New data on the thermal behavior, sublimation, and melting of (hexafluoroacetylacetonato)(cyclooctadiene-1,5)copper, [Cu(cod)(hfac)], have been obtained. The condensed phase was studied by thermal and differential thermal analysis and differential scanning calorimetry. The temperature, enthalpy, and entropy of melting of the complex were determined. The temperature dependence of the saturated vapor pressure of [Cu(cod)(hfac)] in the temperature range 293–337 K was obtained by the Knudsen effusion method with mass spectrometric recording of the gas phase composition. The thermodynamic characteristics of sublimation were calculated at the average temperature over the experimental range and at 298.15 K: Δ_sublH_m^o (Tav) = 94.8 ± 1.5 kJ mol–1; Δ_sublS_m^o (Tav) = 200.9 ± 3.2 J mol–1 K–1; Δ_sublH_m^o (298.15 K) = 95.8 ± 3.1 kJ mol–1; Δ_sublS_m^o (298.15 K) = 203.5 ± 6.6 J mol–1 K–1. The obtained values are compared with data for a similar iridium(I) compound, [Ir(cod)(hfac)]. The results were used formulate approaches to evaluation of the thermodynamic properties of [M(cod)(hfac)] complexes to determine the optimum conditions for the deposition of metal-containing coatings. These approaches are necessary in those cases when compounds of this type (e.g., [Ag(cod)(hfac)]) are hypersensitive to heating and it is impossible to determine reliable thermodynamic characteristics experimentally.

Crystals of copper bis(heptafluorodimethyloctanedionate) (Cu(fod)2) have been grown by evaporation of solvent from solutions. Crystals of monoclinic syngony (I) have been obtained from toluene, while crystals of monoclinic (I) and triclinic (II) syngony have been obtained from acetonitrile. Crystallographic data: P21/c, a = 13.1863 (6), b = 9.8118 (4), c = 10.6997 (6), β = 113.633(2)° for I; 1̅ , a = 10.7941(12), b = 11.4759(14), c = 12.5263(13), α = 115.350(4)°, β = 102.957(4)°, γ = 100.999(4)° for II. Crystal packings I and II have the same structure of molecules. Crystal structures I and II are molecular and consist of discrete Cu(fod)2 molecules. Temperature dependences for saturated vapor pressure have been obtained by flow method for liquid and crystalline (phase I) Cu(fod)2 in the range 314–393 K. Thermal stability of the compound is determined, thermodynamic parameters of sublimation and evaporation have been established.

Получены новые данные о термическом поведении и процессах сублимации и плавления (гексафторацетилацетонато)(циклооктадиен-1,5)меди, [Cu(cod)(hfac)]. Конденсированная фаза исследована методами термического и дифференциального термического анализа и дифференциальной сканирующей калориметрии: определены температура, энтальпия и энтропия плавления комплекса. Эффузионным методом Кнудсена с масс-спектрометрической регистрацией состава газовой фазы получена температурная зависимость давления насыщенного пара [Cu(cod)(hfac)] в интервале температур 293–337 K, рассчитаны термодинамические характеристики процесса сублимации при средней температуре экспериментального интервала и 298.15 K: ΔсублH0m (Tср) = 94.8 ± 1.5 кДж моль-1, ΔсублS0m (Tср) = 200.9 ± 3.2 Дж моль-1 K-1; ΔсублH0m (298.15 K) = 95.8 ± 3.1 кДж моль-1, ΔсублS0m (298.15 K) = 203.5 ± 6.6 Дж моль-1 K-1. Полученные величины сопоставлены с данными по аналогичному соединению иридия(I), [Ir(cod)(hfac)]. Результаты формируют подходы для оценки термодинамических свойств комплексов состава [M(cod)(hfac)] с целью определения оптимальных условий осаждения металлсодержащих покрытий. Подходы необходимы, когда соединения такого типа (например, [Ag(cod)(hfac)]) являются сверхчувствительными к процессу нагревания и отсутствует возможность определения надежных термодинамических характеристик экспериментальным путем.

