Basic XPS Information Section

The Basic XPS Information Section provides fundamental XPS spectra, BE values, FWHM values, BE tables, overlays of key spectra, histograms and a table of XPS parameters.
The Advanced XPS Information Section is a collection of additional spectra, overlays of spectra, peak-fit advice, data collection guidance, material info,
common contaminants, degradation during analysis, auto-oxidation, gas capture study, valence band spectra, Auger spectra, and more.
Published literature references, and website links are summarized at the end of the advanced section.
→  Periodic Table – HomePage                  XPS Database of Polymers                      → Six (6) BE Tables

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Cerium (Ce)

 

Deveroite – Ce2(C2O4)3 · 10H2O	Metal – Ceo	Monazite – Ce(PO4)

 

Page Index
Pure Element Spectra with Peak-fits IMFP and Cross-sections for Pure Element Native Oxide Spectra with Peak-fits Pure Oxide Spectra with Peak-fits	Valence Band Spectra Six (6) Tables of Chemical State BEs  Histograms of NIST BEs Advanced XPS Information Section	Peak-fits and Overlays of Ce Chemical Compounds	Auger Peaks and Spectra Contamination XPS Facts, Guidance, Information Chemical State Spectra from Literature

• Expert Knowledge & Explanations

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Cerium (Ce^o) Metal

Peak-fits, BEs, FWHMs, and Peak Labels

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Cerium (Ceo) Metal Ce (3d) Spectrum – raw spectrum	Cerium (Ceo) Metal Peak-fit of Ce (3d) Spectrum
→  Periodic Table – HomePage
Cerium (Ceo) Metal Ce (3d) Spectrum – extended range	Cerium (Ceo) Metal Peak-fit of Ce (3d3/2) Spectrum
Survey Spectrum of Cerium (Ceo) Metal with Peaks Integrated, Assigned and Labelled
→  Periodic Table  XPS Signals for Cerium, (Ceo) Metal Spin-Orbit Term,  BE (eV) Value, and Scofield σ for Aluminum Kα X-rays (1486 eV, 8.33 Ang) Overlaps Spin-Orbit Term BE (eV) Value Scofield σ from 1486 eV X-rays IMFP (TPP-2M) in Å Ce (3p1/2) 1272 xxx xxx Ce (3p3/2) 1184 12.53 xxx Ce (3d3/2) 901.45 21.12 xxx Ba (Auger) overlaps Ce (3d5/2) 883.56 30.50 xxx C (1s) overlaps Ce (4s) 290 1.24 xxx Cl (2p) overlaps Ce (4p3/2) 207 3.03 xxx Si (2p) & Hg (4f) overlap Ce (4d) 109 6.93 σ:  abbreviation for the term Scofield Photoionization Cross-Section which is used with IMFP and TF to generate RSFs and atom% quantitation Plasmon Peaks Energy Loss Peaks Auger Peaks Energy Loss    Intrinsic Plasmon Peak:  ~xx eV above peak max Expected Bandgap for CeO2: xx  eV Work Function for Ce:  xx eV *Scofield Cross-Section (σ) for C (1s) = 1.0 →  Periodic Table    Valence Band Spectrum from CeO2     Plasmon Peaks from Ceo Metal  Fresh exposed bulk produced by extensive Ar+ ion etching Ce (3d) – Extended Range Spectrum Ce (3d) – Extended Range Spectrum – Vertically Zoomed →  Periodic Table    Ce (LMM) Auger Peaks from Ceo Metal  Fresh exposed bulk produced by extensive Ar+ ion etching Ceo Metal – main Auger peak Ceo Metal – full Auger range   Features Observed xx xx xx →  Periodic Table    Evidence for Breakdown in One-Electron Orbital Concept in Elements Z=46 (Palladium) to Z= 59 (Praseodymium) Rhodium (4s) and (4p) Peakshapes Cerium (4s) and (4p) Peakshapes Praseodymium (4s) and (4p) Peakshapes Reference: G. Wendin, Breakdown of One-Electron Pictures in Photoelectron Spectra, Structure and Bonding Series #45, Springer-Verlag, New York, 1981
Artefacts Caused by Argon Ion Etching
C (1s) from Metal Carbide(s) can form when ion etched Reactive Metal Surfaces capture Residual UHV Gases (CO, H2O, CH4 etc)	Argon Trapped in Ceo can form when Argon Ions are used to removed surface contamination
Side-by-Side Comparison of Cerium Carbonate & Cerium Oxide Ce2CO3 – nH2O & CeO2 Peak-fits, BEs, FWHMs, and Peak Labels
Ce2CO3 – nH2O	CeO2
Ce (3d) from Ce2CO3 – nH2O Flood Gun ON C (1s) at 285.0 eV	Ce (3d) from CeO2 Flood Gun ON Charge Referenced to C (1s) at 285.0 eV
	.
Ce2CO3 – nH2O	CeO2
C (1s) from Ce2CO3-nH2O C (1s) at 285.0 eV Flood Gun ON	C (1s) from CeO2 Flood Gun ON Charge Referenced to C (1s) at 285.0 eV
→  Periodic Table
	.
Ce2CO3 – nH2O	CeO2
O (1s) from Ce2CO3 – nH2O C (1s) at 285.0 eV Flood Gun ON	O (1s) from CeO2 Flood Gun ON Charge Referenced to C (1s) at 285.0 eV
→  Periodic Table

