From "parasitic" association reactions toward the stoichiometry controlled gas phase synthesis of nanoparticles: a theoretically driven challenge for experimentalists

In the present record a model for the gas-phase reactions during the chemical vapor deposition (CVD) processes of group 13-15 materials is presented, based on the results of extensive quantum-chemical modeling. Thermodynamic criteria have been introduced to evaluate the importance of a range of association reactions. For the organometallic and hydride derivatives, association processes are found to be favorable both thermodynamically and kinetically. Formation of high mass association products takes place under CVD conditions, including laser-assisted CVD. Structural and thermodynamic properties of the most important ring and cluster intermediates have been predicted. The stoichiometry-controlled synthesis of the 13-15 ternary alloys and nanoparticles using cluster compounds as single-source precursors is predicted to be viable. The association pathway described may be generalized to the CVD reactions of many binary materials (12-16, 13-16, 13-15, 14-15, 14-16).     

Synthesis of modified vitamin D precursors

Modified vitamin D precursors with oxygen-containing substituents at various positions in the side-chain were obtained using previously synthesized 20-isoxazolin-3-yl-and 20-isoxazolin-5-ylsteroids.Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, 220141 Minsk, Belarus;Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–235, February, 2000.     

Preparation of Nanocrystalline Indium Antimonide Through β-Hydride Elimination from New Indium-Antimony Single-Source Precursors

The 1:1 mole ratio reaction of t-Bu₃In with Sb(SiMe₃)₃ results in the formation of the Lewis acid-base adduct t-Bu₃In Sb(SiMe₃)₃ (1), while the dimeric compound [t-Bu₂InSb(SiMe₃)₂]₂ (2) is isolated from the 1:1 reaction of t-Bu₂InCl with Sb(SiMe₃)₃. Both the 2:1 reactions of t-Bu₂InCl with Sb(SiMe₃)₃ and t-Bu₂InCl with 2 result in the formation of the mixed-bridge compound (3), however, ¹H NMR studies suggest that this compound is unstable in solution. Thermolysis of 1, 2, and t-Bu₃Ga Sb(SiMe₃)₃ (4) results in the formation of nanocrystalline InSb or GaSb through a -hydride elimination pathway.     

Sorption and diffusion of water vapor in polyimide films

Sorption and diffusion of water vapor are investigated gravimetrically for polyimide films. The activity dependence of the solubility and diffusion coefficients, S and D, respectively, is classified under four types: (1) constant S and D type, (2) dual-mode sorption and transport type, (3) dual-mode type followed by a deviation due to a plasticization effect at high vapor activity, and (4) constant S and D type followed by a deviation due to water cluster formation at high activity. For the dual-mode type, the Henry's law component is much larger than the Langmuir component except at low activity, and therefore deviation in behavior from the first type is small. S is larger for polyimides with higher content of polar groups such as carbonyl, carboxyl, and sulfonyl. D is larger for polyimides with a higher fraction of free space, with some exceptions. The polyimide from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and dimethyl-3,7-diaminodibenzothiophene-5, 5-dioxide belongs to the third type and displays both large S and large D. The polyimide from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4,4′-oxydianiline belongs to the fourth type, and has the largest D but rather small S because of the hydrophobic C(CF₃)₂ groups. © 1992 John Wiley & Sons, Inc.     

Synthesis of ferrites: Thermal analysis of some transition metal tris(maleato)ferrates(III)

Thermal analysis of some transition metal ferrimaleate precursors, M₃[Fe(mal)₃]₂·xH₂O (M=Mn, Co, Ni, Cu) has been studied in static air atmosphere from ambient to 600°C. Various physico-chemical techniques, i.e. TG, DTG, DTA, XRD, IR, Mössbauer spectrometry, have been employed to characterize both the intermediates and final products. After dehydration the anhydrous precursors undergo decomposition to yield an iron(II) intermediate, M[Fe^II(mal)₂] (M=Mn, Co, Ni, Cu) in the temperature range 160-275°C. A subsequent oxidative decomposition of iron(II) species leads to the formation of -Fe₂O₃ and MO in the successive stages. Finally a solid-state reaction occurs between the oxides above 400°C resulting in the formation of transition metal ferrites, MFe₂O₄. The ferrites have been obtained at much lower temperature and in less time than in the conventional ceramic method.This revised version was published online in November 2005 with corrections to the Cover Date.     

