Synthesis and Characterization of Mn

doped TiO
2
Nano particles
Namit Anand
1111033
1 Objective
1. Prepare 5 solutions of 0.02 M, 0.04 M, 0.06 M, 0.08 M and 0.1 M of
TiO
2
and 1% MnCl
2
.6H
2
O.
2. Prepare thin lms of the above solutions by Spin Coating.
3. Observe Raman Spectroscopy of the above solutions
2 Introduction
Titanium dioxide, also known as titanium(IV) oxide or titania, is the natu-
rally occurring oxide of titanium, chemical formula TiO
2
. When used as a
pigment, it is called titanium white. Generally it is sourced from ilmenite,
rutile and anatase. It has a wide range of applications, from paint to sun-
screen to food colouring. Titanium dioxide is a white solid inorganic sub-
stance that is thermally stable, non-ammable and poorly soluble in water.
Pigment grade TiO
2
is manufactured to optimise the scattering of visible
light and consequently white opacity. This requires a primary particle size
of approximately half the wavelength of the light to be scattered, that is
half of 400 - 700nm for visible light.
Pigment grade TiO 2 is manufactured in order to maximise the number of
primary particles in this size range (approx. 200 350 nm). However as in all
production processes of particulate materials, there will be a distribution of
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primary particle sizes around the average value and it is likely that a small
fraction of the primary particles are 100 nm.
Ti0
2
nanomaterials (ultrane) are transparent and more eective as UV ab-
sorbers or photocatalysts. The transparency and UV absorbance allow for
eective use as a protective ingredient for sunscreens.
3 Preparing the samples
Our goal is to prepare 5 solutions of TiO2 with 1% MnCl
2
with dierent
molar concentrations, 0.02 M, 0.04 M, 0.06 M, 0.08 M and 0.1 M respectively.
We have taken 10 ml of water in the dierent syringes and kept varying
the amount of TiO
2
powder as per the molar concentrations. We studied
the Raman spectroscopy data of these solutions and compared it with a
standard sample of TiO2 solution Raman Spectra. Then, we made lms of
these solutions with the help of Spin Coating on Silicon chips and retake the
Raman data to match with the previous data.
3.1 Spin Coating
Spin coating is a procedure used to apply uniform thin lms to at sub-
strates. An excess amount of a solution is placed on the substrate, which is
then rotated at high rpm so as to spread the uid by centrifugal force. We
keep on rotating the thin lm till we get the desired thickness. The applied
solvent is usually volatile, and simultaneously evaporates proportional to
the angular speed of spinning. The steps are shown in the gure below:
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Figure 1: Raman Scattering
4 Synthesis of the samples
4.1 Working Formulas:
Amount of TiO
2
required for given concentration and volume of solution is
given by:
Molarity =
W 1000
M V
(1)
Where W= weight of TiO2 in gm, M= Molecular weight of TiO2 = 79.866
gm/mol,
V=Volume of Solution in mL For Mass percentage, we have
Mass percentage =
W
V
100 (2)
where W= weight of MnCl
2
.6H
2
O in gm and V=Volume of Solution in mL
3
4.2 Data for Solutions Used:
Molarity Weight of TiO
2
(gm) Weight of MnCl
2
(gm) Volume of Solution (ml)
0.02 0.016 0.09 10
0.04 0.032 0.09 10
0.08 0.064 0.09 10
0.1 0.079 0.09 10
0.1 0.079 - 10
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5 Raman Spectroscopy
It is the shift in wavelength of the inelastically scattered radiation that pro-
vides the chemical and structural information. Raman shifted photons can
be of either higher or lower energy, depending upon the vibrational state
of the molecule under study. A simplied energy diagram that illustrates
these concepts is shown below. Stokes radiation occurs at lower energy
(longer wavelength) than the Rayleigh radiation, and anti-Stokes radiation
has greater energy. The energy increase or decrease is related to the vibra-
tional energy levels in the ground electronic state of the molecule, and as
such, the observed Raman shift of the Stokes and anti-Stokes features are a
direct measure of the vibrational energies of the molecule.
Figure 2: Raman Scattering
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5.1 Observations
We rst look at the Raman scattering due to pure TiO
2
at 0.01M concen-
tration:
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To look at the change in Raman spectra due to addition of MnCl
2
we
compare two plots of same TiO
2
concentration with and without 1%MnCl
2
:
Figure 3: Raman Shift of 0.1 M TiO
2
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With MnCl
2
:
Figure 4: Raman Shift of 0.1 M TiO
2
with 1% MnCl
2
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Here we have 0.05M TiO
2
:
Figure 5: Raman Scattering
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Here we have 0.08M TiO
2
:
Figure 6: Raman Scattering
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6 Results and Discussion
With the gradient of the peaks from the above plots we can conclude that:
With increasing concentration of Mn there is a decrease in the Raman
shift.
We observe the four peeks of TiO
2
Raman spectra as expected.
7 References
Ulrike Diebold ,The surface science of titanium dioxide,Surface Science
Reports 48 (2003) 53229
www.en.wikipedia.org
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