4. Quantitative X-ray dark-field imaging
4.1. Small-angle X-ray scattering
4.1.2. Theoretical small-angle scattering formalism
The assumption of small scattering angles leads to the mathematical formalism of small-angle X-ray scattering (SAXS). It is derived by solving the Schrödinger equation of a wave
4. Quantitative X-ray dark-field imaging
interacting with a potential. Iteratively solving the Schrödinger equation results in a series expansion for the solution of the scattered wave, which is called the Born series. This ex-pansion can be restricted to its rst term under the assumption of a weak potential. This results in the Born approximation for the solution of the scattered wave [65]. Assuming a weak potential is equivalent to an incoming wave which is constant within the scattering volume. In addition, SAXS also uses the following two geometrical simplications: On one hand, the scattered wave resembles a plane wave as the wavefront's curvature is negli-gible at large a distance. Furthermore, the detector is placed far away from the scattering object and thereforeRD rwhen considering scattering by two electrons separated by~r. Instead of solving the Schrödinger equation to obtain a solution for the scattered wave, we use a phenomenological approach starting from a two electron scenario. Figure 4.2 a) shows a schematic illustration of this case.
Δs1 e
Figure 4.2.: This gure shows a schematic drawing of scattering by two electrons and a geometrical representation of the scattering vector Q~. a) An incoming wave is scattered by two electrons separated by ~r. Due to the path dierence ∆s = ∆s2 −∆s1 the two scattered waves have a phase dierence ∆Φ = (2π/λ)∆s when reaching the detector at distanceRD. For convenience we dene the scattering angle as2θ. b) The phase dierence
∆Φ is obtained by projecting vector~r onto the wavevectors k~0 and k~sc. This is indicated by the dashed lines orthogonal to k~0 and k~sc. Furthermore, the scattering vector Q~ is dened by this geometry as Q~ =k~sc−k~0.
An incoming wave is scattered by two electrons at an angle 2θ. The scattered waves originating from the two electrons travel dierent distances (∆s1 and∆s2) before reaching the detector. The path dierence ∆s2 −∆s1 results in a phase dierence ∆Φ, which is calculated based on geometrical considerations as illustrated in gure 4.2 b). By projecting
40
4.1. Small-angle X-ray scattering
vector~ronto the wave vectors of the incoming and scattered wave,k~0 andk~sc respectively, one obtains the following expression for∆Φ [12]:
∆Φ =−2π
λ (∆s2−∆s1) =−(k~sc~r−k~0~r) = −~r ~Q . (4.4) Here, we dene the scattering vector Q~ as the dierence of the wavevectors k~0 and k~sc. The phase dierence of the two scattered waves has to be considered when calculating the total scattered intensity. This results in the following expression of the scattered wave Ψsc,N(Q)~ for the discrete case ofN electrons [12]:
Ψsc,N(Q) =~ −Ψ0releik0RD RD
N
X
j=1
e−i ~Q ~rj . (4.5) The phase dierences of all N electrons, which are located at a distance r~j from an arbitrary point of origin, are summed up and multiplied with the scattered wave of a single electron (see equation 4.3). The more realistic scenario of a continuous electron distributionρel(~r)requires some further considerations: A small volume dV, also written asd3r, located at position~rcontainsρel(~r)dV electrons that scatter with a phase dierence of exp(−i ~Q~r)compared to an arbitrary point of origin. This is illustrated in gure 4.3.
2θ
RD
r
ρel
(
r)
dV
ψsc ψ0
Figure 4.3.: This gure illustrates X-ray scattering by a continuous electron distribu-tion. An incoming wavefront is scattered by a continuous distribution of electronsρel(~r). Each volume element dV, also written as d3r, of the sample scatters with a strength of relρel(~r)dV. A fraction of the incoming intensity is scattered at an angle2θand is detected at distanceRD.
