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Daniel Bartles
Kevin Wèscher

Raman effect

Advanced internship 2

April 23 - 27, 2018

Tutor: Markus Debatin

Institute of Physics
¨
Faculty of Mathematics and Physics

Albert-Ludwigs-University Freiburg im Breisgau

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Abstracts

In this experiment, different samples are examined for Raman lines, which arise due to the inelastic
scattering of light on these samples. A He-Ne laser, a white light lamp and a mercury vapor lamp
¨
are available as light sources, the spectra of which are measured with a CCD spectrometer or
monochromator with a photomultiplier. The aim of the experiment is to introduce various applications
of Raman spectroscopy, such as determining the temperature of a sulfur sample or determining the
¨
concentration of an unknown water-ethanol mixture. In addition, the advantages and disadvantages
of CCD and monochromator are examined using various measurements.

Using the CCD, the spectra of CCl4, CHCl3, CS2 and the lamps could be successfully measured. In
addition, the temperature of the sulfur sample of (29 ± 2) ÿC and a concentration of (60 ± 20) % of
the unknown mixture were determined. The measurements with the monochromator did not give
particularly strong results due to various technical problems. Only the spectrum of the Hg lamp could
be measured very precisely.
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Table of contents 3

Table of contents
1. Introduction and purpose of the experiment 4

2. Theoretical foundations 2.1. 5

Classic description of the Raman effect. . . . . . . . . . . . . . . ..... 6
2.2. Quantum mechanical description of the Raman effect . . . . . . . . . ..... 7

3. Experimental setup 8
3.1. How a monochromator works. . . . . . . . . . . . . . . . . . . ..... 9

3.2. photomultiplier . . . . . . . . . ....... . . . . . . . . . . . . . . .......9

3.3. CCD spectrometer . . . . . . . ......... . . . . . . . . . . . . . . . . . . . 10

4. Part 1: Measurements with the CCD spectrometer 4.1.

Calibration of the CCD . . . . . ......... . . . . . . . . . . . . 11 . . . . . . . 11
4.2. Determination of the laser wavelength . . . . . . . ....... . . . . . . . . . . . . . 13
4.3. Examination of the polarizing and notch filter. . . . . . . . . . . . . . . . . . . . . . . . 13
4.4. Spectrum of CCl4 and degree of depolarization. . . . . . . . . . . . . . . . . . . . 15
4.5. Spectra of CHCl3 and CS2. . . ....... . . . . . . . . . . . . . . . . . . . 16 . . . . .
4.6. Determining the concentration of an ethanol-water mixture. . . . 17
4.7. Temperature determination of the sulfur sample. . . . . . . . . . . . . . . . . . . . . . 18

5. Part 2: Measurements with the monochromator and PM 5.1. 19

Background and Calibration . ......... . . . . . . . . . . . . . . . . . . . 20
5.2. Examination of the gap width. ....... . . . . . . . . . . . . . . . . . . . . . 21
5.3. Detection limit of the photomultiplier. . . . . . . . . . . . . . . . . . . . . . . . . 22
¨
5.4. Detection probability for polarized light. . . . . . . . . . . . . . . . . . 23
5.5. Spectrum of CCl4 . . . . . . . . ....... . . . . . . . . . . . . . . . . . . . 23
5.6. Spectrum of CHCl3 . . . . . . . ....... . . . . . . . . . . . . . . . . . . . 24
5.7. Determination of the temperature of the sulfur sample . . . . . . . . . . . . . . . . . . . 25

6. Summary and conclusion 26

literature 27

A. Spectra of CHCl3 and CS2 28

B. Determination of the ethanol content 29

C. Sulfur spectra of the CCD 30

D. Sulfur spectra of the monochromator 31

E. Laboratory notebook 33
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¨
1. Introduction and Objective of the Experiment 4

1. Introduction and purpose of the experiment

¨
In this experiment, effects occurring with radiation scattered on liquids and solids are investigated. For
¨
this purpose, the individual tasks of the experiment will first be clarified, then the theoretical basis of the
effects occurring here will be explained in order to better understand the origin of these. Finally, the
structure used to measure the described effects is explained, followed by the description of how the
¨
measurements were carried out and the evaluation with OriginPro 2018G. The introduction is essentially
based on the instructions for the experiment and the scientific work of Pirmin Gohn.
¨
The main aim of the experiment is to learn more about the Raman lines occurring in scattered radiation,
¨
the origin of which is explained in the theory part. In this experiment, various properties of substances are
determined with the Raman lines, which illustrates the practical areas of application of Raman
spectroscopy. The tasks to be completed within the scope of this experiment are as follows:

• Wavelength calibration of monochromator and CCD spectrometer using a Hg

vapor lamp.

• Determination of the long-wave detection limit of the photomultiplier.

• Investigation of the effect of the notch filter on the measured spectrum.

¨
• Measurement of the effect of changes in monochromator slit width.

• Determination of the wavelength of the laser used.

