MnO2 by XPS

Cite as: Surface Science Spectra 6, 31 (1999); [Link]

Published Online: 05 October 2021

Michael A. Stranick

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© 1999 American Vacuum Society.

MnO2 by XPS Accession # 00431
Technique: XPS
Michael A. Stranick Host Material: MnO2 powder
Analytical Sciences Dept., Colgate-Palmolive Co., 909 River Rd., Piscataway, NJ 08854
Instrument: Physical Electronics,
Manganese compounds have many applications in areas such as catalysis, electrochemistry, and Inc. 5600
metallurgy, among others. Distinguishing between the various chemical states of manganese is an Major Elements in Spectrum: Mn,
important aspect of research in many of these areas. It has been shown that the different chemical O
states of manganese can be identified with XPS through the Mn 2p3/2 peak positions, Mn 2p1/2
Minor Elements in Spectrum: C
satellite–Mn 2p1/2 peak separations, Mn 3s multiplet splittings, or Mn Auger parameters. To date,
however, all of these values have not been available in a single reference. In this study, XPS has Printed Spectra: 6
been used to obtain core level, Auger, and valence band spectra for a commercial, high purity MnO2 Spectra in Electronic Record: 10
powder. This submission provides a reference that contains all of the Mn XPS data necessary for the Spectral Category: comparison
identification of MnO2 and also provides information that may be useful for the analysis of other
Original Submission: 12/29/98
Mn compounds. © 1999 American Vacuum Society. 关S1055-5269共99兲00901-9兴
Accepted for Publication: 6/08/99
Keywords: XPS; manganese (IV) oxide

PACS: [Link], [Link], [Link], [Link]

SPECIMEN DESCRIPTION INSTRUMENT PARAMETERS COMMON TO ALL

SPECTRA
Host Material: MnO2 powder
CAS Registry #: 1313-13-9
䊏 Spectrometer
Host Material Characteristics: homogeneous; polycrystalline; Analyzer Mode: constant pass energy
dielectric; inorganic compound; powder Throughput „ T ⴝ E N …: N⫽1
Chemical Name: manganese dioxide Excitation Source Window: none
Source: J. T. Baker Excitation Source: Al K ␣ monochromatic
Host Composition: MnO2 Source Energy: 1486.6 eV
Form: powder, min. 99% purity Source Strength: 400 W
Lot #: J46342 Source Beam Size: 5 mm⫻2 mm
Structure: tetragonal-rutile structure, a⫽0.4398 nm, b⫽0.2873 Analyzer Width: 800 ␮m⫻800 ␮m
nm Signal Mode: multichannel direct
As Received Condition: powder in sealed glass container
Analyzed Region: same as host material
Ex Situ Preparation/Mounting: The powder was ground with
mortar and pestle, then packed inside a 6 mm o.d.⫻3 mm i.d. 䊏 Geometry
s.s. washer, which was affixed to the specimen mount with Incident Angle: 65°
double-sided tape. Source to Analyzer Angle: 90°
In Situ Preparation: none Emission Angle: 25°
Pre-Analysis Beam Exposure: The sample was exposed to the Specimen Azimuthal Angle: 0°
x-ray and flood gun beams for less than 1 min, during sample Acceptance Angle from Analyzer Axis: 0°
alignment and flood gun adjustment.
Analyzer Angular Acceptance Width: 14°⫻14°
Charge Control: A flood gun operated at 21 mA and 12 eV was
used to compensate for sample charging.
Temp. During Analysis: 295 K
DATA ANALYSIS METHOD
Pressure During Analysis: ⬍1.33⫻10⫺6 Pa

INSTRUMENT DESCRIPTION Energy Scale Correction: Peak positions were adjusted by ⫹0.3
eV, using C 1s at 285.0 eV as a reference. The spectra archived
Manufacturer and Model: Physical Electronics, Inc. 5600
in the database are uncorrected.
Analyzer Type: spherical sector
Detector: multichannel resistive plate Recommended Energy-Scale Shift: ⫹0.3 eV

Number of Detector Elements: 16

Peak Shape and Background Method: Peak positions and
Deviations from Standard Analyzer or Lens: Omni Focus III FWHM were determined following Shirley background sub-
lens traction.

