See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/322020991

Broadband antireflective coatings using in-situ novel synthesis of hollow

MgF2 nanoparticles

Article  in  Solar Energy Materials and Solar Cells · December 2017

DOI: 10.1016/j.solmat.2017.12.010

CITATIONS READS

16 609

6 authors, including:

K. Chandra Sekhar Reddy Bhanupriya Das

Center for Research and Advanced Studies of the National Polytechnic Institute Indian Institute of Technology Guwahati
13 PUBLICATIONS   91 CITATIONS    3 PUBLICATIONS   20 CITATIONS   

SEE PROFILE SEE PROFILE

Ganesh Kesavan Shanmugasundaram Sakthivel

National Taipei University of Technology International advanced research for powder metallurgy and new materials
18 PUBLICATIONS   51 CITATIONS    48 PUBLICATIONS   7,753 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Clay based composites for Electrochemical Sensor View project

SnSe based Thermoelectric Materials View project

All content following this page was uploaded by Bhanupriya Das on 26 December 2017.

The user has requested enhancement of the downloaded file.

 Solar Energy Materials and Solar Cells 176 (2018) 259–265

Contents lists available at ScienceDirect

Solar Energy Materials and Solar Cells

journal homepage: www.elsevier.com/locate/solmat

Broad band antireflective coatings using novel in-situ synthesis of hollow T

MgF2 nanoparticles
⁎
K. Chandra Sekhar Reddy, D. Karthik, D. Bhanupriya, K. Ganesh, M. Ramakrishna, S. Sakthivel
Centre for Solar Energy Materials, International Advanced research centre for powder metallurgy and New materials, Balapur PO, Hyderabad 500 005, India

A R T I C L E I N F O A B S T R A C T

Keywords: A high performance antireflective (AR) should be a thin film with low refractive index, highly transparent,
Antireflective coating economical, and highly durable. In this paper, we present a novel synthesis of hollow Magnesium Fluoride
Hollow (MgF2) nanoparticles, which is used to produce a high performance broadband antireflective coating. A for-
Magnesium fluoride mation–deformation-reformation route has been adopted to synthesize nanoparticles with hexagonal structure
Nanoparticle layer
and cavities, which are crystalline and dispersible in any polar solvent. This facile synthesis route is a major
Broadband
breakthrough to achieve high performance broadband antireflective coating with an average transmittance of
98.3% in the visible range (400–800 nm) and 96.2% in active solar range (300–1500 nm). No significant drop in
the efficiency was observed with antireflective-coated cover glass on the c-Si solar cell, whereas 6–7% efficiency
loss was observed with uncoated glass. This can be a promising approach to develop high performance anti-
reflective dielectric layer, which will enhance the overall performance of photovoltaic and solar thermal systems.