¨
• Determination of the detection probability for vertically and horizontally polarized light

• Determination of the concentration of ethanol in an ethanol-water mixture

• Determination of the temperature of a sulfur preparation

• Determination of the Raman lines of different preparations and the assignment of these lines to the
normal vibrations of the different molecules. ¨

• Measurement of the spectrum of CCl4 with and without ÿ1/2 plates and determination from this
the degree of depolarization of the individual Raman lines.
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2. Theoretical foundations 5

2. Theoretical foundations
In order to better understand the Raman effect investigated in this experiment, the theoretical
¨
processes that occur in it are explained physically here. The classical picture of physics is sufficient
¨
for parts of this description, while for others the quantum mechanical description has to be used.
¨
¨
The Raman effect is based on the inelastic scattering of molecules with light. The light is absorbed
¨
by the molecule, which then goes into an excited vibrational state, from which it decays back to a
¨
lower state. If this new state now differs in the energy, which comes from the molecular vibration,
¨
then the photo emitted during de-excitation differs in its energy (or also frequency) from the incident
one.
Thus, in the spectrum emitted by the sample, in addition to the main maximum (Rayleigh peak), at
¨
which the molecule falls into the same state, further pairs of maxima (Stokes lines) can be identified,
their distance from the Rayleigh peak depends on the energy difference of the vibrational modes of
the molecule.

¨
Fig. 1: Vibrational energy transitionsleading to Stokes, Rayleigh and Anti-Stokes scattering. The
¨
different intensities of Stokes and Anti-Stokes can only be described quantum mechanically.
[2]
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2. Theoretical foundations 6

2.1. Classic description of the Raman effect

The Raman effect is classically described by the dipole moment of the different molecules. The dipole moment,
which is generated by a specific electric field, such as a light beam in a molecule, depends on the spatial
direction and is described by a polarizability ¨tensor ÿ :

p(t) = ÿ E (t ) (1)
ÿ ÿxx ÿxy ÿxz ÿ
ÿ=
ÿxy ÿyy ÿyz (2)
ÿÿÿ ÿÿÿ

ÿxz ÿyz ÿzz

The polarizability tensor is symmetric. If light is now used as the electric field in the above equation, the field
exhibits a periodic behavior and it follows for the above equation:

p(t) = ÿ E 0 cos ( ÿ0t) (3)

Rayleigh scattering can be derived from this, because if the polarizability tensor ÿ is not zero, then light with
the same angular frequency ÿ0 is emitted.
¨
However, the molecules themselves now also have the abilityto carry out various oscillations themselves. Due
¨
to this, however, the polarizability tensor changes with the
distance of the cores. According to Taylor, this is given in the first order by:
dÿ
ÿ(r) ÿ ÿ(r0) + |r=ro (r ÿ r0) dr (4)
¨
Here r0 is the equilibrium position of the molecular vibration and r is the deflection.¨ If
now also including that the oscillation and thus also the change of the distance from the rest position takes
place periodically with a certain angular frequency ÿs , the for the ¨ ¨
polarizability to:

ÿ(t) = ÿ0 + ÿ1 cos(ÿst) (5)

¨ ¨
For rotations, which can also appear in the molecule, there is still a factor of two in the cosine. Inserting this
¨ ¨
into the formula for the dipole moment of the molecule, we get:

p(t) =(ÿ0 + ÿ1 cos(ÿst))E 0 cos(ÿ0t) (6)

1 1 =ÿ0E 0 cos(ÿ0t) + ÿ1E 0
cos((ÿ0 + ÿs)t) + ÿ1E 0 cos((ÿ0 ÿ ÿs)t) 2 2 (7)

The first term is again the pre-existing Rayleigh term, in which the frequency of the scattered light corresponds
to that of the incident light. The second and third terms are the anti-Stokes and Stokes lines of the scatter
spectrum, respectively. Their frequency is shifted the same distance from the Rayleigh peak, one to higher
and one to lower frequencies. These are the classically expected Raman lines. From the theory one can see
that the lines only exist if the polarization tensor ÿ changes during oscillations, i.e. ÿ1 = = 0. However, what
cannot yet be explained with the classical approach is that the Stokes and anti-Stokes lines do not have the
da
same intensities
dr in practice.

Another variable that is relevant for Raman lines is the degree of depolarization. It specifies the ratio of light
¨
polarized parallel and perpendicular to the polarization of the original radiation:

2
Iÿ = 3ÿ
ÿz = 2 (8th)
I 45¯ÿ2 + 4ÿ
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2. Theoretical foundations 7

Here ¯ÿ and ÿ are constants that depend on the polarizability tensor of the molecule:

1
ÿ¯ = (9)
3 1 (ÿxx + ÿyy + ÿzz)
2 2
ÿ=2 ((ÿxx ÿ ÿzz) + (ÿyy ÿ ÿzz) + (ÿzz ÿ ÿxx) 2 + 6(ÿxy + ÿyz + ÿxz)) (10)

2.2. Quantum mechanical description of the Raman effect

The different intensities of the Stokes and anti-Stokes lines can also be explained by quantum mechanics. The
different intensities are due to the fact that the distribution of the vibrational states of the molecules follows
¨
the Boltzmann distribution. Since the initial states of Stokes and Anti-Stokes are different, the intensities of
these two lines also depend on how populated their initial states are:

IStokes nope
ÿ exp(Ea ÿ Ee ) = exp(hÿ¯ÿ = ) (11)
IAnti-Stokes N/A kBT kBT

In the last step it was used that the energy difference between the lower energy state (a) and the higher energy
state (e) is exactly the energy difference between the Stokes and anti-Stokes scattered radiation. where ÿ¯ÿ is
the frequency shift between Stokes and anti-Stokes.