Survey Spectrum of Cerium Carbonate, Ce₂CO₃-nH₂O
with Peaks Integrated, Assigned and Labelled

 

→  Periodic Table 

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Survey Spectrum of Cerium Oxide, CeO₂
with Peaks Integrated, Assigned and Labelled

→  Periodic Table  

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Overlays of Ce (3d) Spectra for
Cerium Ce^o metal, Ce₂CO₃, and CeO₂

Caution: BEs from Grounded Native Oxides can be Misleading if Flood Gun is ON

Overlay of Ceo metal and Ce2CO3 – Ce (3d) Native Oxide C (1s) = 285.0 eV (Flood gun OFF) Chemical Shift:  -1.1 eV	Overlay of Ceo metal and CeO2 – Ce (3d) Pure Oxide C (1s) = 285.0 eV Chemical Shift:  -1.8 eV
→  Periodic Table	Copyright ©:  The XPS Library

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Overlay of Ce (3d)
Ce^o Metal, Ce₂CO₃ , & CeO₂

Features Observed

• xx
• xx
• xx

→  Periodic Table 

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Valence Band Spectra
Ce₂CO₃, CeO₂ 

Ce2CO3 Pressed powder	CeO2  Flood gun is ON,  Charge referenced so C (1s) = 285.0 eV
Overlay of Valence Band Spectra for Ce2CO3 and CeO2

Features Observed

• xx
• xx
• xx

→  Periodic Table 

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Cerium Minerals, Gemstones, and Chemical Compounds
Bastnäsite – Ce(CO3)F	Percleveite – Ce2Si2O7	Tancaite – FeCe(MoO4)3 · 3H2O	Fergusonite – CeNbO4 · 0.3H2O

→  Periodic Table 

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Six (6) Chemical State Tables of Ce (3d_5/2) BEs

 

• The XPS Library Spectra-Base
• PHI Handbook
• Thermo-Scientific Website
• XPSfitting Website
• Techdb Website
• NIST Website

→  Periodic Table 

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Notes of Caution when using Published BEs and BE Tables from Insulators and Conductors:

