Phase Identification RMS

03.04.
2017
PHASE IDENTIFICATION BY EBSD

The standard procedure
G. Nolze
Federal Institute for Materials Research and Testing
Outline
1. What is a phase?
2. Why phase identification by EBSD and what

do we need it for?
3. Information content of an EBSD pattern
4. Some rules and recommendations
5. Examples
03.04.2017 G. Nolze: Phase identification: The standard procedure 2

What is a phase?
In crystallography a (crystalline) phase is defined by a stoichiome-

trically uniform region which has a distinct crystal structure.
In a phase all physical properties like density, refraction, diffraction,
magnetization etc. as well as the chemical composition are
essentially uniform. ( non-essential: e.g. crystal habit, or different
varieties of minerals like corundum, ruby and sapphire)
Special cases:
Isostructural phases (different composition, same structure type, e.g.
all fcc materials like Al, Cu, Ni, Co, Fe, Ag, Au)
Polymorphism (same composition, different structures, e.g. calcite/
aragonite, rutile/anatase/baddeleyite, diamond/graphite, ferrite/austenite)
Polytypism (layers of nearly identical structure and composition are
stacked in a different sequence, e.g. SiC, has more than 170 polytypes).
Solid solutions (mixed crystals, i.e. a continuous variation of the chemical
composition (substitution) which does not affect the crystal structure type but
the lattice parameters)
Phase identification (ID)
In materials science powder X-ray diffractometry (PXRD) is

used as standard technique to identify and quantify
crystalline phases.
A powder-diffraction pattern is like a fingerprint of a phase.

PXRD does not even require any chemical information since the
translation-lattice variation (peak position) in combination with the
crystal structure (peak intensity) is practically unique for any phase,
and the technique is sensitive enough.
However, there are a very few scenarios where PXRD does

not work properly
and alternative techniques are required which are
commonly limited as well and therefore not in general used.

PXRD limitations
Standard PXRD does not work if

the phase fraction is too small (i.e. the peak intensities are too low),
the grain size is too big (i.e. the number of crystals is too small),
the material is high-textured (i.e. peak intensities do not match), or
the sample shape (bulk vs. powder) is not suitable to be analyzed
in a powder diffractometer.
Alternatives for small precipitates?

Phase ID on single or a few individual grains is not only expensive,
but also less accurate and more complicated for single-crystal
XRD at a synchrotron facility. Diffraction in TEM
However, TEM requires a special sample preparation and is often also not
available. Moreover, because of their size TEM samples always bear the risk
to be of low statistical relevance.

Phase ID in SEM
Benefits compared to TEM:

A common SEM/EBSD sample is much bigger than a TEM sample.
After collecting experience sample preparation is comparatively
easy and not much more difficult than for light microscopy.
We can go from very low to very high magnification!
Use light microscopy before you start to work in SEM!
Benefits compared to light microscopy

EBSD can be performed at higher magnification and combined
with other analytical techniques like EDS, WDS, XRF, CL etc.
Quantitative description (phase fraction)?

An accurate microstructure description requires all phases which
have to be identified correctly.
However, a quantitative description is often questionable!
(for statistical reasons but also since phases may disappear during preparation)

What do we need for Phase ID?
1. A high-quality EBSD pattern (noise-poor, not automatically high-

resolved).
2. The projection-center position (pattern center & source-to-screen

distance, cross-checked on a known cubic phase).
3. The approximate chemical composition of the volume which

formed the EBSD pattern (typically by EDS).
4. One or more crystal-structure databases which are suitable for

an automatic search (free tools like COD* are not directly usable) and a
software (license) for a full-automatic retrieve which uses the
qualitative or semi-quantitative chemical information as primary
discrimination and creates a list of possible candidates.
5. A software which tries to index the EBSD patterns using all

remaining candidates and evaluates their degree of match.
* Crystal Open Database

Phase ID in known materials
Often, we know the material, its chemical composition, the phase diagram,
and the sample history. This reduces possible candidates considerably.
Please note: Experts in PXRD usually do not see more than 400 phases in their
entire life compared to several hundreds of thousands database entries.
Some recommendations:
Concentrate first on phases which are known for this material.
Check the literature and make a list which phases are possible and have
been observed or discovered already.
Contact the owner of the sample which phases might be conceivable.
Simplify the chemical composition and ignore minor elements.
Because of pseudosymmetry reasons (easier handling), evaluate high-

symmetric phases first, then check phases of lower symmetry.