¨
If one looks at the intensities for Stokes and anti-Stokes radiation expected from quantum mechanics, then
¨
another term, dependent on the frequency difference, results for the expected ratio:

4
IStokes = (ÿ0 ÿ ÿ¯ÿ)
4 exp(hÿ¯ÿ ) (12)
IAnti-Stokes (ÿ0 + ÿ¯ÿ) kBT
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3. Experimental setup 8th

3. Experimental setup

The experimental setup essentially consists of a laser whose light is directed onto an apparatus in which various
scattering cells can be used. CCl ¨ CHCl3, CS2, a water-ethanol mixture and a sulfur sample are available for this. 4,
¨
The polarized light from the laser can be ÿ
2
-tiles are rotated. The scattered light will

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¨
analyze it. Two options are available for the further structure of the experiment. In the first, the light beam is deflected
¨
with a mirror and focused with a lens into a CCD spectrometer (the workings of some important devices are explained
in the following parts). The signal from the CCD can then be evaluated using a computer.

spectrometer,
Alternatively,
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SpectraSuite

Figure 4.2.: Block diagram of the experiment with the CCD spectrometer

4.1.1. Laser

A laser is used for Raman spectroscopy due to its high intensity. Another
advantage of a laser is the ability to generate monochromatic light with a very
high level of coherence. LASER stands for "Light Amplification by Stimulated
Emission of Radiation".
The laser is therefore based on the principle of stimulated emission. The basic
elementsFig.necessary for a lasersetup
2: Experimental structure
using are an theoptically active medium, (left)
CCD spectrometer a or the monochromator (right). [2]
resonator and a source that supplies energy to the medium, this is called
pumping. The medium is brought into the resonator and the medium is excited
by the energy source. This leads to controlled light amplification. The waves
emitted are reflected several times in the resonator and then exit the resonator
(e.g.
If the energy through
frequency-doubled aconverted
a photomultiplier.
amplifiedis suppliedsemi-transparent
andNd-YAG The
by irradiation,
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(Nd+ ions (Nd:Neodymium)
is also referred toin as
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"optical pumping". A
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By embedding
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of the most
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used laboratory
the
energy levels are split. The ground state has five that can be evaluated.
the pumping level has three sub-states. The laser is pumped with a diode. By varying the diode wavelength, four pump levels with a high
degree of efficiency can 3 be stimulated. After frequency doubling, the laser emits
crystal.
for a wavelength
stability,
among
available,
The as
NdYag
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in the lamp the into
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the Rayleigh andphosphate
filterpeak aofnotch
the laser.
filter

¨
33
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3. Experimental setup 9

3.1. How a monochromator works

of different
this experiment,
wavelengths. For4.1.3.
a setup consisting
the Monochromator
thisintensity
purpose,
of a monochromator
of the
the light In
radiation
is broken
followed
down byinto
a photomultiplier
its spectrum inisthe usedmonochromator
to demonstrate
and, ideally, the monochromator is used for spectral decomposition of the incident light. In the present
monochromator, the light is first deflected by a mirror before only one frequency is emitted.
parallelizes it. The collimatedIt works
with
light likeon
a falls
mirror.this:
The Ingrating
a concavethe monochromator,
mirror
breaksanddown a the
is thrown light
reflection hits
parallel atoparabolic
gratinga rotatable
and then mirror
ontothat
grating
another
parabolic mirror, which again converts light into its spectral components through
interference on light
the grating.
intensity offurther.
analyzed the mirror isThese
out
the are
deflected
light is then
function is toalso
again.
bundled be focused,
In with
the
explained. and
scheme,
another finally
arrives
concave
the atthe
deflectionnow
amirror
certain monochromatically
mirrors
onto
frequency
the
areexit
omitted,
slit,
and where
can fanned
since
then
the
only
be
¨

Fig. 3: Schematic structure of the monochromator used in this experiment. [2] Figure 4.7.: Schematic structure of a monochromator [Mon]

As with a normal grating, the reflection grating forms a spectrum of single In the
figure it is easy to see how rays with different frequencies are exposed to un len light, i.e. maxima can be
determined at certain angles, with maxima being reflected at different angles (blue
ray and black ray). The lattice of light of smaller wavelengths appearing at smaller angles than those of light.
The apparatus can be rotatedwavelengths.
with a motor,The
so that the entire
reflection spectrum
grating can be
is rotatable traversed
at various with larger
speeds equivalent to
wavelength 0.05 Å/s to 5 Å/s by a small electric motor. That's how it can be. scan a specific
range in small steps.

3.2. photomultiplier
The intensity of the photons of a certain wavelength, which is separated by the monochromator, is
measured with a photomultiplier. The photomultiplier converts a light signal into a measurable electrical
signal. This happens when the incoming photons release 37 electrons from a cathode. The ejected electrons
are then accelerated by an electric field to the first in a large series of dynodes, which they strike and knock
out more electrons due to the higher momentum. This happens a few more times, the electrons are
accelerated to other dynodes and knock more electrons out of the material before they hit the anode and
become a voltage signal there.
 2. A strong electric field accelerates these photoelectrons
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3. In the course of the acceleration, the photoelectrons hit several dynodes, other
electrodes with a low work function, from which each impinging electron knocks 10
out 3-10 secondary
electrons. The number of electrons increases like an avalanche.

