Nanoscale electronic properties of conjugated polymers and nanocrystals

The objective of this thesis is the exploration and characterisation of the nanoscale electronic properties of conjugated polymers and nanocrystals. In Chapter 2, the first application of conducting-probe atomic force microscopy (CP-AFM)-based displacement-voltage (z-V) spectroscopy to local measurement of electronic properties of conjugated polymer thin films is reported. Charge injection thresholds along with corresponding single particle gap and exciton binding energies are determined for a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] thin film. By performing measurements across a grid of locations on the film, a series of exciton binding energy distributions are identified. The variation in measured exciton binding energies is in contrast to the smoothness of the film suggesting that the variation may be attributable to differences in the nano-environment of the polymer molecules within the film at each measurement location. In Chapter 3, the CP-AFM-based z-V spectroscopy method is extended for the first time to local, room temperature measurements of the Coulomb blockade voltage thresholds arising from sequential single electron charging of 28 kDa Au nanocrystal arrays. The fluid-like properties of the nanocrystal arrays enable reproducible formation of nanoscale probe-array-substrate junctions, allowing the influence of background charge on the electronic properties of the array to be identified. CP-AFM also allows complementary topography and phase data to be acquired before and after spectroscopy measurements, enabling comparison of local array morphology with local measurements of the Coulomb blockade thresholds. In Chapter 4, melt-assisted template wetting is applied for the first time to massively parallel fabrication of poly-(3-hexylthiophene) nanowires. The structural characteristics of the wires are first presented. Two-terminal electrical measurements of individual nanowires, utilising a CP-AFM tip as the source electrode, are then used to obtain the intrinsic nanowire resistivity and the total nanowire-electrode contact resistance subsequently allowing single nanowire hole mobility and mean nanowire-electrode barrier height values to be estimated. In Chapter 5, solution-assisted template wetting is used for fabrication of fluorene-dithiophene co-polymer nanowires. The structural characteristics of these wires are also presented. Two-terminal electrical measurements of individual nanowires indicate barrier formation at the nanowire-electrode interfaces and measured resistivity values suggest doping of the nanowires, possibly due to air exposure. The first report of single conjugated polymer nanowires as ultra-miniature photodetectors is presented, with single wire devices yielding external quantum efficiencies ~ 0.1 % and responsivities ~ 0.4 mA/W under monochromatic illumination.

Quantifying data quality for clinical trials using electronic data capture.

BACKGROUND: Historically, only partial assessments of data quality have been performed in clinical trials, for which the most common method of measuring database error rates has been to compare the case report form (CRF) to database entries and count discrepancies. Importantly, errors arising from medical record abstraction and transcription are rarely evaluated as part of such quality assessments. Electronic Data Capture (EDC) technology has had a further impact, as paper CRFs typically leveraged for quality measurement are not used in EDC processes. METHODS AND PRINCIPAL FINDINGS: The National Institute on Drug Abuse Treatment Clinical Trials Network has developed, implemented, and evaluated methodology for holistically assessing data quality on EDC trials. We characterize the average source-to-database error rate (14.3 errors per 10,000 fields) for the first year of use of the new evaluation method. This error rate was significantly lower than the average of published error rates for source-to-database audits, and was similar to CRF-to-database error rates reported in the published literature. We attribute this largely to an absence of medical record abstraction on the trials we examined, and to an outpatient setting characterized by less acute patient conditions. CONCLUSIONS: Historically, medical record abstraction is the most significant source of error by an order of magnitude, and should be measured and managed during the course of clinical trials. Source-to-database error rates are highly dependent on the amount of structured data collection in the clinical setting and on the complexity of the medical record, dependencies that should be considered when developing data quality benchmarks.

