Comparative study of thermal behavior of a series beta-diketonate precursors for chemical vapor deposition of lithium-containing films

• Published in: Vacuum Vol. 215; p. 112359
• Main Authors: Turgambaeva, Asiya E., Urkasym kyzy, Samara, Korolkov, Ilya V., Maksimovskiy, Evgene A., Syrokvashin, Mikhail M., Stabnikov, Pavel A., Krisyuk, Vladislav V.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01-09-2023
• Subjects: ALD precursors; Deposition mechanism; Lithium containing films; Lithium diketonates; MOCVD precursors; TFLBs; Thermal stability; MOCVD precursors; Deposition mechanism; Lithium containing films; Lithium diketonates; ALD precursors; TFLBs; Thermal stability
• ISSN: 0042-207X; 1879-2715
• DOI: 10.1016/j.vacuum.2023.112359

Five volatile lithium beta-diketonates: Li(tmhd) (1), Li(pta) (2), LiL (3), LiLF (4), Li(tmha) (5) (tmhd = 2,2,6,6-tetramethyl-heptane-3,5-dionate, pta = 1,1,1-trifluoro-5,5-dimethyl-hexane-2,4-dionate, L = 2-methoxy-2,6,6-trimethyl-heptane-3,5-dionate, LF = 1,1,1-trifluoro-5-methoxy-5-methyl-hexane-2,4-dionate, tmha = 2,2,6,6-tetramethyl-heptane-3-imino-5-onate) and lithium alkoxide Li(OtBu) (6) were examined by combination of several complementary methods to study their thermal behavior in solid and gas phase and to check their suitability as precursors for chemical vapor deposition of Li-containing films. The best storage stability was observed for 3 and 4. Thermal gravimetric analysis and vacuum sublimation test were used to compare stability of the complexes under vaporization. In situ mass spectrometry was used to study the gas phase composition and the surface decomposition chemistry. Diketonate complexes 1, 3-5 passed into the gas phase as tetranuclear particles. Upon further heating, they split into binuclear species. The binuclear species thermolysis is responsible for the film deposition. The vapor thermal stability in oxygen increases in the row 3 > 1>5 > 2>4 > 6. CVD films obtained at 500 °C in the presence of oxygen using 1, 3 and 5 consisted of Li2CO3. LiF films can be obtained using 2, while 4 allow one to obtain the Li metal films in the oxygen presence on both Si and Pt/Si substrates.
•Lithium beta-diketonates with improved storage stability.•Lithium beta-diketonates vaporize as tetranuclear molecules.•New precursors for Li-containing film materials.•Lithium metal films chemical vapor deposition in oxygen presence.