Rho Rh2O3 Native RhOx RhCl3 Rh2S3 Rh(OH)3 Rh2(OAc)4  K3(RhCl6) RhCl(P(C6H5)3)3 Pt90Rh10

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


 

Rhodium (Rh)

 

Rhodium Chloride – RhCl3 Rhodium – Rho Rhodium Bromide – RhBr3

 

  Page Index
  • Expert Knowledge & Explanations


Rhodium (Rho) Metal

Peak-fits, BEs, FWHMs, and Peak Labels


  .
Rhodium (Rho) Metal
Rh (3d) Spectrum – raw spectrum

ion etched clean
Rhodium (Rho) Metal
Peak-fit of Rh (3d) Spectrum
w/o asymm

 Periodic Table – HomePage  
Rhodium (Rho) Metal
Rh (3d) Spectrum –
extended range 
Rhodium (Rho) Metal
Peak-fit of Rh (3d) Spectrum (w asymm)
 

 

Survey Spectrum of Rhodium (Rho) Metal

with Peaks Integrated, Assigned and Labelled



 Periodic Table 

XPS Signals for Rhodium, (Rho) 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
Rh (3s) 628 2.70 12.4
Rh (3p1/2) 521  3.64 13.8
Na (Auger) overlaps Rh (3p3/2) 496 7.21 13.8
Rh (3d3/2) 311.7  5.80 15.7
Mg (Auger) overlaps Rh (3d5/2) 307.0  8.39 15.7
Rh (4s) 81 0.56 17.9
Rh (4p) 47 1.75 18.3

σ:  abbreviation for the term Scofield Photoionization Cross-Section which are used with IMFP and TF to generate RSFs and atom% quantitation

Auger Peaks

Energy Loss:  ~xx eV above peak max
Expected Bandgap for Rh2O3: 1.2 – 1.4 eV
Work Function for Rh2O3:  xx eV

*Scofield Cross-Section (σ) for C (1s) = 1.0

 Periodic Table 


 

Rh (4s) and (4p) Signals from Rho Metal
Fresh exposed bulk produced by extensive Ar+ ion etching

Rh (4s) and Rh (4p)

 


 

Valence Band Spectrum from Rhodium, Rho Metal
 Fresh exposed bulk produced by extensive Ar+ ion etching

 


 

Plasmon Peaks from Rho Metal
 Fresh exposed bulk produced by extensive Ar+ ion etching

Rh (3d) – Extended Range Spectrum Rh (3d) Extended Range Spectrum – Vertically Zoomed
 Periodic Table 

 

Rh (LMM) Auger Peaks from Rho Metal
 Fresh exposed bulk produced by extensive Ar+ ion etching

Rho Metal – main Auger peak Rho Metal – all Auger peaks
 

Features Observed

  • xx
  • xx
  • xx

 Periodic Table 


 

Artefacts Caused by Argon Ion Etching

Rhodium Carbide(s)

can form when ion etched Reactive Metal Surfaces capture
Residual UHV Gases (CO, H2O, CH4 etc)

Argon Trapped in Rho

can form when Argon Ions are used
to removed surface contamination


 

Side-by-Side Comparison of
Rh Native Oxide & Rhodium Oxide (Rh2O3)
Peak-fits, BEs, FWHMs, and Peak Labels

Rh Native Oxide Rh2O3
Rh (3d) from Rh Native Oxide
Flood Gun OFF
As-Measured, C (1s) at 284.6 eV 
Rh (3d) from Rh2O3 – pellet
Flood Gun OFF
Sample Conductive, C (1s) at 284.7 eV

 Periodic Table 

 
Rh Native Oxide Rh2O3
C (1s) from Rh Native Oxide
As-Measured, C (1s) at 284.6 eV
Flood Gun OFF

C (1s) from Rh2O3– pellet 
Flood Gun OFF
Sample Conductive, C (1s) at 284.7 eV

 


 Periodic Table 

 
Rh Native Oxide Rh2O3
O (1s) from Rh Native Oxide
As-Measured, C (1s) at 284.6 eV (Flood Gun OFF)

O (1s) from Rh2O3 – pellet
Flood Gun OFF, Sample Conductive, C (1s) at 284.7 eV

 Periodic Table

 


 

Survey Spectrum of Rhodium (Rh) Native Oxide
with Peaks Integrated, Assigned and Labelled

 Periodic Table 


 

 

