Deposition of osmium thin films using pyrazolate complexes as CVD source reagents

Abstract

The reaction of Os 3 (CO) 12 with 1.2 eq. of pyrazole (3,5-(CF 3 ) 2 -pz)H at 190 uC affords triosmium complex Os 3 (CO) 10 (3,5-(CF 3 ) 2 -pz)(m-H) (1) as the isolable product. Upon further treatment with excess pyrazole (3,5-(CF 3 ) 2 -pz)H under more forcing conditions, complex 1 converts to a diosmium pyrazolate complex [Os(CO) 3 (3,5-(CF 3 ) 2 -pz)] 2 (2) in high yield. These osmium complexes are characterized by spectroscopic methods and single crystal X-ray diffraction study, showing the expected triangular and linear Os-Os backbone and with one and two bridging pyrazolate ligands for complexes 1 and 2, respectively. The thermal properties are studied by TG analysis and the deposition experiments are carried out using a cold-wall CVD apparatus. The as-deposited thin films are characterized using XPS, XRD and SEM and electrical resistivity measurement. It seems that the Os metal thin films are best deposited at an optimal temperature of 450-500 uC and using complex 2 as the source reagent.

π-stacking intercalation and reductant assisted stabilization of osmium organosol for catalysis and SERS applications

“…Among them, are the well-known wet chemical methods, chemical vapor deposition (CVD), electro deposition and pulsed laser deposition (PLD) in recent years. [14][15][16] There are few reports for the fruitful preparation of Os NPs with different sizes and morphologies such as nano-wires, 17 nano-clusters, 18 wire-like aggregates in an organic-aqueous hybrid medium 19 and thin lms. 15 Krämer et al prepared iron, ruthenium, and osmium NPs using a metal carbonyl precursor as starting material.…”

“…[14][15][16] There are few reports for the fruitful preparation of Os NPs with different sizes and morphologies such as nano-wires, 17 nano-clusters, 18 wire-like aggregates in an organic-aqueous hybrid medium 19 and thin lms. 15 Krämer et al prepared iron, ruthenium, and osmium NPs using a metal carbonyl precursor as starting material. 12 Os thin lm was fabricated from osmacene at higher temperature by atomic layer deposition technique.…”

Osmium Organosol on DNA: Application in Catalytic Hydrogenation Reaction and in SERS Studies

“…As a result of various properties of Os and its oxides, Os metal is a demanding material to manufacture and work with. Different types of routes have been employed for the formation of Os NPs mostly in thin film form, for example, chemical vapor deposition (CVD), physical vapor deposition (PVD), electrodeposition, vacuum pyrolysis, and sol–gel techniques. Os metal generally alloys with other materials like Os doped SnO 2 used as a sensor and Os–Pd NPs used in catalytic reactions. , Different types of biomolecules like amino acids, peptides, and protein have been used as a template and as a stabilizing agent during NPs synthesis.…”

A Study of Unsaturated Pyrazolate-Bridged Diruthenium Carbonyl Complexes

“…Alternatively, the same reaction product can be isolated in comparable yield via heating of a hexane solution of Ru 3 (CO) 12 and (dmpz)H in a stainless steel autoclave (170 °C, 24 h). In this case, the reaction conditions are akin to those used for the synthesis of the diosmium pyrazolate complex [Os 2 (CO) 6 (hfpz) 2 ], hfpz = 3,5-bis(trifluoromethyl)pyrazolate, described in the literature . Interestingly, both the literature report and our experimental observation have revealed that complex 1a does not lose CO even at elevated temperature and under vacuum.…”