Diana Wilkinson

Low-temperature approach to high-yield and reproducible syntheses of high-quality small-sized PbSe colloidal nanocrystals for photovoltaic applications.

Small-sized PbSe nanocrystals (NCs) were synthesized at low temperature such as 50-80 °C with high reaction yield (up to 100%), high quality, and high synthetic reproducibility, via a noninjection-based one-pot approach. These small-sized PbSe NCs with their first excitonic absorption in wavelength shorter than 1200 nm (corresponding to size < ∼3.7 nm) were developed for photovoltaic applications requiring a large quantity of materials. These colloidal PbSe NCs, also called quantum dots, are high-quality, in terms of narrow size distribution with a typical standard deviation of ∼7-9%, excellent optical properties with high quantum yield of ∼50-90% and small full width at half-maximum of ∼130-150 nm of their band-gap photoemission peaks, and high storage stability. Our synthetic design aimed at promotion of the formation of PbSe monomers for fast and sizable nucleation with the presence of a large number of nuclei at low temperature. For formation of the PbSe monomer, our low-temperature approach suggests the existence of two pathways of Pb-Se (route a) and Pb-P (route b) complexes. Either pathway may dominate, depending on the method used and its experimental conditions. Experimentally, a reducing/nucleation agent, diphenylphosphine, was added to enhance route b. The present study addresses two challenging issues in the NC community, the monomer formation mechanism and the reproducible syntheses of small-sized NCs with high yield and high quality and large-scale capability, bringing insight to the fundamental understanding of optimization of the NC yield and quality via control of the precursor complex reactivity and thus nucleation/growth. Such advances in colloidal science should, in turn, promote the development of next-generation low-cost and high-efficiency solar cells. Schottky-type solar cells using our PbSe NCs as the active material have achieved the highest power conversion efficiency of 2.82%, in comparison with the same type of solar cells using other PbSe NCs, under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm(2).

Low-temperature noninjection approach to homogeneously-alloyed PbSe(x)S(1-x) colloidal nanocrystals for photovoltaic applications.

Homogeneously alloyed PbSe(x)S(1-x) nanocrystals (NCs) with their excitonic absorption peaks in wavelength shorter than 1200 nm were developed for photovoltaic (PV) applications. Schottky-type solar cells fabricated with our PbSe₀.₃S₀.₇ NCs as their active materials reached a high power conversion efficiency (PCE) of 3.44%, with an open circuit voltage (V(oc)) of 0.49 V, short circuit photocurrent (J(sc)) of 13.09 mA/cm², and fill factor (FF) of 0.54 under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm². The syntheses of the small-sized colloidal PbSe(x)S(1-x) NCs were carried out at low temperature (60 °C) with long growth periods (such as 45 min) via a one-pot noninjection-based approach in 1-octadecene (ODE), featuring high reaction yield, high product quality, and high synthetic reproducibility. This low-temperature approach employed Pb(oleate)₂ as a Pb precursor and air-stable low-cost thioacetamide (TAA) as a S source instead of air-sensitive high-cost bis(trimethylsilyl)sulfide ((TMS)₂S), with n-tributylphosphine selenide (TBPSe) as a Se precursor instead of n-trioctylphosphine selenide (TOPSe). The reactivity difference of TOPSe made from commercial TOP 90% and TBPSe made from commercial TBP 97% and TBP 99% was addressed with in situ observation of the temporal evolution of NC absorption and with ³¹P nuclear magnetic resonance (NMR). Furthermore, the addition of a strong reducing/nucleation agent diphenylphosphine (DPP) promoted the reactivity of the Pb precursor through the formation of a Pb-P complex, which is much more reactive than Pb(oleate)₂. Thus, the reactivity of TBPSe was increased more than that of TAA. The larger the DPP-to-Pb feed molar ratio, the more the Pb-P complex, the higher the Se amount in the resulting homogeneously alloyed PbSe(x)S(1-x) NCs. Therefore, the use of DPP allowed reactivity match of the Se and S precursors and led to sizable nucleation at low temperature so that long growth periods became feasible. The present study brings insight into the formation mechanism of monomers, nucleation/growth of colloidal composition-tunable NCs, and materials design and synthesis for next-generation low-cost and high-efficiency solar cells.

Highly-photoluminescent ZnSe nanocrystals via a non-injection-based approach with precursor reactivity elevated by a secondary phosphine.

Highly-photoluminescent ZnSe quantum dots with 72% quantum yield and 22 nm full width at half maximum were synthesized with more reactive precursors via a non-injection approach with high synthetic reproducibility; (31)P NMR provided insight into the formation mechanisms of ZnSe monomers.

Issues, considerations and recommendations on emergency preparedness for vulnerable population groups

The Workshop on Emergency Preparedness for Vulnerable Population Groups was held on 2 and 3 March 2009 in Ottawa, ON, Canada. The purpose of the workshop was to enhance communications within the emergency community response network and to identify the needs and gaps of emergency preparedness against chemical, biological, radiological, nuclear and explosives events for vulnerable population groups. The workshop was organised to enable extensive round-table discussions and provide a summary of key issues, considerations and recommendations for emergency response planners.

