1.

2 Calculation of the x-ray reflection pattern 5

Fresnel reflectivity RF2 = r2 is the measurable quantity.

 ki,z − k1,z 2
 
RF2 (q) = 
  (1.8a)
ki,z + k1,z 

1
≈ (4πre ρe )2 for q & 3qc (1.8b)
q4
q
Here, ki,z = k0,z = −k sin αi and kj,z = −k n2j − cos2 αi denote the complex z-components
of the incident wave vector and of the transmitted wave vector in medium j with a refractive
index nj 5 . In the visible range of the electromagnetic spectrum the reflectivity depends
strongly on the polarization. For x-rays, the probed angles α are very small, thus the
polarization dependence is negligible.
Due to multiple scattering effects, the reflected intensity√is almost unity for incident
angles smaller than the critical angle of total reflection αc ≈ 2δ 6 . After this plateau, the
reflectivity drops rapidly, following asymptotically a q −4 decay. In the regime q & 3qc , which
is equivalent to RF2 . 10−3 , the exact expression Eq. (1.8a) coincides very well with the
kinematical approximation Eq. (1.8b), omitting multiple scattering effects (see Sec. 1.2.5).

1.2.4 Multiple interfaces and the slab model

More complex systems may exhibit a rich vertical structure at the interface. Such a profile
can often be divided in a series of slabs with well defined interfaces. For each single interface
(j, j + 1) the amplitudes of the reflected and transmitted wave can be calculated using
Fresnels formulae (see Eq. (1.7) and Fig. 1.5). A consistent solution of the associated slab
profile combines these independent reflection coefficients rj,j+1 by including the respective
retardations between the different layers.

Recursive Parratt formalism

A layered structure of N slabs, including the top layer (j = 0) and the bulk substrate (j =
N − 1), each with a refractive index nj , is shown in Fig. 1.57 . One possible implementation
for solving the reflection problem from multiple interfaces consistently, is the recursive
Parratt formalism [6, 12, 13]. The reflectivity R2 = |X0 |2 is calculated from the squared
modulus of the transition coefficient8 X0 , which can be derived, starting from the vanishing

5
For a single interface the refractive index of the semi-infinite bulk substrate is denoted by n1 , i.e. j = 1.
6
Due to absorption, (β > 0) the reflected intensity is always less than unity, even for angles smaller than
the critical angle of total reflection.
7
The indexation of the slabs is arbitrary and inconsistently used in literature. Here, the notation of the
program for data analysis, which was developed within this thesis, is used. The C++ syntax suggests
arrays of N elements labeled from 0 to N − 1.
8 R
The transition coefficient Xj = Tjj is the ratio between the reflected and transmitted wave amplitudes
at the interface j, in accordance to Fig. 1.5.
1.2 Calculation of the x-ray reflection pattern 6

Abbildung 1.4: Reflectivity plotted

against the vertical mo-
mentum transfer. There
Abbildung 1.3: Example with two inter- is destructive interfe-
faces. The reflectivity is rence where there is a
given by  red line and constructive
R = | B1 +B
A0
2 +···
|2 interference in between.

coefficient at the semi-infinite bulk substrate (XN −1 = 0), recursively via

(rj,j+1 + Xj+1 ϕj+1,j )

Xj = ϕj,j (1.9a)
(1 + rj,j+1 Xj+1 ϕj+1,j )

(kj,z − kj+1,z )
rj,j+1 = (1.9b)
(kj,z + kj+1,z )

ϕl,m = exp −2iei(l+m)π kl,z zm .

(1.9c)

Interfacial roughness and Parratt formalism

In a real system, the electron density profile ρe (z), and therefore also the refractive index
profile n (z) at an interface never follows a Heaviside step function Θ (z − z0 ) as assumed
in Sec. 1.2.3. At least atomic corrugation in the 1 Å regime is present.
For a single interface, following an error function or hyperbolic tangent profile, the reflec-
ted and transmitted wave amplitudes can be calculated analytically by solving Maxwell’s
equations [8, 14]. For an error function profile n (z) ∝ 21 [1 + erf (z)] a reflection coefficient
0 2
r0,1 = r0,1 e−kz is obtained. The reflection coefficient at a rough interface is modified from
r0,1 introduced in Eq. (1.9b) by an exponential damping term. A more detailed analysis in
second order DWBA9 theory performed by de Boer [15] shows that not only the averaged
vertical profile, but also the in-plane correlations of the roughness determine the exact
form of the damping factor. For uncorrelated roughness, the Nevot-Croce (NC) result is
valid, whereas for an interface with correlated roughness the Beckmann-Spizzichino (BS)
9
Distorted Wave Born Approximation
1.2 Calculation of the x-ray reflection pattern 7

