Low‐Temperature Atomic Layer Deposition of Copper Metal Thin Films: Self‐Limiting Surface Reaction of Copper Dimethylamino‐2‐propoxide with Diethylzinc

A uniform, conformal, pure copper metal thin film was grown at very low substrate temperatures (100–120 °C) on Si(100) substrates by atomic layer deposition involving the ligand exchange of [Cu(OCHMeCH₂NMe₂)₂] with Et₂Zn (see scheme). Patterned copper thin films of Cu nanotubes (diameter 150 nm, length 12 μm) were fabricated.

     

Preparation and characterization of intercalated misfit-layer compounds and natural superlattices

This paper presents the preparation and characterization of the new types of misfit-layer compounds and natural superlattices consisting of Ce_xNb_1−x−y□_yS (Q′) and Ni_zNbS₂ (H) layers, where □ is an atomic deficit at a metal site. A Q′ layer is larger by about 1 Å in thickness than a CeS (Q) layer in (CeS)_1.16NbS₂. They are prepared by chemical vapor transport reaction in a closed silica tube under quasi-equilibrium conditions. The 1Q′/3H type of compound are grown as a single crystal while the 1Q′/4H type of compound is grown as composite crystals with the 1Q′/3H and 1Q/2H compounds. Natural superlattices which have a long period in a direction perpendicular to layers are found. Their chemical formulae are given by (Ce_xNb_1−x−y□_yS)_m(Ni_z)_n−m(NbS₂)_n, where m and n are integers. It is found from an X-ray-photoelectron spectroscopy (XPS) study that Nb affects the valence and the bonding of Ce in the Q′ layers. It is in a higher oxidation state than Nb in NbS₂ layers. A scanning tunneling microscope (STM) study shows that some of the superlattices form a hexagonal supercell in the (a,b)-plane and behave as a narrow-gap semiconductor so that no STM images are obtained at bias voltage less than 0.3 eV.     

Cu-N Films grown by reactive MSIP: Constitution, structure and morphology

Cu-N layers were deposited on Si-100 wafers and amorphous carbon coated platinum nets at low temperatures (< 100 °C) by means of Reactive Magnetron Sputtering Ion Plating (MSIP). For this, a Cu-target was sputtered in rf-mode in a nitrogen plasma, and the influence of the parameters sputtering power and nitrogen partial pressure on composition, structure, texture and morphology of the Cu-N layers was investigated. The analysis with EPMA, XPS, HEED, XRD, TEM and SEM yielded the following results: With appropriate settings of the process parameters the nitrogen content of the films could be controlled-in this investigation between 0 to 28 at-%. The HEED analysis shows, that at the near surface region films with a nitrogen content in the range of 16–28 at-% were grown with DO₉ structure of Cu₃N. The films were textured: [100] in the case of 16–26.3 at-% nitrogen, [210] + [110] at 28 at-%. XRD analysis of the crystal structure of the bulk of a nitrogen-rich film (26.3 at-% nitrogen) confirm the result of HEED analysis. In the bulk of the nitrogen-poor film (16.4 at-%) two phases were detected, metallic copper with Al structure and Cu₃N with DO₉ structure. XPS analysis revealed that all films were oxidized at the surface to Cu₂O.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

Dielectric properties of a filled epoxy resin: Effect of thermal treatments

Dielectric measurements have been performed at several frequencies on samples of a cycloaliphatic epoxy resin filled with aluminum hydroxide. The samples were thermally treated at three different temperatures for times up to 2,000 hours. At low aging temperatures and times an improvement of the characteristics is observed due perhaps to an assessment of the bulk of the polymer and more precisely to a change in the free volume. At high temperatures and times a thermo-oxidation involving layers deeper and deeper becomes the predominant mechanism responsible of the decrease in the properties with respect to the virgin material. T _g, tan and versust _a, generalized curves are finally presented useful to predict the behaviour for aging times not easily experienced.Thanks are due to Magrini-Galileo, Italy, for supplying the samples and to C.N.R., Italy, for financial support.     

Preparation of spherical,mixed SiO2/TiO2 particles by the sol technique

Preparation of silica, titania and mixed silica/titania particles has been studied. The region for formation of monodisperse SiO₂ particles in the phase diagram tetraethyl orthosilicate (TEOS)-ethanol-H₂O was studied as a function of NH₃ concentration at room temperature. Titania particles could be prepared at lowered temperatures and concentration of ammonia up to 0.01 M. The size of SiO₂ particles was 0.03–1 m whereas TiO₂ particles were size range 0.5–0.8 m. Mixed SiO₂/TiO₂ particles were prepared from prehydrolyzed TEOS/EtOH solutions by adding tetraethyl orthotitanate (TEOT). This was accomplished at 3°C and slightly alkaline solutions. The final particle size of the mixed particles was about 0.3 m.     

