Transcript Casainfotalk_v9

Introduction to Data Analysis
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Downloading CasaXPS
Online tutorials, resources, manuals, videos
Low resolution analysis, calculating atomic %
File Handling, report generation (slide 7)
High resolution analysis
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Peak fits (Gaussian-Lorentzian, Voigt, Doniach-Sunjic)
Atomic % (tags)
Chemical shifts
Propagating analysis to multiple data sets
Propagating analyses
Overlayer notes
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Introduction to CasaXPS
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Cornell site license: Free to any Cornell user, get registration code from manager
Sorry, not available for Macs.
Current download v.2.3.15 at http://www.casaxps.com/casaxps2315.htm
version 2.3.16 http://www.casaxps.com/berlin
http://www.casaxps.com/help_manual/ (help files and videos)
development http://www.casaxps.com/2317dev/download.htm
If you have an old version of Casa, simply replace your current
• Casa.exe executable file
• .hlp folder
• This will ensure that you keep your current library and settings
– The Casa folder should stay intact and not split up, the folder can be moved
around on disk or flash drive and run from any computer. You can create a
shortcut to CasaXPS.exe but don’t move CasaXPS.exe from the folder
• Can be used to analyze XPS, Auger, SIMS data and more
• Actively upgraded by author, Neal Fairley
• Can import almost any data file and save as ISO 14976 (VAMAS) format for easy
exchange between laboratories
• Web Manual
• Casa Cookbook (~$60) available from RBD or Acolyte Science
• Incorporated into data processing short courses by John Grant and others
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Other
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XPS information http://www.casaxps.com/help_manual/XPSInformation/
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CasaXPS eManuals (Yellow Book) http://www.casaxps.com/ebooks/ebooks.htm
Quantifying survey and high resolution data
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Peak fitting of high resolution data
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http://www.casaxps.com/help_manual/manual_updates/peak_fitting_in_xps.pdf
Curve Fitting of Polymers
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(video) http://www.casaxps.com/cam4/quant-survey/quant-survey.html
http://www.casaxps.com/help_manual/manual_updates/Basics_Quantification_of_XPS_Spectra.pdf
http://www.casaxps.com/help_manual/curve_fitting_polymers.htm
Estimating errors http://www.casaxps.com/cam4/Quant-With-Tags/Calculate-error-bars/Calculate-error-bars.html
Error analysis http://www.casaxps.com/help_manual/error_analysis.htm
Force quantification
File format conversion http://www.casaxps.com/help_manual/file_converters/file_conversion_filters.htm
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Analysis Using one Wide Scan
(see http://www.casaxps.com/cam4/quant-survey/quant-survey.html)
survey
x 10
3
1.
2.
12
10
Counts
8
Open the scan by double-clicking on the data block
Click on the Library icon
, or press F10. Click on the
Periodic Table tab.
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6
4
2
1000
800
600
400
200
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4.
0
Bi ndi ng E nergy (eV)
5.
survey
P os .
286.0000
533.0000
159.0000
576.0000
369.0000
348.0000
FWH M
3.2078
3.5914
3.0702
2.4159
2.1172
2.2925
A rea
25587.311
23086.879
14969.929
16352.663
1403.565
1319.974
3.
A t%
71.46
22.01
1.69
3.90
0.22
0.73
Cr 2p
10
N ame
C 1s
O 1s
Bi 4f
Cr 2p
A g 3d
Ca 2p
C 1s
12
3
O 1s
x 10
8
Bi 4f
Ag 3d
Ca 2p
CPS
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6
5.
4
Important: verify that regions are correct. If a doublet region
(Cr 2p, e.g.) only encloses a singlet, click F7 or the Quantify
icon. When the Regions tab is selected, adjust the gray
bars around the regions to obtain a proper background that
intersects the noise at a reasonable point.
Backgrounds are typically Shirley for metals and Linear for
polymers.
Some regions may need to be added manually.
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2
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800
600
Bi ndi ng E nergy (eV)
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Select elements, verify transitions that appear with data
Can also go to the Element Table tab, click on the spectrum, and
highlight transition in the Element Table.
