Thomas D. Durbin

Atomic layer epitaxy of silicon by dichlorosilane studied with core level spectroscopy

The chemisorption and reaction of dichlorosilane (SiH2Cl2) with Si(111) and Si(100) surfaces is investigated with core‐level soft x‐ray photoelectron spectroscopy employing synchrotron radiation, in order to ascertain the surface chemistry involved in atomic layer epitaxy (ALE). Exposures to 8 kL of SiH2Cl2 were performed as a function of sample temperature in the range from room temperature to 800 °C. At all temperatures, SiH2Cl2 chemisorbs dissociatively forming silicon monochloride surface species. The coverage of monochloride displays a maximum for exposures at ∼600 °C. Under all conditions studied, larger chlorine coverages are observed on Si(100) than on Si(111). A Si surface that was first saturated with SiH2Cl2 at 600 °C was subsequently exposed to H2 at 600 °C, and no reaction occurred. These results indicate that recent models for silicon ALE are incorrect. An alternative method for low‐temperature ALE of Si is proposed, in which SiH2Cl2 is adsorbed onto Si at 600 °C and Cl is removed via reaction with atomic H.

Evaluation of the European PMP Methodologies during On-Road and Chassis Dynamometer Testing for DPF Equipped Heavy-Duty Diesel Vehicles

This study evaluated the UN-ECE Particle Measurement Programme (PMP) protocol for the measurement of solid particle number emissions under laboratory and on-road conditions for two passive diesel particle filters (DPF)–equipped medium and heavy-heavy duty diesel vehicles. The PMP number emissions were lower than the European light-duty certification value (9.6 × 1011 #/mi) for all standardized cycles, but exceeded this value during some higher load on-road driving conditions. Particle number measurements were generally less variable than those of the PM mass for the on-road testing, but had comparable or greater variability than PM mass for the laboratory measurements due to outliers. These outliers appear to be real events that are not apparent with integrated filter methods. The particle number measurements for the low cut point CPCs (3–7 nm) below the PMP system were approximately an order of magnitude higher than those for the PMP-compliant CPC (23 nm), indicating the presence of a large fraction of solid sub-23 nm particles. Although such particles are defined as solid by the PMP method, their actual state is unknown. Nucleation particles with a large sulfate contribution formed under a variety of conditions when the exhaust temperature near the DPF exceeded a “critical” temperature, typically >300°C.

Evaluation of the Impacts of Biodiesel and Second Generation Biofuels on NOx Emissions for CARB Diesel Fuels

The impact of biodiesel and second generation biofuels on nitrogen oxides (NO(x)) emissions from heavy-duty engines was investigated using a California Air Resources Board (CARB) certified diesel fuel. Two heavy-duty engines, a 2006 engine with no exhaust aftertreatment, and a 2007 engine with a diesel particle filter (DPF), were tested on an engine dynamometer over four different test cycles. Emissions from soy- and animal-based biodiesels, a hydrotreated renewable diesel, and a gas to liquid (GTL) fuel were evaluated at blend levels from 5 to 100%. NO(x) emissions consistently increased with increasing biodiesel blend level, while increasing renewable diesel and GTL blends showed NO(x) emissions reductions with blend level. NO(x) increases ranged from 1.5% to 6.9% for B20, 6.4% to 18.2% for B50, and 14.1% to 47.1% for B100. The soy-biodiesel showed higher NO(x) emissions increases compared to the animal-biodiesel. NO(x) emissions neutrality with the CARB diesel was achieved by blending GTL or renewable diesel fuels with various levels of biodiesel or by using di-tert-butyl peroxide (DTBP). It appears that the impact of biodiesel on NO(x) emissions might be a more important consideration when blended with CARB diesel or similar fuels, and that some form of NO(x) mitigation might be needed for biodiesel blends with such fuels.

Stimulated desorption of Cl+ and the chemisorption of Cl2 on Si(111)-7×7 and Si(100)-2×1

The chemisorption of Cl2 on Si(111)-7 × 7 and Si(100)-2 × 1 and the mechanism for stimulated desorption of Cl+ from Si are studied with soft X-ray photoelectron spectroscopy (SXPS) and photon-stimulated desorption (PSD). It is shown that Cl2 interacts with Si(111)-7 × 7 at room temperature to form mono-, di- and tri-chlorides, while primarily monochlorides are formed on Si(100)-2 × 1. These differences are explained in terms of the reconstructions of each clean surface. The stimulated desorption of Cl+ ions has a threshold at ~ 20 eV that results from a direct excitation of a Cl 3s electron to an unoccupied Cl antibonding level. No direct desorption of Cl+ ions is observed at the Si 2p edge. Differences between the mechanisms for F+ and Cl+ desorption from Si are discussed.