1. Introduction
Broadband Anti-Reflective Coatings (BARCs) is an advanced ap-
proach to develop high transparent thin films to suppress Fresnel re-
flection in broad range of solar spectrum (300−2500 nm). BARCs has
attracted significant research interest, because of its wide range of ap-
plications such as solar cells, high power lasers, optical coatings, ar-
chitectural glasses, windscreens and display panels [1–10]. There is a
great scope for utilization of BARC'S in the field of solar energy.
However, AR coatings should have maximum transfer of incident light,
so that there would be feasible to achieve efficiency [11,12].
Nano metric particle sizes and homogenous pore distribution with a
pore size smaller than the wavelength of light (i.e., mesoporosity:
2–50 nm) are major requirements for obtaining broadband AR coating.
Refractive index and porosity are related by,
npc = [(1 − P /100)(n dc 2 − 1) + 1]1/2
npc = [(1-P/100)(ndc −1)+1] Where npc denote the refractive in-
2 1/2
dices of porous and ndc denote densified coatings respectively, while P
is the porosity percentage [1].
To achieve broadband anti-reflective coatings, one of the common
approaches is to chemically modify the surface of the substrate, which
reduces the refractions considerably. As this process involves controlled
etching (8–40 min) using Hydrofluoric acid (HF) to grade the existing
pores and hence can greatly affect the mechanical strength of the
substrate [13]. Liu et al. developed BARCs where zero percentage of
reflectance was observed over a wide range of wavelengths, when the
substrates are etched by using acid mixture but this kind of develop-
ment of BARCs required longer duration [3].
Many groups have succeeded in generating mesoporous dielectric
film, which exhibited high antireflective properties [8,9,12,14–17].
Kuo et al., [17] developed porous polymer films for AR application
using polystyrene/polyvinylpyrrolidone (PS/PVP) via phase separation
using dip-coating technique. However, the generation and sustenance
of such a periodic mesoporous structure during synthesis and proces-
sing has been a challenge [18].
Moreover, MgF2 is widely used for AR coating because of its high
optical transparency over wide wavelength, low refractive index, large
energy bandgap and low optical losses as well. [19–22]. Synthesis of
MgF2 and its application as AR coating have been extensively studied,
because of its excellent optical properties [23–28]. Apart from material
(1)
characteristics, different kind of morphologies for the particles such as
hollow spherical particles, platelets, cubes, prismatic particles, na-
norods of MgF2 etc., have also attracted greater interests due to their
intriguing structure-induced properties and widespread applications
[29–32]. Current preparation methods for synthesis of magnesium
fluoride although shows potential for industrial applications however
the requirement of high-temperature processing, rigid conditions, spe-
cific and complicated synthetic equipment, use of harmful chemicals
creates difficulty in view of safety and environmental regulations in

⁎
Corresponding author.
E-mail address: ssakthivel@arci.res.in (S. Sakthivel).