Survey Spectrum of Rhodium Oxide, Rh2O
Peaks Integrated Assigned and Labelled

 Periodic Table  


Overlays of Rh (3d) Spectra for
Rh Native Oxide and Rh2O3

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

 Overlay of Rho metal and Rh Native Oxide – Rh (3d)
Native Oxide C (1s) = 284.6 eV
(Flood gun OFF
 Overlay of Rho metal and Rh2O3 – Rh (3d)
Pure Oxide C (1s) = 284.7 eV
Sample is conductive, Chemical Shift between Rh and Rh2O3 is:  1.5 eV
 Periodic Table  Copyright ©:  The XPS Library 

 

Overlay of Rh (3d)
Rho Metal, Rh Native Oxide, & Rh2O3 

Features Observed

  • xx
  • xx
  • xx

 Periodic Table 


 

Valence Band Spectra
Rho, Rh2O3

Rho
Ion etched clean
Rh2O3 – pellet
Sample is conductive, Flood gun is OFF,  C (1s) at  284.7 eV


Overlay of Valence Band Spectra
for Rho metal and Rh2O3

Features Observed

  • xx
  • xx
  • xx

 Periodic Table 



 

Rhodium Minerals, Gemstones, and Chemical Compounds

 

Minakawaite – RhSb Cuprorhodosite – (Cu0.5Fe0.5)Rh3S4 Bowieite – Rh2S3

 Periodic Table 



 

Six (6) Chemical State Tables of Rh (3d5/2) BEs

 

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

 Periodic Table 



 

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 (2p3) 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 (3d5/2) 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 


Table #1

Rh (3d5/2) 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
Rh 45 Rh (N*10) 306.4 eV 307.4 eV 284.8 eV Avg BE – NIST
Rh 45 Rh – element 307.2 eV 285.0 eV The XPS Library
Rh 45 Rh2O3 (N*3) 308.2 ev 308.9 eV 284.8 eV Avg BE – NIST
Rh 45 Rh-2O3 308.5 eV 285.0 eV The XPS Library
Rh 45 Rh-I3 (N*2) 308.6 eV 284.8 eV Avg BE – NIST
Rh 45 Rh2S3 (N*1) 308.8 eV 284.8 eV Avg BE – NIST
Rh 45 Rh-Cl3 (N*8) 310.1 eV 310.2 eV 284.8 eV Avg BE – NIST
Rh 45 K3RhF6 (N*1) 312.2 eV 284.8 eV Avg BE – NIST
Rh 45 Rh-(OH)3 285.0 eV The XPS Library
Rh 45 Rh-CO3 285.0 eV The XPS Library
Rh 45 Rh-F3 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 (3d5/2) BE = 932.62 eV and Au (4f7/2) 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 


Table #2

Rh (3d5/2) Chemical State BEs from:  “PHI Handbook”

C (1s) BE = 284.8 eV

 Periodic Table 

Copyright ©:  Ulvac-PHI


Table #3

Rh (3d5/2) Chemical State BEs from:  “Thermo-Scientific” Website

C (1s) BE = 284.8 eV

Chemical state Binding energy (eV),
Rh (3d5/2)
Rh metal 307.6
Native oxide 308.8

 Periodic Table 

Copyright ©:  Thermo Scientific 


Table #4

Rh (3d5/2) 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

 Periodic Table 

Copyright ©:  Mark Beisinger


Table #5

Rh (3d5/2) 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
Rh 3d5/2 Rh 307.2 ±0.1 307.1 307.2
Rh 3d5/2 ClRh(Ph3P)3 307.5 ±0.3 307.2 307.7
Rh 3d5/2 Br6Rh(Ph3P)3 308.0 ±0.3 307.7 308.3
Rh 3d5/2 Rh2O3 308.5 ±0.4 308.1 308.9
Rh 3d5/2 Cl2Rh2(cyclooctadiene)2 308.7 ±0.3 308.4 309.0
Rh 3d5/2 Rh2(OAc)4・2H2O 309.0 ±0.3 308.7 309.3
Rh 3d5/2 Halides 309.3 ±0.8 308.5 310.1
Rh 3d5/2 Cl3Rh(Ph3P)3 309.7 ±0.3 309.4 310.0
Rh 3d5/2 Cl6Rh(Ph3P)3 309.7 ±0.3 309.4 310.0
Rh 3d5/2 Rh(NH2CH2COO)3・H2O 310.4 ±0.4 310.0 310.7

 

 Periodic Table 



 


Histograms of NIST BEs for Rh (3d5/2) BEs
Important Note:  NIST Database defines Adventitious Hydrocarbon C (1s) BE = 284.8 eV for all insulators.

