19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 1 X-ray Diffraction Techniques for Materials Characterization

$Page 1: 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 1 X-ray Diffraction Techniques for Materials Characterization$
19-Jun-07 BIMR workshop on characterization of m19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutronsaterials with Electrons, Photons and Neutrons

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X-ray Diffraction Techniques X-ray Diffraction Techniques for Materials Characterizationfor Materials Characterization

Jim BrittenJim BrittenMcMaster Analytical X-ray McMaster Analytical X-ray (MAX) Diffraction Facility(MAX) Diffraction Facility

Chemistry / BIMRChemistry / BIMR


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OUTLINEOUTLINE

DiffractionDiffraction Single Crystal DiffractionSingle Crystal Diffraction XRD – Powder DiffractionXRD – Powder Diffraction XRDXRD22 – 2D Powder Diffraction – 2D Powder Diffraction XRDXRD33 – 3D Polycrystal Diffraction – 3D Polycrystal Diffraction Diffuse and Incommensurate ScatteringDiffuse and Incommensurate Scattering CLS – Brockhouse X-ray Diffraction and CLS – Brockhouse X-ray Diffraction and

Scattering Sector and moreScattering Sector and more


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DiffractionDiffraction

Sub-nanoscale measurements (Sub-nanoscale measurements (Ǻ)Ǻ) Interatomic distances ~ 0.8 to 3.5 Interatomic distances ~ 0.8 to 3.5 ǺǺ

Use ‘Hard’ X-rays as ruler, ~ 0.2 to 3.0 ǺUse ‘Hard’ X-rays as ruler, ~ 0.2 to 3.0 Ǻ X-rays interact with electronsX-rays interact with electrons

Scattering power increases linearly with atomic Scattering power increases linearly with atomic numbernumber

Assume elastic absorption and emissionAssume elastic absorption and emission Each atom becomes X-ray source at Each atom becomes X-ray source at λλ


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Atomic electron Atomic electron cloud causes cloud causes exponential drop-exponential drop-off of scattering off of scattering power away from power away from incident X-ray incident X-ray beam direction beam direction (compare to (compare to neutrons!)neutrons!)

From Pecharsky and Zavalij


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The diffraction pattern is the resultant of The diffraction pattern is the resultant of scattering from a group of atomsscattering from a group of atoms FFhklhkl = = ΣΣ f faaexp(hx+ky+lz)exp(hx+ky+lz)

If the group of atoms (unit cell) is repeated If the group of atoms (unit cell) is repeated periodically in 3D, single crystal diffraction periodically in 3D, single crystal diffraction restricts h,k,l to integers, and results in restricts h,k,l to integers, and results in Bragg diffraction spots.Bragg diffraction spots.


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Single Crystal DiffractionSingle Crystal Diffraction

Bragg’s law for single crystal diffractionBragg’s law for single crystal diffraction nnλλ = 2d sin = 2d sinθθ

http://www.eserc.stonybrook.edu/ProjectJhttp://www.eserc.stonybrook.edu/ProjectJava/Bragg/index.htmlava/Bragg/index.html

Map diffraction pattern into Reciprocal Map diffraction pattern into Reciprocal SpaceSpace


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88




99


Symmetry of packing determines crystal classSymmetry of packing determines crystal class Anorthic, monoclinic, orthorhombic, trigonal, Anorthic, monoclinic, orthorhombic, trigonal,

tetragonal, hexagonal, cubictetragonal, hexagonal, cubic

Symmetry elements define one of 230 space Symmetry elements define one of 230 space groupsgroups

Point symmetry of unit cell determines Point symmetry of unit cell determines symmetry of diffraction patternsymmetry of diffraction pattern

Translational symmetry elements result in Translational symmetry elements result in systematically absent Bragg spots.systematically absent Bragg spots.