• Accuracy of Published BEs
  • The accuracy depends on the calibration BEs used to calibrate the energy scale of the instrument.  Cu (2p_3/2) BE can vary from 932.2 to 932.8 eV for old publications 
  • Different authors use different BEs for the C (1s) BE of the hydrocarbons found in adventitious carbon that appears on all materials and samples.  From 284.2 to 285.3 eV
  • The accuracy depends on when the authors last checked or adjusted their energy scale to produce the expected calibration BEs
• Worldwide Differences in Energy Scale Calibrations
  • For various reasons authors still use older energy scale calibrations 
  • Some authors still adjust their energy scale so Cu (2p_3/2) appears at 932.2 eV or 932.8 eV because this is what the maker taught them
  • This range causes BEs in the higher BE end to be larger than expected 
  • This variation increases significantly above 600 eV BE
• Charge Compensation
  • Samples that behave as true insulators normally require the use of a charge neutralizer (electron flood gun with or without Ar+ ions) so that the measured chemical state spectra can be produced without peak-shape distortions or sloping tails on the low BE side of the peak envelop. 
  • Floating all samples (conductive, semi-conductive, and non-conductive) and always using the electron flood gun is considered to produce more reliable BEs and is recommended.
• Charge Referencing Methods for Insulators
  • Charge referencing is a common method, but it can produce results that are less reliable.
  • When an electron flood gun is used, the BE scale will usually shift to lower BE values by 0.01 to 5.0 eV depending on your voltage setting. Normally, to correct for this flood gun induced shift, the BE of the hydrocarbon C (1s) peak maximum from adventitious carbon is used to correct for the charge induced shift.
  • The hydrocarbon peak is normally the largest peak at the lowest BE. 
  • Depending on your preference or training, the C (1s) BE assigned to this hydrocarbon peak varies from 284.8 to 285.0 eV.  Other BEs can be as low as 284.2 eV or as high as 285.3 eV
  • Native oxides that still show the pure metal can suffer differential charging that causes the C (1s) and the O (1s) and the Metal Oxide BE to be larger
  • When using the electron flood gun, the instrument operator should adjust the voltage and the XY position of the electron flood gun to produce peaks from a strong XPS signal (eg O (1s) or C (1s) having the most narrow FWHM and the lowest experimentally measured BE. 

→  Periodic Table 

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Table #1

Ce (3d_5/2) Chemical State BEs from:  “The XPS Library Spectra-Base”

C (1s) BE = 285.0 eV for TXL BEs
and C (1s) BE = 284.8 eV for NIST BEs

Element	Atomic #	Compound	As-Measured by TXL or NIST Average BE	Largest BE	Hydrocarbon C (1s) BE	Source
Ce	58	Ce – element	883.6 eV		285.0 eV	The XPS Library
Ce	58	Ce-2O3			285.0 eV	The XPS Library
Ce	58	Ce2-CO3	882.4 eV		285.0 eV	The XPS Library
Ce	58	Ce-O2	881.9 eV		285.0 eV	The XPS Library
Ce	58	Ce -F4			285.0 eV	The XPS Library

Charge Referencing Notes

• (N*number) identifies the number of NIST BEs that were averaged to produce the BE in the middle column.
• The XPS Library uses Binding Energy Scale Calibration with Cu (2p3/2) BE = 932.62 eV and Au (3d_7/2) BE = 83.98 eV.  BE (eV) Uncertainty Range:  +/- 0.2 eV
• Charge Referencing of insulators is defined such that the Adventitious Hydrocarbon C (1s) BE (eV) = 285.0 eV.  NIST uses C (1s) BE = 284.8 eV 
• Note:   Ion etching removes adventitious carbon, implants Ar (+), changes conductivity of surface, and degrades chemistry of various chemical states.
• Note:  Ion Etching changes BE of C (1s) hydrocarbon peak.
• TXL – abbreviation for: “The XPS Library” (https://xpslibrary.com).  NIST:  National Institute for Science and Technology (in USA)

→  Periodic Table 

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Table #2

Ce (3d_5/2) Chemical State BEs from:  “PHI Handbook”

C (1s) BE = 284.8 eV

→  Periodic Table 

Copyright ©:  Ulvac-PHI

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Table #3

Ce (3d_5/2) Chemical State BEs from:  “Thermo-Scientific” Website

C (1s) BE = 284.8 eV

Chemical state	Binding energy (eV), Ce (3d5/2)
Ce (IV) oxide	~882 eV
Ce (III) oxide	~880 eV