Surface Science Spectra, Vol. 6, No. 1, 1999 1055-5269/99/6(1)/31/8/$15.00 © 1999 American Vacuum Society 31
Quantitation Method: Atomic concentrations were calculated us- 2. V. Di Castro and G. Polzonetti, J. Electron. Spectrosc. Relat.
ing PHI PC-Access software and PHI sensitivity factors. Peak Phenom. 48, 117 共1989兲.
areas were determined following Shirley background subtrac- 3. B. R. Strohmeier and D. M. Hercules, J. Phys. Chem. 88, 4922
tion. 共1984兲.
4. J. C. Carver, G. K. Schweitzer, and T. A. Carlson, J. Chem.
Phys. 57, 973 共1972兲.
REFERENCES 5. M. Oki and K. Hirokawa, J. Electron. Spectrosc. Relat. Phenom.
1. H. W. Nesbitt and D. Banerjee, Am. Miner. 83, 305 共1998兲. 8, 475 共1976兲.

SPECTRAL FEATURES TABLE

Spectrum Element/ Peak Peak Width Peak Area Sensitivity Concen- Peak
ID # Transition Energy FWHM „eV-cts/s… Factor tration Assignment
„eV… „eV… „at. %…

00431-02a,b Mn 2p 3/2 642.4 2.55 ¯ ¯ ¯ Mn共IV兲,

MnO2
00431-02b Mn 2p 1/2 654.1 2.90 ¯ ¯ ¯ Mn共IV兲,
MnO2
00431-02c Mn 2p 1/2 665.9 ¯ ¯ ¯ ¯ Mn共IV兲 satellite,
MnO2
00431-03d O 1s 529.6 0.91 16102 5.148 64.4 O2⫺,
MnO2
00431-04b,e Mn 3s 84.7 2.63 ¯ ¯ ¯ Mn共IV兲,
MnO2
00431-04b,e Mn 3s 89.1 ¯ ¯ ¯ ¯ Mn共IV兲,
MnO2
00431-05f Mn 3p 49.8 2.01 2875 1.664 35.6 Mn共IV兲,
MnO2
00431-07 Mn L 3 M 2,3M 4,5 901.8 ¯ ¯ ¯ ¯ Mn共IV兲,
MnO2
00431-08g C 1s 285.0 ¯ ¯ ¯ ¯ CHx
a
Peak asymmetry is due to multiplet splitting. See Ref. 1 for detailed peak shape analysis.
b
Peak position was determined from the midpoint of the FWHM, following Shirley background subtraction.
c
Mn 2p1/2 satellite–Mn 2p1/2 peak separation is 11.8 eV.
d
Peak position determined by curve fitting; the high BE shoulder is due to surface hydroxyl (19%) and adsorbed water (17%). These species have
little or no effect on Mn peak positions or satellite splittings.
e
Mn 3s multiplet splitting is 4.4 eV.
f
Due to peak asymmetry, the reported peak center is at the peak height maximum.
g
Peak position determined by curve fitting; low levels of C–O bonded species are also present. The binding energies suggest these species are
organic in nature. This C contamination has little or no effect on Mn peak positions or satellite splittings.

Comment to Spectral Features Table: All of the data reported above are consistent with that found in the literature, Refs. 1–5.

