Xray Diffraction Techniques for Materials Characterization Jim Britten

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

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

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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 3

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

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

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

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

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

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

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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 10

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) 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 11

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

Single Crystal Diffraction 3 D 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|-|Fc 2|| 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 13

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 C 2/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 § § § x y z U(eq) ___________________ Ni(1) 0. 5000 Ni(2) 0. 2330(1) 0 P(1). 1251(1) 0. 5968(2) O(1). 0722(1). 5000. 2116(2) O(2). 0880(1). 2232. 7173(2) O(3). 0934(1) 0. 2721(2) O(4). 2357(1) 0. 6928(2) Na(1). 2658(1) 0. 2119(2) H(1). 1288. 5000. 2453 . 006(1). 005(1). 007(1). 008(1). 006(1). 012(1). 022(1). 008(14) § Peter Tremaine, Liliana Trevani – Guelph University 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 14

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

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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 16

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

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

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

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

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

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

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

XRD 2 – 2 D Powder Diffraction § Nano-layers - solid solution of Au & Pt Pt: (80. 188, 9659) (SS: 79. 5, 7325) (Au: 77. 643, 6850) 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 24

XRD 2 – 2 D 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 Kα 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 = 300 s wt. % C is calculated from the measured lattice parameter of the retained austenite 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 25

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

XRD 2 – 2 D Powder Diffraction § (1 1 1) orientations for Cd. Te on Sr. Ti. O 3 (100) 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 27

XRD 2 – 2 D Powder Diffraction A B C D 5 um 0 0 5 um § The Role of Substrate Surface Termination in the Deposition of (111) Cd. Te on (0001) Sapphire § S. Neretina, P. Mascher, R. A. Hughes, J. F. Britten, J. S. Preston, N. V. Sochinskii § 2 D-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). 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 28

XRD 2 – 2 D 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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 29

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

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

XRD 2 – 2 D Powder Diffraction § SAXS on a single crystal instrument § Parallel focused Cu RA, SMART 6000 CCD 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 32

XRD 2 – 2 D Powder Diffraction § Residual stress analyses § Choose high angle line § 7 to 10 frames at various orientations, ~1 hr § 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) 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 33

XRD 2 – 2 D Powder Diffraction Principle stresses 310 σ2 = - 486 MPa σ1 = - 394 MPa Compressive biaxial stress for 5% elongated TRIP steel 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 34

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

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

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

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

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

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

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

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

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

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

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

Canadian Light Source Hard X-ray Diffraction Capabilities § Hard X-ray Micro. Analysis (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 (Sy. LMAND) Brockhouse X-ray Diffraction and Scattering Sector 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 Micro. Analysis (HXMA) § Description: The Hard X-ray Micro-Analysis (HXMA) beamline at CLS 06 ID-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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 47

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

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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 49

Canadian Light Source Hard X-ray Diffraction Capabilities § Synchrotron Laboratory for Micro And Nano Devices (Sy. LMAND) § Description: Sy. LMAND 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 Sy. LMAND 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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 50

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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 51

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 19 -Jun-07 BIMR workshop on characterization of materials with Electrons, Photons and Neutrons 52