Instrumentation and Measurements (XRD) Dr. Christophe Fontugne - - PowerPoint PPT Presentation

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• Dr. Christophe Fontugne

R&D Instrument manager MAUD 2018

November 26, 2018

Instrumentation and Measurements (XRD)

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Sum m ary

Presentation of ThermoFisher X-ray part (very quick) Interaction X-ray and matter (no maths, good for digestion) XRD basics Powder Thin Layer Stress Texture XRD setup : Some important parameters defining an instrument Some real XRD examples : Dynamic studies on Equinox 100 Combined XRD/XRF on Equinox 100 Phase transition at (not very) high temperature on Equinox 3000 Texture/Stress Combination on Equinox 6000

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EDXRF Stand-alone Powder XRD WDXRF Integrated XRF and XRD

XRF: Elemental analysis

ARL OPTIM’X: Surprising performance in WDXRF ARL 9900 Series Integrated XRF-XRD ARL PERFORM’X High performance sequential XRF

XRD: Analysis of structure, crystallography phases or compounds

ARL EQUINOX Series from benchtop XRD to advanced research XRD ARL QUANT’X Top performance bench-top EDXRF

(>4000 customers)

Thermo Scientific XRF and XRD Product Portfolio : Strong And Complementary Technologies

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Therm o Fisher Scientific – I nel Brand

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Therm o Fisher Scientific – XRD research

Z.A. C.D. 405 45410 ARTENAY , France T + 33 (0)2 3880 4545 F + 33 (0)2 3880 0814

Key figures

Creation : 1974 of INEL SAS INEL integrates Thermo Fisher in Feb. 2016 Staff 2015 : 20 employees 80% technically qualified (PhD, Engineers and technicians) Staff seniority average: 10 years

Resources

All technical and human resources are situated in our headquarter in France :

• Research & Development, technical assistance
• Informatics tools development & assistance
• Mechanical parts design & metrology
• X-Ray diffraction systems assembling
• Installation & After Sales Services for instrumentation
• Components and electronic cards design & integration

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When a photon does encounter an atomic particle, it transfers energy to the particle. The energy may be reemitted back the way it came (reflected), scattered in a different direction or transmitted forward into the material. Wave-matter interaction

e-

λ

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I nteraction w ave-m atter

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The energy of photons used for optical spectroscopic measurements of various quanta

EHz : exahertz (1018) - ZHz : zettahertz (1021) - YHz : yottahertz (1024)

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W ave-m atter interaction

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X-rays Production : classically by excitation of external electronic level with electron beam

Bragg's law d θ θ

d = λ 2 sin θ

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X-Ray Diffraction basics (1/3)

• Planes of atoms act like a diffraction grating
• Constructive & destructive interference lead to peaks

in scattered intensity

• Values of λ & d determines 2θ

Bragg’s law : nλ= 2d sinθ

• Where
• n = order of radiation
• λ= wavelength of radiation
• 2d = latice spacing of crystallites in the powder

sample for XRD

• θ = Bragg angle

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X-Ray Diffraction basics (2/3)

Peak positiond-spacings Peak intensitynature and atomic positions in planes

With XRD we measure distances... … nothing more

Chemical composition Phases Structure …..

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X-Ray Diffraction basics (3/3)

DATABASE

Pattern Halite (NaCl)... ... should give this pattern

Source : wikimedia

DATABASE

Without a Database we can not do much...

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One important issue with XRD : isomorphism

This is one real issue with XRD

Pattern

AgS2Sb has the same structure as NaCl !!!

A complementary technique sensitive to chemistry is helpful (XRF…)

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THIN LAYER (GiXRD)

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What is called thin layer

Substrate Layer

Issue 1

To control penetration depth of X-Rays

Issue 2

Speed : if layer is really thin (few nm)

Issue 3

Often quality of signal is poor due to a lack of cristallinity

Issue 4

Sometimes detector dynamic required is really high (epitaxial layers) GiXRD (or thin layer) is used to see the first few nm to µm of sample surface…. … Therefore at least motorized

• mega and Z are required (thin

layer attachement or Equinox 5000

• r 6000)

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Information obtained 1/2

• Bump spacing : information on thickness
• Bump decay : information on roughness

(angstrom scale)

• Thin is easy (less than 300 nm) thick is very

difficult.

