DEPARTMENT OF SCIENCE & TECHNOLOGY

TECHNOLOGY BHAVAN, NEW MEHRAULI ROAD

NEW DELHI-110016

FAST TRACK SCHEME FOR YOUNG SCIENTISTS

“Synthesis and characterization of rare earths doped lanthanum and

gadolinium oxide nanoparticles for luminescence applications”

PROJECT COMPLETION REPORT

(01.10.2013 to 30.09.2016)

Subject Area: Physical Sciences

Submitted by
PRINCIPAL INVESTIGATOR: Dr. R.SRINIVASAN
Reference Number : SR/FTP/PS-086/2012 dated 09.09.2013

DEPARTMENT OF PHYSICS
P.S.R ENGINEERING COLLEGE
(Autonomous Institution – Affiliated to Anna University, Chennai)
(Accredited by NACC and listed under 12(b) of the UGC act,1956)
SEVALPATTI, SIVAKSI-626 140
VIRDHUNAGAR DISTRICT
TAMILNADU
0
 PROJECT COMPLETION REPORT

(01.10.2013 to 30.09.2016)

1. Title of the Project: “ Synthesis and characterization of rare earths doped lanthanum
and gadolinium oxide nanoparticles for luminescence applications”
(DST No: SR/FTP/PS-086/2012 dated 09.09.2013)

2. Principal Investigator (Name & Address):

Dr. R.SRINIVASAN
Associate Professor
Department of Physics
P.S.R.Engineering College
Sevalpatti, Sivakasi-626 140
Virdhunagar District
Tamilnadu
Tel: 04562-239600, 8012531325
Email: [email protected]

3. Implementing Institution:
P.S.R.Engineering College
(Autonomous Institution – Affiliated to Anna University, Chennai)
(Accredited by NACC and listed under 12(b) of the UGC act,1956)
Sevalpatti, Sivakasi-626 140
Virdhunagar District
Tamilnadu
4. Date of Commencement: 01-10-2013

5. Planned date of completion: 30.09.2016

6. Actual date of completion: 30.09.2016

7. Objectives as stated in the Project Proposal:

Broad area of Research: Physical Science
Specialization: Nanomaterials
Project Summary

In recent years, the field of rare earth oxide based nanoluminescence is highly important
to develop the new display devices like LED and other light emitting sources. The main
problem found in this field is to optimize the grain size of the nanoparticles for getting higher
quantum efficiency of the radiation. For this purpose, selection of the synthesis method is
very important to control the grain size of the nanoparticles. Apart from this, the optical
properties of the nanoparticles are highly influenced by morphology of the nanoparticles.
This luminescence field integrates the various disciplines such as physics, chemistry and

1
materials science due to the various applications. This provides the new platform to
understand the material properties in the nanometer regime. Hence, an effort is to be made to
develop high quality luminescence materials from rare earth doped lanthanum and
gadolinium oxide nanoparticles
Objectives

1. Develop suitable methods (Sol-gel and Precipitation method) to prepare pure and rare
earths (Europium, Samarium, etc) doped Lanthanum and gadolinium oxide
nanoparticles.

2. Optimize the rare earth dopant concentration in gadolinium and lanthanum oxide
hosts.
3. Develop a colour coordinate diagram for pure and rare earths doped lanthanum and
gadolinium oxide hosts.
4. Explore the quantum yield of the emitted radiation in different hosts like
lanthanum and gadolinium oxides.

8. Deviation made from original objectives if any, while implementing the project
and reasons thereof:
There is no deviation from original objectives of the project. As per our
objectives, first part of the project is preparation of pure lanthanum oxide (La2O3) and
gadolinium oxide (Gd2O3) nanoparticles using sol-gel and co-precipitation method. After
optimization, among two methods, it is found that sol-gel method is good for preparation of
above mentioned nanoparticles. In Second part of the project, same method is adopted for
rare earth doped europium and cerium doped lanthanum oxide nanoparticles.