https://doi.org/10.1016/j.solmat.2017.12.010
Received 14 October 2017; Received in revised form 5 December 2017; Accepted 9 December 2017
0927-0248/ © 2017 Elsevier B.V. All rights reserved.
K. Chandra Sekhar Reddy et al.
industrial applications [33]. Only a few reported the development of
antireflective coatings incorporating MgF2 nanoparticles [12,28,33,34],
but these also inferred that creating nanoscale hollow structures in a
controlled manner is a great challenge [33]. Conventional strategy re-
lies on hard or soft templates. Formation of shell with the target ma-
terial on the template followed by removal of the template generates
the hollow structure. However, the preparation of hollow nanoparticle
by such methods are expensive and time consuming process [35].
Preferably, templates free technique which requires the self-assembly of
the desired material under practical conditions could be a better choice
for economic development of hollow nanoparticles. Literature has re-
ported that the formation of hollow microspheres is based on initial
assembly of nano fluorides in presence of crystal size controlling agents
namely Cetyl trimethyl ammonium bromide (CTAB), Polyethlene glycol
(PEG) using solvothermal and micro emulsion routes [36,37]. Hollow
microspheres of MgF2 were prepared using Magnesium Nitrate
(MgNO3) as precursor by microwave-assisted ionic liquid solvothermal
method at 150 °C for 30 min [36].
Only a few reports are reported on hollow MgF2 nanoparticles in-
corporation in AR coating. Cui et al. [38] synthesized hollow MgF2
nanoparticles by high heat treatment method, however long duration of
the process and low overall transmissivity in the visible range makes it
unfavorable. Hence, the synthesis of uniform hollow nanoparticles is
strongly limited. Grosso et al. [39] obtained porous, resistant and semi-
crystalline thin films of magnesium oxyfluoride. They obtained this
through liquid deposition, which is followed by a flash and thermal
treatment of porous magnesium oxyfluoride vesicles using Magnesium
acetate and Trifluoroacetic acid. The porosity induced accounts for its
ultralow refractive index (n700 nm =1.09). They claimed that the
magnesium oxyfluoride films developed are insensitive to water, which
allows for better environmental stability and longer lifetime. On the
other hand, hydrophobization is necessary for highly porous silica
layers to achieve adequate weather and mechanical stability, whereas
MgF2 which is hydrophobic material shows relatively high weather
stability [40]. Ding et al. prepared a double layer Broadband antire-
flective coating of MgF2 nanocrystals [41]. They generated hollow ve-
sicles of MgF2 nanocrystals guided by carboxyl groups by time-depen-
dent heat treatment of highly concentrated MgF2 sols for 24 h at 150 °C,
which in turn reduced the refractive index from 1.38 to 1.2. The lack of
wide tunable range of refractive index with ultralow refractive index
limits the optical performance of broadband AR coatings. They high-
lighted the need of fabricating broadband AR coating with the help of
simple sol-gel technique without post treatment to tune the refractive
index.
The purpose of present study is to generate crystalline MgF2 nano-
particles with porous structure and to obtain a single layer broadband
AR coating with high optical performance and environmental stability.
In this connection, we have previously succeeded in generating high
crystalline inkbottle type mesoporous nanoparticle synthesized by a
deformation-reformation route from coarse commercial MgF2 hydrate
particles for stable antireflective coating with high optical performance
[42]. However, the present study describes a novel facile route for the
synthesis of hollow MgF2 nanoparticles for Antireflective application.
High optical transparency values were observed i.e. > 98% in the
visible range and > 96% over a wide range of wavelengths from visible
to NIR and easily tailorable refractive index. Unlike the earlier ap-
proaches, hollow MgF2 nanoparticles by in-situ synthesis of formation-
deformation-reformation route from Magnesium acetate and Hydro
fluoric acid precursors, these nanoparticles are crystalline, uniform and
well dispersed in polar solvents. The main advantage of this method is