Investigation into the performance of turbulence models for fluid flow and heat transfer phenomena in electronic applications

Computational Fluid Dynamics (CFD) is gradually becoming a powerful and almost essential tool for the design, development and optimization of engineering applications. However the mathematical modelling of the erratic turbulent motion remains the key issue when tackling such flow phenomena. The reliability of CFD analysis depends heavily on the turbulence model employed together with the wall functions implemented. In order to resolve the abrupt changes in the turbulent energy and other parameters situated at near wall regions a particularly fine mesh is necessary which inevitably increases the computer storage and run-time requirements. Turbulence modelling can be considered to be one of the three key elements in CFD. Precise mathematical theories have evolved for the other two key elements, grid generation and algorithm development. The principal objective of turbulence modelling is to enhance computational procedures of efficient accuracy to reproduce the main structures of three dimensional fluid flows. The flow within an electronic system can be characterized as being in a transitional state due to the low velocities and relatively small dimensions encountered. This paper presents simulated CFD results for an investigation into the predictive capability of turbulence models when considering both fluid flow and heat transfer phenomena. Also a new two-layer hybrid kε / kl turbulence model for electronic application areas will be presented which holds the advantages of being cheap in terms of the computational mesh required and is also economical with regards to run-time.

Temperature measurement in children with cancer: an evaluation

There is little agreement as to the most appropriate thermometer, the anatomical site to carry out temperature measurement in children with cancer, or the type of thermometer preferred by the patients. The authors carried out this study to assess temperature measurement in children with cancer who were admitted for febrile episodes. The body temperatures of children with cancer who were admitted consecutively between January and October 2005 to the paediatric department because of febrile episodes were measured on admission and over the next 24–36 hours using an electronic thermometer sublingually as the standard reference site. These measurements were compared with those obtained with two ear-based thermometers, a forehead thermometer, and from the axilla (representing current practice). The parents were asked about the type of thermometer they used at home and the children were asked about the type of thermometer they preferred. There were 34 admissions during this period, of which 19 (56%) were confirmed as febrile. Altogether, 108 sets of temperature measurements were obtained, producing a total of 540 measurements from these admissions. Measurements with the two ear-based thermometers in febrile children achieved higher sensitivity than that with axillary and the forehead measurements. The ear-based thermometer was the most common type used at home while the forehead thermometer was the one preferred by the children. In conclusion, ear-based temperature measurements in febrile children were more accurate than axillary and forehead temperature measurements. The current practice of axillary temperature measurement needs to be re-considered.

Fast Response Exhaust Gas Temperature Measurement in IC Engines

The harsh environment presented by engines, particularly in the exhaust systems, often necessitates the use of robust and therefore low bandwidth temperature sensors. Consequently, high frequencies are attenuated in the output. One technique for addressing this problem involves measuring the gas temperature using two sensors with different time-constants and mathematically reconstructing the true gas temperature from the resulting signals. Such a technique has been applied in gas turbine, rocket motor and combustion research. A new reconstruction technique based on difference equations has been developed and its effectiveness proven theoretically. The algorithms have been successfully tested and proven on experimental data from a rig that produces cyclic temperature variations. These tests highlighted that the separation of the thermocouple junctions must be very small to ensure that both sensors are subjected to the same gas temperatures. Exhaust gas temperatures were recorded by an array of thermocouples during transient operation of a high performance two-stroke engine. The results show that the increase in bandwidth arising from the dual sensor technique allowed accurate measurement of exhaust gas temperature with relatively robust thermocouples. Finally, an array of very fine thermocouples (12.5 - 50 microns) was used to measure the in-cycle temperature variation in the exhaust.

Fairness measurement for adaptive packet schedulers

An equation is presented for calculating the fairness of dynamically adaptive packet schedulers such as dynamic weighted fair queuing (DWFQ). The fairness of static packet schedulers such as weighted fair queue (WFQ) can be found using the widely accepted Worst-case Fair Index. The fairness of DWFQ can be measured using an Adapted Worst-case Fairness Index (AWFI). The AWFI enables a direct comparison of fairness properties of the DWFQ or other dynamically adaptive schedulers with static/non-adaptive schedulers.