• XRR (X-Ray Reflectometry)

Unique feature for a desktop instrument

X-Ray Reflectivity curve 5nm Nb layer X-Ray Reflectivity curve 10nm Ni layer

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Information obtained 1 / 2 … continued

Stack of 128 W/Si layers on Silicon substrate W = 1.1nm Si = 2.2nm

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Information 2/2… Diffraction of course

4µm Ni layer on Iron Ω increases

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What is Epitaxie?

Au on TbPC2 Thin layer but with nearly same structure as a single crystal.

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STRESS

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What is (residual) stress

• A simple cubic structure

d d d

d Is always the same 2θ Is always the same

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Some violence…… Sample larger than before Sample smaller than before

DEFORMATION

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…. At atomic level

d d d d1 d2 d3

d1 < d < d2 & d3

d2 = d3 in case of uniaxial stress

d changes implies that 2 theta changes

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Just for fun

Texture measurement Using Precix robotic system

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TEXTURE

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What is called texture?

Powder or random texture Preferred orientation / texture

Texture means classically deviation from random texture

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Why do we have texture sometime

Extrusion Cold rolling Geology And many other things….

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Instrument is designed to retrieve the information we are looking for. It allows to measure and quantify physical parameters (length, weight, power, energy, time…) Instrument

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X-ray diffraction setup Environment

Elastic coherent interaction : reflectometrie : investigation on thin film for measuring thickness, roughness and density diffraction : investigation on phases absorption : imaging and radiography. Incoherent elastic interaction : diffusion by a rough surface or cristalline defects.

=> instrumental configuration adapted according to:

• type of measurement
• type of sample
• accuracy of the result

X-ray Source

• ptic

sample Detection Instrument Diffraction Small angle measurements Grazing measurements

Performances depends on the instrumental function

Powder, fibres, bulk 2D or 3D bulk 2D Powder, fibres, bulk 2D

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Function source

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A light emission characterized by :

• a spectral range
• a solid angle
• intensity
• dimension and shape of the source

Optimizing the characteristics of a source allows to focus on a given interaction

fluorescence imaging diffraction reflection diffusion Spectral range large large Monochromatic (excepted Laue) monochromatic monochromatic Solid angle Few degrees Large (60°) Small to parallel

• r focusing

Very small Very small or focusing Source size Small or large Small for resolution improvment small small small Source shape point/linear point Point or linear linear Point or linear Molybdenum spectrum vs the applied voltage

This is achieved by using appropriate optics (1D, 2D, monochromator, mirror, collimator, slits ...)

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Function source : shaping the beam

Flat graphite ka1+ka2 Flat Ge or flat Si Channel-cut Kirkpatrick Baez Convergent beam Divergent beam Single collimation pin-hole

An optic is characterized by :

• mosaicity

→ spectral range

• a capture angle

→ beam size

• divergence

→ resolution

Monochromaticity Focusing Divergence

filter

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Effect of optic: com parison betw een high resolution and high flux

2theta 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16 Intensity 32 000 30 000 28 000 26 000 24 000 22 000 20 000 18 000 16 000 14 000 12 000 10 000 8 000 6 000 4 000 2 000

Graphite monochromator Ge111 monochromator

pozzolana

Blue Green ACQTIME 300 VOLTAGE 35 CURRENT 35 WAVELENGTH 1.54056000 COMMENT1 inc=10 SFspin ACQTIME 27815 VOLTAGE 35 CURRENT 35 WAVELENGTH 1.54056 COMMENT1 inc=8 spin

2theta 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16 14 12 10 8 6 4 Intensity 11 000 10 500 10 000 9 500 9 000 8 500 8 000 7 500 7 000 6 500 6 000 5 500 5 000 4 500 4 000 3 500 3 000 2 500 2 000 1 500 1 000 500

