62th Annual Conference on Applications of X-ray Analysis: SAND2013-6234C

Denver X-ray Conference Workshop

5 August 2013, 9AM-Noon, Meadowbrook, Westin Westminster Hotel

BASIC TO INTERMEDIATE
XRD ANALYSIS

Mark A. Rodriguez
Sandia National Laboratories
Albuquerque, NM 87185-1411

Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company,

for the United States Department of Energy’s National Nuclear Security Administration
under contract DE-AC04-94AL85000.
 What kinds of samples can we
measure?

Thin films
Single crystals
100 - 500 mm
Bulk samples

Single Crystal
Powders
Textured
1 mg - 5 gms

Random
 XRD flow chart

Crystalline? No Amorphous

Yes

Form of sample?

Thin film Bulk Powder

< 0.05 mm (50nm) 0.05 mm to 50 mm > 100 mm

“nano”
Single Crystal
Powder X-ray diffractometery (PXRD) Crystal structure
i.e. space group,
lattice parameters,
atom positions,
thermal ellipsoids,
Bond lengths & angles
molecule packing
predicted density
 Powder
Standard XRD
0.05 mm to 50 mm

Powder X-ray diffractometery (PXRD)

Phase identification: What is this stuff?

Phase fraction quantification via RIR: How much is there?

Out-of-plane preferred orientation: Is sample non-random?

crystallite size / micro-strain: What can I learn about the crystallites?

Lattice parameter indexation / cell refinement: What is the cell?

Phase fraction
No Known structure? Yes space group,
lattice parameters,
atom positions,
site occupancy,
Structure Solution from model Rietveld thermal ellipsoids,
Powder Data (SSPD) refinement Bond lengths & angles
molecule packing
predicted density
size/strain
Nano-crystalline Powder

< 0.05 mm (50nm)

Mo tube: l = 0.7107 Å

Powder X-ray Diffractometery (PXRD) Atomic pair distribution function (aPDF)

Phase identification? Known structure?

Out-of-plane preferred orientation:
aPDF
crystallite size / micro-strain:
refinement

space group,
lattice parameters,
atom positions,
site occupancy,
thermal ellipsoids,
Bond lengths & angles
molecule packing
predicted density
size/strain
 Thin stuff Thin film

Powder X-ray Diffractometery (PXRD) High Resolution

XRD
Phase identification: Grazing Incidence
Phase fraction quantification via RIR:
XRD Lattice parameter mismatch

Reciprocal space mapping

Out-of-plane preferred orientation:
Diffuse scattering
crystallite size / micro-strain:
Thin film modeling
Lattice parameter indexation / cell refinement:

X-ray Reflectivity
(XRR)
Texture attachment
Both out-of-plane & in-plane texture
Film thickness
Pole figures
Film roughness
ODF (orientation distribution function)
Film density
Residual stress analysis
 Bulk Can’t grind it

Powder X-ray Diffractometery (PXRD)

Phase identification:

Phase fraction quantification via RIR: Texture attachment

Out-of-plane preferred orientation:
Both out-of-plane & in-plane texture
crystallite size / micro-strain:
Pole figures
Lattice parameter indexation / cell refinement:
ODF (orientation distribution function)

Residual stress analysis

Random? No

Yes
Phase fraction
No Known structure? Yes space group,
lattice parameters,
atom positions,
site occupancy,
Structure solution model Rietveld thermal ellipsoids,
From powder (SSFP) refinement Bond lengths & angles
molecule packing
predicted density
size/strain
Single Crystal
 Single-Crystal XRD is a reasonably mature science and
is becoming routine for many materials systems

3 hour
automated
data collection
~1 Gb

Bruker Single-Crystal diffractometer

with Apex CCD detector

Solved
Frame integration
Structure
Structure solution in < 4 hrs
Refinement
~30 min
Sn3(THME)2
Powder
 For the rest of us who have something other than a big single
crystal, there is the world of powder diffraction characterization

Powder
Anatomy of a powder XRD pattern
0.05 mm to 50 mm

Detector path
Bragg’s Law d, I “Fingerprint”
l = 2dsinq  phase
l
d= d  index & unit cell
2sinq
I  site occupancy
1.9201 Å & phase fraction
47.303o 2q
2 FWHM crystallite
size & micro-strain
First step in a typical analysis is the straightforward qualitative phase ID.