Nature of Sub-23-nm Particles Downstream of the European Particle Measurement Programme (PMP)-Compliant System: A Real-Time Data Perspective

This study provides an evaluation of the nature of sub-23-nm particles downstream of the European Particulate Measurement Programme (PMP) methodology, with prescribed cycles and on-road flow-of-traffic driving conditions. Particle number concentrations and size distributions were measured using two PMP measurement systems running simultaneously. For this analysis, the focus is on the real-time results from multiple instruments. The results revealed that a significant fraction of particles downstream of both PMP systems for all tested cycles were below 11 nm. The fraction of sub-11-nm particles observed downstream of the PMP system decreased when the overall dilution ratio of one PMP system was increased from 300 to 1500, suggesting those sub-11-nm particles were formed through re-nucleation of semivolatile precursors. When the evaporation tube temperature was increased from 300°C to 500°C, no difference in particle number concentrations was observed, suggesting that incomplete evaporation of semivolatile particles did not contribute to those sub-11-nm particles. Particle emissions were about one order of magnitude higher during flow-of-traffic driving along a highway with a steep grade than during the prescribed driving cycles. During the same flow-of-traffic condition, a sudden jump in PMP operationally defined solid particle concentration was observed, while the accumulation mode particle concentrations in the constant volume sampling (CVS) tunnel measured by an engine exhaust particle sizer (EEPS) only showed a slight increase. This discrepancy was attributed to the extensive growth of the re-nucleated particles downstream of the PMP systems. Copyright 2012 American Association for Aerosol Research

Determination of Suspended Exhaust PM Mass for Light-Duty Vehicles

This study provides one of the first evaluations of the integrated particle size distribution (IPSD) method in comparison with the current gravimetric method for measuring particulate matter (PM) emissions from light-duty vehicles. The IPSD method combines particle size distributions with size dependent particle effective density to determine mass concentrations of suspended particles. The method allows for simultaneous determination of particle mass, particle surface area, and particle number concentrations. It will provide a greater understanding of PM mass emissions at low levels, and therefore has the potential to complement the current gravimetric method at low PM emission levels. Six vehicles, including three gasoline direct injected (GDI) vehicles, two port fuel injected (PFI) vehicles, and one diesel vehicle, were tested over the Federal Test Procedure (FTP) driving cycle on a light-duty chassis dynamometer. PM mass emissions were determined by the gravimetric (MGravimetric) and IPSD (MIPSD) methods. The results show a systematic bias between methods, with the MIPSD underestimating particle mass relative to MGravimetric (MIPSD = 0.63 × MGravimetric), although there is a relatively strong correlation (R2=0.79) between the methods. The real-time MIPSD showed that more than 55% of the PM mass comes from the first 100 seconds of the FTP for GDI vehicles.

Evaluating the Effects of Aromatics Content in Gasoline on Gaseous and Particulate Matter Emissions from SI-PFI and SIDI Vehicles.

We assessed the emissions response of a fleet of seven light-duty gasoline vehicles for gasoline fuel aromatic content while operating over the LA92 driving cycle. The test fleet consisted of model year 2012 vehicles equipped with spark-ignition (SI) and either port fuel injection (PFI) or direct injection (DI) technology. Three gasoline fuels were blended to meet a range of total aromatics targets (15%, 25%, and 35% by volume) while holding other fuel properties relatively constant within specified ranges, and a fourth fuel was formulated to meet a 35% by volume total aromatics target but with a higher octane number. Our results showed statistically significant increases in carbon monoxide, nonmethane hydrocarbon, particulate matter (PM) mass, particle number, and black carbon emissions with increasing aromatics content for all seven vehicles tested. Only one vehicle showed a statistically significant increase in total hydrocarbon emissions. The monoaromatic hydrocarbon species that were evaluated showed increases with increasing aromatic content in the fuel. Changes in fuel composition had no statistically significant effect on the emissions of nitrogen oxides (NOx), formaldehyde, or acetaldehyde. A good correlation was also found between the PM index and PM mass and number emissions for all vehicle/fuel combinations with the total aromatics group being a significant contributor to the total PM index followed by naphthalenes and indenes.

