2eV−1 by the POCl3 annealing at 1000 °C. The peak field-effect mobility of 4H-SiC MOSFETs on (0001) Si-face processed with POCl3 annealing at 1000 °C was approximately 90 cm2/Vs. The high channel mobility is attributed to the reduced interface state density near the conduction band edge.

Point Defect (PD) mediated diffusion of phosphorous in silicon is studied in order to address the long standing open problem of PD-Dopant pair lifetime. A novel experimental method is suggested to increase PD-P pair lifetime for better observability and experimental resolution. In the experiment, phosphorous is implanted, followed by low temperature poly-Si deposition with in-situ doped phosphorous. The P profile shows, after low temperature (<650°C) in-situ phosphorous doped poly-Si deposition, an exponential dependence of two orders of magnitude for a significant depth scale. This indicates that the PD-P pairs survive long-range diffusion before dissociating in the Si lattice. As a result, the lifetime of PD-P pair was extracted and this provides a physical basis for TCAD simulation at the atomic scale.

Hafnium(IV) oxide (HfO2) has replaced silicon oxide as a gate dielectric material in leading edge CMOS technology, providing significant improvement in gate performance for field effect transistors (FETs). We are currently exploring this high-k dielectric for its use in nucleic acid-based FET biosensors. Due to its intrinsic negative charge, label-free detection of DNA can be achieved in the gate region of high-sensitivity FET devices. Previous work has shown that phosphates and phosphonates coordinate specifically onto metal oxide substrates including aluminum and titanium oxides. This property can therefore be exploited for direct immobilization of biomolecules such as nucleic acids. Our work demonstrates that 5’ phosphate-terminated single stranded DNA (ssDNA) can be directly immobilized onto HfO2 surfaces, without the need for additional chemical modification or crosslinking. Non-phosphorylated ssDNA does not form stable surface interactions with HfO2, indicating that immobilization is dependent upon the 5’ terminal phosphate. Further work has shown that surface immobilized ssDNA can be hybridized to complementary target DNA and that sequence-based hybridization specificity is preserved. These results suggest that the direct DNA-HfO2 immobilization strategy can enable nucleic acid-based biosensing assays on HfO2 terminated surfaces. This work will further enable high sensitivity electrical detection of biological targets utilizing transistor-based technologies.

Germanium has regained attention in the semiconductor industry for MOSFET application because of the higher mobility of carriers – two times higher mobility for electrons and four times for holes – as compared to silicon. In the opposite of the Silicon, the major issue with Germanium is to limit the n-dopant diffusion. Usual n-dopants (Phosphorus and Arsenic for example) are not electrically activated at an acceptable level without a large diffusion of the doping profile and a substantial dose loss. In this work, we have studied the influence of low energy and dose implant (15KeV to 40KeV @ 8E13 to 1E15at.cm−2) and low temperature anneal (515°C to 600°C) on diffusion, exodiffusion and activation of the phosphorus dopant into Germanium. The annealing steps were made in RTP furnace, the chemical profile and electrically active profiles were extracted by using Secondary-Ion-Mass Spectroscopy (SIMS) and sheet resistance measurement (Rs). To investigate the implantation-induced defects in depth, cross-sectional micrographs were made by using Transmission Electron Microscopy (TEM). Experimental results show that we achieved an efficient activation level by tuning both dose implant and anneal temperature, limiting the exodiffusion with pratically no diffusion of the dopant. We also show that very abrupt profile can be achieved with appropriate implant and thermal annealing conditions. To limit the leakage current in devices, we suppose we have to limit the defects generated during the implantation. Specially for dopant activation temperature anneal below 550°C, we have shown and observed by cross-sectional micrograph that the defects are totally removed by addition of a pre step of annealing at 400°C.

