Initial growth of chemical-vapor-deposited Ru from bis(hexafluoroacetylacetonate)dicarbonyl ruthenium

Metal–Organic Derivatives with Fluorinated Ligands as Precursors for Inorganic Nanomaterials

“…Later, Puddephatt et al and Chi et al synthesized several heteroleptic allyl−β-diketonate and allyl−ketoiminate complexes of palladium, respectively, with required volatility and thermal stability for CVD applications. 420 39,147,424 As compared to the organometallic ruthenium CVD precursors Ru 3 (CO) 12 425−427 and [Ru(CO) 4 (hexafluoro-2-butyne)], 428 the isolated mixed-ligand complexes [Ru-(CO) 2 (hfac) 2 ], 147,407 [Ru(CO) 2 (amak F ) 2 ], and [Ru(COD)-(amak F ) 2 ] 39 had better stability and could be volatilized at temperatures below 250°C. Deposition of the Ru thin film was achieved using a H 2 carrier gas or a mixture of 2% oxygen in argon.…”

Atomic Layer Modulation of Multicomponent Thin Films through Combination of Experimental and Theoretical Approaches

“…Figure shows the top view images of DFT-optimized adsorption structures of Carish and TMA. On the pure metallic Ru substrate, adsorption of the Carish precursor was found to occur dissociatively even without presence of H or OH on the surface, as shown in the chemical equation below: On the other hand, on oxide subrates with OH groups as in the current study, the precursor can be expected to partially lose its ligands. , The heteroleptic Carish precursor is expected to adsorb via losing CO ligands as the byproduct, retaining the diketonate ligands and forming dative bonds with OH groups ( E ads = +1.24 eV, chemical equation , Figure a). While it is also possible to form another adsorption structure, via protonation of the diketonate ligands, retention of CO, and formation of direct Ru–O bonds, such a structure is highly endothermic ( E ads = +2.39 eV, chemical equation , not shown) and, thus, ignored. For adsorption of TMA, the Al atom of TMA was adsorbed on the O atom of the surface hydroxyl (−OH). , While TMA is known to produce a mixture of −Al­(CH 3 ) and −Al­(CH 3 ) 2 upon adsorption onto the substrate surface, ,− in the interest of clarity in the discussion, we have assumed −Al­(CH 3 ) to be the only surface product of TMA ( E ads = −3.11 eV, chemical equation , Figure b). Then, coadsorption of Carish and TMA as in the C-T and T-C sequences is considered.…”

“…On the pure metallic Ru substrate, adsorption of the Carish precursor was found to occur dissociatively even without presence of H or OH on the surface, 24 as shown in the chemical equation I below: On the other hand, on oxide subrates with OH groups as in the current study, the precursor can be expected to partially lose its ligands. 32,33 The heteroleptic Carish precursor is expected to adsorb via losing CO ligands as the byproduct, retaining the For adsorption of TMA, the Al atom of TMA was adsorbed on the O atom of the surface hydroxyl (−OH). 34,35 While TMA is known to produce a mixture of −Al(CH 3 ) and −Al(CH 3 ) 2 upon adsorption onto the substrate surface, 34,36−38 in the interest of clarity in the discussion, we have assumed −Al(CH 3 ) to be the only surface product of TMA (E ads = −3.11 eV, chemical equation IV, Figure 2b).…”

Ruthenium complexes as precursors for chemical vapor-deposition (CVD)

“…Cheng et al 109 investigated the initial growth behavior of ruthenium (Ru) on Si (100) surfaces from (Ru(hfac) 2 (CO) 2 ) in a temperature range of 548 # T # 623 K using atomic force microscopy and X-ray photoelectron spectroscopy. The Volmer- Weber growth 110 dominates the initial stage of the deposition for the growing sample and the nucleation rate increases with increasing substrate surface termination sites.…”