A convenient synthesis of nanocrystalline chalcopyrite,CuFeS2 using single‐source precursors

Nanocrystalline chalcopyrite (CuFeS₂) have been synthesized using single‐source precursors, CuL₂ and Cu(LH)₂Cl₂ (where LH = monoacetylferrocene thiosemicarbazone) by pyrolysis and solvothermal decomposition methods. The nanocrystals were characterized by UV–visible spectroscopy, X‐ray powder diffraction, transmission electron microscopy and energy dispersive X‐ray analysis. The magnetic character was determined by the hysteresis loop. CuFeS₂ nanocrystallites prepared by the pyrolysis of CuL₂ and Cu(LH)₂Cl₂ have a cubic phase and rod‐like morphology with diameters of about 18 and 15 nm, respectively, and lengths of about 195–390 and 100–145 nm, respectively. However, CuFeS₂ nanoparticles obtained by solvothermal route from CuL₂ and Cu(LH)₂Cl₂, which are capped with ethylene glycol, possess a nearly spherical shape with an average grain size of 16 and 11 nm, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

The Reaction Of Metal Trialkyls With Benzo[H]Quinolin-10-ol

IntroductionThechemistryoforganoaluminum,organogalliumandorganoindiumcomplexeshasattractedmuchat'tentionduenotonlytotheirinterestingstructuralandchemicalpropertiesbutalsotheirapplicationinsemiconductormaterialsl-5.InthecourseofourstudiesonexploringvolatileMOCVDprecursorsthathavethepropertiesoflowertoxicityandhigherstability,wehaverecentlyreportedonthesynthesisandcharacterizationofintermolecularadducts'-',novelbondingmodecomplexes",',andthecomplexesinwhichN/Omixed-donorcrownethersasligands'l'…     

Assessment of the Nature of Depolarization Current in Thermally Treated Kapton Polyimide

Pyrolysis of normally insulating aromatic polyimide is known to impart electrical conductivity to the polymer due to the formation of carbonized regions in an insulating matrix with a concomitant change in the polymer’s structural arrangement. The wholly pyrolyzed polyimide is potentially useful for specific applications in certain types of semiconductor devices because of the polyimide’s insulator/conductor transition which creates a barrier type conduction. Pyrolysis, however, degrades the required mechanical integrity of the polyimide for construction of such devices. In order to evaluate the fundamental aspects of barrier conduction by high voltage electron transfer from metal contact that can still produce measurable current in thermally treated non-pyrolyzed polyimide, the nature of depolarization in Kapton was assessed by the thermally stimulated depolarization current (TSDC) technique. The results show that thermal treatment of polyimide without pyrolysis and therefore without loss of mechanical integrity offers a viable means of steady electron conduction for semiconductor operation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Plasma-enhanced atomic layer deposition of Co using Co(MeCp)2 precursor

Cobalt (Co) thermal or plasma enhanced atomic layer deposition (PE-ALD) was investigated using a novel metal organic precursor, Co(MeCp)₂, and NH₃ or H₂ or their plasma as a reactant. The growth characteristics, electrical and microstructural properties were investigated. Especially, PE-ALD produced Co thin films at low growth temperature down to 100 °C. Interestingly, the low temperature growth of Co films showed the formation of columnar structure at substrate temperature below 300 °C. The growth characteristics and films properties of PE-ALD Co using bis(η-methylcyclopentadienyl) Co(II) (Co(MeCp)₂) was compared with those of PE-ALD Co using other Cp based metal organic precursors, bis-cyclopentadienyl cobalt (II) (CoCp₂) and cyclopentadienyl isopropyl acetamidinato-cobalt (Co(CpAMD)).     

Polymerization and nanocomposites properties of multifunctional methylmethacrylate POSS

Thermally induced polymerization of multifunctional methylmethacrylate POSS (MMA‐POSS) was studied in this work for preparation of polymer/POSS nanocomposites. The polymerization of MMA‐POSS could be promoted with benzoyl peroxide (BPO). Self‐assembly of POSS into a layer‐by‐layer structure in the MMA‐POSS polymer (TP‐MMA‐POSS) is observed with a transmission electron microscopy. An ultra‐low‐k value of about 1.85 is measured with TP‐MMA‐POSS. In addition, polyimide‐POSS nanocomposites are also prepared. These nanocomposites demonstrate good homogeneity and enhanced mechanical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5157–5166, 2008