Measurement of Quenching Coefficients and Developement of Calibration Methods for Quantitative Spectroscopy of Plasma at Elevated Pressures

Measurements of collisional de-excitation (quenching) coefficients required for the interpretation of emission and fluorescence spectroscopic measurements are reported. Particular attention is turned on argon transitions which are of interest for actinometric determinations of atomic ground state populations and on fluorescence lines originating from excited atoms and noble gases in connection with two-photon excitation (TALIF) of atomic radicals. A novel method is described which allows to infer quenching coefficients for collisions with molecular hydrogen of noble gas states in the energy range up to 24 eV. The excitation is performed in these experiments by collisions of energetic electrons in the sheath of an RF excited hydrogen plasma during the field reversal phase which lasts about 10 ns. We describe in addition a calibration method - including quenching effects - for the determination by TALIF of absolute atomic radical densities of hydrogen, nitrogen and oxygen using two-photon resonances in noble gases close by the resonances of the species mentioned. The paper closes with first ideas on a novel technique to bypass quenching effects in TALIF by introducing an additional, controllable loss by photoionization that will allow quenching-free determination of absolute atomic densities with prevalent nanosecond laser systems in situations where collisional de-excitation dominates over spontaneous emission.

In situ measurement of UHF wearable antenna radiation efficiency using a reverberation chamber

The radiation efficiency and resonance frequency of five compact antennas worn by nine individual test subjects was measured at 2.45 GHz in a reverberation chamber. The results show that, despite significant differences in body mass, wearable antenna radiation efficiency had a standard deviation less than 0.6 dB and the resonance frequency shift was less than 1% between test subjects. Variability in the radiation efficiency and resonance frequency shift between antennas was largely dependant on body tissue coupling which is related to both antenna geometry and radiation characteristics. The reverberation chamber measurements were validated using a synthetic tissue phantom and compared with results obtained in a spherical near field chamber and finite-difference time-domain (FDTD) simulation.

Thermal conductivity measurement of liquids in a microfluidic device

A new microfluidic-based approach to measuring liquid thermal conductivity is developed to address the requirement in many practical applications for measurements using small (microlitre) sample size and integration into a compact device. The approach also gives the possibility of high-throughput testing. A resistance heater and temperature sensor are incorporated into a glass microfluidic chip to allow transmission and detection of a planar thermal wave crossing a thin layer of the sample. The device is designed so that heat transfer is locally one-dimensional during a short initial time period. This allows the detected temperature transient to be separated into two distinct components: a short-time, purely one-dimensional part from which sample thermal conductivity can be determined and a remaining long-time part containing the effects of three-dimensionality and of the finite size of surrounding thermal reservoirs. Identification of the one-dimensional component yields a steady temperature difference from which sample thermal conductivity can be determined. Calibration is required to give correct representation of changing heater resistance, system layer thicknesses and solid material thermal conductivities with temperature. In this preliminary study, methanol/water mixtures are measured at atmospheric pressure over the temperature range 30-50A degrees C. The results show that the device has produced a measurement accuracy of within 2.5% over the range of thermal conductivity and temperature of the tests. A relation between measurement uncertainty and the geometric and thermal properties of the system is derived and this is used to identify ways that error could be further reduced.

The synthesis and electronic structure of a novel [NiS4Fe2(CO)(6)] radical cluster: Implications for the active site of the [NiFe] hydrogenases

A novel [Ni'S-4'Fe-2(CO)(6)] cluster (1: 'S-4'=(CH3C6H3S2)(2)(CH2)(3)) has been synthesised, structurally characterised and has been shown to undergo a chemically reversible reduction process at -1.31 V versus Fc(+)/Fc to generate the EPR-active monoanion 1(-). Multifrequency Q-, X- and S-band EPR spectra of Ni-61-enriched 1(-) show a well-resolved quartet hyperfine splitting in the low-field region due to the interaction with a single Ni-61 (I = 3/2) nucleus. Simulations of the EPR spectra require the introduction of a single angle of non-coincidence between g, and A(1), and g(3) and A(3) to reproduce all of the features in the S- and X-band spectra. This behaviour provides a rare example of the detection and measurement of non-coincidence effects from frozen-solution EPR spectra without the need for single-crystal measurements, and in which the S-band experiment is sensitive to the non-coincidence. An analysis of the EPR spectra of 1(-) reveals a 24% Ni contribution to the SOMO in 1(-), supporting a delocalisation of the spin-density across the NiFe2 cluster. This observation is supported by IR spectroscopic results which show that the CO stretching frequencies, v(CO), shift to lower frequency by about 70 cm(-1) when 1 is reduced to 1(-). Density functional calculations provide a framework for the interpretation of the spectroscopic properties of 1(-) and suggest that the SOMO is delocalised over the whole cluster, but with little S-centre participation. This electronic structure contrasts with that of the Ni-A, -B, -C and -L forms of [NiFe] hydrogenase in which there is considerable S participation in the SOMO.