that it is a one pot experimental design to develop hollow nanoparticles
without using any template or porous forming chemicals. Particles
synthesized by this route and AR film formation have excellent re-
producibility, facile and greater applicability than any other conven-
tional method of preparation of hollow nanoparticles and their films.
260
Solar Energy Materials and Solar Cells 176 (2018) 259–265
2. Experimental section
2.1. Preparation of Hollow MgF2 nanoparticles
The chemicals required for synthesis of hollow MgF2 nanoparticles
are commercially available. 12.8 g of anhydrous Magnesium Acetate
Tetra hydrate (Mg (CH3COO)2 4H2O) was mixed with 60 ml of n-pro-
panol, under vigorous stirring at room temperature. To this mixture,
5 ml of Hydro Fluoric acid (HF −37%, Merck Millipore) is added fol-
lowed by mechanical stirring for 30 min. After gel formation, 5 ml of
Hydrochloric acid (HCl −37%, Merck Millipore), 2 ml of de-ionized
water was added to the suspension in turns. The mixture was stirred for
an hour. After formation of a transparent solution, the mixer is then
transferred into Teflon lined stainless steel autoclave which was then
treated at 180 °C by varying time durations of 30 min, 1 h, 2 h, and 4 h,
(Hollow Nano Particle = HNP-1, HNP-2, HNP-3, HNP-4 respectively)
and gradually cooled (5ᵒC per minute) to room temperature to obtain
MgF2 nanoparticles. After the autoclave treatment, any residue or im-
purities present in the autoclave mixture can be separated by cen-
trifugation, using acetone and 2-butanone and dried under vacuum at
60 °C for 4 h to obtain fine powder of MgF2 nanoparticles have good
yield (> 80%). The powder thus obtained could be easily dispersed in
any polar solvents to prepare the coating solution with high uniformity.
2.2. Deposition of MgF2 coating film
The procedure followed for deposition of MgF2 AR thin films is as
follows. High uniform hollow Magnesium fluoride nanoparticles were
dispersed in 90:10 ratios of ethanol and Isopropoxyethanol (Alfa Aesar)
mixer to obtain a low viscous, transparent solution so as to develop
uniform coatings on pre-treated glass substrates using dip-coating
technique, without any binder/additive being used. After coating,
substrates were treated at 100 °C for 1hr. It was observed that the film
showed a high antireflection property (> 98% T in the visible range)
even at a low curing temperature (< 80 °C) making it suitable for
polymer substrates. This process makes it suitable for temperature
sensitive substrates like heat sensitive polymers thereby facilitating
other fields of application.
2.3. Characterization
The optical transmittance (λ) of glass samples were measured with a
Varian Cary 5000 UV–Vis–NIR spectrophotometer attached with
transmittance accessory in the spectral range of 200–3300 nm. Surface
morphology of the nanoparticles and Antireflective coating structure
were characterized by Transmission Electron Microscopy (JEOL JEM-
2100F), Field Emission Scanning Electron Microscopy (Hitachi model
S4300SE/N) and X ray diffractions (Bruker AX D8 XRD). High-resolu-
tion images were taken when TEM was operated at 200kv. CuKα is used
as the X-ray source in the XRD equipment. Brunauer, Emmett, and
Teller (BET) analysis (11–2370) Gemini, Micromeritics, USA) is used to
analyze the pore size distribution, pore structure and surface area.
Spectroscopic ellipsometer (J.A. Woollam, USA, Model: M-2000V) is
used to measure Film thickness, refractive index and porosity of the
hollow nanoparticles films.
3. Results and discussion
Synthesis of the hollow MgF2 nanoparticles as illustrated in Fig. 1
follows three important steps namely formation of micron size MgF2
particles, deformation of micron size particles on reacting with hydro-
chloric acid to form MgCl2 and reformation of the particles to generate
hollow MgF2 nanoparticles in a controlled environment by lyothermal
synthesis. Following the above sequential steps, four different MgF2
hollow nanoparticles (HNP-1, HNP-2, HNP-3 and HNP4), were pre-
pared by only by altering the process duration (i.e. 30 min, 1 h, 2hr and
K. Chandra Sekhar Reddy et al.
4 h) but by keeping other parameters constant, like amount of pre-
cursors (Magnesium and Fluorine), HCl/H2O and process temperature
