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Thermochemical study of fluorinated magnesium BETA-DIKETONATE complexes: development of a promising class of volatile MOCVD precursors Full article

Journal The Journal of Chemical Thermodynamics
ISSN: 1096-3626 , E-ISSN: 0021-9614
Output data Year: 2026, Volume: 216, Article number : 107659, Pages count : 13 DOI: 10.1016/j.jct.2026.107659
Tags Magnesium beta-diketonates; DSC; Static method with glass membrane gauge-manometer; Vapor pressure; Thermodynamic characteristics; Melting and evaporation processes; Thermodynamic simulation
Authors Zelenina L.N. 1,2 , Nazarova A.A. 1 , Vikulova E.S. 1 , Makarenko А.М. 1 , Urbach A.A. 2 , Gelfond N.V. 1
Affiliations
1 Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, Russian Federation
2 Novosibirsk State University, 2 Pirogova Str.., 630090 Novosibirsk, Russian Federation

Funding (2)

1 FWUZ-2025-0004
2 Russian Science Foundation

Abstract: Heteroligand fluorinated magnesium beta-diketonate complexes are favorable precursors for metal-organic chemical vapor deposition (MOCVD) due to their availability, stability, high volatility and versatility for producing both oxide and fluoride films. Quantitative and reliable thermal data for these compounds are needed both to design of new effective precursors and to optimize the vaporization conditions precisely. Therefore, a thermochemical study of two complexes of this type, Mg(tmeda)(hfac)2 and Mg(tmeda)(ptac)2 (tmeda = N,N,N′,N-tetramethylethylenediamine, hfac = hexafluoroacetylacetonate, ptac = pivaloyltrifluoroacetonate), has been carried out for the first time. The thermal behavior of the complexes in the condensed phase was investigated by differential scanning calorimetry and the thermodynamic parameters of phase transitions (Ttr, ΔtrH°Ttr) were determined. The pressure of the saturated and unsaturated vapors of the complexes has been measured by the static method with a membrane-gauge manometer and a transpiration method in a wide interval of temperatures: 348–524 K for Mg(tmeda)(ptac)2 and 323–492 K for Mg(tmeda)(hfac)2. As a result of this study the thermal stability of compounds under study was established and based on the data on unsaturated vapors, it was concluded that both complexes pass into the gas phase in the form of a monomer. Equations approximating the dependences of saturated vapor pressure on temperature and also the enthalpies and entropies of sublimation (ΔsubH°T, ΔsubS°T) and vaporization (ΔvapH°T, ΔvapS°T) were determined from the experimental data. All thermodynamic values were obtained for the first time. In addition, thermodynamic simulation of MOCVD processes with the participation of the studied complexes as precursors was performed to provide a basis for selecting the conditions for the formation of MgF2 and MgO films using O2 and O2/H2O as co-reagents.
Cite: Zelenina L.N. , Nazarova A.A. , Vikulova E.S. , Makarenko А.М. , Urbach A.A. , Gelfond N.V.
Thermochemical study of fluorinated magnesium BETA-DIKETONATE complexes: development of a promising class of volatile MOCVD precursors
The Journal of Chemical Thermodynamics. 2026. V.216. 107659 :1-13. DOI: 10.1016/j.jct.2026.107659 Scopus OpenAlex
Dates:
Submitted: Aug 7, 2025
Accepted: Feb 25, 2026
Published online: Mar 2, 2026
Published print: Jul 31, 2026
Identifiers:
≡ Scopus: 2-s2.0-105031897303
≡ OpenAlex: W7133221124
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