Phase ID finds
hits for cubic ZrO2
and FeO (Wustite)

Does my answer make sense?

Is there a way I can check it?
XRF can be used for a quick check of the chemistry for the specimen.

XRF shows strong signal for Fe and Zr elements

There is also the presence of Hf and Y as well.

You might need to do some investigating…..

Y is used to stabilize the cubic ZrO2 phase.

Hf is likely a contaminant in the Zirconia.
Typically, analysis software allows you to fit the peak profiles. This is important
because quantitative phase fraction depends on relative peak areas, and
accurate 2q positions (i.e. d values) will improve lattice parameter refinements.

Difference pattern

Inserted peak
prior to profile
refinement
After profile fitting, the difference pattern looks essentially flat, indicating that
the peak areas are modeled well. This information can be now used for
quantitative analysis.

Difference pattern

Peak after
Profile fitting

Refined peak areas

Semi-quantitative analysis via Reference Intensity Ratios (I/Icorundum) can be
generated in most software via reported RIR values from the PDF database.

88 ± 9 %
ZrO2 12 ± 1 %
(Tazheranite) FeO
(Wustite)

ZrO2 ZrO2
ZrO2 (200) Profile fit (220)
(111) Wustite peaks

Based on peak intensities

Separation of micro-strain broadening from crystallite size broadening
can be done based on FWHM changes with 2q angle.

Estimated
crystallite size
~0.2 mm
(upper bound)

Fit micro-strain
value ~ 0.1 %

Conclusion: it looks like ZrO2 peak broadening is mostly

due to micro-strain.
If the unit cell is known from the PDF entry, you can usually perform a
lattice parameter refinement based on peak positions for a given phase.

Cubic ZrO2 FN
Lattice parameter
a = 5.1403(3) Å
Lattice parameters and
Vegard’s Law
 The idea behind Vegard’s law is based on the concept of Solid-Solution.
.

Imagine I am making an alloy from two pure metals of similar structure.

Nickel Copper
cubic cubic
Fm3m Fm3m

aNi = 3.524 Å

aCu = 3.615 Å
The lattice parameter
of the synthesized
alloy will fall between
the end members as aalloy = (x) aNi + (1-x) aCu
an “atomic” weighted
average of the mixed Where x is the atomic fraction
metals. of each constituent.

aNi < aalloy < aCu

Therefore, if we plot the lattice parameter vs. mole percent of the mixture
we should be able to predict what the lattice parameter will be at any
given composition for an alloy of NixCu1-x

3.64

3.62
Lattice Parameter (Angstroms)

aCu = 3.615 Å
3.60
Ni0.4Cu0.6
3.58

a = 3.579 Å
3.56

3.54

3.52
aNi = 3.524 Å
3.50
0 20 40 60 80 100

Mole percent Cu

Likewise, if we measure the lattice parameter of an alloyed mixture

we should be able to predict its chemical composition.
 Here is an example of Vegard’s law Er ErH2
Fluorite
in a series of ErH2-xDx compositions. structure
5.130
H or D
ErH2
Lattice parameter (Angstroms)

5.125

The difference between

ErH2 and ErD2 is only
0.0112 Angstroms!!
5.120

ErD2
a = 5.1287 -1.1120e-4x
5.115
0 25 50 75 100

Mole percent deuterium

Rodriguez, et al, (2008) Powder Diffraction 23 259-264.

For Rietveld structure refinement a high-quality dataset is
usually required so I ran the sample overnight.

What’s this?
The overnight scan picked up two more phases that are present
at low concentrations as seen in this zoomed range.

Monoclinic ZrO2
(Baddeleyite) Iron (metal)
For low concentration phases it is very important to make sure the small
peak profiles are fit properly for accurate phase fraction quantification.

Rietveld
refinement

Monoclinic
ZrO2 Iron

Rietveld
Refinement
performed
using GSAS
Rietveld structure refinement yields much more accurate quantitative analysis
along with structural parameters and even sensitivity to Fe deficiency in FeO.

Cubic ZrO2
79.5 ± 0.2 wt% Iron
a = 5.1403(2) Å 1.0 ± 0.2 wt%
a = 2.866(2) Å

Fe0.87O
19.0 ± 0.2 wt%

a = 4.3022(6) Å
Monoclinic ZrO2
0.5 ± 0.2 wt%
a = 5.17(3) Å
b = 5.19(3) Å This is about as good as you will
c = 5.32(1) Å get to the grail for this sample
b = 99.2(2) o
 Rietveld structure refinement was used
to find cations in Zeolite 3A powder.

