title: Effects of laser energy and wavelength on the analysis of LiFePO₄ using laser assisted atom probe tomography.
abstract: The effects of laser wavelength (355 nm and 532 nm) and laser pulse energy on the quantitative analysis of LiFePO₄ by atom probe tomography are considered. A systematic investigation of ultraviolet (UV, 355 nm) and green (532 nm) laser assisted field evaporation has revealed distinctly different behaviors. With the use of a UV laser, the major issue was identified as the preferential loss of oxygen (up to 10 at%) while other elements (Li, Fe and P) were observed to be close to nominal ratios. Lowering the laser energy per pulse to 1 pJ/pulse from 50 pJ/pulse increased the observed oxygen concentration to nearer its correct stoichiometry, which was also well correlated with systematically higher concentrations of (16)O₂(+) ions. Green laser assisted field evaporation led to the selective loss of Li (~33% deficiency) and a relatively minor O deficiency. The loss of Li is likely a result of selective dc evaporation of Li between or after laser pulses. Comparison of the UV and green laser data suggests that the green wavelength energy was absorbed less efficiently than the UV wavelength because of differences in absorption at 355 and 532 nm for LiFePO₄. Plotting of multihit events on Saxey plots also revealed a strong neutral O2 loss from molecular dissociation, but quantification of this loss was insufficient to account for the observed oxygen deficiency.
authors.affiliation: Department of NanoEngineering, University of California San Diego, CA 92093, USA.
authors.forename: Dhamodaran
authors.initials: D
authors.lastname: Santhanagopalan
authors.affiliation: Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA 99354, USA.
authors.forename: Daniel K
authors.initials: DK
authors.lastname: Schreiber
authors.affiliation: Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99354, USA.
authors.forename: Daniel E
authors.initials: DE
authors.lastname: Perea
authors.affiliation: Central Analytical Facility, University of Alabama, Tuscaloosa, AL 35487, USA.
authors.forename: Richard L
authors.initials: RL
authors.lastname: Martens
authors.affiliation: Department of Chemistry, Stony Brook University, Stony Brook, NY 11790-3400, USA.
authors.forename: Yuri
authors.initials: Y
authors.lastname: Janssen
authors.affiliation: Department of Chemistry, Stony Brook University, Stony Brook, NY 11790-3400, USA; Department of Chemistry, Brookhaven National Laboratory, Upton, NY 11793-5000, USA.
authors.forename: Peter
authors.initials: P
authors.lastname: Khalifah
authors.affiliation: Department of NanoEngineering, University of California San Diego, CA 92093, USA. Electronic address: shirleymeng@ucsd.edu.
authors.forename: Ying Shirley
authors.initials: YS
authors.lastname: Meng
keywords: Atom probe tomography; LiFePO(4); Molecular dissociation; Oxides; Stoichiometry