32 Surface Science Spectra, Vol. 6, No. 1, 1999 MnO2 by XPS

 ANALYZER CALIBRATION TABLE

Spectrum Element/ Peak Peak Width Peak Area Sensitivity Concen- Peak
ID # Transition Energy FWHM „eV-cts/s… Factor tration Assignment
„eV… „eV… „at. %…

00434-01a Cu 2p 3/2 932.65 1.10 197260 ¯ ¯ Cu metal

00435-01 a
Au 4 f 7/2 84.02 0.90 119128 ¯ ¯ Au metal
a
Sputter cleaned sample, measured using Mg K ␣ radiation at 5.85 eV pass energy and 0.025 eV/step. Peak position and FWHM were determined
by curve fitting.

GUIDE TO FIGURES

Spectrum Spectral Sample

Multiplier Baseline Comment #
„Accession… # Region Voltage*

431-1 Survey ⫺0.3 1 0

431-2 Mn 2p ⫺0.3 1 0
431-3 O 1s ⫺0.3 1 0
431-4 Mn 3s ⫺0.3 1 0
431-5 Mn 3p ⫺0.3 1 0
431-6 Valence Band ⫺0.3 1 0
431-7 Mn L 3 M 2,3M 4,5 ⫺0.3 1 0
431-8 C 1s ⫺0.3 1 0
434-1 †NP‡** Cu 2p 3/2 0 1 0 1
435-1 †NP‡ Au 4 f 7/2 0 1 0 1
*Inferred sample potential relative to spectrometer ground due to charging, flood gun, or other phenomena.
**[NP] signifies not published; digital spectra are archived in SSS database but not reproduced in the printed journal.
1. Calibration spectrum.

Surface Science Spectra, Vol. 6, No. 1, 1999 MnO2 by XPS 33

 Accession # 00431-01

Host Material MnO2 powder

Technique XPS
Spectral Region survey
Instrument Physical Electronics, Inc. 5600
Excitation Source Al K ␣ monochromatic
Source Energy 1486.6 eV
Source Strength 400 W
Source Size 2 mm⫻5 mm
Analyzer Type spherical sector
Incident Angle 65°
Emission Angle 25°
Analyzer Pass Energy 187.85 eV
Analyzer Resolution 1.9 eV
Total Signal Accumulation Time 578 s
Total Elapsed Time 578 s
Number of Scans 21
Effective Detector Width 1.9 eV
Comment Low levels of Si and Al impurities from an unknown
source were also observed in the survey spectrum.

34 Surface Science Spectra, Vol. 6, No. 1, 1999 MnO2 by XPS

 䊏 Accession #: 00431-02
䊏 Host Material: MnO2 powder
䊏 Technique: XPS
䊏 Spectral Region: Mn 2 p
Instrument: Physical Electronics,
Inc. 5600
Excitation Source: Al K ␣
monochromatic
Source Energy: 1486.6 eV
Source Strength: 400 W
Source Size: 2 mm⫻5 mm
Incident Angle: 65°
Analyzer Type: spherical sector
Analyzer Pass Energy: 11.75 eV
Analyzer Resolution: 0.12 eV
Emission Angle: 25°
Total Signal Accumulation Time:
2880 s
Total Elapsed Time: 2880 s
Number of Scans: 64
Effective Detector Width: 0.12 eV

䊏 Accession #: 00431-03
䊏 Host Material: MnO2 powder
䊏 Technique: XPS
䊏 Spectral Region: O 1 s
Instrument: Physical Electronics,
Inc. 5600
Excitation Source: Al K ␣
monochromatic
Source Energy: 1486.6 eV
Source Strength: 400 W
Source Size: 2 mm⫻5 mm
Incident Angle: 65°
Analyzer Type: spherical sector
Analyzer Pass Energy: 11.75 eV
Analyzer Resolution: 0.12 eV
Emission Angle: 25°
Total Signal Accumulation Time:
80 s
Total Elapsed Time: 80 s
Number of Scans: 4
Effective Detector Width: 0.12 eV