I was given ICP results

Where are Na, K,

difference curve
and Ca
cations located?
 Rietveld Refinement results
matched well with ICP analysis.
O3 O1
Molar O2 Molar
content content
Na Ca
ICP 0.37 ICP 0.13
XRD 0.40(3) XRD 0.14(2)

O3 Molar
O2 Water
content molecules
K
ICP 0.34
XRD 0.32(3)
Here is an example of nanocrystalline Au powder contaminated with salt.

Powder

< 0.05 mm (50nm)

“nano”

Low Q (Cu) radiation

Sample shows broad peaks

for nanocrystalline Au along
with large crystals of NaCl.
A Rietveld structure refinement of powder data reported the
expected lattice parameter values for Au and NaCl phases.
expected

Au a = 4.078(2) Å 4.079

Au vol = 67.8(1) Å3
Rwp = 9.41 %
Au Biso = 0.6 Å2
Rp = 7.39 %
c2 = 1.492
NaCl a = 5.639(1) Å 5.640

NaCl vol = 179.3(1) Å3

NaCl Biso = 2.1 Å2

Wt fraction:
Au: 34.6(5) %
NaCl: 65.4(5) %

Crystallite size for Au ~8 nm.

High Q XRD data can be measured for the purposes of generating
an atomic Pair-Distribution Function (aPDF).

Vive Au nanopowder with NaCl

contamination – high Q data

F(Q) is
the total
scattering
structure Qmax = 14 Å-1
function
The atomic pair distribution function (aPDF) of a nanomaterial can
be helpful for characterization purposes.
Nearest neighbor (NN) distances can be derived
from the atomic pair distribution function (aPDF) Expected Au NN distances
2.88 4.08 4.99 5.77 6.45 7.06 7.63
6
2.86
4.95
Helpful for determining coordination 4 7.59
6.42
2
G(r) function can be refined in

G(r)
a similar fashion as Rietveld
4.11 5.62
refinement of XRD pattern 0 7.00

-2

-4

2 4 6 8
NN distance (Å)
Thin Films
Even running this film sample overnight in standard q-2q configuration does
not reveal any signal for a crystalline film presence on the Silicon substrate.

Thin film
Very thin cellulose film

Single Crystal
Silicon (400)
substrate
Setup of Grazing Incidence X-ray Diffraction (GIXRD)
employs parallel beam optics.

Detector
scans 2q
Very fine slits

X-ray
tube
Special soller-slit
Sample fixed at attachment
a very low angle
(~ 1.0o q )
 GIXRD analysis of film shows reasonable match to cellulose Ib.

Si Laue
Grazing angle = 2.0o peak

Grazing angle = 1.0o

Cellulose crystallite
Grazing angle = 0.5o size estimated from
(200) FWHM is
approximately 4 nm

08143
 Reflectivity is a low-angle technique
for analysis of thin films
Focusing
mirror
detector

X-ray Film density

tube
At very low angles X-rays determines
undergo total external reflection critical angle

At some critical angle

X-rays penetrate film
and intensity drops
 Reflectivity setup
Sample stage with
height, level, and
knife edge adjustment

Solid-state detector
Cu X-ray source with fine receiving slits
with mirror optic
and adjustable
incident slit width

Scintag X1 diffractometer system

Note: alignment is very important. Specimen film must be centered at the maximum
of the specular reflection intensity, which is usually < 0.2o wide.
Here is an example of successfully modeling reflectivity
data from a very thin Silane film on a Si wafer.