→  Periodic Table 

Copyright ©:  Thermo Scientific 

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Table #4

Ce (3d_5/2) Chemical State BEs from:  “XPSfitting” Website

Chemical State BE Table derived by Averaging BEs in the NIST XPS database of BEs
C (1s) BE = 284.8 eV

 

BE tables from Rare Earths are not available

→  Periodic Table 

Copyright ©:  Mark Beisinger

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Table #5

Ce (3d_5/2) Chemical State BEs from:  “Techdb.podzone.net” Website

 

XPS Spectra – Chemical Shift | Binding Energy
C (1s) BE = 284.6 eV

XPS(X線光電子分光法)スペクトル 化学状態 化学シフト ケミカルシフト Element Level Compound B.E.(eV) min max Ce 3d5/2 CeO2 882.2 ±0.4 881.8 ～ 882.5 Ce 3d5/2 CeAl2 883.5 ±0.3 883.2 ～ 883.8 Ce 3d5/2 CeCu2Si2 883.7 ±0.3 883.4 ～ 883.9 Ce 3d5/2 Ce 884.0 ±0.3 883.7 ～ 884.2 Ce 3d5/2 CePd3 884.3 ±0.3 884.0 ～ 884.6 Ce 3d5/2 CeSe 884.3 ±0.3 884.0 ～ 884.6 Ce 3d5/2 CeH3 886.1 ±0.3 885.8 ～ 886.3

→  Periodic Table 

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Histograms of NIST BEs for Ce (3d_5/2) BEs

Important Note:  NIST Database defines Adventitious Hydrocarbon C (1s) BE = 284.8 eV for all insulators.

Histogram indicates:  883.7 eV for Ceo based on 3 literature BEs

Table #6

NIST Database of Ce (3d_5/2) Binding Energies

NIST Standard Reference Database 20, Version 4.1

Data compiled and evaluated
by
Alexander V. Naumkin, Anna Kraut-Vass, Stephen W. Gaarenstroom, and Cedric J. Powell
©2012 copyright by the U.S. Secretary of Commerce on behalf of the United States of America. All rights reserved.

Important Note:  NIST Database defines Adventitious Hydrocarbon C (1s) BE = 284.8 eV for all insulators.

 

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Statistical Analysis of Binding Energies in NIST XPS Database of BEs

 

 

→  Periodic Table 

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Advanced XPS Information Section

Expert Knowledge, Spectra, Features, Guidance and Cautions
for XPS Research Studies on Cerium Based Materials

 

 

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Expert Knowledge Explanations

→  Periodic Table 

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Cerium Chemical Compounds

 

Peak-fits and Overlays of Chemical State Spectra

Pure Cerium:  Ce (3d) Cu (2p3/2) BE = 932.6 eV	CeO2:  Ce (3d) C (1s) BE = 285.0 eV	CeF4:  Ce (3d) C (1s) BE = 285.0 eV

Features Observed

• xx
• xx
• xx

→  Periodic Table 

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Overlay of Ce (3d) Spectra shown Above

C (1s) BE = 285.0 eV

 

 →  Periodic Table 

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Cerium Oxide (CeO₂)
pressed pellet

Survey Spectrum from CeO2 Flood gun is ON, C (1s) BE = 285.0 eV	Ce (3d) Chemical State Spectrum from CeO2 Flood gun is ON, C (1s) BE = 285.0 eV
	.
O (1s) Chemical State Spectrum from CeO2 Flood gun is ON, C (1s) BE = 285.0 eV	C (1s) Chemical State Spectrum from CeO2 Flood gun is ON, C (1s) BE = 285.0 eV
	.
Valence Band Spectrum from CeO2 Flood gun is ON, C (1s) BE = 285.0 eV
	na

Shake-up Features
for CeO₂

CeO2  – Ce (3d)

 

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Multiplet Splitting Features
for Cerium Compounds

