X-ray Diffraction: Basics and Applications

Dr. T. K. Chaudhuri, Professor and Head Dr. K. C. Patel Research and Development Centre

INTRODUCTION: HISTORY

What are X-rays?

Soft X-rays: 0.12 to 12 keV (10 to 0.10 nm) Hard X-rays: 12 to 120 keV (0.10 to 0.01 nm) -------- penetrates solid objects; used for diagnostic radiography and crystallography.

History of X-ray : Timeline 1895 X-rays discovered by Roentgen 1914 First diffraction pattern of a crystal made by Knipping and von Laue 1915 Theory to determine crystal structure from diffraction pattern developed by Bragg 1916 First to study polycrystalline powder : Debye and Scherrer

1953 DNA structure solved by Watson and Crick

Now Diffraction improved by computer technology; methods used to determine atomic structures and in medical applications

 Wilhelm Conrad Rntgen discovered X-Rays in 1895 X-ray : unknown ray Won 1901 Nobel prize in Physics
Wilhelm Conrad Rntgen (1845-1923)

Bertha Rntgens Hand 8 Nov, 1895

A modern radiograph of a hand

Max von Laue (1897-1960)

The first kind of scatter process to be recognised was discovered by Max von Laue who was awarded the Nobel prize for physics in 1914 "for his discovery of the diffraction of Xrays by crystals". His collaborators Walter Friedrich and Paul Knipping took the picture on the bottom left in 1912. It shows how a beam of X-rays is scattered into a characteristic pattern by a crystal. In this case it is copper sulphate.

The X-ray diffraction pattern of a pure substance is like a fingerprint of the substance. The powder diffraction method is thus ideally suited for characterization and identification of polycrystalline phases.

Braggs Law

Sir William Henry Bragg (1862-1942)

William Lawrence Bragg (1890-1971)

The father and son team of Sir William Henry and William Lawrence Bragg were awarded the Nobel prize for physics "for their services in the analysis of crystal structure by means of Xrays in 1915. Bragg's law was an extremely important discovery and formed the basis for the whole of what is now known as crystallography. This technique is one of the most widely used structural analysis techniques and plays a major role in fields as diverse as structural biology and materials science.

BASICS

Crystalline materials are characterized by the orderly periodic arrangements of atoms.

The (200) planes of atoms in NaCl The (220) planes of atoms in NaCl

The unit cell is the basic repeating unit that defines a crystal. Parallel planes of atoms intersecting the unit cell are used to define directions and distances in the crystal. These crystallographic planes are identified by Miller indices.

The atoms in a crystal are a periodic array of coherent scatterers and thus can diffract X-rays
Diffraction occurs when each object in a periodic array scatters radiation coherently, producing concerted constructive interference at specific angles. The electrons in an atom coherently scatter light. The electrons interact with the oscillating electric field of the light wave. Atoms in a crystal form a periodic array of coherent scatterers. The wavelength of X rays are similar to the distance between atoms. Diffraction from different planes of atoms produces a diffraction pattern, which contains information about the atomic arrangement within the crystal X Rays are also reflected, scattered incoherently, absorbed, refracted, and transmitted when they interact with matter.

Braggs law

2d hkl sin

dhkl dhkl

Braggs law: condition for constructive interference dhkl determines peak positions. Type of atoms determines peak intensity

X-RAY DIFFRACTION METHODS

X-Ray Diffraction Method

Laue
Orientation Single Crystal Polychromatic Beam Fixed Angle

Rotating Crystal
Lattice constant Single Crystal Monochromatic Beam Variable Angle

Powder
Lattice Parameters Polycrystal (powdered) Monochromatic Beam Variable Angle

Single Crystals
Individual reciprocal lattice points (with specific hkl) projected onto the detector

Used to determine the electron density within a unit cell

Powder XRD
Random crystallites combine to form spheres of reflection spheres will always intersect the Ewald sphere, at the detector: diffraction rings at angle

Debye Scherrer Camera

A very small amount of powdered material is sealed into a fine capillary tube made from glass that does not diffract x-rays. The specimen is placed in the Debye Scherrer camera and is accurately aligned to be in the centre of the camera. X-rays enter the camera through a collimator.

