Purdue University

INTRODUCTION

• X-ray scattering techniques are non-destructive analytical techniques that reveal information about the
crystallographic structure, chemical composition, and physical properties of materials and thin films.

• These techniques are based on observing the scattered intensity of an X-ray beam hitting a sample as a
function of incident and scattered angle, polarization, and wavelength/energy.

• Materials that do not have long range order may also be studied by scattering methods that rely on elastic
scattering of monochromatic X-rays: Small angle X-ray scattering (SAXS) probes structure in the nanometer
to micrometer range by measuring scattering intensity at scattering angles 2θ close to 0°

1. The SAXS guide, Getting acquainted with the principles, 3rd edition, Heimo Schnablegger and Yashveer Singh, Anton Paar
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• What are X-rays?
• X-rays are electro-magnetic (EM) waves with wavelengths <0.3nm. They possess alternative electric and magnetic
fields that aid in propagation of the wave.
• Two main X-ray interaction with matter
• Absorption – X-ray energy is absorbed by atom and electron is expelled. As a consequence, an electron drops to the
lower energy state by releasing a fluorescent X-ray
• Scattering – Can be Compton scattering (inelastic) or Thompson scattering (elastic)
• Compton scattering occurs when a photon hitting an electron looses its energy. Hence the scattered wave has a
different wave length than incident beam and no phase relationship with incident beam. As a result of inelastic
scattering, they cannot produce interference patterns and does not have carry any structure information. These
are usually background radiation.
• Thompson Scattering occurs when a photon hitting an electron does not loose energy. The electrons that was hit
begin to oscillate and emit EM radiations with same frequencies as the incident radiation. The emitted EM waves
from neighboring atoms oscillate and produce coherent waves that interfere at the detector. The patterns
generated provide structure information of the particles.
For SAXS data acquisition we require minimal absorption and more scattering. Hence optimal sample thickness dopt
depends on the absorption coefficient µ of the material and wavelength of the X-ray source (in this case Cu-Kα )
𝒅𝒐𝒑𝒕=1/µ
1. The SAXS guide, Getting acquainted with the principles, 3 rd edition, Heimo Schnablegger and Yashveer Singh, Anton Paar
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 • When X-rays are scattered at atoms, every atom emits spherical waves.
• Since these waves are in synchrony with the incident plane waves, they produce interference patterns on the detector (constructive (in-
phase bright spots) and destructive (out of phase – dark spots) interference).
• Scattering patterns acquired are usually presented as a function of q (1/nm) or in q-space.
Q = (4𝝅 sin(θ)) /λ
• Scattering of one particle which is made of many atoms can be explained as the interference pattern produced by all the waves that are sent
to the detector from every electron/atom inside the particle. The square of sum of all these amplitudes result in a characteristic shape/form
to the of the particle and is called “Form Factor” [P(q)].
Form factor P(q) of a
particle is an interference
pattern created from
oscillations of which are
typical of particles shape

• When particles are densely packed (concentrated samples), the distances relative to each other come into the same order of magnitude as
the distances inside the particle. The interference pattern will hence contain contribution from neighboring particles. This addition to
interference pattern is multiplied with the form factor and is know as “Structure factor” [S(q)].
red green SAX Profile (red) of a
concentrated particle dispersion
blue is the product of (green) Form
factor of single particle with
(blue) structure factor of particle
positions
1. The SAXS guide, Getting acquainted with the principles, 3rd edition, Heimo Schnablegger and Yashveer Singh, Anton Paar
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SAXS Equipment at Purdue

4 3
7
5, 6

1 2

Components
1. Cooling system
2. High Voltage Source
3. X-ray Source
4. Collimation systems
5. Sample chamber for sample mounting and translation of stage
6. Beam stop
7. Detector
https://www.anton-paar.com/us-en/products/group/saxs/ 5
Schematic of Experiment

Collimation

X-Ray source

• X-rays are emitted from a X-ray source and pass through the collimation system.
• The colimitation system reduces X-rays into parallel beam of desired shape.
• When X-ray falls on the nano-structure in the sample, the variation in electron density in the sample scatter x-rays from primary beam.
• A beam stop is used to prevent damage to detector by cutting off the incident beam and permitting the scattered rays to pass and be
detected.
• The scattered beam falls on the detector and what is represented on the detector is the amplitude of the Fourier transform of the beam

Sphere shows Poly dispersity gives

Aligned or elongated
up as oscillating superposition of
particles show up as
function scatter functions
anisotropic scatter function
(smooth function)

1. https://www-ssrl.slac.stanford.edu/~saxs/download/weiss_intro.pdf
2. http://www.lookingatnothing.com/ 6
Data Analysis and Manipulation

