Synthesis and structures of zirconium amide-iodide complexes

Area of Science:

• Materials Science
• Inorganic Chemistry
• Chemical Engineering

Background:

• Zirconium nitride (ZrN) films are crucial for various applications due to their unique properties.
• Developing efficient precursors for ZrN deposition is essential for advancing thin-film technologies.

Purpose of the Study:

• Synthesize and characterize novel zirconium amide-iodide complexes.
• Evaluate their potential as precursors for chemical vapor deposition (CVD) of zirconium nitride films.
• Identify the most promising precursor based on physical properties.

Main Methods:

• Synthesis of six zirconium amide-iodide complexes (Zr(NR(2))(4-n)I(n)) via reaction of ZrI(4) and Zr(NR(2))(4).
• X-ray crystallographic analysis of selected complexes (Zr(NMe(2))(3)I, Zr(NEt(2))(2)I(2), Zr(NEt(2))I(3)).
• Solution characterization using NMR spectroscopy and molecular weight determination.

Main Results:

• Solid-state structures revealed dimeric and polymeric structures for the synthesized complexes.
• Zr(NMe(2))(3)I and Zr(NEt(2))(2)I(2) form discrete dimers in the solid state.
• Zr(NEt(2))I(3) forms a polymer of dimers in the solid state.
• NMR data and molecular weight determination suggest Zr(NEt(2))(3)I is monomeric in solution.
• Zr(NEt(2))(3)I exhibits favorable physical properties for CVD precursor applications.

Conclusions:

• A series of zirconium amide-iodide complexes were successfully synthesized.
• Structural characterization provided insights into their solid-state aggregation behavior.
• Zr(NEt(2))(3)I emerged as the most promising precursor candidate for zirconium nitride thin film deposition due to its advantageous physical properties.