2010 Kindeya Thesis PDF

Implementation of a CCD detector to dual-
broadband rotational CARS and

measurements on N2O
Master of Science thesis August

by Alem Kindeya 2010
Division of Combustion Physics

Department of Physics
Lund University
2010
ALEM KINDEYA
MASTER THESIS REPORT
Division of Combustion Physics, Lund University Page 2

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ALEM KINDEYA
Implementation of a CCD detector to dual-broadband

rotational CARS and measurements on N2O
Master of Science thesis
Alem Kindeya

Department of Physics
Faculty of Engineering LTH
LUND UNIVERSITY

2010
ALEM KINDEYA
© Alem Kindeya
Lund Reports on Combustion physics, LRCP-141
Lund, Sweden, August 2010
Alem Kindeya
Department of physics
Faculty of Engineering LTH
Lund University
P.O.Box 118
S-221 00 Lund, Sweden

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ALEM KINDEYA
Abstract
The master thesis work involved the implementation of a CCD detector to a dual-
broadband rotational coherent anti-Stokes Raman spectroscopy (DB-RCARS) setup, and
temperature measurements on N2O. This included the investigation of seven different
setting options of the detector to identify the best possible option of the camera regarding
a good precision temperature measurement. Additionally, a theoretical library for N2O at
room temperature and atmospheric pressure condition was developed. The spectroscopic
constants of the molecule are the inputs of the temperature library.
The temperature precision was found to be marginally influenced by the three basic
setting options (pre-amplifier, readout rate and binning). This indicates that it is possible
to choose any level within these setting options as long as the signal level is high (on the
order of thousand of counts). The precision was found to be independent of the binning of
pixels in the spectral dimension. The high sensitivity and high capacity output amplifiers
gave similar precision, but the signal is around five times stronger for the former
amplifier than the later. The threshold intensity above which it is possible to achieve the
smallest possible precision for the current CCD camera was identified for full vertical
binning mode to be around 1000 counts.
The measurements on N2O were made to understand the spectroscopic features of the
molecule and try to evaluate its potential for temperature measurement purposes. As a
result, the value of temperature precision was found to be better than for N2. Generally,
the N2O molecule showed a good potential for temperature measurements at room
temperature conditions.

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Contents
Abstract..........................................................................................................5
Contents..........................................................................................................7
Chapter 1: Introduction...............................................................................9
1.1. Purpose of the project.......................................................... 10
1.2. General overview................................................................. 10
Chapter 2: Background Physics................................................................11

2.1. Rotational energy of molecules........................................... 12
2.2. Laser- based Combustion Diagnostic techniques............... 13
Chapter 3: Coherent anti-Stokes Raman spectroscopy (CARS)........... 14

3.1. Introduction......................................................................14
3.2. Dual-broadband rotational CARS....................................16
3.2.1. Experimental Setup of rotational CARS...... 17
Chapter 4: Andor CCD Camera.............................................................. 18

4.1. Safe Camera Operation.................................................... 19
4.1.1. Environmental Conditions................................ 20
4.1.2. Cooling............................................................. 20
4.2. Working principle of CCD detector................................ 23
4.2.1. Preamplifier gain............................................... 24
4.2.2. Readout rates..................................................... 25
4.2.3. Binning.............................................................. 26
4.3. CCD Performance........................................................... 27
4.3.1. High Sensitivity (HS) output amplifier............. 27
4.3.2. High Capacity (HC) output amplifier................ 28
Chapter 5: Experimental Work...............................................................30

5.1. Implementation of CCD Camera and testing procedure......30
5.2. N2O for temperature measurement..................................... 41
Chapter 6: Result and Discussion............................................................. 43

6.1 Detector Investigation........................................................ 43
6.1.1 Pre-amplifier gain............................................. 43
6.1.2 Read-out rates................................................... 47
6.1.3 Binning.............................................................. 50
6.1.4 Signal strength.................................................. 53

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6.1.5 Instrument function............................................54

6.1.6 Influence of intensity on precision and SSQ.... 57
6.1.7 Comparison of FVB and Multi-track mode...... 61
6.2 Measurement on N2O......................................................... 64
6.2.1 Temperature Precision....................................... 64
Chapter 7: Summary and Outlook........................................................... 69
Reference......................................................................................................71
Acknowledgement.......................................................................................74
Appendix......................................................................................................75

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Chapter 1
Introduction
The global energy need is expected to increase the coming decades because of many
reasons: fast economic growth of some developing countries, expansion of high level
facilities in developed countries, the global population increase in developing countries,
etc. This energy might come from different sources, but combustion has been the basic
sources of energy for many years. People were hugely dependent on combustion through
years for heating, cooking and related activities. The dependence of energy from
combustion processes is expected to increase for the future as well. This means that
combustion processes will continue to be the main source of energy despite it has
negative impact to the environment as it causes global warming which is a burning issue
this time. Figure 1.1[1] shows a prognosis of the global energy need until 2060. Therefore,
combustion has to be efficient to generate highest possible energy from certain amount of
fuel, and to minimize environmental impact. To make a combustion process very
efficient, the process should be understood more clearly on a molecular level.
Unfortunately, this is not easy, because, the combustion process is very complicated since
it involves many elementary reactions and often has complex fluid flow. To really
understand the basic processes, there is a demand for high spatial and temporal resolution
measurements. The need for spatial resolution, temporal resolution and the importance
for non-intrusive measurement are the main reasons for the development of laser based
combustion diagnostic techniques. There are many laser based techniques which can be
used for diagnostic purposes as discussed in chapter two. The technique used in the
current study is dual-broadband rotational coherent anti-stock Raman spectroscopy (DB-
RCARS), which previously has shown to be a good technique for temperature
measurements. Nitrogen is usually probed with this technique.
New and renewable

sources
Organic and
fossil fuel
Figure 1.1: Plot of global energy use as a function of years. The use of organic and fossil
fuel is expected to increase at least until 2020 and then remain relatively constant [1].

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1.1. Purpose of the project

The main aim of this project is to implement a new CCD camera to a dual-broadband
rotational coherent anti-Stokes Raman spectroscopy (DB-RCARS) setup and test options
of the CCD detector to achieve high precision temperature measurements. The second
aim is to develop a theoretical library for N2O and make temperature evaluations. This
helps to understand spectroscopic features of the molecule since the theoretical library is
developed using spectroscopic constants (rotational constant, line width, non-resonance
susceptibility, statistical weight, etc.). The current work is limited to measure room
temperature at atmospheric pressure conditions. But, the outlook of doing this
investigation is to extend the capability for temperature measurement purposes in a real
combustion environment since temperature is one important ingredient of the combustion
process which can be used as an input to model the reality.
1.2. General overview

The two main tasks which were done in this project are detector investigation and
measurement on N2O. The first task regarding detector investigation was basically the
main task of the project. The final goal of this investigation was to identify the best
possible setting option of the CCD detector to achieve a high precision temperature
measurement. Seven different investigations were made throughout the work. It is shown
that many options do not affect the precision very much. Examples of these are: pre-
amplifier setting, binning and readout rates.
The second task was code development for N2O using the spectroscopic parameters
for the molecule. The experimental data on N2O was fitted with theoretical library as
discussed in Chapter 6. The temperature was evaluated to check how good the new code
will work at room temperature condition as compared to N2 measurement. In general, the
new code looks to be promising for room temperature and atmospheric pressure
measurement. To sum up, the measurement on N2O shows that it has a potential to
measure temperature, but it needs a detailed study to investigate the diagnostic capability.

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Chapter 2
Background Physics
The energy-level diagrams of molecules are significantly more complicated than those of
atoms. This is because of the fact that molecules have different states corresponding to
vibrational and rotational motion apart from the energy level to different electronic
arrangements. The electronic transitions which happens when valence electron of the
molecule are excited from one level to another, vibrational transitions which happens due
to periodic displacement of the atom in the molecule from its equilibrium positions and
the rotational transitions due to rotation of the molecule about its center of gravity. These
all possible states are quantized to certain discrete energy level which shows energy
quantization according to the concept of quantum mechanics. The solution for the
Schrödinger equation gives the energy of each quantum level. Transitions can take place
between levels E1 and E2 provided the appropriate amount of energy ΔE = E2 - E1, can
either be absorbed or emitted by the system [2], see Figure 2.1.
E2
ΔE
E1
Figure 2.1: Schematic diagram for two rotational energy levels.
According to Planck, the absorbed or emitted radiation can assume the form of
electromagnetic radiation which can be expressed in a simple form as can be seen in
equation 2.1 [2].
E
v (2.1)
h
where h is Planck‟s constant and ΔE is the energy difference between two rotational
levels. The electromagnetic radiation emitted from the molecule carries spectral
information about the probed species. The knowledge of the energy difference between
two rotational levels helps to probe a certain molecule using different techniques based
on the kind of information which is needed to be investigated. For instance, the spectrum
from the CARS signal gives temperature information. The principle of rotational
transition and the use of different laser based combustion diagnostic techniques have
been discussed in section 2.1 and section 2.2 respectively.

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2.1. Rotational energy of molecules
The rigid rotator of diatomic molecule can be given as an example to show how to model
the rotational energy, see Figure 2.2. The molecule rotating about its center of gravity has
a certain moment of inertia due to its mass. The masses m1 and m2 have moment of
inertia I1 and I2, respectively. The length (R) of the rigid bond between m1 and m2 is
given by the sum of the radius of both masses rotating about the center. The moment of
inertia of the whole system can be expressed as follows:
I  m1r12  m2 r22 (2.2)
Assuming that the measurement is being made from the center of mass point for a two
mass system, then the center of mass condition can be as follows: m1r1  m2 r2 [3], where r1
and r2 locate the masses and the center of mass lies on the line connecting the two
masses. Substituting this expression into equation 2.2, the final expression for the total
moment of inertia will be:
m1m2 2
I R   R2 (2.3)
m1  m2
where μ is reduced mass, and R is the sum of r1 and r2.
Figure 2.2: Schematic diagram of a rigid rotator rotating about the center of gravity
(center of mass) [3]
The solution for the Schrödinger equation gives the allowed rotational energy level of a
rigid diatomic molecule using the following expression [2]:
h2
EJ  2 J ( J  1)  BJ ( J  1) (2.4)
8 I
where J = 0, 1, 2… , are rotational levels, I is the moment of inertia and B is the
rotational constant, which is typical for an individual molecule. Finally, it has to be
known that the consideration of rigid body rotator is just an approximation since all
bonds are elastic to some extent especially at high J-quantum numbers. In general, the
whole discussion of diatomic molecules could apply to polyatomic linear molecules [2].
But, polyatomic molecules have smaller rotational constants because of heavy mass.

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2.2. Laser- based Combustion Diagnostic techniques
Laser-based diagnostic techniques are very crucial tools to understand the combustion
process [4]. These can be classified as coherent and incoherent techniques. Examples of
coherent technique are polarization Spectroscopy, CARS, etc, which are basically used to
probe major species. These have strong laser like signals and they are interference
tolerant which is good, but the process is non-linear and the spectra are fairly
complicated. Incoherent techniques such as laser induced fluorescence (LIF) and Raman
scattering are linear processes, which are used to probe minor species. The good thing
with incoherent techniques is that they are intensity independent, but the large solid angle
and interference sensitive nature can be regarded as limitations. Another example of an
incoherent technique is Rayleigh scattering which is an elastic scattering process. This is
used to measure temperature if mixture composition is known. Both LIF and Rayleigh
scattering can be used for 2-D imaging. The schematic diagram of different scattering
processes is given in Figure 2.3.
Figure 2.3: Schematic diagram of Rayleigh scattering, anti-Stokes and Stokes Raman
scattering on the left side. LIF is normally emitted towards the shorter wavelength
indicated in the middle diagram. Near resonance Raman scattering is shown on the right
side [4]
The CARS technique could be used in rotational or vibrational approach depending on

which energy state or branch is probed. This technique is mostly used for temperature
measurement purposes, but it can also be used to measure concentration. In rotational
CARS process nitrogen molecule is often probed to measure temperature in a combustion
environment. The main reason is that, nitrogen is found throughout the combustion
process (from reactant to product in a fuel + air mixture) since it is an inert gas. This
helps to follow the combustion process of a flame. Air contains roughly about 78 % of
nitrogen and about 21 % oxygen, which means that the concentration of nitrogen is high
in fuel air combustion. Additionally, the fact that nitrogen is a major species makes it a
good candidate for temperature measurements using the CARS technique. The physics
behind the CARS process and its effectiveness for temperature measurements is
explained in chapter three.

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Chapter 3
Coherent anti-Stokes Raman spectroscopy (CARS)
3.1. Introduction
Coherent anti-stokes Raman spectroscopy (CARS) was experimentally discovered at

Ford in 1965 by P.D. Marker and R.W. Terhune [5]. The intention of their study was to
investigate different nonlinear optical effects arising from an induced optical polarization
third order in the electric field strength. The CARS process is a four wave mixing process
based on the nonlinear process via the third order susceptibility ( ). Then the CARS
signal is a result of the non-linear response of the molecule for an electric field. In other
words, three laser beams are focused to a measurement point. If the difference between
the two laser beams is in a vibrational or rotational resonance with a certain molecule, an
oscillating polarization with a Raman frequency (ωR = ω1- ω2) will be induced [6]. Then
the CARS signal will be the sum of Raman frequency (ωR) and the frequency of the
probe beam (laser 3 at 532 nm), see Figure 3.1.
Q-branch transition S-branch transition
Figure 3.1: Energy level diagram for vibrational CARS process (a), and pure rotational
CARS process (b). Qv –branch transitions are between two vibrational levels (v → v+1)
within the same rotational states. Sv –branch transitions are between two rotational
levels (J → J+2) within the same vibrational level [6].

