Remarkable Influence of molecular structure of N,N'-unsymmetrically substituted 1,3-amidinate and -guanidinate on the Volatility and the Thermal Stability of Precursors for HfO 2 Films via Liquid Injection-MOCVD

The identification of appropriate ligand-metal combinations, which successfully present the features of : (i) having acceptable melting point, (ii) being more thermally stable than hafnium alkylamides, (iii) having sufficient volatility for vapor phase distribution and (iv) enabling the deposition by LI-MOCVD and ALD of hafnium containing thin films, should go through new generations of well-behaved molecular precursors. We report herein the chemical design and full characterizations of a portfolio of novel mono- and di- amidinate and guanidinate alkylamide hafnium complexes of N,N'-unsymmetrically substituted 1,3-amidinate and 1,3-guanidinate [R'-N=CX-NR"]xHf(NR2)4-x (R'≠ R" = Et, iPr, tBu ; R = Me or Et ; X = Me or NMe2 ; x = 1 or 2). We will exemplify the remarkable influence of the molecular structure on the melting point, the volatility and the thermal stability (see figure 1) and the nature (cubic, monoclinic) of HfO2 thin films by LI-MOCVD.