(180 °C).
Structural study of hollow nanoparticles:
The two indispensable factors for antireflective properties of MgF2
AR coatings are (a) thickness and (b) refractive index. Proper tuning of
these two parameters is in turn dependent on the shape and size of
nanoparticles. The present study is focused on understanding the me-
chanism behind the formation of the hollow nanoparticles and the
parameters governing the antireflective performance. In contrast to the
earlier work of hollow nanoparticles reported by Ding et al. [41] where
the intervention of the carboxyl group guided the MgF2 nanocrystals to
assemble into hollow vesicle structure. The formation of hollow nano-
particles by the novel route of formation-deformation-reformation is
caused by the strong binding tendency of fluoride ions towards alkaline
earth metals aiding the formation of 3D hollow nanoparticles. Besides,
driven by the tendency to lower its own surface energy such somewhat
self-assembly is a spontaneous process for nanoparticles. Autoclaving at
180ᵒC leads to complete elimination of acetic acid because of its reac-
tion with the alcohol in the disperse medium to form propyl acetate
[43]. As put forward by Murata et al. [43], autoclave treatment has
effect on disperse medium, particle and film, we propose that the high
temperature and pressure during autoclave process assisted the F- ions
from reformed HF acid to bridge Mg2+ ions in the newly formed
Magnesium Chloride (MgCl2) which consequently resulted in the de-
velopment of the hollow nanoparticles.
TEM / HRTEM study of the particle morphology (Fig. 2a, b, c, d, e
and f) reveals that structure of majority particles are hexagonal in shape
with cavities. The range of particle dimensions in width and length
were measured to be 3–16 nm × 6–21 nm, 8–24 nm × 9–24 nm,
10–24 nm × 12–28 nm and 10–26 nm × 11–30 nm for HNP-1, HNP-2,
HNP-3 and MNP-4, respectively. The average particle size was esti-
mated to be around 13 nm, 16 nm, 18 and 19 nm for HNP-1, HNP-2,
HNP-3 and HNP-4, respectively. Moreover, the average wall thickness
size of the particles was observed to be 3.2, 2.4, 1.8 and 1.2 nm for
HNP-1, HNP-2, HNP-3 and HNP-4, respectively. It is observed that the
average dimension of the particle has increased with increase in process
duration. However, the particle wall thickness has decreased with in-
crease in process duration. A typical Selected Area Electron Diffraction
(SAED) pattern of the hollow MgF2 nanoparticles (Fig. 2f) shows
polycrystalline diffraction ring patterns. According to SAED analysis,
Tetragonal crystalline phase of particles is indicated by the diffraction
planes (110), (111), (121), (210), (301). The lattice fringe spacing of
0.362 nm of SAED pattern can also be well indexed to the (110) plane of
the tetragonal structure of MgF2. This is in good agreement with the
results obtained from X-ray diffraction analysis (Fig. 3). All the
261
Solar Energy Materials and Solar Cells 176 (2018) 259–265
Fig. 1. Procedure for synthesis of Hollow MgF2 nanoparticles.
diffraction peaks can be readily indexed to a pure tetragonal phase
which are in good agreement with the standard value of tetragonal
MgF2 (JCPDS card No. 00–041–1443) [44]. The absence of any de-
tectable peak shift or other phase in XRD pattern reveals the simplicity
of the method employed to synthesize pure MgF2 nanoparticles.
Moreover, to determine pore size distributions and type of pores
generated, N2 adsorption - desorption isotherms were studied for the
selected hollow particle synthesized at 30 min duration (HNP1). Fig. 4
shows typical type IV isotherms which are characteristic of mesoporous
structure [45,46]. The shape of the hysteresis loop according to IUPAC
is classified as of the H2 type. The average pore diameter of HNP1
hollow nanoparticles was found to be around 4.89 nm. Moreover, it
exhibits an improved uniformity in pore size distribution. The surface
area of crystalline hollow MgF2 nanoparticles (HNP1) synthesized by
this novel route exhibits a surface area of 102 m2/g which is unusually
very high when compared to that of the commercially available crys-
talline MgF2 (Aldrich), 0.4 m2/g this is mainly due to mesoporous
structure of the particles. This observation is consistent with our pre-