This work is devoted to the study of the effect of the position of fluorine substituents in the molecules of tetrafluorosubstituted zinc phthalocyanines on their saturated vapor pressure. For this purpose, the temperature dependence of the saturated vapor pressure of zinc phthalocyanines with fluorine substituents in the peripheral (ZnPcF 4 -p) and non-peripheral (ZnPcF 4 -np) positions of the phthalocyanine ring has been studied by the Knudsen method with mass spectrometric recording of the composition of the gas phase and the thermodynamic parameters of vaporization were calculated. The data obtained for ZnPcF 4 -p and ZnPcF 4 -np with unsubstituted and hexadecafluorosubstituted zinc phthalocyanines are compared in terms of analysis of intermolecular interactions in the crystals of these compounds. It has been shown that tetrafluorosubstituted phthalocyanines have a higher vapor pressure than their unsubstituted (ZnPc) and hexadecafluorosubstituted (ZnPcF 16 ) derivatives. In this case, the enthalpy of sublimation increases in the series ZnPcF 4 -p < ZnPcF 4 -np < ZnPc < ZnPcF 16 .

Three volatile mixed-metal precursors [ZrL4Pb(hfa)2] (1), [ZrL4PbL2] (2), and [ZrL4La(dpm)3] (3) (L = 2-methoxy-2,6,6-trimethyl-3,5-heptanedionate; dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate; hfa = 1,1,1,5,5,5-hexafluore-2,4-pentanedionate) are used to prepare ZrO2-based multicomponent films by metalorganic chemical vapor deposition (MOCVD). The deposition experiments are carried out in a hot-wall reactor at 600-750 °C on silicon substrates under 20 Torr in the presence of oxygen. According to X-ray powder diffraction, the main crystal phases in the films prepared from precursors 1 and 2 are solid solutions based on tetragonal and cubic ZrO2. Lead does not form separate crystal phases but is dissolved in the oxide form within the ZrO2 matrix, as is indicated by X-ray photoelectron spectroscopy data. La2Zr2O7 films are prepared from 3 using two ways of precursor supply: evaporation in argon and by direct liquid injection (DLI). It is shown that the composition and structure of obtained films are determined by the precursor composition. The results obtained for thermal behavior of precursors in condensed and gas phases are discussed.

Синтезирована серия трис-дипивалоилметанатов Ln(III) с фенантролином состава Ln(thd)3Phen (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb). Установлено, что все аддукты изоструктурны с ранее известными комплексами La(thd)3Phen, Tb(thd)3Phen и Dy(thd)3Phen. Определены кристаллические структуры комплексов Sm(thd)3Phen (I) и Eu(thd)3Phen (II) при 150(2) K (пр. гр. P-1, a = 10.8590(5) Å, b = 12.3049(6) Å, с = 18.4479(10) Å, α = 80.210(2)°, β = 87.499(2)°, γ = 68.799(2)°, V = 2264.3(2) Å3, Z = 2; пр. гр. P-1, a = 10.8788(3) Å, b = 12.3009(3) Å, с = 18.4309(5) Å, α = 80.3644(9)°, β = 87.5440(10)°, γ = 68.7376(8)°, V = 2265.7(1) Å3, Z = 2 соответственно). Кристаллические структуры I и II являются молекулярными и состоят из изолированных молекул Ln(thd)3Phen (Ln = Sm(III), Eu(III)). Наибольшие квантовые выходы люминесценции для данной серии аддуктов установлены для Eu(thd)3Phen (10 %) и Sm(thd)3Phen (1.5 %). Термогравиметрические исследования (ТГ) показали, что летучесть аддуктов слабо уменьшается от Pr(thd)3Phen до Yb(thd)3Phen; их точки плавления близки к известным по литературным данным.

Nanocrystalline iridium coatings on hafnium carbide and tantalum carbide substrates are prepared by chemical vapor deposition (MOCVD) at 600°С. Subsequent high-temperature treatment at 1100°С gives rise to chemical reactions between iridium and hafnium carbide or tantalum carbide to yield nanosized substitutional intermetallic solid solutions MIr3 – x and evolve free carbon. The occurrence of intermetallic interaction is proved by X-ray photoelectron (XPS) spectroscopy.