Determining relative rates of cellulose dissolution in ionic liquids through in situ viscosity measurement

Using in situ viscosity measurement, the rate of cellulose dissolution in a number of ionic liquids has been determined allowing their performance as solvents to be quantitatively assessed. 1-Butyl-3-methylimidazolium ethanoate was shown to dissolve cellulose faster than analogous ionic liquids with chloride or dimethylphosphate anions. Analysis of the data highlights the influence of both anion basicity and relative concentration on the rate of dissolution.

Measurement of the full stress tensor in a crystal using photoluminescence from point defects: The example of nitrogen vacancy centers in diamond

We introduce a method for measuring the full stress tensor in a crystal utilising the properties of individual point defects. By measuring the perturbation to the electronic states of three point defects with C 3 v symmetry in a cubic crystal, sufficient information is obtained to construct all six independent components of the symmetric stress tensor. We demonstrate the method using photoluminescence from nitrogen-vacancy colour centers in diamond. The method breaks the inverse relationship between spatial resolution and sensitivity that is inherent to existing bulk strain measurement techniques, and thus, offers a route to nanoscale strain mapping in diamond and other materials in which individual point defects can be interrogated.

Optical measurement of the temporal delay between two ultra-short and focussed laser pluses

Temporal overlapping of ultra-short and focussed laser pulses is a particularly challenging task, as this timescale lies orders of magnitude below the typical range of fast electronic devices. Here we present an optical technique that allows for the measurement of the temporal delay between two focussed and ultra-short laser pulses. This method is virtually applicable to any focussing geometry and relative intensity of the two lasers. Experimental implementation of this technique provides excellent quantitative agreement with theoretical expectations. The proposed technique will prove highly beneficial for high-power multiple-beam laser experiments.

Systematic Review of the Measurement Properties of Tools Used to Measure Behaviour Problems in Young Children with Autism

Background
Behaviour problems are common in young children with autism spectrum disorder (ASD). There are many different tools used to measure behavior problems but little is known about their validity for the population.

Objectives
To evaluate the measurement properties of behaviour problems tools used in evaluation of intervention or observational research studies with children with ASD up to the age of six years.

Methods
Behaviour measurement tools were identified as part of a larger, two stage, systematic review. First, sixteen major electronic databases, as well as grey literature and research registers were searched, and tools used listed and categorized. Second, using methodological filters, we searched for articles examining the measurement properties of the tools in use with young children with ASD in ERIC, MEDLINE, EMBASE, CINAHL, and PsycINFO. The quality of these papers was then evaluated using the COSMIN checklist.

Results
We identified twelve tools which had been used to measure behaviour problems in young children with ASD, and fifteen studies which investigated the measurement properties of six of these tools. There was no evidence available for the remaining six tools. Two questionnaires were found to be the most robust in their measurement properties, the Child Behavior Checklist and the Home Situations Questionnaire—Pervasive Developmental Disorders version.

Conclusions
We found patchy evidence on reliability and validity, for only a few of the tools used to measure behaviour problems in young children with ASD. More systematic research is required on measurement properties of tools for use in this population, in particular to establish responsiveness to change which is essential in measurement of outcomes of intervention.

PROSPERO Registration Number

CRD42012002223