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The induced polarization of the CARS process is a nonlinear function of the applied
electromagnetic field which is expressed as follows:
(3.1)
The third order susceptibility ( ) contains spectral (temperature) information and it is

the heart of CARS process. The susceptibility can be further divided into two terms: the
resonance susceptibility which contains the information about molecular resonances and
the Boltzmann population distribution. The second is non-resonance term which is related
to the electronic response of molecules in the probe volume [6].
The overall CARS signal can be expressed as [4]:
(3.2)
where is the CARS signal frequency, , & are intensities of the three laser
beams involved in the process, is the CARS suceptibility of the medium, l is the
interaction length in the probe volume and the term in bracket represents the extent to
which the phase-matching conditions is fulfilled. If the phase-matching condition is
fulfilled, this term will assume a value of 1. The phase mismatch factor ( ) and
interaction length (l) depends on the geometry of the three mixing beams and they
determine the intensity of CARS signal (S) [4]. Different phase matching schemes can be
employed, but there is a trade-off between spatial resolution and signal strength. The
signal strength is higher for collinear phase matching schemes, but the spatial resolution
will be lower due to extended interaction length. Thus the beams have to be crossed in
order to improve the spatial resolution. The principle of planar BOXCARS phase
matching is to arrange the three beams in such a manner that the two beams are
superimposed on top of each other and propagate parallel to the third beam. A schematic
diagram of collinear and planar BOXCARS phase matching can be seen in Figure 3.2[7].
Figure 3.2: Phase-matching schemes: (a) Collinear phase matching and

(b) planar BOXCARS phase matching [7]

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3.2. Dual-broadband rotational CARS
The pure rotational CARS technique was first developed in the beginning of 1980 as an
alternative for the viberational CARS technique [8]. But, a big improvement was
achieved when dual-broadband rotational CARS was demonstrated in 1986 [9]. The idea
of the dual-broadband approach is to replace the two narrow beams (pump and Stokes
beams) by broadband beams from a dye laser using a red stable dye, see Figure 3.3. The
dye is pumped by Nd:YAG laser at 1064 nm which is frequency doubled to give laser
light at 532 nm. About 90 % of the light from the Nd:YAG laser is used to pump the dye
laser and the rest (10 %) with a narrow band width (FWHM = 0.7 cm-1) is used as a probe
beam. The advantage of using broadband pump and Stokes beams is basically to achieve
a spectral averaging effect which then improves temperature precision. Additionally, the
use of a broadband dye laser gives a complete rotational CARS spectrum from a single
shot measurement. The frequency of the narrow probe beam comes out very close to the
CARS spectrum. The stray light from the 532 nm beam should then be suppressed using
an appropriate optical filter since it sometimes can be difficult to make measurements
without discriminating the stray light.
Figure 3.3: Schematic view of an energy level diagram for Dual broadband rotational
CARS process, where and are broadband lasers and 3 is a narrow band laser [6].
Generally speaking, a rotating molecule has a time-dependent polarizability. This means

that the molecule is Raman active, then it will give rotational CARS signals for the
transitions J→J+2 (∆J= ±2). The origin of the selection rule is from the fact that the
polarizability returns to its initial value twice for each revolution.

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3.2.1 Experimental Setup of rotational CARS
The experimental arrangement of dual-broadband rotational CARS is shown in Figure

3.4. The Nd:YAG laser at 1064 nm, frequency doubled to produce green laser light (at
wavelength of 532 nm). Part of the green light is split-off (about 10 %) before the dye
laser to be used in the CARS experiment and the remaining green light will be used to
pump the dye laser [10]. The dye laser peaks around 630 nm and it has bandwidth of about
250 cm-1. There are also different optical components used in the setup such as lenses
beam splitters, filters etc.
Figure 3.4: Experimental setup of dual-broadband rotational CARS. BS, beam splitter;
D, dichronic mirror; L, lens; IP, Interaction point; BD, beam dump; and SP, short-pass
filter[10].

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Chapter 4
Andor CCD Camera

The Andor Newton camera has many setting modes that can be chosen depending on
different kinds of investigations. Design of the system is reasonably advanced and the
cooling system involves vacuum conditions which can achieve efficient cooling [11]. The
maximum temperature difference that a thermoelectric (TE) device can achieve depends
on the heat load created by the CCD, number of cooling stages of the TE-cooler and
operating current. The highest sensitivity of the detector system is usually achieved at a
very low temperature, so that, the system must be operated in a vacuum to cool the sensor
[12]
. To say the cooling system is efficient, the sensor should be the coldest component of
the camera. Figure 4.1 shows the physical arrangement of different components inside
the camera.
Figure 4.1: UltraVacTM metal hermetic vacuum sealing technology. This design allows
for the requirement of only one window in front of the sensor enabling maximum photon
throughput [12].
This camera has also back-illumination sensor structure which helps to get high
sensitivity and high signal-to-noise ratio. Back illumination is a sensor structure which
increases the amount of light entering each pixel. The front-illuminated system on the
other hand has obstacles such as metal wiring and transistors in-front of the sensor [13]. In
other words, the incident light in a back-illumination sensor structure reaches the sensor
without facing any obstacles. This helps to achieve a better signal-to-noise ratio than that
of front- illuminated sensor structure. Figure 4.2 shows the back-illumination and front-
illumination structures.

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Figure 4.2: Front-illuminated structure in the left and, back-illuminated structure in the
right [13].
4.1. Safe Camera Operation
Safety is an important issue for a long lasting service of any equipment especially
electronic devices such as CCD detectors since they are more sensitive. The Andor CCD
camera is a precision scientific instrument containing fragile components such as the
sensor, which can be destroyed unless it is handled with care. Andor plc has marked a
number of screws on the detector head with red paints to prevent tampering since there
are no user-serviceable parts inside the camera, see Figure 4.3. If these screws are
adjusted for some reason, the warranty of the camera will be void [11]. Additionally, due
attention should be given for some equipment which can cause problems for the camera.
Example: plasma source, pulsed discharge optical source, radio frequency generator and
x-ray instruments [11]. Some of the most basic safety precautions and safe camera
operation are discussed in sections 4.1.1 and 4.1.2.
Figure 4.3: Newton CCD camera. The screws marked in red are not user-serviceable [11]

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4.1.1. Environmental Conditions

Conducive environmental condition can be considered as a pre-requisite for safe camera
operation. This makes the camera to function without having an external influence which
can affect the measurement results or it can further damage the detector. The Andor plc
has listed some standard environmental conditions which are important to be considered
as can be seen below [11]:
 5 V dc with 15 Watts
 7.5 V dc with 30 Watts (PS-25 only)
 ± 25 V dc with 3 Watts
 Indoor use only
 Temperature 5 °C to 40 °C
 Maximum relative humidity 80 % for temperature up to 31 °C, decreasing
linearly to 50 % relative humidity at 40 °C
The points listed above are some of the safety precaution which should be implemented
in any kind of measurement as far as favorable environmental condition is concerned.
Read the user manual for more detail information about safety precaution [11]
4.1.2. Cooling
Detector cooling is an important process of decreasing the temperature of the CCD chip
and to reduce the noise created due to temperature. This means, cooling the CCD detector
helps to reduce the dark signal and its associated noise. The CCD is cooled using a
thermoelectric cooler (TE). The working principle of TE cooler is actually acting as a
heat pump, i.e. it achieves temperature difference by transferring heat from its „cold side‟
(the CCD-chip) to its „hot side‟ (the built in heat sink) [11]. This implies that the minimum
absolute operating temperature of the CCD depends on the temperature of the heat sink.
But, the failure to control the temperature could result in head overheating or it may
disable the system. Overheating may occur if either of the following occurs [11]:
 The air vents on the side of the head are accidentally blocked or there is
insufficient or no water flow.
 If using air cooling and have selected deep cooling for PS-25 (the CCD
implemented in the current work). Note: Air cooling may not be possible if
the ambient air temperature is over 20 °C.
To protect the detector from overheating, a thermal switch has been attached to the heat
sink. If the temperature of the heat sink rises above 47 °C, the current supply to the cooler
will cut out and a buzzer will sound. Once the head has cooled, the cut-out will
automatically reset [11]. This all information shows that it is very important to cool the
detector for an accurate temperature measurement and from safety point of view. The two
ways of cooling the detector in the current system are air cooling and water cooling.

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Only air cooling has been used in the current work although the camera has both cooling
options. Air cooling is the simplest way of cooling, but it will not achieve as low
operating temperature as water cooling. Note: “The fan does not operate until the heat
sink temperature has reached between 20 °C and 22 °C. It is therefore quiet normal for
the fan not to operate when the system is first switched on [11]”. Generally speaking,
temperature of the heat sink should be 10 °C hotter than room temperature, in order to
transfer heat efficiently to the surrounding air. The table below is a guide to the minimum
achievable operating temperature [11].
Table 4.1: Evacuated housing – high performance air cooling with power supply unit [11].
Air Temperature External PSU box
20 °C -70 °C
25 °C -68 °C
30 °C -66 °C
The other way of cooling a detector is water cooling. This is a very effective method of
cooling the detector since the flow of water through the heat sink removes heat very
efficiently. The difference between water cooling and air cooling is that the minimum
temperature of the CCD only depends on the water temperature for water cooling
method, but for air cooling it only depends on the air temperature. The table below is a
guide to the minimum CCD operating temperature for various water temperatures [11].
Table 4.2: Evacuated housing – high performance water cooling with power
supply unit [11].
Water Temperature External PSU box
10 °C -100 °C
15 °C -98 °C
20 °C -96 °C
25 °C -94 °C
If the cooling water is at too low temperature, condensation may happen which is
unwanted. Checking the connectors where the water tubes are attached can usually give
sign if there is condensation. “Never use water that has been chilled below the dew
point of the ambient environment to cool the detector [11]”. The dew point is used to
calculate the minimum temperature the cooling water should be set before leading to
condensation, see Figure 4.4. For example, using PS-25 (the current camera) it needs 10
°C cooling water to guarantee performance down to -100 °C. Humidity is also a big
factor for condensation to happen. For instance, 10 °C water temperature at a dry air can
be effective to cool the detector but, the same temperature in a humid condition could
result in condensation. Therefore, one has to use a bit higher temperature (Example: 20
°C or more) in such situations. Actually, the air cooling was enough at least for this work,
but, water cooling can be used for future measurement if there is a need. Finally, the
reader can see the user manual for more information about safety precaution and safe
camera operation.

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Figure 4.4: Plot of relative humidity versus dew point. Ambient temperature: 20 °C, 22
°C, 24 °C, 26 °C, 28 °C, 30 °C [11].

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4.2. Working principle of CCD detector
The working principle of the CCD detector involves different sequential stages
throughout the data collection process. The first stage of all is the moment where the light
and matter interacts to produce charges via the process called photoelectric effect. This
is a process of generating electrons when a photon hits the semi-conductor surface (the
sensor). During this process electrons jump from the valence band to conduction band
after overcoming the potential barrier of about 1.26 eV then the electron leaves a hole
behind (at the valence band) which is considered to be a positive charge. The electron in
the valence band will now be free to move and it may also recombine with the hole, but
the electric field introduced in the CCD helps to keep both electron and the hole apart.
The electrons will be collected in a potential well which is created by the electrodes, see
Figure 4.5. During the exposure, the central electrode of each pixel is maintained at
higher potential in order to keep the electrons in the potential well. Then, the electrons
will drift away to the next electrode at the end of the exposure, due to change in potential.
By changing the potentials in a synchronized manner, the electrons will be transferred
horizontally from one pixel to the other, and it will be guided to the shift register
(counting device). Finally, the output register sends each charge package to an output
amplifier where charges are digitized and stored in to a computer hard disk. The readout
rate process is described in section 4.2.2.
Figure 4.5: The principle of photoelectric effect in a CCD detector. The charges are
collected in a potential well [14].
The charge transport explained above has to be digitized using an analog-to-

digital converter (A/D converter). The A/D converter is an electric circuit which helps to
convert analog signal to binary digital information (Example: counts, numbers…). The
input information to this circuit is usually continuous voltage within certain range, for
bits
instance 0 to 10 Volts. This voltage has to be divided by the count values (2 ) [15]. To
make the concept understandable, an example showing the way of calculating the voltage
width and, the number of counts is given as follows. Example: A 4 bit A/D converter has
24 = 16 different counts, which ranges from 0 to 15. If the 10 Volt input is divided by 16
counts, the voltage width will be 0.625 volts. The voltage width could be different
depending on the number of bits of the analog-to-digital converter. This means that the
voltage width of a 6 bit A/D convertor with an input voltage of 10 volt is about 0.156
volts and 64 counts. Generally, the output of an A/D convertor is a binary signal, and that

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binary signal encodes the analog input voltage, so that the output is some sort of digital
number [15]. The explanation given so far is more of a highlight about the working
principle of an A/D converter, but the discussion may not be enough from electronics
point of view.
Coming back to the current detector, the Andor CCD has different setting modes
which can be easily manipulated to test the best possible option for a more precise
temperature measurement. The main setting options which were tested in the current
work are basically three: pre-amplifier gain, readout rate and binning. Apart from these,
there are four different modes which are tested as well despite they are interrelated
somehow with one of the three modes. The idea of the next discussion (in sections 4.2.1,
4.2.2 and 4.2.3) is mainly to give a specific explanation about the three setting options, so
that the previous discussion about the general working principle of the CCD detector will
be more understandable.
4.2.1. Preamplifier gain
A CCD can have a much larger dynamic range than can be faithfully reproduced with the
current analog-to-digital (A/D) converter. So that, to use the full capacity of the dynamic
range and to optimize the camera performance it is necessary to allow different pre-
amplifier gain [16]. The dynamic range is a dimensionless quantity which is expressed as
the ratio of linear full well (electron) and read noise (electron). This quantity helps to
check whether A/D converter has used the full capacity of the CCD and then creates a
condition to select which pre-amplifier setting to use. For example, a certain
spectroscopic camera with model DU920N-BV has a readout noise <4e and a single pixel
dynamic range 125,000 to 1. But, a camera with 16 bit A/D converter has only 65536
different levels. This shows that the A/ D converter can not cover the full dynamic range.
So, the limited range of A/D converter effectively creates a new noise source [16]. From
the above example, one can see that the pre-amplifier gain should be set sufficiently high
so that the overall system noise can be minimized.
In general, the function of a pre-amplifier is to amplify a low level signal to a

detectable (line level) signal prior to readout. This means that the low signal (rotational
CARS signal) coming from the source has to be pre-amplified first. This can be done by
providing some level of gain (using pre-amplifier gain setting) to make the signal
detectable then the signal will be further amplified by the output amplifier before being
transmitted to the output device, usually a computer. The sensitivity of the detector varies
depending on the choice of pre-amplifier gain values. When the gain value increases,
smaller number of electrons is needed to make the analog to digital conversion (A/D
count), which means the sensitivity of the sensor is higher. Therefore; a lot of counts will
be recorded and a very strong output signal will be achieved. Generally speaking, the pre-
amplifier gain setting significantly determines the output video signal coming out of CCD
and it helps to control the sensitivity of the detector. But, of course, a small number of
electrons are required to achieve analog to digital count (A/D count) if the gain setting is
higher (Example: x4).

