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X - R AY E N E R G Y D I S P E R S I V E S P E C T RO S C O P Y: OV E RV I E W, A P P L I C AT I O N S , & A N A LYS I S
D AV E S TA L L A , M . S .
S E N I O R R E S E A R C H T E C H N I C I A N , E L E C T RO N M I C RO S C O P Y C O R E
& P H . D. C A N D I D AT E , P H Y S I C S
U N I V E R S I T Y O F M I S S O U R I
Electron Microscopy CoreUniversity of Missouri
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ABOUT ME
• Ph.D candidate in physics (ant. grad: June 2017) with Prof. Peter Pfeifer
– Dissertation focuses on H2 and CH4 storage via adsorption in carbonaceous materials
– Characterization: XPS, XRD, U/SAXS, U/SANS, PGAA, FTIR, N2 sorption (BET)
– Experience with synthesizing raw (high-Σ carbons) and functionalized (B-doped carbons, bulk C3N4)
materials
– Technical experience includes Mathematica programming and Arduino microcontroller
design/implementation
• Hired as Senior Research Technician 9/2016
– EMC user since 2010
– Travelled to Bruker HQ 11/14-17 for “Nano Analytics QUANTAX User School”
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E-BEAM INTERACTIONQuanta/Hitachi/Scios
JEOL/F30
F30
Quanta/Hitachi/Scios/F30
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CHARACTERISTIC X-RAYS
e- beam
incident electron
secondary electron
generation
Incident electrons scatter
electrons from the
sample, resulting in
secondary electron
generation for imaging.
The electron ejection
results in a vacancy in it’s
former orbital.
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CHARACTERISTIC X-RAYS
e- beam
Ex-ray = Eshell1 – Eshell2
Electrons from higher orbitals
will fill this vacancy as is
energetically favorable.
As the electron jumps to a
lower energy state, it emits the
excess energy (ΔE) in the form of an x-ray photon.
The energies associated with these transitions are unique and well-tabulated.
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CHARACTERISTIC X-RAYS
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SI-LI VS. SDD
SDD design – significant improvements to collection efficiency!
capable of detecting elements as low as B
Si-Li detectors: ~10,000-20,000 CPS, above which data becomes unreliable
SDD detectors: routinely >100,000 CPS
specifications list upwards of 1,500,000 CPS possible
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HIGH THROUGHPUT ON BRUKER EDS SYSTEM AT EMC
High count rate (routinely work at ~150-200kcps) generates remarkable
data output - with the exception of mapping, quantifiable EDS data
collection comprises a marginal amount of instrument time.
Bruker Esprit – powerful microanalysis suite associated with the
QUANTAX detector. Unlimited network license allows users to the
software on their own machines and process data offsite: all instrument
time can be dedicated to maximizing the amount of data collected!
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ESPRIT: 4 MAIN ANALYSES
Increasing
spatial
information
‘Higher order’ analyses retain
functionalities of earlier ones
Windowed mode
Fullscreen mode
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I. SPECTRUM COLLECTION
• Collects a spectrum
across the entire
imaged area
• ~20s / scan
• Peak deconvolution
aids in identification
from overlapping
features
• Standards-based &
standardless quant.
available
• Many options for
easy plot generation
and exporting
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SPECTRUM ACQUISITION
• Total counts in spectrum
• Fixed real/live time
• Counts across a particular element’s
energy region
• Manual: collect until requisite statistics are
achieved
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PEAK IDENTIFICATION
• Manual selection of elements
• Auto ID for well-resolved features
• Finder tool: highlight a region, and the
software will list lines that fall within that
region in order of ‘likelihood’: α > β > γ,
distance from line from the center of the
region, etc
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ONLINE PEAK DECONVOLUTION
Initial assignments appear
to successfully account
for all features present
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ONLINE PEAK DECONVOLUTION
Reconstruction of elemental lines
shows that Kβ signals (calculated from associated Kα lines) don’t account for all detected counts
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ONLINE PEAK DECONVOLUTION
Deconvolution indicates
the presence of Mn and V
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II. OBJECT ANALYSIS
User-defined
regions:
• Point
• Rectangle
• Oval
• Freeform
polygon
• Iterative
auto grid
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III. LINE ANALYSIS
• Collects elemental
profiles across a
user-defined line
• Good for analyzing
phase interfaces
and non-discrete
boundaries
• ~5min / scan
• Can generate/
analyze/quantify a
spectrum across
entire line or a
selected segment
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IV. HYPERMAPPING
• Distinct from traditional
elemental maps, which
was essentially ‘filtered’
imaging: elements
predetermined &
individually collected
• Collected as a data cube:
spatial information from
pixels in x & y, each with
associated spectral
information (“z-axis”)
• A single collection yields
virtually limitless data
upon post-processing
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IV. HYPERMAPPING
• MASSIVE amount of data
(600x400 image has 240k
individual spectra) – most
versatile method
• Elemental maps
• Object analysis
• Line analysis
• Phase deconvolution
• ~10-20 min / region
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INDIVIDUAL/COMPOSITE MAPS
Can generate individual and
composite maps for any
combination of elements
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PHASE ANALYSIS
Identify discrete chemical phases via CPU-aided
analysis or manual assignment
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ELEMENTAL HEAT MAP
BSE Image Standard Al Map
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ELEMENTAL HEAT MAP
BSE Image Standard Al Map
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MAXIMUM PIXEL SPECTRUMReference BSE Image Associated elemental map
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MAXIMUM PIXEL SPECTRUM
Maximum pixel spectrum
Indicates the presence of several
additional elements, each of which may
only exist in single-digit no. of pixels
Net hypermap spectrum
Represents the sum of each energy
channel’s counts across ALL analyzed
pixels – high spatial concentrations
dominate
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MAXIMUM PIXEL SPECTRUMReference BSE Image ‘Trace’ features map
Most features comprise significantly less than 0.1wt% in the bulk, below the accepted detection limit of EDS
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PARTICLE ANALYSIS
• Image analysis utility independent of X-ray data
• Particles are partitioned from CPU-aided filtering and binarization
• A number of different geometric characteristics can be quantified
• May be followed by EDS measurements in defined particle regions for joint particle/phase
analysis
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PARTICLE ANALYSIS
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VARIABLE Z
15 mm4 mm
WD = 9mm WD = 50mm
Field of view is limited by working distance; most EDS systems
require a fixed WD for sufficient counting (detector must be
pointed at sample surface). EMC QUANTAX system is capable of
alignment to longer working distances for wider analysis regions