Fig. 4: Schematic structure of the photomultiplier used in this experiment. [2]

Figure 4.8.: Schematic structure of a photomultiplier [Pho]

spectrometer , A potential
with gradient
the result that along the dynodes is created by a voltage divider. 3.3. CCD
the electrons are accelerated further and further and the desired effect occurs. Depending
was usedcharge)
coupled on
in some thecan
atand
the number
parts
anode
instead ofofthe
dynodes,
be measured
and therea as
ver-
anThe
themonochromator
photomultiplier other
usedmeasuring
electrical
is
amplification
signal.
to measure device,
factor of
thethe which
spectruminis
original this experiment
photocurrent.
a CCD (charge
This accumulates

devices). The way it works is similar to the structure of the monochromator and photomultiplier. The light
entering through a small slit is again broken down into its spectral components using a grating with a
mirror. In the CCD spectrometer, however, not all areas of the spectrum are slowly run through with a
motor, but the spectrum hits a surface made up of many semiconductor pixels (about 2800 of these
¨
pixels are relevant for measuring the light).
¨ For each photon that hits one of these semiconductor pixels,
an electron-hole pair is created in the semiconductor and remains trapped in a potential well. After some
time, the individual pixels can then be evaluated by opening a gate and the electron-hole pairs trapped in
38
the potential wells are measured.

Since these are proportional to the intensity falling on the pixel, the intensity of the light that lies in the
spectral range of a pixel is obtained.

Fig. 5: Schematic structure of4.9.:the

Figure CCD
Inner workings spectrometer
of the used
OceanOptics USB2000+ (courtesy in this
of OceanOptics experiment. [2]
Germany
Gmbh)

The advantage of the CCD compared to the monochromator with a photomultiplier is that the data can
be read out here within a few seconds, while longer measurement times are required with the other setup
in order to obtain good accuracy. But this is exactly where the advantage of the monochromator lies. Due
40
to slow motor speeds, significantly better accuracies can be achieved with this setup within longer
measurement times.
¨
The accuracy of the measuring devices is determined by the width of the peaks, the intensities are
Poisson distributed and therefore carry the statistical uncertainty ÿ N.
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4. Part 1: Measurements with the CCD spectrometer 11

4. Part 1: Measurements with the CCD spectrometer

¨
The implementation of the measurements with the CCD and the evaluation of the data is described
¨
below. As a first step, the beam path for the measurement with the CCD had to be optimized. For this
purpose, the laser beam was reflected at low power with the sulfur sample in the middle of the beam
path and focused with the lenses in the entrance opening of the CCD. Since the focal lengths of the
lenses were not stored anywhere, they were estimated using a flashlight and a screen, resulting in f1
¨
ÿ 20 cm for the first lens (parallelization) and f2 ÿ 7 cm for the second lens (focusing on the detector).
¨
The intensity was then observed using the SpektraSuite software and maximized by fine adjustment
of the lenses. This allowed the individual measurements to be carried out, the chronological order can
¨
be found in the scan of the laboratory book E. The measurements were carried out with the dark
current correction activated, which automatically minimized the background noise in the CCD and
¨
thus made a background measurement superfluous. Voigt functions were used in the evaluation to
¨
determine the peaks

V (x) = (G ÿ L)(x) = G(ÿ )L(x ÿ ÿ )dÿ

are used, which

¨ describe the convolution of a Gaussian
¨ (G) and a Lorentzian (L) function and are well
suited for spectral analyses. The FWHM, which reliably describesthe width of the peaks, was chosen
as the measure for the resolution of the CCD.

4.1. Calibration of the CCD

¨
The calibration of the CCD was checked with the help of the mercury vapor lamp. This was installed in
¨
the beam path behind the scattering cell and its spectrum was measured and averaged over 20
individual measurements of 500 ms each. This happened automatically in the measurement software.
In order to examine the calibration of the CCD, the wavelengths of the peaks were determined, for
¨
which purpose a sum of Voigt fits was applied to the entire spectrum, see Fig.
6. Its parameter xc represented the midpoint of the peaks, the FWHM was given as the uncertainty of
these values.

Fig. 6: Spectrum of the mercury vapor lamp with Voigt fit to determine the peaks.
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4. Part 1: Measurements with the CCD spectrometer 12

Table 1 lists the peaks determined and the reference values1 of the lines in the Hg spectrum. As can be seen, the
uncertainties of the measured values agree very well with the reference values. ¨

Tab. 1: Comparison of measured peaks and reference values.

line reference value [nm] wavelength [nm]
blue 435.83 435.4 ± 1.0

green 546.07 545.8 ± 0.9

576.96 576.7 ± 0.7
orange
579.07 578.8 ± 0.7

Theoretically, two more peaks would have been expected, the cyan line at 493.60 nm and the red line at 614.95 nm,
which is just within the measuring range of the CCD (418.45 nm to 617.57 nm). However, these two lines only have a
low intensity, which is why they were lost in the noise.

¨
In order to be able to adapt the further measurement data, a calibration line was determined, see Fig. 7:

ÿcalibrated = a + b ÿmeas ,

with the parameters a = 0.940 69 nm and b = 0.998 81 from the fit.