CeF3 –  Multiplet Splitting for Ce (3d)	CeO2  – Multiplet Splitting Peaks for Ce (3d)

 

Features Observed

• xx
• xx
• xx

→  Periodic Table 

 

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Cerium Chemical Compounds

 

Cerium Fluoride, CeF₄

Survey Spectrum	Ce (3d) Spectrum
	.
C (1s) Spectrum	F (1s) Spectrum
	.
Valence Band Spectrum

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Cerium Fluoride, CeF₃
(crystalline)

Survey Spectrum	Ce (3d) Spectrum
	.
C (1s) Spectrum	F (1s) Spectrum
	.
Valence Band Spectrum	Ce (4d) Spectrum
Overlay of Valence Band and Ce (3d) Spectra from CeF3 and CeF4
Valence Band Spectra Overlay	Ce (3d) Spectra Overlay

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Cerium Sulfate, Ce₂(SO₄)₃

Survey Spectrum	Ce (3d) Spectrum
	.
C (1s) Spectrum	O (1s) Spectrum
	.
Valence Band Spectrum	S (2p) Spectrum

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Ammonium Cerium Sulfate, NH₄Ce(SO₄)_2
(powder)

Survey Spectrum	Ce (3d5/2) Spectrum
	.
C (1s) Spectrum	O (1s) Spectrum
	.
Valence Band Spectrum	S (2p) Spectrum
	.
N (1s) Spectrum
Overlay of Spectra from NH4Ce(SO4)2 and Ce2(SO4)3
Valence Band Spectra	Ce (3d) Spectra

 

→  Periodic Table 

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Quantitation Details and Information

Quantitation by XPS is often incorrectly done, in many laboratories, by integrating only the main peak, ignoring the Electron Loss peak, and the satellites that appear as much as 30 eV above the main peak.  By ignoring the electron loss peak and the satellites, the accuracy of the atom% quantitation is in error.

When using theoretically calculated Scofield cross-section values, the data must be corrected for the transmission function effect, use the calculated TPP-2M IMFP values, the pass energy effect on the transmission function, and the peak area used for calculation must include the electron loss peak area, shake-up peak area, multiplet-splitting peak area, and satellites that occur within 30 eV of the main peak.

 

Quantitation from Pure, Homogeneous Binary Compound
composed of Cerium – CeO2

This section is focused on measuring and reporting the atom % quantitation that results by using:

• Scofield cross-sections,
• Spectra corrected to be free from Transmission Function effects
• A Pass Energy that does not saturate the detector system in the low KE range (BE = 1000-1400 eV)
• A focused beam of X-ray smaller than the field of view of the lens
• An angle between the lens and the source that is ~55 deg that negates the effects of beta-asymmetry
• TPP-2M inelastic mean free path values, and
• Either a linear background or an iterated Shirley (Sherwood-Proctor) background to define peak areas

The results show here are examples of a method being developed that is expected to improve the “accuracy” or “reliaCelity” of the atom % values produced by XPS.

 

→  Periodic Table 

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Cerium Alloys

XxCu	XxCu
→  Periodic Table
XxCu	XxCu

 

Copyright ©:  The XPS Library 

 

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XPS Facts, Guidance & Information

→  Periodic Table 

		Element		Cerium (Ce)
		Primary XPS peak used for Peak-fitting:		Ce (3d5/2)
		Spin-Orbit (S-O) splitting for Primary Peak:		Spin-Orbit splitting for “d” Orbital, ΔBE = 18.5 eV
		Binding Energy (BE) of Primary XPS Signal:		883.8 eV
		Scofield Cross-Section (σ) Value:		Ce (3d5/2) = 30.50       Ce (3d3/2) = 21.12
		Conductivity:		Ce resistivity =   Native Oxide suffers Differential Charing
		Range of Ce (3d5/2) Chemical State BEs:		882 – 888 eV range   (Ceo to CeF3)
		Signals from other elements that overlap Ce (3d5/2) Primary Peak:		xxx
		Bulk Plasmons:		~xx eV above peak max for pure
		Shake-up Peaks:		xx
		Multiplet Splitting Peaks:		xx
		General Information about XXX Compounds:		xx
		Cautions – Chemical Poison Warning		xx

