Quantifying the Impact of Nanoparticle Coatings and Nonuniformities on XPS Analysis: Gold/Silver Core–Shell Nanoparticles
详细信息 查看全文
- 作者：Yung-Chen Wang ; Mark. H. Engelhard ; Donald R. Baer ; David G. Castner
- 刊名：Analytical Chemistry
- 出版年：2016
- 出版时间：April 5, 2016
- 年：2016
- 卷：88
- 期：7
- 页码：3917-3925
- 全文大小：445K
- ISSN：1520-6882
文摘
Spectral modeling of photoelectrons can serve as a valuable tool when combined with X-ray photoelectron spectroscopy (XPS) analysis. Herein, a new version of the NIST Simulation of Electron Spectra for Surface Analysis (SESSA 2.0) software, capable of directly simulating spherical multilayer NPs, was applied to model citrate stabilized Au/Ag-core/shell nanoparticles (NPs). The NPs were characterized using XPS and scanning transmission electron microscopy (STEM) to determine the composition and morphology of the NPs. The Au/Ag-core/shell NPs were observed to be polydispersed in size, nonspherical, and contain off-centered Au-cores. Using the average NP dimensions determined from STEM analysis, SESSA spectral modeling indicated that washed Au/Ag-core–shell NPs were stabilized with a 0.8 nm layer of sodium citrate and a 0.05 nm (one wash) or 0.025 nm (two wash) layer of adventitious hydrocarbon, but did not fully account for the observed XPS signal from the Au-core. This was addressed by a series of simulations and normalizations to account for contributions of NP nonsphericity and off-centered Au-cores. Both of these nonuniformities reduce the effective Ag-shell thickness, which effect the Au-core photoelectron intensity. The off-centered cores had the greatest impact for the particles in this study. When the contributions from the geometrical nonuniformities are included in the simulations, the SESSA generated elemental compositions that matched the XPS elemental compositions. This work demonstrates how spectral modeling software such as SESSA, when combined with experimental XPS and STEM measurements, advances the ability to quantitatively assess overlayer thicknesses for multilayer core–shell NPs and deal with complex, nonideal geometrical properties.