Authors Accepted Manuscript

Wide band gap of Strontium doped Hafnium oxide

nanoparticles
for
opto-electronic
device
applications - Synthesis and characterisation
J. Manikantan, H.B. Ramalingam, B. Chandar
Shekar, B. Murugan, R. Ranjith Kumar, J. Sai
Santhoshi
www.elsevier.com

PII:
DOI:
Reference:

S0167-577X(16)31304-0
http://dx.doi.org/10.1016/j.matlet.2016.08.026
MLBLUE21310

To appear in: Materials Letters

Received date: 1 June 2016
Revised date: 24 July 2016
Accepted date: 6 August 2016
Cite this article as: J. Manikantan, H.B. Ramalingam, B. Chandar Shekar, B.
Murugan, R. Ranjith Kumar and J. Sai Santhoshi, Wide band gap of Strontium
doped Hafnium oxide nanoparticles for opto-electronic device applications Synthesis
and
characterisation, Materials
Letters,
http://dx.doi.org/10.1016/j.matlet.2016.08.026
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Wide band gap of Strontium doped Hafnium oxide nanoparticles for opto-electronic device
applications - Synthesis and characterisation
J. Manikantan

e-mail jm.manikantan@gmail.com

Associate Professor
Department of Physics,
Sri Ranganathar Institute of Engineering and Technology,
Coimbatore, Tamilnadu, India.
H. B. Ramalingam

e-mail hbramalingamhb@gmail.com

Reader in Physics,
Department of Physics,
Government Arts College,
Udumalpet, Tamilnadu, India.
B. Chandar Shekar

e-mail chandar.bellan@gmail.com

Assistant Professor
Department of Physics,
Nanotechnology Research Lab,
Kongunadu College of Arts and Science,
Coimbatore, Tamilnadu, India.
B. Murugan

e-mail bmurugan.coonoor@gmail.com

Professor & Head

Department of Physics,
Government Arts College,
Ooty, The Nilgiris, Tamilnadu, India.
R. Ranjith Kumar

e-mail biotechranjith@gmail.com

Research Division,
The Nilgiris Education and Research Foundation,
The Nilgiris, Tamilnadu, India.
J. Sai Santhoshi

e-mail jsaisanthoshi@gmail.com

Assistant Professor
Department of Chemistry,
INFO Institute of Engineering,

Coimbatore, Tamilnadu, India.

#Corresponding Author Address

H. B. Ramalingam
Reader in Physics,
Department of Physics
Government Arts College
Udumalpet, Tamilnadu, India.
Phone: (+91) 9585626435
E-mail: jm.manikantan@gmail.com, and hbramalingamhb@gmail.com

ABSTRACT
Strontium doped HfO2 nanoparticles (Sr-HfO2 NPs) were synthesized by a simple coprecipitation method. FTIR and EDAX spectroscopy analysis shows stoichiometries
compositions of HfO2 NPs are pure. X-Ray diffraction pattern analysis revealed that the calcined
NPs shown the polycrystalline nature of the orthorhombic phase structure. TEM analysis
revealed that the morphology of the calcined NPs was spherical in shape with less agglomeration
and the crystallite size was about 30 nm. UV Visible spectroscopy analysis revealed that the
optical band gap energy of calcined NPs was 5.4 eV.

Keywords: Nanoparticles, FTIR, Optical materials and properties

1. Introduction
High-k dielectrics have attracted much attention of researchers because of their wide
range of micro and nanoelectronics applications such as Organic Light Emitting Diodes (OLED),
Dynamic Random Access Memories (DRAM), emerging nanodevices as a surface passivation
layer on high-efficiency crystalline silicon solar cells and for a variety of micro
electromechanical systems[1-3]. Due to impressive properties of HfO2 like dielectric constant,
wide bandgap, mechanical, chemical and electrical they are used in electronic manufacturing
applications, for example optoelectronics, electronics, optics, structural ceramics and magnetoelectronics. Hybrid structures of HfO2 obtained by integration with graphene which gives
openings to combine the versatile functionalities of oxides of graphene based high-speed nano
electronics [4-6]. In nano-electronics industry HfO2 has been identified as the best material for
the replacement of SiO2 because of its high dielectric constant and stability in contact with Si
[7]. Doping has been widely used and recognized as an effective way to improve the
performance of oxide materials. So a controllable resistive mechanism of the doped-oxide must
be established to improve the uniformity of the devices [8]. In the present work, we report Sr

doped HfO2 NPs by a co-precipitation method. To the best of our knowledge so far, no other Sr
doped HfO2 orthorhombic structure was reported.
2.

