Ceramics International xxx (xxxx) xxx–xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

High energy (150 MeV) Fe11+ ion beam induced modifications of physico-
chemical and photoluminescence properties of high-k dielectric
nanocrystalline zirconium oxide thin films
Vishnu Chauhana, Rashi Guptaa, V. Kumara, J. Rama, F. Singhb, M. Prasadc, S. Kumard, S. Ojhab,
P.A. Alvie, R. Mehraf, Rajesh Kumara,∗
a
University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, New Delhi, 110078, India
b
Materials Sciences Group, Inter University Accelerator Centre, New Delhi, 110067, India
c
Transducers and Actuators Group, CSIR-Central Electronics Engineering Research Institute, Pilani, 333031, Rajasthan, India
d
Department of Applied Physics, Amity School of Applied Sciences, Amity University, Gurgaon, 122413, Haryana, India
e
Department of Physics, Banasthali Vidyapith, Banasthali, 304022, Rajasthan, India
f
Department of Physics, Dr. B. R. Ambedkar National Institute of Technology, Jalandhar, 144001, Punjab, India

A R T I C LE I N FO A B S T R A C T

Keywords: This work presents the influence of dominated electronic energy loss over nuclear energy loss induced by swift
SHI heavy ion (SHI) irradiation on the physico-chemical, optical and other properties of RF grown zirconium oxide
ZrO2 (ZrO2) thin films. For this purpose, thin films of ZrO2 grown on glass substrate were irradiated by 150 MeV Fe11+
XRD ions with a range of fluence from 2E12 to 5E13 ions/cm2 to understand the mechanism of induced modifications
UV–Vis.
and defects generation. The XRD results confirmed that the virgin and irradiated ZrO2 thin films were crystalline
PL
FTIR
in nature with monoclinic and tetragonal structure. The crystallite size varied from 19.93 nm to 46.43 nm with
RBS varying ion fluence. Strain, dislocation density and stacking fault were used to investigate the changes in
structural parameters. Tauc's plot method was employed for the quantitative evaluation of optical energy band
gap (Eg) that exist in the range of 4.45–4.62 eV. The transmittance (%) of the virgin and Fe11+ ions irradiated
samples was determined in the range of 35.69–66.09% using UV–Vis. spectroscopy. Further, the refractive index
was determined using different methods significantly depends on the optical band gap. The broad PL emission
peaks were obtained at 375 nm and 440 nm with the excitation wavelength (λex.) of 300 nm. The variation in PL
intensity with increasing ion fluence was attributed to the creation or annihilation of primary or complex de-
fects. FTIR spectroscopy was employed for the analysis of chemical modifications in vibrational bonds of samples
and the band obtained 660 cm−1was assigned to the asymmetrically coupled Zr–O–Zr stretching which presents
the strong vibration in samples. The band intensity increased up to the fluence 5E12 ions/cm2 and decreased at a
higher fluence of 1E13 ions/cm2. Rutherford backscattering spectroscopy technique was used to determine the
thickness (165 nm) of the samples.

1. Introduction vacancies on its surface [1,2]. It has been an interesting material due to
its exciting properties such as high mechanical strength, high flexural
During last few decades, there has been vigorous development by strength (> 1000 MPa), stability to high temperatures, high melting
researchers as well as industries in the field of ZrO2 thin films due to point, high rusting resistance, catalytic behavior in dehydration, high-
their unique and fascinating properties and extensive applications. The dielectric constant (∼25), low electrical conductivity, high hardness
significant role of zirconium oxide in optical and electronic applications and good chemical stability [3–10]. In addition to these properties,
helps to understand its fundamental interest of mechanism that how ZrO2 has interesting optical properties such as low optical loss, large
high densities of electronic excitation influence the various properties optical band gap, low absorption, high refractive index and high
of ZrO2 thin films. Zirconia is a wide band gap (5–7eV) p-type semi- transparency in visible and near IR region [11–13]. The existing lit-
conductor with good natural color and exhibit copious oxygen erature on the ZrO2 thin films grown by various techniques shows

∗
Corresponding author.
E-mail address: kumarrrpi@gmail.com (R. Kumar).

https://doi.org/10.1016/j.ceramint.2019.06.124
Received 7 May 2019; Received in revised form 22 May 2019; Accepted 11 June 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Vishnu Chauhan, et al., Ceramics International, https://doi.org/10.1016/j.ceramint.2019.06.124
V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

remarkable changes in their optical properties. These properties which dE/dX = (dE/dX)nuc. + (dE/dX)elec. + (dE/dX)rad.
are recommend it as useful support for a large number of applications.
In the radiative process so-called bremsstrahlung and Cerenkov ra-
As compared to the other ceramics, the desirable optical properties of
diation, the energy loss is very small can be neglected. The mechanisms
zirconium oxide such as shading adaptation and drop in the thickness
of nuclear and electronic energy losses are entirely different. The Sn
layer of veneer ceramic are useful to obtain the desired color [3]. As
dominates at low energies in the keV range (∼10keV/amu) and pro-
above mentioned properties of zirconium oxide depend upon the
duce atomic size point defects, cascade of collision with nuclei and
method of synthesis. Due to its favorable optical properties, it has been
cluster of defects. The Se dominates at high energies in the MeV to GeV
used in passivation and protective coatings, protective mirrors, high
range [43–45]. The modifications induced in materials by swift heavy
power lasers, optical filters, beam splitters and industrial application in
ions irradiation are well explained by Coulomb explosion (CE) and
optoelectronics and optical devices [14–17]. Moreover, zirconium
Thermal Spike (TS) models [46–48]. Thermal spike model well explains
oxide has attained great deal of attention towards its exceptionally
that mechanism of irradiation with SHI. SHI produces secondary elec-
important applications in metal–insulator–metal (MIM) capacitors [18],
trons of various energies along the path of incident ion. These higher
solid oxide fuel cells [19], metal-oxide semiconductor (MOS) [20] and
energy travel far away from the track leaving behind a path of posi-
memory devices [21]. Availability of very few literature on the physical
tively charged ions and lower energy electrons transfer their energy to
and chemical study of zirconium oxide thin films and its wide range of
atomic lattice by electron-phonon interaction and comes in equilibrium
significant applications has motivated researchers to synthesize ZrO2
with in very less time i.e. 10−15s. This induces a rise in local tem-
thin films using various synthesis techniques. A. Hojabri has in-
perature along the ion track for a very short duration of time leading to
vestigated the effect of thermal annealing on physical and optical
redistribution of atoms in the material [49–51]. A survey of the avail-
properties of RF sputtered ZrO2 thin films on silicon and quartz sub-
able literature on ion-induced modifications and deposition of several
strate [22].C. M. Lopez et al. deposited the ZrO2 thin films by thermal
oxide thin films reveals that the ZrO2 shows the remarkable changes in
oxidation on Si and SiO2 coated wafers. The optical properties were
optical properties of the material by the effects of ion beam irradiation
determined by using spectroscopic ellipsometry (SE) method and a
[52]. The significant change in UV–visible absorption spectra and op-
theoretical model was used to describe the variation of refractive index
tical density was observed as the YSZ samples irradiated by 2.4 GeV
with incident photon energy [23].U. S. Patel et al. have reported the
Lead (Pb), 1.4 GeV Xenon (Xe) and 2.2 GeV Gold (Au) ion irradiation
effect of different Ar partial pressure used to synthesize ZrO2 thin films
[46]. The decrease in optical energy band gap and transmittance was
and observed variation in optical band gap and refractive index with
observed by 120 MeV Ag9+ ion beam irradiation in ZrO2 thin films as
increasing Ar partial pressure [24]. A large literate is available on
synthesized by sol-gel technique. The evolution of direct bands elec-
structural and optical properties of this material but a very few reports
tronic structure can be ascribed to the existence of oxygen point defects
are available on its photoluminescence (PL) properties. The character-
between valence band and conduction band [53]. M. Rawat et al. in-
ization and enhancement in PL properties of ZrO2 may be used for the
vestigated the modifications induced in electronic and local structure of
future development of information storage devices and other important
Ag (120 MeV) and Ni (130 MeV)ion irradiated ZrO2 thin films by using
applications [25]. The photoluminescence of the oxide materials is
X-ray absorption spectroscopy (XAS) technique and the presence of the
caused by relaxation of electrons and holes on F- centres called oxygen
strain (induced by energetic ion irradiation) in ZrO2 thin films was well
vacancies [9]. R. E. González studied the photoluminescence properties
observed by stiffening of Micro- Raman modes of monoclinic phase
of ZrO2 nanostructures synthesized by the hydrothermal method [26].
[54]. Optical band gap engineering of ZrO2 deals with the shifting of
ZrO2 thin films can be grown by a number of different techniques in-
the emission spectra from Ultraviolet (UV) region to the visible region.
cluding atomic layer deposition technique [27], chemical vapour de-
So, the study based on the variation of optical band gap would be useful
position [7], DC magnetron sputtering [28], physical vapour deposition
for understanding the performance of devices in high radiation en-
[29], chemical bath deposition [30], surface sol-gel method [31], ion
gineering [55]. Several studies of different oxide materials such as
beam sputtering [32] and radio frequency sputtering [33]. Zirconium
Al2O3 [56], CdO [57], LiNbO3 [58], Ga2O3 [59], ZnO [60] and SnO2
oxide has three different structures: (i) monoclinic structure is stable at
[61] are available for the modification induced in optical properties of
1170 °C (ii) tetragonal structure is stable in the temperature range of
thin films under SHI irradiation. However, very less literature is
1170–2370 °C and (iii) cubic structure is estimated above the tem-
available on ion irradiated modification of optical properties of zirconia
perature of 2370 °C. Among all these three structures, a cubic structure
thin films. The high energy ion beam irradiation of 200 MeV Au re-
is considered as the most desirable structure for various potential ap-
sulted into the change in optical density of yttria stabilized zirconia
plications because the ionic conductivity of ZrO2 is important at high
samples [37]. J. Desforges et al. analyzed the optical properties of the
temperature [34–36]. The investigations of radiation-induced an effect
ZrO2 thin films when exposed to ultraviolet irradiation for different
on oxide materials is old phenomenon but synthesis and modifications
hours. They studied that the transmittance increased with the irradia-
of the oxide materials by ion irradiation techniques sustain this old
tion time, also refractive index and extinction coefficient found to be
phenomenon in present time and development of materials research for
lesser in case of UV- exposed ZrO2 thin films [8]. Hence, ZrO2 thin films
the sake of the community is step-by-step process [37,38]. To the best
were characterized by XRD and UV–Visible spectroscopy which was
of our knowledge, very few reports are available on the investigation of
used to examine the crystallographic parameters and optical analysis
SHI irradiation induced modifications on physical and chemical prop-
(transmittance and absorbance etc.) respectively of virgin and irra-
erties of ZrO2thinfilms. The SHI interaction with matter serves as an
diated samples. Further, the optical parameters such as optical band
efficient tool to engineer the physico-chemical and photoluminescence
gap, refractive index and skin depth were also calculated. The PL
properties at the nanoscale [39]. SHI can modify the material properties
emission spectrum was recorded at room temperature by using photo-
in a targeted manner to obtain desired properties [40]. When swift
luminescence (PL) spectroscopy. Fourier transform infrared (FTIR)
heavy ions interact with the electrons of the atoms of material they lose
spectroscopy was used for the analysis of chemical modifications in
their energy without disturbing the nuclei constituted by the lattice.
vibrational bonds of the samples. Rutherford Backscattering spectro-
The deposited energy into the electrons of the atoms causes modifica-
metry was used to calculate the film thickness of the samples.
tion of material via electron-phonon interaction. The swift heavy ions
traversing into solid material lose their energy by types of collision: (i)
elastic collision called nuclear energy loss (ii) inelastic collision called 2. Experimental details
electronic energy loss. The energy loss (dE/dX) has three constituents as
given [41,42]. Zirconium oxide thin films were grown on glass substrate using
Radio Frequency (RF) magnetron sputtering technique. High purity

