stanford synchrotron radiation lightsource introduction to ... · introduction to synchrotron x-ray...
TRANSCRIPT
![Page 1: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/1.jpg)
Stanford Synchrotron Radiation Lightsource
Introduction to Synchrotron X-ray Scattering Techniques
Mike Toney, SSRL Materials Sciences Division
1. Why do x-ray scattering?2. Basics of an x-ray scattering experiment3. SSRL scattering beamlines4. Some examples
SAXS: porous filmsPowder: Pd nanoparticlesTextured films: ZnO nanostructures
5. Summary
20 nm
10x
(11L)
(02L)
(12L)
(20L)
(21L)
(13L)(22L)
(14L)
(23L)(31L)
(24L)
20 nm
10x
(11L)
(02L)
(12L)
(20L)
(21L)
(13L)(22L)
(14L)
(23L)(31L)
(24L)
![Page 2: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/2.jpg)
Why do SR X-ray scattering?Materials properties are caused or affected by their physical structure and morphologyImprove your materials by understanding the structure.
• Phase identification & quantify• Where are the atoms: Atomic or
molecular arrangement, crystal & surface structure
• Strain, lattice parameters (unit cell size)• Grain/crystallite size (diffraction)• Pore/particle size (SAXS)• Other defects & disorder (faults,
positional disorder)• Crystallite orientation or texture
hcpfcc
![Page 3: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/3.jpg)
SR Scattering Experiment
monochromator• double crystal• Si(111) or Si(220)• LN or water cooled• selects wavelength
source
beam
M0 mirror• cylindrical or toroidal• Rhodium-coated silicon• harmonic rejection, power filter, collimating or focusing
slits (horz or vert)• variable aperture• define beam shape
and acceptance
sample
kincidentscattered
k’
Q = k’ - k
All you care about is Qcollect I(Q)
Area detector
Point detector
![Page 4: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/4.jpg)
SR Scattering Experiment
kincidentscattered
k’
Q = k’ - k
All you care about is Q
Area detector
Point detector
At SSRL:• Area detector: 11-3• Point detectors: 2-1, 7-2, 10-2• SAXS: 1-4
collect I(Q)
0 1 2 3 410-2
10-1
100
101
102
103
104
105
1 2 3 4Q (Å)
010-2
10-1
100
101
102
103
104
105
I(Q)
(arb
. uni
ts)
Diffraction:peaks
Scattering:the rest
![Page 5: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/5.jpg)
SR Scattering ExperimentBeamline 2-1 7-2 & 10-2 11-3Detector Point (mostly) Point Area
Advantages
Dis-advantages
Used for
High resolutionAccurate peak position and shapeWeak peaksVariable energyReflectivity
High resolutionAccurate peak position and shapeWeak peaksVariable energy4 degrees of motion
Fast measurementCollect (nearly) whole pattern
SlowOnly 2 axes of motion
SlowCan be difficult to find textured peaksComplicated
Fixed wavelengthLow resolutionPeak shape and position inaccurateWeak peaks difficult
PowdersPhase determinationReflectivity-2
Anomalous diffraction
Single crystalsGrazing-incidenceAnomalous diffractionSurface studiesAnomalous diffraction
TextureReal time experimentsPolycrystalline, small grainsThin films
1-5
![Page 6: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/6.jpg)
SR Scattering Experiment
= scattering angleQ = (4 ) sin
incidentscattered
Detector
Q
Area detector (11-3) AdvantagesFast measurementCollect whole pattern
DisadvantagesFixed wavelengthLow resolutionPeak shape & position inaccurateWeak peaks difficult
Used forTexture (crystallite orientation)Real time experiments
(electrochemistry, stress-strain)Polycrystalline, small grainsThin films
![Page 7: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/7.jpg)
SR Scattering ExperimentArea detector (1-5) - clone of 11-3 Used for
Texture (crystallite orientation)Thin films
AdvantagesFast measurementCollect whole pattern
DisadvantagesLow resolutioninaccurate peak shape /positionWeak peaks difficult
Detector
incident scattered
Detector
Q
Goal: Easy, seamless access for students from universities when research requires higher intensity & resolution than laboratory sources.
