# X-ray techniques Basic Introduction Alla Arakcheeva.

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X-ray techniques Basic Introduction Alla Arakcheeva

X-ray techniques. Basis introduction
X-rays is the most important discovery in recent history Who have enlightened our world? Sources of X-rays Interaction of X-rays and matter Methods based on X-ray spectroscopy (XRS) Methods based on X-ray diffractometry (XRD) Using synchrotron radiation Synchrotron or home laboratory?

The X-ray has been voted as the most important discovery in recent history
… by 50’000 participants in a British Science Museum poll, which had been carried out in 2009 The X-ray machine Penicillin The DNA double helix “X-rays have radically changed the way we see and understand our world” “X-rays allowed to look inside without any damage of solids and to see a human body without any operation”

Who have enlightened our world?
Beginners 1895 Wilhelm Konrad Roentgen discovered and described properties of new rays, which he called X-rays 1901 The First Nobel Prize for Physics He held a demonstration with his first X-Ray pictures, along with one of his wife's hand.

Who have enlightened our world?
Beginners 1899 H. Haga and C. Wind discovered the X-Rays diffraction by a slit The X-rays are electromagnetic waves with l ~ 1 Å

Who have enlightened our world?
Beginners 1904 Charles Barkla discovered the secondary (characteristic) X-ray radiation of elements, which depends on their atomic weight Decelerated or «braking» or «white» X-ray radiation K 1917 Nobel Prize in Physics

Who have enlightened our world?
Beginners 1912 Max von Laue discovered diffraction of X-rays by crystals Laue’s equations: S . a = n1 (integer) S . b = n2 (integer) S . c = n3 (integer) S - scattering vector a, b, c - lattice vectors { 1914 Nobel Prize in Physics

Who have enlightened our world?
Beginners 1912 Sir William Lawrence Bragg derived Bragg's Law

Who have enlightened our world?
Beginners 1915 Sir William Henry Bragg and William Lawrence Bragg jointly received Nobel Prize in Physics "for their services in the analysis of crystal structure by means of X-rays” Start of X-ray crystallography: C (diamond), NaCl, KCl, KBr, KI, CF2, ZnS, FeS2, CaCO3, …

26 Nobel Prizes were awarded for achievements related to X-ray techniques
Ribosome 2009 Chemistry V. Ramakrishnan, T.A. Steitz, A.E. Yonath Studies of the structure and function of the ribosome 2011 Chemistry Daniel Shechtman "for the discovery of quasicrystals"

X-rays X-rays are electromagnetic waves, l ~ 10-11 – 10-8 m
X-rays appear when electrons are accelerating or decelerating X-rays interact with electrons

Sources of X-rays 1. X-ray tubes operate in laboratory devices Scheme
Thermo-emitted electrons Water cooling system Voltage cathode heating Accelerating voltage Ua ~ 50kV

Sources of X-rays 2. Synchrotron radiation
The X-ray flux is 104 – 106 times more intense than in the X-ray tube

Sources of X-rays European Synchrotron radiation Facility (ESRF), Grenoble: Energy of one beam 6 GeV Circumference 844 m Accelerator of electrons Beam lines

Sources of X-rays European Synchrotron radiation Facility (ESRF), Grenoble: Energy of one beam 6 GeV A single beam line

Sources of X-rays European Synchrotron radiation Facility (ESRF), Grenoble: Energy of one beam 6 GeV A management team Experimental facilities A single beam line

Sources of X-rays European Synchrotron radiation Facility (ESRF), Grenoble: Energy of one beam 6 GeV

Sources of X-rays European Synchrotron radiation Facility (ESRF), Grenoble: Energy of one beam 6 GeV 41 beam-lines are managed by 19 countries

Sources of X-rays European Synchrotron radiation Facility (ESRF), Grenoble: Energy of one beam 6 GeV Inside of a beam line

Come back in 15 minutes

Basis of X-ray analysis
Interaction of X-rays and matter Elastic scatering Inelastic interactions Diffraction Methods based on X-ray diffractmetry (XRD) Methods based on X-ray spectrometry (XRS)

Method based on X-ray spectroscopy
(XRS) X-ray fluorescence spectroscopy X-ray tomography Extended X-ray absorption spectrometry (EXAFS)

How it works at synchrotron (ESRF, Grenoble)
Method Results Areas of application X-ray fluorescence spectroscopy Chemical analysis Tiny sample or tiny area under study Art & Archeology, Materials, Geology, Biomedicine, Environmental science How it works at synchrotron (ESRF, Grenoble) Scheme

Method based on X-ray spectroscopy
(XRS) X-ray fluorescence spectroscopy X-ray tomography Extended X-ray absorption spectrometry (EXAFS)

Silicon chip stacking in microelectronics
Method Results Areas of application X-ray tomography - Absorption - Fluorescence 3D maping of - Morphology - Chemistry - Construction materials - Microelectronics - Nuclear materials - Soft materials (polymers, cells, bone) How it works (ESRF, Grenoble) Scheme 3µm Silicon chip stacking in microelectronics

Method based on the X-ray spectroscopy
(XRS) X-ray fluorescence spectroscopy X-ray tomography Extended X-ray absorption spectrometry (EXAFS)

How it works (ESRF, Grenoble)
Method Results Areas of application Extended X-ray absorption spectrometry EXAFS – Extended X-ray Absorption Fine Structure Local atomic enviroment - Disordered matter (amorphous, liquids) - Surfaces, interfaces - Multiphase systems - Heterostructures Catalytic system, alloys, ceramics, corrosions, semiconductors, … How it works (ESRF, Grenoble) Local structure vs Oxygen Storage Capacity in mixed oxides Nagai et. Al. Catalysis Today (2002)

