M.Theiss Hard- and Software for Optical Spectroscopy
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Analysis of optical spectra bycomputer simulation - frombasics to batch modeby Wolfgang Theiss

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Printed: 25.11.2002, 00:09 in Aachen, Germany

Analysis of optical spectra by computer simulation

Contents

I

Table of Contents
Foreword

2

Part I Title

3

Part II Why using spectrum simulation?

3

1 Overview ................................................................................................................................... 3
2 Multilayer ...................................................................................................................................
stacks - no alternative
3
3 Avoid approximations...................................................................................................................................
of simple analytical methods
5
4 Use spectrum...................................................................................................................................
simulation to check spectrometer hardware
5
5 Spectrum ...................................................................................................................................
simulation is very educational
6
6 Spectrum ...................................................................................................................................
simulation as pre-cursor of thin film design
7

Part III Basics of spectrum simulation

9

1 Overview ................................................................................................................................... 9
2 Optical constants................................................................................................................................... 9
3 Layer stacks,...................................................................................................................................
wave propagation
10
4 Spectra ................................................................................................................................... 14
5 Parameter...................................................................................................................................
fitting
15

Part IV The key to success: Opticalconstant models

15

1 Overview................................................................................................................................... 15
2 Drude model................................................................................................................................... 16
3 Oscillator...................................................................................................................................
models
18
4 Interband...................................................................................................................................
transition models
19
5 Varying composition:...................................................................................................................................
Master models
21
6 Composite...................................................................................................................................
materials: Effective dielectric functions
21

Part V Examples

22

1 Overview................................................................................................................................... 22
2 Batch fit ...................................................................................................................................
example22
3 Ellipsometrie:...................................................................................................................................
Investigate unknown semiconductor
24
4 Analyzing...................................................................................................................................
several spectra simultaneously
25

Index

0

Foreword

This document gives a short summary of several talks and documents about
spectrum simulation.
All the pictures are just screen shots, not prepared explicitly for this document.
In between the pictures there are comments that should guide you from slide toslide.
Most of the slides in the talks are interactive pictures: You can vary slider
positions and see what happens to the spectra. Unfortunately, in this static
document these dynamical impressions cannot be reproduced.
In the graphs displaying optical constants the real part is drawn blue, theimaginary one is given in red.
In the case of spectrum fits, the measured spectra are always in red, thesimulated spectra in blue.
All simulations have been performed with our SCOUT software which iscommercially available.

Aachen, November 2002

Analysis of optical spectra by computer simulation

1

Title

3

Title
Title, author, company and overview:2

Why using spectrum simulation?

2.1

Overview
Analyzing optical spectra by computer simulation (based on physical models) is a standard methodin spectroscopic ellipsometry. In the case of reflectance and transmittance spectroscopy it is not
yet well-established. Here are some reasons for applying this method:
1.
2.
3.
4.
5.

2.2

In the case of multilayer stacks there is no alternative
Simple data analysis procedures are usually based on some crude assumptions which can be
avoided using a simulation approach
Simulated spectra can be used to check the qualitiy of spectroscopic measurements
Spectrum simulation is ideal for teaching optics and spectroscopy
Well-working simulations of measured data can be pre-cursors of successful designs of thinfilm products

Multilayer stacks - no alternative
In the case of multilayer stacks there is no alternative to spectrum simulation. Only on the basis ofa physical model the complicated spectral features can be understood. The example below shows
the comparison of the measured (red) and simulated reflectance (blue) of a stack of 11 layers on
silicon:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Why using spectrum simulation?

4

The increase of one of the layer thicknesses (layer 5, marked yellow) by 10 nm leads tocomplicated variations of the spectrum which can only be handled by a reliable physical model:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

2.3

Why using spectrum simulation?

5

Avoid approximations of simple analytical methods
Simple analytical methods are most often based on simplifying assumptions. Examples of simple
evaluation procedures are· the conversion of transmittance spectra to absorbance· the conversion of diffuse reflectance spectra to so-called Kubelka-Munk functions· thickness analysis of reflectance or transmittance spectra by the Fourier-transform technique· direct determination of optical constants from reflectance and transmittance measurements inthe case of simple geometries
All these methods can be replaced by spectrum simulation which can be applied avoiding most of
the simplifying assumptions.
However, spectrum simulation is not as easy as the techniques mentioned above, and thedevelopment of a suitable optical model may require some time and experience.

2.4

Use spectrum simulation to check spectrometer hardware
Simulated spectra of well-known and reproducible samples can be used to check the performanceof experimental setups.
A quick, simple and very useful test for reflectance accessories is to compare the measured
reflectance of a silicon wafer (for a given angle of incidence and polarization) with simulated data.
The simulation can be based on literature data for the optical constants of silicon (and the nativeoxide on top of the wafer):

A similar simple test for correct reflectance and transmittance measurements can be done withconventional microscope slides. The measured spectra should not differ from the simulated ones
by more than 1 or 2 percent:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

2.5

Why using spectrum simulation?