Методом РСА изучено строение двух β-дикетонатов Al(III) и Fe(III) с γ-замещенным лигандом при 150(2) K. Кристаллографические данные для Al(γ-Me-hd)3 (I): пространственная группа P–1, a = 10.855(1) Å, b = 11.129(1) Å, с = 11.894(1) Å, α = 85.634(3)°, β = 73.118(3)°, γ = 66.771(3)°, V = 1262.2(2) Å3, Z = 2, R1 = 0.0438; для Fe(γ-Me-hd)3 (II): пространственная группа P21/с, a = 10.0374(5) Å, b = 17.0798(7) Å, с = 15.7213(6) Å, β = 107.459(1)°, V = 2571.1(2) Å3, Z = 4, R = 0.0364. Соединения I и II изотипны, так как имеют одинаковые по строению молекулы, но кристаллизуются в разных сингониях. Кристаллические структуры I и II молекулярные и состоят из дискретных молекул M(γ-Me-hd)3 (M = Al, Fe). Термогравиметрические исследования показали, что комплексы I и II обладают близкой летучестью. Для комплекса Cu(γ-Me-hd)2 (III) проведено измерение давления насыщенного пара методом Кнудсена в интервале температур 100—150 °C, установлены термодинамические параметры сублимации и исследован термолиз паров.

Три летучих смешанно-металльных прекурсора [ZrL4Pb(hfa)2] (1), [ZrL4PbL2] (2) и [ZrL4La(dpm)3] (3) (L = 2-метокси-2,6,6-триметил-3,5-гептандионат; dpm = 2,2,6,6-тетраметил-3,5-гептандионат; hfa = 1,1,1,5,5,5-гексафтор-2,4-пентандионат) использованы для химического осаждения из газовой фазы (MOCVD) многокомпонентных пленок на основе оксида циркония. Эксперименты по осаждению проводились в реакторе с горячими стенками в диапазоне 600—750 °C на кремниевых подложках при 20 Торр, в присутствии кислорода. Рентгенофазовый анализ показал, что прекурсоры 1 и 2 дают пленки, где основные кристаллические фазы — это твердые растворы на основе тетрагональной и кубической ZrO2. Свинец не образует отдельные кристаллические фазы, однако по данным рентгенофотоэлектронной спектроскопии он растворен в матрице ZrO2 в виде оксида. Из 3 получены пленки La2Zr2O7 с использованием двух способов подачи прекурсора: испарение в потоке аргона и в системе прямого впрыска раствора (DLI). показано, что состав и структура полученных пленок определяются составом используемого предшественника. Обсуждаются результаты исследования термического поведения прекурсоров в конденсированной и газовой фазе.

The structures of two Al(III) and Fe(III) β-diketonates with a γ-substituted ligand are studied by single crystal X-ray diffraction at 150(2) K. Crystallographic data for Al(γ-Me-hd)3 (I) are: space group $$P\bar{1}$$ , a = 10.855(1) Å, b = 11.129(1) Å, с = 11.894(1) Å, α = 85.634(3)°, F0200062 = 73.118(3)°, γ = 66.771(3)°, V = 1262.2(2) Å3, Z = 2, R1 = 0.0438. For Fe(γ-Me-hd)3 (II): space group P21/с, a = 10.0374(5) Å, b = 17.0798(7) Å, с = 15.7213(6) Å, F0200062 = 107.459(1)°, V = 2571.1(2) Å3, Z = 4, R1 = 0.0364. Compounds I and II are isotypical because their molecules have the same structure but crystallize in different crystal systems. The crystal structures of I and II are molecular and consist of discrete M(γ-Me-hd)3 (M = Al, Fe) molecules. Thermogravimetric studies show that complexes I and II are similarly volatile. For Cu(γ-Me-hd)2 complex (III) the saturated vapor pressure is measured by the Knudsen method in the temperature range 100-150 °C. Sublimation thermodynamic parameters are found and vapor thermolysis is investigated.