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V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

Table 1 caused by iron ions were determined using SRIM and TRIM software
Parameters determined from SRIM for 150 MeV Fe11+ ions irradiation [62]. Further, the values of projected range (Rp), longitudinal (LTs) and
Zirconium oxide thin films. lateral (Ls) straggling were also determined using SRIM and TRIM
Ion energy Se (eV/Å) Sn (eV/Å) Rp (Å) LTs(Å) Ls (Å) program as mentioned in Table 1. Ion collision was evaluated by depth
versus Y axis plot and the simulation of 3000 ions anticipated for Fe ion
150.00 MeV 1.212E+03 1.585E+00 14.38 μm 5632 Å 6143 Å trajectories within the targeted ZrO2 material as displayed in Fig. 1. The
TRIM program was used in detailed calculation with full damage cas-
cade mode [63]. Fig. 2. (Left panel) displays generated Zr and O recoil
distribution profile for Fe11+ ions in ZrO2 thin films in irradiation
range. Since the displacement energy for Zr atoms is less than the O
atoms. Fig. 2. (Right panel) displays the profile of target displacement
and target vacancies in the irradiation range due to collision with Fe11+
ions. The target vacancies and target displacement (26/Ions) generated
are similar in irradiation region.

2.1. Characterizations

The prepared virgin and irradiated samples were characterized for

its structural, optical, chemical and depth profiling properties using
XRD, UV–Vis. spectroscopy, Fourier transform infrared (FTIR) spec-
troscopy and Rutherford backscattering spectrometry (RBS). XRD pat-
terns were recorded by use of PANalytical system Cu Kα radiation
(λ = 1.54 Å, voltage and current 40 kV and 45 mA respectively) with an
angular range of 20–70°. UV–Vis spectroscopy of samples was done in
the range about 200–600 nm with the help of UV–Visible U-3300
spectrophotometer. Room temperature photoluminescence properties
of virgin and irradiated samples were studied using the instrument
(Horiba Canada PTI QM-8450-11-C) Luminescence Spectrometer in the
Fig. 1. Ion collision effect of 150 MeV Fe11+ swift heavy ion irradiation.
spectral range of 325–570 nm with the wavelength of 300 and 310 nm
as the excitation source. FTIR of the samples was performed using
argon (Ar) gas was used as sputtering gas and deposition was carried Bruker Alpha-T Attenuated Total Reflection (ATR)-FTIR spectrometer.
out at room temperature (RT). Before deposition, substrates were che- Depth profiling of the samples was done using Rutherford back-
mically treated with H2SO4, H2O2 and HF to remove the contaminants scattering spectrometry in channeling condition using 5SDH-1.7 MV
on the surface. The grown thin films were annealed for 24 h at 500 °C Tandem accelerator at IUAC New Delhi, India. The energy of the He2+
and named as a virgin sample. Further, annealed samples (1 × 1 cm2) ion beam was 2 MeV.
were irradiated with 150 MeV iron ions at the fluence of 2E12, 5E12,
1E13 and 5E13 ions/cm2 in a high vacuum chamber at 1 × 10−6 mbar
with a charge state of 11+ from 15 UD Pelletron tandem accelerator at 3. Results and discussion
IUAC New Delhi, India. The energy (150 MeV) of Fe11+ ions was chosen
such that it could entirely cross the thin films. A constant current of 1 3.1. Crystallographic structure
particle nanoampere (pnA) was sustained throughout the irradiation.
The electronic stopping power (Se) and nuclear stopping power (Sn) Virgin and 150 MeV Fe11+ irradiated ZrO2 thin films were char-
acterized by X-Ray Diffractometer (XRD) technique. The structural

Fig. 2. (Left panel) profile of Zr and O ion recoils in the irradiated range due to collision with Fe11+ ion. (Right panel) generated target displacement and target
vacancies profile for Fe11+ ion beam in ZrO2 thin films in irradiated range.

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V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

Table 2
Determination of crystallite size of monoclinic (210) and tetragonal (112) phase
using Scherrer method, Dislocation density (Dd), Strain and Stacking fault (š)
virgin and irradiated ZrO2 thin films.
Fluence Scherrer method Dislocation Strain Stacking
(ions/ density Dd (10−4) fault (š)
cm2) 2θ L (nm) 2θ L (nm) (1014 m−2)

Virgin 39.55 38.55 50.28 19.93 6.97 7.74 0.39979

2E12 39.47 46.43 50.28 24.78 4.63 6.39 0.39982
5E12 39.48 44.11 50.24 21.83 5.13 6.73 0.39993
1E13 39.55 42.00 50.33 21.32 5.66 7.06 0.39920
5E13 39.52 40.09 50.23 20.38 6.22 7.40 0.39972

Fig. 3. XRD patterns of virgin and 150 MeV Fe11+ ion irradiated ZrO2 thin films
at different fluence.