Experimental Methods

2.1

Materials
High purity research grade Hafnium Chloride (HfCl4) and Strontium Hydroxide

Octahydrate (Sr (OH)2. 8H2O) were purchased from Alfa Aesar.

2.2

Synthesis of Sr doped HfO2 NPs

The Sr doped HfO2 NPs were synthesized by a co-precipitation method. Hafnium

tetrachloride (HfCl4) and Strontium Hydroxide Octahydrate (Sr(OH)2.8H2O) were used as

starting precursors. A 0.04M (50ml) aqueous solution of (Sr(OH)2.8H2O) was added drop-bydrop into a 0.01M (50ml) aqueous solution of HfCl4 kept at 85C were subjected to vigorous
stirring by a magnetic stirrer for 5 hrs and ensured that the total dissolution of precursors. Then
drop wise addition of ammonia into this mixture solution resulted in yielding a white color
precipitate resin of Sr doped hafnium hydroxide. The Sr doped hafnium hydroxide was washed
thoroughly with distilled water and then centrifuge at 3000 rpm for ten minutes in order to
eliminate residuals. The procedure was repeated for ten times to eliminate impurity. The yield Sr
doped hafnium hydroxide precipitate resin was dried in microwave oven kept at 110C for 3 hrs
and then collected into a silica crucible and then calcined at 300C for 3 hrs to get pure
crystalline Sr doped hafnium oxide NPs.
2.3

Characterization of Sr doped HfO2 NPs

X-ray diffraction (Shimadzu, XRD 6000, Japan) was analyzed for the range of 10 to 80

by powder X-ray diffractometer using Cu-K radiation (1.5406 A). The stoichiometries
composition of NPs was analyzed by Energy Dispersive X-Ray spectroscopy (JEOL, JSM 6390,
Japan). The atomic and weight percentage of the existing elements were calculated by using
EDAX spectrum. The various functional molecules (groups) of NPs were analyzed by Fourier
Transform Infrared spectroscopy (JASCO FT/IR-680) for the range of 400 to 4000 cm-1.
Transmission Electron Microscopy analysis (PHILIPS, CM 200, Operating voltages : 20-200kV
Resolution :2.4 A) was used to examine the morphology. Selected Area Electron Diffraction
pattern is used to analyze phase structure and crystallinity of NPs. Optical properties such as

reflectance, absorbance and band gap energy of NPs were analyzed by UV- Visible spectroscopy
(JASCO V670, Japan) for the range of 200 to 2000 nm.
3. Results and discussion
3.1

Structural analysis of Sr doped HfO2 NPs

The X-ray diffraction pattern of Sr doped HfO2 NPs is shown in Fig.1. The XRD pattern

revealed that the NPs have a polycrystalline structure with orthorhombic phase. The superior
orientation plane and diffracting angle of orthorhombic NPs is (211) at 2 = 30.336. The other
peaks at 2 values of 15.19, 24.53, 36.60, 39.84, 44.92, 50.51, 51.30, 58.93, 61.60,
72.32, 76.43 are respectively to correspond (200), (210), (102), (410), (302), (022), (402),
(231), (512), (323) and (432) orientation planes. The observed diffraction pattern of Sr doped
HfO2 NPs is consistent with standard JCPDS file (83-0808). A peak observed in the diffraction
pattern at an angle 35.62 and correspond to (110) orientation plane. This may be due to the
doping of Strontium (Sr). No other impurity peaks were observed in the diffraction pattern
revealed that prepared NPs are of high purity and crystalline in nature. The crystallite size of Sr
doped HfO2 NPs were calculated by the Debye-Scherrer equation [9]

K
cos

(1)

where D average crystallite size, K- shape factor (0.9), - wavelength of Cu K radiation

(1.541A), - Full Width Half Maximum (FWHM) of reflection (in radians) located at 2 and

- angle of reflection (in degrees) was used to relate the crystallite size to the line broadening.
The average crystallite size was found to be about 33 nm.

Fig.1. X-ray diffraction pattern of Sr doped HfO2 NPs.