Histogram indicates:  307.0 eV for Rho based on 10 literature BEs Histogram indicates:  308.8 eV for Rh2O3 based on 4 literature BEs

Table #6


NIST Database of Rh (3d5/2) 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.

Element Spectral Line Formula Energy (eV) Reference
Rh 3d5/2 Rh 306.10  Click
Rh 3d5/2 Rh 306.40  Click
Rh 3d5/2 Rh 307.00  Click
Rh 3d5/2 Rh 307.00  Click
Rh 3d5/2 Rh 307.16  Click
Rh 3d5/2 Rh 307.18  Click
Rh 3d5/2 Rh 307.20  Click
Rh 3d5/2 Rh 307.20  Click
Rh 3d5/2 Rh 307.20  Click
Rh 3d5/2 [RhCl(C2H4)2]2 307.30  Click
Rh 3d5/2 [RhCl(P(C6H5)3)3] 307.30  Click
Rh 3d5/2 Rh 307.30  Click
Rh 3d5/2 Pt90Rh10 307.30  Click
Rh 3d5/2 [RhCl(P(C6H5)3)3] 307.40  Click
Rh 3d5/2 [RhCl(P(C6H5)3)3] 307.40  Click
Rh 3d5/2 [RhCl(P(C6H5)3)3] 307.40  Click
Rh 3d5/2 Rh 307.40  Click
Rh 3d5/2 Rh 307.40  Click
Rh 3d5/2 [Rh2Cl2(P(C6H5)3)4] 307.50  Click
Rh 3d5/2 [RhCl(P(C6H5)3)3] 307.60  Click
Rh 3d5/2 [Rh2(C8H12)2(SC6F5)2] 307.60  Click
Rh 3d5/2 [RhCl(P(C6H5)3)3] 307.80  Click
Rh 3d5/2 [RhBr6(P(C6H5)3)3] 307.90  Click
Rh 3d5/2 [RhBr((C6H5)3P)3] 307.90  Click
Rh 3d5/2 [RhI(P(C6H5)3)3] 308.00  Click
Rh 3d5/2 [Rh(C8H12)(SC6F5)(P(C6H5)3)] 308.00  Click
Rh 3d5/2 [Rh(SC6H5)(C8H12)(-CH2C-H(C6H4)PH2)] 308.10  Click
Rh 3d5/2 [RhCl(C2H4)(P(C6H5)3)2] 308.20  Click
Rh 3d5/2 [Rh2(CH3COS)4(C5H5N)2] 308.20  Click
Rh 3d5/2 [Rh2(CH3COS)4(C5H5N)2] 308.20  Click
Rh 3d5/2 (C8H12)RhCl2Rh(C8H12) 308.20  Click
Rh 3d5/2 (C8H12)RhCl2Rh(C8H12) 308.20  Click
Rh 3d5/2 [Rh(NO)((C6H5)3P)3] 308.20  Click
Rh 3d5/2 [Rh(NO)((C6H5)3P)3] 308.20  Click
Rh 3d5/2 Rh2O3 308.20  Click
Rh 3d5/2 [RhCl(C8H12)(-CH2C-H(C6H4)PH2)] 308.20  Click
Rh 3d5/2 [Rh(SC6H5)(C8H12)(-CH2C-H(C6H4)PH2)] 308.20  Click
Rh 3d5/2 Rh(P(C6H5)3)2COCl 308.20  Click
Rh 3d5/2 [RhBr(O)(P(C6H5)3)2] 308.30  Click
Rh 3d5/2 [RhCl(O)(P(C6H5)3)2] 308.30  Click
Rh 3d5/2 [RhCl(C8H12)(-CH2C-H(C6H4)PH2)] 308.30  Click
Rh 3d5/2 [RhCl(C8H12)(-CH2C-H(C6H4)PH2)] 308.30  Click
Rh 3d5/2 [Rh(CO)Cl(P(C6H5)3)2] 308.40  Click
Rh 3d5/2 BaRh2O4 308.40  Click
Rh 3d5/2 Cs2[Rh2Cl2(CH3COS)4] 308.50  Click