 Powder Diffraction or polycrystalline diffraction Samples: powder, sintered pellets, coatings, engine blocks, True random sample results into continuous Debye cone. linear diffraction pattern: detector scans through an arc that intersects each Debye cone at a single point

MEASUREMENT OF XRD: DIFFRACTOMETERS

Bragg-Brentano geometry

Detector X-ray tube w 2

Incident angle w is always of the detector angle 2 . - :2 instrument, the tube is fixed, the sample rotates at /min and the detector rotates at 2 /min. - : instrument, the sample is fixed and the tube rotates at a rate /min and the detector rotates at a rate of /min.

Phillips XPert

1.Quantitative Phase Analysis and Transmission 2.Thin film analysis 3.Reflectivity 4.Small angle Xray scattering

Rigaku Ultima IV

1. 2. 3. 4.

Powder diffraction Thin film diffraction Small angle scattering In-plane scattering

Bruker D8 Advance

1. 2. 3. 4. 5.

powder samples crystallite size determination micro strain analysis residual stress analysis preferred orientation

Shimadzu LabX XRD-6000

1. Powder Diffraction 2. Independent dual axis -2 linkage drive 3. independent 2 axis and axis drives are selectable

Scintag xrd 2000 pole figure

1.Quantitative Phase Analysis and Transmission 2.Thin film analysis 3.Reflectivity 4.Small angle Xray scattering 5. Pole Figure (phi-omega scan)

Bruker D2 Phaser
1. 2. 3. 4. 5. Faster desktop unit Powder diffraction No external chiller unit Accurate and faster solid state detector Useful for cement, industrial mineral, chemistry, pharma applications

Rigaku Miniflex II
1. General XRD 2. Phase composition analysis

X-ray diffractographs: Analysis

Bragg-Brentano diffractometer For single crystals

Only those family of planes whose normal bisect the angle made by incident and reflected rays will give peaks Here only (100) and (200) but not (110)

For polycrystalline / powder sample

Randomly oriented crystallites throughout: peaks due to all families of planes Basic assumption of powder diffraction: equal no. of crystallites for all families of planes oriented to diffract

X-Ray Diffraction pattern

Particle size and defects

Peak shapes

Peak relative intensities Background Peak positions

10 20 2 30 40

Atomic distribution in the unit cell

c b

Unit cell Symmetry and size

Diffuse scattering, sample holder, matrix, amorphous phases, etc...

Powder diffraction data consists of a record of photon intensity versus detector angle 2.
Diffraction data can be reduced to a list of peak positions and intensities Each dhkl corresponds to a family of atomic planes {hkl} individual planes cannot be resolved- this is a limitation of powder diffraction versus single crystal diffraction
Raw Data
Position [2q] 25.2000 Intensity [cts] 372.0000

Reduced dI list hkl dhkl () Relative Intensity (%) 49.8 85.8 36.1 1.9 100.0 1.4

25.2400
25.2800 25.3200 25.3600 25.4000 25.4400

460.0000
576.0000 752.0000 1088.0000 1488.0000 1892.0000

{012} {104} {110} {006} {113} {202}

3.4935 2.5583 2.3852 2.1701 2.0903 1.9680

25.4800
25.5200 25.5600 25.6000 25.6400 25.6800

2104.0000
1720.0000 1216.0000 732.0000 456.0000 380.0000

25.7200

328.0000

Diffraction patterns are best reported using dhkl and relative intensity rather than 2 and absolute intensity.
Why? - 2 depends on instrumental characteristics such as - dhkl is an intrinsic, instrument-independent, material property

- absolute intensity can vary due to instrumental and experimental parameters - relative intensities should be instrument independent.
Peak areas are much more reliable than peak heights as a measure of intensity

