X-rays•X-ray crystallography •X-ray spectrometry X-rays Cu K α E = 8.05 keV λ= 1.541 Å...
Transcript of X-rays•X-ray crystallography •X-ray spectrometry X-rays Cu K α E = 8.05 keV λ= 1.541 Å...
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X-rays
Wilhelm K. Roentgen (1845-1923) NP in Physics 1901
•X-ray Radiography -absorption is a function of Z and density
•X-ray crystallography
•X-ray spectrometry
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X-rays
Cu Kα E = 8.05 keV λ = 1.541 Å
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Interaction of Electrons withMatter
Emission of electromagnetic radiation:•Characteristic radiation, discrete energies•Bremsstrahlung, continuous energy distribution•Luminiscence (UV or visible region)
Electron emission:•Backscattered electrons (BSE)•Auger electrons•Secondary electron emission (SE)
Effects in the Target:•Electron Absorption (ABS)•Heat
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X-ray Tubes
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Tungsten wire at 1200-1800 °C(about 35 mA heating current)
High Voltage 20-60 kV High
max. power 2.2-3 kW
Typical operating values
Cu: 40 kV, 35 mA
Mo: 45 kV, 35 mA
X-ray Tubes
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Spectrum of the X-ray tube
Characteristic radiation
Bremstrahlung (white radiation)
Emax= E0 = e×V0
E = (h×c)/λ
λmin
)(398.12A)(
00min kVVeV
hc==λ
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Characteristic X-ray radiation
Primary (incident) electron
X-ray (fluorescence)photon Kα
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•n = 1, 2, 3…. (principal quantum number), corresponds to K, L, M... shells
•l = 0, 1, ..., n-1 (orbital quantum number)
•j =| l±s|; s = 1/2 (spin-orbit coupling)
•mj = j, j-1, j-2, ..., -j
•Transition only, whenΔn ≥ 1, Δl = 1, Δj = 0 or 1
Selection Rules
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Selection RulesM = 2J + 1
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Allowed Transitions
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Mosley’s Law (for multiple electron atoms)
1/λ = c⋅(Z-σ)2⋅(1/n12 - 1/n2
2)
•Z = atomic number•σ = shielding constant•n = quantum number
Decreasing wavelength λ with increasing Z
√ΰ(Kα) = √ ¾R (Z − 1)
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Characteristic Wavelengths
Element Kα2 Kα1 Kβ K abs. edge
Cu 1.54433 1.54051 1.39217 1.3801.38102
Mo 0.713543 0.70926 0.62099 0.61977
Ag 0.563775 0.559363 0.49701 0.48580.48701
W 0.213813 0.208992 0.17950 0.17837
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X-ray Absorption
At the absorption edge, the incidentX-ray quantum is energetic enough toknock an electron out of the orbital
Absorption edge
μ = absorption coefficient
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Monochromatisation of X-rays
•Filters (Ni filter for Cu Kα)
•Crystal Monochromators
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Sample Holders
Capillary
Transmission
Reflection
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Detection of X-rays
•Film (in the linear range, Guinier, Debye-Scherrer, precessioncameras)•Gas Proportional Counter•Si(Li) solid state detector (powder diffractometers)•Scintillation counter (photocathode, dynodes, 4-circle diffractometer,Stoe powder diffractometer)•Position Sensitive Detectors (1D or 2D, Stoe powder diffractometer)•Image Plate Detectors (2D detection, Stoe IPDS)•CCD Detectors (Bruker SMART system)
Detectors•convert energies of individual photons to electric current•convert current into voltage pulses that are counted
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Image plate detectors•Metal plate, 18 cm diameter, coated with Eu2+doped BaFBr•X-rays ionize Eu2+ to Eu3+ and the electrons are trapped incolor centers•Read out process with red laser leads to emission of bluelight, when electrons return to ground state•The blue light is amplified by a photomultiplier andrecorded as a pixel image
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Detector properties
•quantum-counting efficiency
•linearity
•energy proportionality
•resolution
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Resolution
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William Bragg (1912)
n.λ = 2 d sin Θ
X-ray Powder Diffraction
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Single crystals
polycrystalline
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Different Geometries of Powder Diffractometers
• Debye-Scherrer
• Bragg-Brentano
• Guinier
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Debye-Scherrer
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Debye-Scherrer
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Bragg-Brentano
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Information Extracted from Diffraction Experiments
• Determination of known phases
• Crystallinity
• Determination of lattice constants
• Structure solution
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Crystalline and Amorphous Phases
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(110) (200) (211)
X-ray powder diffraction pattern of Fe
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Quantity
QualityLine position is given by interplanar distance
d and wavelenght λ
d = λ / 2 sin Θ
More complicated, volume fraction
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Wavelength [nm]Anode Kα1 [100] Kα2 [50] Kβ1
Betafilter
Cr 0.228970 0.229361 0.208487 VFe 0.193604 0.193998 0.175661 MnCo 0.178897 0.179285 0.162079 FeCu 0.154056 0.154439 0.139222 NiMo 0.070930 0.071359 0.063229 Zr
d = λ / 2 sin Θ ... longer λ ... better multiplet separation... shorter λ ... more lines
Bcc crystal, Cu radiationa = 1.5 nm --> 2Θ = 11.8a = 1.2 nm --> 2Θ = 14.8a = 0.9 nm --> 2Θ = 19.7a = 0.6 nm --> 2Θ = 29.8a = 0.3 nm --> 2Θ = 61.8
Selecting radiation
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LINE HEIGHT- integral intensity
- quantitative analysis- texture
LINIE POSITION- qualitative (phase)
analysis- lattice macrodistortions
LINIE WIDTH- size of diffracting
domains- lattice microdistortions
GAUSS I(x) = A exp (-x2/a2)LORENTZ I(x) = A exp [1+(x2/a2)]-1
Mod. LORENTZ I(x) = A exp [1+(x2/a2)]-2
PEARSON VII I(x) = A exp [1+(x2/a2)]-n
Pseudo – VOIGT I(x) = A [cL(x) + (1-c)G(x)]
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???
(111)
(200) (220) (311) (222) (400)
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(111)
(222)
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Phase analysisPhasePhase analysisanalysis ZrO2 + Y2O3
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Results
of phase
analysis
ResultsResults
ofof phasephase
analysisanalysis
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Databases
• ICSD (Karlsruhe, inorganics, single crystal data)
• CSD (Cambridge, organics, organometallics, sc data)
• NRCC CRYSTMET (metals)
•PDB (proteins, Brookhaven)
•NIST (NBS)
•JCPDS = ICDD (PDF files, 60000 patterns)
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Which of these is not involved in thediffraction of X-rays through a crystal?
a Electron transitions
b Crystallographic planes
c Nuclear interactions
d Constructive interference
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What is the largest wavelength of radiation that willbe diffracted by a lattice plane of the interplanarspacing d?
a 0.5d
b d
c 2d
d No limit