9. Experimental work giving full details of experimental set up, methods adopted, data
Collected supported by necessary table, charts, diagrams & photographs:
9.1 Synthesis of gadolinium and lanthanum oxide nanoparticles (without doping)

As per our objectives, first part of the project is preparation of pure lanthanum oxide
(La2O3) and gadolinium oxide (Gd2O3) nanoparticles using sol-gel and co-precipitation
method. After optimization, among two methods, it is found that sol-gel method is good for
preparation of above mentioned nanoparticles.

Gd2O3 and La2O3 nanoparticles were prpepared by sol-gel method using the
Gadolinium nitrate hexahydrate (Gd(NO3)3.6H2O and (La2(NO3)3.6H2O nanoparticles
respectively usiong sodium hydroxide (NaOH) pellets are prectpitating agent.
2
 Figure.1 Experimental procedure for preparation of Gd2O3/La2O3 nanoparticles

0.1 Molar solution of (Gd(NO3)3.6H2O) and 0.2 Molar soution of NaOH were taken
in two different beakers respectively for the prepartion of Gd2O3 nanoparticles. The NaOH
solution was slowly added with (Gd(NO3)3.6H2O) solution, the precipitaion is formed in the
beaker containning (Gd(NO3)3.6H2O) solution. Then the preciptate is washed with distilled
water and dried. Finally fine nanoparticles are obtained. The preparation procedure explained
in Figure.1. After the preparation, particles were annealed at 900◦C for good crystalline
structure. Same procedure was followed for preparation of Lanthanum oxide nanoparticles.

9.2 Europium and cerium doped lanthanide oxide nanoparticles

In second phase of the project Europium and cerium doped lanthanum oxide
nanoparticles prepared by sol-gel method. Prepared particles were characterized by different
characterization techniques.
9.2.1 Preparation of europium and cerium doped lanthanum oxide nanoparticles
The same sol-gel method is adopted for preparation of 1 % europium doped
and cerium doped lanthanum oxide nanoparticles. 0.1 M solution consisting of Europium
nitrate (0.099) and samarium nitrate (0.001) and 0.2 Molar soution of NaOH were taken in
two different beakers respectively for the prepartion of europium doped lanthanum oxide
nanoprticles. The NaOH solution was slowly added with europium and lanthanum oxide
nitrate solutions, the precipitaion is formed in the beaker containning europium and
lanthanum oxide nitrate solutions. Then the preciptate is washed with distilled water and
dried. Finally fine nanoparticles are obtained. After the preparation, particles were annealed
at 900◦C for good crystalline structure. Same procedure was followed for preparation of 1%
cerium doped lanthanum oxide nanoparticles.

3
9.3 Characterization Techniques

The prepared Gd2O3, La2O3, Eu and Ce doped La2O3 nanoparticles were characterized
by different characterization techniques. X-ray diffraction techiniue is used to find the crystal
structure of the nanoparticles. The surafce moropholgy of the paprticles were stuided using
Scanning electron microscope (SEM). Elemental analysis carried out by Energy dispersive
spectroscopy. The excitation and emission peak recorded by Jasco Spectrofluorometer
(Purchased from this project).

JASCO SPECTROFLUOROMETER

10. Detailed analysis of results indicating contributions made towards increasing the
state of knowledge in the subject:

10.1 Results and analysis (Gadolinium Oxide nanoparticles)

10.1.1 Structurral Analysis

Figure 2 shows Powder X-ray diffraction pattern of the Gd2O3 nanoparticles. Cubic
structure of the Gd2O3 nanoparticles was confirmed by powder X-ray diffraction pattern. The
average grain size (d) was estimated from the broadening of XRD peaks, using Scherrer’s
equation. The estimated grain size of the nanoparticles is 20 nm
Intensity (a.u)

10 20 30 40 50 60 70 80
2 theta

Figure 2: Powder X-ray diffraction pattern of the Gd2O3 nanoparticles

4
 10.1.2 SEM and EDS analysis
The SEM image of the annealed sample (Gd2O3) is shown in the Figure 3. SEM image
shows the aggregated nature of secondary particles which are made up of agglomeration of
many primary particles.