APPLICATIONS OF X-ray Diffraction

Application of XRD
Differentiation between crystalline and amorphous materials

Gas

Intensity

Intensity

Diffraction angle 2

Liquid Amorphous

Crystal

Intensity

Diffraction angle 2

Diffraction angle 2

Applications of Powder XRD

Phase Composition of a Sample Quantitative Phase Analysis: relative amount of each phase Unit cell lattice parameters and Bravais lattice symmetry Index peak positions Lattice parameters also effect of stress and doping Residual Strain (macrostrain) Crystal Structure By full profile Rietveld refinement Epitaxy/Texture/Orientation Crystallite Size and Microstrain by peak broadening Other defects (stacking faults, etc.) from peak shapes and width

Diffraction peak parameters and their applications

Peak position -Unit cell parameter refinement -Pattern indexing -Space group determination -Anisotropic thermal exapansion -Microstress analysis (sin2y method) -Phase identification Intensity -Phase abundance -Reaction kinetics -crystal structure analysis (full profile) -phase identification -texture analysis

Width and shape -Instrumental resolution function -Microstructure -Crystallite size -Size distribution -Lattice distortion -Structure mistakes -Dislocations -Composition gradient Non ambient and dynamic diffraction -Reaction kinetics

Phase Identification
Diffraction pattern of each phase is its fingerprint

Phases with the same chemical composition can have drastically different diffraction patterns.
peak position and intensity used to detect particular phase

Powder Diffraction File (PDF) or JCPDS File

Maintained by Joint Committee on Powder Diffraction Standards Standard for thousands of crystalline phases. Over 200,000 diffraction patterns. Quicker phase search by computer assistance Other useful information like reference also

Quantitative Phase Analysis

To Know amount of each phase Relative peak intensity proportional to relative phase amount Thus quantitative phase analysis: to find const. of proportionality RIR method: fast and semiquantitative results Whole pattern fitting/Rietveld refinement: accurate but complicated
60 50 40 30 20 10 0 0 0.2 0.4 0.6 0.8 1 X(phase a)/X(phase b)

I(phase a)/I(phase b) ..

Unit Cell Lattice Parameter Refinement

By accurate measurement of peak positions over long range measure peak positions with a peak search algorithm or profile fitting profile fitting is more accurate but more time consuming Can be use to quantify the effect due to alloying, substitutional doping, temperature and pressure, etc identify and correct for systematic errors such as specimen displacement and zero shift

Crystallite Size and Microstrain

Both small crystallite (<120nm) & microstrain cause peak broadening Crystallite size from peak broadening using Scherrer relation must know contribution of peak width from the instrument Williamson-Hull plot can let you separate microstrain and crystallite size
00-043-1002> Cerianite- 2 CeO

K B2 L cos

Intensity (a.u.) 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 2 (deg.)

What is Crystallite size?

Crystallite size

Particle size

Preferred Orientation (texture)

Preferred orientation of crystallites can create a systematic variation in diffraction peak intensities can qualitatively analyze using a 1D diffraction pattern a pole figure maps the intensity of a single peak as a function of tilt and rotation of the sample this can be used to quantify the texture
10.0

(111)

00-004-0784> Gold - Au

8.0

Intensity(Counts)

(311)
6.0

(200) (220)

4.0

2.0

(222) (400)

x10

40

50

60

70

80

90

100

Two-Theta (deg)

COMPONENTS OF X-RAY DIFFRACTOMETER

Essential Parts of the Diffractometer

X-ray Tube: the source of X Rays Incident-beam optics: condition the X-ray beam before it hits the sample The goniometer: the platform that holds and moves the sample, optics, detector, and/or tube The sample & sample holder Receiving-side optics: condition the X-ray beam after it has encountered the sample Detector: count the number of X Rays scattered by the sample