Surface Science Spectra, Vol. 6, No. 1, 1999 MnO2 by XPS 35

 䊏 Accession #: 00431-04
䊏 Host Material: MnO2 powder
䊏 Technique: XPS
䊏 Spectral Region: Mn 3 s
Instrument: Physical Electronics,
Inc. 5600
Excitation Source: Al K ␣
monochromatic
Source Energy: 1486.6 eV
Source Strength: 400 W
Source Size: 2 mm⫻5 mm
Incident Angle: 65°
Analyzer Type: spherical sector
Analyzer Pass Energy: 11.75 eV
Analyzer Resolution: 0.12 eV
Emission Angle: 25°
Total Signal Accumulation Time:
2560 s
Total Elapsed Time: 2560 s
Number of Scans: 128
Effective Detector Width: 0.12 eV

䊏 Accession #: 00431-05
䊏 Host Material: MnO2 powder
䊏 Technique: XPS
䊏 Spectral Region: Mn 3 p
Instrument: Physical Electronics,
Inc. 5600
Excitation Source: Al K ␣
monochromatic
Source Energy: 1486.6 eV
Source Strength: 400 W
Source Size: 2 mm⫻5 mm
Incident Angle: 65°
Analyzer Type: spherical sector
Analyzer Pass Energy: 11.75 eV
Analyzer Resolution: 0.12 eV
Emission Angle: 25°
Total Signal Accumulation Time:
2560 s
Total Elapsed Time: 2560 s
Number of Scans: 128
Effective Detector Width: 0.12 eV

36 Surface Science Spectra, Vol. 6, No. 1, 1999 MnO2 by XPS

 䊏 Accession #: 00431-06
䊏 Host Material: MnO2 powder
䊏 Technique: XPS
䊏 Spectral Region: Mn valence
band
Instrument: Physical Electronics,
Inc. 5600
Excitation Source: Al K ␣
monochromatic
Source Energy: 1486.6 eV
Source Strength: 400 W
Source Size: 2 mm⫻5 mm
Incident Angle: 65°
Analyzer Type: spherical sector
Analyzer Pass Energy: 11.75 eV
Analyzer Resolution: 0.12 eV
Emission Angle: 25°
Total Signal Accumulation Time:
2176 s
Total Elapsed Time: 2176 s
Number of Scans: 128
Effective Detector Width: 0.12 eV

䊏 Accession #: 00431-07
䊏 Host Material: MnO2 powder
䊏 Technique: XPS
䊏 Spectral Region:
Mn L 3 M 2,3 M 4,5
Instrument: Physical Electronics,
Inc. 5600
Excitation Source: Al K ␣
monochromatic
Source Energy: 1486.6 eV
Source Strength: 400 W
Source Size: 2 mm⫻5 mm
Incident Angle: 65°
Analyzer Type: spherical sector
Analyzer Pass Energy: 11.75 eV
Analyzer Resolution: 0.12 eV
Emission Angle: 25°
Total Signal Accumulation Time:
5120 s
Total Elapsed Time: 5120 s
Number of Scans: 128
Effective Detector Width: 0.12 eV

Surface Science Spectra, Vol. 6, No. 1, 1999 MnO2 by XPS 37

 䊏 Accession #: 00431-08
䊏 Host Material: MnO2 powder
䊏 Technique: XPS
䊏 Spectral Region: C 1 s
Instrument: Physical Electronics,
Inc. 5600
Excitation Source: Al K ␣
monochromatic
Source Energy: 1486.6 eV
Source Strength: 400 W
Source Size: 2 mm⫻5 mm
Incident Angle: 65°
Analyzer Type: spherical sector
Analyzer Pass Energy: 11.75 eV
Analyzer Resolution: 0.12 eV
Emission Angle: 25°
Total Signal Accumulation Time:
1920 s
Total Elapsed Time: 1920 s
Number of Scans: 96
Effective Detector Width: 0.12 eV

38 Surface Science Spectra, Vol. 6, No. 1, 1999 MnO2 by XPS