The challenge of phase selection
In contrast, for a really unknown material we have only a very limited

knowledge about possible phases which might have been formed locally.
Additional complications are:

Databases are full of phase entries with the same crystal structure but
described by different lattice parameters.
Which is the best phase description for the current material?
Databases are full of crystal structures (minerals) defined by different
symmetries or even crystal systems.
Which phase description matches best for the present problem?
In solid-solution materials chemical composition and lattice-parameter
ratios may change in an EBSD-relevant magnitude.
Which composition and lattice parameters have to be used?
Sometimes the chemical signal does not match any phase in a database.
Which phase should then be selected, and how reliable is any
conclusion?
Information content

Information content

Information contentas far as we know



An EBSD pattern
represents the full
information about
the translation lattice
but also about the crystal
structure (atomic arrangement).

Presently used information content
Currently, for phase

ID only the lattice-
parameter ratios and
angles have any effect.
The match of the band edges
happens on a subjective level.
Lattice parameters
It is the finger print of a phase.

PXRD can be used to simultaneously identify several phases in
a mixture without any chemical information.
Unfortunately, like many other electron diffraction techniques EBSD
is assumed to be very insensitive regarding lattice parameters.
However, accuracy and precision are clearly better than presently
claimed, although it will never reach XRD techniques!
EBSDL derives lattice parameters as well as the Bravais

lattice type from a single EBSD pattern and promises a high
confidence level. L. Li and M. Han J. Appl. Cryst. 48 (2015),107-115
The lattice-parameter ratios and a, b, g may reach a precision
better than 1%.
The lattice parameters itself have precisions between 35%.
Main request: the band positions and edges are well visible,
i.e., defect-rich phases like martensite are presently out of discussion.

Detection of Kikuchi-band positions
The automatic detection of the band positions is based on the

Hough or Radon transformation which turns all linear intensity
distributions (bands) into point-type features.
For a maximum precision in peak detection a high resolution in
Hough space is recommended which is not in general helpful
e.g. because of their static application (cf. fixed butterfly filter).
Recommendation:
For phase ID, band centres are currently still better drawn by
hand or at least manually readjusted.
Please note:
Crossing (narrow) bands ALWAYS intersect in a single point!
Do not define too many bands, especially if the used software
does not consider any information about the band intensity which is
not identical to the commonly used reflector intensity.

Workflow Phase ID
The EDS signal is used to generate a list of possible candidates.

After an indexing attempt for each phase, a new subset is derived
which lists all remaining phases sorted by their (mis)match.
The mismatch between experimental and theoretical band
positions is calculated and called
- confidence index CI (EDAX-TSL),
- mean angular deviation MAD (Oxford Instr.), or
- band mismatch BMM (Bruker).
It represents a semi-quantitative quality criterion only.
As far as I know, the band widths as well as the band intensities
are not evaluated, only the band positions!
Ideal case: There is only one remaining phase which describes
all drawn band centres, their widths (!) and the
chemical composition correctly.

Phase ID: The difficult case
Worst case: There is no phase candidate at all! Why?
Measured composition is far away from being correct!

(experimental error, operator mistake)
There is no phase with this approximate composition.

(EDS list is already empty! Wrong (fake) elements?)
There is really no phase with this band distribution.

(EDS list is not empty but there is no crystallographic solution.)
The pattern centre is incorrect.

(Must be really wrong and not only inaccurate!)
Please note: Band detection is never that wrong but affects the
quality of the match and thus also the phase ranking.

How trustful is the EDS signal?
Please keep in mind: The interpretation of the EDS signal is based on

several assumptions which are perhaps not fulfilled, e.g.
The high sample tilt is not considered.

Improper corrections (background, ZAF or phi-rho-Z*).
The sample possibly contains non-detectable light elements?
Misinterpreted elements caused by peak overlapping?
The signal comes perhaps from another volume (matrix effect
in case of small particles, thin layers or surface-near residual
parts).
The sample shows a considerable charging (landing energy?).
Critical elements like C and N are considered but do not exist.
* basically Z (element) and A (absorption), one needs to apply fluorescence as well

What to do if no phase is found?
The chemistry is (partially) incorrect!

- Check the EDS analysis setup!
- Delete minor elements! Exclude C and/or N. Include light elements.
- Acquire spectra from other positions and compare the compositions!
- Use BSE images to cross-check the derived composition!
- How big is the approximate information volume, i.e., the visible lateral
dimension (magnification)? (matrix effect)
- Check for possible charging? (look for the background)
Structure type exists, but not with these elements!

- Change the retrieve model, i.e., look for a subset of elements only!
- Substitute elements of the same main or transition group!
Crystal structure is unknown but phase is known!

- If you have OIM and the respective licence you can search additionally in a
powder diffraction database (PDF) and uses reflectors derived from X-ray
powder data.

What to do if only phases with low
match?
The chemistry is partially incorrect!

(see slide before)
The band positions do not really match!