Parafocusing geometry of Bragg-Brentano Diffractometer

Detector moves maintaining 2 angle wrt incident ray Sample maintains angle wrt incident ray Parafocussing: reflected rays from again collimated onto detector
F: X-ray source DS: incident-beam divergence-limiting slit SS: Soller slit assembly S: sample RS: diffracted-beam receiving slit C: monochromator crystal AS: the anti-scatter slit

X-radiation sources
Sealed X-ray tubes operate at 1.8 to 3 kW. Rotating anode X-ray tubes have efficient heat distribution: operate at 9-18 kW >produce much more flux . X-ray generation: rapid decceleration of es onto W target
(vacuum) H2O In H2O Out

Be window

Cu e-

ANODE Be window

XRAYS FILAMENT (cathode)

XRAYS

metal

glass (vacuum)

The target must be water cooled. The target and filament must be contained in a vacuum.

AC CURRENT

X rays production
Electrons from the filament strike the target anode, producing characteristic radiations of anode via the photoelectric effect. Monochromator for filtering particular wavelength

L M

Spectral Contamination in Diffraction Patterns

Ka1

Ka1

Ka2

Ka2 Ka1 Ka2

Kb

W La1

The Ka1 & Ka2 doublet will almost always be present Very expensive optics can remove the Ka2 line Ka1 & Ka2 overlap heavily at low angles and are more separated at high angles W lines form as the tube ages: the W filament contaminates the target anode and becomes a new X-ray source W and Kb lines can be removed with optics

Wavelengths for X-Radiation are Sometimes Updated

Copper Anodes Cu Ka1 Cu Ka2 Cu Kb Bearden (1967) 1.54056 1.54439 1.39220 Holzer et al. (1997) 1.540598 1.544426 1.392250 Cobalt Anodes Co Ka1 Co Ka2 Co Kb Bearden (1967) 1.788965 1.792850 1.62079 Holzer et al. (1997) 1.789010 1.792900 1.620830

Molybdenum Anodes Mo Ka1 Mo Ka2 0.709300 0.713590 0.709319 0.713609

Chromium Anodes Cr Ka1 Cr Ka2 2.28970 2.293606 2.289760 2.293663

Mo Kb

0.632288

0.632305

Cr Kb

2.08487

2.084920

X-ray Shutter
X-rays exit the tube through X-ray transparent Be windows. X-Ray safety shutters contain the beam so that you may work in the diffractometer without being exposed to the X-rays. Being aware of the status of the shutters is the most important factor in working safely with X rays.
H2O In H2O Out

XRAYS Be window

Cu
Primary Shutter Secondary Shutter Solenoid

ANODE Be window

eXRAYS FILAMENT (cathode) metal

glass (vacuum) (vacuum)

AC CURRENT

SAFETY SHUTTERS

Requirement of X-ray optics

2d hkl sin
X Rays from an X-ray tube are: divergent contain multiple characteristic wavelengths as well as Bremmsstrahlung radiation Optics are used to: limit divergence of the X-ray beam refocus X rays into parallel paths remove unwanted wavelengths

Divergence slits

The slits block X-rays that have too great a divergence. The size of the divergence slit influences peak intensity and peak shapes. Narrow divergence slits: reduce the intensity of the X-ray beam reduce the length of the X-ray beam hitting the sample produce sharper peaks the instrumental resolution is improved so that closely spaced peaks can be resolved.

Monochromators
crystal monochromator: to select one wavelength of radiation and provide energy discrimination. An incident-beam monochromator might be used to select only Ka1 radiation for the tube source.

A diffracted-beam monochromator, may be used to remove fluoresced photons, Kb, or W-contimination photons from reaching the detector.