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4.2.2. Readout rates

Readout rate is the rate at which pixels (charges) are read in a sequential manner from the
shift register. The readout process is that, each set of pixels in the column of the CCD
chip will be filled by charges generated due to the photoelectric effect and then the first
set of pixels in a row will be read out, then the rest continues sequentially (the cycle starts
all over again until all the charges have been read). Figure 4.6 illustrates the readout
sequence of full resolution image which allows data to be recorded for each individual
element on the CCD-chip.
Figure 4.6: Readout mode of full resolution image. Charge in frame shifted vertically by
one row, so that the bottom row of charge moves in to the shift register [11].
The readout rate can be set high or low based on the need in the experiments. For
instance, high readout rates are needed when there is high repetition rate for the laser
source. The high readout rate gives large number of frame per second (image/second).
But, the readout noise is increased because of the characteristics in the read out process.
The readout time or the time it takes between two recordings by the camera should be
considered to minimize the readout noise. This means that, the readout process needs
time to transfer charges, but if the time to do this process is not enough, the readout noise
will increase.
Generally, the readout rate determines the frame rate of a certain image. This is
usually determined by pixels/second as can be seen in the equation given below
(Equation: 6.1).
 image   line   pixel 

Read out rate      …………………………………… (6.1)
 sec ond   image   line 

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4.2.3. Binning
Binning can be defined as the process of forming super pixels. This is the sum of a
number of pixels and it will be readout as a single pixel. The horizontal and vertical
binning parameter will determine the dimension of the super pixels as can be seen in
Figure 4.7 [11]. The Andor CCD camera software presents a selection of binning patterns
(1x1 pixels, 2x2 pixels, 4x4 pixels, 8x8 pixels and 16x16 pixels). The first pattern 1x1
pixels is the initial situation where the image is in a full resolution, but when binning
pattern 2x2 has chosen for instance, the full resolution image at 2048 pixels for the CCD-
chip of the current camera will be notionally divided in to super pixels each measure 2x2
pixel and then gives a new CCD-chip dimension of 1024 pixels. The super pixel then
provides a single signal for readout despite it contains a number of pixels.
Figure 4.7: Full resolution image with 2-dimensional pixel matrix (left image) and super-
pixel image with 2-dimensional pixels matrix (right image). The binning parameter
determines the dimension of super pixels [11].
The importance of binning is basically to minimize storage space, to induce faster

processing speed and to achieve higher signal-to noise ratio. The expression for the
signal-to-noise-ratio (SNR) is given in equation 6.1. This equation shows that the SNR
can be improved when the number of binned pixels (M) increases. But, it usually costs
the resolution of an image.
Mp t
SNR= (6.1)
Mp t  MDt  N 2 r
Where:
 P is incident photon flux density
 t is exposure time (integration time)
 N r – Read out noise
 η- Quantum efficiency
 M represents number of binned pixels

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4.3. CCD Performance

This high performance instrument has been individually built by order and tested with
Andor‟s ISO 9001: 2000 quality regime [11]. A lot of system tests were made by the
company. An example can be the system sensitivity which is calculated in photoelectrons
per A/D count. These all investigations can help to judge the performance of the camera.
There are two output amplifier options (high capacity and high sensitivity settings) in this
CCD camera. The principle and performance of both modes are discussed in the next
sections 4.3.1 and 4.3.2.
4.3.1. High Sensitivity (HS) output amplifier

Sensitivity is a term which can be described by the quantum efficiency of a sensor. This
means that, the probability of producing photoelectrons when a photon is absorbed
describes the efficiency of the sensor. For instance, a high sensitivity sensor can achieve
single photon detection since it has very high quantum efficiency. Photons of different
wavelength have different probabilities of producing photoelectrons and this probability
is usually expressed by quantum efficiency (QE) or spectral response, which is the
number of electrons that will be produced per unit photon energy. The quantum
efficiency curves are given in Figure 4.8, for different CCD structures.
Figure 4.8: Plot of quantum efficiency (%) versus wavelength (nm). BU, back-
illuminated CCD UV enhanced 350 nm optimized; BV, back-illuminated CCD VIS
optimized; FI, front-illuminated CCD; UV, front-illuminated CCD with UV coating;
UVB, back-illuminated CCD with UV coating; BR-DD, back-illuminated deep depletion
CCD with fringe suppression; OE, open electrode CCD; BU2, back-illuminated CCD UV
enhanced, 250 nm optimized [17].

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To be specific, this high resolution spectroscopic sensor has a capacity of delivering 95 %

quantum efficiency with all multi-megahertz readout. The output saturation electron for
high sensitivity and high capacity modes is 150000 and 600000 counts respectively, and
the dark current at -100 °C is about 0.00007electrons/pixel/second [18].
4.3.2. High Capacity (HC) output amplifier
The high capacity output amplifier is an important setting to optimize the dynamic range.
The dynamic range can be defined as the resolution of a given analog-to-digital
converter, that in most cases is given as a power of base 2, (2X). This means that an 8 bit
resolution corresponds to 256 steps (gray level), which can be used to subdivide or
convert the full scale voltage signal [19]. The resolution directly corresponds to the
theoretical maximum limit of the converter devices, see Table 4.3. Analog-to-digital
converters have an average conversion uncertainty which can reduce the resolution for
practical application.
Table 4.3: An example showing the dynamic range for a given analog-to-digital
converter with a certain resolution [19]
Resolution (bit), X→2X Dynamic range of analog- Dynamic range of analog-
to-digital conversion to-digital(A/D) conversion
(digitized steps) in decibel(dB)
8 256 48.2
10 1024 60.2
12 4096 72.3
14 16384 84.3
16 65536 96.3
The discussion so far was concerned about the physics behind high sensitivity and
high capacity output amplifiers, but, now the focus will be on the difference between HS
and HC settings physically. The dual output amplifier allows software selection between
high sensitivity and high capacity modes of operation, so that the sensitivity and dynamic
range of capacity can be optimized to suit the operation condition. The choice of high
sensitivity mode enables the system to operate at a low noise conditions. This means that
the charge integration process enhances the sensitivity by increasing the available light
intensity to boost signal strength. This is done by extending the charge- integration time
(exposure time). But, the extended exposure time could result dark current which is a
challenge unless sufficient cooling is provided, since dark current noise increases in
proportion with exposure time. The dark noise is generated by the flow of dark current in
the silicone, and it is temperature dependent. Generally speaking, the high sensitivity
mode means the low noise condition, this will be achieved by decreasing the three
sources of noise and enhance the intensity using extended charge-integration time. The
readout noise can be suppressed by using low-speed readout and low noise circuit
technology. The shot noise can be reduced by decreasing the statistical fluctuation in the
signal using a CCD with a high Quantum efficiency (QE) [20]. A greater statistical
fluctuation in signal means a greater shot noise.

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On the other hand, the high capacity mode can be used to improve the dynamic range of a
sensor. There are two ways of increasing the dynamic range, the first one is, decreasing
the minimum detection limit (the smallest possible signal), and the second option is, to
increase the largest possible signal before saturation. These two possible ways can
increase the dynamic range. The largest possible signal is directly proportional to the full
well capacity of the pixel and the lowest signal is the noise level when the sensor is not
exposed to light. The full well capacity is a term which describes the capacity to hold the
electrons in each pixel that are generated from photons. After exposure of the sensor to a
light source, each pixel in a semiconductor will absorb photons and generate electrons to
be collected in a well (bucket). The level of each bucket will be assigned a value of 0 and
255 for an empty bucket (pure black) and full bucket (pure white) respectively. Pixels
with a large exposed surface can collect more photons than small pixels during the
exposure time that is needed to prevent the bright pixel from overflowing to a
neighboring pixel [21]. If the charge flow over the neighboring pixel occurs, the so called
blooming could happen. Generally, the larger pixels have higher full well capacity which
means higher dynamic range. This implies that the high capacity setting increases
dynamic range by increasing the full well capacity. Therefore, more electrons can be
collected in high capacity mode than high sensitivity mode as it was quantitatively
described at the end of section 4.2.1.
A more accurate quantitative description of output electrons per A/D count was
made by the company (Andor plc which is the produces of the current camera with model
DU940P) as can be seen in Table 4.4. The main intention of this is to test the system
sensitivity for both high sensitivity and high capacity modes in different preamplifier
setting and various readout rates.
Table 4.4: Andor plc test of system sensitivity for HS and HC modes [11].
A/D Rate Pre-amplifier High sensitivity (HS) High capacity (HC)
(MHz All 16 bit) setting output electron per A/D output electron per A/D
count count
3 x1 3.8 17.3
3 x2 2.0 8.9
3 x4 1.0 4.4
1.0 x1 3.9 18.0
1.0 x2 2.0 9.2
1.0 x4 0.9 4.4
0.05 x1 4.0 18.3
0.05 x2 2.0 9.4
0.05 x4 1.0 4.5
Saturation signal per pixel 83457

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Chapter 5
Experimental Work
The main intention of the whole investigation was basically to achieve as good
temperature precision as possible by looking at different setting possibilities. The starting
point of the experimental work was to install the new CCD camera physically and also to
install the system software needed to run the camera. A number of experiments were
done in the current work to check different options of the Andor CCD camera. Pure
Nitrogen and Argon were used for the whole investigation of the detector. The N2O
measurements were also done to check the possibility of developing a good theoretical
model (Develop code using the spectroscopic constants for N2O) that can best fit with the
experimental spectrum. Additionally, it is believed that the capability of N2O library can
be extended to higher temperatures as long as accurate spectroscopic parameters are
introduced. The detailed procedure followed throughout the experimental work has been
discussed in the next sections given below.
5.1. Implementation of CCD Camera and testing procedures
The hardware implementation phase of the work includes putting the new CCD camera
and external shutter on the right position. As can be seen in Figure 5.1, a metal tube
which goes all the way to the box where the Czerny Turner spectrometer is aligned has
been mounted with the detector. The external shutter has been attached at the end of the
tube inside the box. The shutter controller kept outside the box has an on/off button to
select between keeping detector open to take a signal or closed when there is a need to
align the spectrometer or at the end of the work. This helps to use the detector safely.
Figure 5.1: Picture of general setup overview in the left, and position of CCD camera
and shutter controller on the right side (zoomed image).

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After the implementation of the physical part, then the Andor Software package which
comes together with the CCD was installed. The software has a user-friendly interface
which enables to vary most important settings during the investigation. Then the camera
was tested for the first time to get the first Rotational CARS signal from air which was
really fascinating at least for me as a student “Yes! I know the temperature in the room…”
Some experiments were performed after making sure that the CCD works in a good way.
This was basically done to get acquainted with the system and also test how reasonable
temperatures can be measured using the new detector.
The real experiments which were done for the purpose of CCD investigation have
been performed in a more procedural manner. A total of seven different tests were made
throughout the whole project as can be seen in chapter 6 of the report. The procedure
listed below has been implemented in all investigations to minimize errors related to the
experimental procedure.
 The first step in every measurement is usually taking air spectrum at room
temperature. This helps to spectrally calibrate the spectrum. The nitrogen peak in
the air spectrum at the point 123.18 cm-1 is usually taken as a reference point as
can be seen in the Figure 5.2. The only reason for this is because it is easily
identified. This peak corresponds to the S-branch transition J=14 → J= 16 in the
N2 spectrum. Therefore, the channel number (in pixels) in this specific calibration
point is an input for the FORTRAN program used to calculate temperature.