When all peaks are identified, click Create Regions
Verify that regions are correct. If a doublet region (Cr 2p, e.g.)
only encloses a singlet, click F7 or the Quantify icon. When the
Regions tab is clicked, adjust the gray bars around the regions.
To zoom in, draw a box around a peak, and click inside the box.
Use these icons to shift the data.
Zoom in on a peak
F7, in Regions tab, click Create.
Make sure region name is correct, type in ‘# Na 1s’ to change a
region and the RSF value. The ‘#’ command utilizes information
in the library.
0
By default, CasaXPS will look for the peak with the greatest RSF value
In the case of a doublet, CasaXPS may assign a doublet region to a single peak
To change the default peak, open the CasaXPS_quant.lib file and add/replace the peak
transition you prefer, from CasaXPS.lib
Analysis Using two Survey Scans (taken at same pass energy)
survey
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3
12
10
Counts
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6
4
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2
1000
800
600
400
200
0
Bi ndi ng E nergy (eV)
Bi 4f
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90
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85
Bi 4f
Counts
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75
Remove any previously made annotation in Annotation History. Highlight and delete.
Click on the Quantification tab. Click Apply and a table will appear on the spectrum.
Highlight the blocks of data that you want added to the table and the smaller survey
scan information should appear.
survey
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65
180
175
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160
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145
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Variable
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Bi ndi ng E nergy (eV)
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Name
C 1s
O 1s
Cr 2p
Ag 3d
Ca 2p
Bi 4f
Pos.
286.0000
531.0000
576.0000
369.0000
348.0000
160.8000
Area
15845.007
22073.187
20220.893
3106.319
1102.955
730.251
At%
62.07
29.51
6.77
0.68
0.85
0.12
C 1s
x 10
Cr 2p
x 10
Trace elements near the sensitivity level of XPS (~0.1-0.5%) may
not show up well in a few survey scans. In this example, 10 survey
scans of a chrome film do not indicate a bismuth peak, while 40
survey scans around 160eV show a small Bi 4f doublet. To utilize
two (or more) survey scans:
Open the scan where the Atomic% table should go.
Add regions to all survey scans (follow instructions on previous
slide). In this example, the Bi 4f region should not be in both
spectra, just one.
Click F9, or the Annotation icon
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O 1s
x 10
Ag 3d
Ca 2p
Counts
8
6
4
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1000
800
600
Bi ndi ng E nergy (eV)
400
200
0
File Handling
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Click “EDIT MODE” to see any original file names
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FG means Flood Gun was used for charge compensation
FGG means the Flood Gun and Grid were used for charge compensation
_0, _30, _55, e.g. refer to the emission angle for ARXPS. _0 is the sample normal (deepest analysis). If no
angle is given 55-degrees is assumed.
– You may edit the blockID or sampleID by clicking on the “?” icon to the left of EditMode
– Can rename species and transitions as well
If rows are not already arranged, select all blocks in a row and click ‘edit by row’
– Choose a variable label (e.g. sample, time, depth, etc.)
– Choose a variable value higher than the # of blocks you have.
– Repeat to sort each block into its label#
Blocks should be sorted into columns by peak transition
– Using the ‘species/transition’ icon, label the element and transition (survey, Au 4f, C 1s, e.g.)
– Or, open the element Library(F10)
• Click on your peak to narrow the element table down
• Select your peak/transition (C1s, Au4f, Au 4f 7/2, etc. )
• Click ‘edit Block Species/Trans’
• Click OK and your data block will go under its own column (C1s, Au4f, etc. )
Clicking the trash-can ‘delete Vamas blocks’ will delete all highlighted blocks (cannot undo)
Clicking the clipboard for ‘copy/paste Vamas blocks’ will add all highlighted blocks into the current
data set. Even blocks from other Vamas files can be copied if highlighted.