Fig. 7: Spectrum of the mercury vapor lamp.

1Source: National Institute of Standards and Technology

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4. Part 1: Measurements with the CCD spectrometer 13

4.2. Determination of the laser wavelength

To determine the laser wavelength, the laser beam was reflected at a current of 0.55 A with a sheet of paper
into the beam path. The spectrum was then averaged over 100 measurements over 10 s each. The
¨
wavelength of the laser could thus be determined by means of a Voigt fit
from

ÿlaser = (532.2 ± 0.7)nm

¨
to be determined. This value agrees well with the manufacturer's specification of 532 nm, for which
unfortunately no uncertainty was given.

Fig. 8: Section of the recorded spectrum with the Rayleigh peak of the laser.

4.3. Examination of the polarizing and notch filter

¨
In order to be able to assess for further measurements whether the notch filter should be used, its influence
¨
on the spectrum of the white light lamp was determined, for which it was recorded once with and without a
filter for 10 ¨ 10 s, see Fig. 9.

Fig. 9: Comparison of the white light spectrum with and without a notch filter.
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4. Part 1: Measurements with the CCD spectrometer 14

As can be seen from the figure, the filter only lets through a minimum of the intensity in the range of the
laser wavelength, the cut in the spectrum (marked red) has an approximate width of (17 ± 1) nm ,
depending on whether you measure at the edge of the spectrum or at the minimum. This is very
compatible with the manufacturer's specification of 17 nm. Comparing the intensities at the laser
wavelength resulted in an attenuation factor of about 8.2 %. The notch filter should therefore be well
suited to measuring spectra with Raman lines that are far apart without the influence of the Rayleigh
peak or to saturate with it.

Fig. 10: Ratio of vertically to horizontally polarized light.

¨
The detection probability for vertically (90 ÿ ) and
¨ horizontally (0ÿ ) polarized light was ¨also checked with
the white light lamp. A polarizing filter was available for this purpose, which could be installed behind the
double mirror. The resulting spectra (also measured over 10 ¨ 10 s) and their ratio Iÿ/ I are shown in
Figure 10. This shows that up to a wavelength of 520 nm, horizontally polarized light is better detected,
but beyond that, vertically polarized light predominates. ¨
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4. Part 1: Measurements with the CCD spectrometer 15

4.4. Spectrum of CCl4 and degree of depolarization

In this part of the experiment, the spectrum of carbon tetrachloride was analyzed and its degree of
polarization determined. First, the measurement was carried out with and without the half-lamella plate. It
¨
was noticeable that some additional peaks appeared with theplate. Figure 11 shows the Raman lines
determined, including four Stokes and three anti-Stokes lines.

Fig. 11: Spectrum and Raman lines of CCl4.

Furthermore, the horizontally and vertically polarized spectrum was measured both with and without the
half-wave plate and the intensities of the visible peaks were compared when using the plate, giving the
degree of depolarization in 12 .

Fig. 12: Determination of the degree of depolarization.

By comparing
¨ the intensities (see Fig. 13), conclusions could also be drawn about the polarization of the
ÿ
laser: By using the polarizing filter in the 90 setting, the CCD detected higher intensities, i.e. it was more
¨
sensitive to vertically polarized light. Now, when using the half-lamella plate, it was shown that the intensity
also increased there and even new peaks appeared. This means that the half-wave plate produced
vertically polarized light, which in turn means that the laser was horizontally polarized.
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4. Part 1: Measurements with the CCD spectrometer 16

Fig. 13: Comparison of the spectra with different polarizations.

4.5. Spectra of CHCl3 and CS2

¨
Chloroform and carbon disulphide were available as further samples. These were each measured with all combinations of
notch filter and half-wave plate in order to determine the Raman lines for the best combination (filter and plate). Two
Stokes lines could be determined in each of the two spectra; this can be seen in Figure 14; the remaining spectra can be
found in Appendix A. Although other lines could be guessed at, they could not be determined with sufficient accuracy.

Fig. 14: Raman lines of CHCl3 and CS2.

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4. Part 1: Measurements with the CCD spectrometer 17

4.6. Determination of the concentration of an ethanol-water mixture

One of the samples to be examined in this experiment was an ethanol-water mixture of unknown
concentration that had to be determined. An additional measuring vessel was provided as an aid, in
which one's own mixtures could be prepared. A total of eight different mixtures between 0 and 100%
ethanol were measured, with one measurement taking · 10 s at full laser power. The measured spectra,
¨
over 5 see Fig. 15 and B, were then examined for peaks that were amplified by the addition of ethanol.
¨
Unfortunately, only one such peak at around 577 nm could be detected. An attempt was made to
improve this by using the notch filter, which unfortunately did not bring any added value due to the
strong noise.

Fig. 15: Excerpt from the spectra of water and pure ethanol.

¨
The peak found could now be measured with sufficient accuracy in five of the spectra. The intensity
was determined using Lorentz fits, which calculate a separate parameter for the height in Origin. The
¨
ethanol concentration was then plotted against this peak height, see Table 2 and Figure 16.