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Crystal size 1 to 500 Crystal size 1 to 500 μμm – need minimum m – need minimum volumevolume

200 - 500 200 - 500 μμm X-ray m X-ray point source (Mo)point source (Mo)

Transmission expt.Transmission expt. CCD area detectorCCD area detector 3 or 4 circle 3 or 4 circle

goniometergoniometer


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Data collectionData collection Rotate crystal in beam ~0.36Rotate crystal in beam ~0.36° during CCD ° during CCD

acquisitionacquisition Collect contiguous frames to scan reciprocal Collect contiguous frames to scan reciprocal

spacespace Rotate sample on alternate axes to complete Rotate sample on alternate axes to complete

coverage of asymmetric diffraction volumecoverage of asymmetric diffraction volume Redundancy helps (aniso. abs. corr., S/N)Redundancy helps (aniso. abs. corr., S/N)


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3D reciprocal space

2θ increases radially

Resolution increases radially

Reciprocal cell indexed on lattice

Spot intensities depend on atom types and positions

Fourier transform of F’s (√I) with phases gives ρ(r)

Refine model by least squares minimization of ω||Fo

2|-|Fc2||


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Single Crystal DiffractionSingle Crystal Diffraction HH22NaNa22NiNi33OO1010PP22 , or , or NaNa22NiNi33(OH)(OH)22(PO(PO44))22

Space group C2/m, Z = 2Space group C2/m, Z = 2 a = 14.2292(7), b = 5.6786(3), c = 4.9249(2)a = 14.2292(7), b = 5.6786(3), c = 4.9249(2)ǺǺ, , αα = 90, = 90, ββ = 104.328(3), = 104.328(3), γγ = 90 = 90°°

Atom positionsAtom positions xx yy zz U(eq)U(eq) ____________________________________________________________________________ Ni(1)Ni(1) 00 .5000.5000 .5000.5000 .006(1).006(1) Ni(2)Ni(2) 00 .2330(1).2330(1) 00 .006(1).006(1) P(1)P(1) .1251(1).1251(1) 00 .5968(2).5968(2) .005(1).005(1) O(1)O(1) .0722(1).0722(1) .5000.5000 .2116(2).2116(2) .007(1).007(1) O(2)O(2) .0880(1).0880(1) .2232.2232 .7173(2).7173(2) .008(1).008(1) O(3)O(3) .0934(1).0934(1) 00 .2721(2).2721(2) .006(1).006(1) O(4)O(4) .2357(1).2357(1) 00 .6928(2).6928(2) .012(1).012(1) Na(1)Na(1) .2658(1).2658(1) 00 .2119(2).2119(2) .022(1).022(1) H(1)H(1) .1288.1288 .5000.5000 .2453.2453 .008(14).008(14)

Peter Tremaine, Liliana Trevani – Guelph UniversityPeter Tremaine, Liliana Trevani – Guelph University


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Single crystalsSingle crystals


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XRD – Powder DiffractionXRD – Powder Diffraction

Major method of materials characterizationMajor method of materials characterization Identification, ‘fingerprinting’Identification, ‘fingerprinting’ Quantitative phase analysisQuantitative phase analysis Rietveld structure refinementRietveld structure refinement Ab initioAb initio structure solution structure solution

Use a bucket of microcrystals: 1 – 20 Use a bucket of microcrystals: 1 – 20 μμmm Need uniform orientation distribution Need uniform orientation distribution

Transmission and reflection geometries, line sourceTransmission and reflection geometries, line source ““Fundamentals of Powder Diffraction and Structural Fundamentals of Powder Diffraction and Structural

Characterization of Materials”Characterization of Materials” Vitalij K. Pecharski and Peter Y. ZavalijVitalij K. Pecharski and Peter Y. Zavalij


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XRD – Powder DiffractionXRD – Powder DiffractionCalculated ideal powder pattern from single crystal structure.


2020



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XRDXRD22 – 2D Powder Diffraction – 2D Powder Diffraction


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XRDXRD22 – 2D Powder Diffraction – 2D Powder Diffraction Micro layers of Au & Pt sheetMicro layers of Au & Pt sheet

Purdy, GarretPurdy, Garret Au on top layer Au on top layer Notice the texture from rolling of sheetsNotice the texture from rolling of sheets

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

3000

3500

4000

4500

5000

5500

6000

6500

7000

7500

Inte

nsi

ty

2 Theta


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Nano-layers - solid solution of Au & PtNano-layers - solid solution of Au & Pt