vious work on inkbottle type mesoporous MgF2 nanoparticles [42] and
other reported works of mesoporous MgF2 materials [47,48].
The refractive index (η) and the absorption coefficient (k) of the
hollow MgF2 nanoparticle layer were determined over a wavelength
range of 300–1500 nm using Spectroscopic Ellipsometry. By fitting the
values of ψ and Δ with a non-absorbing Cauchy layer where Δ and ψ
and of the detected signal corresponds to the phase difference between
these two polarization directions and magnitude of the ratio between
the two polarization directions respectively. The refractive index and
thickness are computed using an optical model, which is shown in the
Fig. 5. At 25 °C and 40% relative humidity, the refractive index was
found to be 1.21 at λ = 550 nm when the film thickness was 109 nm
which is lower than the optimum refractive index value of 1.23 re-
quired for zero reflectance on a glass substrate. The hollow structure of
the particles has contributed to such low value of refractive index. The
value of absorption coefficient is zero in the ellipsometry spectra, a fact
which proves that the data depicted in Fig. 5 shows the effects of light
scattering phenomena caused by the hollow nanoparticles when light
falls on the substrate, and no absorption of light has taken place.
Compared to HNP1 hollow nanoparticles the other hollow nano-
particles (HNP2, HNP3 and HNP4) exhibit a higher RI value due to such
reason the layers prepared from other hollow particles transmit little
lower radiations both in the visible and NIR range. It is mainly due to
increase in particle size by prolonging process duration which ac-
cording to Rayleigh scattering explains the high refractive index value
[1].
Ellipsometry using WVASE software is used to estimate the porosity
in AR film. These porosity values are in good agreement with the values
K. Chandra Sekhar Reddy et al.
Fig. 2. TEM and HRTEM images of Hollow MgF2 nanoparticles composite nanoparticles; (a), (b), (c) and (d); TEM micrographs of HNP1, HNP2, HNP3 and HNP4; (e) HR-TEM micrograph
of HNP1; (f) Selected area electron diffraction (SAED) pattern of HNP1.
Fig. 3. XRD pattern of hollow MgF2 nanoparticles as prepared at 180ᵒC for 30 min
(HNP1).
calculated by a method described by Lee et al. [49]. Table 1 comprises
the data obtained from ellipsometry analysis; the porosity in the AR
films comprised of hollow MgF2 nanoparticles was determined to be
42% and 40% for HNP-1 and HNP-2, whereas the porosity in films
made from other hollow MgF2 nanoparticles (HNP-3 and HNP-4) was
observed to be much lower. The reason could be a structural collapsing
(hollow structure) of nanoparticles due to a low wall thickness. This
may be because of large particle size which contributes greater light
scattering and low transmittance exhibited by films comprising of HNP-
3and HNP-4 nanoparticles.
Samples are also analyzed with FESEM for surface morphology
Focused Ion Beam (FIB) for cross sectional and AFM for topography are
shown in the Fig. 6. FE-SEM surface morphology of thin film generated
by HNP1 hollow nanoparticles (Fig. 6a) revealed the spherical mor-
phology due to compression of hollow particles by the sintering process.
262
Solar Energy Materials and Solar Cells 176 (2018) 259–265
Fig. 4. N2 adsorption - desorption isotherms of hollow MgF2 nanoparticles (HNP-1).
From FIB cross-sectional image (Fig. 6b), the film thickness of the de-
posited AR film comprising HNP-1 hollow MgF2 nanoparticles was
estimated to be around 92 ± 5 nm. It is comparable to the film thick-
ness value determined from ellipsometry analysis. AFM topography
image represented in Fig. 6c clearly reveals that the film has a porous
surface. Surface roughness of the film was found to be 5.6 nm.
The mechanical stability of the film was analyzed by pencil hardness
test. The pencil hardness test on the film cured at lower temperatures
showed low mechanical stability (2HB) but coatings cured at higher
temperatures (> 400 °C) showed scratch resistance equivalent to 4 H.
3.1. Optical performance of hollow MgF2 nanoparticle single layer
To obtain highly efficient antireflective coatings, different coating
K. Chandra Sekhar Reddy et al. Solar Energy Materials and Solar Cells 176 (2018) 259–265