Copyright ©:  The XPS Library 

→  Periodic Table 

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Information Useful for Peak-fitting Ce (3d_5/2)

• FWHM (eV) of Ce (3d_5/2) for Pure Ce^o :  ~2.4 eV using 50 eV Pass Energy after ion etching:
• FWHM (eV) of Ce (3d_5/2) for CeO2:  ~2.0 eV using 50 eV Pass Energy  (before ion etching)
• Binding Energy (BE) of Primary Signal used for Measuring Chemical State Spectra:  883.8 eV for Ce (3d_5/2) with +/- 0.2 uncertainty
• List of XPS Peaks that can Overlap Peak-fit results for Ce (3d_5/2):  xxx

→  Periodic Table 

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General Guidelines for Peak-fitting XPS Signals

• Typical Energy Resolution for Pass Energy (PE) setting used to measure Chemical State Spectra on Various XPS Instruments
  • Ag (3d_5/2) FWHM (eV) = ~0.90 eV for PE 50 on Thermo K-Alpha
  • Ag (3d_5/2) FWHM (eV) = ~1.00 eV for PE 80 on Kratos Nova
  • Ag (3d_5/2) FWHM (eV) = ~0.95 eV for PE 45 on PHI VersaProbe
  • Ag (3d_5/2) FWHM (eV) = ~0.85 eV for PE 50 on SSI S-Probe
• FWHM (eV) of Pure Elements: Ranges from 0.4 to 1.0 eV across the periodic table
• FWHM of Chemical State Peaks in any Chemical Compound:  Ranges from 1.1 to 1.6 eV  (in rare cases FWHM can be 1.8 to 2.0 eV)
• FWHM of Pure Element versus FWHM of Oxide:  Pure element FWHM << Oxide FWHM  (e.g. 0.8 vs 1.5 eV, roughly 2x)
• If FWHM Greater than 1.6 eV:  When a peak FWHM is larger than 1.6 eV, it is best to add another peak to the peak-fit envelop.
• BE (eV) Difference in Chemical States: The difference in chemical state BEs is typically 1.0-1.3 eV apart.  In rare cases, <0.8 eV.
• Number of Peaks to Use:  Use minimum. Do not use peaks with FWHM < 1.0 eV unless it is a or a conductive compound.
• Typical Peak-Shape:  80% G: 20% L,   or Voigt : 1.4 eV Gaussian and 0.5 eV Lorentzian
• Spin-Orbit Splitting of Two Peaks (due to Coupling):  The ratio of the two (2) peak areas must be constrained.
• Constraints used on Peak-fitting: typically constrain the peak area ratios based on the Scofield cross-section values
• Asymmetry for Conductive materials:  20-30% with increased Lorentzian %
• Peak-fitting “2s” or “3s” Peaks:  Often need to use 50-60% Lorentzian peak-shape

Notes:

• Other Oxidation States can appear as small peaks when peak-fitting
• Pure element signals normally have asymmetric tails that should be included in the peak-fit.
• Gaseous state materials often display asymmetric tails due to vibrational broadening.
• Peak-fits of C (1s) in polymers include an asymmetric tail when the energy resolution is very high.
• Binding energy shifts of some compounds are negative due to unusual electron polarization.

