Synthesis of Zirconium Guanidinate Complexes and the Formation of Zirconium Carbonitride via Low Pressure CVD

Abstract

Thin films of zirconium carbonitride have been deposited on glass at 600°C from two novel guanidinate precursors: [ZrCp′{η 2 -( i PrN) 2 CNMe 2 } 2 Cl] (1) and [ZrCp′ 2 {η 2 -( i PrN) 2 CNMe 2 }Cl] (2) (Cp′ ) monomethylcyclopentadienyl). Both compounds 1 and 2 were structurally characterized by X-ray crystallography. The films grown via low pressure chemical vapor deposition (LPCVD) from compound 1 were mirrorlike with a red-brown sheen whereas those from 2 were gray. Chlorine was present in the films although the levels were no higher than 3 at.%. These two compounds clearly show how the coordination environment around the metal center affects the composition of the film, as films from 1 were nitrogen rich and those from 2 were carbon rich. The films were uniform, adhesive, abrasion resistant, conformal, and hard, being resistant to scratching with steel and brass scalpels.

Atmospheric Pressure Chemical Vapour Deposition of TiCl4 and tBuAsH2 to Form Titanium Arsenide Thin Films

“…[4][5][6][7] Additionally, we have used silylamines and azides as precursors, which resulted in high quality TiN films, [8][9][10] and this methodology can be extended to other transition metal nitrides. [11] As the understanding of the roles of the precursor have developed, more user-friendly (i.e. safer and easier to handle) precursors have been introduced that have proved capable of not only depositing at much lower deposition temperatures, but also in producing high quality deposits.…”

Novel ion pairs obtained from the reaction of titanium(IV) halides with simple arsane ligands

“…The deposition of transition metal pnictide thin films is a growing area of research, owing mainly to the useful properties of these films, examples being TiN (Carmalt et al, 2002;Newport et al, 2002), ZrN (Potts et al, 2009), TiP (Blackman et al, 2004), TiAs (Thomas, Blackman et al, 2010), CoAs (Senzaki & Gladfelter, 1994;Klingan et al, 1995) and MnAs (Lane et al, 1994). Such films are often grown by chemical vapour deposition (CVD).…”

Di-μ-chlorido-bis[dichloridobis(methylamido-κN)bis(methylamine-κN)titanium(IV)]

“…As part of recent work into the synthesis of molecular precursors for the deposition of transition metal pnictide thin films (Potts et al, 2009;Thomas, Blackman et al, 2010;Thomas et al, 2011), we recently reported an unusual ligand-exchange reaction between TiCl 4 and As(NMe 2 ) 3 (Thomas, Pugh et al, 2010). The reaction of one equivalent of As(NMe 2 ) 3 with TiCl 4 did not afford the 1:1 adduct [TiCl 4 {As(NMe 2 ) 3 }].…”