Rh 3d5/2 Cs2[Rh2Cl2(CH3COS)4] 308.50  Click
Rh 3d5/2 [Rh2(CH3COS)4((CH3)2SO)2] 308.50  Click
Rh 3d5/2 [Rh2(CH3COS)4((CH3)2SO)2] 308.50  Click
Rh 3d5/2 [Rh2((CH3)2NCHO)2((C6H5)COS)4] 308.50  Click
Rh 3d5/2 [Rh2(CH3COO)4(C5H4NCN)] 308.50  Click
Rh 3d5/2 [Rh2(C6H5COS)4(C5H5N)2] 308.50  Click
Rh 3d5/2 [Rh2(CH3CN)2(CH3COS)4] 308.50  Click
Rh 3d5/2 [Rh2(H2O)2(CH3COS)4] 308.50  Click
Rh 3d5/2 [Rh(H)(CO)(P(C6H5)3)2] 308.50  Click
Rh 3d5/2 K2[Rh2(CH3COS)4](CNS)2 308.50  Click
Rh 3d5/2 (C8H12)RhCl2Rh(C8H12) 308.50  Click
Rh 3d5/2 [Rh(CO)Cl(P(C6H5)3)2] 308.50  Click
Rh 3d5/2 [Rh(H)(CO)(P(C6H5)3)3] 308.50  Click
Rh 3d5/2 KRhO2 308.50  Click
Rh 3d5/2 [RhC5(CH3)5Cl2]2 308.50  Click
Rh 3d5/2 acrylic resin – NCRh(P(C6H5)3)2Cl 308.50  Click
Rh 3d5/2 [Rh2((CH3)2SO)2(C6H5COS)4] 308.60  Click
Rh 3d5/2 [Rh2(CH3COSH)2(CH3COS)4] 308.60  Click
Rh 3d5/2 [Rh2(C6H5COS)4] 308.60  Click
Rh 3d5/2 PbRh2O4 308.60  Click
Rh 3d5/2 RhI3 308.60  Click
Rh 3d5/2 RhI3 308.60  Click
Rh 3d5/2 [Rh(O2CCF3)NBD]2 308.60  Click
Rh 3d5/2 [RhCl(CO)2(P(C6H5)3)] 308.70  Click
Rh 3d5/2 [RhCl(CO)2(P(C6H5)3)] 308.70  Click
Rh 3d5/2 [RhCl(C2H4)(P(C6H5)3)2] 308.70  Click
Rh 3d5/2 [Rh2(CH3COS)4] 308.70  Click
Rh 3d5/2 [Rh2(O2C(C3H7))4] 308.70  Click
Rh 3d5/2 (C8H12)RhCl2Rh(C8H12) 308.70  Click
Rh 3d5/2 [RhI(O)(P(C6H5)3)2] 308.70  Click
Rh 3d5/2 [Rh(CO)Cl(P(C6H5)3)2] 308.70  Click
Rh 3d5/2 [Rh(CO)Cl(P(C6H5)3)2] 308.70  Click
Rh 3d5/2 Rh2O3 308.70  Click
Rh 3d5/2 ZnRh2O4 308.70  Click
Rh 3d5/2 Rh(P(C6H5)3)3COCl 308.70  Click
Rh 3d5/2 [RhCl(C2H4)]2 308.80  Click
Rh 3d5/2 [RhCl(C2H4)]2 308.80  Click
Rh 3d5/2 [Rh2(HCOO)4].H2O 308.80  Click
Rh 3d5/2 [Rh2(C6H5COO)4(C5H5N)2] 308.80  Click
Rh 3d5/2 [Rh2(C2H5OH)2((CH3)3CCOO)4] 308.80  Click
Rh 3d5/2 Rh6(CO)16 308.80  Click
Rh 3d5/2 Rh2(C2H3O2)4 308.80  Click
Rh 3d5/2 Rh2(C2H3O2)4 308.80  Click
Rh 3d5/2 Rh2(C2H3O2)4 308.80  Click
Rh 3d5/2 (C8H12)RhCl2Rh(C8H12) 308.80  Click
Rh 3d5/2 [Rh(CO)Cl(P(C6H5)3)2] 308.80  Click
Rh 3d5/2 [Rh(OH)(CO)(P(C6H5)3)2] 308.80  Click
Rh 3d5/2 Rh(C2H3O2)2 308.80  Click
Rh 3d5/2 CaRh2O4 308.80  Click
Rh 3d5/2 CoRh2O4 308.80  Click