Drag on a metallic or nonmetallic particle exposed to a rarefied plasma flow

Drag force on a metallic or nonmetallic spherical particle exposed to a plasma flow is studied for the extreme case of a free-molecule regime. Analytical expressions are derived for the drag components due to, respectively, atoms, ions, and electrons and for the total drag on the whole sphere due to all the gas species. It has been shown that the drag is proportional to the square of the particle radius or the drag coefficient is independent of the particle radius. At low gas temperatures with a negligible degree of ionization, the drag is caused mainly by atoms and could be predicted by using the well-known drag expression given in ordinary-temperature rarefied gas dynamics. On the other hand, the drag is caused mainly by ions at high plasma temperatures with a great degree of ionization. The contribution of electrons to the total drag is always negligible. Ignoring gas ionization at high plasma temperatures would overestimate the particle drag. There is a little difference between metallic and nonmetallic spheres in their total drag forces, with a slightly higher value for a metallic sphere at high plasma temperatures, but usually such a small difference could be neglected in engineering calculations. The drag increases rapidly with increasing gas pressure or oncoming speed ratio. For a two-temperature plasma, the drag increases at low electron temperatures but decreases at high electron temperatures with the increase in the electron/heavy-particle temperature ratio.Nomenclature C _d Drag coefficient - e Elementary charge - f _D,F _D Local and total drag (N/m ² andN) - f ^– Velocity distribution function for incident gas particles - f ⁺ Velocity distribution function for reflected gas particles - k Boltzmann's constant - m Gas particle mass (kg) - n Number density of gas species (m ^–3) - P ^–,P ⁺ Surface pressure due to incident and reflected gas particles - R ₀ Sphere radius (m) - S Speed ratio,S _j=U/(2kT _j/m_j)^1/2 - T _e,T _h Electron and heavy-particle (atom, ion) temperature - T _w Wall temperature - U Oncoming plasma flow velocity - v _x, v_y, v_z Velocity components of gas particles in thex, y, andz directions (m/sec) - v Thermal motion speed of gas particles,v _j =(8kT _j /m _j )^1/2 - v _ze Smallestv _z of electrons which could reach the sphere surface,v _ze=(2e/m _e)^1/2 (m/sec) - v _zw Value ofv _z of ions or electrons as arriving at the sphere surface (m/sec) - Center angle - Gas density (kg/m³) - Shear stress (N/m²) - Absolute value of the floating potential (V) - , Local and total particle fluxes incident to the surface - a Atoms - e Electrons - h Heavy particles - i Ions - j jth gas species - m Metallic sphere - mn Nonmetallic sphere A preliminary version of this paper was presented at the Eighth International Symposium on Plasma Chemistry held in Tokyo, September 1987.     

Low-temperature heat capacity of β-glycine and a phase transition at 252 K

Low-temperature heat capacity of unstable -glycine was measured in a temperature range 5.5 to 295 K, and thermodynamic functions were calculated. At very low temperatures, heat capacity fits a sum of cubic (Debye) and linear terms: C_p=aT+bT ³. The linear contribution increases with temperature and disappears at the second-order phase transition near 252 K which was observed for the first time.     

Apparent molar heat capacity and relative enthalpy of aqueous NaOH between 323 and 523K

The apparent molar heat capacity, C _p,, of aqueous NaOH has been measured at temperatures between 50 and 250°C and molalities from 0.05 to 1.5 mol-kg^–1. Enthalpies of dilution L were also determined at 99°C and apparent molar relative enthalpies L were calculated up to 1.9 m. Measurements were performed by means of a flow calorimetric apparatus constructed in our laboratory and standardized for C _p, and L with aqueous Na₂SO₄ and with the formation of water from its ions, respectively. Characteristics and performance of this calorimeter are described in detail. Pitzer's semiempirical equations are used for the representation of the results and a general fitting of C _p, data is reported using also recent literature values measured between 4 and 55°C. The fitted parameters are finally utilized, through an integration procedure, to derive a general equation to calculate L at any temperature between 4 and 250°C.     