Tab. 2: Fit results

ethanol content [%] peak height
20±1 19±116
40±1 761±109
60±1 1079±114
80±1 1064±120
100±1 1739 ± 107

A function for determining the concentration was then determined by means of a linear regression,
¨
with which a concentration of (62 ± 20) % results for the unknown mixture.
The relatively large uncertainty of this value is due to the inaccuracy of the intensity determination,
which could not be further optimized due to the strong noise.
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4. Part 1: Measurements with the CCD spectrometer 18

Fig. 16: Determination of the intensity of the unknown mixture and linear regression of the
concentrations.

4.7. Temperature determination of the sulfur sample

To determine the temperature in a sulfur sample, its spectrum was recorded for different laser settings in
10 · 300 ms measurements. By using the notch filter it was possible to display two Raman lines very
precisely, see Fig. 17 and Appendix C.

Fig. 17: Sulfur spectrum with Lorentz fits using the notch filter and with a full laser
perfomance.

The intensities and wavelengths of the two Raman lines were determined separately with Lor entzfits,
fitting between the Rayleigh peak and the corresponding edge in order to minimize the influence of the
plateau-like background on the height. The peaks were clearly visible up to a laser current of 0.6 A, below
which the anti-Stokes line was overlaid with too much noise to be able to fit it satisfactorily.
¨

The temperature dependence of the measurements was now determined by rearranging equation (12)
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5. Part 2: Measurements with the monochromator and PM 19

derived:
4
IS
hÿ¯ÿ / ÿ0 + ÿ¯ÿ
T= ·
kB ln IAS
ÿ0 ÿ ÿ¯ÿ
2 2 2
sIAS sIS
kBT ·
sT = IAS + IS ,
hÿ¯ÿ
c
with ÿ¯ÿ = 12
(ÿAS ÿ ÿS) and the laser frequency ÿ0 = ÿLaser . The errors in the frequencies were neglected in
this calculation, since their relative errors were at least a factor of 10 smaller than those in the intensities. The
temperature of the sample could now be determined using the above formulas, see Table 3.

Tab. 3: Temperature calculation T /

Current [A] ÿAS/ nm IAS ÿS/ nm IAS K T / ÿC
1.5 519.14 6821 545.77 50865 306.1 ± 1.5 32.99 ± 1.5
1.4 519.13 5818 545.77 44469 302, 8 ± 1, 4 29, 60 ± 1, 4 519.15 3700
1.3 545.78 28558 301, 3 ± 1, 4 28, 19 ± 1, 4 519.14 3288 545, 78 25423
1.2 301. 2 ± 1. 4 28. 08 ± 1. 4 519.12 2659 545.76 20610 301. 0 ± 1. 4
1.1 27. 80 ± 1. 4 519.11 2215 545.76 17244 300. 4 ± 1.4 27.25 ± 1.4 _
1.0

0.9 519.10 1900 545.75 14535 302.8 ±1.4 29.62 ± 1.4 519.11 1309
0.8 545.75 10095 301.6±1.5 28.42 ± 1.5 519.10 770 545 75 5943 301.6±
0.7 1.6 28.41 ±1.6 519.10 371 545.76 2786 305.3 ± 1.9 32.14 ± 1.9
0.6

This resulted in an average temperature of the sample of (29 ± 2) ÿC. Compared to the room temperature it
seems that the intensities were overestimated by the fits. However, it is also possible that the sample has
heated up due to the irradiation with the laser, which is also indicated by the relatively constant temperature at
the different laser settings.

5. Part 2: Measurements with the monochromator and PM

¨
For the measurements with the monochromator, the beam path first had to be readjusted and focused on the
entrance slit of the monochromator. This turned out to be problematic because the lens mounting carriage
could not be installed directly in front of the slit and a compromise had to be made between the stability of the
structure and good focusing. Before starting the first measurements, the cooling circuit for the photomultiplier
¨ ¨
had to be activated to protect it from damage. Furthermore, the electronics responsible for the signal ur
¨
processing had to be adjusted using an oscilloscope. The gain could be set on the timing filter and individual
¨
energy windows set on the TSCA.

Before each data acquisition with the monochromator, the respective spectrum had to be measured in order to
¨
find the optimal settings for stepping speed and slit width. These values can be found in measurement protocol
E, as well as the energy window and laser settings.
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5. Part 2: Measurements with the monochromator and PM 20

5.1. background and calibration

In contrast to the CCD, the background correction on the monochromator had to be carried out manually.
¨
For this purpose, the dark pulse rate of the photomultiplier was recorded after a warm-up time of approx. 2
h, see Fig. 18.

Fig. 18: Dark pulse rate of the photomultiplier.

The linear increase in the dark pulse rate did not correspond to the expectation of a flat distribution. This
¨
could be due to cooling problems or a defect in the PM. Unfortunately, this behavior was noticed too late
¨
during the test, which is why no solution to the problem could be found due to time constraints.

Fig. 19: Spectrum of the Hg lamp.

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5. Part 2: Measurements with the monochromator and PM 21

The calibration of the monochromator was analogous to the previous procedure: the peaks of the Hg spectrum
(Fig. 19) were determined using Voigt functions and these were compared with the reference values. In this
case, the monochromator was able to find all expected lines within the error limits, which was a good argument
¨
for its accuracy.