75 76 77 78 79 80 81 824000

4500

5000

5500

6000

6500

7000

7500

8000

8500

9000

9500

10000

Inte

nsi

ty

2 Theta

Pt: (80.188, 9659)

(SS: 79.5, 7325)(Au: 77.643, 6850)


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XRDXRD22 – 2D Powder Diffraction – 2D Powder Diffraction Compare the Ferrite (110), (200) and (211) peaks and Compare the Ferrite (110), (200) and (211) peaks and

Austenite (111), (200) and (220) peaks (2Austenite (111), (200) and (220) peaks (2θθ = 18 to 38) = 18 to 38) X-ray diffraction performed using Mo KX-ray diffraction performed using Mo Kαα radiationradiation Detector moved back to 17 cm to improve the Detector moved back to 17 cm to improve the

resolutionresolution Detector position: 2Detector position: 2θθ = -28 = -28 Sample position: Sample position: ωω = 166, = 166, χχ = 55, = 55, φφ = 0 to 50 = 0 to 50 Time = 300sTime = 300s wt. % C is calculated from the measured lattice wt. % C is calculated from the measured lattice

parameter of the retained austeniteparameter of the retained austenite

37.53736.53635.53534.53433.53332.53231.53130.53029.52928.52827.52726.52625.52524.52423.52322.52221.52120.52019.519

17,000

16,000

15,000

14,000

13,000

12,000

11,000

10,000

9,000

8,000

7,000

6,000

5,000

4,000

3,000

2,000

1,000

0

-1,000

-2,000

-3,000

-4,000

-5,000

ferrite 78.21 %

austenite 6.36 %

martensite 15.43 %

37.53736.53635.53534.53433.53332.53231.53130.53029.52928.52827.52726.52625.52524.52423.52322.52221.52120.52019.519

17,000

16,000

15,000

14,000

13,000

12,000

11,000

10,000

9,000

8,000

7,000

6,000

5,000

4,000

3,000

2,000

1,000

0

-1,000

-2,000

-3,000

-4,000

-5,000

ferrite 78.21 %

austenite 6.36 %

martensite 15.43 %


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XRDXRD22 – 2D Powder Diffraction – 2D Powder Diffraction Texture analysis – Texture analysis –

crystallite orientationscrystallite orientations 55° frames for coarse ° frames for coarse

texturestextures 1° frames for sharp 1° frames for sharp

featuresfeatures

Generate stereographic Generate stereographic projection for chosen 2projection for chosen 2θθ


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(1 1 1) orientations for (1 1 1) orientations for CdTe on SrTiOCdTe on SrTiO33 (100) (100)


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The Role of Substrate Surface Termination in the Deposition of (111) CdTe on The Role of Substrate Surface Termination in the Deposition of (111) CdTe on (0001) Sapphire(0001) Sapphire S. Neretina, P. MascherS. Neretina, P. Mascher, , R. A. Hughes, J. F. Britten, J. S. PrestonR. A. Hughes, J. F. Britten, J. S. Preston , , N. V. SochinskiiN. V. Sochinskii

2D-XRD data and the corresponding AFM images showing the evolution of the 2D-XRD data and the corresponding AFM images showing the evolution of the domain structure and surface morphology as the substrate termination evolves from domain structure and surface morphology as the substrate termination evolves from oxygen to aluminum (left to right). oxygen to aluminum (left to right).

A C

0 5 um

B

0 5 um 0 5 um

D

0 5 um

A B C D


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Polymer diffraction – WAXSPolymer diffraction – WAXS Fraction of polymer crystallineFraction of polymer crystalline Fraction of polymer fibrousFraction of polymer fibrous Fraction of polymer amorphousFraction of polymer amorphous Texture as a result of preparationTexture as a result of preparation

Polymer diffraction – SAXSPolymer diffraction – SAXS Nanoscale interactionsNanoscale interactions Polymer profilesPolymer profiles


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Fiber axis∥[001]

Polyethylene(PE)


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Microfiber axial direction


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XRDXRD22 – 2D Powder Diffraction – 2D Powder Diffraction SAXS on a single crystal instrumentSAXS on a single crystal instrument Parallel focused Cu RA, SMART6000 CCDParallel focused Cu RA, SMART6000 CCD