The thermodynamic viability of yttria-stabilized zirconia pH sensors for high temperature aqueous solutions

The thermodynamic viability of the yttria-stabilized zirconia sensor (YSZS) [H₂O, H⁺/ZrO₂(Y₂O₃)/HgO/Hg] for the measurement of pH in high temperature aqueous solutions is evaluated by measuring potentials for this electrode and a conventional hydrogen electrode (HE) against a common reference electrode in a variety of solutions [0.01m H₃PO₄, 1m Na₂SO₄, 0.01m B(OH)₃+0.01m KOH, and 0.01m KOH] at temperatures from 298.15K (25°C) to 573.115K (300°C). In order to compare theoretical and experimental potentials for the cell

Some Mechanisms of SiO2 Micro-tubes Formation in Plasma Jet

A chamotte rod is transformed in vapors through chemical reactions, at temperatures exceeding 5000 K. SiO₂ micro-tubes formation is determined by a low vapor concentration and a stable vapor flow, along the streamlines of the plasma jet, and, respectively, by the difusion processes, in non-stationary regime, inside the liquid membrane. A mass of SiO₂ vapor, in the range of 0.5×10^–8 kg–10×10^–8 kg, allows one to obtain micro-tubes with the outer diameter between 6.2 and 28.8 m and the inner diameter between 3.8 and 12.2 m.     

Formation of perovskite phase mixed metal oxides via thermal decomposition of metal-organic complexes with bifunctional ligands

Single-source metal precursors designed to form crystalline perovskite phase mixed metal oxides at low temperatures have been synthesized using -hydroxycarboxylates and alkoxides as ligands. Divalent salts of Ba, Sr, Ca and Pb, [A(O₂CCR₂OH)₂], R = H, Me, were formed from the reaction between ACO₃ and HO₂CCR₂OH in which the hydroxyl group is free to react with metal alkoxide compounds B(OR)₄ where B=Ti, Zr, Sn. These compounds react to eliminate two equivalents of alcohol producing precursors with fixed stoichiometry as shown by the equation: A(O₂CCR₂OH)₂+B(OR)₄ A(O₂CCR₂O)₂B(OR)₂+2HOR. The reaction product is only slightly soluble in pyridine, however upon hydrolysis these compounds form clear solutions from which yellow powders can be isolated by removal of the solvent. Thermolysis of these powders in the temperature range 300–350°C yields perovskite ABO₃. Aqueous solutions of these powders can also be used to form sub-micron sized particles of ABO₃ materials via aerosol processing techniques. In control experiments it was shown that Pb(O₂CCH₂OPh)₂ does not react with metal alkoxide compounds. As a result perovskite PbTiO₃ is not formed below 550°C. Solutions for spin coating thin films can be formed by dissolution of the powder in ethanol, but the crystallization behavior is quite different compared to the bulk powders.     

Hollow Silicon Carbide Nanostructures

Hollow silicon carbide nanostructures with length up to 1 m have been produced for the first time along with threadlike structures. The preparation of SiC nanostructures from silicon and carbon at 1000-1100 °C was carried out without prior gasification of these elements. The growth of SiC nanostructures involves a step featuring atomization of silicon and carbon at such low temperatures. The growth of SiC nanotubes upon the reduction of carbon by SiO₂ in the initial period of the preparation proceeds with their predominant formation as bundles. Silicon carbide may correspond to the highly textured -modification.     

Effect of Niobium Modifications to PZT (53/47) Thin Films Made by a Sol-Gel Route

Niobium-modified lead zirconate titanate thin films (PNZT) with nominal compositions, Pb_(1–0.5x) (Zr_0.53 Ti_0.47)_1–x Nb _x O₃:x = 0.02–0.07, have been prepared using a diol based sol-gel route. Single-layer (0.5 m) films were fabricated on platinised silicon substrates by spin-coating. The effect of niobium additions with regard to phase development, microstructure, and ferroelectric and dielectric properties were investigated for different annealing temperatures. For comparison, unmodified PZT films were also prepared. Niobium substitution increased the crystallisation temperatures for perovskite PNZT phase formation. The values of remanent polarisation P _r and dielectric constant _r were found to decrease with the introduction of Nb. For example, in films heated at 700°C for 15 min, the P _r value of an unmodified PZT film was 31 C cm^–2, compared to 17 C cm^–2 for an x = 0.05 PNZT film, whilst respective relative permittivity values fell from 1190 to 600. The highest Nb concentration film, x = 0.07, did not display any switchable polarisation characteristics, which is consistent with high levels of intermediate pyrochlore phase.     

Physico-chemical studies on the chelation behaviour of acenaphthenequinone monothiosemicarbazone (AQTS) with some bivalent metal ions

Summary The stability constants of the chelates formed from acenaphthenequinone monothiosemicarbazone and magnesium(II), manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) or cadmium(II) have been determined pH-metrically in 75% v/v aqueous dioxan at various ionic strengths of NaClO₄ and at different temperatures. The method of Bjerrum and Calvin^{(1, 2)} as modified by Irving and Rossotti⁽³⁾, has been used to determine the ñ and pL values. The stability constants were calculated on an IBM 360 FORTRAN-IV computer patterned after that of Sullivanet al. ⁽⁴⁾ to give _n values using a weighted least squares method. The S_min, values were also calculated. The thermodynamic stability constant has been determined by extrapolating the log K₁ vs plot at zero ionic strength. The other thermodynamic functions have been calculated from the stability constants obtained for different temperatures at constant ionic strength. The bivalent metal stability sequence of AQTS chelates is in agreement with reported metal orders for other chelating reagents. The order of free energies and enthalpies of chelate formation for AQTS are: Mn²⁺2+2+2+>Zn²⁺.     