Fig. 5. Effect of process duration on the refractive index of single layer AR coating.

Fig. 7. Optical transmittance of AR films comprised of different hollow nanoparticles

Table 1 compared to bare glass plate.
Layer thickness, porosity, refractive index and Transmittance values of AR films using
different Hollow nanoparticles synthesized from different process duration.

Sample Layer Thickness (nm) % porosity Refractive index at 550 nm

HNP1 109 42 1.21

HNP2 125 40 1.23
HNP3 141 28 1.28
HNP4 145 18 1.34

sols are prepared by dispersing these synthesized nanoparticles (HNP-1,

HNP-2, HNP-3 and HNP-4) in ethanol and isopropoxyethanol mixture.
These were subsequently coated on PV cover glass plate. All these
coatings, which comprised of hollow nanoparticles found to exhibit
attractive antireflection property in a broad spectral range
(400–1500 nm). Fig. 7 summarizes that transmittance spectrum of four
different hollow particles synthesized by altering the process duration.
The average transmittance value achieved for HNP1 was 98.38% at
visible range (400–800 nm), 96.25% at broad spectral range
(400–1500 nm), contrary to 91.1% at visible range (400–800 nm), and
91.4% at broad spectral range (400–1500 nm) for glass plate without Fig. 8. Current-voltage characteristics of c-Si solar cell with AR coated films comprised of
AR coating. The transmittance of AR coated glass plate using HNP-2, different hollow nanoparticles compared to pristine c-Si and c-Si solar cell covered with
bare glass plate.
HNP-3 and HNP-4 hollow nanoparticles were enhanced from 91.1% to
97.99%, 95.01%, and 92.00% average T in visible range (400–800 nm)
and in solar region (400–1500 nm) the average T enhanced from 91.4% particles. The performance of AR coatings was analyzed by comparing
to 95.61%, 93.76%, and 92.81% respectively. In addition, the optical coated and uncoated glass plate. The performance comparison of pris-
transmittances of AR films generated by HNP-3 and HNP-4 hollow tine c-Si solar cell was done under similar condition. The current-vol-
nanoparticles are drastically reduced compared to AR films generated tage characteristics of both coated and uncoated were studied for c-Si
by HNP-1 and HNP-2, which is due to the reduction of porosity (see solar cell for the same illumination (100mWcm−2, Air Mass 1.5 G). The
Table 1) in the films mainly caused by the structural collapsing of results are shown in Fig. 8. Table 2 lists the detailed device parameters.
hollow nanoparticles. The reason could be the low wall thickness of the The uncoated glass plate placed on the top of c-Si solar cell reduces the
JSC from 29.22 to 27.02mAcm−2; accordingly, HNP1 coated glass plate