Rh 3d5/2 Rh2S3 308.80  Click
Rh 3d5/2 LaRhO3 308.80  Click
Rh 3d5/2 [Rh2((CH3)2SO)2(C6H5COO)4] 308.90  Click
Rh 3d5/2 BeRh2O4 308.90  Click
Rh 3d5/2 [Rh(C5H4N)2(HCOO)4] 308.90  Click
Rh 3d5/2 [RhAsBr4(C6H5)4].H2O 308.90  Click
Rh 3d5/2 LiRhO2 308.90  Click
Rh 3d5/2 Rh2O3 308.90  Click
Rh 3d5/2 (C6H4S4)RhCl3.H2O 308.90  Click
Rh 3d5/2 [RhCl(C6H5NCO)2(P(C6H5)3)2] 309.00  Click
Rh 3d5/2 [Rh2(CH3COO)4(C5H5N)2] 309.00  Click
Rh 3d5/2 [Rh2(CH3COO)4(C5H5N)2] 309.00  Click
Rh 3d5/2 [Rh2(CH3COO)4((CH3)2SO)2] 309.00  Click
Rh 3d5/2 [Rh2(NH3)2(CH3COO)4] 309.00  Click
Rh 3d5/2 [Rh2(H2O)2(CH3COO)4] 309.00  Click
Rh 3d5/2 [Rh2(H2O)2(CH3COO)4] 309.00  Click
Rh 3d5/2 [Rh2(H2O)2(CH3COO)4] 309.00  Click
Rh 3d5/2 K4[Rh2Br4(CH3COO)4] 309.00  Click
Rh 3d5/2 K4[Rh2Cl4(CH3COO)4] 309.00  Click
Rh 3d5/2 [Rh2(CO)4Cl2] 309.00  Click
Rh 3d5/2 [RhCl2(CH3OC6H4NN)(P(C6H5)3)2] 309.00  Click
Rh 3d5/2 [RhC5(CH3)5MoO4]4.2H2O 309.00  Click
Rh 3d5/2 [RhCl2(CHCH2)(P(C6H5)3)3] 309.10  Click
Rh 3d5/2 [RhCl(C2F4)(P(C6H5)3)2] 309.10  Click
Rh 3d5/2 Cs2[Rh2Cl2(CH3COO)4] 309.10  Click
Rh 3d5/2 Cs2[Rh2Cl2(CH3COO)4] 309.10  Click
Rh 3d5/2 Cs2[Rh2Cl2(HCOO)4] 309.10  Click
Rh 3d5/2 Cs2[Rh2Cl2(HCOO)4] 309.10  Click
Rh 3d5/2 [Rh2((CH3)2OS)2(HCOO)4] 309.10  Click
Rh 3d5/2 K2[Rh2(CH3COO)4(NO2)2] 309.10  Click
Rh 3d5/2 [RhAs(C6H5)4]Br4.CH3CN 309.10  Click
Rh 3d5/2 [RhCl2(CH3OC6H4CO)(P(C6H5)3)2] 309.10  Click
Rh 3d5/2 Rh2O3 309.10  Click
Rh 3d5/2 [Rh2Cl2(P(C6H5)3)4] 309.20  Click
Rh 3d5/2 Cs2[Rh2Br2(HCOO)4] 309.20  Click
Rh 3d5/2 Cs2[Rh2Br2(HCOO)4] 309.20  Click
Rh 3d5/2 [RhH(P(C6H5)3)3] 309.20  Click
Rh 3d5/2 [RhCl2(NO2C6H4NN)(P(C6H5)3)2] 309.20  Click
Rh 3d5/2 [RhCl2(C6H5)(P(C6H5)3)2] 309.20  Click
Rh 3d5/2 [RhCl2(CH3C6H4NN)(P(C6H5)3)2] 309.20  Click
Rh 3d5/2 [RhCl(P(C6H5)3)3] 309.20  Click
Rh 3d5/2 [RhCl2((C6H5)3P)2(CH3(CH2)14)] 309.20  Click
Rh 3d5/2 RhNbO4 309.20  Click
Rh 3d5/2 RhVO4 309.20  Click
Rh 3d5/2 Rh2MoO6 309.20  Click
Rh 3d5/2 Pt90Rh10 309.20  Click
Rh 3d5/2 [(C2H5)4N]2[Rh2((C4H8N)C(O)O)2((C4H7N)C(O)O)2] 309.20  Click
Rh 3d5/2 Rh2O3 309.20  Click