analysis determines the Full width at half maximum (FWHM), crystal-

lite size via Scherrer method, strain, dislocation density and Stacking
fault probability using the XRD patterns. Fig. 3 depicts the XRD patterns
of virgin and 150 MeV Fe11+ ion irradiated ZrO2 thin films at different
doses of 2E12, 5E12, 1E13 and 5E13 ions/cm2. XRD patterns were re-
corded in the range of 2θ from 25° to 70° and depict that the thin films
are crystalline in nature. The XRD patterns show the polycrystalline
nature of the ZrO2 material. The observed XRD patterns affirmed the
monoclinic and tetragonal phase of zirconium oxide thin films. The
experimental XRD data was compared with the JCPDs. The reflections
of the peak oriented the Miller indices as (111), (210), (112), (211) and
(231) at peak positions (2θ) 31.50°, 39.55°, 44.80°, 45.78° and 66.16° Fig. 4. Variation of crystallite size with different irradiation fluence for ZrO2
well matches with (JCPDs. 70–2491) which have a monoclinic structure thin films.
with space group of P21/c (14). The well pronounced ZrO2 peak was
observed at (2θ) peak position 43.17° and 50.28° oriented at (102) and tetragonal structure for virgin and irradiated thin films is tabulated in
(112) planes respectively and corresponds to the tetragonal structure of Table 2. Fig. 4 shows the variation of crystallite size with ion fluence. R.
ZrO2 (JCPDs No. 81–1544) with the space group P42/nmc (137). It is Kumaravel et al. have reported a decrease in crystallite size after SHI
revealed that no significant shift in the angular position of diffraction irradiation [69]. But in our work, the crystallite size increased for lower
peaks was determined after Fe11+ ion irradiation. The appreciable fluence 2E12 ions/cm2 subsequently decreased with increasing the ion
variation in the intensity of the peaks was observed in virgin and ir- fluence up to 5E13 ions/cm2. The increment in crystallite size for lower
radiated samples. It can be clearly observed that there is no substantial fluence might be attributed to the reduction in the concentration of
change in diffraction peak position (2θ) and FWHM of the peaks. The oxygen vacancies and release of stress between the grains. For higher
change in the width of the peak provides the deviation in perfect fluence 5E12 ions/cm2, 1E13 ions/cm2 and 5E13 ions/cm2, the incre-
crystallinity of the virgin and irradiated thin films. As a result, careful ment in FWHM or reduction in crystallite size may be due to the gen-
observations express that there is an appreciable change in peak in- eration of lattice defects in the nanostructure by 150 MeV Fe11+ ion
tensity with increasing the ion dose. The intensity of the peaks at dif- beam [70]. The evolution of lattice strain has been carried out for virgin
ferent peak positions is increased with increasing the ion dose up to the and irradiated samples using the following relation [71].
fluence of 5E13 ions/cm2. It is noticed that the increase in peak in-
β cosθ
tensity accounted for the effect of swift heavy ions on scattering factor. S=
4 (2)
Appreciable enhancement in the peak intensity might be attributed to
change in the electronic density in the crystallographic position and this The lattice strain was determined for (210) plane of monoclinic
enhancement in peak intensity is a clear indication of improvement in structure of zirconium oxide thin films. Initially, the determined lattice
crystallinity of the thin films [64]. The crystallite size of the monoclinic strain was found to decrease for lower fluence as compared to virgin
and tetragonal phase was determined using the plane (210) and (112) sample and increased up to the higher fluence of 5E13 ions/cm2. The
respectively. The peak width is used to determine the crystallite size (L) increase in strain is ascribed to generation of point defects due to swift
and lattice strain (S) of the samples. Debye-Scherrer's method was heavy ion irradiation which causes the systematic shifting of atoms
employed to calculate the crystallite size using FWHM of the samples from their original position. During the high energy irradiation process,
[65–68]. the energy lost by the highly energetic ions generates some defects
kλ (point or extended defects) which cause the degradation of crystalline
L= quality with increasing the ion fluence [70,72]. A dislocation is con-
β cosθ (1)
sidered as irregularity or crystallographic defect in the crystal structure.
where, L is the crystallite size, k is shape factor constant (0.94), λ is the The movement of dislocations is hindered by other dislocations exist in
wavelength of X-ray used, θ is the Bragg angle and β is FWHM selected the material. Statistically, dislocations are a sort of topological defects.
for the particular peak. The evaluated crystallite size of monoclinic and Hence, the dislocation density (Dd) signifies the magnitude of defects

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V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

samples, it is observed that the transmittance is low in the Ultraviolet

region. But invisible region of the spectra, the curves shows the high
transmittance of energy. An easy look at spectra shows a progressive
increase in value of transmittance (%) as the fluence increased up to
5E12 ions/cm2. Further, the transmittance (%) decreased for the ZrO2
thin films irradiated at higher fluence 1E13 and 5E13 ions/cm2. This
continuous increment in transmittance (35.69–66.09%) up to the flu-
ence of 5E12 ions/cm2 is ascribed to improvement crystallinity of the
sample after irradiation [81]. For the higher fluence, the reduction in
transmittance might be due to the generation of localized energy levels
between valence and conduction band [82]. Further, an absorption
edge is used to determine the optical energy band gap of materials. The
optical band gap (Eg) of ZrO2 thin films have been evaluated by using
the Tauc relation [83,84].

(αhν)n = Z (hν- Eg) (5)

Where, Z is proportionality constant, α is known as absorption

Fig. 5. Variation of strain and dislocation density with different irradiation coefficient, ν is the frequency, h represents plank's constant, Eg is op-
fluence for virgin and irradiated ZrO2 thin films.
tical band gap energy and the value of n determine the type of transi-
tion. It is 2 and ½ for direct and indirect band transition respectively.
present in the film. Dislocation density provides the information about The absorption coefficient (α) is evaluated using the relation α = 2.303
the deformation of the lattice sight in the well-arranged crystal lattice (A/t), where A is absorbance and t is the thickness of the sample. The
of the material. It can be generated in material unlike point defects, value of photon energy (hν) extrapolated to α = 0 provides an ab-
vacancies etc. [73]. Moreover, a larger amount of dislocation density sorption edge which corresponds to optical band gap energy. Fig. 8
indicates the greater hardness. displays the plot of (αhν)2 vs. hν for virgin and irradiated zirconium
The number of dislocations in a unit volume is known as dislocation oxide thin films. Fig. 9. shows the variation in the value of band gap
density which was evaluated by crystallite size using the following re- energy of virgin and irradiated samples. At lower fluence, the value of
lation [74]. band gap increased from 4.45 to 4.62 eV as compared to virgin sample
1 and it is found to be decreased from 4.62 to 4.53 eV at higher fluence.
Dd = The optical band gap of ZrO2 thin films increased at lower fluence
L2 (3)
(2E12 – 5E12 ions/cm2) due to Burstein – Moss (B-M) shift [85]. The
where, L is the crystallite size of the thin films. The determined values reduction in optical band gap can be described on the basis of the
of dislocation density (d) for virgin and irradiated ZrO2 thin films are thermal spike model. This model explains that the interaction of swift
tabulated in Table 2. Fig. 5 depicts the variation of strain and disloca- heavy ions with the material leads to transfer of their energy to the
tion density with ion fluence. target electrons which results into the electronic excitation from lower
In crystallography, stacking fault is considered as planer defect and energy states to higher energy states. In this process, the vacancies are
it is a kind of defect describes the disordering of crystallographic planes created in these states. By the process of Auger effect, these generated
[75,76]. Stacking fault probability (š) was determined from the fol- vacancies are immediately filled by the outer electrons which causes
lowing relation [77,78]. vacancy cascade process which leads to breaking of bonds and ioniza-
Δ(2θ) ⎤ tion of the atoms responsible for changing the local structural order
Š= 0.2529⋅⎡ results into decrease in the band gap of the material [62,86]. Further,
⎣ tanθ ⎦ (4)
the decrease in band gap may be due to the radiation induced defects
Fig. 6 depicts the stacking fault of the virgin and irradiated samples like antisite oxygen and oxygen vacancies. The high energy irradiation
as evaluated by the inverse of the slope of the linear fitting determined induced lattice damage defects levels of oxygen below the conduction
from the plotting between 2θ and tanθ. band that results into decrease in band gap [60,69]. The band gap also
decreases due to formation of band tail states that effect the properties
3.2. Absorbance, transmittance and band gap of most of the semiconductor optoelectronic devices [59]. Costantini
et al. [37] focused on point defects formation in yttria stabilized zir-
The optical properties were analyzed for virgin and Fe11+ ions ir- conia by 200 MeV Iodine and 2.6 GeV Uranium high energy ion irra-
radiated zirconia samples with a range of ion fluence of 2E12, 5E12, diation samples. They showed the generation of color centres: oxygen
1E13 and 5E13 ions/cm2 by UV–Vis spectrophotometer. UV–Visible mono-divacancy as determined by electron paramagnetic resonance
absorption of ZrO2 thin films, deposited on glass substrate was per- spectroscopy. The change in the value of optical band gap concludes
formed in a spectral range of 250 nm–600 nm at room temperature that the SHI irradiation can tailor the properties by creating controlled
(RT). However, it is noted that the swift heavy ion irradiation of iron defects [87]. The determined values of optical band gap and transmit-
ions on ZrO2 samples initially causes a blue-shift in absorption edge for tance (%) are mentioned in Table 3. Several studies have reported the
the lower dose as compared to the virgin sample. But for the higher band gap of zirconium oxide thin films. In contrast, S. Venkataraj et al.
dose, Fe ions irradiation causes a red-shift in absorption edge. Careful have reported that the optical energy band gap lies in the range of
observation reveals that iron ions irradiation cause slight variation in (4.52–4.67 eV) of zirconia thin films prepared by DC magnetron sput-
shifting of absorption edge with increasing the ion fluence as displayed tering as a function of oxygen flow rate (2.9–4.0 sccm) [88].V. Sunke
in Fig. 7. Increase in optical band gap is governed by the blue shift and et al. determined the increased in band gap (3.49–5.48 eV) of DC
alternately for the decrease in optical band gap [79]. The optical magnetron sputtered ZrO2 thin films when thermally oxidized at a
transmittance of ZrO2 films were also studied at RT with the wave- temperature of 300 °C–500 °C [89]. H. Rath et al. reported the change in
length taken in the range of 250 nm–800 nm. Fig. 7 inset displays the the band gap by the influence of 297 MeV and 511 MeV Ni ion irra-
virgin and irradiated zirconia thin films are optically transparent. The diation on TiO2 material [90]. Moreover, the change in band gap in-
transmittance of samples lies in the range of 35.69–66.09% and poly- dicates that swift heavy ions create lattice disorder by the effect of
crystalline ZrO2 thin films depict an optical fringe [80]. For all the

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V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