Spectra can be copied to the clipboard or saved as an EMF
Data is saved in Vamas format
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Exporting Data
Shifting Data
Exporting data to text
Highlight the blocks to be exported and
click:
– Click the ‘Save Tab ASCII’ icon
– Choose file name
– Export as rows of tables
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Exporting Atomic %’s as a report
Highlight the blocks to be exported and
click:
– F7, Quantify
– Click the Report Spec. tab
– Click on the regions/transitions, or
just click ‘All’
– Click Area Report
– Save file to save as text file
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Processing (F8) can be used to shift data
– Click on the ‘Calibration’ tab
– Click on your peak and a Measured energy
will appear
– Type in the true intensity and click ‘Apply’
– Can be applied to Regions and
Components by checking boxes
Note:
– SSI system is calibrated to Au4f at 84/88eV
– CasaXPS defaults to 83/87eV
– Can go into the CasaXPS.lib file and
change the Au4f7/2 to 84eV and Au4f5/2 to
88eV
Can reverse data shifts by clicking on the
‘Processing History’ tab and removing any
commands
Peaks/Components: Fitting Data
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Note: It will help if your block Species/Transition is
named correctly, or the default lineshape will be
GL(30) instead of what you have in the library
Create a region around your peak(s)
Click the ‘Components’ tab
Click ‘Create Component’
– If the peak is selected in the Element table,
the component will have the peak name
(Au4f7/2 e.g.)
– Can also type in “# Au 4f 7/2” in the ‘Name’
field to bring up the library RSF value
When you click on a peak, you can:
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See the residual at the top, in black, which you would
like to be flat when fit well. The next created peak will
be inserted where the largest negative residual lies.
Drag the top of the peak to change Area and Position
Drag the side of the peak to change FWHM
Repeat for # of components you need
Click ‘Fit Components’ to obtain a fit to the data
Components can be removed by selecting and
clicking ‘Cut’
Spin-Orbit Splitting
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Very subjective
Can use two separate
regions to define both
peaks
Can use a Shirley/linear
background (v.2.3.13
only)
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Type ‘OS’ into region
background field
Can use a linear
background
Can constrain peak areas
to theoretical values
Constraints (components)
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Can create Component Constraints:
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In the component fields, make sure you
press enter, don’t click after entering a
value
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Position (eV)
– Known chemical shifts
– Can set X,Y in the constraints field
where X is lower limit and Y is upper
limit
– A+1.2 means 1.2 eV higher than
position of peak A
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FWHM
– May vary with transition or chemical
shift
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Area
– 4f 7/2 peak area should be 4f5/2
area*1.3333 (4:3 ratio)
– 3p 5/2 = 3d 3/2 *1.5 (3:2 ratio)
– 2p 3/2 = 2p 1/2 *2 (2:1 ratio)
– A*1.333 would constrain the peak to
1.333 times the area of peak A
Displaying Component Table
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Each component can have a unique Name
Open the ‘Tile Annotation’(F9) box
Click the Quantification tab
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Click table type for components, regions,
or both
Click ‘Apply’
Annotation History
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Can click the Components tab if only
comparing components
Can click the Regions tab for comparing
regions
Can move the table by click and dragging
the red box that appears
Can remove the table by deleting the
annotation history line
Advanced: Propagating Analyses
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You can propagate the following analyses:
– Regions
– Components
– Processing and more
– Careful propagating too much
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Bring up the spectrum you would like to propagate
Highlight the blocks you would like to propagate to
Either right-click the spectrum, OR click the ‘Propagate to Selection’ icon
– Your selected blocks should appear and allow you to choose what you would
like to propagate (regions, components, processing, annotation, etc.)
Selected spectra will have parameters applied
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Overlayer Effects
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Copper thin film on gold
Heterogeneous structure
Buried thick copper layer
between gold
Copper substrate beneath gold
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Overlayer Effects
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A pure gold sample would show
equal atomic% for all peaks
An overlayer will cause the
lower KE (higher BE) peaks to
be reduced in area
The data here indicate a
Carbon overlayer (C peak at
284 eV) that is attenuating the
Au peaks at higher BE’s
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