ATOMIC AND MOLECULAR SPECTROSCOPY LAB

PHYS 450- Advanced Lab

Thushani De Silva
PHYS 450 – 04/30/2018
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Table of Content
List of Figures .................................................................................................................................. 2
Introduction .................................................................................................................................... 3
Experimental Setup ......................................................................................................................... 4
Raman Spectroscopy................................................................................................................... 4
Laser Induced Breakdown Spectroscopy (LIBS) .......................................................................... 5
Data analysis ................................................................................................................................... 7
LIBS .............................................................................................................................................. 7
Raman Spectroscopy................................................................................................................... 7
Results and Conclusions................................................................................................................ 10
LIBS ............................................................................................................................................ 10
Raman Spectroscopy................................................................................................................. 10
References .................................................................................................................................... 11
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List of Figures
Figure 1 : Basic Raman setup .......................................................................................................... 4
Figure 2 : Raman spectroscopy setup ............................................................................................. 4
Figure 3: Focused graphene sample ............................................................................................... 5
Figure 4 : LIBS setup ........................................................................................................................ 6
Figure 5 : Graph of wavelength vs intensity for the unknown sample, obtained from LIBS .......... 7
Figure 6 : Raman Spectroscopy for the unknown sample1 ............................................................ 8
Figure 7 : Raman Spectroscopy for the unknown sample2 ............................................................ 8
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Introduction
Laser spectroscopy is the method of exiting a sample by exposing it to a laser beam and extracting
characteristic light source that can be analyzed by a spectrometer. This is a study of how light
interacts with matter (Demtröder, n.d.). The main two areas that were observed in this lab was
the Atomic Emission spectroscopy and Raman spectroscopy.
The Raman spectroscopy can be used to analyze the biological samples at the molecule level
(Movasaghi, 2007). By doing so it is possible to identify the chemical characteristics of the sample.
The applications of this spread out to a wide area in medical imaging and cancer cell detection
(Ximei Qian, et al., 2007). The light source emits a light beam near Infrared (IR) with a wavelength
at 785 nm which is manipulated by lenses and other optics to direct on to the sample. A CW laser
which gives a liner light is being used for this purpose. It’s possible to use an Ultra Violet (UV)
beam instead of IR which is more powerful. But some major drawbacks of UV light sources are
high cost and possible damages to the sample. Once the sample is exposed to the light beam, the
scattered light is then collected. A major part of this scatters light is due to Rayleigh scattering.
Which is at the same length as the light emitted from the source. But a small portion will be due
to the inelastic scattering (there will be a shift) that occurs due to interaction with molecules.
This portion of scattered light only depends on the biological sample and not on the excitation
light. After filtering out the light due to Rayleigh scattering, the remaining inelastic scattering
light is directed to the spectrometer to analyze. Resulting in-elastically scattered light is then
analyzed using a spectrometer. Using data mining techniques and mathematical methods,
valuable information about the sample can be extracted (Ferraro, 2003).
In atomic emission spectroscopy or laser induced breakdown spectroscopy (LIBS), more focus is
given to atomic composition rather than chemical characteristics. A high energy laser pulse (pulse
rate of 30 picoseconds) is used as the excitation light, which will be focused on the sample (using
lenses). This would atomized and excite the sample and bring it to the state of a plasma, resulting
in an emission of photons (Similar to making a tiny sun out of the sample that emits photos and
dies in milliseconds). These photons are collected and analyzed using a spectrometer which
would reveal the details about the atom (FANTONI, et al., 2006).
A similar technique is used by NASA to research about the possibility of the existence of water in
the planet Mars.
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Experimental Setup
Raman Spectroscopy
The following figure illustrates the basic outline of the Raman spectroscopy setup.

Optical setup that

Light Source Biological
manipulate the light beam
Sample
towards the sample

Optical setup to filter

Spectrometer out the Rayleigh
scattering and direct to
spectrometer

Figure 1 : Basic Raman setup

Raman spectroscopy is most suitable for analyzing covalent bonds while for analysis of polar
bonds, IR is preferred.

Spectrometer

Biological sample

Figure 2 : Raman spectroscopy setup

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Once the sample is placed on the glass slide, it is possible to focus using the microscope. To obtain
the Raman spectroscopy, the sample was then exposed to a near IR laser. Usually, the analysis is
carried out with a lower grating at the beginning. Once a peak had been located, it’s possible to
increase the grating. The two samples we observed in this lab are a sample of Silicon (Si) and a
sample of graphene dissolved in alcohol.