6

Spectrum simulation is very educational
Using a spectrum simulation software, you can easily try what happens if you· change a layer thickness· use a different substrate· change the angle of incidence· work with a polarizer· add a surface oxide· ....
All these investigations can be done without any experimental effort and costs.
The example below shows how the optical properties of charge carriers (electrons, holes) can be
explained by interactive variation of the relevant quantities such as concentration and damping:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

2.6

Why using spectrum simulation?

7

Spectrum simulation as pre-cursor of thin film design
Successful analysis of measured spectra of single and multiple layers can be pre-cursors of
reliable thin film design. If the optical constants of the used materials are known, and if interface
effects of multilayers are understood and included in the model, one can predict and design theproperties of new thin film products with a minimum of experimental work.
Thin film design is very similar to thin film analysis. First a target function (e.g. a wanted reflectancespectrum, a certain color or an integral transmittance value) is defined. Then some of the model
parameters like layer thicknesses are (interactively or automatically) varied until the target isreached.
As an example the transmittance and reflectance spectra (45 deg angle of incidence) of an opticalfilter (dichroic mirror) is shown below. The task of the layer stack is to separate radiation below andabove 550 nm in a color display device (beamer):© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Why using spectrum simulation?

8

Spectrum simulation is widely used to design and optimize architectural glass coatings. Based ongood optical constant models for sputtered oxides and metals, the appearance of multilayer
coatings on glass panes is predicted with high precision. The example given below shows
measured and simulated spectra of a so-called solar control coating and the corresponding colors:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Why using spectrum simulation?

3

Basics of spectrum simulation

3.1

Overview

9

Analysis of optical spectra by computer simulation is done in 5 steps:
1.
2.
3.
4.
5.

3.2

Define the optical constants of all materials in the system
Setup the layer stacks
Define the spectra which are to be computed and compared to measured ones
Select the model parameters that are to be varied ('fitted') in order to minimize the difference
between simulated and measured spectra
Change the model in an interactive or automatic way until the measured data are reproducedwith acceptable quality

Optical constants
Materials appear in Maxwell's equations via the complex dielectric function. The square root of thisquantitiy is called the refractive index. Both the refractive index as well as the dielectric function are
sometimes called 'Optical constants'.
Each material has a very characteristic frequency dependence of its optical constants. The key togood spectrum simulation results is the right choice of optical constant models. This very important
issue will be discussed in a separate section below.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

3.3

Basics of spectrum simulation

10

Layer stacks, wave propagation
Light waves are partially reflected and transmitted at interfaces between two materials withdifferent optical constants. The amplitudes of the reflected and transmitted waves are given by
Fresnel's equations:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Basics of spectrum simulation

11

In the case of a single layer between two 'halfspaces' the total reflected and transmitted waves are
the sum of many partial waves. The summation can be done conveniently making use of ageometric series:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Basics of spectrum simulation

12

The phase shift f leads to interference fringes in the case of a transparent layer:

The amplitude of the reflected and transmitted wave of a multilayer stack can be computed using amatrix method or by recursively applying the result for a single layer (the geometric series shown
above) as sketched below. The 'recursion method' can easily be extended to the case of thicklayers (like glass plates) which do not exhibit interference fringes in optical spectra (incoherent
superposition).

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Basics of spectrum simulation

13

If the thickness of a layer is not constant within the illuminated sample spot one has to averagereflectance values for different values of the thickness. This can be done with low computational
effort if the Fourier transform of the thickness distribution can be computed analytically. Here is an
example of a Gaussian thickness distribution showing the influence of the thickness averaging to
the envelope of the interference pattern:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

3.4

Basics of spectrum simulation

14

SpectraSpectrum simulation can be done easily for· reflectance· transmittance· ellipsometry· ATR (attenuated total reflection)at arbitrary angles of incidence and polarization.
The SCOUT software of M.Theiss Hard- and Software also contains a method for the simulation ofphotoluminescence or fluorescence spectra:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Basics of spectrum simulation

15

In the case of multiple spectrum fits each spectrum should have an individual weight for thecomputation of the total fit deviation (i.e. the difference between measured and simulated
spectrum).