A series of Ln(III) tris-dipivaloylmethanates with phenanthroline with the composition Ln(thd)3Phen (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) is synthesized. It is found that all adducts are isostructural with previously known La(thd)3Phen, Tb(thd)3Phen, and Dy(thd)3Phen complexes. Crystal structures of Sm(thd)3Phen (I) and Eu(thd)3Phen (II) complexes are determined at 150(2) K (space group $$P\overline 1 $$, a = 10.8590(5) Å, b = 12.3049(6) Å, c = 18.4479(10) Å, α = 80.210(2)°, β = 87.499(2)°, γ = 68.799(2)°, V = 2264.3(2) Å3, Z = 2; space group $$P\overline 1 $$, a = 10.8788(3) Å, b = 12.3009(3) Å, c = 18.4309(5) Å, α = 80.3644(9)°, β = 87.5440(10)°, γ = 68.7376(8)°, V = 2265.7(1) Å3, Z = 2 respectively). Crystal structures of I and II consist of isolated Ln(thd)3Phen molecules (Ln = Sm(III), Eu(III)). The highest luminescence quantum yields for this series of adducts are established for Eu(thd)3Phen (10%) and Sm(thd)3Phen (1.5%). Thermogravimetric studies show that the volatility of adducts weakly increases from Pr(thd)3Phen to Yb(thd)3Phen. Their melting points are close to the reported data.

The optical quality HfxTi1−xO2 films with a wide range of the Hf/Ti ratio were prepared on Si (100) substrates by the ALD method with the use of tetrakis(ethylmethylamido)hafnium(IV) (Hf(NC2H5CH3)4, TEMAH) and titanium(IV) chloride TiCl4 as Hf and Ti precursors, respectively. The H2O vapor was applied as oxygen source. The structural properties of the as-deposited and annealed films were evaluated by the XRD analysis. The Hf/Ti ratio in the films was measured by energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The dispersive optical constants were obtained by spectroscopic ellipsometry over the photon energy range of E = 1.12–4.96 eV. The specific growth kinetics is observed for 0 < x < 1. The optical constants wide-range tuning is reached in the HfxTi1−xO2 (x = 0–1) films via the chemical composition variation and annealing.

To provide the necessary electrical conductivity of microchannel plates, it is proposed that a thin RuOx film be used by means of its pulsed metalorganic chemical vapor deposition onto the walls of the channels. The chemical composition, structure, electrical conductivity, and secondary electron emission are studied using satellite samples. The RuOx film is shown to have a globular structure with a characteristic size of ~100 nm. The core of each globule (average size, ~21 nm) represents a mixture of the Ru and RuO2 phases with a ratio of nearly 4 : 6. The other part of the globule is amorphous with a Ru : RuO2 ratio of ~5.4 : 4.6. The electrical conductivity of the films has a metallic character. The secondary-electron-emission coefficient of RuOx increases from 2.5 to ~4 after annealing in air at temperatures up to 800°C.

To the best of our knowledge, it is the first time that the method of chemical vapor deposition (MOCVD) with platinum(II) bis(acetylacetonate) (Pt(acac)2) is used to obtain platinum coatings on the cathodes and anodes of the electrodes for pacemakers. The deposition processes are carried out under reduced pressure in the presence of oxygen. The phase and elemental composition, structure, and morphology of the coatings are examined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). Platinum coatings with a columnar structure are prepared in the temperature range 280-340°C. An increase in the deposition temperature leads to a change in the structure of the coatings and reduction in their thickness. Cyclic voltammetry (CV) is used to estimate the specific capacities of the platinum coatings on the cathodes and anodes, the maximum values of which are 426 mC/cm2 and 1160 mC/cm2, respectively.

Ligands with Schiff bases are obtained in the condensation of propylenediamine (pda) or 2,2-dimethylpropylenediamine (dmpda) with acetylacetone (Hacac) in the 1:2 molar ratio. The ligands are characterized by the elemental analysis methods, T melt = 90–92 °C for pda(Hacac)2 (pda(acac)2 is N,N′-propylene-bis(acetylacetoniminato) (2-)), T melt = 84–86 °C for dmpda(Hacac)2 (dmpda(acac)2 is N,N′-2,2-dimethylpropylene-bis(acetylacetoniminato) (2-)). The tautomerism of the ligands is established by the single crystal X-ray diffraction (XRD) analysis, IR spectroscopy, and 1H, 13C NMR spectrometry. The synthesized complexes [Cu(pda(acac)2)] (1), T melt = 121–122 °C and [Cu(dmpda(acac)2)] (2), T melt = 156–158 °C are studied by the XRD method. In both complexes, copper atoms have a planar square geometry, and the chelate bond lengths and angles are: Cu-O ≈ Cu-N 1.903(2)–1.942(3) Å, ∠O-Cu-N = 94.44(12)–94.99(12)° for 1 and Cu-O ≈ Cu-N 1.909(1)–1.943(2) Å, ∠O-Cu-N = 94.63(6)° for 2. By the thermogravimetric method it is found that both complexes can be passed practically quantitatively into the gas phase.

