Effect of Cu Species on Optical and Structural Properties of

Sm+3 Doped Glass

Presented by : Muhammad Qasim Khan

SP20/RPH-021/LHR

Supervisor: Dr. Arslan Usman

Co-Supervisor: Dr. Junaid Amjad

|Department of Physics
|COMSATS University Islamabad
06/03/2023
 CONTENTS
 Problem Statement
 Objective
 Introduction
 Materials
 Methodology
 Characterization Techniques
 Results and Discussions
 Conclusion
 References

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 PROBLEM STATEMENT

The intensity of 4f intraband transitions of the rare earth ions such

as Sm3+ is weak and needs to be improved. A doping method of
metal Cu NPs is proposed and characterized to enhance the
intensity of the PL signal for these materials

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 OBJECTIVE

The main purpose of this research is to prepare Sm3+ doped

borophosphate glasses and propose Cu NPs to enhance the
emission signal.

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 INTRODUCTION OF GLASS
 Glass is a non-crystalline, often transparent amorphous solid

 Glass has no sharp melting point

 Glass is most often formed by rapid cooling (quenching) of the molten form

 The most common applications of glass in optics are as lenses, windows, mirrors,

and prisms

 Glass is made of 3 components i.e. Glass Former, Glass Modifier and Glass Intermediate

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 PHOSPHATE GLASS
 Phosphate glass is a class of optical glasses

 Instead of SiO2 in silicate glasses, the glass forming substrate is P2O5.

 Phosphate glasses can be advantageous over silica glasses for optical

fibers with high concentration of doping rare earth ions.

 Phosphate glass act as efficient heat absorbers when iron oxide is added.

 Phosphate glasses have three forms, hexagonal, tetragonal, and orthorhombic.

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 BOROPHOSPHATE GLASS

 Combination of two network former B2O3, P2O5 in the Borophosphate glass

 The interaction between the B2O3 and the P2O5 network produces a strong
network former mixing effects that leads to enhanced glass transition
temperatures and ionic conductivities
 Combination of P2O5 and B2O3 increase chemical durability of glass sample
 Doping of rare earth Samarium (Sm+3) in glass composition also modifies
the properties of glass.

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 MATERIALS
 Phosphorous Pentoxide (P2O5)
 Sodium per Oxide (Na2O2)
 Boron Trioxide (B2O3)
 Copper oxide (CuO)
 Samarium oxide (Sm2O3)

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Sr No Sample Composition P2O5 Na2O2 B2O3 CuO Sm2O3
ID
1 Q0 20P2O5 -30Na2O2 - 1.64 1.35 2.01 0 0.1
50B2O3

2 Q1 20P2O5 -30Na2O2 - 1.64 1.35 2.01 0.02 0.1

50B2O3

3 Q2 20P2O5 -30Na2O2 - 1.64 1.35 2.01 0.04 0.1

50B2O3

4 Q3 20P2O5 -30Na2O2 - 1.64 1.35 2.01 0.06 0.1

50B2O3

5 Q4 20P2O5 -30Na2O2 - 1.64 1.35 2.01 0.08 0.1

50B2O3

6 Q5 20P2O5 -30Na2O2 - 1.64 1.35 2.01 0.10 0.1

50B2O3

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 METHODOLOGY
The glass samples of composition 20P2O5 , 50B2O3 , 30Na2O2 , Sm2O3 = 0.1wt
% and different wt% of CuO (0, 0.02, 0.04, 0.06, 0.08, 0.1) NPs were
prepared by melt quenching technique in Pt crucibles

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 The chemicals were thoroughly mixed in appropriate proportions in form
of powder and placed into an electric furnace for melting at a temperature
of 1100-1200 °C for about 15-20 minutes.

 After complete melting, the melt was poured onto a stainless-steel plate
and cooled down for few minutes.

 Glass samples were prepared of 2mm thickness.

