Titanium

View Categories

Titanium

9 min read

Orbitals and Energies #

Note – these are listed in BINDING ENERGY

 

Ti 2p ≈ 454 eV

Ti 2s ≈ 566 eV

Ti 3s ≈ 59 eV

Ti 3p ≈ 34 eV

TiO2 by XPS - Survey spectrum with peak markers
TiO2 by XPS - Survey spectrum with peak markers

Doublet Separations #

Ti 2p (metal) = 6.1 eV

Ti 2p (nitride) = 6.0 eV

Ti 2p (oxide) = 5.7 eV

XPS of Ti 2p with doublet separation

Common Overlaps for Ti 2p #

Ru 3p – Ta 4p – In 3d – Er 4s – Os 4p – Bi 4d

Ti metal by XPS - Ti 2p peaks with overlap markers
Ti metal by XPS - Ti 2p peaks with overlap markers

Auger Energies #

Note – these are listed in KINETIC ENERGY

 

Ti LMM ≈ 410 eV

Common Binding Energies – Ti 2p #

Species #

B.E. / eV #

Charge Ref #

Reference #

Ti Metal

454

Au 4f (84 eV)

TiO2

455.3

Au 4f (84 eV)

TiN

459.3

Au 4f (84 eV)

Ti2O3

456.6

C 1s (284.6 eV)

TiO

454.4

C 1s (284.6 eV)

TiS2

456

C 1s (284.6 eV)

TiS3

455.9

C 1s (284.6 eV)

Theory and Background #

Calculations confirm there is some multiplet structure associated with Ti(II) and Ti(III) free ions, though this may not be well resolved in XPS spectra.
 
The sources do not specifically discuss shake-up satellites in titanium spectra, but it is mentioned that shake-up structure can complicate the interpretation of transition metal 2p spectra.(6)
TiO2 XPS spectrum
P-25 TiO2 Ti 2p XP spectrum

Experimental Advice #

TiO2 is readily reduced by Ar+ sputtering, forming suboxides.

TiO2 etching showing formation of reduced species

Data Analysis Guidance #

XPS of titanium is typically performed on the 2p region. Unlike later first row TMs Ti 2p does not undergo multiplet splittings in it’s compounds, due to a lack of unpaired d-electrons. Ti 2p does, however, feature asymmetric peak broadening due to a Coster-Kronig transition and so care should be taken when peak fitting. The Ti 2p1/2 may be fit with a FWHM wider than that of the Ti 2p3/2.

Ti 2p peaks are mostly uncomplicated doublets (Figure 1) with a separation of around 6 eV (see table 1).

The exception to this is titanium nitride (TiN) which exhibits a complex structure including shake-up peaks, bulk and surface plasmons.(2)

 

Figure 2: Ti 2p spectra recorded from Anatase TiO2.(3)

Reference Datasets #

 

Coming soon

References #

  1. Kumar, S., et al. (2017). “P25@ CoAl layered double hydroxide heterojunction nanocomposites for CO2 photocatalytic reduction.” Applied Catalysis B: Environmental 209: 394-404. Read it online here.
  2. Jaeger, D. and J. Patscheider (2013). “Single crystalline oxygen-free titanium nitride by XPS.” Surface Science Spectra 20(1): 1-8. Read it online here.
  3. Badrinarayanan, S., et al. (1989). “XPS studies of nitrogen ion implanted zirconium and titanium.” Journal of Electron Spectroscopy and Related Phenomena 49(3): 303-309. Read it online here.
  4. Diebold, U. and T. Madey (1996). “TiO2 by XPS.” Surface Science Spectra 4(3): 227-231. Read it online here.
  5. Gonbeau, D., et al. (1991). “XPS study of thin films of titanium oxysulfides.” Surface science 254(1-3): 81-89. Read it online here.
  6. Biesinger, Mark C., et al. “Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn.” Applied surface science 257.3 (2010): 887-898. Read it online here.