3.5

Parameter fitting
The last steps of spectrum analysis by computer simulation are the selection and adjustment of
those model parameters which are to be determined by the method. Since the total fit deviation will
depend on the fit parameter values in a very nonlinear and in most cases unpredictable way, there
may be many local minima in addition to the wanted global minimum of the fit deviation. Although
there are minimization algorithms which may escape from local minima, they are usually very slow
and their application is not recommended for spectrum fitting.
It is more efficient in most cases to reduce the parameter ranges before the actual minimization
work starts. This can be done interactively or by appropriate automatic test computations. A
common problem, for example, is to find the right interference fringe order in the simulated
spectrum. This can be solved quite often by scanning the thickness value on a fixed set of values
in a pre-defined search range ('grid fit'). Taking the best thickness value of this test series as
starting value for the thickness turned out to be sufficient in many cases.

4

The key to success: Optical constant models

4.1

Overview
The most important step in spectrum simulation is the choice of the optical constants. If thematerials in the system under investigation cannot be described with fixed literature data, flexible
models have to be used. Three basic types of excitations are possible in most materials:· Acceleration of free charge carriers by the electric field of the light wave, usually described by the© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation
The key to success: Optical constant models

16

Drude model or its extensions· Excitation of vibrational modes, i.e. oscillations of charged parts of molecules or crystal lattices.
Vibrational modes are taken into account using oscillator models.
· Optical interband transitions of the electronic system. These phenomena can be described byoscillator terms, Tauc-Lorentz models in the case of crystalline materials or OJL models in thecase of amorphous systems.
Quite often there is a large gap between the vibrational modes in the infrared and interband
transitions in the UV. In this case the material is more or less transparent in the visible, with a small
imaginary part of the refractive index, and an increase of the real part from the red to the blue
(normal dispersion). In the range 1 ... 3 eV in the example below the optical constants could beapproximated by the phenomenological Cauchy formula. However, if possible, the application of aphysical model is preferred.

4.2

Drude model
The classical Drude model of free charge carriers leads to a simple expression of the susceptibility
with only two parameters, the plasma frequency and the damping constant. If the effective mass isknown, these quantities can be directly related to the charge carrier density and their mobility, or
the resistivity of the material. In most cases of doped semiconductors or metals the Drude model
works quite well.
However, sometimes the simple Drude model is not appropriate as shown below for the case of an
ITO layer on glass.The fit in the whole spectral range suffers from the assumption of a constantdamping of the electrons, independent of frequency. In this case the electron mobility is limited byscattering at ionized impurities (the doping atoms), an effect which leads to a certain frequency
dependence of the damping constant.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation
The key to success: Optical constant models

17

An extended Drude model with a (still quite simple) frequency dependent damping constant leads
to a significant improvement of the fit with much more reliable results for the film thickness and theother model parameters such as gap energy and resistivity:© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation
The key to success: Optical constant models

4.3

18

Oscillator models
Vibrational modes (with resonance frequencies that depend on the masses of the atomic coresand the strength of the restoring forces) leave 'finger prints' of a material in the infrared. These areused in numerous applications for material identification in the chemical industry.
A rough description can be achieved by summing up harmonic oscillator terms with threeparameters: The resonance frequency, the damping constant (which determines the halfwidth ofthe corresponding absorption band) and the so-called oscillator strength (which is proportional tothe concentration of the microscopic oscillators).

Extensions of the harmonic oscillator model are required if the line shape is not a Lorentzian. Witha fourth oscillator parameter, the so-called Kim model (shown below) can describe both Gaussianand Lorentzian line shapes of absorption bands, and any lineshape in between these two
extremes.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation
The key to success: Optical constant models

4.4

19

Interband transition models
Interband transition models are not easy to model. They are usually quite asymmetric, very strong
and in most cases several transitions overlap each other. Often it is not even easy to see how
many excitations one should use.
In addition, theoretical quantum mechanical considerations result in expressions for the imaginary
part of the dielectric function only. The corresponding real part must be constructed making use of
the Kramers-Kroning relation. Fortunately, the required Hilbert transform can be performed in two
steps with Fast Fourier Transform algorithms which makes the computations reasonably fast on
modern computers.
The so-called OJL model shown below has turned out to be very successful for amorphous oxides
and nitrides. The list of materials that can be described with this still rather simple model contains
SiOx, GeOx, BiOx, TiOx, SnOx, ZnOx, ...

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation
The key to success: Optical constant models

20

The example below shows the fit of a reflectance and transmittance spectrum of a SiOx layer on
glass, making use of the OJL model:

Crystalline materials can be described quite well by a sum of several Tauc-Lorentz models for© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation
The key to success: Optical constant models

21

interband transitions. An example will be shown in the next section.

4.5

Varying composition: Master models
Materials with varying composition like non-stochiometric oxides or ternary or quaternarycompound semiconductors have - of course - optical constants that change with composition. The
example below shows the case of AlGaAs with varying Al content.
A model based on 8 Tauc-Lorentz interband transition terms has been fitted to literature data
available for several Al content (x) values. 33 parameters like gap energies and damping contants
have been determined for each individual value of x. Then the development of each parameter withx has been described by suitable polynomial expressions such that a smooth variation of the
optical constant model with Al content x is achieved. This so-called master model is used todescribe the optical properties of a AlGaAs superlattice with alternating layers of high and low Al
content.