Graphite monochromator Ge111 monochromator

zeolite

Blue Green ACQTIME 1800 VOLTAGE 35 CURRENT 35 WAVELENGTH 1.54056000 ACQTIME 18000 VOLTAGE 35 CURRENT 35 WAVELENGTH 1.54056

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Effect of w avelength

Mixture of minerals

Cukα Cokα

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Function detection

0 D Detection : Acquisition is done Stepwise 2θ and statistics are time dependent 1 D Detection : Acquisition is done in snapshots Statistics is time dependent 2 D Detection : Acquisition is done in snapshots Statistics is time dependent Texture information but point beam required

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Existing instruments and applications Instruments

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ARL Equinox 100: A bench-top XRD for routine XRD-Performance with Convenience

Description

• Desktop (680 x 582 x 524mm)
• Lightweight 75 Kg
• Easy to install, run and maintain
• No Alignment needed
• MicroSource coupled Smart Optics™
• No external cooling
• No external gas supply
• Standard electric plug
• <200W Total power consumption
• 6 Positions auto-sampler (optional)
• Thin layer attachment (optional)
• Only 1 LAN cable for communication

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Equinox 100 : Powder sample holders Sample changer : 6 Positions SSRT : spinning sample holder Controlled atmosphere sample spinner (SSCA)

The « must be »… excepted if

• ther spinner is provided

Air sensitive samples Slightly radioactive (alpha particles) Gas reaction at room temperature

Capillaries

Organic samples Clays….. Slow, adapted to labs Museums Forensic For extremely low quantities.

Gandolfi Mount

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Equinox 100 resolution comparable to any standard XRD Equinox 100 : Performance (Sensitivity and Resolution)

Peak/Background equivalent to high power XRD ZnO 10sec acquisition

LaB6 Equinox 100’ sensitivity enables fast measurement times even with its low X-ray power

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Na-gluten

Reflection Transmission

Equinox 100 : Transmission Gandolfi Mount Capillaries

Unique feature for a desktop instrument

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Equinox 100 : Dynamic studies 5 minutes acquisitions cycled over 2 hours. Al2S3 oxydation in air (used in explosive)

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Equinox 100 : Dynamic studies, RbNO3 Room temperature 180°C 260°C 292°C Complete experiment takes about 2 hours

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XRD/XRF combination inside an Equinox 100

20 sec 20 sec

Oxidation layer on steel belt

No phase containing manganese is obviously identified with XRD, but with XRF we evidence manganese.

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SOLSA project: bulk sample mapping at mm scale

Data fusion: merging imaging-XRD-XRF data In order to perform correlation

Mapping sample holder on E100

bulk sample mapping at mm scale

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Equinox 3000 / 3500 : Configuration example

Multilayer mirror optic Runs with Anton Paar XRK900 reaction chamber

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Equinox 3000 / 3500 : Application example

• J. Mater. Chem., A 2013 , 1, 5628

Photovoltaic Application (Solar Cell)

(CH3NH3)PbI3 Structural change Vs temperature.

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Equinox 3000 / 3500 : Configuration example

Buehler HDK1.4 Automatic sample dilatation correction

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Equinox 3000 / 3500 : High temperature work

Glass crystallization at high temperature

CONDITIONS : power : 38kV – 38mA, Furnace : FUR1200 acquisition: 3min

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How do we see that with XRD?

X/Y stage for mapping Motorized elevator Texture analysis software (Labotex) Stress analysis software (Diffstress) Compatible with CPS590 (risk of collision between detector and χ with CPS120) Possible hot domed stage

Equinox 6000

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Random texture (i.e. no texture)

Random Aluminum standard texture

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Orthorombic texture

Aluminum Orthorombic texture, standard sample

If sample is textured, relative intensities of peaks will change depending on sample orientation vs beam.

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Just a thought…. If we process the sample hard enough to get texture don’t we create also stress? If we have stress do we possibly have also texture?

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Extruded Zr sample

calculation experimental

Tilted because of about 600MPa applied stress during process

Data processing with MAUD

ISBN: 978-1-84821-198-8

Large detector Lots of information