Population Density, Particulate Emission Characterization, and Impact on the Particulate Inventory of Smoking Vehicles in the South Coast Air Quality Management District

The impact of high-particulate-emission vehicles on the total light-duty vehicle particulate emission inventory in the South Coast Air Quality Management District (SCAQMD) has been estimated by an analysis of the SCAQMDs CUT-SMOG database, a field survey of smoking vehicles, and particulate emissions testing of representative smoking vehicles. The field study, carried out at 61 sites throughout the SCAQMD, showed that 1.11%-1.75% of the vehicles in the light-duty fleet emit visible smoke. This fleet of smoking vehicles is composed mainly of older vehicles, 8 to 18 years of age. Particulate emission testing of 23 smoking vehicles gave an average Federal Test Procedure (FTP) weighted emission rate of 399 mg/mi with a range of 64-2,323 mg/mi, while the average IM240 emission rate was 346 mg/mi, with a range from 13-1,807 mg/mi. The contribution of light-duty smoking vehicles to the particulate emissions inventory in the SCAQMD is estimated to be 0.51-0.81 tons per day.

Assessing the Impacts of Ethanol and Isobutanol on Gaseous and Particulate Emissions from Flexible Fuel Vehicles

This study investigated the effects of higher ethanol blends and an isobutanol blend on the criteria emissions, fuel economy, gaseous toxic pollutants, and particulate emissions from two flexible-fuel vehicles equipped with spark ignition engines, with one wall-guided direct injection and one port fuel injection configuration. Both vehicles were tested over triplicate Federal Test Procedure (FTP) and Unified Cycles (UC) using a chassis dynamometer. Emissions of nonmethane hydrocarbons (NMHC) and carbon monoxide (CO) showed some statistically significant reductions with higher alcohol fuels, while total hydrocarbons (THC) and nitrogen oxides (NOx) did not show strong fuel effects. Acetaldehyde emissions exhibited sharp increases with higher ethanol blends for both vehicles, whereas butyraldehyde emissions showed higher emissions for the butanol blend relative to the ethanol blends at a statistically significant level. Particulate matter (PM) mass, number, and soot mass emissions showed strong reductions with increasing alcohol content in gasoline. Particulate emissions were found to be clearly influenced by certain fuel parameters including oxygen content, hydrogen content, and aromatics content.

Comparison of Vehicle Exhaust Particle Size Distributions Measured by SMPS and EEPS During Steady-State Conditions

Fast-sizing spectrometers, such as the TSI Engine Exhaust Particle Sizer (EEPS), have been widely used to measure transient particle size distributions of vehicle exhaust. Recently, size distributions measured during different test cycles have begun to be used for calculating suspended particulate mass; however, several recent evaluations have shown some deficiencies in this approach and discrepancies relative to the gravimetric reference method. The EEPS converts electrical charge carried by particles into size distributions based on mobility classification and a specific calibration, and TSI recently released a matrix optimized for vehicle emissions as described by Wang et al. (Submitteda). This study evaluates the performance of the new matrix (soot matrix) relative to the original matrix (default matrix) and reference size distributions measured by a scanning mobility particle sizer (SMPS). Steady-state particle size distributions were generated from the following five sources to evaluate exhaust particulates with various morphologies estimated by mass-mobility scaling exponent: (1) A diesel generator operating on ultralow sulfur diesel, (2) a diesel generator operating on biodiesel, (3) a gasoline direct-injection vehicle operating at two speeds, (4) a conventional port-fuel injection gasoline vehicle, and (4) a light-duty diesel (LDD) vehicle equipped with a diesel particulate filter. Generally, the new soot matrix achieved much better agreement with the SMPS reference for particles smaller than 30 nm and larger than 100 nm, and also broadened the accumulation mode distribution that was previously too narrow using the default matrix. However, EEPS distributions still did not agree with SMPS reference measurements when challenged by a strong nucleation mode during high-load operation of the LDD vehicle. This work quantifies the range of accuracy that can be expected when measuring particle size distribution, number concentration, and integrated particle mass of vehicle emissions when using the new static calibration derived based on the properties of classical diesel soot. Copyright 2015 American Association for Aerosol Research