Metabolism of 210Po in rats: volatile 210Po in excreta

Polonium-210 ((210)Po) is one of the most toxic radionuclides and was used as a poison in the Alexander Litvinenko case. In this study of the metabolism of (210)Po in rats, volatile (210)Po in excreta was measured, filling a knowledge gap of the previous studies. Five rats were intravenously administrated with 2 kBq and another five with 10 kBq of (210)Po (citrate form). They were housed in a glass Metabowl system for 4 d following the administration. Volatile (210)Po from the excreta was collected in a trapping system filled with liquid scintillation cocktail and was measured by liquid scintillation counting. Results showed that the daily excretion of volatile (210)Po by the rats is in a very small percentage (0.002-0.009 %) of the administered amounts. However, if the administered amount is large, the excretion of volatile (210)Po can be significant.

Using biometrics and active RFID to improve security and safety in mass casualty management

In a mass casualty incident, it is necessary to control the access to the incident-site to maintain site security and to obtain accurate and real-time incident data. Currently, first responders are identified by their badges and/or uniforms, and may need to on-scene-triage patients using a tag-classification system. Potential security and safety problems may develop because the badges could be duplicated or cloned, uniforms could be found at thrift stores, and the paper tags may have limitations in preserving information during documentation. In this paper, we present a combined approach that uses biometric technology to verify the identity of first responders and radio frequency identification (RFID) technology to assist in triage of mass casualty victims. In contrast to other proposals that recommend smart cards to carry biometric data and use passive RFID tags as triage tags; we propose using active RFID wristband to perform both verification and triage functions.

Method for imaging quantum dots during exposure to gamma radiation

Quantum dots have been used in a wide variety of biomedical applications. A key advantage of these particles is that their optical properties depend predictably on size, which enables tuning of the emission wavelength. Recently, it was found that CdSe/ZnS quantum dots lose their ability to photoluminescence after exposure to gamma radiation (J. Phys. Chem. C., 113: 2580-2585 (2009). A method for readout of the loss of quantum dot photoluminescence during exposure to radiation could enable a multitude of real-time dosimetry applications. Here, we report on a method to image photoluminescence from quantum dots from a distance and under ambient lighting conditions. The approach was to construct and test a time-gated imaging system that incorporated pulsed illumination. The system was constructed from a pulsed green laser (Nd:YAG, 20 pulses/s, 5 ns pulse duration, ~5 mJ/pulse), a time-gated camera (LaVision Picostar, 2 ns gate width), and optical components to enable coaxial illumination and imaging. Using the system to image samples of equivalent concentration to the previous end-point work, quantum dot photoluminescence was measureable under ambient room lighting at a distance of 25 cm from the sample with a signal to background of 7.5:1. Continuous exposure of samples to pulsed laser produced no measureable loss of photoluminescence over a time period of one hour. With improvements to the light collection optics the range of the system is expected to increase to several metres, which will enable imaging of samples during exposure to a gamma radiation source.

Medical preparedness for chemical, biological, radiological, nuclear, and explosives (CBRNE) events: gaps and recommendations

The Workshop on Medical Preparedness for Chemical, Biological, Radiological, Nuclear, and Explosives (CBRNE) events: national scan was held on 20 and 21 May 2010 at the Diefenbunker Museum in Ottawa, Canada. The purpose of the workshop was to provide the CBRNE Research and Technology Initiative with a Canadian national profile of existing capabilities and anticipated gaps in casualty management consistent with the community emergency response requirements. The workshop was organised to enable extensive round-table discussions and provide a summary of key gaps and recommendations for emergency response planners.

Use of a dual-labelled oligonucleotide as a DNA dosemeter for radiological exposure detection.

A reporter molecule consisting of a synthetic oligonucleotide is being characterised for a novel damage detection scenario for its potential use as a field-deployable, personal deoxyribonucleic acid (DNA) dosemeter for radiation detection. This dosemeter is devoid of any biological properties other than being naked DNA and therefore has no DNA repair capabilities. It supports biodosimetry techniques, which require lengthy analysis of cells from irradiated individuals, and improves upon inorganic dosimetry, thereby providing for a more relevant means of measuring the accumulated dose from a potentially mixed-radiation field. Radiation-induced single strand breaks (SSBs) within the DNA result in a quantifiable fluorescent signal. Proof of concept has been achieved over 250 mGy-10 Gy dose range in radiation fields from ⁶⁰Co, with similar results seen using a linear accelerator X-ray source. Further refinements to both the molecule and the exposure/detection platform are expected to lead to enhanced levels of detection for mixed-field radiological events.

Acellular comet assay: a tool for assessing variables influencing the alkaline comet assay

In this study, an acellular modification to the alkaline comet assay to further evaluate key variables within the assay that may influence the outcome of genotoxicity studies is described. This acellular comet assay can detect differences of 0.2 Gy of (60)Co gamma-ray radiation between 0 and 1 Gy and differences of 1 Gy between 0 and 8 Gy; thus, this assay is applicable for a wide range of DNA damage levels. It is also shown that DNA damage from different radiation energies was not significantly different from (60)Co gamma-ray. This assay displayed a statistical increase in DNA damage due to uncontrolled exposure to natural light; however, the slope of the dose-response curve for light-exposed samples was similar to that for samples protected from light. A comparison of the alkaline comet assay with the acellular comet assay allowed for the intrinsic repair capacity of the alkaline comet assay to be quantified.