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Title: Effects of laser energy and wavelength on the analysis of LiFePO₄ using laser assisted atom probe tomography

Journal Article · · Ultramicroscopy
 [1];  [2];  [2];  [3];  [4];  [5];  [1]
  1. Univ. of California, San Diego, CA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Univ. of Alabama, Tuscaloosa, AL (United States)
  4. Stony Brook Univ., NY (United States)
  5. Stony Brook Univ., NY (United States); Brookhaven National Lab., Upton, NY (United States)

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 ¹⁶O₂⁺ 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.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
SC00112704; SC0001294; AC05-76RL01830; NSF-MRI-0722631
OSTI ID:
1182519
Alternate ID(s):
OSTI ID: 1247882
Report Number(s):
BNL-107514-2015-JA; R&D Project: CO009; KC0302010
Journal Information:
Ultramicroscopy, Vol. 148, Issue C; ISSN 0304-3991
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 51 works
Citation information provided by
Web of Science

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Cited By (3)

Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes journal August 2015
Three-dimensional nanoscale characterisation of materials by atom probe tomography journal November 2016
Behavior of molecules and molecular ions near a field emitter journal March 2016