Quantitative Auger depth profiling of LPCVD and PECVD silicon nitride films

Summary Thin silicon nitride films (100–210 nm) with refractive indices varying from 1.90 to 2.10 were deposited on silicon substrates by low pressure chemical vapour deposition (LPCVD) and plasma enhanced chemical vapour deposition (PECVD). Rutherford backscattering spectrometry (RBS), ellipsometry, surface profiling measurements and Auger electron spectroscopy (AES) in combination with Ar⁺ sputtering were used to characterize these films. We have found that the use of (p-p)heights of the Si LVV and N KLL Auger transitions in the first derivative of the energy distribution (dN(E)/dE) leads to an accurate determination of the silicon nitride composition in Auger depth profiles over a wide range of atomic Si/N ratios. Moreover, we have shown that the Si KLL Auger transition, generally considered to be a better probe than the low energy Si LVV Auger transition in determining the chemical composition of silicon nitride layers, leads to deviating results.

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Quantitative Auger-Tiefenprofilanalyse von LPCVD- und PECVD-Siliciumnitridfilmen

     

Some aspects of the precipitation of Feα crystallites in the FePC amorphous alloy

The precipitation of Fe_α in some FePC amorphous alloys has been followed in situ by using neutron diffraction with a multidetector covering 80° (2θ). The quantity of Fe_α which precipitates before the final crystallization of the remaining amorphous phase is a function of the composition of the alloy but is independent of the heating rate. The alloy tends toward a mixture of Fe_α + am′ whose composition is about Fe₇₅(PC)₂₅. The crystallization of am′ occurs as soon as the excess of iron in the amorphous matrix is precipitated. We conclude that the excess of iron stabilizes the amorphous phase.     

Utility of the tandem Pauson-Khand reaction in the construction of tetracycles

The scope of the tandem Pauson-Khand reaction has been explored for the regiospecific construction of [5.5.5.5]- and [5.6.6.5]tetracyclic systems via the photolytic method of Livinghouse. The rapid regiospecific entry into the two dicyclopentapentanoid systems 17 and 29 was accomplished from the key diene-diynes 11 and 19b. A photochemically mediated catalytic tandem Pauson-Khand cyclization was employed to prepare the parent ring systems of dicyclopenta[a,e]pentalene (from 19b) and dicyclopenta[a,f]pentalene (from 11) in regiospecific fashion in a one-pot process. Under these conditions, conversion of acyclic diene-diyne 16 into tetracyclic system 17 was achieved in 74% yield, while a similar process was employed to convert 28 into tetracycle 29 in 90% yield. This is much improved over the previous conditions that employed NMO. Six carbon-carbon bonds were generated in this process constituting up to 98% yield for each carbon-carbon bond so formed. Furthermore, tetracyclic [5.6.6.5] systems such as dicyclopenta[b,g]decalins 37, 38, and 40 were prepared from similar diene-diyne precursors via the tandem Pauson-Khand cyclization. Importantly, acetal 36 provided the desired cis-fused [5.6.6.5] system 38a (via 40a/b) in stereospecific fashion. This reaction is unique in that it provides a cis-decalin ring system; moreover, the yield of each of the six carbon-carbon bonds formed in this process was at least 89%. The structure of cis diol 38a was confirmed by X-ray crystallography.     

Energy partition for the linear radial wave equation

We consider the radial free wave equation in all dimensions and derive asymptotic formulas for the space partition of the energy, as time goes to infinity. We show that the exterior energy estimate, which Duyckaerts et al. obtained in odd dimensions (Duyckaerts et al., J Eur Math Soc 13:533–599, 2011; J Eur Math Soc, 2013) fails in even dimensions. Positive results for restricted classes of data are obtained.     

Multitime dynamic programming for multiple integral actions

This paper introduces a new type of dynamic programming PDE for optimal control problems with performance criteria involving multiple integrals. The main novel feature of the multitime dynamic programming PDE, relative to the standard Hamilton-Jacobi-Bellman PDE, is that it is connected to the multitime maximum principle and is of divergence type. Introducing a generating vector field for the maximum value function, we present an interesting and useful connection between the multitime maximum principle and the multitime dynamic programming, characterizing the optimal control by means of a multitime Hamilton-Jacobi-Bellman (divergence) PDE that may be viewed as a feedback law. Section 1 recalls the multitime maximum principle. Section 2 shows how a multitime control dynamics determines the multitime Hamilton-Jacobi-Bellman PDE via a generating vector field of the value function. Section 3 gives an example of two-time dynamics with nine velocities proving that our theory works well. Section 4 shows that the Hamilton PDEs are characteristic PDEs of multitime Hamilton-Jacobi PDE and that the costates in the multitime maximum principle are in fact gradients of the components of the generating vector field.     

Intramolecular homolytic substitution of sulfinates and sulfinamides--a computational study

Ab initio and density functional theory (DFT) calculations predict that intramolecular homolytic substitution by alkyl radicals at the sulfur atom in sulfinates proceeds through a smooth transition state in which the attacking and leaving radicals adopt a near collinear arrangement. When forming a five-membered ring and the leaving radical is methyl, G3(MP2)-RAD//ROBHandHLYP/6-311++G(d,p) calculations predict that this reaction proceeds with an activation energy (ΔE(1)(?)) of 43.2 kJ mol(-1). ROBHandHLYP/6-311++G(d,p) calculations suggest that the formation of five-membered rings through intramolecular homolytic substitution by aryl radicals at the sulfur atom in sulfinates and sulfinamides, with expulsion of phenyl radicals, proceeds with the involvement of hypervalent intermediates. These intermediates further dissociate to the observed products, with overall energy barriers of 45-68 kJ mol(-1), depending on the system of interest. In each case, homolytic addition to the phenyl group competes with substitution, with calculated barriers of 51-78 kJ mol(-1). This computational study complements and provides insight into previous experimental observations.     

Carbonyl-inserted organo-hybrids of a Dawson-type phosphovanadotungstate: scope and chemoselective oxidation catalysis

The Dawson-type polyoxometalate (POM) [P(2)V(3)W(15)O(62)](9-) is a prototype for inclusion of carbonyls of amides, ureas, carbamates, and thiocarbamates into polyoxometallic structures. The carbonyl-inserted POMs catalyze the oxidation of sulfides. Chemoselectivity depends primarily on the proton content of the POM, but it is also influenced by the organic substituent.