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0.9
0.8
0.7 J (14) → J (16) in N2

Rel. Intensity (arb.units)
0.6
X: 123.2
Y: 0.4699
0.5
0.4
0.3
0.2
0.1
0
0 20 40 60 80 100 120 140 160 180 200
-1
Raman shift (cm )
Figure 5.2: Average Air spectrum at room temperature and atmospheric pressure.
Accumulated spectrum, detector view (appearance of the spectrum in the detector without
being flipped)
 The second step which has been followed was measurement on N2. In every
experiment throughout the whole work, 500 single shot nitrogen spectra were
recorded first, and then followed by 500 nitrogen background spectra (used to
subtract background from single shot spectra later in the evaluation). Then, 500
Argon spectra were collected followed by 500 Argon background spectra. The
importance of recording Argon spectra is basically to compensate the influence of
finite laser profile on the resonant spectrum of N2. This is because of the fact that
both the resonant and non-resonant spectrums are affected in the same way by the
finite laser profile of the broadband dye laser. Then the final Nitrogen spectrum
which is ready for evaluation will be in the following form:
NitrogenEvaluated 
 Nitrogenspectra  Nitrogenbackground spectra 
…………… (5.1)
 ArgonSpectra  ArgonBackground spectra 
 The third step in this investigation was to find the best instrument function using
the FORTRAN program (Optslit) developed by Christian Brackmann [22]. The
FWHM values of Gauss and Lorenz line profile were found after running Optslit.
The Voigt line profile used to convolute the theoretical library of N2 is the

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convolution of full width at half maximum (FWHM) of Gauss and Lorenz line
profiles. Generally, the program (version by L.Martinsson, February 24, 1993)
reads a theoretical library and convolves the spectra with a Lorenz, Gauss or
Voigt slit function of specified width using Fourier transformations. A lot of
Matlab routines were also used to process the data. These Matlab codes were used
first, to generate the spectral file of single shot (SingleShot.dat format) and
accumulated shot (AccumulatedShot.dat format) which is an input for Optslit
program. Second, to process the output data received from FORTRAN program
so that temperature values and relative standard deviation (or precision) can be
calculated. Some of the Matlab codes used in the current work were the
following: To identify the reference line from air spectrum (AirSpectrum.m), to
check if the shapes of the Argon spectra were equal throughout the measurement
series (ArgonTest.m), to generate spectral data (AccumulatedShot.dat and
SingleShot.dat) as an input for FORTRAN program (printOutfile.m), to
calculate the standard deviation, Precision and Average SSQ
(CalculatePreStdAvg.m). These routines can be seen in the appendix A1, A2, A3
and A4 respectively. In fact, a lot more Matlab routines are required to make
temperature evaluation, but, the FORTRAN program is the basic one for
temperature evaluation purposes.
 The next step which is usually recommended to be done before doing any kind of
analysis of the data is to test the shape of Argon spectra. As explained earlier,
every nitrogen spectrum should be divided by an averaged Argon spectrum to
compensate the influence of finite line profile of broadband dye laser on the
resonant spectrum of N2. So that, the shape of the Argon spectrum should be the
same throughout certain measurement series in order to make the division. The
importance is basically to equally compensate the finite laser profile effect on the
resonant spectrum, see Figure 5.3. The way to do this is to plot a number of
normalized Argon spectra on the same plane as can be seen in Figure 5.4, then all
Argon spectra measured should lay on top of each other. Then the data will be
valid to make temperature calculations from the theoretical library developed for
the Nitrogen molecule. If for some reason, the Argon spectra do not lay on top of
each other, it means that the shape has changed during the measurement series
and this will result a bad temperature analysis. Hence; it is recommended to make
measurements again if such situation happens.

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1000
HS-X1
900 HS-X2
HS-X4
800
HC-X1
HC-X2
700
Intensity(count) HC-X4
600
500
400
300
200
100
0
0 50 100 150 200 250 300
Wavenumber (cm-1)
Figure 5.3: Plot of six different Argon spectra averaged over 500 spectra for six different
measurements (pre-amplifier gain: x1, x2 and x4 for each High capacity (HC) and High
sensitivity setting (HS)).
500
HS-X1
450 HS-X2
HS-X4
400
HC-X1
HC-X2
350
HC-X4
Normalized Intensity
300
250
200
150
100
50
0
0 50 100 150 200 250 300
Wavenumber (cm-1)
Figure 5.4: Plot of six normalized Argon spectra lay on top of each other. Pre-amplifier
gain: x1, x2 and x4 have been considered for each High capacity (HC) and High
sensitivity setting (HS) options. It indicates the shape of all Argon spectra is the same. It
is good result since all Argon spectra lay on top of each other.

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 The last step of the whole process is calculation of the temperature either from the
single shot spectra or average spectrum depending on the condition. Evaluation of
averaged spectra is preferable if there is stationary condition like room
temperature measurement that has been done in the current work. This is because
the averaged spectrum has a very nice envelope function which makes
temperature calculations more precise as can be seen in Figure 5.5. However;
single shots must be evaluated in the case of non stationary conditions despite
single shot spectra have hugely varying rotational line intensities in a random
way (not a good envelop function) as can be seen in the two different single shot
spectra in Figure 5.6 plotted in blue and green colors . Evaluation of single shot
spectra is very important in cases like turbulent flames where many parameters
vary in time. In such kind of situations, it is difficult to rely only on the average
spectrum rather the single shot spectra must be evaluated. The measurement made
throughout the whole project was basically in stationary conditions, so the use of
averaging is acceptable although single shot spectrum has been evaluated as well.
In addition to this; the relative standard deviation (precision) has been calculated
for each investigation to identify the best possible way of running the camera. The
relative standard deviation is expressed as: standard deviation divided by average
temperature. This value determines how accurate the technique is on a single-shot
basis. By looking at the value for the precision, one can evaluate the quality of
certain technique since precision is a measure of how accurate the technique is on
a single-shot basis. Lower value of precision means better technique. Generally
speaking, the choice of average or single shot evaluation mainly depends on the
condition in which temperature measurement is made.
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250
-1
Raman shift (cm )
Figure 5.5: Plot of Relative intensity (Arbitrary unit) versus Raman shift (cm-1). Average
nitrogen spectrum over 500 spectra. The spectrum has smooth envelope function.

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0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250
-1
Raman shift (cm )
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250
Raman shift (cm-1)
Figure 5.6: Plots of Intensity (counts) versus Wavenumber of two Single shot nitrogen
spectra. They are plotted in blue and green colors respectively. Shot-to-shot variation is
clearly observed. None of spectra have a good envelope function.

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The difference between single shot and average spectrum is more pronounced in
case of Argon spectrum as can be seen in the Figure 5.7 plotted in red and blue colors
respectively. This shows that the shape of the Argon spectrum is very important for
temperature evaluation. Argon spectra are basically used to compensate the influence of
the finite laser profile on the resonant N2 spectra.
200
180
160
140
Intensity (Counts)
120
100
80
60
40
20
0
0 50 100 150 200 250 300
Wavenumber(cm-1)
250
200
Intensity (Counts)
150
100
50
0
0 50 100 150 200 250 300
Wavenumber(cm-1)
Figure 5.7: Plot of Intensity (counts) versus Wave number of an average Argon spectrum
(blue color) and single shot Argon spectrum (red color).

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The ultimate goal of making spectral analysis for temperature measurement was basically
to come out with some useful information regarding precision by implementing the above
mentioned procedures. The way to get this information has been explained earlier in this
chapter and the fitted average nitrogen spectrum can be seen in Figure 5.8. The plot
shows experimental spectrum, theoretical spectrum and the difference between the two
(experiment spectrum –theory spectrum) plotted in the same plane. This helps to identify
qualitatively, how good the experimental spectrum is fitted with theoretical spectra,
which then leads to a good judgment of the average temperature. Finally, it has to be
explained that Figure 5.8 reveals how a fitted spectrum looks like in all other setting
options, because they all show similar behavior except the difference in the quality of the
fit and temperature values of specific cases.
1.2
experiment
theory
1 experiment - theory
0.8
0.6
0.4
0.2
-0.2
0 50 100 150 200 250
-1
Raman shift (cm )
Figure 5.8: Plot of Relative intensity (arbitrary unit) versus Raman shift (cm-1). High
capacity setting, pre-amplifier gain-x1 and readout rate 1MHz were used in the
measurement.
Table 5.1: Evaluated values for the spectrum shown in Figure 5.8
T CFIX SSQ CFIX T VARY SSQ VARY DISP. REF. CH. NR.
299.097 68.772 297.512 44.100 0.12566 123.247 0.63315

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Where, T CFIX and SSQ CFIX is starting temperature and initial SSQ respectively at
the beginning of fitting. After floating both temperature, concentration, dispersion,
reference channel and non-resonance susceptibility, more accurate values for temperature
(T VARY), dispersion (DISP.), reference channel (REF. CH.) and non-resonance
susceptibility (NR.) is found as can be seen in table 5.1. The minimized parameter for the
non-linear least-squares fitting routine is the Sum-of-Squares (SSQ) [23]. The expression
for SSQ can be seen in Equation 5.2. This is used as a measure of how good the fitting
has been made and it should be as small as possible in order to achieve a better
temperature analysis.
2
 
n
SSQ = Wi IiTheory  IiExperiment
i 1
(5.2)
Theory
where I i and I iExperiment are the theoretical and experimental intensities at each point
„i‟ in the spectrum respectively, and Wi is a weight factor for pixel „i‟ [23].
Evaluation of the average spectrum is not always enough entity to correctly determine
temperature in certain combustion environment since average data gives limited
information. Due to this reason, the single shot spectra have been evaluated for all
investigations made throughout the whole work. The individual temperatures of 500
consecutive single-shot spectra are plotted as can be seen in Figure 5.9. The standard
deviation and precision for High capacity setting (Preamplifier gain- x1, Read out rate-1
MHz) has been calculated in every analysis of the current work.
340
Single-shot T
Mean T
330 StandardDeviation
320
310
Temperature (K)
X: 482
300 Y: 297
290
280
270
260
0 50 100 150 200 250 300 350 400 450 500
Number of spectra
Figure 5.9: plot of Temperature (K) versus Number of spectra. The single shot
temperature with red circle shows that the non-resonance susceptibility (NR) is not fitted
for these spectra. The average temperature for 500 single-shot spectra is 297K.

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At the last but not least, the plot of Temperature versus SSQ has been checked in every
investigation to assess the spread of the temperature of all 500 spectra, see Figure 5.10.
This kind of plot helps to see if there are some badly fitted spectra which affect the total
result of temperature precision. Actually, there is no need to remove any spectrum in the
analysis if the spectral spread is uniform on both sides of the average temperature value,
but sometimes there might be a need to remove few spectra which are less important to
the overall evaluation or because they hardly reflect the real temperature of combustion
environment. One important issue the reader has to be aware is that this Figure 5.10 is
given just to show how the spread should look like for a good distribution of single shot
spectra, but the detailed analysis is given in the result part of the report. The evaluation of
temperature for the number of spectra with SSQ<1200 gives a better precision than
evaluating the whole spectra. This shows that the spectra with SSQ >1200 might have
badly fitted spectra which negatively influence the true temperature information. Hence,
this is the way how the temperature analysis has been made throughout the whole work.
330
Single-shot SSQ Vs T
320
310
Temperature (K)
300
290
280
270
0 200 400 600 800 1000 1200 1400 1600 1800 2000
SSQ
5.10: Plot of Temperature versus SSQ for all 500 spectra. High capacity output amplifier
has been used.

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5.2. N2O for temperature measurement
The Nitrous oxide (N2O) molecule (called laughing gas) was first discovered by an
English scientist clergyman Joseph Priestly in 1793[24]. His discovery follows two steps
to create N2O. First, he had to expose ammonia nitrate (NH4NO3), and iron filings (a very
small pieces of iron which is like a powder), to heat. Second, the resulting gas, NO, was
passed through water to remove any toxic by product, see the reaction 5.2.
2NO + H2O + Fe N2O + Fe (OH)2 (5.2)
This molecule has been used for different purposes for many years, such as an anesthetic
in clinical industry and in medicine [24]. Additionally, it has been used as a speed boost
for cars by increasing cylinder efficiency. It is characterized by non-toxic nature,
transparent look, and linear structure. It is made up of, two nitrogen and one oxygen
atoms. Having said this much about the story, and the use of N2O, it is time to explain the
potential of N2O molecule for temperature measurement purposes using CARS
technique. The measurement on N2O is the second part of the project apart from detector
investigation. All the procedures (Argon spectral shape, air reference, evaluation of the
average and single shot spectra etc) which have been implemented in the CCD
investigation using N2 were also used in this case. The main reason to use N2O for
temperature measurement purposes is to check the possibility of developing a good
theoretical model (develop code using the spectroscopic constants for N2O) that can best
fit to the experimental spectrum for room temperature condition. Additionally, this
investigation could give an indication about the potential of the molecule for some
applications of certain interest to measure temperature. In principle, N2O could give a
better precision than N2 because of the fact that the former has a lot of lines to be
evaluated while making a fit than the latter. This means that the smaller rotational
constant results in close rotational line as can be seen in Figure 5.8. The rotational
constant which is one of the factors that determines the number of spectral lines is mainly
dependent on the mass of the molecule. In this case, N2O is heavier than the N2 molecule
which means it has higher moment of inertia and smaller rotational constant. The general
expression for the rotational constant of a rigid rotator can be seen in Equation 5.3. To get
a quantitative value out of the N2O spectrum or to make temperature evaluation using this
molecule, a theoretical library has to be generated by introducing the molecular constants
for N2O. For example: rotational constant, statistical weight, line width (due to self-
broadening), rotational-vibration interaction, etc. The accuracy of temperature evaluation
depends on how precise the molecular parameters are. This makes temperature evaluation
of CARS spectrum very difficult although it gives strong laser like signal.
2 2
B  (5.3)
2I 2 R 2
 h 
where: μ - is the reduced mass, - is the reduced Planck‟s constant   , R - is the
 2 
radius of the rotation axis.