Phase I: Reconfigured bending magnet for thin film x-ray diffraction. Stanford Nanocharacterization Laboratory will pilot access
Pil Sung Jo, graduate student in the Materials Sciences department of Stanford, setting up diffraction experiment on organic semiconductors
![Page 8: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/8.jpg)
SR Scattering Experiment
incident x-rays
diffracted x-rays
sample
Point detector (2-1)
= scattering angleQ = (4 ) sin
AdvantagesHigh resolutionAccurate peak position & shapeWeak peaksVariable energyReflectivity
DisadvantagesSlowOnly 2 degrees of motion ( , 2 )
Used forPowdersPhase determinationReflectivityAnomalous diffraction
-2 measurements
![Page 9: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/9.jpg)
SR Scattering ExperimentPoint detector (7-2/ 10-2)
= scattering angleQ = (4 ) sin
AdvantagesHigh resolutionAccurate peak position & shapeWeak peaksVariable energy4 degrees of motion ( , 2 , , )
DisadvantagesSlowComplicated Can be difficult to find peaks
Used forSingle crystalsGrazing-incidenceAnomalous diffractionThin filmsSurface studies
incident x-rays
diffracted x-rays
sample
![Page 10: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/10.jpg)
sample
incident x-rays
diffracted x-rays
sample
SR Scattering ExperimentPoint detector (7-2/ 10-2)
![Page 11: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/11.jpg)
Types of scattering experiments• Small Angle X-ray Scattering (SAXS)
– probes structures 1-100 nm• Powder Diffraction, including in-situ
– random or isotropic; nanoparticles– poor crystalline order
• Thin Films: random, textured, epitaxial– wide variety
• Surface Scattering/monolayers– atomic structure at surface or interface
iron metalFe oxide
![Page 12: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/12.jpg)
Lengths Accessed by Probes
1 nm1 m
XRDSAXSUSAXS
![Page 13: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/13.jpg)
Summary: SR Scattering
• Q is important variable: measure I(Q)
• choose Q to match length scale
• variety of materials
hcpfcc
• Phase identification & quantify• Where are the atoms: crystal &
surface structure• Strain, lattice parameters• Grain/crystallite size• Pore/particle size• Other defects & disorder• Crystallite orientation or texture
What can we learn:SR Scattering:
iron metalFe oxide
![Page 14: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/14.jpg)
Small Angle Scattering
|Q| = (4 )sin
• Measure I(Q) with Q 0.0001 – 1 Å-1
• Scattering from 1-100 nm density inhomogeneities
kincidentscattered
k’Q = k’ - kQ
100
101
102
103
104
105
106
107
Inte
nsity
[cm
-1]
0.001 0.01 0.1 1
q [A-1
]
Sample A Sample B Sample C Sample D Sample E Sample F
APS 15-ID-D USAXS
![Page 15: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/15.jpg)
Small Angle ScatteringScattering from density inhomogeneities with sizes 1-100 nm
• nanoparticles (catalysts, bio-oxides, geo-oxides)• nanoporous materials• co-polymers• dendimers• supramolecular assemblies• micelles• colloids• metallic glasses
![Page 16: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/16.jpg)
Small Angle Scattering
• Need large Q range:1/D Q 10/D<~ <~
Hexagonal packedcylinders
Isolated particlesor pores with diameter D
D
Q-4
![Page 17: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/17.jpg)
Example 1: Nanoporous Films
Spin coat MSSQ/Porogensolution
Heat to 450°C, at5°C/min under argon
Cool to room temperature
1.
2.
3.
Matrix: Methyl Silsesquioxane (MSSQ), CH3SiO1.5
Porogen (thermally labile polymer): copolymer poly(methyl methacrylate-co-dimethylaminoethyl methacrylate) or P(MMA-co-DMAEMA)
Argon
Spin Coat
MSSQ crosslinks at 200°CPoragen fully degrades at 400°C
Huang et al, Appl. Phys. Lett. 81, 2232 (2002)Huang et al., Chem. Mater. 14, 3676 (2002)Magbitang, Adv. Materials. 17, 1031 (2005)
IBMElbert HuangJonathan HedstromHo-Cheol KimTeddie MagbitangRobert MillerWilli Volksen
![Page 18: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/18.jpg)
Huang et al, Appl. Phys. Lett. 81, 2232 (2002)
Nanoporous Films: SAXS Results
Find:• reasonably small pores (good)• broad distribution of pore sizes
(bad)• size increases with loading =>
agglomeration (bad)
![Page 19: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/19.jpg)
Goal: obtain representative real space picture (correct size scale and extent of interconnection)
• Cahn, J.W., J. Chem. Phys. 42, 93 (1965).• Berk, N.F. Phys. Rev. Lett. 58, 2718 (1987) & Phys. Rev. A 44, 5069 (1991).• Jinnai, H., et al., Phys. Rev. E 61, 6773 (2000).• Teubner, M., Europhys. Lett. 14, 403 (1991).• Hedstrom et al., Langmuir 20, 1535 (2004)
Approximations:morphology is “disordered” or random with no preferred directionmorphology described by cosine waves:
with random phase and directionnon-random distribution of wavelengths
(from SAXS)
Nanoporous Film Morphology
![Page 20: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/20.jpg)
Summary: SAXS• Isolated Particles/Pores (not ordered)
Obtain average size & particle/pore size distribution (need large Q range)
• (More) Ordered Structuresparticle/pore spacing and morphology
• Dense Network of Pores/ParticlesObtain representative morphologyGood for interconnected & bicontinuousmorphologies
John Pople, up next!