Fig. 6. Plot between tanθ and 2θ for (a) virgin and Fe11+ ion irradiated ZrO2 thin films at fluence (b) 2E12 (c) 5E12 (d) 1E13 and (e) 5E13 ions/cm2. The slope of the
liner fitting was used to determine the stacking fault.

dense electronic excitation in the material. This can be the formation of the controlling of refractive index (n) and band gap (Eg) plays a sig-
defects level i.e., shallow energy levels near conduction band. This can nificant role. The correlation between these parameters is necessary for
be responsible for the transition from valence band to those levels in- the determination of the refractive index of newly developed materials
stead to band-to-band transition (BBT) which results in a change in the [93,94]. The RI of virgin and Fe ions irradiated ZrO2 samples was
band gap. The decrease in the optical band gap provides an indication calculated by using different models given by different research group.
of increase in oxygen vacancies of the ZrO2 lattice due to the ion irra- The first equation was provided by Moss who suggested that all
diation. Although the change in the value of band gap might be due to energy levels are scaled down by a factor of n4 in the dielectric medium
modification of density of surface defects induced in the lattice of zir- [95].
conium oxide [91].
n4 = K/Eg (6)
3.2.1. Refractive index and skin depth where K is constant which is equal to 95. This equation does not hold
The refractive index (RI) of a material is the fundamental and good for low and high energy band gap materials.
technological importance due to application in various optical devices N. M. Ravindra et al. proposed the equation that suggests the direct
[92]. The band structure of the material relies on band gap and re- relation between band gap and refractive index [96].
fractive index. The transparency of incident spectral radiation is also
determined by RI of the material. Among several optical parameters, n = 4.84–0.62 Eg (7)

6
V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

Table 3
Transmittance (%), direct optical band gap (Eg) and refracted index determined
from Reddy (R), Moss (M), Ravindra (RI) and V. Kumar (VK) of virgin and
irradiated ZrO2 thin films.
Fluence (ions/cm2) T (%) Eg (eV) (Refractive index)

R M RI VK

Virgin 35.69 4.45 1.743 1.479 1.321 2.077

2E12 65.25 4.59 1.714 1.457 1.234 2.056
5E12 66.09 4.62 1.708 1.452 1.215 2.052
1E13 58.75 4.56 1.720 1.462 1.252 2.061
5E13 52.81 4.53 1.726 1.466 1.271 2.065

Fig. 7. Optical absorption and inset transmittance (%) spectra of ZrO2 virgin
and irradiated thin films with 150 MeV Fe11+ beam at different fluence.

Fig. 10. Plot of variation of refractive index with ion fluence determined using
the method proposed by Reddy et al.

Further, Reddy et al. have given the modified form of Moss relation
which provide the empirical relation between RI and energy band gap
[97].

12.417
n=
2
Eg − 0.316 (8)
Fig. 8. Tauc plots of (αhν) vs. photon energy by linear extrapolations to de-
termine the direct band gap values of virgin and irradiated samples.
The values of the refractive index determined using this relation are
plotted in Fig. 10. The equation proposed by Reddy et al. provide a
better agreement with the experiment value as compared to Moss
model. All the above-proposed equations have some limitations for low
or high band gap materials. Consequently, V. Kumar et al. approached
to a relation to determine the refractive index of mixed materials in-
cluding group IV,III-IV and II-IV, semiconductor, halides, insulators and
oxide materials [97].

n= Z Ekg (9)

where, Z and k are constant 3.6668 and −0.32234 respectively. The

estimated values of the refractive index using all the above relations are
listed in Table 3. It is observed that the value of refractive index slightly
decreased up to the dose of 5E12 ions. cm−2 and slightly increased for
the dose of 1E13 and 5E13 ions. cm−2. Many researchers observed the
decreased value of the refractive index in the range of 2.18–2.04 as the
ZrO2 thin films were grown by DC magnetron sputtering [22] .P. S.
Chaudhari et al. reported the increase in the value of the refractive
index indicates the phase transition due to swift heavy ion beam irra-
Fig. 9. Plot of variation in value of direct band gap vs. ion fluence of ZrO2 diation in silicon oxide thin films [98].
virgin and irradiated thin films. The classical skin depth or penetration depth (χ) is defined as the
distance at which the amplitude of electromagnetic wave decreased by
a factor ‘e’ after traversing a thickness [99]. It can be determined using
the following relation [100,101].

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V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

Fig. 11. Skin depth vs. photon energy of virgin and Fe11+ ions irradiated zir-
Fig. 12. PL emission spectra of virgin and irradiated ZrO2 thin films with an
conia thin films at different ion fluence of 2E12, 5E12, 1E13 and 5E13 ions/
excitation wavelength of 300 nm.
cm2.

1
χ=
α (10)

The skin depth is related to the factor of the absorption coefficient.

Fig. 11 depicts the variation of penetration depth as a function of in-
cident photon energy for virgin and Fe11+ ions irradiated zirconium
oxide thin films with different fluence. For lower photo incident energy,
skin depth increases up to the certain photo energy of 2.24 eV, due to
reduction in the probability of absorption [99]. Further, skin depth
decreases beyond the incident photon energy and then it becomes zero
at a certain value of photon energy. The wavelength and energy at
which skin depth becomes zero is called cut off wavelength (λ cut − off )
and cut-off energy (Ecut − off ) respectively [102]. The value of Ecut − off was
determined 5.34 eV. As a function of fluence, the skin depth increased
up to the fluence of 5E12 ions/cm2 and decreased at higher fluence.

3.3. Photoluminescence study

Photoluminescence is a very sensitive technique for determining the

sample quality, structural defects i.e. oxygen vacancy, interstitials and Fig. 13. PL spectra of virgin ZrO2 sample with an excitation wavelength of
optical properties of the materials. Photoluminescence (PL) emission 300 nm and 310 nm in the wavelength range 325–570 nm.
spectra of virgin and irradiated samples were determined from (Horiba
Canada PTI QM-8450-11-C) Luminescence Spectrometer in the wave- nanocrystaline thin films at lower fluence [104]. Moreover, the incre-
length range 325–570 nm. The photoluminescence spectra of virgin and ment in PL intensity at lower fluence is attributed to the increase in the
irradiated ZrO2 thin films using iron ions (Fe11+) with a different flu- concentration of defects. The generation of point defects in the lattice
ence of 2E12, 5E12, 1E13 and 5E13 ions/cm2 are presented in Fig. 12 at might be due to the atomic displacement which is caused by the ions,
an excitation wavelength of 300 nm. Fig. 13 presents the PL spectra of neutrons and fast electrons. Moreover, the radiation dose of the ions
the virgin sample at an excitation wavelength of 300 nm and 310 nm. In must be very high for the formation of complex defects from the
Fig. 12, it is observed that the PL peaks of the broad emission bands of random association of point defects. Hence, swift heavy ions irradiation
the virgin and irradiated sample are almost the same in same wave- is considered as very high density excitation for the formation of high
length position but having variation in intensities for different ion defects density along the ion track [105]. At fluence of 1E13 and 5E13
fluence. PL results indicate that ion fluence does not alter the lumi- ions/cm2, the generation of exciton takes place which might be trapped
nescence mechanism of zirconium oxide thin films. The broad PL by the defects. Hence, when ZrO2 thin films were irradiated at higher
emission spectra is due to the formation of defects (oxygen vacancies fluence, PL intensity reduced as compared with the lower fluence
and oxygen interstitials) [43]. The virgin and irradiated samples have samples [106]. The decrease in photoluminescence intensity of emis-
two photoluminescence bands peaked at 375 nm and 440 nm. A broad sion spectra might be due to the annihilation of primary defects and
emission band at 375 nm is UV emission. Another, broad emission band generation of complex defects. H.S. Lokesha et al. reported the incre-
peaked at 440 nm is ascribed to the blue emission [103]. The intensity ment in photoluminescence properties of ZrO2:Dy3+ under SHI irra-
of PL emission bands of virgin sample is weak as compared to the ir- diation of 100 MeV Ni7+ ions beam [107]. The trend of the peak in-
radiated samples. For lower fluence, 2E12 and 5E12 ions/cm2 the in- tensity of PL spectra as a function a ion fluence is well agreement with
tensity of both the bands is maximum and then reduced for the higher the optical study. Similar PL spectra was observed by L. Chen et al. [15]
fluence. It is attractive that swift heavy irradiation of 150 MeV Fe ion for yttria-stabilized zirconia thin films irradiated by 500 keV Xe6+ ion
enhances the quantum efficiency and emission range of ZrO2

8
V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

Fig. 15. RBS spectra of virgin ZrO2 thin film.