- the lattice-parameter ratios deviate from the real phase
(different composition)
- especially in case of a cubic phase: the projection centre is
inaccurate
- pseudosymmetric phase
(the real phase has a different translation lattice but a similar
crystal structure)
The band widths show considerable differences!

- All: the lattice parameters are considerably wrong (wrong phase)
- Only some: - wrong Bravais lattice (wrong phase) ?
- pseudosymmetric phase, e.g., polytype ?
What to do if more than a single phase
match?
The best matching phase is assumed to be the correct solution.

However, because of the high degree of uncertainty every
information should be cross-checked:
the lattice-parameter ratios (band centres) ,
the lattice parameters (band widths), and
the chemical composition.
Check also the projection centre for safety!

(Dont optimize the projection centre by an unknown phase!
Especially for unexpected phases look again in literature and talk to

colleagues who are more experienced. Even the best matching phase
can be wrong if the chemical composition is incorrect.
Consider alternative explanation like nano-twins, stacking faults etc.

Example: Ferro-silicon
In Ferro-silicon Al and Sr
impurities may form
intermetallic phases
(please note the different
grey scales)
Also the pattern-

quality map suggests
different phases.
In case of very exotic
element combinations
some of the observed
Si phases are not listed in
a crystal-structure
database.
Because of combined EDS the acquisition time is higher than
for EBSD alone. For a map with 750,000 points: 6:54:35h.
What can be done?
07.04.2017
03.04.2017 27 Nolze: Phase identification: The standard procedure
G. 27
Unknown structure
EDS shows: Si, Fe, Al

In a database of more than
200.000 entries only 19
are compounds containing
Si, Fe, and Al
No fit with EBSD pattern
Extended search option:
Si + Fe + any other
element:
441 candidates
Best candidate is:
DyFe4Si10
with a fit of 11 of 12 bands
Cubic phases are easier since a:b:c = 1:1:1!

AlFe4Si10
07.04.2017
G. 29
Solution
Finally 8 phases have

been discovered
Si (cubic)
AlFeSi2 (orthorhom.
FeSi2 (tetragonal)
SrSi2 (cubic)
AlSr3Si23 (cubic)
AlSrSi (hexagonal)
Sr4Si7 (tetragonal)
AlFe2Si10 (monoclinic)
Zero solution are only caused by cracks and holes.
07.04.2017
G. 30
Example: Arsenides, diarsenides and
triarsenides from Bou-Azzer (Morocco)
Isabel Fanlo, Universidad de Zaragoza
133
Simultaneous EBSD
and EDS acquisition 132
EPMA results
131
S As Fe Co Ni
[at%] [at%] [at%] [at%] [at%]
130
133 31.0 34.9 2.1 31.9
129
132 10.2 55.4 3.5 30.9
80m
131 2.3 63.5 9.4 24.8
130 0.4 65.3 19.6 14.7 PQ BSEEBSD Cross-
(mean Z) correlation
129 2.7 62.9 23.9 10.5 of EBSD
patterns

EDS maps and known minerals
1.02 -0.02
0.92 0.08
0.82 0.18
EDS acquisition Electron probe

0.71 0.29
MS2
during EBSD 0.61 0.39 micro analysis
measurement S 0.51 0.49 All other
0.41 0.59
0.31 MeAsS 0.69

133
0.20 0.80
131,
0.10 130, 132 0.90
129 MeAs MeAs

0.00 2 1.00
1.02 0.92 0.82 0.71 0.61 0.51 0.41 0.31 0.20 0.10 0.00
MeAs3 As

EDS maps and known minerals
MeAsS MeAs MeAs2 MeAs3

33% As 50% As 67% As 75% As
1.02 -0.02
0.92 0.08
0.82 0.18
0.71 0.29
MS2
0.61 0.39
S 0.51 0.49 All other
0.41 0.59
0.31 MeAsS 0.69

133
0.20 0.80
131,
0.10 130, 132 0.90
129 MeAs MeAs

0.00 2 1.00
1.02 0.92 0.82 0.71 0.61 0.51 0.41 0.31 0.20 0.10 0.00
MeAs3 As

Phase approximation by EDS
Co Fe Ni As S
CoAsS (+Ni)
CoAs (+Fe, S)
CoAs2 (+Fe, S)
FeAs2 (+Co)
CoAs3 (+Fe, S)
Fe
1.02
0.92
There is neither NiAsS (Gerstorffite) nor NiAs2 0.82
0.71
(Rammelsbergite). Fe 0.61
0.51
Practically, everywhere As and S but also Fe and Co substitute 0.41
0.31
each other. 0.20
0.10
0.00
0.00 0.10 0.20 0.31 0.41 0.51 0.61 0.71 0.82 0.92 1.02
Co
Co

