1. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 1 X-ray Diffraction Techniques for Materials Characterization Jim Britten McMaster Analytical X-ray (MAX) Diffraction Facility Chemistry / BIMR

2. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 2 OUTLINE  Diffraction  Single Crystal Diffraction  XRD – Powder Diffraction  XRD 2 – 2D Powder Diffraction  XRD 3 – 3D Polycrystal Diffraction  Diffuse and Incommensurate Scattering  CLS – Brockhouse X-ray Diffraction and Scattering Sector and more

3. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 3 Diffraction  Sub-nanoscale measurements (Ǻ)  Interatomic distances ~ 0.8 to 3.5 Ǻ  Use ‘Hard’ X-rays as ruler, ~ 0.2 to 3.0 Ǻ  X-rays interact with electrons  Scattering power increases linearly with atomic number  Assume elastic absorption and emission  Each atom becomes X-ray source at λ

4. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 4 Diffraction  Atomic electron cloud causes exponential drop- off of scattering power away from incident X-ray beam direction (compare to neutrons!) From Pecharsky and Zavalij

5. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 5 Diffraction  The diffraction pattern is the resultant of scattering from a group of atoms  F hkl = Σ f a exp(hx+ky+lz)  If the group of atoms (unit cell) is repeated periodically in 3D, single crystal diffraction restricts h,k,l to integers, and results in Bragg diffraction spots.

6. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 6 Single Crystal Diffraction  Bragg’s law for single crystal diffraction  nλ = 2d sinθ  http://www.eserc.stonybrook.edu/ProjectJa va/Bragg/index.html http://www.eserc.stonybrook.edu/ProjectJa va/Bragg/index.html http://www.eserc.stonybrook.edu/ProjectJa va/Bragg/index.html  Map diffraction pattern into Reciprocal Space

7. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 7 Single Crystal Diffraction From Pecharsky and Zavalij

8. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 8 Single Crystal Diffraction From Pecharsky and Zavalij

9. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 9 Single Crystal Diffraction  Symmetry of packing determines crystal class  Anorthic, monoclinic, orthorhombic, trigonal, tetragonal, hexagonal, cubic  Symmetry elements define one of 230 space groups  Point symmetry of unit cell determines symmetry of diffraction pattern  Translational symmetry elements result in systematically absent Bragg spots.

10. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 10 Single Crystal Diffraction  Crystal size 1 to 500 μm – need minimum volume  200 - 500 μm X-ray point source (Mo)  Transmission expt.  CCD area detector  3 or 4 circle goniometer

11. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 11 Single Crystal Diffraction  Data collection  Rotate crystal in beam ~0.36° during CCD acquisition  Collect contiguous frames to scan reciprocal space  Rotate sample on alternate axes to complete coverage of asymmetric diffraction volume  Redundancy helps (aniso. abs. corr., S/N)

12. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 12 Single Crystal Diffraction

13. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 13 Single Crystal Diffraction 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||F o 2 |-|F c 2 ||

14. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 14 Single Crystal Diffraction  H 2 Na 2 Ni 3 O 10 P 2, or Na 2 Ni 3 (OH) 2 (PO 4 ) 2  Space group C2/m, Z = 2  a = 14.2292(7), b = 5.6786(3), c = 4.9249(2)Ǻ, α = 90, β = 104.328(3), γ = 90°  Atom positions  xyzU(eq)  ______________________________________  Ni(1)0.5000.5000.006(1)  Ni(2)0.2330(1)0.006(1)  P(1).1251(1)0.5968(2).005(1)  O(1).0722(1).5000.2116(2).007(1)  O(2).0880(1).2232.7173(2).008(1)  O(3).0934(1)0.2721(2).006(1)  O(4).2357(1)0.6928(2).012(1)  Na(1).2658(1)0.2119(2).022(1)  H(1).1288.5000.2453.008(14)  Peter Tremaine, Liliana Trevani – Guelph University

15. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 15 Single crystals

16. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 16 XRD – Powder Diffraction  Major method of materials characterization  Identification, ‘fingerprinting’  Quantitative phase analysis  Rietveld structure refinement  Ab initio structure solution  Use a bucket of microcrystals: 1 – 20 μm  Need uniform orientation distribution  Transmission and reflection geometries, line source  “Fundamentals of Powder Diffraction and Structural Characterization of Materials”  Vitalij K. Pecharski and Peter Y. Zavalij

17. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 17 XRD – Powder Diffraction

18. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 18 XRD – Powder Diffraction

19. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 19 XRD – Powder Diffraction Calculated ideal powder pattern from single crystal structure.

20. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 20 XRD – Powder Diffraction

21. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 21 XRD 2 – 2D Powder Diffraction

22. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 22 XRD 2 – 2D Powder Diffraction

23. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 23 XRD 2 – 2D Powder Diffraction  Micro layers of Au & Pt sheet  Purdy, Garret  Au on top layer  Notice the texture from rolling of sheets

24. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 24 XRD 2 – 2D Powder Diffraction  Nano-layers - solid solution of Au & Pt Pt: (80.188, 9659) (SS: 79.5, 7325) (Au: 77.643, 6850)

25. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 25 XRD 2 – 2D Powder Diffraction  Compare the Ferrite (110), (200) and (211) peaks and Austenite (111), (200) and (220) peaks (2θ = 18 to 38)  X-ray diffraction performed using Mo K α radiation  Detector moved back to 17 cm to improve the resolution  Detector position: 2θ = -28  Sample position: ω = 166, χ = 55, φ = 0 to 50  Time = 300s  wt. % C is calculated from the measured lattice parameter of the retained austenite

26. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 26 XRD 2 – 2D Powder Diffraction  Texture analysis – crystallite orientations  5° frames for coarse textures  1° frames for sharp features  Generate stereographic projection for chosen 2θ

27. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 27 XRD 2 – 2D Powder Diffraction  (1 1 1) orientations for CdTe on SrTiO 3 (100)

28. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 28 XRD 2 – 2D Powder Diffraction  The Role of Substrate Surface Termination in the Deposition of (111) CdTe on (0001) Sapphire  S. Neretina, P. Mascher, R. A. Hughes, J. F. Britten, J. S. Preston, N. V. Sochinskii  2D-XRD data and the corresponding AFM images showing the evolution of the domain structure and surface morphology as the substrate termination evolves from oxygen to aluminum (left to right). A C 0 5 um B 0 0 D 0 ABCD

29. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 29 XRD 2 – 2D Powder Diffraction  Polymer diffraction – WAXS  Fraction of polymer crystalline  Fraction of polymer fibrous  Fraction of polymer amorphous  Texture as a result of preparation  Polymer diffraction – SAXS  Nanoscale interactions  Polymer profiles

30. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 30 XRD 2 – 2D Powder Diffraction Fiber axis ∥ [001] Polyethylene(PE)

31. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 31 XRD 2 – 2D Powder Diffraction

32. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 32 XRD 2 – 2D Powder Diffraction  SAXS on a single crystal instrument  Parallel focused Cu RA, SMART6000 CCD

33. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 33 XRD 2 – 2D Powder Diffraction  Residual stress analyses  Choose high angle line  7 to 10 frames at various orientations, ~1hr  Co or Cr radiation best, Cu okay, Mo useless  Find peak position (2θ) for several hundred points  Bi- or Tri-axial stress elements calculated from deviations from circle (or sphere)

34. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 34 XRD 2 – 2D Powder Diffraction σ 1 = - 394 MPa σ 2 = - 486 MPa Principle stresses Compressive biaxial stress for 5% elongated TRIP steel 310

35. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 35 XRD 3 – 3D Polycrystal Diffraction  When we scan around φ or ω for orientation information for a polycrystalline solid using a 2D detector, we are storing 3D reciprocal space information  Why not have a look at it???  MAX3D can display the full diffraction volume  http://www.chemistry.mcmaster.ca/facilities/xray/MAX3D.htm http://www.chemistry.mcmaster.ca/facilities/xray/MAX3D.htm

36. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 36 XRD 3 – 3D Polycrystal Diffraction  Texture scan of Au/Pt system  Concentric shells at Bragg allowed 1/d  Hot spots show crystallite orientation distribution for each reflection

37. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 37 XRD 3 – 3D Polycrystal Diffraction  Texture of CdTe film on SrTiO 3  All nanocrystals have 111 direction normal to substrate  Several preferred rotational orientations, with ‘Gaussian’ distribution

38. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 38 XRD 3 – 3D Polycrystal Diffraction  Observe all ‘pole figures’ at once  Scan reciprocal space volume with 2θ probe

39. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 39 XRD 3 – 3D Polycrystal Diffraction  Compare 111 pole figure at ~23° 2θ

40. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 40 Diffuse and Incommensurate Scattering  Incommensurate Lattices  Gaulin, Dabkowska, Dr. J.P.

41. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 41 Diffuse and Incommensurate Scattering  LuFe 2 O 4 - Young-June Kim

42. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 42 Diffuse and Incommensurate Scattering

43. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 43 Diffuse and Incommensurate Scattering 9° Slice of Reciprocal Space for LuFe 2 O 4 at various temperatures -160C 24C 80C

44. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 44 Diffuse and Incommensurate Scattering

45. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 45 Diffuse and Incommensurate Scattering

46. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 46 Canadian Light Source Hard X-ray Diffraction Capabilities  Hard X-ray MicroAnalysis (HXMA)  Canadian Macromolecular Crystallography Facility (CMCF 1 and CMCF 2)  Very Sensitive Elemental and Structural Probe Employing Radiation from a Synchrotron (VESPERS)  Synchrotron Laboratory for Micro And Nano Devices (SyLMAND)  Brockhouse X-ray Diffraction and Scattering Sector

47. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 47 Canadian Light Source Hard X-ray Diffraction Capabilities  Hard X-ray MicroAnalysis (HXMA)  Description: The Hard X-ray Micro-Analysis (HXMA) beamline at CLS 06ID-1 is a multipurpose hard X-ray beamline, based on a 63 pole superconducting wiggler. The HXMA has been designed to provide the community with XAFS, K-B mirror microprobe, and x-ray diffraction capabilities.  Techniques:  X-ray Absorption Fine Structure (XAFS)  Microprobe  Diffraction

48. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 48 Canadian Light Source Hard X-ray Diffraction Capabilities  Canadian Macromolecular Crystallography Facility (CMCF 1 and CMCF 2)  Description: The scientific goal of the 08ID-1 beamline is to operate a protein crystallography beamline suitable for studying small crystals and crystals with large unit cells.

49. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 49 Canadian Light Source Hard X-ray Diffraction Capabilities  Very Sensitive Elemental and Structural Probe Employing Radiation from a Synchrotron (VESPERS)  Description: VESPER is a hard x-ray microprobe capable of providing a high level of complementary structural and analytical information. The techniques of x-ray diffraction and x-ray fluorescence spectroscopy are employed to analyze a microscopic volume in the sample. Multi-bandpass and pink beam capability are built in to meet variable requirements.  Techniques:  X-ray Laue Diffraction  X-ray Fluorescence Spectroscopy  X-ray Absorption Near Edge Structure  Differential Aperture X-ray Microscopy  Multi-bandpass and pink beam capability

50. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 50 Canadian Light Source Hard X-ray Diffraction Capabilities  Synchrotron Laboratory for Micro And Nano Devices (SyLMAND)  Description: SyLMAND will be dedicated to research in and fabrication of polymer microstructures. The combination with subsequent process steps, such as metallization of the polymer templates, allows a huge variety of micro-electro-mechanical systems (MEMS) applications in fields such as radio frequency MEMS, micromechanics, optics/photonics and biomedical. The SyLMAND facility will consist of a dedicated beamline as well as a process support cleanroom laboratories required to run the individual process steps.  Techniques:  Deep X-ray lithography  LIGA process lithography steps

51. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 51 Canadian Light Source Hard X-ray Diffraction Capabilities  Brockhouse X-ray Diffraction and Scattering Sector  For materials characterization!  CFI funding in place  Operational in 2011  2 ID beamlines  Scattering physics hutch  Powder diffraction hutch  High energy, high flux, extreme environments  Single crystal hutch  Micro crystals, resonance scattering, charge density

52. 19-Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 52 THANKS FOR YOUR ATTENTION!  Thanks to CLS for support for this session  Thanks to researchers whose data I used  Thanks to CHEM 739 (XRD 2 ) students for stolen slides