A new heteroleptic complex Cu(ki)(hfa) = Cu(ONC5H8)(O2C5F6H), where ki = pentane-2-imino-4-onato (ketoiminate) and hfa = 1,1,1,5,5,5-hexafluoro-pentane-2,4-dionato (hexafluoroacetylacetonate), has been obtained and its two crystalline modifications were characterized. The isolated polymorphs have different crystal symmetry and crystal packing of the molecules. Crystal data for the monomeric alpha-modification are: a = 16.4648(14), b = 16.4648(14), c = 4.9308(6), space group P (4) over bar, Z = 4, D-calc = 1.832 g/cm(3). Crystal data for the dimeric beta-modification are: a = 6.9718(14), b = 8.5694(17), c = 11.859(2), alpha = 87.81(3)degrees, beta = 77.96(3)degrees, gamma = 68.14(3)degrees, space group P (1) over bar, Z = 2, D-calc = 1.906 g/cm(3). Results of the TG/DTA study of the compound in the condensed phase and the mass spectrometric investigation in the vapor phase are discussed. The reported compound is thermally stable and sublimes in vacuum without decomposition into homoleptic complexes. For both polymorphs the temperature dependence of the saturated vapor pressure was measured by the Knudsen effusion method with the mass spectrometric recording of the gas phase composition within the range 322-343 K. (c) 2012 Elsevier Ltd. All rights reserved.

Two octahedral nickel complexes namely Ni(pda)(hfac)2 and Ni(pda)(thd)2 (pda—1,3-diaminopropane, hfac—1,1,1,5,5,5-hexafluoro-2,4-pentanedionato (−), thd—2,2,6,6-tetramethyl-3,5-heptanedionato (−)) were tested in a Metal-Organic Chemical Vapor Deposition (MOCVD) process. Based on density functional theory (DFT) calculations, the thermodynamic stability of molecules in the gas phase was estimated. The intramolecular bond was found in case of complex Ni(pda)(hfac)2. The different fragmentation mechanisms of complexes in the gas phase were examined by double focusing sector (DFS) mass spectrometry. According to TG/DTA analyses and P/T measurements compounds have good volatility. Deposition conditions resulting in one phase Ni films were established. Films compositions and structures were confirmed by XRD, EXAFS, XPS, and SEM. According to XRD and SEM, the average crystallite sizes and thicknesses of films deposited from Ni(pda)(hfac)2 were 12–34nm and 135–320nm, whereas from Ni(pda)(thd)2 they were 10–24nm and 100–380nm, respectively. The dependences of films thicknesses as a function of substrate temperatures have shown that complex Ni(pda)(hfac)2 is more stable in the gas phase than Ni(pda)(thd)2.

The matrix of a photonic crystal was deposited with gold nanoparticles and thin films using MOCVD technique. Nanoparticles were obtained in a pulse pressure MOCVD reactor; Me2Au(thd) (thd=2,2,6,6-tetramethyl-3,5-heptanedionato) was used as a precursor. The deposition of thin gold coating was carried out in a stagnant-flow MOCVD reactor, Me2Au(OAc) (OAc=acetate) was used as a precursor. It was demonstrated that deposition conditions affect the morphology of nanoparticles deposited from Me2Au(thd). An increase in the evaporator temperature was found to cause an increase in the concentration of gold nanoparticles on the surface of SiO2 microspheres, whereas their size is almost unchanged. Increasing the deposition temperature results in an increase in the size of the nanoparticles. Using the system of gold nanoparticles – fluorescein, we demonstrated that luminescence is enhanced by a factor of 2 as compared to the pure dye. We performed the deposition of thin gold films onto SiO2 microspheres and demonstrated that the thickness of gold coating is affected by the deposition temperature. Optical characteristics inherent in photonic crystals formed from gold microspheres were studied. The amount of impurities in the films is less than 3%.