Fig. 14. FTIR spectra of virgin and 150 MeV Fe11+ ions irradiated ZrO2 samples
with different ion fluence of 2E12 ions/cm2, 5E12 ions/cm2 and 1E13 ions/cm2. vibration [115]. Careful observation of the peaks reveals that there is
little shifting in the band position of the peaks 1240 cm−1 and
beam. They detected two strong broad emission centered at 420 nm and 1337 cm−1 towards the lower wave-number for the fluence of 5E12
530 nm (green emission) ascribed to band-edge transition and existence ions/cm2 and 1E13 ions/cm2. This important feature of continuous
of oxygen vacancies (FAA) respectively in the surface of YSZ samples. In shifting of the peak towards lower wave-number can be elucidated as a
Fig. 13, it is observed that there is not much difference in PL emission relief of high compressive stress of zirconium oxide thin films by ion
band spectra of ZrO2 virgin sample by taking the different excitation beam irradiation [116,117].
wavelength except the variation in intensity of bands. For the excitation
wavelength (λexc.) of 300 nm, the intensity of the band peaked at 3.5. Rutherford Backscattering Spectrometry
440 nm is greater than the intensity of the band centered at 375 nm.
While for the excitation wavelength of 310 nm, the intensity of the The characteristics of Rutherford Backscattering Spectrometry make
bands at 440 nm was more as compared to the intensity of the band it mainly useful for investigation of thin/multi-layer films. RBS is par-
appeared at 375 nm. ticularly used for determination of depth profile of heavier elements in
light element matrices. RBS spectra are recorded in RBS yield or in-
3.4. FTIR results tensity counts versus energy channel number. The energy, intensity
counts and FWHM of the peak give the information of elemental
Fourier transform infrared (FTIR) spectroscopy was used for the composition and thickness of the layer [117]. The RBS measurements
analysis of chemical modifications in vibrational bonds of RF grown were carried out with a beam of 2 MeV He2+ ions, stable beam current
ZrO2 thin films irradiated with 150 MeV Fe11+ ions beam with a range 20 nA incident on the sample and with charge of 10 μC. The spectra of
of different fluence as depicted in Fig. 14. The influence of Fe ion ir- virgin ZrO2 sample is presented in Fig. 15. The XRUMP code was used
radiation on zirconium oxide thin films can be clearly observed in FTIR to simulate the experimental data to provide the information of the
spectra under similar conditions. FTIR spectra of virgin and irradiated thickness profile of the sample [118]. The FWHM of the Zr peak ob-
thin films show peaks at 660 cm−1, 715 cm−1, 1240 cm−1, 1337 cm−1 tained at channel no. 1586.83 provide the thickness of the sample. It
and 1557 cm−1 as depicted in Fig. 14. It is expected an IR active mode can be inferred from the simulation (not shown here) that the thickness
at a lower wave number of 660 cm−1 and assigned to the asymme- of the thin films is 165 nm.
trically coupled asymmetric Zr–O–Zr stretching. The intensity of the
peak at this position is increased up to the intermediate fluence of 5E12 4. Conclusions
ions/cm2 and decreased at higher fluence 1E13 ions/cm2. The peak at
this region of lower wave-number presents the strong vibration of all Physico-chemical and Optical modifications of RF grown ZrO2 thin
the samples. The variation in intensity and area under this peak sig- films were studied with reference to 150 MeV Fe11+ swift heavy ion
nifying the change in chemical composition or chemical modification beam irradiation. After irradiation, the structural, optical and chemical
induced by Fe ion beam irradiation [108]. Further, there is no sig- properties were found to be tailored owing to the modifications induced
nificant change in intensity of the peaks of irradiated samples as com- by the dense electronic excitation of SHI in ZrO2 samples. XRD patterns
pared with virgin sample for the bands 715 cm−1, 1240 cm−1, revealed that the virgin as well as irradiated thin films were highly
1337 cm−1 and 1557 cm−1. This signifies the high resistance of zirco- crystalline in nature. Appreciable enhancement in the peak intensity
nium oxide to ionic radiation [109,110]. The IR spectrum of virgin and might be due to change in the electronic density in the crystallographic
Fe irradiated thin films shows a peak at 715 cm−1. This peak can be position. The change in strain is due to a change in defects density that
essentially assigned to the asymmetric motion of oxygen (O) atoms w. varies with increasing ion fluence. The study has shown the influence
r.t the center of symmetry. Consequently, this mode is due to asym- on optical band gap and transmittance (%) varied from 4.45 eV to
metric O–Zr–O stretching and formed by the movements of zirconium 4.62 eV and from 35.69 to 66.09% respectively after ion beam irra-
(Zr) and oxygen (O) atoms [111]. The FTIR transmittance band at diation of zirconium oxide samples. The variation in the value of optical
1240 cm−1 and illustrates the evident of Zr–O stretches [112]. The peak band gap may be due to modification of the density of surface defects
at 1337 cm−1 is ascribed to the absorption of non-bridging OH groups induced in the lattice of zirconium oxide. The refractive index of virgin
[113]. The peak towards the high wave-number at 1565 cm−1 is at- and irradiated samples was found to be decreased up to a particular
tributed to the Zr–OH vibration [114]. According to H. Liu et al., the fluence 5E12 ions/cm2 and increased at higher fluence as determined
band appeared at 1340 cm−1 and 1590 cm−1 ascribed to O–H bending by different methods. The reduction on PL emission intensity at 440 nm