We present the results of extensive ab initio simulations for phosphorus clustering and diffusion in silicon and the application of these results in a state-of-the-art process simulator. The specific defects and the parameters that are investigated are selected according to the needs of diffusion and activation models, taking into account the availability of experimental data, the capabilities of current ab initio methods and the requirements for advanced technology development. The calculated formation energies, binding energies and migration barriers are used to determine a good starting point for the calibration of a new charged cluster model implemented in the process simulator. The defect species V, I, P, PV, PI, PI2, P2, P2V, P2I, P3, P3V, P3I and P4V are considered in all relevant charge states. The ab initio results are discussed as well as the transfer of this information into the process simulation model and the impact on model quality.

The contribution of dietary Ca and P in renal stone formation is debated. Thus, the main objective was to investigate if there were any differences in the dietary, serum and urine values of Ca and P in stone formers (SF) compared with healthy controls (HC). The secondary aim was to analyse if dietary, serum and urine Ca and P correlated. The study enrolled ten patients with renal stones admitted for stone removal and ten healthy controls. Their dietary macronutrients, Ca and P intakes were calculated from 2-d dietary records. On the second day of dietary record 24-h urine was collected and on the third day morning a 5 ml blood sample was collected. Biochemical analyses were conducted for serum and urine Ca, P and uric acid with qualitative renal stone analysis. All the dietary intakes and urine P were significantly higher (P < 0·05) in SF than in HC. Correlation results showed that in SF dietary Ca correlated to serum and urine Ca. No such correlations were seen for P. Additionally, in SF urine Ca correlated to dietary proteins and fats but not to carbohydrates. None of the biochemical values lay outside the normal range of values. The study suggests urine P rather than urine Ca to be probably at work in the formation of renal stones. Limitation of protein intake with normal Ca intakes could provide a suitable measure to avoid renal stone formation.

Carbon co-implantation after pre-amorphization implantation (PAI) has been studied for Boron shallow implants and can be also used to reduce Phosphorus diffusion. The expected role of Carbon is to trap Si interstitials responsible of Phosphorus diffusion. A known drawback of this kind of co-implantation is junction leakage caused by Carbon deep levels. To find a compromise between diffusion reduction and leakages, it is necessary to optimize the location and the amount of Carbon with respect to Si interstitials.

In this work, we present full sheet experiments optimizing Carbon implanted energy and dose in order to minimize Phosphorus diffusion. First, we performed a PAI with Germanium. Then Carbon was implanted at several energies and doses to locate its projected range (Rp) at various locations with respect to the Phosphorus peak and the amorphous/crystalline interface. Finally the Phosphorus implant was placed completely within the amorphized area. Dopants were activated by a spike anneal at 1080°C, 1055°C or 1000°C. SIMS analysis and Rs measurements were used to understand Carbon action on Phosphorus diffusion and activation. The role of C in suppressing P diffusion is discussed in regards of the specificities of P diffusion mechanism.

As silicon transistor dimensions scale down, transient enhanced diffusion of n-type dopants has become a major barrier toward achieving required junction depths for transistors. In this paper, we use density functional calculations to identify a pathway by which silicon interstitials can mediate As and P diffusion. We show that As-silicon interstitial and P-silicon interstitial pairs in the neutral and negative charge states diffuse via a mechanism in which the dopant is bond-centered at energy minima and threefold coordinated at the high energy saddle point during dopant migration. For both As-silicon interstitial and P-silicon interstitial pairs, we conclude that the neutral pairs will dominate under intrinsic conditions while the neutral and negatively charged pairs will both contribute under heavily doped extrinsic conditions.

The dependence of phosphorus doping on crystal face and C/Si ratio in the epitaxial growth of 4H-SiC using phosphine were investigated. Phosphorus incorporation was highest on off-axis (000-1) and lowest on off-axis (0001). Phosphorus incorporation on (11-20) came between that on off-axis (0001) and (000-1). With increasing C/Si ratio from 0.5 to 2.5, phosphorus incorporation increased on (11-20) and off-axis (000-1). Phosphorus incorporation on off-axis (0001) showed unclear C/Si ratio dependence. On (000-1), the highest phosphorus concentration of 2 × 1018cm-3 was obtained by an increasing PH3 flow rate. The roughness, growth rate, and surface morphology of the high phosphorus doped epilayer were investigated.

