X-ray powder diffraction – a practical guide
Dinnebier 0; InternationalTables 0; Will 0; Young 0; Pecharsky 0
Radiation hitting condensed matter
NEUTRONS X-RAYS ELECTRONS
Wavelength range 0.4 - 10 Å 0.1 - 5 Å 0 .04 - 0.2 Å
Energy range 0.001 - 0.5 eV 3000 - 100000 eV 6000 - 120000 eV
Cross-section 10-25 barns 10-25 Z2 barns ~10-22 barns
Penetration depth ~ cm ~ µm ~ nm
Typical flux 1011 s-1 m-2 1024 s-1 m-2 1026 s-1 m-2
Beam size mm-cm µm-mm nm-µm
Small crystals, powders, Surfaces, thin films, grains,
Typical sample Any bulk sample
surfaces gases
Diffraction Microscopy
Diffraction
Photon absorption Diffraction
Techniques Inelastic scattering
Photoemission Emission spectroscopy
Reflectivity
Inelastic scattering EELS
Magnetic/crystal
structures Crystal structures,
collective excitations electronic microstructure
Phenomena (phonons, spin waves) transitions crystal structures
electronic excitations (photoemission, electronic transitions
(crystal-field, spin- absorption),
orbit)
X-ray hitting condensed matter
Cullity 114
X-ray hitting condensed matter
Dinnebier Pre6
Debye-Scherrer cones from a polycrystalline sample
Cullity 98
Bragg-Brentano and Guinier diffractometer
Dinnebier 34, 35_1, 35_2, 37
Bragg-Brentano diffractometer with monochromator
Dinnebier 36
Generation of x-ray
Dinnebier 22
Generation of x-ray
Optimum voltage ~4 times characteristic energy (~30 kV for Cu anodes)
Dinnebier 23, 24
Generation of x-ray
Suppression of Kβ radiation by filter with lighter neighbor element in periodic table
Cullity 20, 21
Samples for x-ray powder diffraction
Well prepared samples at the right sample holder is the key for success!!!
Dinnebier 42_1, 42_2
Samples for x-ray powder diffraction
Hygiene in preparing the powder is the second key for success!!!
Dinnebier 42_1, 42_2
Samples for x-ray powder diffraction
Cullity 283
Bragg-Brentano diffractometer for the desk
Dinnebier 36
Example: growth of PrAuSi out of Sn flux
Which phases are present? E. D. Mun: PM721-Ex1a
Phase analysis with the PDF database
PDF_DataBase 1; 2; 3; 4
Example: growth of PrAuSi out of Sn flux
Which elements can/must be present? E. D. Mun: PM721-Ex1b
Example: growth of PrAuSi out of Sn flux
If your phase is not in the database – search for isostructural compounds...
E. D. Mun: PM721-Ex1g
Powdercell
The best tool to calculate diffraction pattern, to verify structure data and more...Powdercell 1
Powdercell
The best tool to calculate diffraction pattern, to verify structure data and more...Powdercell 2
Powdercell
The best tool to calculate diffraction pattern, to verify structure data and more...Powdercell 3
Powdercell
Verify the structure data visually and via plausible bonding length!!! Powdercell 1
Powdercell
Extract the reflection list: (hkl) – position - intensity Powdercell 5
Example: growth of YbPtBi with partial element substitution
YbPtBi
Nice crystals of parent compound E. D. Mun: PM935-Ex2a
Example: growth of YbPtBi with partial element substitution
YbPtBi0.9Sb0.1
Yb0.9Lu0.1PtBi
YbPt0.9Au0.1Bi
YbPtBi
Which phases were grown successfully? E. D. Mun: PM935-Ex2b
Example: growth of YbPtBi with partial element substitution
YbPtBi0.9Sb0.1
Yb0.9Lu0.1PtBi
YbPt0.9Au0.1Bi
YbPtBi
Only YbPt0.9Au0.1Bi was grown successfully. E. D. Mun: PM935-Ex2c
Example: growth of Ba(Fe1-xCox)2As2
x = 0.10
PM915
PM892
PM871
Preparation of samples with same stoichiometry is reproducible. N. Ni: PM871-Ex3a
Example: growth of Ba(Fe1-xCox)2As2
x = 0.15
x = 0.125
x = 0.10
x = 0.075
x = 0.05
x = 0.025
x=0
Preparation of samples with varying stoichiometry seems also successful.N. Ni: PM871-Ex3b
Example: growth of Ba(Fe1-xCox)2As2
x = 0.15
x = 0.125
x = 0.10
x = 0.075
x = 0.05
x = 0.025
x=0
Use of “inner” standard a MUST. N. Ni: PM871-Ex3e
Position of Bragg reflections in powder pattern
Pecharsky-MSE535-5 5; 13
Example: growth of Ba(Fe1-xCox)2As2
x = 0.15
x = 0.125
x = 0.10
x = 0.075
x = 0.05
x = 0.025
x=0
Combined analysis of series of Bragg reflections (main phase + standard) necessary.
N. Ni: PM871-Ex3c
Combined fitting of Bragg reflections
Pecharsky-MSE535-5 12;
Example: growth of Ba(Fe1-xCox)2As2
Realized stoichiometry by WDS study; Vegard’s law for lattice parameter
NNi_PhysRevB_78_214515 2; 3
Example: preparation of RFeAs(O/F)
High-temperature x-ray diffraction with 2-dimensional detector Rimg3307; 3318
Example: preparation of RFeAs(O/F)
undoped
F doped
High-temperature x-ray diffraction with 2-dimensional detector McCallum 1; 2
Example: preparation of RFeAs(O/F)
F doped undoped
Temperature
Temperature-dependent x-ray diffraction (20 sec. pattern) SDas 1
Example: preparation of RFeAs(O/F)
F doped undoped
Te
m
pe
ra
t ur
e
Temperature-dependent x-ray diffraction (20 sec. pattern) SDas 2
Example: preparation of RFeAs(O/F)
F doped undoped
Crystalline phase fraction determined by Rietveld analysis SDas 3
Example: preparation of RFeAs(O/F)
undoped
F doped
Unit-cell volume of RFeAs(O/F) phase determined by Rietveld analysis SDas 4
