This paper summarizes some of the essential aspects of silicon-nanowire growth and of their electrical properties. In the first part, a brief description of the different growth techniques is given, though the general focus of this work is on chemical vapor deposition of silicon nanowires. The advantages and disadvantages of the different catalyst materials for silicon-wire growth are discussed at length. Thereafter, in the second part, three thermodynamic aspects of silicon-wire growth via the vapor–liquid–solid mechanism are presented and discussed. These are the expansion of the base of epitaxially grown Si wires, a stability criterion regarding the surface tension of the catalyst droplet, and the consequences of the Gibbs–Thomson effect for the silicon wire growth velocity. The third part is dedicated to the electrical properties of silicon nanowires. First, different silicon nanowire doping techniques are discussed. Attention is then focused on the diameter dependence of dopant ionization and the influence of interface trap states on the charge carrier density in silicon nanowires. It is concluded by a section on charge carrier mobility and mobility measurements.

/pdf/silicon-nanowires-a-review-on-aspects-of-their-growth-and-20jrcf5p99.pdf

Silicon Nanowires: A Review on Aspects of their Growth and their Electrical Properties

2.4. Molecular Beam Epitaxy 366 2.5. Laser Ablation 367 2.6. Silicon Monoxide Evaporation 367 3. Catalyst Materials 368 3.1. Gold as Catalyst 368 3.2. Alternative Catalyst Materials 369 3.2.1. Type-A, Au-like Catalysts 370 3.2.2. Type-B, Low Si Solubility Catalysts 371 3.2.3. Type-C, Silicide Forming Catalysts 371 4. Crystallography 372 5. Heterostructures 373 6. Surface Induced Lowering of the Eutectic Temperature 375

/pdf/growth-thermodynamics-and-electrical-properties-of-silicon-4d1d5a5ree.pdf

Growth, thermodynamics, and electrical properties of silicon nanowires.

Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube, and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition-delay times. The influence of temperature, pressure, and mixture composition on ignition delay has been characterized. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated b...

https://hal.archives-ouvertes.fr/hal-00369809/document

An Experimental and Kinetic Modeling Study of the Oxidation of the Four Isomers of Butanol

Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition delay times. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated by comparison to the shock tube measurements. Reaction flux and sensitivity analysis indicate that the consumption of 1 butanol and iso-butanol, the most reactive isomers, takes place primarily by H-atom abstraction resulting in the formation of radicals, the decomposition of which yields highly reactive branching agents, H-atoms and OH radicals. Conversely, the consumption of tert butanol and 2-butanol, the least reactive isomers, takes place primarily via dehydration, resulting in the formation of alkenes, which lead to resonance stabilized radicals with very low reactivity. To our knowledge, the ignition delay measurements and oxidation mechanism presented here for 2-butanol, iso-butanol, and tert butanol are the first of their kind..

pdf/an-experimental-and-kinetic-modelling-study-of-the-oxidation-2ivw8kniul.pdf

An experimental and kinetic modelling study of the oxidation of the four isomers of butanol

A compendium of phase change enthalpies published in 2010 is updated to include the period 1880–2015. Phase change enthalpies including fusion, vaporization, and sublimation enthalpies are included for organic, organometallic, and a few inorganic compounds. Part 1 of this compendium includes organic compounds from C1 to C10. Part 2 of this compendium, to be published separately, will include organic and organometallic compounds from C11 to C192. Sufficient data are presently available to permit thermodynamic cycles to be constructed as an independent means of evaluating the reliability of the data. Temperature adjustments of phase change enthalpies from the temperature of measurement to the standard reference temperature, T = 298.15 K, and a protocol for doing so are briefly discussed.

Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C1-C10

Part I: Kinetic data for the static system silane pyrolysis (from 640–703 K, 60–400 torr) are presented. For conversion from 3–30%, first-order kinetics are obtained, with silane loss rates equal to half the hydrogen formation rates. At conversions greater than 40%, rate inhibition attributable to the back reaction of hydrogen with silylene occurs. Overall reaction rates are not surface sensitive, but disilane and trisilane yield maxima under some conditions are. A nonchain mechanism capable of describing quantitatively all stages of the silane pyrolysis is proposed. Post 1.0% initiation is both homogeneous (gas phase) and heterogeneous (on the walls), and reaction intermediates are silylenes and disilenes. Free radicals are not involved at any stage of the reaction. Rate data at high conversions and with added hydrogen provide kinetics for the addition of silylene to hydrogen [reaction (−1)1] relative to its addition to silane [reaction (2)]: k−1,/k2 = 10−0.65 × e−3200 cal/RT. With E2 = 1300 cal, this gives a high pressure activation energy for silylene insertion into hydrogen of E−1 = 8200 cal.