Metod based on X-ray diffraction
(XRD) Single crystal and powder XRD X-ray topography Small and Wide-Angle Scattering (SAXS/WAXS) Diffraction

The universal method for discovery !
Results Areas of application Single crystal XRD - Symmetry and lattice constants - Molecular and/or Atomic structure - Chemical bonds - Refined chemical composition - Electron density distribution Chemical crystallography of - inorganics - organometalics - small and macro molecules in Physics, Chemistry, Life Sciences, Mineralogy, Materials, Metallurgy The universal method for discovery ! W. H. Bragg and W. L. Bragg Nobel Prize in 1915 V. Ramakrishnan, T. A. Steitz, A. E. Yonath Nobel Prize in 2009 NaCl Ribosome

Single crystal XRD Typical study
Confirmation of expected structure of a new small molecule compound A new second-order nonlinear optical material 4-bromo-4’nitrobenzylidene aniline (BNBA), C13H9BrN2O2

Single crystal XRD Typical study
Confirmation of expected structure of a new small molecule compound 18’234 measured reflections; T = 173 K Single crystal 4-bromo-4’nitrobenzylidene aniline (BNBA), A new second-order nonlinear optical material

Single crystal XRD Typical study
Confirmation of expected structure of a new small molecule compound Expected result: monoclinic crystallographic system Unexpected Result: Non-traditional, (3+1)D symmetry – A2(a0g)0 h Hhklm = ha* + kb* + lc* + mq (de Wolff, P.M. , 1974) Satellites q H4001 H4000 mtw l Bragg’s reflections Hhkl = ha* + kb* + lc* (W. L. Bragg, 1912)

A new second-order nonlinear optical material
Single crystal XRD Typical study Confirmation of expected structure of a new small molecule compound Expected result: Structure of the small molecule 4-bromo-4’nitrobenzylidene aniline (BNBA), A new second-order nonlinear optical material

Single crystal XRD Typical study
Confirmation of expected structure of a new small molecule compound Expected result: H-bonds between molecules Unexpected Result: Aperiodic distribution of the H-bonds 4-bromo-4’nitrobenzylidene aniline (BNBA), A new second-order nonlinear optical material

Single crystal XRD Typical study
Confirmation of expected structure of a new small molecule compound Unexpected Result: Splitting of molecule at 293 K 4-bromo-4’nitrobenzylidene aniline (BNBA), A new second-order nonlinear optical material

Universal method for routine work
Results Areas of application Powder XRD For single phase material - Symmetry and lattice constants - Atomic ordering - Chemical bonds For poly-phasic Material - Phase composition - Grain size - Micro-strain distribution Chemical crystallography of - inorganics - organometalics - small molecules in Physics, Chemistry, Life Sciences, Mineralogy, Materials, Metallurgy Universal method for routine work

Powder XRD Typical tasks Degree of crystallinity Time of annealing 180
180 Diffraction (scattering) angle 2q

Powder XRD Typical tasks Phase identification
Identification of (NH4)6(NiMo9O32).6H2O Experimental profile and Referred lines from PDF Typical tasks Phase identification > 600’000 reference materials are currently listed in the Powder Diffraction File Database

Powder XRD Typical tasks Crystal structure determination
and refinement BiCu5O3S BiOCuS Bi (known), BiOCuS (known), BiCu5O3S (unknown before) !

Powder XRD Typical tasks Phase analysis quantitative & qualitative 1
Paint sample from ancient Ethiopian icons 2 1 2

Powder XRD Typical tasks Anisotropic micro-strain distribution

Methods based on X-ray diffraction (XRD)
Single crystal and powder XRD X-ray topography Small and Wide-Angle Scattering (SAXS/WAXS) Diffraction

X-ray diffraction imaging or X-ray-topography
Method Results Areas of application X-ray-topography or X-ray diffraction imaging Imaging defects Dislocations Stacking faults Scratches Inclusions Nearly perfect crystals - Microelectronics - optoelectronics - Photovoltaic silicon - Optics - … Objects nearly perfect crystals How it works at ESRF (Grenoble)

Methods based on X-ray diffraction (XRD)
Single crystal and powder XRD X-ray topography Small and Wide-Angle Scattering (SAXS/WAXS) Diffraction

How it works Method Results Areas of application
Small and Wide Angle Scattering (SAXS / WAXS) Micro- and nano-structure and phase behavior of multi-components systems - Texture - Preferable orientations - Degree of crystallinity Soft condensed matter - polymers, fibers Nanocrystalline structures - biological objects - films, surfaces, interfaces - In-situ studies How it works Solid Submelted Randomly aligned domains Recrystallized µm and nm scales of analyzed object Scattering angles: 0.1 – 10o Preferentially aligned domains

Micro / nano X-ray diffraction using synchrotron radiation (ESRF)
Specific features Non-destructive techniques High flux X-ray energy: typical 8-24 keV up to 100 keV at HE beamline Focused beam (100 nm) Scanning diffraction with spatial resolution Micro/nano size of analyzed object (down to 100 nm) Applications Single polymer fiber diffraction Scanning diffraction of polymer films Grazing incidence micro-diffraction on surfaces Chemical micro-crystallography Structure of Individual powder grain

Synchrotron or home laboratory?
Synchrotron laboratory Home Laboratory Higher resolution Higher flux Quick counting times in experiments Precise characterization of a local area (down to nano scale) Lower overall cost of a study Ease accessibility Easy to use Quick average characterization of a large volume (down to µm scale) Advanced and precise study General and average characteristics Use synchrotron radiation if you are ready To explore new fields To reconsider some theories Use laboratory devices if you are going To confirm traditional views To add a new item to a well known list

Thank you for your attention !