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In this work, the measurement on N2O was made at room temperature condition so that
the probability to populate higher order rotational levels is believed to be negligible. Due
to this reason, the theoretical library for N2O has been developed by only introducing
rotational constant, statistical weight, line width, some centrifugal distortion terms and
non-resonance susceptibility. According to the book by Gerhard Herzberg, F.R.S.C [25],
the rotational constant for N2O molecule is 0.4191 cm-1. The statistical weights
(degeneracy factor) of all rotational levels are 1 for the nitrous oxide (N2O) molecule, and
no hyperfine structure was found for this molecule in the HITRAN data base [26]. The
only cause for N2O line broadening in this investigation should be due to self broadening
(N2O-N2O) since pure N2O has been flowed through the measurement point. G.D.T.
Tejwani and P.Varanasi [27] has made theoretical line width calculations in N2O-N2O.
The result for the self broadening become in good agreement with Goody‟s [28] derived
estimate of half width for quantum numbers from m=1 to m= 60. The non-resonant
susceptibility for N2O is not a well known value. But, the investigation made at the
United Technology Center, East Hartford [29] shows that the non-resonance susceptibility
of N2O is about double that of N2. The centrifugal distortion constant De ,αe and γe are
also calculated for N2O by Josef Pliva[30]. Hence, all the above mentioned spectroscopic
constants have been introduced to the N2O.dat file in the Polylib. Then the theoretical
library (libN2O.lib format) has been generated in order to use for temperature evaluation
purposes in the N2O measurement. The N2O.dat file format is given in the appendix B1.
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
-20 0 20 40 60 80 100 120 140
-1
Raman shift (cm )
Figure 5.8: Plot of Intensity (counts) versus Wavenumber (cm-1) for N2O molecule. An
experimental spectrum averaged from 500 single-shot spectra.

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Chapter 6
Result and Discussion

This chapter is the heart of the whole project as it includes the important analysis which
was done throughout the diploma work. As it was explained in the introductory part of
the report, this work covers two important investigations: The detector investigation
which is the major part of the work and measurement on N2O.
6.1 Detector Investigation
The aim of this investigation is basically to evaluate possible options of the Andor CCD
Camera and produce a clear procedure how to run the camera in a good way so that a
better temperature precision can be achieved for the Rotational CARS measurement
technique. All measurements regarding the detector investigation has been made using
pure Nitrogen gas and pure Argon (used to compensate the influence of finite laser
profile on the resonant spectrum of N2) at room temperature and atmospheric pressure
conditions. About seven different investigations have been performed in this part to get
all important information needed, as presented below.
6.1.1 Pre-amplifier gain

The pre-amplifier gain setting is used to amplify a low level signal to a detectable signal
prior to readout. The basic settings implemented in this investigation were: pre-amplifier
gain (x1, x2 and x4), read out rate (1 MHz at 16 bit) and full vertical binning (FVB)
mode. All 500 spectra have been evaluated in this setting. The CCD used in the current
work has an output amplifier option of high capacity and high sensitivity settings. These
two output amplifiers can be coupled with different pre-amplifier gain (x1, x2 or x4).
The two basic investigations made in this case were basically temperature precision
at different pre-amplifier gain and the change in precision of consecutive 100 spectra
from all 500 spectra collected at a time. As can be seen in these two plots (Figure 6.1 and
Figure 6.2) for high capacity and high sensitivity settings respectively, the temperature
precision is not affected much by the variation in the pre-amplifier gain. As a result, the
value of precision ranges from 2.6% to 4.4% regardless of which pre-amplifier gain used.
Additionally, it has been found that there is shot-to-shot variation among every 100
spectra of the whole 500 spectra in both settings regardless of pre-amplifier settings. To
be specific, the precision values for Pre-amp x1, pre-amp x2 and pre-amp x4 are about
0.040 ± 0.003, 0.033 ± 0.005, 0.031 ± 0.001, respectively.
From those results, one can say that, it is possible to use all three pre-amplifier
setting (x1, x2 and x4) options with out affecting much the temperature precision as long
as the CARS signal is sufficient. In other words, trying to improve temperature precision
by simply changing pre-amplifier gain will not make significant difference. Although it is

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difficult to draw conclusion from the change in precision in every 100 spectra, the
precision is slightly better for pre-amp x4 than pre-amp x2 and pre-amp x1 seems to be
the least good. In general, the result indicates that one should use averaging over many
spectra in order to make better precision temperature measurement. Otherwise, large
variation in evaluated temperature will be found. The average values of precision for high
capacity setting (Figure 6.1) are 3.9 % for pre-amp x1, 3.5% for pre-amp x2 and 3.1% for
pre-amp x4.
0.05
pre-amp x1
0.045 pre-amp x2
pre-amp x4
0.04
0.035
0.03
Precision
0.025
0.02
0.015
0.01
0.005
0
0 1 2 3 4 5 6 7 8
Consecutive 100 spectra
Figure 6.1: Temperature precision versus consecutive 100 spectra for the high capacity
option. For every pre-amplifier setting, five measurements have been made and 100
spectra were evaluated in each case. Precision of every hundred spectra has been
calculated to check if there is shot-to-shot variation. Pre-amplifier gains x1, x2 and x4
were used.

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Similarly, the average values of precision for high sensitivity setting (Figure 6.2)
are 3.22 % for pre-amp x1, 3.24 % for pre-amp x2, and 3.54% for pre-amp x4. This
shows that the precision improves a little with decreasing preamplifier gain.
Nevertheless, it is not very significant difference to make conclusion from this result.
0.05
pre-amp x1
0.045 pre-amp x2
pre-amp x4
0.04
0.035
0.03
Precision
0.025
0.02
0.015
0.01
0.005
0
0 1 2 3 4 5 6 7 8
Figure 6.2: Precision using different pre-amplifier settings for high sensitivity output
amplifier. For every pre-amplifier setting in high sensitivity, five measurements have
been taken and the numbers of spectra evaluated were 100 in each case.

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The other test made regarding pre-amplifier gain setting was to compare the two output
amplifiers (high sensitivity and high capacity) with regards precision level able to
achieve. The same data has been used as of Figure 6.1 and Figure 6.2. As a result, the
precision for both settings lay in a very narrow range (3 % to 3.5 % roughly) as can be
seen in Figure 6.3. This implies; the result still illustrates no major difference between
them. The selection freedom seems to be guaranteed regarding pre-amplifier gain as far
as temperature precision is concerned. Overall, this investigation was more or less able to
show similarity rather than differences.
0.05
High Capacity
0.045 High senitivity
0.04
0.035
0.03
Precision
0.025
0.02
0.015
0.01
0.005
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Pre-amplifier gain setting
Figure 6.3: Plot of temperature precision in different pre-amplifier setting (x1, x2, and
x4) options for the high capacity and high sensitivity output amplifiers. The temperature
precision difference between High capacity and High sensitivity looks to be similar.

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6.1.2 Readout rates
Readout rate is the rate at which pixels are read in a sequential manner from the shift
register. The purpose of this investigation was to check what happens to the precision if
the readout rate is varied, to see if the readout rate can really change the precision in
consecutive 100 spectra and also to make comparison between the precision levels of
high capacity and high sensitivity output amplifier settings at different readout rates. The
temperature precision for different readout rates (3MHz, 1MHz and 0.05 MHz) have been
investigated in similar way as the case of Pre-amplifier gain which was discussed in
section 6.1.1. The pre-amplifier setting used was x1 in a full vertical binning (FVB)
mode. The whole analysis was done for both high capacity and high sensitivity output
amplifier settings. The plot of precision as a function of consecutive 100 spectra for all
three readout rates is shown in Figure 6.4 for high capacity output amplifier setting. The
precision lays in the range of 3 % to 4 % for all readout rates. The difference in precision
between consecutive 100 spectra was also evident in all of the three cases. However; it is
still difficult to prefer one readout rate from the other as far as temperature precision is
concerned. This is because, all readout rates shows a variation within the given range
regardless of choosing high or low rate. The other important issue which should be
realized is that, the shot-to-shot variation of consecutive 100 spectra is not affected much
by the readout rate.
0.05
1 MHz
0.045 3 MHz
0.05 MHz
0.04
0.035
0.03
Precision
0.025
0.02
0.015
0.01
0.005
0
0 1 2 3 4 5 6 7 8
Figure 6.4: Plot of precision versus consecutive 100 spectra for different readout rates
(1MHz, 3MHz and 0.05MHz and high capacity setting). FVB mode and x1 pre-amplifier
setting have been used in this investigation. All 500 in a sequence of 100 each have been
evaluated.
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A similar investigation has been made for the high sensitivity output amplifier as can be
seen in Figure 6.5. The precision varies in the range of 2.7 % to 4.1 % for all readout
rates. This shows that the conclusion will be quite similar with high capacity setting case.
From those two investigations, it can be concluded that the influence of choosing
different readout rates is very small or may be negligible for the temperature precision.
0.05
1 MHz
0.045 3 MHz
0.05 MHz
0.04
0.035
0.03
Precision
0.025
0.02
0.015
0.01
0.005
0
0 1 2 3 4 5 6 7 8
Figure 6.5: Plot of precision versus consecutive 100 spectra for different readout rates
(1MHz, 3MHz and 0.05MHz) and high sensitivity setting. FVB mode and x1 pre-amplifier
setting have been used in this investigation. All 500 in a sequence of 100 each have been
evaluated.

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The third investigation was intentionally made to check the difference in precision when
using high capacity or high sensitivity setting as can be seen in Figure 6.6. It then came
out with a result which shows that a selection freedom is still granted specially at high (3
MHz) and low (0.05 MHz) readout rates. At 1 MHz the high capacity setting looks to
have better precision than high sensitivity, but it is too difficult to make conclusion based
on this point (the range of precision is 3.1 % to 3.7%). Therefore; it can be concluded that
both output amplifier settings are almost equally good to make temperature measurement
as long as precision in the main concern.
0.05
High Capacity-x1
0.045 High Sensitivity-x1
0.04
0.035
0.03
Precision
0.025
0.02
0.015
0.01
0.005
0
0 0.5 1 1.5 2 2.5 3 3.5 4
Readout rate
Figure 6.6: Plot of precision versus readout rate for both high sensitivity and high
capacity settings. The numbers of spectra evaluated were on average: 400 spectra for
high capacity and 350 spectra for high sensitivity setting since only SSQ<600 were
evaluated.

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6.1.3 Binning
Binning is a process of forming a super pixel as it was explained in chapter 4. The

objective of this analysis is to check the influence of horizontal binning to precision and
SSQ. The setting implemented in this case was: High Sensitivity output amplifier,
preamplifier gain-x1, read out rate-1MHz at 16 bit. This setting has been used equally
to all binning patterns (bin 1, bin 2, bin 4, and bin 8). Figure 6.7 shows that the
temperature precision is in the range of 2.7 % to 3.2 % for the horizontal binning options
bin 1, bin 2, bin 4, and bin 8. But, it is difficult to draw conclusion about that, since the
temperature precision does not seem to have a big correlation with binning. Therefore,
one can use any binning option as far as precision is concerned.
0.04
0.035
0.03
0.025
Precision
0.02
0.015
0.01
0.005
0
0 1 2 3 4 5 6 7 8 9 10
Horizontal binning
Figure 6.7: Plot of Precision versus horizontal binning (bin 1, bin 2, bin 4, and bin 8).
The precision looks to be rarely affected by binning. 500 single shot spectra have been
evaluated in this case.

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In similar manner, the influence of binning on the Sum-of-Squares (SSQ) was

investigated as can be seen in Figure 6.8. The value of SSQ decreases exponentially with
increasing horizontal binning. The SSQ gets higher when we go to lower binning options
(bin 2 and bin 1). The reason for this is basically due to the fact that binned spectrum
(Example: bin 8) has fewer fitting points and, errors in the fitting of the individual line
gets less impact. In general, the lower the SSQ the better the fit it will become if the SSQ
comparison are normally performed for a spectrum with constant number of fitting
points.
70
60
50
40
SSQ
30
20
10
0
0 1 2 3 4 5 6 7 8 9 10
Horizontal binning
Figure 6.8: Plot of SSQ versus horizontal binning (bin 1, bin 2, bin 4, and bin 8). The
value of SSQ decreases with increasing binning from bin 1 to bin 8.

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The results from the four different binning options (bin 1, bin 2, bin 4 and bin 8) are
plotted in Figure 6.9. The numbers of spectra are 500 for each binning option. The
distributions indicate that the SSQ value for bin 1 > bin 2 > bin 4 > bin 8. This helps to
understand what happens to the spectral fit as the horizontal binning increases.
330
bin 1
bin 2
320 bin 4
bin 8
310
Temperature
300
290
280
270
260
0 200 400 600 800 1000 1200 1400
SSQ
Figure 6.9: Plot of Temperature versus SSQ for different binning options (bin 1, bin 2,
bin 4 and bin 8). 500 spectra were evaluated for each case.

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6.1.4 Signal strength
High signal-to-noise ratio is usually needed to extract useful information from

measurements. The CARS signal strength is actually good enough for measurement
purposes since it is a laser like coherent signal which is created by implementing the
phase matching conditions for three different lasers focused to a point. The rotational
CARS signal strength could be affected by the use of some optical equipment such as the
filter which is basically used to block the stray light from the laser source at wavelength
532nm. This investigation regarding signal strength is concerned to verify which output
amplifier should be used if one needs to have a strong output signal from the same input.
The Andor CCD camera used in the current work has two options for the output amplifier
(High sensitivity and High capacity) and both have three possible setting options (x1, x2
and x4) as can be seen in Figure 6.10. A high sensitivity (x4) and high capacity (x4) CCD
setting means high quantum efficiency sensor with large exposure time, and high
dynamic range respectively. The signal strength for high sensitivity output setting is a bit
more than five times as big as the signal strength of high capacity setting, see Figure
6.10. This implies that, the high sensitivity output amplifier setting is more preferable
than high capacity setting as far as signal strength is concerned.
4
x 10
3.5
High capacity
High sensitivity
3
2.5
Signal strength
1.5
0.5
0
0 1 2 3 4 5 6
Pre-amplifier gain
Figure 6.10: Plot of signal strength versus pre-amplifier gain(x1, x2 and x4) for High
capacity and high sensitivity settings. The signal strength for the high sensitivity is twice
as big as High capacity setting as can be seen in the figure.