Other optics:
limit divergence of the X-ray Parallel Plate Collimator & Soller beam Slits block divergent X-rays, but Divergence limiting slits do not restrict beam size like a divergent slit Parallel plate collimators Soller slits refocus X rays into parallel paths parallel-beam optics parabolic mirrors and capillary lenses focusing mirrors and lenses remove unwanted wavelengths monochromators Gbel Mirrors and capillary lenses Kb filters

collect a large portion of the divergent beam and refocus it into a nearly parallel beam

Detectors
point detectors observe one point of space at a time slow, but compatible with most/all optics scintillation and gas proportional detectors count all photons, within an energy window, that hit them Si(Li) detectors can electronically analyze or filter wavelengths position sensitive detectors linear PSDs observe all photons scattered along a line from 2 to 10 long 2D area detectors observe all photons scattered along a conic section gas proportional (gas on wire; microgap anodes) limited resolution, issues with deadtime and saturation CCD limited in size, expensive solid state real-time multiple semiconductor strips high speed with high resolution, robust

SAMPLE / SPECIMEN PREPARATION

Preparing a powder specimen

An ideal powder sample should have many crystallites in random orientations the distribution of orientations should be smooth and equally distributed amongst all orientations If the crystallites in a sample are very large, there will not be a smooth distribution of crystal orientations. You will not get a powder average diffraction pattern. crystallites should be <10mm in size to get good powder statistics Large crystallite sizes and non-random crystallite orientations both lead to peak intensity variation the measured diffraction pattern will not agree with that expected from an ideal powder the measured diffraction pattern will not agree with reference patterns in the Powder Diffraction File (PDF) database

Important characteristics of samples for XRPD

a flat plate sample for XRPD should have a smooth flat surface if the surface is not smooth and flat, X-ray absorption may reduce the intensity of low angle peaks parallel-beam optics can be used to analyze samples with odd shapes or rought surfaces Densely packed Randomly oriented grains/crystallites Grain size less than 10 microns Infinitely thick

XRD EXAMPLES

XRD of ZnO powder : polycrystalline

JCPDF:36 -1451 Miller indices 2 I/Io 2 I/Io % d, nm (hkl) d (nm) (degree) (degree) % 31.569 34.228 36.054 47.281 56.396 62.607 66.124 67.704 68.997 72.295 76.828 81.207 89.303 92.487 95.050 98.802 102.742 103.981 107.313 110.033 116.078 56.91 0.2831 61.39 0.2617 100.00 0.2489 22.60 0.1920 38.92 0.1630 34.37 5.52 28. 75 12.50 2.91 3.84 2.17 7.95 2.7 3 8.83 2.97 3.55 6.22 0.65 3.82 7.98 0.1482 0.1411 0.1382 0.1359 0.1305 0.1239 0.1183 0.1096 0.1066 0.1044 0.1014 0.0986 0.0977 0.0956 0.0940 0.0907 (100) (002) (101) (102) (110) (103) (200) (112) (201) (004) (202) (104) (203) (210) (211) (114) (212) (105) (204) (300) (213) (302) (006) (205) (106) (214) (220) 31.769 34.421 36.252 47.538 56.602 62.862 66.378 67.961 69.098 72.560 76.953 81.368 89.605 92.781 95.301 98.609 102.942 104.130 10 7.426 110.388 116.274 121.567 125.183 133.925 136.513 138.505 142.910 57 44 100 23 32 29 4 23 11 2 4 1 7 3 6 4 2 5 1 3 8 4 1 3 1 2 3 0.2814 0.2603 0.2475 0.1911 0.1624 0.1477 0.1407 0.1378 0.1358 0.1301 0.1238 0.1181 0.1093 0.1063 0.1042 0.1015 0.0984 0.0976 0.0955 0.0938 0.0906 0.0882 0.0867 0.0837 0.0829 0.0823 0.0812

ZnO powder

ZnO flowers 3-5 mm

ZnO nanorod-array films deposited on glass substrate: preferred orientation

Texture Coefficient, TC
TC(002) =
____________________________________________________________________________________________________________

I(002)/Io(002)

1/3 {I(100)/Io(100)+I(002)/Io(002) + I(101)/Io(101)}

where I = the measured intensity; Io = the standard intensity (JCPDS: 36-1451)