Conformational isomerisin of phosphorus-containing fullerenyl radicals

ESR spectra of phosphorus-containing fullerenyl radicals^.C₆₀-P(O)(OPr¹)₂ and^. C₆₀-P(O)(OEt)Ph were studied at low temperatures (193–273 K). A decrease in the rate of rotation of organophosphorus group around the C-P bond results first in line broadening and then in the appearance of two doublets due to two extreme conformations, which have differentg-factors and hyperfine coupling constants (HCC) of the unpaired electron with the³¹P nucleus. The kinetic and thermodynamic parameters of the conformational isomerism were calculated.The widely used appellation of such radicals as dialkoxyphosphonyl ones does not correspond to the IUPAC nomenclature.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1671–1673, September, 1994.This work was supported by the Russian Foundation for Basic Research (Projects No. 93-03-18725 and 93-03-4101).     

Analysis of chromium(III)-fluoride-complexes by ion chromatography

A method for the ion chromatographic separation of cationic CrF_x-species in aqueous acidic solutions with photometric detection is described. CrF₃-, CrF⁺₂- and CrF²⁺-species can be separated on a commercial cation-exchange column using HCl/2,3-diaminopropionic acid (DAP) as eluent. The chromium(III)-complexes are converted with 2,6- pyridinedicarboxylic acid (PDCA) into the violet [Cr(PDCA)₂]^--complex at temperatures >90°C by post-column derivatisation for the subsequent spectrophotometric detection at =335 nm. Iron- and nickel-ions do not disturb the determination even in concentrations higher than those of the chromium (III)-ions.     

Wet Chemical Deposition of Crystalline,Redispersable ATO and ITO Nanoparticles

A new wet chemical concept to produce coatings by dip, spin or spray processes is presented. It is based on the preparation of solutions made of crystalline nanoparticles fully redispersable in a solvent. It is exemplified for the preparation of SnO₂ : Sb (ATO) and In₂O₃ : Sn (ITO) transparent conducting coatings. The process combines the advantages of using particles having already a low resistivity and the possibility to sinter the coatings at low temperature. The particles are prepared using an in-situ monitoring of the surface energy to control the growth of the particles and to avoid their agglomeration. The dried powders can be fully redispersed in alcohol (ITO) or water (ATO). Single layers with thickness up to 200 nm (ATO) and 400 nm (ITO) have been fabricated. The sheet resistance of the coatings decreases with the sintering temperature. Typical values are 430 for ATO (550°C) and 380 for ITO (550°C). Sols made by redispersing the powders in organosilanes allow to produce coatings at low temperature with antistatic (R > 100 k) and anti-glare properties (R > 100 k, 60 to 80 gloss units).     

Thermal transformations of α-H6P2Mo18O62·nH2O heteropolyacid

According to the ³¹P NMR spectroscopy, heteropolyacid (HPA) H₆P₂Mo₁₈O₆₂·nH₂O (P₂Mo₁₈), -isomer of the Dawson structure, transforms upon heating above 80 °C partially (up to 30%) to -isomer, in which both polar groups Mo₃O₁₃ of the heteropolyanion are turned by 60° around the N₃ axis, and partially to -isomer in which only one group is turned. The - and -isomers of P₂Mo₁₈ have been found for the first time. Their transformation into the -isomer occurs upon rehydration in one week in air and in 1 h in an aqueous solution. HPA P₂Mo₁₈ decomposes on heating up to 350 °C to HPA H₃PMo₁₂O₄₀ (PMo₁₂) and a previously unknown phase of the HPMo₆I₂₁ composition, which in its turn decomposes at 375 °C to molybdenyl phosphates and IiI₃. The PMo₁₂ decomposition occurs via two routes to form the same products at temperatures of 400 and 450 °C with corresponding exotherms of IiI₃ crystallization.     

Determination of the stability constant for acetic acid in synthetic seawater media at various temperatures and salinities

The stability constant (association constant) for acetic acid in synthetic seawater was determined for salinities in the range 5 to 40, in 0.4M and 0.7M ionic strength sodium chloride and at temperatures between 5 and 45°C. The minimum in the log K₁ vs. temperature curve is displaced towards higher temperatures as the ionic strength of NaCl increases. For synthetic seawater solutions, H is independent of temperature but does depend on salinity.