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6.1.5 Instrument function
The instrument function used in the current work was a Voigt line profile as it was
explained in the experimental part of the report. This line profile is basically the
convolution of Gauss and Lorenz line profiles. An investigation was made to check the
influence of resolution on the line profiles when the position of the CCD detector goes
away from the point of focus. By changing the CCD detector position the width of the
instrument function varied as can be seen in Figure 6.11. The full width at half maximum
(FWHM) value for both Gaussian and Lorentzian line profiles was evaluated from the
instrument function at each measurement positions. From this figure, one can see that the
FWHM of Gaussian line profile increases with increasing the distance while the FWHM
for Lorentzian line profile remains reasonably constant. This shows that the change in
resolution of CCD camera is much correlated with a Gaussian line profile. So, the Voigt
profile should be the convolution of bigger gauss profile and reasonably constant
Lorentzian line profiles.
0.9
Gaussian profile
0.8 Lorentzian profile
0.7
0.6
Fitting parameter
0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5 6 7 8
CCD camera position
Figure 6.11: Plot of the fitting parameters of the instrument function versus CCD camera
position. As we go farther from focus the resolution decreases and the lines will be
broader. The FWHM of Gauss line profile increase with increasing distance while the
Lorentzian line profile remains constant. This shows that it is necessary to increase the
FWHM of gauss line profile when the lines are broader to make a good fit.

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In similar manner, the temperature precision and SSQ were checked at different
measurement positions of the detector. This helps to figure out the correlation of detector
resolution with precision and SSQ. As a result, the change in distance (and thereby
resolution) of the camera does not affect the temperature precision and SSQ as can be
seen in Figure 6.12 and Figure 6.13 respectively. The average precision as a function of
distance is about (3.3 ± 0.1) % and the average SSQ value as a function of CCD position
is in the range 301- 304.
0.04
0.035
0.03
0.025
Precision
0.02
0.015
0.01
0.005
0
0 1 2 3 4 5 6 7 8
CCD camera position
Figure 6.12: Precision versus Measurement position for SSQ < 1000. The precision is
not affected much in this range of CCD position as long as all temperatures values with
SSQ<1000 are considered.

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400
350
300
250
SSQ
200
150
100
50
0
0 1 2 3 4 5 6 7 8
CCD camera position
Figure 6.13: Average SSQ versus Measurement position for SSQ < 1000. The SSQ seems
to be constant in all positions of the x-axis within the limit given above.
Table 6.1: Number of evaluated spectra, measurement positions & Fitting parameters
used for the spectrums shown in Figure 6.11, Figure 6.12 & Figure 6.13
Spectra Fitting parameters
evaluated Position Precision Average Gauss Lorenz
(mm) SSQ profile profile
487 33 0.0332 303.0722 0.325 0.125
493 35 0.0340 301.9624 0.325 0.125
494 37 0.0334 303.3468 0.5 0.1
499 39 0.0329 302.8662 0.575 0.125
500 41 0.0328 302.5933 0.6 0.175
482 43 0.0332 302.0747 0.725 0.15

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6.1.6 Influence of intensity on precision and SSQ

The relative standard deviation (here called precision) is an important quantity which is
used to evaluate the technique implemented in a certain measurement, and the SSQ also
indicates how good an experimental spectrum is fitted with theoretical spectrum. The
idea of this investigation was to identify the minimum peak intensity (counts) that must
be achieved on the detector to get rid of detector noise contribution to the overall
precision and to check the correlation between peak intensity value and SSQ. This means
that the intensity above the minimum value does not change much the precision and SSQ
while intensity less than the minimum value will give worse temperature precision and
SSQ values. Figure 6.14 shows that, minimum peak intensity about 1000 counts is
needed to keep the precision as good as possible for the full vertical binning mode (FVB).
Peak intensity value less than about 1000 counts results in worse precision.
0.08
FVB mode
0.07
0.06
0.05
Precision
0.04
0.03
0.02
0.01
0
1 2 3 4
10 10 10 10
Average intensity (counts)
Figure 6.14: Precision versus Average intensity for the FVB mode. 500 single shot
spectra were evaluated. The temperature precision improves with increasing intensity
until 1000 Counts. And the precision shows the same result with in the intensity range of
1000 up to the maximum intensity before saturation.

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In similar manner, the average SSQ was plotted as function of average peak signal
intensity as can be seen in Figure 6.15. The minimum peak intensity needed to keep the
SSQ value relatively constant is about 1000 counts. The SSQ value remains relatively
constant or decreases slightly at higher intensity (greater than 1000). The last point with
intensity 32055 counts has SSQ value of about 1014. This could be due to saturation of
the detector.
3000
FVB mode
2500
2000
Average SSQ
1500
1000
500
0
1 2 3 4 5
10 10 10 10 10
Figure 6.15: Average SSQ versus Average peak signal intensity for FVB mode. 500
single shot spectra were evaluated. The SSQ value of FVB is lowered with increasing
signal intensity until it reaches around 1000 counts, then it remains almost constant at
any maximum intensity before saturation.

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The other investigation made regarding binning options was the multi-track mode. This
mode is a full vertical binning of a limited number of rows on the CCD chip containing
the signal (pixels containing the CARS spectrum). The main idea of doing that was to
investigate its effect on precision and SSQ. In order to do that, a certain track which
contains the CARS spectrum was selected from the CCD chip to run the camera in a
multi-track mode. As a result, the spectrum was found in an area of around 25 vertical
pixels (2048x25). A similar investigation was implemented to multi-track mode as of
FVB mode. The minimum peak intensity or threshold looks to be difficult to identify in
multi-track mode as can be seen in Figure 6.16. The worst precision found in this case
was the first point at around 30 counts which is very low intensity. Hence, it is only
possible to say that the precision shows improvement with increasing intensity,
otherwise, it is hard to put a certain threshold.
0.07
Multi-track mode
0.06
0.05
0.04
Percision
0.03
0.02
0.01
0
1 2 3 4 5
10 10 10 10 10
Figure 6.16: Precision versus average signal intensity for the multi-track mode. 500
single shot spectra were evaluated. The precision shows slight improvement with
increasing average intensity. However, the temperature precision will be worst for a
signal less than or equal to 180 counts due to lower signal.

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The plot of average SSQ versus peak intensity given in Figure 6.17 indicates that the fit is
getting worse for an intensity value less than about 1000 counts. The average intensity
above 1000 counts gives relatively constant value of SSQ. Generally, the precision
decreases with increasing number of counts for a multi-track mode.
3000
Multi-track mode
2500
2000
Average SSQ
1500
1000
500
0
1 2 3 4 5
10 10 10 10 10
Figure 6.17: Average SSQ versus Average intensity for the Multi-track mode. The curve
show that the average SSQ for 500 single shot spectra decreases with increasing average
intensity up to around 1000 counts. Above 1000 counts, the average SSQ is relatively
constant except for the highest average intensity. But, this increase in SSQ is expected
due to detector saturation.

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6.1.7 Comparison between Full vertical binning and Multi-track modes
The main idea of this comparison is to investigate the influence of CCD noise
contribution from the pixels which do not have spectral information. In other words, the
CCD chip used in the current work has 2048x512 pixel sizes but, the rotational CARS
signal only covers around 25 pixels (like 2048x25). In such cases, the full vertical
binning (FVB) will simply add noise to the overall signal. However, multi-track mode
can neglect those pixels since it only bins the selected pixel. In principle, multi-track
mode could give a better precision if CCD readout noise is dominating factor for the
overall noise contributions. Figure 6.18 shows that the temperature precision of both FVB
and multi-track modes are about the same especially at high enough intensity (greater
than 1000). The FVB mode gives relatively worse temperature precision for intensity less
than about 200 counts. This shows that multi-track mode is preferable at low intensity
conditions since the CCD readout noise contribution could be bigger in such situations.
0.08
FVB mode
Multi-track mode
0.07
0.06
0.05
Precision
0.04
0.03
0.02
0.01
0
1 2 3 4 5
10 10 10 10 10
Figure 6.18: Precision of measurements using multi-track and FVB modes as a function
of average intensity. Both have almost similar precision levels for intensity values greater
than or equal to 200 counts. For low intensity multi-track mode looks to be more
preferable than FVB mode. This could be due to the fact that there will be noise
contribution from some of the pixel in the FVB which were removed in the multi-track
mode.

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A similar comparison has been made to evaluate the difference in SSQ between FVB and
multi-track mode as can be seen in Figure 6.19. The average SSQ decreases with
increasing peak intensity. This could mean that it is possible to use both FVB and multi-
track modes in that region as far as SSQ is concerned, but one has to be careful when
choosing highest possible intensity which can give an improved precision before
saturation. Because, a very high signal could saturate the detector and it may result in
worse SSQ as can be seen in the last measurement points. In general, multi-track mode
looks to be preferable for low intensity signal in comparison with FVB mode.
3000
FVB mode
Multi-track mode
2500
2000
Average SSQ
1500
1000
500
0
1 2 3 4 5
10 10 10 10 10
Figure 6.19: Plot of average SSQ versus average intensity (counts).Both the FVB and
multi-track modes have similar values regarding SSQ for signal intensity greater than
1000 counts. The SSQ value is very sensitive for an intensity value of less than 1000
counts
Table 6.2: High and low signal intensity for both FVB and multi-track modes. At low
signal, the precision for multi-track mode is better than FVB mode. But, at high enough
signal level, both can be used or FVB binning may be a bit better than multi-track mode.
High signal Intensity Low signal Intensity
(Counts) (Counts)
FVB mode 0.0303 9305 0.0502 263
Multi-track mode 0.0341 9740 0.0404 309

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To sum up, the relative standard deviation (called precision in our case) is a measure of
dispersion or scattering around the mean value. The smallest the value of precision the
better the technique will be and the higher value of precision means the worse technique.
The value of precision achieved in the present study regarding detector investigation was
found to be 3% - 4% on average (which means 8-11K temperature roughly). Previous
studies of DB-RCARS thermometry shows that the value of precision achieved at room
temperature condition was found to be 4% - 5% [31]. Similarly, standard deviation of 5-6K
(which means that a precision of about 1.7% - 2% roughly) was achieved using modeless
dye laser at room temperature [32]. The above result indicates that the temperature
precision achieved in the current investigation is reasonably good as compared with the
precision of DB-RCARS at room temperature with a multimode Nd:YAG laser and a
conventional dye laser. But, the investigation by F. Vestin, M. Afzelius and P-E
Bengtsson using modeless dye laser lowered the standard deviation of conventional dye
laser by 50% [32].

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6.2 Measurement on N2O
Nitrous oxide (N2O) has been used for different purposes like medicine, as it has been
explained in chapter 5. But, it is not used for temperature measurement purposes in
combustion applications, since it should be noted that the concentration of N2O is very
low in hydrocarbon combustion which makes it difficult to probe the molecule via the
CARS technique. Due to this reason, there is almost no chance to follow the combustion
process by probing N2O. The spectroscopic constants of this molecule are not well known
quantities as compared to nitrogen (N2). But, the accuracy of temperature evaluation via
CARS technique depends on the accuracy of spectroscopic constants of the molecule
which are inputs to develop the theoretical library. Generally speaking, the idea of this
investigation is just to test N2O molecule for temperature measurement at room
temperature and atmospheric pressure conditions. The detail analysis is described in
section 6.2.1.
6.2.1 Temperature Precision

The temperature precision was calculated in this investigation for both N2O and N2
molecules. The measurement was made at the same conditions for both molecules (pre-
amplifier gain x1, readout rate 1 MHz at 16 bit and high sensitivity output amplifier
settings). The fitted spectrum of the N2O molecule shows that the theoretical library
developed for this molecule works quite well at room temperature conditions, but, it can
be improved even more until a more reliable temperature value is measured, see Figure
6.20.
1.2
experiment
theory
1
experiment - theory
0.8
0.6
0.4
0.2
-0.2
-20 0 20 40 60 80 100 120 140
Raman shift (cm -1)
Figure 6.20: Plot of the N2O fitted spectrum averaged over 500 spectra.

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Although the N2O library works at room temperature conditions, the evaluated average
temperature is very high (317.805 K) as compared to room temperature condition which
is roughly about (296 ± 2) K , see table 6.4.
277.447 183.792 317.805 25.978 0.12656 61.139 1.86812
This higher evaluated temperature of N2O could be due to different reasons. For instance,
the Raman line widths of the molecule can influence the temperature unless a very
accurate value is introduced to the library. The line widths of N2O [27] and N2 [33] due to
self broadening are given in Figure 6.21 for the rotational quantum number (J=1 to J=60).
By looking at this figure, one can see that there is a significant difference between the
two molecules. This implies that a less accurate line width parameter could bias
temperature information by giving high or lower temperature than it should be.
Therefore, a more accurate line width value is needed in the current work as well to get
the temperature lower than the already evaluated value.
0.12
N2O-N2O
N2-N2
0.1
0.08
Raman line width
0.06
0.04
0.02
0
0 10 20 30 40 50 60
Rotational level (J)
Figure 6.21: Plot of line width versus rotational quantum number (J=1 to J=60) for the
N2O- N2O [27] (blue color) and N2- N2 [33](red color) self broadening.