Part II: An analysis is made of each rate constant of the silane mechanism and the modeling results are compared with experimental results. Agreement is excellent. It is concluded that the dominant sink reaction for silylene intermediates is 1,2—H2 elimination from disilane (followed by Si2H4 polymerization and wall deposition). The model is in accord with slow isomerization between disilene and silylsilylene and near exclusive 1,2—H2 elimination from Si2H6. It is also concluded that disilene is about 10 kcal/mol more stable than silylsilylene and that the activation energy for isomerization of silylsilylene to disilene is greater than 26 kcal/mol.

Mechanism of the silane decomposition. I. Silane loss kinetics and rate inhibition by hydrogen. II. Modeling of the silane decomposition (all stages of reaction)

An examination of the product-catalyzed reaction of trimethylgallium with arsine

The homogeneous gas-phase thermal decomposition kinetics of germane have been measured in a single-pulse shock tube between 950 and 1060 K at pressures around 4000 torr. The initial decomposition is GeH4 GeH2 + H2 in its pressure-dependent regime, with log k = 13.83 ± 0.78 – 50,750 ± 3570 cal/2.303RT. RRKM calculations suggest that the high-pressure Arrhenius parameters are log k GeH4(M ∞) = 15.5 – 54,300 cal/2.303RT. Extrapolations to static system pyrolysis conditions (T ∼ 600 K, P ∼ 200 torr) give homogeneous reaction rates which are much slower than those observed, hence the static system pyrolysis of germane must be predominantly heterogeneous. Shock-initiated pyrolysis reaction stoichiometry is 2 mol H2 per mole GeH4, suggesting that the subsequent decomposition of germylene is essentially quantitative. Investigations of the hydrogen product yields for pyrolysis of GeD4 in oCH3 further indicate that the germylene decomposition reaction is mainly GeH2 H2 + Ge, but that a small amount of reaction to H atoms may also occur.

Kinetics and mechanism of the germane decomposition

The static system decomposition kinetics of disilane (, 538–587 K and 10–500 Torr), are reported. Reaction rate constants are weakly pressure dependent, and best fits of the data are realized with RRKM fall-off calculations using logA1,∞ = 15.75 and E1,∞ = 52,200 cal. These parameters yield AHf0(SiH2)298 = (63.5 − Eb, c) kcal mol,−1 where Eb, c is the activation energy for the back reaction at 550 K, M = 1 std state. Five other silylene heat-of-formation values (ranging from 63.9 – Eb, c to 66.0 - Eb, c kcal mol−1) are deduced from the reported decomposition kinetics of trisilane and methyldisilane, and from the reported absolute and relative rate constants for silylene insertions into H2 and SiH4. Assuming Eb, c = 0, an average value of ΔHf0(SiH2) = 64.3 ± 0.3 kcal mol−1 is obtained. Also, a recalculation of the activation energy for silylene insertion into H2, based in part on the new disilane decomposition Arrhenius parameters, gives (0.6 + Eb, c) kcal mol−1, in good agreement with theoretical calculations.

The decomposition kinetics of disilane and the heat of formation of silylene

The decomposition kinetics of disilane with added butadiene, trisilane both neat and with added butadiene, trimethylsilane or H 2 , and normal and iso-tetrasilane both neat and in the presence of added butadiene are reported; Arrhenius parameters of the primary dissociation reactions are determined : A-factors suggest that polysilane decompositions (1) have similar intrinsic activation entropies (△S∼6.2±5 e.u.) and (2) have activation energies which increase with increasing reaction endothermicities. Relative trapping efficiencies of SiH 4 , Si 2 H 6 , Si 3 H 8 , C 4 H 6 , Me 3 SiH, and h 2 toward SiH 2 and SiH 3 SiH are also determined. Other results include the heat of formation of silylsilylene △H f ° (Sih 3 SiH)=75.3 Kcal/mol, and the activation energy for 1,1-H 2 elimination from disilane (E H2 =57.8 kcal/mol)

Thermal decomposition kinetics of polysilanes: Disilane, trisilane, and tetrasilane

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