![Page 21: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/21.jpg)
Example 2: Nanoparticles
+ H2
Motivation:• Pd absorbs hydrogen at an
atomic level• Clusters behave differently to
bulk• Pd clusters:
– size dependence– surface/volume ratio
![Page 22: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/22.jpg)
Nanoparticles: X-ray diffraction
k’Q = k – k’
kk
k’Q = k – k’
k
Reflection Transmission
Point detector(2-1, 7-2)
![Page 23: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/23.jpg)
Nanoparticles: X-ray diffraction
Ingham et al., Phys. Rev. B 78 245408 (2008).
In-situ Experiments – more laterAPS sector 12
![Page 24: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/24.jpg)
Summary: Nanoparticles
Apurva, Linda, Marc, Misra, Yezhou: this afternoon
This work:• Observe peaks
corresponding to fcc Pd• Lattice expansion upon
addition of hydrogen• Dependence on cluster
size
Powder diffraction:• Phase identification• Structure determination• Strain• Crystallite size• Defects• In situ measurements• Transmission and
reflection geometries
k’Q = k – k’
kk
k’Q = k – k’
k
![Page 25: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/25.jpg)
Example 3: ZnOMotivation:•ZnO exhibits a wide variety of nanostructures•Electrochemical processing has many advantages•Experimental parameters determine morphology
100
002
How does crystallography affect the growth of the nanostructures?
![Page 26: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/26.jpg)
Thin Film DiffractionArea
Detector
incident
~ degQ scattered
Beam line11-3 incidentscattered
Detector
Q
![Page 27: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/27.jpg)
ZnO: experimentsEx situ:
100
002
002
100
101
Au
Au
Au
102102
200
![Page 28: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/28.jpg)
ZnO: SummarySummary:•Texture increases with deposition time•Nanostructures are oriented along 002 direction•Films deposited at less negative electrochemical potentials have poorer epitaxy
100
002
Thin films and texture:• Surfaces, interfaces• Structure, strain• Orientation• Crystallite size in-plane
and out-of-plane
Arturas, Chad, Stefan, Chris, this afternoon
![Page 29: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/29.jpg)
Summary• Typical SR x-ray scattering experiment & some examples:
porous films, nanoparticles, textured films
• To be covered in this workshop: • Films: random, textured, epitaxial• SAXS• Powder• Poorly ordered • Surfaces
Speaker Mug Shots
![Page 30: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/30.jpg)
Bibliography
• B Warren, “X-ray Diffraction”, Dover (1990): $7.58 & eligible for FREE Super Saver Shipping on
• BD Cullity & SR Stock, “X-ray Diffraction”, Prentice Hall (2001): $159.16.
• J Als-Nielsen & D McMorrow, “Elements of Modern X-ray Physics”, Wiley (2001): $92.89.
![Page 31: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/31.jpg)
More Bibliography• M. Tolan, “X-ray Scattering from Soft-Matter: Materials Science and Basic
Research”, Springer (1998).• RL Snyder, K. Fiala & HJ Bunge, Eds., “Defect and Microstructure Analysis by
Diffraction”, Oxford (1999).• V Holy, U Pietsch, T Baumbach, “High-Resolution X-Ray Scattering: From
Thin Films to Lateral Nanostructures”, Springer-Verlag, (2004)• O Glatter, “Small Angle X-Ray Scattering”, Academic (1982).• “Modern Aspects of Small Angle X-Ray Scattering”, H. Brumberger (Editor),
Springer (1994).• Int. Union of Crystallography: Links to everything crystallographic.
www.iucr.org . See : www.iucr.org/cww-top/edu.index.html and also Teaching and Education in Crystallography: www.minerals.csiro.au/mirror/w3vlc/edu.index.html.
• Structural data for thousands of minerals: database.iem.ac.ru/mincryst/ • Lawrence Berkeley: X-ray interactions with matter, data & calculations www-
cxro.lbl.gov/optical_constants/ • International Centre for Diffraction Data - purveyors of the Powder Diffraction
File (PDF) www.icdd.com
![Page 32: Stanford Synchrotron Radiation Lightsource Introduction to ... · Introduction to Synchrotron X-ray Scattering Techniques Mike Toney, SSRL Materials Sciences Division 1. Why do x-ray](https://reader033.vdocument.in/reader033/viewer/2022042805/5f6467c91278ee29d62808c6/html5/thumbnails/32.jpg)