Fluid phosphorus exhibits a macroscopic phase separation during a pressure-induced first-order phase transition between low-density fluid and high-density fluid. Solidification process of the phase-separated fluid sample was monitored by x-ray radiography and the obtained solid sample was investigated by optical and scanning electron microscopy. A solid mixture of black parts and red parts was obtained from the phase-separated sample. Three different morphologies were observed in the red part of the sample.

A mineralogical and geochemical study of soils developed from the unmined Coles Hill uranium deposit (Virginia) was undertaken to determine how phosphorous influences the speciation of uranium in an oxidizing soil/saprolite system typical of the eastern US. This paper presents mineralogical and geochemical results that identify and quantify the processes by which uranium has been sequestered in these soils. It was found that uranium is not leached from the saturated soil zone (saprolites) overlying the deposit due to the formation of a sparingly soluble uranyl phosphate mineral of the meta-autunite group. The concentration of uranium in the saprolites is approximately 1000 mg uranium per kg of saprolite. It was also found that a significant amount of uranium was retained in the unsaturated soil zone overlying uranium-rich saprolites. The uranium concentration in the unsaturated soils is approximately 200 mg uranium per kg of soil (20 times higher than uranium concentrations in similar soils adjacent to the deposit). Mineralogical evidence indicates that uranium in this zone is sequestered by a barium-strontium-calcium aluminum phosphate mineral of the crandallite group (gorceixite). This mineral is intimately inter-grown with iron and manganese oxides that also contain uranium. The amount of uranium associated with both the aluminum phosphates (as much as 1.4 weight percent) has been measured by electron microprobe microanalyses and the geochemical conditions under which these minerals formed has been studied using thermodynamic reaction path modeling. The geochemical data and modeling results suggests the meta-autunite group minerals present in the saprolites overlying the deposit are unstable in the unsaturated zone soils overlying the deposit due to a decrease in soil pH (down to a pH of 4.5) at depths less than 5 meters below the surface. Mineralogical observations suggest that, once exposed to the unsaturated environment, the meta-autunite group minerals react to form U(VI)-bearing aluminum phosphates.

Binary silicophosphate glasses containing between 7 and 35 mol% P2O5 were made by conventional melt quenching techniques and characterized by 29Si and 31P NMR spectroscopy. 31P and 29Si NMR data show that, as the P2O5 content is raised in these glasses, the network connectivity is decreased by a dilution of the silicate network with less polymerized Q3 phosphate groups. In addition to such changes in the network structure, 29Si NMR spectra for the most P2O5-rich glasses reveal the presence of silicon atoms with 5- and 6-fold coordination. These species increase in concentration with increasing P2O5 above approximately 30 mol% P2O5. Self-nucleating SiP2O7 glass-ceramics can be formed from the binary silicophosphate glasses with >25mol% P2O5. 29Si and 31P NMR results were used to monitor the crystallization of SiP2O7 by providing details on amount of crystallinity, relative grain sizes and even composition of the residual glassy matrix. Stabilization of octahedral Si as well as the onset of phase separation correlates with propensity for crystallization of SiP2O7 during subsequent heat treatment.

As extensions have been up till now always used in N-MOS transistors with an activation anneal. Here, we show that also alternative doping by P can result in junction extensions that are extremely abrupt and shallow thus suitable for upcoming transistor technologies. P extensions are manufactured by amorphization, carbon co-implantation and conventional rapid thermal annealing (RTA). The impact of Si interstitials (Sii) flux suppression on the formation of P junction extensions during RTA is demonstrated. We have concluded that optimization of implants followed by RTA spike offers excellent extensions with depth Xj = 20 nm (taken at 5 × 1018 at./cm3), abruptness 3 nm/dec. and Rs = 326 Ω. Successful implementation of these junctions is straightforward for N-MOS devices with 30 nm gate length and results in an improved short channel effects with respect to the As reference.