Rh 3d5/2 [RhCl3(P(CH3)2C6H5)3] 309.30  Click
Rh 3d5/2 K2[Rh2(HCOO)4(NO2)2] 309.30  Click
Rh 3d5/2 [Rh(As(C6H5)4)]Cl4.2H2O 309.30  Click
Rh 3d5/2 [RhCl2(NO)(P(C6H5)3)2] 309.30  Click
Rh 3d5/2 [Rh(H)(CO)(P(C6H5)3)3] 309.30  Click
Rh 3d5/2 Pt90Rh10 309.30  Click
Rh 3d5/2 RhO2.2H2O 309.30  Click
Rh 3d5/2 [RhCl(CS2)(P(C6H5)3)3] 309.40  Click
Rh 3d5/2 [RhCl(CS2)(P(C6H5)3)3] 309.40  Click
Rh 3d5/2 [Rh2(C2H5OH)2(CCl3COO)4] 309.40  Click
Rh 3d5/2 [Rh2(CF3COO)4(C5H5N)2] 309.40  Click
Rh 3d5/2 [Rh2(HCOO)4(NH2C6H4COOH)2] 309.40  Click
Rh 3d5/2 [Rh2(HSC6H4COO)4].6H2O 309.40  Click
Rh 3d5/2 [RhCl2(C6H5CO)(P(C6H5)3)2] 309.40  Click
Rh 3d5/2 [RhCl2(CO)((C6H5)3P)2(CH3(CH2)14(C6H4))] 309.40  Click
Rh 3d5/2 Rh2O3 309.40  Click
Rh 3d5/2 Rh2WO6 309.40  Click
Rh 3d5/2 Pt90Rh10 309.40  Click
Rh 3d5/2 Rh4(CO)12/C 309.40  Click
Rh 3d5/2 Rh6(CO)16/C 309.40  Click
Rh 3d5/2 K[Rh(C2H3O2)2(NO2)] 309.50  Click
Rh 3d5/2 Cs2[Rh2Br(HCOO)4(NO2)] 309.50  Click
Rh 3d5/2 K2[Rh2(CH3COO)4(NO2)2] 309.50  Click
Rh 3d5/2 RhTaO4 309.50  Click
Rh 3d5/2 ZrH1.40Rh0.20((CH3)2C12H8N4))0.40(PO4)2.2.5H2O 309.50  Click
Rh 3d5/2 ZrH1.46Rh0.18(C10H8N2)0.25(PO4)2.1.9H2O 309.50  Click
Rh 3d5/2 ZrHxRh0.66(PO4)2.4H2O 309.50  Click
Rh 3d5/2 ZrRh0.66(PO4)2.4H2O 309.50  Click
Rh 3d5/2 ZrH1.46Rh0.18(C12H8N4)0.37(PO4)2.2H2O 309.50  Click
Rh 3d5/2 [RhCl3(CH3CN)(P(C6H5)3)2] 309.60  Click
Rh 3d5/2 [Rh(NH3)3]I3 309.60  Click
Rh 3d5/2 C29H34N4(Rh(CO)2)2 309.60  Click
Rh 3d5/2 Rh4(CO)12/AlOx 309.60  Click
Rh 3d5/2 Rh6(CO)16/AlOx 309.60  Click
Rh 3d5/2 Rh2O3.5H2O 309.60  Click
Rh 3d5/2 [RhCl6(P(C6H5)3)3] 309.70  Click
Rh 3d5/2 [Rh2(C2H5OH)2(CF3COO)4] 309.70  Click
Rh 3d5/2 [RhCl3(P(C6H5)3)3] 309.70  Click
Rh 3d5/2 [RhCl3(P(C6H5)3)3] 309.70  Click
Rh 3d5/2 [RhCl3(P(C6H5)3)3] 309.70  Click
Rh 3d5/2 [RhCl3(S(C2H5)2)3] 309.80  Click
Rh 3d5/2 [RhCl3(S(C2H5)2)3] 309.80  Click
Rh 3d5/2 K3[RhCl6] 309.80  Click
Rh 3d5/2 K3[RhCl6] 309.80  Click
Rh 3d5/2 K3[RhCl6] 309.80  Click
Rh 3d5/2 [RhAs(C6H5)4]Cl4.CH3CN 309.80  Click
Rh 3d5/2 [RhCl2(CO)(C6H5)(P(C6H5)3)2] 309.80  Click
Rh 3d5/2 [RhCl3(P(C6H5)3)3] 309.80  Click