Data Analysis
• A SAXS signal contain information about shape and size particles (also distances).
• These information are agglomerated in a SAXS pattern.
• These contributions are impossible to separate without external information (i.e. particle shape, a certain distribution, etc…)

Data Analysis Manipulation

• Retrieve particles information processing experimental data by means of mathematical transformations to a assumed shape
• From an assumed particle distribution, calculate the scattering intensity in order to try to fit the experimental data

1. http://people.unipmn.it/gcroce/download/theory.pdf 7
 Object Sizes

• Classical analysis involves fitting scattering patterns Mono particle distribution Poly dispersity
with know objects
• More complex the shape of the object more
complex the fitting
• We can get both shape and size distribution
depending on appropriated data fitting
• The shape, size and distribution of particles affect
the data acquired.
Example:
• For mono particle distribution, a smaller particle scatters lesser than larger particles, hence they would have lesser intensity and appear at larger angles than the
large particles.
• For poly dispersity, the scatter pattern would be an average of scattering from particles of all sizes in the material

Mono particle distribution Poly dispersity Scattering Intensity vs particle size Scattering angle vs particle size
1. http://people.unipmn.it/gcroce/download/theory.pdf
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2. http://www.lookingatnothing.com/
 Data Treatment

• After acquiring the 2D Scatter pattern, the data is described onto 1D profile of Intensity vs q-space by box or Pie averaging
Data averaging Schematic Examples of different data sets

• Background subtraction is done by subtracting the sample intensity curves with respect to the matrix intensity curves.

Green – Matrix Intensity

Red - Sample Intensity ∆𝐼 𝑞 = 𝐼𝑆, exp 𝑞 − 𝐼𝑀, exp(𝑞)
Blue - Corrected Intensity

• After background subtraction, the data can be analyzed by Model-free approach of Model dependent approach.
1. The SAXS guide, Getting acquainted with the principles, 3rd edition, Heimo Schnablegger and Yashveer Singh, Anton Paar
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2. http://www.msg.ucsf.edu/XRayLab/SAXS-Lit/SAXS_Basics.pdf
• Resolution of the data acquired is dependent on the wavelength of the radiation source. The range is usually defined as
qmin<q<qmax
qmin<q<qmax
Q range in experiment
Dmax ͌ 𝝅 /qmax
v
Dmin ͌ 𝝅 /qmin

• Guinier Approximation
Form factor P(q) can be approximated by a gaussian curve at small angles. The curvature of this gaussian is due to the overall
size of the particles.
2 2
𝑅 𝑞 / )
P(q) ͌ a0 . e-( 𝑔 3
Rg is called Gyration Radius. It contains no information on shape or structure of particles; however, if the structure of the
particles can be assumed, then Rg can be used to calculate particle dimension.
a0 is a factor depending on particle orientation
1. The SAXS guide, Getting acquainted with the principles, 3rd edition, Heimo Schnablegger and Yashveer Singh, Anton Paar
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 • By converting to log scale, we get

ln ∆𝐼 𝑞 = ln 𝑎0 − (𝑅𝑔2 q2/3)

Log scale conversion

Intensity vs q space Ln(Intensity) vs q space sq.

Rg and a0 are determined by straight line fitting from slope −(𝑅𝑔2 /3) and intercept (ln(a)0))

1. The SAXS guide, Getting acquainted with the principles, 3rd edition, Heimo Schnablegger and Yashveer Singh, Anton Paar
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2. http://people.unipmn.it/gcroce/download/theory.pdf
Information that can be amassed from SAXS

• Structural information
• Radius of gyration (globular, cross-sectional etc.)
• Molecular weight (monomer, dimer, multimer and so on)
• Pair-distance distribution function
• Low-resolution envelope of molecule and ab-initio structures (about 1nm
resolution)
• Unfolded vs folded (Kratky plot)
• Interaction potentials

1. https://www-ssrl.slac.stanford.edu/~saxs/download/weiss_intro.pdf 12
Difference between SAXS and TEM

• SAXS vs. TEM Transmission Electron Microscopy (TEM) cover the same dimensional range
investigated by SAXS, the two techniques are complementary.
• TEM is good for: Direct and detailed image, local details, local surface, and faithful representation
of local complexities.
• SAXS is good for: Global parameters and distribution, different sample states(solid, wet or
solutions samples…), no destructive/artifacts in sample preparation and in-situ transition study
• The two techniques are complementary: - TEM needs SAXS to obtain significant sampling and
make quantitative statements - SAXS needs TEM for clues about the shape of particles for use in
data analysis

1. http://people.unipmn.it/gcroce/download/theory.pdf 13
Thank You

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