 Those samples then will be characterized by using UV-Vis, Raman, PL

and FTIR spectroscopies.
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 CHARACTERIZATIONS TECHNIQUES

The characterization Techniques used in this research are:

 FTIR spectroscopy
 Raman spectroscopy
 PL spectroscopy
 UV-Vis spectroscopy

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RESULTS

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 RAMAN RESULT

 The band at 344 cm-1 is

because of deformation
vibration of P2O5
 The band at 478 cm-1 relates
with PO- bond and associated
with symmetric stretching
 The band at 680 cm-1 is due
to glass modifier Na2O2

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 RAMAN RESULT
 The band at 811 cm–1 in is related to
the symmetric stretching of P–O
 The band at 917 cm–1 is due to the P–
O symmetric stretching vibrations of
non-bridging oxygen
 The band at 988 cm-1 relates with
asymmetry stretching mode of P–O–P
bond
 The band at 1286 cm-1 is responsible
for the symmetry-stretching vibration
of O–P–O units in the metaphosphates
glass network

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 FTIR RESULT
 The IR bands seen at 657 cm-1 are
attributed to P–O bond vibrations
 Asymmetric stretching vibrations of
the P–O–P bond correlate to the band
at 702cm–1
 The low absorption peak of about 785
cm-1 is due to the symmetric stretching
vibration of the P–O–P connections
 The peak at 961 cm-1 is caused by the
asymmetric stretching vibration of
bridging oxygen atoms in the P–O–P
link.

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 FTIR RESULT
 At 1196 cm–1 asymmetric
stretching vibration of modes was
overlaid by the 1422 cm–1
symmetric stretching vibrations of
the P–O bond
 At 1580 cm-1 water molecules or
O–H bending vibration is
centered.

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 FTIR RESULT
 The peak at 2268 cm-1 is caused
by O–H bond stretching vibrations
 The band at 2929 cm-1 is due to
the O–H bond stretching
vibrations
 The peak at 3213 cm-1 is
attributed to the O–H stretching of
water

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 PL RESULT
• The spectra contain two intense bands
at 597 and 568 nm, which correspond
to the 4
G5/2→6H7/2 and G5/2→6H5/2
4

transitions, respectively, as well as a

moderate intensity 4G5/2→6H9/2 (647
nm) and a faint emission peak
4
G5/2→6H9/2 (704 nm) in the visible
region.

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 UV RESULT

The transition from ground

state 6H5/2 to several excited

state 4I13/2, 6F11/2, 6F9/2, and

6
F7/2

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DIRECT AND INDIRECT BAND GAP

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DIRECT AND INDIRECT BAND GAP

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DIRECT AND INDIRECT BAND GAP

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DIRECT AND INDIRECT BAND GAP

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DIRECT AND INDIRECT BAND GAP

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CONCLUSION

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 Borophosphate glasses were prepared by melt quench technique and characterized for identification of

structural modifications.

 The FTIR spectroscopy showed functional groups and bonds of B 2O3 and P2O5 which confirms the presence

of non-bridging oxygen atoms (NBOs).

 Raman spectra confirms the presence of vibration from PO2O2- tetrahedral which is attached with boron

atoms, represent the boroxol rings as well as phosphate rings and the presence of terminal phosphate

tetrahedral is also confirmed.

The signatures of Sm3+ ions were observed due to transition from 4G5/2→6H5/2 states, the low energy SPR band

of Cu NPs and the excited state 6H5/2 in Sm3+ ions produce resonance with plasmonic of Cu NPs. The effect of

Plasmonics Diluent has been observed which is due to incorporation of metallic NPs

Metallic NPs reduce the effect of rare earth ions due to the excitation or de-excitation energy transform

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REFERENCES

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 Videau, J.-J., J. Portier, and B. Piriou, Raman spectroscopic studies of
fluorophosphate glasses. Journal of Non-Crystalline Solids, 1982. 48(2-3): p. 385-
392.
 Ibrahim, A., et al., Mixed alkali effect and samarium ions effectiveness on the
structural, optical and non-linear optical properties of borate glass. Journal of
Non-Crystalline Solids, 2018. 495: p. 67-74
 Malchukova, E. and B. Boizot, Spectroscopic properties and luminescence decay
behavior of pristine and β-irradiated Sm-doped borosilicate glasses. Journal of
Luminescence, 2021. 229: p. 117662.
 Morrell, B., et al., Optically erasable samarium-doped fluorophosphate glasses for
high-dose measurements in microbeam radiation therapy. Journal of Applied
Physics, 2014. 115(6): p. 063107.

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THANKYOU

06/03/2023