Serious candidates
CoAsS (+Ni) CoAs (+Fe, S) CoAs2 (+Fe, S) FeAs2 (+Co) CoAs3 (+Fe, S)
33% 50% 66% 75%
As
Phase approximation by EBSD
Alloclasite Alloclasite Alloclasite

Glaucodot Glaucodot Glaucodot
Langisite Langisite
Clinosafflorite
Alloclasite Alloclasite Alloclasite

Glaucodot Glaucodot Safflorite
Langisite Langisite Lllingite
Clinosafflorite Clinosafflorite Skutterudite
Safflorite Safflorite
Lllingite
Skutterudite

Probable solutions
CoAsS (+Ni) CoAs (+Fe, S) CoAs2 (+Fe, S) FeAs2 (+Co) CoAs3 (+Fe, S)
?
33% 50% 66% 75%
As
Phase comparison

Different projection directions

Take-home messages
Phase ID with EBSD and EDS requires advanced knowledge about both
techniques, but also some crystallographic expertise.
One weak point is the different information volume of EDS compared to
EBSD. This can be partially compensated by multiple measurements.
Databases do not contain all phases.
Multiple phase entries and numerous pseudosymmetric descriptions
complicate the phase selection.
Band positions already define the lattice-parameter ratios. They are
already quite phase-sensitive. The more accurate the band positions the more
reliable the phase ID.
In case of an unsatisfying match: Replace some bands especially if many
bands appear with a similar intensity.
A high hit rate during orientation mapping is no proof of a correct phase.
It only tells you that the lattice parameter ratio and the reflector list of the
selected phase are similar.

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03.04.

PHASE IDENTIFICATION BY EBSD

2. Why phase identification by EBSD and what

3. Information content of an EBSD pattern

4. Some rules and recommendations

03.04.2017 G. Nolze: Phase identification: The standard procedure 2

In crystallography a (crystalline) phase is defined by a stoichiome-

In materials science powder X-ray diffractometry (PXRD) is

A powder-diffraction pattern is like a fingerprint of a phase.

However, there are a very few scenarios where PXRD does

03.04.2017 G. Nolze: Phase identification: The standard procedure 4

Standard PXRD does not work if

Alternatives for small precipitates?

03.04.2017 G. Nolze: Phase identification: The standard procedure 5

Benefits compared to TEM:

Benefits compared to light microscopy

Quantitative description (phase fraction)?

03.04.2017 G. Nolze: Phase identification: The standard procedure 6

1. A high-quality EBSD pattern (noise-poor, not automatically high-

2. The projection-center position (pattern center & source-to-screen

3. The approximate chemical composition of the volume which

4. One or more crystal-structure databases which are suitable for

5. A software which tries to index the EBSD patterns using all

* Crystal Open Database

Contact the owner of the sample which phases might be conceivable.

Simplify the chemical composition and ignore minor elements.

Because of pseudosymmetry reasons (easier handling), evaluate high-

03.04.2017 G. Nolze: Phase identification: The standard procedure 8

In contrast, for a really unknown material we have only a very limited

Additional complications are:

03.04.2017 G. Nolze: Phase identification: The standard procedure 10

03.04.2017 G. Nolze: Phase identification: The standard procedure 11

03.04.2017 G. Nolze: Phase identification: The standard procedure 12

03.04.2017 G. Nolze: Phase identification: The standard procedure 13

03.04.2017 G. Nolze: Phase identification: The standard procedure 14

03.04.2017 G. Nolze: Phase identification: The standard procedure 15

Currently, for phase

It is the finger print of a phase.

EBSDL derives lattice parameters as well as the Bravais

03.04.2017 G. Nolze: Phase identification: The standard procedure 17

The automatic detection of the band positions is based on the

03.04.2017 G. Nolze: Phase identification: The standard procedure 19

The EDS signal is used to generate a list of possible candidates.

03.04.2017 G. Nolze: Phase identification: The standard procedure 20

Worst case: There is no phase candidate at all! Why?

Measured composition is far away from being correct!

There is no phase with this approximate composition.

There is really no phase with this band distribution.

The pattern centre is incorrect.

03.04.2017 G. Nolze: Phase identification: The standard procedure 21

Please keep in mind: The interpretation of the EDS signal is based on

The high sample tilt is not considered.

* basically Z (element) and A (absorption), one needs to apply fluorescence as well

The chemistry is (partially) incorrect!

Structure type exists, but not with these elements!

Crystal structure is unknown but phase is known!

03.04.2017 G. Nolze: Phase identification: The standard procedure 24

The chemistry is partially incorrect!

The band positions do not really match!

The band widths show considerable differences!

The best matching phase is assumed to be the correct solution.

the lattice-parameter ratios (band centres) ,

the lattice parameters (band widths), and