9
V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

was observed with increase in ion fluence due to formation of defects [11] E. Ritter, Optical film materials and their applications, Appl. Optic. 15 (1976)
during SHI irradiation. The excitation wavelength varied form 2318–2827.
[12] F. Stetter, R. Esselborn, N. Harder, M. Friz, P. Tolles, New materials for optical thin
300 nm–310 nm does not change the PL emission spectra except the films, Appl. Optic. 15 (1976) 2315–2317.
change in the intensity of the emission band. The FTIR spectra depicted [13] S. Zhao, F. Ma, K.W. Xu, H.F. Liang, Optical properties and structural character-
the chemical modifications in vibrational bonds of virgin and irradiated ization of bias sputtered ZrO2 films, J. Alloy. Comp. 453 (2008) 453–457.
[14] K. Koski, J. Hölsä, P. Juliet, Properties of zirconium oxide thin films deposited by
samples. The peaks towards the lower wave number display the strong pulsed reactive magnetron sputtering, Surf. Coating. Technol. 120–121 (1999)
vibration and little shifting of the band 1240 cm−1 and 1337 cm−1at 303–312.
higher fluence may be due to the relief of high compressive stress of [15] L. Chen, Y. Chang, Q. Guo, J. Zhang, F. Wan, Y. Long, Phase stability , grain
growth and photoluminescence property of nanocrystalline yttria-stabilized zir-
thin films by swift heavy ion beam irradiation. The integration of fra- conia film under 500 keV Xe6+ ion irradiation, Nucl. Instrum. Methods Phys. Res.
mework on the detailed optical study of ions irradiated ZrO2 thin films B. 328 (2014) 84–88.
grown by RF sputtering is currently emerging and promising approach [16] S. Harasek, H. Wanzenboeck, B. Basnar, J. Smoliner, J. Brenner, H. Stoeri,
E. Gornik, E. Bertagnolli, Metal-organic chemical vapor deposition and nanoscale
for the suitable applications in high reflectivity mirrors, optical sensors
characterization of zirconium oxide thin films, Thin Solid Films 414 (2002)
and wear resistant protective coatings. 199–204.
[17] S. Jena, R.B. Tokas, N. Kamble, S. Thakur, D. Bhattacharyya, N.K. Sahoo,
Acknowledgments Investigation of elastic and optical properties of electron beam evaporated ZrO2 –
MgO composite thin fi lms, Thin Solid Films 537 (2013) 163–170.
[18] S. Lee, H. Kim, P.C. Mcintyre, K.C. Saraswat, J. Byun, S. Lee, H. Kim,
One of the authors Dr. Rajesh Kumar is thankful to Inter University P.C. Mcintyre, Atomic layer deposition of on W for metal – insulator – metal ca-
Accelerator Center (IUAC), New Delhi, India, research project (Ref: pacitor application Atomic layer deposition of ZrO2 on W for metal – insulator –
metal capacitor application, Appl. Phys. Lett. 82 (2005) 2874–2876.
IUAC/XIII.3A/59319) and the FRGS Project No. GGSIPU/DRC/FRGS/ [19] R.M. Ormerod, Solid oxide fuel cells, Chem. Soc. Rev. 32 (2003) 17–28.
2019/1553/15 for provide financial assistance in the concerned for the [20] I. Vrejoiu, D.G. Matei, M. Morar, G. Epurescu, A. Ferrari, M. Balucani,
smooth completion of this research work. Mr. V. Chauhan would like to G. Lamedica, G. Dinescu, C. Grigoriu, M. Dinescu, Properties of ZrO 2 thin films
prepared by laser ablation, Mater. Sci. Semicond. Process. 5 (2003) 253–257.
acknowledge for Senior Research Fellowship (UGC-SRF) provided by [21] C.-Y. Lin, C.-Y. Wu, C.-Y. Wu, C.-C. Lin, T.-Y. Tseng, Memory effect of RF sputtered
the University Grants Commission (UGC), Govt. of India, New Delhi, ZrO2 thin films, Thin Solid Films 516 (2007) 444–448.
India. One of the authors Dr. R. Kumar is sincere thanks to Prof. N. [22] A. Hojabri, Structural and optical characterization of ZrO2 thin films grown on
silicon and quartz substrates, J. Theor. Appl. Phys. 10 (2016) 219–224.
Koratkar for providing the RF sputtering facility at Rensselaer [23] C.M. Lopez, N.A. Suvorova, E.A. Irene, A.A. Suvorova, M. Saunders, C.M. Lopez,
Polytechnic Institute (RPI), New York, USA. The authors (R. Kumar and N.A. Suvorova, E.A. Irene, Film interfaces with Si and SiO2, J. Appl. Phys. 98
V. Chauhan) acknowledge to University Science Instrument Centre (2005) 033506-6.
[24] U.S. Patel, K.H. Patel, K.V. Chauhan, A.K. Chawla, S.K. Rawal, Investigation of
(USIC), Department of Physics & Astrophysics, and University of Delhi,
various properties for zirconium oxide films synthesized by sputtering, Procedia.
India for providing PL measurements. We would also like to thank Technol. 23 (2016) 336–343.
editor and reviewers for their effort and expertise in reviewing this [25] B.J.L. Gole, S.M. Prokes, J.D. Stout, O.J. Glembocki, R. Yang, Unique properties of
research paper that helped in further improving the quality and stan- selectively formed zirconia nanostructures, Adv. Mater. 18 (2006) 664–667.
[26] R. Espinoza-gonzález, E. Mosquera, Í. Moglia, R. Villarroel, V. M. Fuenzalida
dard of the manuscript. Hydrothermal growth and characterization of zirconia nanostructures on non-
stoichiometric zirconium oxide, Ceram. Int. (2014) 1–8, https://doi.org/10.1016/
Appendix A. Supplementary data j.ceramint.2014.07.034.
[27] E.P. Gusev, E. Cartier, D.A. Buchanan, M. Gribelyuk, M. Copel, Ultrathin high-K
metal oxides on silicon : processing , characterization and integration issues,
Supplementary data to this article can be found online at https:// Microelectron. Eng. 59 (2001) 341–349.
doi.org/10.1016/j.ceramint.2019.06.124. [28] S. Prasanna, M.R.G.S. Jayakumar, M.D. Kannan, V. Ganesan, Dielectric properties
of DC reactive magnetron sputtered Al2O3 thin films, Thin Solid Films 520 (2012)
2689–2694.
References [29] E. Zalnezhad, A.M.S. Hamouda, J. Jaworski, Y. Do Kim, From zirconium nano-
grains to zirconia nanoneedles, Nat. Publ. Sci. Rep. (2016) 1–9, https://doi.org/
10.1038/srep33282.
[1] A.S. Keiteb, E. Saion, A. Zakaria, N. Soltani, Structural and optical properties of
[30] D.A. Neumayer, E. Cartier, Materials characterization of chemical solution de-
zirconia nanoparticles by thermal treatment synthesis, J. Nanomater. (2016),
position Materials characterization of ZrO2 – SiO2 and HfO2 – SiO2 binary oxides
https://doi.org/10.1155/2016/1913609.
deposited by chemical solution deposition, J. Appl. Phys. 90 (2001) 1801–1808.
[2] J.P. Chang, Y. Lin, K. Chu, J.P. Chang, Y. Lin, K. Chu, Rapid thermal chemical
[31] B. Tack, J. Cho, K. Hee, K. Min, K. Shin, D. Sung, Zirconium oxide dielectric layer
vapordeposition of zirconium oxide for metal-oxide- semiconductor field effect
grown by a surface sol e gel method for low-voltage , hysteresis-free , and high-
transistor application Rapid thermal chemical vapor deposition of zirconium oxide
mobility polymer field effect transistors, Org. Electron. 28 (2016) 1–5.
for metal-oxide-semiconductor field effect transistor application, J. Vac. Sci.
[32] M. Matsuoka, S. Isotani, J.F.D. Chubaci, S. Miyake, Y. Setsuhara, K. Ogata,
Technol., B 19 (2006) 1782–1787, https://doi.org/10.1116/1.1396639.
N. Kuratani, Influence of ion energy and arrival rate on x-ray crystallographic
[3] S.S. Atsu, M.A. Kilicarslan, H.C. Kucukesmen, P.S. Aka, Effect of zirconium-oxide
properties of thin ZrOx films prepared on Si (111) substrate by ion-beam assisted
ceramic surface treatments on the bond strength to adhesive resin, J. Prosthet.
deposition, J. Appl. Phys. 88 (2000) 3773–3775.
Dent 95 (2006) 430–436.
[33] G. Gottardi, N. Laidani, V. Micheli, R. Bartali, M. Anderle, Effects of Oxygen
[4] Y. Su, H. Cui, Q. Li, S. Gao, J. Ku, Strong adsorption of phosphate by amorphous
Concentration in the Ar/O2 Plasma on the Bulk Structure and Surface Properties of
zirconium oxidenanoparticles, Water Res. 47 (2013) 5018–5026.
RF Reactively Sputtered Zirconia Thin Films, vol. 202, (2008), pp. 2332–2337.
[5] V.I. Pârvulescu, H. Bonnemann, V. Pârvulescu, U. Endruschat, A. Rufinska, Ch
[34] T.K. Gupta, J.H. Bechtold, R.C. Kuznicki, L.H. Cadoff, B.R. Rossing, Stabilization of
W. Lehmann, B. Tesche, G. Poncelet, Preparation and characterisation of meso-
tetragonal phase in polycrystalline zirconia, J. Mater. Sci. 12 (1977) 2421–2426.
porous zirconium oxide, Appl. Catal. Gen. 214 (2001) 273–287.
[35] E. Hafele, K. Kaltenmaier, U. Schonauer, Application of the ZrO, sensor in de-
[6] Y. Nakano, T. Iizuka, H. Hattori, K. Tanabe, Surface properties of zirconium oxide
termination of pollutant gases, Sens. Actuators, B 4 (1991) 525–527.
and its catalytic activity for lsomerization of I-butene, J. Catal. 57 (1979) l–10.
[36] S. Manjunatha, R. Hari Krishna, Tiju Thomas, B.S. Panigrahi,
[7] B. Cho, J. Wang, L. Sha, J.P. Chang, B. Cho, J. Wang, L. Sha, J.P. Chang, Tuning
M.S. Dharmaprakash, Moss-burstein Effect in Stable, Cubic ZrO2: Eu+3
the electrical properties of zirconium oxide thin films, Appl. Phys. Lett. 80 (2003)
Nanophosphors Derived from Rapid Microwave-Assisted Solution-Combustion
1052–1054.
Technique, Materials Research Bulletin (2017), https://doi.org/10.1016/j.
[8] J. Desforges, L. Robichaud, S. Gauvin, Determination of optical properties of thin
materresbull.2017.10.006.
films from ketteler-helmholtz dispersion Relations : application to the case of ul-
[37] J. Costantini, F. Beuneu, Point defects induced in yttria-stabilized zirconia by
traviolet irradiated zirconium oxide, Adv. Mater. Sci. Eng. (2017), https://doi.org/
electron and swift heavy ion irradiations, J. Phys. Condens. Matter 23 (2011)
10.1155/2017/8285230.
115902 9pp.
[9] V.V. Lozanov, V.E. Prokip, V.R. Shayapov, A.S. Berezin, N.I. Baklanova,
[38] V.V.S. Kumar, Effect of 750 keV Argon ion irradiation on nc ZnO-SiOx thin films,
Photoluminescence properties of zirconium and hafnium germanates obtained
Appl. Surf. Sci. 351 (2015) 819–823.
through different chemical routes, Ceram. Int. (2018), https://doi.org/10.1016/j.
[39] W. Bolse, Atomic transport in thin film systems under heavy ion bombardment,
ceramint.2018.07.080.
Surf. Coating. Technol. 58–159 (2002) 1–7.
[10] W. Li, J. Liu, Z. Sun, T. Liu, J. Lu, S. Gao, C. He, R. Cao, J. Luo, Integration of
[40] W. Bolse, Self-organised nano-structuring of thin oxide-films under swift heavy ion
metal-organic frameworks into an electrochemical dielectric thin film for elec-
bombardment, Nucl. Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater.
tronic applications, Nat. Commun. (2016), https://doi.org/10.1038/
Atoms 244 (2006) 8–14.
ncomms11830.
[41] D.K. Avasthi, G.K. Mehta, Ion Matter Interact. Swift Heavy Ions for Materials