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The good thing with temperature measurement on N2O is actually, its high accuracy
measurement capability at room temperature. In chapter 5 of the report, it has been
explained that the small rotational constant of this molecule can be considered as one
reason for the existence of many rotational lines which gives an extra advantage to make
a fit. This idea looks to be correct according to the evaluation made in the current work.
Smaller value of relative standard deviation (precision) means that the temperature
precision is higher. The standard deviation, mean temperature and single shot
temperature distributions of 500 single shot spectra for N2O are plotted as can be seen in
Figure 6.22. The calculated values of standard deviation, precision and average SSQ are
given in table 6.5.
328
Single-shot T
326 Mean T
StandardDeviation
324
322
Temperature (K)
X: 482
Y: 320.4
320
318
316
314
312
0 50 100 150 200 250 300 350 400 450 500
Number of spectra
Figure 6.22: Plot of Temperature (K) versus Number of spectra. The average
temperature for 500 single-shot spectra is 320.4K.
Standard deviation Precision Average SSQ for single shot spectra
2.3964 0.0075 151.0061

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Similarly, temperature measurement on N2 was made for a comparison purposes. The

evaluated temperature of N2 molecule is lower than that of N2O, and it is closer to room
temperature conditions. This could be because of the fact that the N2 library was
developed using relatively accurate spectroscopic parameters. That‟s why it has been
always said that the precision of temperature evaluation using CARS technique is
dependent on the accuracy of spectroscopic parameters. The averaged spectrum of N2
molecule fits very well with theoretical spectrum as can be seen in Figure 6.23. The
evaluated values of the fitted spectrum are given in table 6.6.
1.2
experiment
theory
1
experiment - theory
0.8
0.6
0.4
0.2
-0.2
0 20 40 60 80 100 120 140 160 180
-1
Raman shift (cm )
Figure 6.23: Plot of relative intensity versus Raman shift for N2 molecule. Average
spectrum over 500 spectra is evaluated.
2
300.322 38.400 299.173 30.033 0.12555 123.290 0.65460

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The standard deviation, mean temperature and single shot temperature distributions of
500 single shot spectra for N2 molecule are plotted as can be seen in Figure 6.24. The
temperature precision value for N2 is worse than that of N2O. The Standard deviation,
precision and average SSQ values are given in table 6.7.
340
Single-shot T
Mean T
330 StandardDeviation
320
Temperature (K)
310
X: 480
Y: 299.6
300
290
280
270
0 50 100 150 200 250 300 350 400 450 500
Number of spectra
Figure 6.24: Plot of temperature versus number of spectra for N2 molecule. Average
temperature is 299.6 K
Standard deviation Precision Average SSQ for single shot spectra
10.1182 0.0338 335.6975
In general, the value given in table 6.5 implies that the temperature precision can
be improved by using N2O molecule instead of N2 at room temperature and atmospheric
pressure conditions considering the concentrations of both molecules are equal in certain
environment. However, the average value of temperature measured from N2O is higher
than the value from N2 molecule. This indicates that the N2O library has to be improved
by introducing accurate spectroscopic parameters. Apart from that, the N2O molecule
looks to be promising at least for room temperature evaluation purposes.

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Chapter 7
Summary and Outlook

In the current work, two basic investigations have been performed. The first task was to
implement a CCD detector into dual-broadband coherent anti-Stokes Raman
spectroscopy (DB-CARS) and test different possible setting options in view of achieving
a good precision temperature measurement. The second one was measurement on N2O to
evaluate temperature using the theoretical library (code) which was developed for that
purpose. In the detector investigation part of the work, seven different tests were made.
The three setting options, namely: pre-amplifier gain (x1, x2, x4), readout rates (1 MHz,
3 MHz, 0.05 MHz) and binning (bin1, bin2, bin4, bin8) indicates that the choice of
different levels within a specified mode does not make any significant difference on the
value of temperature precision. The sum-of-squares (SSQ) for the first two setting
options (preamplifier setting and readout rates ) was also not influenced by the choice of
any levels (x1, x2.. or 1MHz, 3 MHZ.. ) within the same setting option. But, the value of
SSQ decreases (become a good fit) with increasing binning (from bin1 to bin4). This is
because of the fact that the higher binning option involves fewer fitting points and errors
in the fitting of the individual line gets less impact.
The high capacity and high sensitivity output amplifier settings were checked to see if
there is a difference in temperature precision and signal strength. As a result, it has been
found that, both output amplifiers have almost similar precision values regardless of any
other setting option are used. This gives selection freedom of output amplifiers as far as
temperature precision is concerned and the signal level is high. However, the signal
strength of high sensitivity mode is a factor of five times greater than high capacity mode.
This indicates that one has to be very careful to choose the output amplifiers if the signal
strength is the main concern of a certain measurement.
The CCD camera was moved a certain distance away from the original position (point
of focus) to investigate the correlation with the slit functions. This influenced the slit
function of the Gaussian profile while Lorentzian line profile remains unaffected. The
full width at half maximum (FWHM) of Gaussian line profile increases with increasing
the distance away from the focus point of the detector, but the Lorentzian line profile
remains reasonably constant. This shows that the change in resolution of CCD camera is
much more correlated with a Gaussian line profile than Lorentzian. Therefore, the Voigt
line profile should be the convolution of bigger gauss profile and reasonably constant
Lorentzian line profiles. However, the change in distance (and there by resolution) of the
camera does not affect the temperature precision and SSQ. The instrument function
implemented in the current work was Voigt line profile.
The minimum peak intensity (counts) that must be achieved on the detector to get rid
of detector noise contribution to the overall precision was identified for full vertical
binning (FVB) mode, but it is very difficult to put a threshold for multi-track mode since

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it looks to be constant for all measurement points except for the first (the smallest)
intensity. The SSQ gets worse if the peak intensity is less than the threshold for both FVB
and multi-track modes. But, it remains relatively unchanged for any value greater than
the threshold intensity before saturation. In general, the FVB and multi-track modes have
fairly similar levels of precision and SSQ if the peak intensity is sufficiently high, but it is
reasonable to say that the multi-track mode is preferable when the intensity is low.
The measurement on N2O came out with some interesting results regarding temperature
precision. The values of average temperature and precision for N2O and N2 molecules
were compared in this investigation. The average temperature of the former molecule was
found to be higher than the later. This could be due to the less accurate theoretical library
of N2O especially the line widths. But, the value of temperature precision turns out to be
much lower (which means high precision) for N2O than its counter part. This indicates
that N2O has a good potential to be implemented for diagnostic purposes. Nevertheless,
this molecule has to be studied well, to really understand the basic features and, to get
accurate spectroscopic parameters.
To sum up, the detector investigation and N2O measurement performed in the current
work creates an opportunity to understand the capability of the CCD detector, and to see
the potential of N2O molecule for temperature measurement purposes. The temperature
precision which can be achieved using the current detector can be further improved by
smoothing the non-resonant spectrum (Argon spectrum in our case). This implies that the
shape (or can be said the smoothness) of the Argon spectrum has a big influence for
temperature precision. Therefore, a more detailed investigation is needed in this regard to
push the quality of CARS thermometry to the next limit regarding precision. The other
interesting thing in this work was the high temperature precision achieved using N2O
measurement. Hence, the outlook of the second investigation (N2O measurement) is that,
the theoretical code can be improved, so that, it will be applicable for higher temperature
measurements conditions where the concentration of N2O is higher. Generally, this work
gives a good insight of the CARS process and an ambitious bright future to produce a
better CARS thermometry for a real-world diagnostic application.

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Reference
1. H. Paetz, Introduction of company and services, VDE-ISE Pte. Ltd, January 18,
2010, Singapore.
http://www.sedb.com/etc/medialib/downloads/pdf_documents_for.Par.57249.File.t
mp/Speech%20By%20Mr%20Henry%20Paetz.pdf.(2010.08.18)
2. C. N. Banwell and Elaine M. McCash, Fundamentals of molecular spectroscopy, 4th

edition, 1994, London: The McGraw-Hill Companies.
3. http://hyperphysics.phy-astr.gsu.edu/hbase/molecule/rotrig.html (2010.07.25)
4. Eckbreth, A C 1996, Laser diagnostics for combustion Temperature and Species 2nd
edition (London: Gordon and Breach).
5. P.D. Marker and R.W. Terhune, Study of optical effects due to an induced
polarization third order in the electric field strength, phys.Rev.137,A801- A818
(1965).
6. C. Brackmann, J. Bood, M. Afzelius and P.E. Bengtsson1, Thermometry in internal
combustion engine via dual-broadband rotational CARS, Measurement in science
and technology.15 (2004) R13-R25.
7. Per-Erik Bengtsson, personal communication.
8. L.P. Goss, J.W. Fleming, and W.A. Steele W A 1980, Pure rotational coherent anti-
stocks Raman scattering of simple gases Opt.Lett 5 347-7
9. M. Alden, P.E. Bengtsson and H. Edner 1986, Rotational CARS generation through
a multiple four-color interaction, Appl. Opt. 25 4493–500
10. F. Vestin, and P.E. Bengtsson, Rotational CARS for simultaneous measurement of
temperature and concentrations of N2, O2, CO, and CO2 demonstrated in a CO/air
diffusion flame, Combustion physics, Lund institute of technology, Sweden,
proceeding of combustion Institute 32 (2009) 847-854.
11. User‟s Guide to the: ANDORTM TECHNOLOGY, NEWTONEM CAMERA, Andor

technology plc 2008.
12. http://www.andor.com/pdfs/downloads/spectroscopy.pdf (2010.08.18)
13. http://www.dpreview.com/news/0908/09080601sonycmos.asp (2010.08.18)
14. Brian M. Tissue, 1996

http://elchem.kaist.ac.kr/vt/chem-ed/optics/detector/ccd.htm (2010.08.23)
15. http://www.facstaff.bucknell.edu/mastascu/elessonshtml/Interfaces/ConvAD.html
(2010.07.01)

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16. http://www.andor.com/learning/digital_cameras/?docid=328 (2010.06.15)
17. https://www.andor.com/pdfs/specs/Newton_CCD.pdf (2010.06.12)
18. http://www.andor.com/scientific_cameras/newton/models/default.aspx?iProductCod
eID=19 (2010.06.28)
19. http://www.pco.de/fileadmin/user_upload/db/download/pco_cooKe_kb_dynamic_0
504.pdf (2010.06.28)
20. http://jp.hamamatsu.com/resources/products/sys/pdf/eng/e_dctn1.pdf (2010.06.30)
21. http://www.dpreview.com/learn/?/key=dynamic+range (2010.06.12)
22. F. Vestin‟s doctoral thesis, Development of dual-broadband rotational CARS for

applied flame diagnostics, division of combustion Physics, department of physics,
Lund University, Sweden, p. 61.
23. F. Vestin, M. Afzelius and P.E. Bengtsson, Improved species concentration

measurement using a species specific weighting procedure on rotational CARS
spectra, Journal of Raman spectroscopy. 36:95-101(2005)
24. D.peters, Nitrous oxide: A serious study of laughing matter, Molecular modeling
using computational chemistry methods (Lew Acampora), July 13, 2002.
(2010.08.18)
http://education.uncc.edu/cmste/Document%20HoldOLD/NITROUS%20OXIDE2.doc
25. G. Herzberg, Molecular spectra and molecular structure, Van Nostrand Reinhold
Company (1945).
26. M.Simockova et al, Journal of quantitative spectroscopy and Radiative transfer

98(2006) 130-155.
27. G.D.T. Tejwani and P.Varanasi, Theoretical line widths in N2O-N2O and N2O-AIR
collisions, state university of New York (1971).
28. A. Goldman, D.G. Murcray, F.H.Murcray, W.J.Williams, T.G.Kyle and J.N.Brooks

J. opt. Soc. Am. 60 (1970), p. 1466.
29. The authors are with United Technologies Research Center, East Hartford,
Connecticut 06108, Optical Society of America (1984).
30. Josef Pliva, Molecular constants of 14 N 2 16O , Department of Physics, the Ohio state
University, Columbus, Ohio 43210, Journal of molecular spectroscopy 27,461-488
(1968)
31. Alden M, Bengtsson P-E, Edner H, Kroll S and Nilsson D 1989 “ Rotational CARS:
a comparison of different techniques with emphasis on accuracy in temperature
determination” Appl.Opt. 28 3206-19

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32. F. Vestin, M. Afzelius, and P.E. Bengtsson “ Improved temperature precision in

rotational coherent anti-stokes Raman spectroscopy with a modeless dye laser”
February 2006, vol.45,No 4
33. L. Martinsson, P.E. Bengtsson, M. Alden, and S. Kröll, A test of different rotational
Raman line width models: Accuracy of rotational coherent anti-Stokes Raman
scattering thermometry in nitrogen from 295 to 1850 K, J.Chem.Phy.99(4), 15
August 1993.

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Acknowledgement
First and foremost I would like to thank the Almighty God for reasons too numerous to
mention and beyond words to describe. You given me the power to stay motivated all the
time and pursue my dreams. I could never have done this without the faith I have in you,
the Almighty.
I am heartily thankful to my supervisor Professor Per-Erik Bengtsson. He has been a

significance presence in my life. His ability to probe beneath the text is a true gift, and his
optimistic insights have strengthened this study significantly. I have never seen even a
single day that he stops believing in me which was very important synergy of the whole
work. I will always be thankful for giving me this opportunity to really understand the
fundamental science, and am looking for upcoming opportunities in the near future. I also
want to thank Alexis Bolin for his kind and tirelessly help every time when I needed it.
Overall, I feel so privileged to work in the CARS group which is a wonderful research
team with a great ambition of coming up with a new ideas.
I would like to thank my family, especially my mother. She is my inspiration to do thing

right in life. As a teenager I was so much into proving how independent I was, that I
failed to appreciate that one‟s family is an irreplaceable gift. Thank you, Mom, for being
so patient and forgiving with my teenage growing pains. It would be very difficult to be
successful without your words of encouragement regardless of very long distance
between us. I am extremely happy to be part of such a loving, understanding and
supportive family.
Finally, I am so grateful to all staffs of combustion physics division for their welcoming
behavior which makes my first days in the department to be interesting and productive. I
offer my regards to all of those who supported me in any respect during the completion of
the project. I believe that the foundation for being a future researcher was well built
during my stay in this division.