Fig. 3:SEM Micrograph Fig. 4:EDS Spectrum

Fig. 4 shows the EDS spectra of the annealed Gd2O3nanoparticles. The EDS spectra confirm
the presence of gadolinium and oxygen in prepared nanoparticles.
10.1.3 PL Spectra Analysis:

The emission spectrum of Gadolinium oxide nanoparticles measured by excited at

230 nm as shown in the Figure 5. The photoluminescence experiments at room temperature
shows, a deep emission band at 400 nm. This peak may arise due to recombination of a
delocalized electron close to the conduction band with a single charged state of surface
oxygen vacancy. The luminescence excitation spectrum of Gd2O3 was monitored at 400 nm
and it is shown in Figure 6.
Intensity (a.u)

Intensity (a.u)

300 325 350 375 400 425 260 280 300 320 340 360

Wavelength (nm) wavelength (nm)

Fig. 5: Emission Spectrum Fig. 6: Excitation Spectrum

5
10.2 Results and analysis (Lanthanum Oxide nanoparticles)

10.2.1 Structurral Analysis

Figure 7 shows Powder X-ray diffraction pattern of the La2O3 nanoparticles.

Hexagonal structure of the La2O3 nanoparticles was confirmed by powder X-ray diffraction
pattern. The broadening of the peaks confirms that the particles were in the order of
nanometer range. Average grain size of the particles was estimated from Scherrer equation,
average particle size was 50 nm.
Intensity (a.u)

10 20 30 40 50 60 70 80
2 Theta (Deg)

Figure 7: Powder X-ray diffraction pattern of the La2O3 nanoparticles

10.2.2 SEM and EDS analysis

Fig. 8:SEM Micrograph Fig.9:EDS Spectrum

The SEM image of the La2O3 is shown in the Figure 8. SEM image shows the aggregated
nature of secondary particles which are made up of agglomeration of many primary spherical
particles. Fig. 9 shows the EDS spectra of the La2O3nanoparticles. The EDS spectra confirm
the presence of lanthanum and oxygen in prepared nanoparticles.

6
10.2.3 PL Spectra Analysis:

Figure 10 shows the emission spectrum of La2O3 nanoparticles. The emission spectrum
recorded at 230 nm. The mission band found at starting point of the visible region. The
emission peak shift towards shorter wavelength

Intensity (a.u)

300 350 400 450 500

Wavelength (nm)

Fig. 10: Emission Spectrum of La2O3 nanoparticles

10.3 Rare earths (Eu and Ce) lanthanide oxide nanopartcles

10.3.1. Results and analysis (Europium doped Lanthanum Oxide nanoparticles)

10.3.2 X- Ray diffraction Analysis

The X ray diffraction pattern of the annealed (900 ◦C) Eu doped lanthanum
oxide nanoparticles is shown in the figure 11. There is no secondary peak is observed in
diffraction pattern due to the doping of europium. All the peaks are corresponds to lanthanum
oxide nanoparticles
Intensity (a.u)

10 20 30 40 50 60 70 80
2 theta (deg)

Figure 11. Powder X-ray diffraction pattern of the Eu doped La2O3 nanoparticles

7
 The broadening of the peaks confirms that the particles were in the order of
nanometer range. Average grain size of the particles was estimated from Scherrer equation,
average particles size was 55 nm.

10.3.3 PL Spectra Analysis:

Figure 12 shows the emission spectrum of europium doped La2O3 nanoparticles. The
emission spectrum recorded at excitation of 390 nm. The emission spectra have a series of
emission peaks between 600 and 630 nm. The emission spectra show red emission peaks
above 580 nm. The strong red emission band is observed at 615 nm. The luminescence
excitation spectrum of Europium doped La2O3 was monitored at 615 nm and it is shown in
Figure 13.
Intensity (a.u)

Intensity (a.u)

350 400 450 500

600 620 640 660 680 700 720
Wavelength (nm)
Wavelength (nm)