Energy Dispersive X-ray spectroscopy spectrum of Sr doped HfO2 NPs is shown in Fig. 2(a).
The EDAX stoichiometries composition analysis confirmed that the presence of Hf, O and Sr
elements in the as prepared NPs. The weight percentage of elements Hf, O and Sr are
respectively 83.56%, 15.56% and 0.88%. The atomic percentage of elements Hf, O and Sr are
32.27%, 67.04% and 0.69% respectively. It also indicated the absence of any impurities in the
prepared sample. This may be confirmed by XRD analysis.

Fig.2. (a) (EDAX) spectrum of Sr doped HfO2 NPs (b) TEM image and (c) SAED pattern
The TEM image of the NPs shown in fig. 2(b) revealed that the NPs have spherical in shape with
less agglomeration and average particle size of 30 nm. Fig. 2(c) shows the SAED pattern of the
NPs it shows several diffraction rings consisting of some dot patterns. It reveals that NPs are
polycrystalline in nature. The result of observed diffraction rings are in good agreement with Xray diffraction pattern.

Fig.3. FTIR spectrum of Sr doped HfO2 NPs.

Fig. 3. Shows FT- IR spectrum of Sr doped HfO2 NPs taken from the range 400 to 4000 cm-1.
The major peak at 758.02 cm-1, 518.85 cm-1 and 414.7cm-1 is ascribed to the formation of Hf - O

bonds, which are in the IR range (800-400 cm-1) of crystalline hafnium oxide active phonon
modes [10]. The absorption band at 2376.20 cm-1 may be due to CO2 in air [11]. The small
absorption bands at 2881.65 cm-1 and 2932.14 cm-1 may be due to asymmetric and symmetric
C - H stretches [12]. The observed peaks are consistent with previous reports [13] and confirmed
the high purity of the NPs prepared.

Fig. 4. UV-Visible absorption spectra of Sr doped HfO2 NPs. The inset shows the plot of
(handphoton energy (h

The optical properties of the Sr doped HfO2 NPs were analyzed by UV-Visible
spectroscopy. Fig.4. shows UV-visible absorption spectra of Sr doped HfO2 NPs. The
characteristic peak at 230 nm indicates the formation of HfO2 NPs [13]. The optical band gap
energy of the Sr doped HfO2 NPs is obtained from a plot between (handPhoton energy
h asshown in inset figure 4 using the relation [13]

h 2 Ah Eg

(2)

Where absorption coefficient, A constant and Eg band gap energy. The linear fit
of curve extrapolated in photon energy axis hgives optical band gap energy. The obtained
optical band gap of Sr doped HfO2 NPs is Eg = 5.4eV. This result is well consistent with previous
reports on HfO2 [14]. The optical band gap can also be obtained from UV absorption spectra by
extrapolation method[15-16]. The optical band gap energy of the Sr doped HfO2 NPs is obtained
by the relation

Eg

1240 nm

(eV )

(3)

Where g is the wavelength of the intercept from absorption spectra. The obtained optical
band gap energy (Eg) of the Sr doped HfO2 NPs is 5.39 eV which indicates Eg value of Sr doped
HfO2 NPs calculated from above mentioned methods are intercorrelated in agreement with each
other.
The higher absorbance value observed in the wavelength range < 225 nm and between
275 and 350 nm revealed that Sr doped HfO2 NPs could be used as UV- blocking contact lens
and UV absorbing layer in optoelectronic devices.

4. Conclusions
Pure HfO2 NPs were successfully synthesized by a simple and cost effective coprecipitation method with HfCl4 and Sr (OH)2. 8H2O as starting precursors. XRD analysis
revealed polycrystalline structure with orthorhombic phase. The particle size was about 30 nm.
TEM and SAED pattern analysis revealed the spherical shape with less agglomeration and
several diffraction rings consisting of some dot patterns. It also revealed the polycrystalline
nature of the nanoparticles which is analogous with XRD results. The evaluated optical band gap
energy (Eg) was about 5.4 eV and this result was highly consistent with extrapolation method.
The high absorbance observed in the UV region indicates the feasibility of utilizing these NPs as
UV blocking layers in contact lens and UV absorbing layer in optoelectronic devices.

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Highlights

XRD analysis revealed polycrystalline structure with orthorhombic phase. The

particle size was about 30 nm.
The high absorbance observed in the UV region indicates the feasibility of
utilizing these NPs as UV blocking layers in contact lens and UV absorbing layer
in optoelectronic devices.
The optical energy band gap (Eg) was found to be 5.4 eV
The observed optical properties indicated the feasibility of utilizing it as blocking
layer in solar cell applications to enhance the efficiency.

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Graphical Abstract