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Residual stress analysesResidual stress analyses Choose high angle lineChoose high angle line 7 to 10 frames at various orientations, ~1hr7 to 10 frames at various orientations, ~1hr Co or Cr radiation best, Cu okay, Mo uselessCo or Cr radiation best, Cu okay, Mo useless

Find peak position (2Find peak position (2θθ) for several ) for several hundred pointshundred points

Bi- or Tri-axial stress elements calculated Bi- or Tri-axial stress elements calculated from deviations from circle (or sphere)from deviations from circle (or sphere)


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σ1 = - 394 MPa

σ2 = - 486 MPa

Principle stresses

Compressive biaxial stress for 5% elongated TRIP steel

310


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XRDXRD33 – 3D Polycrystal Diffraction – 3D Polycrystal Diffraction

When we scan around When we scan around φφ or or ωω for for orientation information for a polycrystalline orientation information for a polycrystalline solid using a 2D detector, we are storing solid using a 2D detector, we are storing 3D reciprocal space information 3D reciprocal space information

Why not have a look at it???Why not have a look at it??? MAX3D can display the full diffraction volumeMAX3D can display the full diffraction volume http://www.chemistry.mcmaster.ca/facilities/xray/MAX3D.htmhttp://www.chemistry.mcmaster.ca/facilities/xray/MAX3D.htm


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Texture scan of Au/Pt Texture scan of Au/Pt systemsystem

Concentric shells at Concentric shells at Bragg allowed 1/d Bragg allowed 1/d

Hot spots show Hot spots show crystallite orientation crystallite orientation distribution for each distribution for each reflectionreflection


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Texture of CdTe film Texture of CdTe film on SrTiOon SrTiO33

All nanocrystals have All nanocrystals have 111 direction normal 111 direction normal to substrateto substrate

Several preferred Several preferred rotational orientations, rotational orientations, with ‘Gaussian’ with ‘Gaussian’ distributiondistribution


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Observe all ‘pole Observe all ‘pole figures’ at oncefigures’ at once

Scan reciprocal space Scan reciprocal space volume with 2volume with 2θθ probe probe


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Compare 111 pole Compare 111 pole figure at ~23figure at ~23° 2° 2θθ


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Diffuse and Incommensurate Diffuse and Incommensurate ScatteringScattering

Incommensurate Incommensurate LatticesLattices

Gaulin, Dabkowska, Gaulin, Dabkowska, Dr. J.P.Dr. J.P.


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LuFeLuFe22OO4 4 - Young-June Kim - Young-June Kim


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99° Slice of Reciprocal Space for ° Slice of Reciprocal Space for LuFeLuFe22OO4 4

at various temperaturesat various temperatures

-160C 24C 80C


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Canadian Light SourceCanadian Light SourceHard X-ray Diffraction CapabilitiesHard X-ray Diffraction Capabilities

Hard X-ray MicroAnalysis (HXMA)Hard X-ray MicroAnalysis (HXMA) Canadian Macromolecular Crystallography Canadian Macromolecular Crystallography

Facility (CMCF 1 and CMCF 2) Facility (CMCF 1 and CMCF 2) Very Sensitive Elemental and Structural Probe Very Sensitive Elemental and Structural Probe

Employing Radiation from a Synchrotron Employing Radiation from a Synchrotron (VESPERS) (VESPERS)

Synchrotron Laboratory for Micro And Nano Synchrotron Laboratory for Micro And Nano Devices (SyLMAND)Devices (SyLMAND)

Brockhouse X-ray Diffraction and Scattering Brockhouse X-ray Diffraction and Scattering Sector Sector


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Hard X-ray MicroAnalysis (HXMA)Hard X-ray MicroAnalysis (HXMA) Description:Description: The Hard X-ray Micro-Analysis The Hard X-ray Micro-Analysis

(HXMA) beamline at CLS 06ID-1 is a (HXMA) beamline at CLS 06ID-1 is a multipurpose hard X-ray beamline, based on a multipurpose hard X-ray beamline, based on a 63 pole superconducting wiggler. The HXMA 63 pole superconducting wiggler. The HXMA has been designed to provide the community has been designed to provide the community with XAFS, K-B mirror microprobe, and x-ray with XAFS, K-B mirror microprobe, and x-ray diffraction capabilities. diffraction capabilities.