R EF S M ercury - D :\custom er\m ayer\01046\G1\G1_m erge_sec.txt

Silane film Density
A c tual Data F itted Data
108
1.81 g/cm3 107

106

Silane film Roughness 105

In te n s i ty
104
6.5 Å 103

102

Silane Film thickness 101

15.5 Å 1000 2000 3000 4000 5000 6000

S ec onds
7000 8000 9000 10000 11000

Silane
Film thickness from Ellipsometry
SiO2
13.1 Å
Silicon substrate
 Pole-figure analysis can be a big help in
characterizing films and textured metals

Texture cradle adds two additional

degrees of freedom (Chi, Phi)

Phi

Scintag Texture Cradle Attachment

By tilting, we can look at grains that

Chi (or Psi) are not normal to the sample surface
Pinhole collimator
 Texture definitions

Random grain orientation = no texture

Fiber Rolling Texture Bi-Axial

out-of-plane (YES)
out-of-plane (YES) out-of-plane (YES)
in-plane: 1-dimension of
in-plane (NO) in-plane (YES)
freedom, other fixed

b a ab

c c Po wd erCell 2 .0 PowderCell 2.0

c PowderCell 2.0

b a
b a b a b a
c PowderCell 2.0

a b c c c PowderCell 2.0

b a
c PowderCell 2.0 PowderCell 2.0
c
 Pole figure represents a distribution in space of
a given set of lattice planes (hkl).

(100) (110) (200)

All possible orientations of a selected

hkl plane are plotted on a hemisphere
that is then projected onto a planar
http://www.mrl.ucsb.edu/mrl/centralfacilities/xray/xray-basics/index.html#x4
surface (i.e. pole figure)
 Texture analysis is useful for confirming
bi-axial texturing of SrTiO3 on (200) Ni metal.

Bi-axially oriented
SrTiO3 crystals

(200) 90o

45o

Ni substrate

(220) planes shown in red

will diffract at 45o from
(200), each separated by 90o
SrTiO3 (220) pole figure
 Tilting the sample can also make it
possible to measure in-plane strains.

Data for ErD2

thin film
Tensile M
1
2
5-
Er
D(
4
22
2Compressive
)
pe
ak

0
.
0
02
Strain = -0.19% Positive slope:
0
.
0
01 tension
d/do
d/ 0

0
.
0
00

-
0
.0
01
Negative slope:
-
0
.0
02 b
1
=-
1
.9
43
e
-
3
compression
0
.
00.
10.
20.
30.
40.
50.
60.
70.
8

Sin
Si2
n2(
(psi)
Ps
i)
Bulk
 Bulk Sample of Molybdenum for Texture Analysis

Bulk

Molybdenum
metal coupon

Molybdenum
pole-figures
showing
rolling texture

(110) (200) (211)

 SSPD
(structure solution from powder data)
 Temperature (oC)

1100
1000
1200

100
200
300
400
500
600
700
800
900

10
Intensity (SQRT scale:
yellow =high, blue=low)
(002)

(101)

15
(020)

(120)
(021)

20
(301) & (110)
(011)
(210)
(040)
(400)

25
Alumina (012)

Two-Theta (degrees)
(011)
(211)

(111)
(022)
(211) & (202) (140)

(301) & (202)

30

(200)
(040)

(230) (131)
(501) (212)
35
Sometimes we come across new phases that have no ID

La2Ta2O7(OH)2 LaTaO4 LaTaO4

P21/n Pbca A21am
intermediate hi temp
 High resolution powder data was collected at APS 11-BM* and
structure was derived from indexed powder diffraction pattern.
I knew the approximate composition and assumed Ta was in TaO6 building blocks

La2Ta2O7(OH)2

La2Ta2O7(OH)2

*http://11bm.xor.aps.anl.gov/
 Refinement of high resolution powder data yields
excellent quality structural information.

Intensity (arb. units)

La2Ta2O7(OH)2
Rp = 5.6%
l = 0.41317 Å

15 Two-theta (degrees) 25

4 5 6 7 8 9 10 11 12 13 14 15
Two-Theta (degrees)
It is possible to derive the structure from the powder pattern. But it is not by any
means an easy task. Any ability to isolate the compound’s chemistry, density,
symmetry, properties, etc., will aid in directing the crystal solution.

formula La2Ta2O7(OH)2
Space group P21/n
a (Å) 14.1711(6)
b (Å) 3.9303(2)
c (Å) 6.7201(3)
b (o) 91.08

Vol 374.22
Z 2
Rp 0.056
La (x, y, z) 0.299 0.005 0.502
La-O, La-OH
Ta 0.538 0.494 0.729
layer
O1 0.579 0.488 0.419
Ta-O
O2 0.544 0.026 0.712
Octahedra
O3 0.5 0.5 0 layer
O4 0.174 0.015 0.252

OH5 0.198 0.522 0.625

Model of La2Ta2O7(OH)2
Questions?