Tab. 4: Comparison of measured peaks and reference values Line

Reference [ÿA] Monochromator [ÿA]
4046.6 4043.2 ± 2.5
violet
4077.8 4074.6 ± 2.2
blue 4358.3 4355.2 ± 2.7
cyan 4916 4913.3 ± 2.2
green 5460.7 5458.3 ± 2.4 _
5769.6 5767.3 ± 2.2
orange
5790.7 5788.6 ± 2.2 _

A calibration function could then be calculated using the values from Table 4, see Fig. 20. This was applied to
all subsequent spectra.

Fig. 20: Spectrum of the Hg lamp.

5.2. Examination of the gap width

Sometimes the most important parameter in the measurements with the monochromator was the right choice of
¨
the slit width. In order to get a rough feeling about their influence on the spectra, the violet h-line of the Hg lamp
¨
was traced for different settings. Figure 21 shows Voigt functions fitted to the data. This shows that both the
intensity and the width of the peaks increase significantly for larger slit widths. In order to achieve good
¨
measurement accuracy, the smallest possible slit width must be selected, but this must not be too small,
otherwise important peaks will not be resolved.
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5. Part 2: Measurements with the monochromator and PM 22

Fig. 21: Effects of different gap widths between 25 and 200 µm.

5.3. Detection limit of the photomultiplier

Another characteristic of the photomultiplier is its detection limit, which includes wavelengths that can no
longer be reliably detected. To determine this, the spectrum of the white light lamp was measured, see Fig.
22. As expected, the curve visible there should drop exponentially from around 6000 ÿA and tend to a
constant value, but as can be seen from the graphic, the intensity increases at instead. This seems to be the
same effect that was already determined for the dark pulse rate and thus prevents an exact determination of
the detection limit of the photomultiplier.

Fig. 22: Spectrum of the white light lamp.

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5. Part 2: Measurements with the monochromator and PM 23

5.4. Detection probability for polarized light

¨ ¨
The detection probability for polarized light should also be determined for the monochromator, but the
interference effects at the PM also occurred here, so that it was not possible to judge how realistic the
observed behavior is, in which the detector 90ÿ polarized light almost constantly better detected.

Fig. 23: Ratio of vertically to horizontally polarized light.

5.5. Spectrum of CCl4

The spectrum of CCl4 was also measured and evaluated in the same way with the monochromator. First, the
visible lines of the spectrum were determined with half-lamella plates, in this case three Stokes and two anti-
Stokes lines, see Fig. 24.

Fig. 24: Spectrum of CCl4 with and without delay plates.

An attempt was also made to measure the degree of polarization, but the measurements with the polarization
filter only delivered very noisy spectra (Figure 25), which again showed a strong linear increase. An attempt
was made to measure the two visible peaks using the delay plate, but these were shifted in the horizontal
and vertical position and were difficult to compare, which meant that the determination of the degree of
depolarization failed.
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5. Part 2: Measurements with the monochromator and PM 24

Fig. 25: Comparison of the spectra with different polarizations.

5.6. Spectrum of CHCl3

The spectrum of CHCl3 should also be examined with the monochromator, but did not provide any results
¨
for Raman lines, see Fig. 26. When using the polarizing filter, the increasing intensity was extremely
noticeable and was therefore observed more precisely, but no source for this effect could be found be
¨
determined.

Fig. 26: Spectrum of CHCl3 with and without polarizing filter.

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5. Part 2: Measurements with the monochromator and PM 25

5.7. Determination of the temperature of the sulfur sample

Attempts were also made to determine the temperature of the sulfur sample with the monochromator.
For this purpose, the left and right sides of the spectrum were each run through separately in
order to increase the accuracy and not to saturate with the photomultiplier. The spectra can be
found in Appendix D. Analogous to the calculation with the CCD, it was now also possible here
Temperatures can be determined at different laser settings, see Tab. 5:

Tab. 5: Temperature calculation

current [A] ÿAS/ nm IAS ÿS/nm IAS T / K T / ÿC
0.75 1st 6815.53501 ± 18 228 ± 18
1.0
1.25
1.5 5190.89 7993 5458.66 26966.53 480±11 207±11

With an average temperature of (234 ± 23) ÿC, however, this measurement does not seem to
have been successful - the large temperatures stem from the ratio of the intensities.
¨ This could
be due¨to the separate measurement of the peaks, which unfortunately could not be checked
with the overview in Fig. 27.

¨
Fig. 27: Overview spectrum of sulfur.
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6. Summary and conclusion 26

6. Summary and conclusion

In this experiment, different samples were used to illustrate applications of Raman spectroscopy using a
¨
laser. Two detectors were available, a CCD and a monochromator with a photomultiplier. The samples
examined included liquids such as CCl4, CHCl3 and CS2, which could be measured well using a CCD, but
¨
were difficult to evaluate using the monochromator. The CCD could also be used to estimate the concentration
of an unknown water-ethanol mixture using different reference mixtures. In addition, an attempt was made to
determine the temperature of a sulfur sample with both detectors, with the CCD this succeeded with a
relatively realistic value of approx. 29 ÿC, with the monochromator no meaningful result was obtained. A
white light and a mercury vapor lamp were also used to estimate some of the characteristics of the two
detectors. The Hg lamp could be measured much more precisely with the monochromator, and all expected
lines were detected very precisely. This measurement was also very accurate with the CCD, but only on the
intense peaks of the Hg spectrum.