10
V. Chauhan, et al. Ceramics International xxx (xxxx) xxx–xxx

Engineering and Nanostructuring, 2011, pp. 47–66. P.K. Kulria, Effect of swift heavy ion irradiation on structural , optical and elec-
[42] P. Mallick, C. Rath, S. Majumder, R. Biswal, D.C. Agarwal, S. Varma, D.K. Avasthi, trical properties of spray deposited CdO thin films, Radiat. Phys. Chem. 80 (2011)
P.V. Satyam, N.C. Mishra, Evolution of surface morphology of NiO thin films under 435–439.
swift heavy ion irradiation, Appl. Surf. Sci. 256 (2009) 521–523. [70] S. Som, S. Das, S. Dutta, M. Kumar, P. Ritesh, K. Dubey, A comparative study on
[43] D.C. Agarwal, A. Kumar, S.A. Khan, D. Kabiraj, F. Singh, A. Tripathi, J.C. Pivin, the influence of 150 MeV Ni7+ , 120 MeV Ag9+ , and 110 MeV Au8+ swift heavy
R.S. Chauhan, D.K. Avasthi, SHI induced modification of ZnO thin film: optical and ions on the structural and thermoluminescence properties of Y2O3 : Eu3+/Tb3+
structural studies, Nucl. Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater. nanophosphor for dosimetric applications, J. Mater. Sci. 51 (2016) 1278–1291.
Atoms 244 (2006) 136–140. [71] M. Ashraf, S.M.J. Akhtar, A.F. Khan, Z. Ali, A. Qayyum, Effect of annealing on
[44] P. Mallick, C. Rath, J. Prakash, D.K. Mishra, R.J. Choudhary, D.M. Phase, structural and optoelectronic properties of nanostructured ZnSe thin films, J.
A. Tripathi, D.K. Avasthi, D. Kanjilal, N.C. Mishra, Swift heavy ion irradiation Alloy. Comp. 509 (2011) 2414–2419.
induced modification of the microstructure of NiO thin films, Nucl. Instrum. [72] M. Lang, F. Zhang, J. Zhang, C.L. Tracy, A.B. Cusick, J. Vonehr, Z. Chen,
Methods Phys. Res. Sect. B Beam Interact. Mater. Atoms 268 (2010) 1613–1617. C. Trautmann, R.C. Ewing, Swift heavy ion-induced phase transformation in
[45] S.J. Zinkle, V.A. Skuratov, Track formation and dislocation loop interaction in Gd2O3, Nucl. Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater. Atoms 326
spinel irradiated with swift heavy ions, Nucl. Instrum. Methods Phys. Res. Sect. B (2014) 121–125.
Beam Interact. Mater. Atoms 141 (1998) 737–746. [73] K. Sarmah, R. Sarma, H.L. Das, Structural characterization of thermally evapo-
[46] J. Costantini, F. Beuneu, K. Schwartz, C. Trautmann, Generation of colour centres rated CdSe thin films, Chalcogenide Lett. 5 (2008) 153–163.
in yttria-stabilized zirconia by heavy ion irradiations in the GeV range, J. Phys. [74] V. Chauhan, R. Kumar, Dense electronic excitation induced modifications in na-
Condens. Matter 22 (2010) 315402 9pp. nocrystalline zirconium oxide thin films : detailed analysis of optical and surface
[47] V. Kumar, M.K. Jaiswal, R. Gupta, J. Ram, I. Sulania, S. Ojha, X. Sun, N. Koratkar, topographical, Opt. Mater. 89 (2019) 576–590.
R. Kumar, Effect of low energy (keV) ion irradiation on structural , optical and [75] Morris E. Fine, Introduction to chemical and structural defects in crystalline solids,
morphological properties of SnO2–TiO2 nanocomposite thin films, J. Mater. Sci. Treatise on Solid State Chemistry, Vol. 1 Springer, 1921.
Mater. Electron. (2018), https://doi.org/10.1007/s10854-018-9457-6. [76] J.P. Hirth, J. Lothe, Theory of Dislocations, 2 ed., Krieger Pub Co, 0-89464-617-6,
[48] V. Kumar, R. Kumar, Low energy Kr5+ ion beam engineering in the optical, 1992.
structural, surface morphological and electrical properties of RF sputtered TiO2 [77] R.P.I. Adler, H.M. Otte, C.N.J. Wagner, Metall. Trans. 1 (1970) 2375.
thin films, Opt. Mater. 91 (2019) 455–469. [78] R. Gupta, R. Kumar, Influence of low energy ( keV ) negative Li ion implantation
[49] D. Kaoumi, A.T. Motta, R.C. Birtcher, D. Kaoumi, A.T. Motta, R.C. Birtcher, A on properties of electrochemically induced scaffold-based growth of PbSe nano-
thermal spike model of grain growth under irradiation A thermal spike model of wires, J. Mater. Sci. Mater. Electron. (2018), https://doi.org/10.1007/s10854-
grain growth under irradiation, J. Appl. Phys. 104 (2008) 073525-13. 018-0491-1.
[50] A. Sharma, M. Varshney, H.-J. Shin, Y. Kumar, S. Gautam, K.H. Chae, Monoclinic [79] V. Kumar, R. Kumar, S.P. Lochab, N. Singh, Effect of swift heavy ion irradiation on
to tetragonal phase transition in ZrO2 thin films under swift heavy ion irradiation: nanocrystalline CaS : Bi phosphors : structural , optical and luminescence studies,
structural and electronic structure study, Chem. Phys. Lett. 592 (2014) 85–89. Nucl. Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater. Atoms 262 (2007)
[51] V. Kumar, F. Singh, O.M. Ntwaeaborwa, H.C. Swart, Effect of Br+6 ions on the 194–200.
structural, morphological and luminescent properties of ZnO/Si thin films, Appl. [80] M. Miyauchi, H. Tokudome, Nanotube thin films via layer-by-layer assembly Low-
Surf. Sci. 279 (2013) 472–478. reflective and super-hydrophilic properties of titanate or titania nanotube thin
[52] M. Ghanashyam Krishna, K. Narasimha Rao, S. Mohan, A comparative study of the films via layer-by-layer assembly, Thin Solid Films 515 (2006) 2091–2096.
optical properties of zirconia thin films prepared by ion-assisted deposition, Thin [81] V. Chauhan, T. Gupta, P. Singh, P.D. Sahare, N. Koratkar, R. Kumar, Influence of
Solid Films 207 (1992) 248–251. 120 MeV S9+ ion irradiation on structural, optical and morphological properties of
[53] R.C. Ramola, M. Rawat, K. Joshi, A. Das, S.K. Gautam, F. Singh, Electronic ex- zirconium oxide thin films deposited by RF sputtering, Phys. Lett. 383 (2019)
citation in pure and yttrium doped Study of phase transformation induced by 898–907.
electronic excitation in pure and yttrium doped ZrO2 thin films, Mater. Res. [82] S. Chandramohan, R. Sathyamoorthy, P. Sudhagar, D. Kanjilal, D. Kabiraj,
Express 4 (2017) 096401. K. Asokan, Swift heavy ion beam irradiation induced modifications in structural,
[54] M. Rawat, A. Das, D.K. Shukla, P. Rajput, A. Chettah, D.M. Phase, R.C. Ramola, morphological and optical properties of CdS thin films, Nucl. Instrum. Methods
F. Singh, Micro-Raman and electronic structure study on kinetics of electronic Phys. Res. Sect. B Beam Interact. Mater. Atoms 254 (2007) 236–242.
excitations induced monoclinic-to-tetragonal phase transition in zirconium oxide [83] J. Ram, R.G. Singh, R. Gupta, V. Kumar, F. Singh, R. Kumar, Effect of annealing on
films, RSC Adv. 6 (2016) 104425–104432. the surface morphology, Opt. Struct. Prop. Nanodimensional Tungsten Oxide Prep.
[55] R.P. Chauhan, D. Gehlawat, A. Kaur, Ion beam fluence induced variation in optical Coprecipitation Tech. 48 (2019) 1174–1183.
band-gap of ZnO nanowires, J. Exp. Nanosci. 9 (2014) 871–876. [84] M.K. Jaiswal, D. Kanjilal, Rajesh Kumar, Structural and optical studies of 100 MeV
[56] K.S. Jheeta, D.C. Jain, R. Kumar, K.B. Garg, Effect of swift heavy ion irradiation on Au irradiated thin films of tin oxide, Nucl. Instrum. Methods Phys. Res. Sect. B
the optical properties of sapphire, Indian J. Pure Appl. Phys. 46 (2008) 400–402. Beam Interact. Mater. Atoms 314 (2013) 170–175.
[57] S. Kumar, S. Sharma, F. Singh, A. Kapoor, Effect of swift heavy ion irradiation on [85] G.K.A.T. Sarmash, L. Obulapathi, J.R. D, S.R. T, K. Asokan, Structural , optical and
the structural and optical properties of CdO thin films, recent trends in materials electrical properties of heavy ion irradiated CdZnO thin films, Thin Solid Films
and devices, Springer Proc. Phys. (2017) 199–203, https://doi.org/10.1007/978- 605 (2016) 102–107.
3-319-29096-6. [86] V.V. Ison, A.R. Rao, V. Dutta, P.K. Kulriya, D.K. Avasthi, Swift heavy ion induced
[58] C. Chen, L. Pang, Q. Lu, L. Wang, Y. Tan, Z. Wang, Refractive index engineering structural changes in CdS thin films possessing different microstructures : a com-
through swift heavy ion irradiation of LiNbO3 crystal towards improved light parative study Swift heavy ion induced structural changes in CdS thin films pos-
guidance, Sci. Rep. (2017) 1–7, https://doi.org/10.1038/s41598-017-11358-y. sessing, J. Appl. Phys. 106 (2009) 023508-7.
[59] L. Dong, R. Jia, B. Xin, B. Peng, Y. Zhang, Effects of oxygen vacancies on the [87] A. Sharma, K.D. Verma, M. Varshney, D. Singh, M. Singh, Effect of 100 MeV O7+
structural and optical properties of β -Ga2O3, Nat. Publ. Gr. Sci. Rep. (2017) 1–12, ion beam irradiation on structural , optical and electronic properties of SnO2 thin
https://doi.org/10.1038/srep40160. films, Radiat. Eff. Defect Solid 165 (2010) 930–937.
[60] J. Wang, Z. Wang, B. Huang, Y. Ma, Y. Liu, X. Qin, X. Zhang, Y. Dai, Oxygen [88] S. Venkataraj, O. Kappertz, H. Weis, R. Drese, R. Jayavel, M. Wuttig, Structural
vacancy induced band-gap narrowing and enhanced visible light photocatalytic and optical properties of thin zirconium oxide films prepared by reactive direct
activity of ZnO, ACS Appl. Mater. Interfaces 4 (2012) 4024–4030. current magnetron sputtering, J. Appl. Phys. 92 (2002) 3599–3607.
[61] S. Rani, N.K. Puri, S.C. Roy, M.C. Bhatnagar, D. Kanjilal, Effect of swift heavy ion [89] V. Sunke, U. Suda, Structural and optical properties of thermally oxidized zirco-
irradiation on structure, optical, and gas sensing properties of SnO2 thin films, nium dioxide films, Int. Lett. Chem. Phys. Astron. 77 (2018) 15–25 10.18052/
Nucl. Instruments Methods Phys.Res. Sect. B Beam Interact. with Mater. Atoms. www.scipress.com/ILCPA.77.15.
266 (2008) 1987–1992. [90] H. Rath, B.N. Dash, A. Benyagoub, N.C. Mishra, Sensitivity of anatase and rutile
[62] V. Kumar, R. Gupta, J. Ram, P. Singh, V. Kumar, S.K. Sharma, R.S. Katiyar, phases of TiO2 to ion irradiation : examination of the applicability of Coulomb
R. Kumar, High energy 120 MeV Ti9+ ion beam induced modifications in optical, explosion and thermal spike models, Sci. Rep. (2018) 1, https://doi.org/10.1038/
structural and surface morphological properties of titanium dioxide thin films, s41598-018-30281-4.
Vacuum (2018) 1–12, https://doi.org/10.1016/j.vacuum.2018.10.029. [91] H. Thakur, K.K. Sharma, R. Kumar, P. Thakur, Y. Kumar, A.P. Singh, S. Gautam,
[63] J.F. Ziegler, J.P. Biersack, M.D. Ziegler, “SRIM—The Stopping and Range of Ions in K.H. Chae, On the Optical Properties of Ag+15 Ion-Beam-Irradiated TiO2 and SnO2
Matter”, Ion Implantation Press, 2008. Thin Films, (2011), https://doi.org/10.3938/jkps.61.1609.
[64] H.A. Khawal, B.N. Dole, Irradiation effect of defect creation and shifting of the [92] R.R. Reddy, K.R. Gopal, K. Narasimhulu, L.S. Sankara, K.R. Kumar, C.V.K. Reddy,
phonon modes on MnxZn1 – xO thin films, RSC Adv. 7 (2017) 34736–34745. S. Nisar, Correlation between optical electronegativity and refractive index of
[65] R. Gupta, R.P. Chauhan, S.K. Chakarvarti, R. Kumar, Effect of SHI on properties of ternary chalcopyrites, semiconductors , insulators , oxides and alkali halides, Opt.
template synthesized Cu nanowires, Ionics (2018), https://doi.org/10.1007/ Mater. 31 (2008) 209–212.
s11581-018-2578-3. [93] D.K. Ghosh, L.K. Samanta, Refractive indices of some narrow and wide band gap
[66] V. Chauhan, T. Gupta, N. Koratkar, R. Kumar, Studies of the electronic excitation materials, Infrared Phys. 26 (1986) 335–336.
modifications induced by SHI of Au ions in RF sputtered ZrO2 thin films, Mater. [94] R.K. Willard, A.C. Beer (Eds.), Semiconductors and Semimetals, Academic Press,
Sci. Semicond. Process. 88 (2018) 262–272. New York, 1971.
[67] M.K. Jaiswal, R. Kumar, Studies of dense electronic excitation induced modifica- [95] N.M. Ravindra, V.K. Srivastava, Variation of Refractive Insex with Energy Gap in
tion in cobalt doped SnO2 thin films prepared by RF sputtering technique, J. Alloy. Semiconductors vol. 19, (1979), pp. 603–604.
Comp. 648 (2015) 550–558. [96] P. Gupta, R. Ravindra, Comments on the Moss formula, Phys. Stat. Sol. 100 (1980)
[68] M.K. Jaiswal, A. Kumar, D. Kanjilal, T. Mohanty, Swift heavy ion induced topo- 715–719.
graphy changes of Tin oxide thin films, Appl. Surf. Sci. 263 (2012) 586–590. [97] V. Kumar, J.K. Singh, Model for calculating the refractive index of different ma-
[69] R. Kumaravel, K. Ramamurthi, I. Sulania, K. Asokan, D. Kanjilal, D.K. Avasti, terials, Indian J. Pure Appl. Phys. 48 (2010) 571–574.