Figure 3: Focused graphene sample

Laser Induced Breakdown Spectroscopy (LIBS)

The next experiment we observed is analyzing a sample using LIBS. The light source is a pulse
laser that has a pulse rate of 30 picoseconds. The light emitted by the laser is guided using several
optics and focused on the sample using a lens. Since LIBS deteriorate the same, the light source
is programmed to change the area it hit on the sample, after each shot.
The sample is placed on an electronic stage which can be moved manually. The resulted data is
then compared with a standard database. From this analysis, it is possible to determine the
atomic composition.
The LIBS experimental setup is illustrated in figure 4 below.
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Figure 4 : LIBS setup

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Data analysis
LIBS
An unknown sample was analyzed under LIBS set up. For each shot, the measured intensity was
recorded with respect to the relevant wavelength. Afterward, the average intensity was
calculated for each wavelength and the data was plotted using excel. Figure 5 illustrates the final
plot of data obtained from LIBS.
From the following graph, it can be observed that there is a peak, well above the noise level at
279.352nm. By comparing this result with the standard database available at
https://physics.nist.gov/PhysRefData/Handbook/Tables/findinglist4.htm, we can identify the
elements that are presented in our sample (Anon., n.d.).

LIBS spectrum for the unknown sample 1

1860

1840
Peak at 279.352nm
1820
Average of the intensity

1800

1780

1760

1740

1720

1700

1680

1660

1640
185 205 225 245 265 285 305
Wavelength (nm)

Figure 5 : Graph of wavelength vs intensity for the unknown sample, obtained from LIBS

Raman Spectroscopy
A Graphene sample and a Silicon sample was analyzed by the Raman spectroscopy. The data
points related to the resulted Raman shift was plotted against the intensity. By comparing results
obtained, with the standard results available on the internet, we can identify what types of bonds
are presented in the sample. Based on these findings we will be able to figure out which sample
is Graphene and which sample is Silicon.
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Raman Spectroscopy for unknown sample 2

1600
G
1400

1200

1000
D
Intensity

800

600

400
2D
200

0
0 500 1000 1500 2000 2500 3000 3500
-200
Raman Shift (cm-1)

Figure 6 : Raman Spectroscopy for the unknown sample1

After comparing this result with Raman peaks available, we can conclude that the unknown
sample 1 is indeed pristine graphene. The signature peaks D, G and 2D peaks are very well visible
in figure6 (Anon., n.d.).

Raman Spectroscopy for the unknown sample 3

5000
4500
4000
3500
3000
Intensity

2500
2000
1500
1000
500
0
0 100 200 300 400 500 600 700 800 900
Raman Shift (cm-1)

Figure 7 : Raman Spectroscopy for the unknown sample2

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Figure 7 illustrates the Raman shift for the unknown sample 2. By comparing this with the data
available, we can conclude that this result represents Silicon. Therefore, the unknown sample 2
is Silicon (Quiroga-González, et al., 2014).
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Results and Conclusions

LIBS
From the figure 5, it was clear that the resulted peak of LIBS for the unknown sample is located
at 279.352nm. After comparing this with the data set available on the internet, we can conclude
that there was Manganese (Mn) presented in the sample since this value matches with the
standard data for Mn.
However, since we only analyzed a part of the spectrum, there could have been more peaks
related to other elements, presented in the sample. More analysis is required to investigate the
other elements in the sample and conclude what the sample could be.

Raman Spectroscopy
After comparing the results obtained from graphs in figure6 and figure7, we can conclude that
the unknown sample 2 is pristine graphene and the unknown sample 3 is Silicon.
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References
Anon., n.d. Characterization of Graphene by Raman Spectroscopy. [Online]
Available at: https://archive.cnx.org/contents/f06226c5-c2a4-4798-9c75-
b016acea73cd@3/characterization-of-graphene-by-raman-spectroscopy
[Accessed 30 April 2018].
Anon., n.d. NIST. [Online]
Available at: https://physics.nist.gov/PhysRefData/Handbook/Tables/findinglist4.htm
[Accessed 30 April 2018].
Demtröder, W., n.d. Laser Spectroscopy: Basic Concepts and Instrumentation. 3 ed. s.l.:Springer.
FANTONI, R. et al., 2006. LASER INDUCED BREAKDOWN SPECTROSCOPY (LIBS). Italy, Advances in
Spectroscopy for Lasers and Sensing.
Ferraro, J. R., 2003. Introductory Raman Spectroscopy. 2 ed. s.l.:ELSEVIER.
Movasaghi, Z., 2007. Raman Spectroscopy of Biological Tissues. Applied Spectroscopy Review,
42(5).
Quiroga-González, E. et al., 2014. Pore size modulation in electrochemically etched macroporous
p-type silicon monitored by FFT impedance spectroscopy and Raman scattering. Royal society of
chemistry, Volume 16, pp. 255-263.
Ximei Qian, X.-H.P. D. O. A. Q. Y.-G. et al., 2007. In vivo tumor targeting and spectroscopic
detection with surface-enhanced Raman nanoparticle tags. Nature Biotechnology, Volume 26, p.
83–90.