Comparing postdeposition reactions of electrons and radicals with Pt nanostructures created by focused electron beam induced deposition

The ability of electrons and atomic hydrogen (AH) to remove residual chlorine from PtCl₂deposits created fromcis-Pt(CO)₂Cl₂by focused electron beam induced deposition (FEBID) is evaluated. Auger electron spectroscopy (AES) and energy-dispersive X-ray spectroscopy (EDS) measurements as well as thermodynamics calculations support the idea that electrons can remove chlorine from PtCl₂structures via an electron-stimulated desorption (ESD) process. It was found that the effectiveness of electrons to purify deposits greater than a few nanometers in height is compromised by the limited escape depth of the chloride ions generated in the purification step. In contrast, chlorine atoms can be efficiently and completely removed from PtCl₂deposits using AH, regardless of the thickness of the deposit. Although AH was found to be extremely effective at chemically purifying PtCl₂deposits, its viability as a FEBID purification strategy is compromised by the mobility of transient Pt–H species formed during the purification process. Scanning electron microscopy data show that this results in the formation of porous structures and can even cause the deposit to lose structural integrity. However, this phenomenon suggests that the use of AH may be a useful strategy to create high surface area Pt catalysts and may reverse the effects of sintering. In marked contrast to the effect observed with AH, densification of the structure was observed during the postdeposition purification of PtC_xdeposits created from MeCpPtMe₃using atomic oxygen (AO), although the limited penetration depth of AO restricts its effectiveness as a purification strategy to relatively small nanostructures.