The measurements with the CCD always resulted in meaningful measurements on average, and it was
¨
particularly convincing due to the possibilityof measuring entire spectra within short measuring times, which
¨
also allowed the adjustment of the beam path to be checked very well. Significant problems arose when
using the monochromator, such as adjusting the beam path alone was difficult because changes could never
be visualized directly.
The setting of the slit width was also a major complication factor, since by adjusting it it was possible to
measure accurately, but a lot of intensity was lost and it was often difficult to find a compromise between the
two. Another problem factor of the monochromator was its age, the measuring direction of the lattice motor
often jumped in the middle of the measurement and thus ruined entire series of measurements. This
happened especially at low speed settings, where the measurements themselves could take several hours.
However, the photomultiplier probably had the greatest influence on the poor measurement results with the
monochromator, as its dark current rose constantly and thus made some measurements unusable. In
principle, this should have been cooled the whole time and the temperature display of the cooling unit also
¨
showed only slight fluctuations, so it is difficult to assess what caused this effect.
¨

In order to optimize the structure, some new acquisitions should therefore be considered, first and foremost
a monochromator with a photomultiplier. Furthermore, the overall structure should be revised and the
¨
individual components brought to the same height, since the double mirror caused a certain skewness of the
beam, which meant that it did not hit the measuring devices parallel to the direction of detection. In addition,
¨
more leeway in front of the detectors was necessary for a correct adjustment of the lenses in order to be
able to focus really precisely on them, although it would be important for future implementations to record
¨ ¨
the focal lengths of the lenses directly to avoid wasting time in estimating them.
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literature 27

literature
¨
,
[1] Advanced Physics Lab Part 2 Raman Effect, University of Freiburg

[2] P. Gohn, Setup of an experiment on the Raman effect, state examination paper, University of Freiburg

List of Tables

1. Comparison of measured peaks and reference values. . . . . . . . . . . . . . . . . 12

2. Fit Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3. Temperature Calculation . . . . . ......... . . . . . . . . . . . . . . . . . . . 19
4. Comparison of measured peaks and reference values. . . . . . . . . . . . . . . . 21
.
5. Temperature Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

List of Figures
¨
1. Vibrational energy transitions leading to Stokes, Rayleigh and Anti-Stokes scattering. . .
¨
. . . . . . . . . . . . ......... . . . . . . . . . . . . ....... 5
2. Experimental setup using the CCD spectrometer (left) or the mono
chromator (right). [2] . . . . . . . . . . ....... . . . . . . . . . . . . . . . 8th

3. Schematic structure of the monochromator used in this experiment. [2] . . 9

4. Schematic structure of the photomultiplier used in this experiment. [2] . . 10 5. Schematic structure .
of the CCD spectrometer used in this experiment. [2] 10 6. Spectrum of the mercury vapor lamp with
Voigt fit to determine the peaks. 11 7. Spectrum of the mercury vapor lamp. . . . . . . . . . . . . 12 8.
Section of the recorded spectrum with the Rayleigh peak of the . . laser.
. . . 13
. .9..Comparison
. . . . of white light
spectrum with and without notch filter. . . . . . . . . 13 10. Ratio of vertically to horizontally polarized light. .
. . . . .
. . . . . . . . . . . . . 14
11. Spectrum and Raman lines of CCl4. . . . . . . . . . . . . . . . . . . . . . . . . 15
12. Determination of the degree of depolarization. . . . . . . . . . . . . . . . . . . . . . . . 15
13. Comparison of the spectra with different polarizations. . . . . . . . . . . . . 16
14. Raman lines of CHCl3 and CS2. . ....... . . . . . . . . . . . . . . . . . 16
15. Excerpt from the spectra of water and pure ethanol. . . . . . . . . . . . 17
16. Determination of the intensity of the unknown mixture and linear regression of the
concentrations. . . . . . . ......... . . . . . . . . . . . . . . . . . . . 18
17. Sulfur spectrum with Lorentz fits using the notch filter and at full laser power. .
. . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . 18
18. Photomultiplier dark pulse rate. . . . . . . . . . . . . . . . . . . . . . . . . 20
19. Spectrum of the Hg lamp. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
20. Spectrum of the Hg lamp. . . . . . ....... . . . . . . . . . . . . . . . . . . . 21
21. Effects of different gap widths between 25 and 200 µm. . . . . . . . . 22
22. White light lamp spectrum. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
23. Ratio of vertically to horizontally polarized light. . . . . . . . . . . . . . . 23
24. Spectrum of CCl4 with and without delay plates. . . . . . . . . . . . . . 23
25. Comparison of the spectra with different polarizations. . . . . . . . . . . . . 24
26. Spectrum
¨ of CHCl3 with and without polarizing filter. . . . . . . . . . . . . . . . . . . . . 24 25
27. Survey spectrum of sulfur. . . . . . . . . . . . . . . . . . . . . .......
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A. Spectra of CHCl3 and CS2 28

A. Spectra of CHCl3 and CS2

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B. Determination of the ethanol content 29

B. Determination of the ethanol content

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C. Sulfur spectra of the CCD 30

C. Sulfur spectra of the CCD

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D. Sulfur spectra of the monochromator 31

D. Sulfur spectra of the monochromator

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D. Sulfur spectra of the monochromator 32

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E. Laboratory notebook 33

E. Laboratory notebook
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E. Laboratory notebook 34