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[98] P.S. Chaudhari, T.M. Bhave, D. Kanjilal, S.V. Bhoraskar, Swift heavy ion induced 179–183.
growth of nanocrystalline silicon in silicon oxide, J. Appl. Phys. 93 (2009) [109] S. Dey, J.W. Drazin, Y. Wang, J.A. Valdez, T.G. Holesinger, B.P. Uberuaga,
3486–3489. R.H.R. Castro, Radiation tolerance of nanocrystalline Ceramics : insights from yt-
[99] N. Abdulla, H. Mustafa, S. Hashim, R.S. Khaleel, Optical characteristics of ZnO:Al tria stabilized zirconia, Sci. Rep. 5 (7746) (2015) 1–9, https://doi.org/10.1038/
thin films prepared by magnetron sputtering, J. Kerbala Univ. 8 (2010) 224–230. srep07746.
[100] R.S. Khaleel, M. Hameed, Studying the effect of thickness variation on some op- [110] H.S. Virk, P.S. Chandi, A.K. Srivastava, Physical and chemical response of 70 MeV
tical properties of Iron Oxide Thin Films, Diyala J. Pure Sci. 7 (2011) 88–94. carbon ion irradiated Kapton-H polymer, Bull. Mater. Sci. 24 (2001) 529–534.
[101] J.F. Eloy, Power Lasers National School Physics, John Wiley and Sons, Grenoble, [111] E.F. Lopez, V.S. Escribano, Marta Panizza, M.M. Carnasciali, Busca Guido,
France, 1984. Vibrational and electronic spectroscopic properties of zirconia powders, J. Mater.
[102] A.S. Hassanien, A.A. Akl, Effect of Se addition on optical and electrical properties Chem. 11 (2001) 1891–1897.
of chalcogenide CdSSe thin films, Superlattice. Microst. 89 (2016) 153–169. [112] S.L. Panahi, D. Dastan, N. Chaure, Characterization of zirconia nanoparticles
[103] S. Jothi, N. Prithivikumaran, N. Jeyakumaran, Characterization of zirconium grown by sol – gel method synthesis and characterizationof zirconium, Adv. Sci.
oxide thin films prepared by sol - gel method, Int. J. ChemTech Res. 6 (2014) Lett. 22 (2016) 941–944 2016.
1971–1973. [113] S. Jayakumar, P.V. Ananthapadmanabhan, K. Perumal, T.K. Thiyagarajan,
[104] P. Kumar, N. Saxena, K. Gao, F. Singh, A. Agarwal, Effect of swift heavy ions on S.C. Mishra, Characterization of nano-crystalline ZrO2 synthesized via reactive
pulsed laser deposited Ag doped CdS nanocrystalline thin films, Adv. Sci. Lett. 20 plasma processing, Mater. Sci. Eng., B 176 (2011) 894–899.
(2014) 977–984. [114] X. Dou, D. Mohan, C.U. Pittman, S. Yang, Remediating fluoride from water using
[105] C. Dalmasso, P. Iacconi, M. Beauvy, D. Lapraz, E. Balan, G. Calas, Radiation da- hydrous zirconium oxide, Chem. Eng. J 198–199 (2012) 236–245.
mage induced by krypton ions in sintered α -Al2O3 Radiat, Prot. Dosim. 119 [115] H. Liu, X. Sun, C. Yin, C. Hu, Remediating fluoride from water using hydrous
(2006) 222–225. zirconium oxide, J. Hazard Mater 151 (2008) 616–622.
[106] R. Choudhary, R.P. Chauhan, Swift heavy ion induced modifications in optical and [116] P. Widmayer, P. Ziemann, S. Ulrich, H. Ehrhardt, Phase Stability of Stress
electrical properties of cadmium selenide thin films, Electron. Mater. Lett. (2017), Relaxation Effects of Cubic Boron Nitride Thin Films under 350 keV Ion Irradaition
https://doi.org/10.1007/s13391-017-6231-5. vol. 6, (1997), pp. 621–625.
[107] H.S. Lokesha, K.R. Nagabhushana, Fouran Singh, Enhancement in luminescence [117] C.A. Davis, A simple model for the formation of compressive stress in thin films by
properties of ZrO2:Dy3+ under 100 MeV swift Ni7+ ion irradiation, RSC Adv. ion bombardment, Thin Solid Films 226 (2006) 30–34.
(2016), https://doi.org/10.1039/C6RA11520A. [118] G.R. Umapathy, S. Ojha, K. Rani, M. Thakur, R. Mahajan, N.K.S. Chopra,
[108] M.K. Jaiswal, D. Kanjilal, R. Kumar, Swift heavy ion induced modification in D. Kanjilal, Composition profile of thin film target by Rutherford backscattering
morphological and physico-chemical properties of tin oxide nanocomposites, Nucl. Spectrometry, DAE- BRNS Symp 61 (2016) 1038–1039.
Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater. Atoms 315 (2013)

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