Abbildung 1.5: Model

profile
with N
slabs,
including
the top
layer
(j = 0)
and the
semi-
infinite
bulk
substrate
(j =
N − 1).
1.2 Calculation of the x-ray reflection pattern 8

form has to be applied:

2
0
rj,j+1 = rj,j+1 e−2kj,z kj+1,z σj NC (1.10a)

2 2
0
rj,j+1 = rj,j+1 e−2kj,z σj BS (1.10b)

The roughness parameter σj2 denotes the width of the Gaussian associated to the error
function.
A refractive index profile, modeled by a series of slabs including interfacial roughness, is
described by
N
X −1
n (z) = nj (z) (1.11a)
j=0

    
z − zj−1 z − zj
nj (z) = nj erf √ − erf √ . (1.11b)
2σj−1 2σj

In the case of well separated interfaces with

σj  dj and σj  dj−1 for all slabs j, (1.12)

0
the modified reflection coefficients rj,j+1 can be used to calculate the reflection pattern
from the slab model Eq. (1.11) within the Parratt formalism Eq. (1.9).
0
The reflection coefficients rj,j+1 were derived for a single independent interface between
two semi-infinite slabs (i.e. n (z) asymptotically approaches a constant value in the limit
z → ±∞). As soon as the condition Eq. (1.12) is violated, i.e. the slab thickness approaches
the roughness of at least one of the associated interfaces, n (z) does not show distinct slabs
anymore, but a smeared out structure, where different layers interfuse with each other. In
this case the analytically obtained damping factors Eq. (1.10) are not applicable any more
[6] and other analysis methods have to be used.
Nevertheless, in some cases the reflectivity calculated with the exponential damping
factors Eq. (1.10) still gives a good approximation to the real pattern, even in cases where
Eq. (1.12) is strongly violated. The reason is that the intensity from a rough interface
decays rapidly, while the contribution from of a thin layer is relevant mainly for large
momentum transfers qz . In order to detect a layer of d = 5 Å thickness unambiguously,
the reflection pattern has in general to be analyzed at least up to a vertical momentum
−1
transfer of qz = π/d ≈ 0.6 Å . On the other hand, a roughness of σ = 3 Å results in a
damping of the reflected intensity of more than 6 orders of magnitude below the Fresnel
curve in the relevant q range. This example shows that the scattering signal from such a
profile often decays so rapidly that the background level is reached before sensitivity to
the detailed structure is achieved, and limitations of the model become relevant.
1.2 Calculation of the x-ray reflection pattern 9

1.2.5 Kinematical approximation and master formalism

Master formula
In the framework of the kinematical approximation, the x-ray reflectivity R2 (qz ) from a
given continuous electron density profile ρe (z) can be calculated by the so-called master
formula [6, 16]
R2 (q) = RF2 (q) |F (q)|2 (1.13a)
Z +∞
1 dρ (z) iqz
F (q) = dz e . (1.13b)
ρ−∞ − ρ+∞ −∞ dz
In the region of the critical angle where multiple scattering effects are dominant the ki-
nematical approximation is not applicable. On the other hand, Eq. (1.13) is an excellent
approximation in the regime well above the critical
p angle of total reflection, where the re-
flectivity drops below 10−3 , i.e. qz > 3qc = 6λ−1 πre (ρ−∞ − ρ+∞ ). R2 (q) can be separated
into the smooth and rapidly decaying Fresnel reflectivity RF2 (q) (see Eq. 1.8), representing
the reflection from a sharp step of the height h = (ρ+∞ − ρ−∞ ), and the structure factor
F (q), describing the interference pattern caused by the specific electron distribution ρe (z).

Refraction corrections
The presence of the total reflection plateau extending up to the critical angle shifts all the
features in the reflection pattern to slightly higher angles than predicted by the master
formalism. This can be taken into account by the refraction corrections, modifying the
wave vectors qz from Eq. (1.2) to
p
qz0 = 2k0 sin ϑ2 − αc2 . (1.14)
In general, the exact reflectivity falls somewhere in between the values calculated within
master formalism and the ones obtained by including the refraction corrections.

The slab model within the master formalism

Equation (1.13) provides an alternative approach to handle density profiles ρe (r) con-
structed with Eq. (1.11). Especially for profiles where the thickness dj of each slab is not
significantly larger than the respective roughness σj and σj−1 , an independent formalism is
strongly desired. Inserting the profile Eq. (1.11) into Eq. (1.13), the structure factor F (qz )
can be calculated analytically:
N −2
1 X 1 2 2
F (qz ) = (ρe,j+1 − ρe,j ) e 2 σj qz eiqz zj (1.15)
ρe,N −1 − ρe,0 j=0

In analogy, the reflectivity for many other relevant structures such as layering at interfaces
and surfaces, can be calculated directly with Eq. (1.13) within the kinematical approxima-
tion [3, 17, 18].