As the number of electrons increases, we replace the summation in equation 4.5 by an integral over the sample's volume Vr. Thus, the scattered wave is represented as follows [12]:
4. Quantitative X-ray dark-field imaging
Here, the scattering length densityρsl(~r) = relρel(~r)is introduced. Furthermore, we dene the nal integration of this equation as the form factorF(Q)~ of the scattering object [12]:F(Q) =~ Z
Vr
ρsl(~r)e−i ~Q~rd3r . (4.7) Scattering of many equivalent objects separated byRj is described similar to equation 4.5.
In order to obtain the scattered wave, the form factors F(Q~) of all N particles are multi-plied by a phase of exp(−i ~Q ~Rj) and summed up [66]: The term S(Q)~ represents the so-called structure factor. It provides information on the distribution of scattering objects within the sample. The structure factor is negligible, if particles are distributed randomly, while it contributes signicantly, if the object's distri-bution follows a certain pattern or order. Thus, as soon as particle positions are correlated in space, i.e. in the presence of short- or long-range ordering, S(Q)~ strongly aects scat-tering experiments. Going further into detail on the structure factor is beyond the scope of this work. However, it is a useful tool to interpret some of the experimental results presented at a later point. But rst, we continue with the derivation of the dierential scattering cross-section.
To formulate the dierential scattering cross-section using equation 4.2, the squared am-plitude of the scattered wave is calculated by multiplication with its complex conjugate.
This is represented by the following double integral [12]:
Ψ2sc,obj(Q) = Ψ~ sc(RD)Ψ∗sc(RD) = Ψ20
4.1. Small-angle X-ray scattering
According to the Wiener-Khintchine Theorem, the squared amplitude of the scattered wave is given by the Fourier transform of the scattering length density's auto-correlation functionγ(R)~ :
γ(R) =~ Z
VR
ρsl(~r+R)ρ~ sl(~r)d3r . (4.11) Inserting equation 4.10 into equation 4.2 results in following expression for the dierential scattering cross-section for a continuous electron distribution [12, 67]:
dσ For convenience, the dierential scattering cross-section is normalized to the object's vol-umeVR. The normalized cross-section yields the fraction of scattered X-rays observed at scattering vectorQ~. Equation 4.12 emphasizes that scattering experiments determine the Fourier transform of the auto-correlation function of the scattering length density distri-bution. While the dierential scattering cross-section represents the fraction of X-rays scattered by a scattering vector Q~, the total fraction of X-rays scattered in all directions is given by the integral of the dierential scattering cross-section over the full Q~-space:
σ = Z
VQ
dσ
dΩ(Q)d~ 3Q . (4.13)
A further simplication is usually made in SAXS by setting the component of Q~ point-ing along the propagation direction to zero, i.e. here Qz = 0. This is feasible as we assume elastic scattering at small angles for which the energy of scattered X-rays remains unchanged [68]. Consequently, the integration of the dierential scattering cross-section along the z-axis can be carried out:
dσ Here, the projection G(x, y)of the auto-correlation function γ(R)~ along the propagation direction, i.e. here the z-axis, is introduced. The projection is dened as follows [68]:
G(x, y) = 1
4. Quantitative X-ray dark-field imaging
These two denitions yield the equivalent unit-less function G(x, y) with G(0) = 1 and G(±∞) = 0. We therefore introduce the unit-less parameter Γ to the rst denition in equation 4.15 for reasons of normalization. The second denition uses an inverse Fourier transform of equation 4.12, which simplies into a cosine transform assuming γ(R)~ to be a real and even function, becauseexp(i ~Q~r)is equivalent to cos(Q~~r) +isin(Q~~r). Only the cosine transform remains in this case while the sine transform vanishes. By performing the back transformation of equation 4.12 into real-space, structural information is obtained.
Having developed the theoretical tools necessary to interpret scattering data, we now give a brief introduction to a particular neutron scattering technique. Spin-echo small-angle neutron scattering (SESANS) shares some striking physical characteristics with grating-based X-ray imaging. It serves as a basis to transfer the mathematical small-angle scattering formalism to Talbot-Lau interferometry [27].