Lanthanum

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Lanthanum

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Orbitals and Energies #

Note – these are listed in BINDING ENERGY

 

La 3d ≈ 834 eV

La 3p ≈ 1125 eV

La 4s ≈ 275 eV

La 4p ≈ 194 eV

La 4d ≈ 98 eV

La 5s ≈ 35 eV

Lanthanum Chloride Survey With Peak Markers for Ru

Doublet Separations #

La 3d = 16.8 eV

La 4d = 2.85 eV

La 4p = 16.9 eV

XPS of La 3d with doublet separation

Common Overlaps for La 3d #

Ni 2pFe 2s – Tl 4s – Po 4p – In 3s – Te 3p – La MNN (Al Ka X-rays)Ce MNN (Al Ka X-rays)  – F KLL (Al Ka X-rays)

Cu metal by XPS: Cu 2p region with overlapping peak markers
Cu metal by XPS: Cu 2p region with overlapping peak markers

Auger Energies #

Note – these are listed in KINETIC ENERGY

 

La MNN ≈ 622 eV

XPS of La MNN Region

Common Binding Energies – Cu 2p #

Species #

B.E. / eV #

Charge Ref #

Reference #

La Metal

835.7

Au 4f (83.95 eV)

La2O3

834.8

C 1s (285 eV)

La(OH)3

837.2

C 1s (285 eV)

LaS3

837.1

C 1s (284.4 eV)

LaPO4

836.2 – 838.4

C 1s (284.9 eV)

Theory and Background #

Lanthanum metal consists of a typical asymmetric doublet with a spin-orbit separation of 16.8 eV.(1)

Note for below: WordPress does not support underlining characters – so core holes will be described using a bold text-type rather than an underlined text-type. Apologies for the confusion.

Lanthanum compounds however, undergo peak splitting and each spin-orbit coupled peak appears as a doublet (Figure 1). In general, this is due to the formation of one poorly screened final state (ground state – 4fn(3dn) – cf0) and one well-screened final state due to conduction band to 4f charge transfer screening (4fn+1(3dn+1+) – cf1L).(2)

La 3d Unscreened vs Screened

Experimental Advice #

Analysis of lanthanum by XPS is typically performed on the 3d orbitals, which may overlap with Fe 2s, In 3s as well as the KLL auger from flourine and the Ce LMM auger if using Al X-rays (1486.7 eV). Additionally, the La M4,5N4,5N4,5 auger overlaps with the La 3d peaks when using Al X-rays which may complicate peak analysis (can be separately modeled using a twin X-ray source).

Lanthanum oxide is prone to carbonate formation, and as such, heating in vacuo may be required to remove any carbonate layer prior to analysis.

La2O3 carbonate formation from exposure to UHV chamber overnight

Data Analysis Guidance #

The energy separation between the two maxima changes between the oxide and hydroxide, and in fact is often used as a simple method for determining chemical state .(5)

Interestingly, no spin orbit splitting may be observed for the La 4p region due to a Coster-Kronig process(8) but further splittings enable this region to be of use when dealing with lanthanum in XPS (Figure 3).(4)

Species Energy separation / eV Ref
La2O3 4.2 6
La(OH)3 3.9 7

 

La 3d Energy Splittings

Reference Datasets #

 

Coming soon

References #

  1. Islam, M. J., et al. (2020). “The effect of metal precursor on copper phase dispersion and nanoparticle formation for the catalytic transformations of furfural.” Applied Catalysis B: Environmental: 119062. Read it online here.
  2. Miller, A. and G. Simmons (1993). “Copper by XPS.” Surface Science Spectra 2(1): 55-60. Read it online here.
  3. Vasquez, R. (1998). “Cu2O by XPS.” Surface Science Spectra 5(4): 257-261. Read it online here.
  4. Vasquez, R. (1998). “CuO by XPS.” Surface Science Spectra 5(4): 262-266. Read it online here.
  5. Biesinger, M. C. (2017). “Advanced analysis of copper X‐ray photoelectron spectra.” Surface and interface analysis 49(13): 1325-1334. Read it online here.
  6. Thøgersen, A., et al. (2008). “An experimental study of charge distribution in crystalline and amorphous Si nanoclusters in thin silica films.” Journal of Applied Physics 103(2): 024308. Read it online here.
  7. Moretti, G. (1998). “Auger parameter and Wagner plot in the characterization of chemical states by X-ray photoelectron spectroscopy: a review.” Journal of Electron Spectroscopy and Related Phenomena 95(2-3): 95-144. Read it online here.
  8. Batista, J., et al. (2001). “On the structural characteristics of γ-alumina-supported Pd–Cu bimetallic catalysts.” Applied Catalysis A: General 217(1-2): 55-68. Read it online here.
  9. Ghijsen, Jacques, et al. “Electronic structure of Cu 2 O and CuO.” Physical Review B 38.16 (1988): 11322. Read it online here.