Rh 3d5/2 [RhCl2(CO)((C6H5)3P)2(CH3(CH2)14)] 309.80  Click
Rh 3d5/2 RhCl3.3H2O 309.80  Click
Rh 3d5/2 [Rh3(NO)6Cl3] 309.80  Click
Rh 3d5/2 RhCl3 309.80  Click
Rh 3d5/2 [Rh2((CH3)2SO)2(CF3COO)4] 309.90  Click
Rh 3d5/2 K3[Rh(SO3)3].2H2O 309.90  Click
Rh 3d5/2 K3[Rh(SO3)3].2H2O 309.90  Click
Rh 3d5/2 C44H28ClN4Rh 309.90  Click
Rh 3d5/2 Rh(P(C6H5)3)3Cl 309.90  Click
Rh 3d5/2 Na[RhCl4((CH3)2SO)2] 310.00  Click
Rh 3d5/2 [RhCl3(C5NH5)3] 310.00  Click
Rh 3d5/2 [RhCl3(C5NH5)3] 310.00  Click
Rh 3d5/2 RhCl3.3H2O 310.00  Click
Rh 3d5/2 RhCl3.3H2O 310.00  Click
Rh 3d5/2 RhCl3.3H2O 310.00  Click
Rh 3d5/2 RhCl3.3H2O 310.00  Click
Rh 3d5/2 [Rh(NH3)3]Br3 310.00  Click
Rh 3d5/2 C36H44ClN4Rh 310.00  Click
Rh 3d5/2 RhCl3.xH2O 310.00  Click
Rh 3d5/2 RhCl3 310.00  Click
Rh 3d5/2 [RhCl2(C5H5N)4]Cl 310.10  Click
Rh 3d5/2 RhCl3 310.10  Click
Rh 3d5/2 [Rh(NH3)6]Cl3 310.10  Click
Rh 3d5/2 RhCl3.12H2O 310.10  Click
Rh 3d5/2 [RhI2(NH3)5(CH3COS)] 310.20  Click
Rh 3d5/2 RhCl3 310.20  Click
Rh 3d5/2 [Rh(NH3)5Cl]Cl2 310.20  Click
Rh 3d5/2 RhCl3.3H2O 310.20  Click
Rh 3d5/2 [Rh(NH2CH2COO)3] 310.30  Click
Rh 3d5/2 [Rh(NH3)3]Cl3 310.30  Click
Rh 3d5/2 [Rh(NH3)3]Cl3 310.30  Click
Rh 3d5/2 K3[Rh(CN)6] 310.40  Click
Rh 3d5/2 [Rh2(CH3COO)4]ClO4 310.40  Click
Rh 3d5/2 [RhCl3(CO)3(P(C6H5)3)] 310.40  Click
Rh 3d5/2 K3[Rh(NO2)3Cl3] 310.40  Click
Rh 3d5/2 K3[Rh(NO2)3Cl3] 310.40  Click
Rh 3d5/2 [Rh(NH3)6]Cl3 310.50  Click
Rh 3d5/2 [Rh(NH3)6]Cl3 310.50  Click
Rh 3d5/2 K3[Rh(NO2)6] 310.50  Click
Rh 3d5/2 K3[Rh(NO2)6] 310.50  Click
Rh 3d5/2 K3[Rh(NO2)6] 310.50  Click
Rh 3d5/2 Ti[Rh(CN)6] 310.60  Click
Rh 3d5/2 [Rh(NH3)3](NO2)3 310.70  Click
Rh 3d5/2 [Rh(NH3)3](NO2)3 310.70  Click
Rh 3d5/2 [Rh(NH3)5(H2O)](NO3)3 310.80  Click
Rh 3d5/2 [Rh(NH3)3](NO3)3 311.00  Click
Rh 3d5/2 [Rh(NH3)3](NO3)3 311.00  Click
Rh 3d5/2 BiORh6(SO4)8((O2)-)3.14H2O 311.00  Click
Rh 3d5/2 K3[Rh(NO3)6] 311.10  Click
Rh 3d5/2 K3[Rh(NO3)6] 311.10  Click
Rh 3d5/2 K3[Rh(NO3)6] 311.10  Click
Rh 3d5/2 Na2Rh2(H2PO4)2(HPO4)2((O2)-).2H2O 311.20  Click
Rh 3d5/2 [Rh(H2O)6](ClO4)3 311.50  Click
Rh 3d5/2 K3RhF6 312.20  Click