Fig. 12: Emission Spectrum of Eu doped Fig. 13: Excitation spectrum of Eu

annealed La2O3 nanoparticles doped annealed La2O3 nanoparticles

10.4. Results and analysis (Cerium doped Lanthanum Oxide nanoparticles)

10.4.1 X- Ray diffraction Analysis

The X ray diffraction pattern of the annealed (900 ◦C) Ce doped lanthanum oxide
nanoparticles is shown in the figure 14. There is no secondary peak is observed in diffraction
pattern due to the doping of cerium. All the peaks are corresponds to lanthanum oxide
nanoparticles. The broadening of the peaks confirms that the particles were in the order of
nanometer range. Average grain size of the particles was estimated from Scherrer equation,
average particles size was 55 nm.

8
 Intensity (a.u)

10 20 30 40 50 60 70 80
2 theta (deg)

Figure 14. Powder X-ray diffraction pattern of the Ce doped La2O3 nanoparticles

10.4.2 PL Spectra Analysis

Figure 15 shows the emission spectrum of cerium doped La2O3 nanoparticles. The emission
spectrum recorded at excitation of 390 nm. The emission spectra have a series of emission
peaks between 400 and 500 nm. The emission spectra show violet emission peaks above 400
nm. The strong violet emission peak is observed at 404 nm. The luminescence excitation
spectrum of cerium doped Gd2O3 was monitored at 404 nm and it is shown in Figure 16.
Intenstiy (a.u)
Intensity (a.u)

240 270 300 330 360 390

Wavelength (nm)
300 350 400 450 500
Wavelength (nm)

Fig. 15: Emission Spectrum of Ce doped Fig. 16: Excitation spectrum of Ce

annealed La2O3 nanoparticles doped annealed La2O3 nanoparticles

9
11. Conclusions summarizing the achievements and indication of scope for future work:

Sol-gel method is good compared to other methods for rare earth oxide nanoparticles
preparation. Apart from that, This method is suitable for doping other rare earth ions in
lanthanide host. The blue shift is observed in the luminescence spectra of the nanoparticles.
It is planned to dope the ytterbium on lanthanum oxide host. It may be useful for lighting
applications.
12. S&T benefits accrued:
i. List of Research publications
1. Synthesis and characterization of Gadolinium oxide nanoparticles for luminescence
Applications ((Under Preparation)
2. Investigation on Lanthanum oxide nanoparticles prepared by sol gel method.
(Under Preparation)
3. Doping effect of Europium and cerium on lanthanide oxide nanoparticles. (Under
Preparation)
Papers published in Conference Proceedings
1. Investigation on Gadolinium oxide nanoparticles for luminescence applications,
R. Srinivasan, B. Renganathan and A. Chandra Bose in NANO INDIA 2O15,
Sastra University, Thanjavur, January 29&30,2015.
ii. Manpower trained on the project: No Man power provided in this project.
a) Research Scientists or Research Associates : Nil
b) No. of Ph.D. produced: One (Pursuing)
c) Other Technical Personnel trained: One
iii. Patents taken, if any : Nil

13. Financial Position

No Financial Position/ Budget Head Funds Sanctioned Expenditure % of Total cost

(Rs)
I Salaries/ Manpower costs NIL NIL NIL
II Equipment 11,00,000 10,93,750 72.91
III Supplies & Materials 1,40,000 86576 5.77
IV Contingencies 60,000 7,266 0.48
V Travel 10,666 307 0.021
VI Overhead Expenses 1,89,334 1,89,334 12.62
VII Others, if any NIL NIL NIL

10
14. Procurement/ Usage of Equipment

a)
Name of Make/Model Cost (Rs) Date of Utilization Remarks
SNo Equipment Installation Rate (%) regarding
maintenance
1 Spectroflurometer FP 8200 and 10,93,250 23.04.2014 80 Maintained
JASCO, Well
Japan

b) Plans for utilizing the equipment facilities in future

This instrument will be used to study about the emission and excitation spectra of other rare earth
oxide and metal nanoparticles.

Name and Signature with Date

(Dr. R.Srinivasan)
(Principal Investigator)

11