Aligned ZnO nanorod-array

ZnO rod-array film 2 (degree) 31.80 35.10 36.8 48.1 63.45 73.1 I/Io %
2.31 100 2.21 2.11 6.0 3.5

d, nm
0.2852 0.2595 0.2482 0.1944 0.1535 0.1374

Miller indices (hkl)

(100) (002) (101) (102) (103) (004)

JCPDF:36-1451 2 (degree)
31.769 34.421 36.252 47.538 62.862 72.560

I/Io %
57 44 100 23 29 2

d (nm)
0.2814 0.2603 0.2475 0.1911 0.1477 0.1301

200 nm

Biaxially textured YBa2Cu3O7 (YBCO) film on STO substrate

Spray pyrolysis, Thickness: 2 m, JC ~ 1 MA/sq. cm, Orthorhombic
80x103
(006) + STO

50x103
YBCO, (005) reflection

70

Intensity (cps)

(005)

60 50
(002) (003)+ STO

Intensity (cps)

40 30 20 10 0 17 18 19 20 Omega (degrees)

FWHM = 1

40 30 20 10 0 10
(001)

Out of plane texturing / orientation

21 22

(004)

(007)

20

30

40

50

60

2 Theta (degrees)

<--(008)

50x103
YBCO (103) reflection

Intensity (cps)

In plane texturing / orientation

40 30 20 10

FWHM = 1.2

YBCO, (103) reflection

0 0

50

100

150 200 250 Phi (degrees)

300 350

XRD of ZnO nanopowder : use of Scherrer equation

FWHM b = 36.5 -35.93 = 0.57o= ~0.01 rad. Peak Position 2 = 36.218o = 18.019o= ~ 0.316 rad.; Cos = 0.999

Scherrer relation (<100 nm)

K = 0.89, =1.5406 10-10 m Crystallite size = 15 nm

K d bcos

Varying Irradiated area of the sample

the area of your sample that is illuminated by the X-ray beam varies as a function of: incident angle of X rays divergence angle of the X rays at low angles, the beam might be wider than your sample beam spill-off

The constant volume assumption

In a polycrystalline sample of infinite thickness, the change in the irradiated area as the incident angle varies is compensated for by the change in the penetration depth These two factors result in a constant irradiated volume (as area decreases, depth increase; and vice versa) This assumption is important for many aspects of XRPD Matching intensities to those in the PDF reference database Crystal structure refinements Quantitative phase analysis This assumption is not necessarily valid for thin films or small quantities of sample on a ZBH

Sources of Error in XRD Data

Sample Displacement occurs when the sample is not on the focusing circle (or in the center of the goniometer circle) Can be minimized by using a zero background sample holder Can be corrected by using an internal calibration standard Can be analyzed and compensated for with many data analysis algorithms can be eliminated by using parallel-beam optics

Texture analysis Using Pole figures

Totally different setup: 4 circle goniometer

Scan Axes
w

Sample

Detector

Source

Pole Figures
z-axis (sample normal)

(hkl) plane

Equatorial plane y

Projected position of the (hkl) plane f-axis

Projected distance from origin is given by:

r tan (psi/2)

(where r is the radius )

South pole

Schematic diagram showing the construction of a pole figure.

Choosing which planes

Often necessary to use a number of different crystal planes to determine a complicated texture. The planes should be chosen from the theta 2 theta pattern. We need: strongly diffracting planes (high intensity in theta 2 theta) discrete peaks preferably at 2 theta values between 20 degrees and 50 degrees for optimum results.
(110)

x Ag

o LaNiO3

(111)

x
Holder (100) (111)

x
(200) (211)

(200)

Holder

(210)

Interpretation
No general methods sometimes by visual comparisons with known sample an unknown texture or combination of textures can be identified by carrying out a series of pole figures and calculating an Orientation Distribution Function (ODF). Example: c-axis aligned superconducting thin films.

(a)

(b)

Biaxial Texture (105 planes)

Random in-plane alignment