→  Periodic Table 

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Contaminants Specific to Cerium

• Metal develops a thick native oxide due to the reactive nature of clean Cerium.
• The native oxide of Ce O_x is xx nm thick.
• Metal thin films often have a low level of iron (Fe) in the bulk as a contaminant or to strengthen the thin film
• Metal forms a low level of Carbide when the surface is ion etched inside the analysis chamber

 

Commonplace Contaminants

• Carbon and Oxygen are common contaminants that appear on nearly all surfaces. The amount of Carbon usually depends on handling.
• Carbon is usually the major contaminant.  The amount of carbon ranges from 5-50 atom%.
• Carbon contamination is attributed to air-borne organic gases that become trapped by the surface, oils transferred to the surface from packaging containers, static electricity, or handling of the product in the production environment.
• Carbon contamination is normally a mixture of different chemical states of carbon (hydrocarbon, alcohol or ether, and ester or acid).
• Hydrocarbon is the dominant form of carbon contamination. It is normally 2-4x larger than the other chemical states of carbon.
• Carbonate peaks, if they appear, normally appear ~4.5 eV above the hydrocarbon C (1s) peak max BE.
• Low levels of carbonate is common on many s that readily oxidize in the air.
• High levels of carbonate appear on reactive oxides and various hydroxides.  This is due to reaction between the oxide and CO₂ in the air.
• Hydroxide contamination peak is due to the reaction with residual water in the lab air or the vacuum.
• The O (1s) BE of the hydroxide (water) contamination normally appears 0.5 to 1.0 eV above the oxide peak
• Sodium (Na), Potassium (K), Sulfur (S) and Chlorine (Cl) are common trace to low level contaminants
• To find low level contaminants it is very useful to vertically expand the 0-600 eV region of the survey spectrum by 5-10X
• A tiny peak that has 3 or more adjacent data-points above the average noise of the background is considerate to be a real peak
• Carbides can appear after ion etching various reactive s.  Carbides form due to the residual CO and CH₄ in the vacuum.
• Ion etching can produce low oxidation states of the material being analyzed.  These are newly formed contaminants.
• Ion etching polymers by using standard Ar+ ion guns will destroy the polymer, converting it into a graphitic type of carbon

→  Periodic Table 

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Data Collection Guidance

• Chemical state differentiation can be difficult
• Collect principal Ce (3d) peak as well as Ce(4d)
• Long time exposures (high dose) to X-rays can degrade various polymers, catalysts, high oxidation state compounds
• During XPS analysis, water or solvents can be lost due to high vacuum or irradiation with X-rays or Electron flood gun
• Auger signals can sometimes be used to discern chemical state shifts when XPS shifts are very small

→  Periodic Table 

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Data Collection Settings for Cerium (Ce)

• Conductivity:  Cerium readily develops a native oxide that is sensitive to Flood Gun – Differential Charging Possible – float sample recommended
• Primary Peak (XPS Signal) used to measure Chemical State Spectra:  Ce (3d_5/2) at 883.8 eV
• Recommended Pass Energy for Measuring Chemical State Spectrum: 50-100 eV    (Produces Ag (3d_5/2) FWHM ~0.7 eV)
• Recommended # of Scans for Measuring Chemical State Spectrum:  4-5 scans normally   (Use 10-25 scans to improve S/N)
• Dwell Time:  50 msec/point
• Step Size:  0.1 eV/point   (0.1 eV/step or 0.1 eV/channel)
• Standard BE Range for Measuring Chemical State Spectrum:  860- 940 eV
• Recommended Extended BE Range for Measuring Chemical State Spectrum:  860 – 980 eV
• Recommended BE Range for Survey Spectrum:  -10 to 1,100 eV   (above 1,100 eV there are no useful XPS signals, except for Ge, As and Ga, above 1100 is waste of time)
• Typical Time for Survey Spectrum:  3-5 minutes for newer instruments, 5-10 minutes for older instruments
• Typical Time for a single Chemical State Spectrum with high S/N:  5-10 minutes for newer instruments, 10-15 minutes for older instruments 

→  Periodic Table 

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Effects of Argon Ion Etching

• Carbides appear after ion etching Ce and various reactive surfaces.  Carbides form due to the presence of residual CO and CH₄ in the vacuum.
• Ion etching can produce low oxidation states of the material being analyzed.  These are newly formed contaminants.
• Ion etching polymers by using standard Ar+ ion guns will destroy the polymer, converting it into a graphitic type of carbon

→  Periodic Table 

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