Techniques: Techniques: X-ray Absorption Fine Structure (XAFS) X-ray Absorption Fine Structure (XAFS) Microprobe Microprobe Diffraction Diffraction


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Canadian Macromolecular Crystallography Canadian Macromolecular Crystallography Facility (CMCF 1 and CMCF 2)Facility (CMCF 1 and CMCF 2)

Description: Description: The scientific goal of the The scientific goal of the 08ID-1 beamline is to operate a protein 08ID-1 beamline is to operate a protein crystallography beamline suitable for crystallography beamline suitable for studying small crystals and crystals with studying small crystals and crystals with large unit cells. large unit cells.


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Very Sensitive Elemental and Structural Probe Employing Radiation Very Sensitive Elemental and Structural Probe Employing Radiation from a Synchrotron (VESPERS)from a Synchrotron (VESPERS)

Description:Description: VESPER is a hard x-ray microprobe capable of VESPER is a hard x-ray microprobe capable of providing a high level of complementary structural and analytical providing a high level of complementary structural and analytical information. The techniques of x-ray diffraction and x-ray information. The techniques of x-ray diffraction and x-ray fluorescence spectroscopy are employed to analyze a microscopic fluorescence spectroscopy are employed to analyze a microscopic volume in the sample. Multi-bandpass and pink beam capability are volume in the sample. Multi-bandpass and pink beam capability are built in to meet variable requirements. built in to meet variable requirements.

Techniques: Techniques: X-ray Laue Diffraction X-ray Laue Diffraction X-ray Fluorescence Spectroscopy X-ray Fluorescence Spectroscopy X-ray Absorption Near Edge Structure X-ray Absorption Near Edge Structure Differential Aperture X-ray Microscopy Differential Aperture X-ray Microscopy Multi-bandpass and pink beam capability Multi-bandpass and pink beam capability


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Synchrotron Laboratory for Micro And Nano Devices (SyLMAND)Synchrotron Laboratory for Micro And Nano Devices (SyLMAND) Description: SyLMAND will be dedicated to research in and Description: SyLMAND will be dedicated to research in and

fabrication of polymer microstructures. The combination with fabrication of polymer microstructures. The combination with subsequent process steps, such as metallization of the polymer subsequent process steps, such as metallization of the polymer templates, allows a huge variety of micro-electro-mechanical templates, allows a huge variety of micro-electro-mechanical systems (MEMS) applications in fields such as radio frequency systems (MEMS) applications in fields such as radio frequency MEMS, micromechanics, optics/photonics and biomedical. The MEMS, micromechanics, optics/photonics and biomedical. The SyLMAND facility will consist of a dedicated beamline as well as a SyLMAND facility will consist of a dedicated beamline as well as a process support cleanroom laboratories required to run the process support cleanroom laboratories required to run the individual process steps.individual process steps.

Techniques: Techniques: Deep X-ray lithography Deep X-ray lithography LIGA process lithography steps LIGA process lithography steps


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Brockhouse X-ray Diffraction and Scattering Brockhouse X-ray Diffraction and Scattering SectorSector

For materials characterization!For materials characterization! CFI funding in placeCFI funding in place Operational in 2011Operational in 2011 2 ID beamlines2 ID beamlines Scattering physics hutchScattering physics hutch Powder diffraction hutchPowder diffraction hutch

High energy, high flux, extreme environmentsHigh energy, high flux, extreme environments Single crystal hutchSingle crystal hutch

Micro crystals, resonance scattering, charge densityMicro crystals, resonance scattering, charge density


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THANKS FOR YOUR ATTENTION!THANKS FOR YOUR ATTENTION!

Thanks to CLS for support for this sessionThanks to CLS for support for this session Thanks to researchers whose data I usedThanks to researchers whose data I used Thanks to CHEM 739 (XRDThanks to CHEM 739 (XRD22) students for ) students for

stolen slidesstolen slides

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19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 1 X-ray Diffraction Techniques for Materials Characterization