4.6

Composite materials: Effective dielectric functions
Composite materials like clusters embedded in a host, foams, porous materials or suspensions
can be described by so-called effective dielectric functions if the dimensions of the microscopic
inhomogeneities are much smaller than the wavelength of light. They behave like homogeneousmaterials with optical constants which are an average of those of the constituents. So-called
effective medium theories gives mixing rules and formulas. Unfortunately, there is not a single
unique mixing method but several concepts are possible. A discussion of this topic andrecommendations for the right choice of effective medium theories are outside the scope of thisdocument.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

5

Examples5.1

Overview

Examples22

Finally some simple and advanced spectrum simulation applications are presented, in addition tothe ones already shown above. The examples are· Automated analysis of reflectance spectra of Ag layers on glass· Analysis of an unknown new semiconductor with ellipsometry· Simultaneous R and T analysis of CdS layers· Determination of molecular orientation by analysis of several infrared spectra· Porosity profile determination by simultaneous simulation of 8 reflectance spectra· Combined reflectance and ellipsometry analysis of thin films

5.2

Batch fit example
Once a working model for an analytical problem has been developed, spectrum simulation can be
automized in order to process large series of spectra. Here a simple example is presented the goalof which was to determine the sputtering rate of a Ag deposition device.
A sequence of samples have been prepared with sputtering times between 1 and 23 seconds. The
reflectance spectra have been analyzed with a simple model of Ag on glass (based on literature
data for the optical constants). Since only the Ag layer thickness is unknown the fits are done very
quickly.

The next graph shows the obtained thickness values vs. sputtering time. From the slope a
sputtering rate of 1.3 nm/s can be deduced.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Examples23

The plot of the fit deviation shows that the fit is bad for layers below 8 nm thickness. Here themodel does not work well. The reason is the island growth of Ag on glass: Below a certain
thickness threshold there is no continuous Ag film, but rather an island structure. In these cases aneffective medium approach describing an Ag/air mixture is more appropriate.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

5.3

Examples24

Ellipsometrie: Investigate unknown semiconductor
This example demonstrates the determination of the optical constants of an unknown
semiconductor on a SiO2/Si substrate by ellipsometry. Using several Tauc-Lorentz terms thefollowing reasonable fit was achieved:

The fit can be improved introducing a thin surface layer which represents surface roughness. The
layer is an effective medium mixture of the unknown material and air. The obtained opticalconstants differ not very much, but significantly from the ones obtained without surface roughness.
In important cases the assumption of the existance of a surface roughness should be confirmed byan independent method such as AFM.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

5.4

Examples25

Analyzing several spectra simultaneously
In order to increase the reliability of the obtained parameters, one can analyze more than one
spectrum which may result in much more significant spectral information. In the following several'multiple spectra' cases are shown.
In the case of transparent substrates such as glass plates one can measure R and T and analyzeboth spectra. In the example below the thickness of a CdS layer (with surface roughness) isdetermined.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Examples26

Changing the angle of incidence of the illuminating light wave one can change the direction of theelectric field in the sample. The next example shows - as an artificial demo with one model
oscillator - how the reflectivity of a layer of ordered molecules on a substrate changes with angle.
Fitting the spectra recorded at several angles of incidence one can determine the orientation angleof the molecules.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Examples27

Here is a real case of molelcular orientation analysis: For a layer of perylene molecules on a Si
wafer the reflectance spectra taken at several angles of incidence are fitted simultaneously. For
each vibrational mode the orientation angle with respect to the surface normal of the Si wafer could
be determined. From the angular information the absolute orientation of the molecules was finallydeduced.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Examples28

The next example shows the analysis of 8 reflectance spectra (taking at different angles ofincidence and polarization) of a porous polymer on a metal substrate. The porous layer was
sampled in 5 sublayers. For each sublayer the volume fraction of the polymer (f1, ..., f5) was fitted
independently, in addition to the total layer thickness. The 8 spectra contain enough spectral
information for a unique determination of the density profile.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Examples29

Finally an example of a combined reflectance and ellipsometry investigation is given. The opticalconstants of a nitride layer as well as the thickness were to be determined. An OJL model wasused to model the optical constants. Both ellipsometry and reflectance could only be fitted in highquality working with two layer stacks with slightly different nitride thickness. The reason for this isthat the measurements have not been performed on exactly the same sample position.

© 2002 Wolfgang TheissAnalysis of optical spectra by computer simulation

Examples30© 2002 Wolfgang Theiss