 Periodic Table 


 

 

Statistical Analysis of Binding Energies in NIST XPS Database of BEs

 

 

 Periodic Table 


 

Advanced XPS Information Section

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

 


 

Expert Knowledge Explanations

 Periodic Table 


 

Rhodium Chemical Compounds


Peak-fits and Overlays of Chemical State Spectra

Pure Rhodium, Rho:  Rh (3d)
Cu (2p3/2) BE = 932.6 eV
Rh2O3:  Rh (3d)
C (1s) BE = 285.0 eV
RhX3:  Rh (3d)
C (1s) BE = xxx

Features Observed

  • xx
  • xx
  • xx

 Periodic Table 


 

Overlay of Rh (3d) Spectra shown Above

C (1s) BE = 285.0 eV

 

Chemical Shift between Rh and Rh2O3:  1.6 eV
 Chemical Shift between Rh and RhX:  xx eV

 

 Periodic Table 



Rhodium Oxide, Rh
2O3
pressed pellet 

Survey Spectrum from Rh2O3
Flood gun is OFF, sample is conductive
Rh (3d) Chemical State Spectrum from Rh2O3
Flood gun is OFF, sample is conductive

 
O (1s) Chemical State Spectrum from Rh2O3
Flood gun is OFF, sample is conductive
C (1s) Chemical State Spectrum from Rh2O3
Flood gun is OFF, sample is conductive

 
Valence Band Spectrum from Rh2O3
Flood gun is OFF, sample is conductive
Auger Signals from Rh2O3
Flood gun is OFF, sample is conductive

 

Features Observed

  • xx
  • xx
  • xx

 Periodic Table 

 


 

Rhodium Chemical Compounds

 

 Periodic Table 


 

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 Rhodium – RhOx

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 “reliability” of the atom % values produced by XPS.

 

 Periodic Table 


 

Flood Gun Effect on Native Oxide of Rhodium

 

Native Oxide of Rhodium Sheet – Sample GROUNDED

 


 

Native Oxide of Rhodium Sheet – Sample Grounded

Electron Flood Gun:  0 Voltage (FG OFF), Min Voltage versus Max Voltage

Rh (3d) O (1s) C (1s)
 Periodic Table 

 

Rhodium Alloys

   
XxCu XxCu
 Periodic Table   
XxCu XxCu

 

Copyright ©:  The XPS Library 

 



 

XPS Facts, Guidance & Information

    Element Rhodium (Rh)
 
    Primary XPS peak used for Peak-fitting: Rh (3d)  
    Spin-Orbit (S-O) splitting for Primary Peak: Spin-Orbit splitting for “d” orbital, ΔBE = 4.7 eV
 
    Binding Energy (BE) of Primary XPS Signal: 307 eV
 
    Scofield Cross-Section (σ) Value: Rh (3d5/2) = 8.39      Rh (3d3/2) = 5.80
 
    Conductivity: Rh resistivity =  
 
    Range of Rh (3d5/2) Chemical State BEs: xx – xx eV range   (Rho to RhF3)  
Signals from other elements that overlap
Rh (3d5/2) Primary Peak:
  Mg (Auger)
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 



 

Information Useful for Peak-fitting Rh (3d5/2)

  • FWHM (eV) of Rh (3d5/2) for Pure Rho ~0.7eV using 25 eV Pass Energy after ion etching:
  • FWHM (eV) of Rh (3d5/2) for Rh2O3 ~0.9 eV using 50 eV Pass Energy  (before ion etching)
  • Binding Energy (BE) of Primary Signal used for Measuring Chemical State Spectra:  307 eV for Rh (3d5/2) with +/- 0.2 uncertainty
  • List of XPS Peaks that can Overlap Peak-fit results for Rh (3d5/2):  Mg (Auger)

 Periodic Table 


 

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 (3d5/2) FWHM (eV) = ~0.95 eV for PE 50 on Thermo K-Alpha
    • Ag (3d5/2) FWHM (eV) = ~1.00 eV for PE 80 on Kratos Nova
    • Ag (3d5/2) FWHM (eV) = ~0.95 eV for PE 45 on PHI VersaProbe
  • 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.

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 


 

Contaminants Specific to Rhodium

  • Rhodium develops a thick native oxide due to the reactive nature of clean Rhodium.
  • The native oxide of Rh Ox is 1-3 nm thick.
  • Rhodium thin films often have a low level of iron (Fe) in the bulk as a contaminant or to strengthen the thin film
  • Rhodium 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 


 

Data Collection Guidance

  • Chemical state differentiation can be difficult
  • Collect principal Rh (3d) peak
  • 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 


 

Data Collection Settings for Rhodium (Rh)

  • Conductivity:  Rhodium 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:  Rh (3d5/2) at 307 eV
  • Recommended Pass Energy for Measuring Chemical State Spectrum:  40-50 eV    (Produces Ag (3d5/2) 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:  295 – 325 eV
  • Recommended Extended BE Range for Measuring Chemical State Spectrum:  290 – 340 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 and Ga)
  • 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 


 

Effects of Argon Ion Etching

  • Carbides appear after ion etching Rh 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 

Copyright ©:  The XPS Library 


Gas Phase XPS or UPS Spectra


 

Chemical State Spectra from Literature
Rh Native Oxide
Thermo Website:  XPS Simplified
 



End of File