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Electron beam-induced deposition of platinum from Pt(CO)₂Cl₂ and Pt(CO)₂Br₂.

ABSTRACT: Two platinum precursors, Pt(CO)₂Cl₂ and Pt(CO)₂Br₂, were designed for focused electron beam-induced deposition (FEBID) with the aim of producing platinum deposits of higher purity than those deposited from commercially available precursors. In this work, we present the first deposition experiments in a scanning electron microscope (SEM), wherein series of pillars were successfully grown from both precursors. The growth of the pillars was studied as a function of the electron dose and compared to deposits grown from the commercially available precursor MeCpPtMe₃. The composition of the deposits was determined using energy-dispersive X-ray spectroscopy (EDX) and compared to the composition of deposits from MeCpPtMe₃, as well as deposits made in an ultrahigh-vacuum (UHV) environment. A slight increase in metal content and a higher growth rate are achieved in the SEM for deposits from Pt(CO)₂Cl₂ compared to MeCpPtMe₃. However, deposits made from Pt(CO)₂Br₂ show slightly less metal content and a lower growth rate compared to MeCpPtMe₃. With both Pt(CO)₂Cl₂ and Pt(CO)₂Br₂, a marked difference in composition was found between deposits made in the SEM and deposits made in UHV. In addition to Pt, the UHV deposits contained halogen species and little or no carbon, while the SEM deposits contained only small amounts of halogen species but high carbon content. Results from this study highlight the effect that deposition conditions can have on the composition of deposits created by FEBID.

SUBMITTER: Mahgoub A

PROVIDER: S-EPMC7705861 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Electron beam-induced deposition of platinum from Pt(CO)2Cl2 and Pt(CO)2Br2.

Mahgoub Aya A Lu Hang H Thorman Rachel M RM Preradovic Konstantin K Jurca Titel T McElwee-White Lisa L Fairbrother Howard H Hagen Cornelis W CW

Beilstein journal of nanotechnology 20201127

Two platinum precursors, Pt(CO)2Cl2 and Pt(CO)2Br2, were designed for focused electron beam-induced deposition (FEBID) with the aim of producing platinum deposits of higher purity than those deposited from commercially available precursors. In this work, we present the first deposition experiments in a scanning electron microscope (SEM), wherein series of pillars were successfully grown from both precursors. The growth of the pillars was studied as a f ...[more]

PMID: 33299738

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Project description:A Pt-nanocoated layer (thickness of approx. 10-20 nm) with Pt-O-Ce bonds was created through the water radiolysis reaction on a CeO x nanowire (NW), which was induced by electron beam irradiation to the mixed suspension of K2PtCl4 aqueous solution and the CeO x NW. In turn, when Pt-nanocoated CeO x NW/C (Pt/C ratio = 0.2) was used in the cathode layer of a membrane electrode assembly (MEA), both an improved fuel cell performance and stability were achieved. The fuel cell performance observed for the MEA using Pt-nanocoated CeO x NW/C with Pt-O-Ce bonds, which was prepared using the electron beam irradiation method, improved and maintained its performance (observed cell potential of approximately 0.8 V at 100 mW cm-2) from 30 to 140 h after the start of operation. In addition, the activation overpotential at 100 mA cm-2 (0.17 V) obtained for MEA using Pt-nanocoated CeO x NW/C was approximately half of the value at 100 mA cm-2 (0.35 V) of MEA using a standard Pt/C cathode. In contrast, the fuel cell performance (0.775 V at 100 mW cm-2 after 80 h of operation) of MEA using a nanosized Pt-loaded CeO x NW (Pt/C = 0.2), which was prepared using the conventional chemical reduction method, was lower than that of MEA using a Pt-nanocoated CeO x /C cathode and showed reduction after 80 h of operation. It is considered why the nanocoated layer having Pt-O-Ce bonds heterogeneously formed on the surface of the CeO x NW and the bare CeO2 surface consisting of Ce4+ cations would become unstable in an acidic atmosphere. Furthermore, when a conventional low-amount Pt/C cathode (Pt/C = 0.04) was used as the cathode layer of the MEA, its stable performance could not be measured after 80 h of operation as a result of flooding caused by a lowering of electrocatalytic activity on the Pt/C cathode in the MEA. In contrast, a low-amount Pt-nanocoated CeO x NW (Pt/C = 0.04) could maintain a low activation overpotential (0.22 V at 100 mA cm-2) of MEA at the same operation time. Our surface first-principles modeling indicates that the high quality and stable performance observed for the Pt-nanocoated CeO x NW cathode of MEA can be attributed to the formation of a homogeneous electric double layer on the sample. Since the MEA performance can be improved by examining a more effective method of electron beam irradiation to all surfaces of the sample, the present work result shows the usefulness of the electron beam irradiation method in preparing active surfaces. In addition, the quantum beam technology such as the electron beam irradiation method was shown to be useful for increasing both performance and stability of fuel cells.

Dataset Information

Electron beam-induced deposition of platinum from Pt(CO)₂Cl₂ and Pt(CO)₂Br₂.

Publications

Electron beam-induced deposition of platinum from Pt(CO)<sub>2</sub>Cl<sub>2</sub> and Pt(CO)<sub>2</sub>Br<sub>2</sub>.

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