The Preparation and Properties of Volatile Tris(N‑Alkoxycarboxamidato)chromium(III) Complexes as Potential Single-Source Precursors for the MOCVD of Crystalline Chromium Oxide Thin Films

挥发性三(N-烷氧基羧酰胺)铬(III)配合物的制备及性能研究及其作为MOCVD法制备结晶氧化铬薄膜的潜在单源前驱体的应用

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Abstract

The synthesis, characterization, and vapor-phase growth of volatile Cr-(III) complexes as single-source precursors for Cr(2)O(3) thin films are reported. A series of Cr complexesCr-(mdpa)(3) (mdpa = N-methoxy-2,2-dimethylpropanamide) (1), Cr-(edpa)(3) (edpa = N-ethoxy-2,2-dimethylpropanamide) (2), Cr-(empa)(3) (empa = N-ethoxy-2-methylpropanamide) (3), and Cr-(mpa)(3) (mpa = N-methoxypropanamide) (4)were synthesized via salt elimination reactions between CrCl(3)·3THF and N-alkoxy carboxamidate salts. These complexes were characterized by Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis (TGA), single-crystal X-ray diffraction (SC-XRD), Hirshfeld surface analysis, powder X-ray diffraction (PXRD), and vapor pressure measurement. The crystal structure of complex 1 revealed a distorted octahedral geometry with a κ(2) (O,O) binding mode. TGA demonstrated that complex 1 underwent weight loss at 132 °C and no residue remained at 500 °C. The enthalpy of vaporization of 1 was estimated to be 25.58 kJ/mol, making it an optimal precursor for Cr(2)O(3) thin films. The XRD patterns of Cr(2)O(3) films deposited on SiO(2)/Si substrates confirmed their crystalline nature, showing prominent peaks at 2θ = 33.5° and 41.5°. In addition, X-ray photoelectron spectroscopy validated the target Cr/O ratio, supporting the successful formation of Cr(2)O(3) films.

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