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Appendix
A: Matlab Code Samples for rotational CARS temperature evaluation

process
Appendix A1:
To identify the reference line from the air spectrum
“AirReference.m”
clear all
close all
nbrOfSpec=100; % Number of spectra evaluated

npixel=2048; % Number of pixels of CCD chip
path='C:\Documents and Settings\alemkn\Desktop\Rot.CARS BASIC\Andor Camera\N2O\nit\';
spectrumFile1=[path 'Air.dat'];
% Read data
fid=fopen(spectrumFile1);
for k=1:nbrOfSpec
spectrum1(:,k)=fread(fid,npixel,'ushort');
end
fclose(fid);
% Read Data
spectrumFile2=[path 'AirB.dat'];
fid=fopen(spectrumFile2);
for k=1:nbrOfSpec
spectrum2(:,k)=fread(fid,npixel,'ushort');
end
fclose(fid)
)
spectrumAverage=sum(spectrum1,2)/nbrOfSpec;
backgroundAverage=sum(spectrum2,2)/nbrOfSpec;
Sample=spectrumAverage-backgroundAverage; % Subtract background
figure(1)
plot(Sample) % detector view
axis ([0 2048 0 12000])
xlabel('Detector pixel');
ylabel('Intensity (count)');
title('Averaged spectra')

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Appendix A2:
To test the shape of the argon spectra
“ArgonTest.m”
clear all
close all
nbrOfSpec=500;
npixel=2048;
path='C:\Documents and Settings\alemkn\Desktop\Rot.CARS BASIC\Andor
Camera\2010.03.11\Argon Spectra\';%path=[path '\'];
%% Argon
%------------- Read Files----------------------

fid=fopen([path 'argx1.dat']);
for k=1:nbrOfSpec
recordedArgonSS(:,k)=fread(fid,[npixel,1],'ushort');
end
fclose(fid);
fid=fopen([path 'argBx1.dat']);
for k=1:nbrOfSpec
recordedArgonBackgroundSS(:,k)=fread(fid,[npixel,1],'ushort');
end
fclose(fid);
% %------------- Accumulate Spectrum from All Single Shots---------%
accumulatedRecordedArgon1=sum(recordedArgonSS,2)/nbrOfSpec;
accumulatedRecordedArgonBackground1=sum(recordedArgonBackgroundSS,2)/nbrOfSpec;
argon1=accumulatedRecordedArgon1-accumulatedRecordedArgonBackground1;
%------------- Read Files-----------%
for k=1:nbrOfSpec
end
fclose(fid);
for k=1:nbrOfSpec
end
fclose(fid);
% % %------------- Accumulate Spectrum from All Single Shots----------

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%------------- Read Files
for k=1:nbrOfSpec
end
fclose(fid);
for k=1:nbrOfSpec
end
fclose(fid);
% %------------- Accumulate Spectrum from All Single Shots--------
%------------- Read Files-----------
for k=1:nbrOfSpec
end
fclose(fid);
for k=1:nbrOfSpec
end
fclose(fid);
% %------------- Accumulate Spectrum from All Single Shots---------
%------------- Read Files-------------------
for k=1:nbrOfSpec
end
fclose(fid);
for k=1:nbrOfSpec
end
fclose(fid);

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% % %------------- Accumulate Spectrum from All Single Shots---------
%------------- Read Files---------------------
for k=1:nbrOfSpec
end
fclose(fid);
for k=1:nbrOfSpec
end
fclose(fid);
% %------------- Accumulate Spectrum from All Single Shots-------------
% ------------Plot with legend and different colors----------------

figure(1)
hold all
plot(argon1)
plot(argon2)
plot(argon3)
plot(argon4)
plot(argon5)
plot(argon6)
ylabel('Intensity')
xlabel('Detector pixel')
legend('HS-X1','HS-X2','HS-X4','HC-X1','HC-X2','HC-X4') % All six spectra will be plotted in one
axis
axis([0 2048 0 max(argon1)])
% Normalize, to verify same shape(spectral quality)!
figure(3)
hold all
plot(argon1)
plot(argon2/max(argon2)*max(argon1))
ylabel('Normalized Intensity')
xlabel('Detector pixel')
legend('HS-X1','HS-X2','HS-X4','HC-X1','HC-X2','HC-X4')
axis([0 2048 0 max(argon1)])

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Appendix A3:
To generate a spectral data in the form of accumulated shot (AS.dat) and
single shot (SS.dat)
“PrintOutFile.m”
clear all
close all
%% ------------------------------------------------------------
% For processing CARS - spectra recorded with the ANDOR camera.
%
% written by Alexis Bohlin spring 2010.
% -------------------------------------------------------------
nbrOfSpec=500;
npixel=2048;
path='C:\Documents and Settings\alemkn\Desktop\Rot.CARS BASIC\Andor Camera\ReadData
ANDOR\DAT1-Files\';
%% ---------------------------Argon Processing-------------------------
%------------- Read Files-----------------
fid=fopen([path 'argSS.dat']);
for k=1:nbrOfSpec
recordedArgonSS(:,k)=fread(fid,npixel,'ushort');
end
fclose(fid);
fid=fopen([path 'argBSS.dat']);
for k=1:nbrOfSpec
recordedArgonBackgroundSS(:,k)=fread(fid,npixel,'ushort');
end
fclose(fid);
%------------- Accumulate Spectrum from All Single Shots--------------------------
accumulatedRecordedArgon=sum(recordedArgonSS,2)/nbrOfSpec;
accumulatedRecordedArgonBackground=sum(recordedArgonBackgroundSS,2)/nbrOfSpec;
%------------- Reduce Background
argon=accumulatedRecordedArgon-accumulatedRecordedArgonBackground;
%------------- Remove zero and negative values of argon spectrum
for k=1:npixel
if argon(k)<1
argon(k)=1;
end

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end
figure(1)
plot(argon)
axis([0 2048 0 max(argon)+1])
title('Accumulated Argon')
%%--------------------- Nitrogen Processing-----------------
%----- Background - Read File and Accumulate Spectrum from All Single Shots-----
fid=fopen([path 'nitBSS.dat']);
for k=1:nbrOfSpec
recordedNitrogenBackgroundSS(:,k)=fread(fid,npixel,'ushort');
end
fclose(fid);
accumulatedRecordedNitrogenBackground=sum(recordedNitrogenBackgroundSS,2)/nbrOfSpec;
%------ Spectrum - Read File, Reduce Background and Divide by Argon----------
spectrumAccumulated=zeros(npixel,1); % returns 2048 by 1 matrix of zeros
fid=fopen([path 'nitSS.dat']);
for k=1:nbrOfSpec
% -----------------Read File----------------------
recordedNitrogenSS(:,k)=fread(fid,npixel,'ushort');
% ---------------Reduce Background and Divide by Argon--------------------
nitrogenSS(:,k)=(recordedNitrogenSS(:,k)-accumulatedRecordedNitrogenBackground)./argon;
%------------------- Accumulate Spectrum---------------------
spectrumAccumulated=spectrumAccumulated+nitrogenSS(:,k);
% ----Single Shot, Normalize Intensity to 10000 (Required as input for FORTRAN)----
mx=max(nitrogenSS(:,k)); % returns a raw matrix containing the maximum elemnt from eah
column
nitrogenSS(:,k)=nitrogenSS(:,k)*10000/mx;
nitrogenSS(:,k)=flipud(nitrogenSS(:,k)); % Flipped detektor view
end
fclose(fid);

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%------- Plot Accumulated Spectrum (AS) and Print OutFiles AS and SS (Single shot)
% Normalize Intensity to 10000
mx=max(spectrumAccumulated);
spectrumAccumulated=spectrumAccumulated*10000/mx;
spectrumAS=flipud(spectrumAccumulated); % Flipped detektor view
figure(2)
plot(spectrumAccumulated)
title('Accumulated Spectrum Nitrogen, detector view')
figure(3)
plot(spectrumAS)
title('Accumulated Spectrum Nitrogen, flipped detector view')
% Print outFile Accumulated Spectrum
headPrint=[npixel 0 0 0 0];
fid=fopen([path 'AS.dat'] ,'w');
fprintf(fid,'%4.0f %14.6f %14.6f %14.6f %14.6f\n',headPrint);
fprintf(fid,'%14.6f\n',spectrumAS);
fprintf(fid,'\n');
fclose(fid);
% Print OutFile Single Shot
fid=fopen([path 'SS.dat'],'w');
for k=1:nbrOfSpec
fprintf(fid,'%4.0f %14.6f %14.6f %14.6f %14.6f\n',headPrint);
fprintf(fid,'%14.6f\n',nitrogenSS(:,k));
fprintf(fid,'\n');
end
fclose(fid);

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Appendix A4:
To Calculate the Standard deviation, precision and average SSQ
“CalculatePreStdAvg.m”
clear all
close all
% ---------------Read results of Single-shot------------------
path='C:\Documents and Settings\alemkn\Desktop\Rot.CARS BASIC\Andor

Camera\Evaluation\Polyfit\New data\Single shot\N2O\';
[T_VARY SSQ_VARY REF_CH NR] = read_data([path 'evalSS.txt']);
amountOfSpectra=500;
vecOfSpectra=1:amountOfSpectra;
% -----------Mean temperature-----------
meanTemperature=mean(T_VARY);
vecOfmeanT=ones(1,amountOfSpectra)*meanTemperature;
% Calculate Standard Deviation, Precision and average SSQ
StandardDeviation=std(T_VARY)
precision=StandardDeviation/meanTemperature
averageSSQ=mean(SSQ_VARY)
figure(1)
hold on
plot(vecOfSpectra,T_VARY,'.')
plot(vecOfSpectra,vecOfmeanT,'-')
plot(vecOfSpectra,vecOfmeanT+StandardDeviation,'--')
plot(vecOfSpectra,vecOfmeanT-StandardDeviation,'--')
ylabel('Temperature (K)')
xlabel('Number of spectra')
legend('Single-shot T','Mean T','StandardDeviation')
% -------Plot of SSQ versus temperature-----
figure(2)
hold on
plot(SSQ_VARY,T_VARY,'.')
xlabel('SSQ')
ylabel('Temperature (K)')
legend('Single-shot SSQ Vs T')

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Appendix B: Input data file for theoretical library of N2O

Appendix B1:
The N2O.dat file format
Data file N2O.DAT contains spectroscopic constants

and fitted lw-coeficients for N2O
---------------------------------------------------------------------
2358.5849 , 14.33245 , -2.106E-3 , 2.583E-4 ! (1)
0.41901 , 0.172E-6 , 3.449E-3 , -3.0E-6 , 8.320E-9 ! (2)
1.0 , 1.0 ! (3)
1.09768E-8 , 6.91E-25 , 1.4E-16 , 0.0 ! (4)
0.085 , -0.705 , -3.39 , -1.27 , 0.0 , 0.0 ! (5)
---------------------------------------------------------------------
Expl and Refs:
(1) Vibrational constants: Vibrationsfrekvens OMEGAe, Anharmoniska
vibrationskonskonstanter Xe, Ye, Ze;(cm-1)
(2) Rotational constants: Be, De, ALPHAe, GAMMAe, BETAe; (cm-1)
(3) Statistical weights OK!
(4) Rotational-vibrational interaction
(5) Approximation of line widths

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Implementation of a CCD detector to dual-

broadband rotational CARS and

Master of Science thesis August

Division of Combustion Physics

Division of Combustion Physics, Lund University Page 2

Implementation of a CCD detector to dual-broadband

Master of Science thesis

Division of Combustion Physics

Division of Combustion Physics, Lund University Page 3

Division of Combustion Physics, Lund University Page 4

Division of Combustion Physics, Lund University Page 5

Division of Combustion Physics, Lund University Page 6

Chapter 2: Background Physics................................................................11

Chapter 3: Coherent anti-Stokes Raman spectroscopy (CARS)........... 14

Chapter 4: Andor CCD Camera.............................................................. 18

Chapter 5: Experimental Work...............................................................30

Chapter 6: Result and Discussion............................................................. 43

Division of Combustion Physics, Lund University Page 7

6.1.5 Instrument function............................................54

Chapter 7: Summary and Outlook........................................................... 69

Division of Combustion Physics, Lund University Page 8

New and renewable

Division of Combustion Physics, Lund University Page 9

1.1. Purpose of the project

1.2. General overview

Division of Combustion Physics, Lund University Page 10

Figure 2.1: Schematic diagram for two rotational energy levels.

Division of Combustion Physics, Lund University Page 11

2.1. Rotational energy of molecules

I  m1r12  m2 r22 (2.2)

Division of Combustion Physics, Lund University Page 12

2.2. Laser- based Combustion Diagnostic techniques

The CARS technique could be used in rotational or vibrational approach depending on

Division of Combustion Physics, Lund University Page 13

Coherent anti-Stokes Raman spectroscopy (CARS)

Coherent anti-stokes Raman spectroscopy (CARS) was experimentally discovered at

Q-branch transition S-branch transition

Division of Combustion Physics, Lund University Page 14

The third order susceptibility ( ) contains spectral (temperature) information and it is

The overall CARS signal can be expressed as [4]:

Figure 3.2: Phase-matching schemes: (a) Collinear phase matching and

Division of Combustion Physics, Lund University Page 15

3.2. Dual-broadband rotational CARS

Generally speaking, a rotating molecule has a time-dependent polarizability. This means

Division of Combustion Physics, Lund University Page 16

3.2.1 Experimental Setup of rotational CARS

The experimental arrangement of dual-broadband rotational CARS is shown in Figure

Division of Combustion Physics, Lund University Page 17

Andor CCD Camera

Division of Combustion Physics, Lund University Page 18

4.1. Safe Camera Operation

Division of Combustion Physics, Lund University Page 19

4.1.1. Environmental Conditions

Division of Combustion Physics, Lund University Page 20

Division of Combustion Physics, Lund University Page 21

Division of Combustion Physics, Lund University Page 22

4.2. Working principle of CCD detector

The charge transport explained above has to be digitized using an analog-to-

Division of Combustion Physics, Lund University Page 23

4.2.1. Preamplifier gain

In general, the function of a pre-amplifier is to amplify a low level signal to a

Division of Combustion Physics, Lund University Page 24

4.2.2. Readout rates