Fig. 6. (a) FE-SEM surface morphology, (b) FIB cross-sectional image and (c) AFM surface profile of typical AR film comprising hollow MgF2 nanoparticles (HNP-1).

263
K. Chandra Sekhar Reddy et al. Solar Energy Materials and Solar Cells 176 (2018) 259–265

Table 2 multifunctional sol–gel coatings: anti-reflection coatings with enhanced self-

Current-voltage parameters of c-Si solar cell with AR coated films comprised of different cleaning capacity, Sol. Energy Mater. Sol. Cell. 94 (2010) 1081–1088.
hollow nanoparticles compared to pristine c-Si solar cell and c-Si solar cell covered with [8] L. Xu, J. He, Antifogging and antireflection coatings fabricated by integrating solid
bare glass plate. and mesoporous silica nanoparticles without any post-treatments, ACS Appl. Mater.
Interfaces 4 (2012) 3293–3299.
Device JSC (mA.cm-2) VOC (V) FF η (%) Δη (%) [9] S. Guldin, P. Kohn, M. Stefik, J. Song, G. Divitini, F. Ecarla, C. Ducati, U. Wiesner,
U. Steiner, Self-cleaning antireflective optical coatings, Nano Lett. 13 (2013)
5329–5335.
Pristine c-Si 29.22 0.603 0.612 10.77 0.00
[10] H.C. Barshilia, S. John, V. Mahajan, Nanometric multi-scale rough, transparent and
c-Si + uncoated PV glass 27.02 0.604 0.617 10.08 −6.40
anti-reflective ZnO superhydrophobic coatings on high temperature solar absorber
c-Si + HNP1 coated PV 28.63 0.605 0.618 10.70 −0.64
surfaces, Sol. Energy Mater. Sol. Cell. 107 (2012) 219–224.
glass [11] A. Gombert, W. Glaubitt, K. Rose, J. Dreibholz, B. Bläsi, A. Heinzel, D. Sporn,
c-Si + HNP2 coated PV 28.56 0.603 0.620 10.67 −0.92 W. Döll, V. Wittwer, Antireflective transparent covers for solar devices, Sol. Energy
glass 68 (2000) 357–360.
c-Si + HNP3 coated PV 28.41 0.602 0.614 10.50 −2.50 [12] D. Bernsmeier, J. Polte, E. Ortel, T. Krahl, E. Kemnitz, R. Kraehnert, Antireflective
glass coatings with adjustable refractive index and porosity synthesized by micelle-
c-Si + HNP4 coated PV 28.21 0.601 0.604 10.24 −4.90 templated deposition of MgF2 sol particles, ACS Appl. Mater. Interfaces 6 (2014)
glass 19559–19565.
[13] D. Chen, Anti-reflection (AR) coatings made by sol–gel processes: a review, Sol.
Energy Mater. Sol. Cell. 68 (2001) 313–336.
[14] L. Xu, Z. Geng, J. He, G. Zhou, Mechanically robust, thermally stable, broadband
antireflective and superhydrophobic thin films on glass substrates, ACS Appl. Mater.
and a maximum η of 10.70% is observed where as the power efficiency Interfaces 62 (2014) 9029–9035.
(η) of uncoated has decreased from 10.77% to 10.08 %. Incorporating [15] Y. Du, L.E. Luna, W.S. Tan, M.F. Rubner, R.E. Cohen, Hollow silica nanoparticles in
BARCs there were no significant performance losses. A similar trend of UV−visible antireflection coatings for poly (methyl methacrylate) substrates, ACS
Nano 4 (2010) 4308–4316.
efficiency variation was observed for AR coated glass plate placed on [16] X. Li, X. Du, J. He, Self-cleaning antireflective coatings assembled from peculiar
the top of the c-Si solar cell as transmittance trend observed by the mesoporous silica nanoparticles, Langmuir 26 (2010) 13528–13534.
coated glass plate. [17] C.Y. Kuo, Y.Y. Chen, S.Y. Lu, A facile route to create surface porous polymer films
via phase separation for antireflection applications, ACS Appl. Mater. Interfaces 1
(2008) 72–75.
4. Conclusion [18] T. Suteewong, H. Sai, J. Lee, M. Bradbury, T. Hyeon, S.M. Gruner, U. Wiesner,
Ordered mesoporous silica nanoparticles with and without embedded iron oxide
nanoparticles: structure evolution during synthesis, , J. Mater. Chem. 20 (2010)
A novel formation-deformation–reformation route was demon- 7807–7814.
strated in this work for fabricating high performance, broadband anti- [19] H.A. Macleod, Thin-film Optical Filters, fourth ed, CRC press, 2001.
reflective coating by using MgF2 hollow nanoparticles, which enhanced [20] E.D. Palik, Handbook of Optical Constants of Solids II, first ed, Academic Press,
1998.
the transmittance of transparent surfaces significantly. The incorpora-
[21] S. Fujihara, M. Tada, T. Kimura, Controlling factors for the conversion of tri-
tion of AR coating in glass plate resulted in average transmission which fluoroacetate sols into thin metal fluoride coatings, J. Sol.-Gel Sci. Technol. 19
is greater than 98% in the range from 400 to 800 nm and greater than (2000) 311–314.
[22] J.D. Bass, C. Boissiere, L. Nicole, D. Grosso, C. Sanchez, Thermally induced porosity
96% average T in the solar range from (400 –1500) nm. BARC coated
in CSD MgF2-based optical coatings: an easy method to tune the refractive index,
protection glass plate has led to increase the efficiency by 5.8% for c-Si Chem. Mater. 20 (2008) 5550–5556.
solar cell. This is a very good approach for producing high optical [23] J.K. Murthy, U. Grob, S. Rudiger, E. Kemnitz, J.M. Winfield, Sol–gel-fluorination
performance AR coating which can be cured at low temperature synthesis of amorphous magnesium fluoride, J. Solid State Chem. 179 (2006)
739–746.
(100 °C). Highly uniform, pinhole free, defect less coatings can be [24] H.Y. Hsueh, H.Y. Chen, M.S. She, C.K. Chen, R.M. Ho, S. Gwo, H. Hasegawa,
produced for large substrate with simple inexpensive dip coating. We E.L. Thomas, Inorganic gyroid with exceptionally low refractive index from block
anticipate that our approach of producing broadband antireflective copolymer templating, Nano Lett. 10 (2010) 4994–5000.
[25] D. Jacob, F. Peiro, E. Quesnel, D. Ristau, Microstructure and composition of MgF2
coating will be promising for all sort of solar and optical devices those optical coatings grown on Si substrate by PVD and IBS processes, Thin Solid Films.
require trapping of sunlight over a wide spectrum. 360 (2000) 133–138.
[26] S. Fujihara, M. Tada, T. Kimura, Preparation and characterization of MgF2 thin
films by a trifluoroacetic acid method, Thin Solid Films. 304 (1997) 252–255.
Acknowledgement [27] M.E. Fragala, R.G. Toro, P. Rossi, P. Dapporto, G. Malandrino, Synthesis, char-
acterization, and mass transport properties of a self-generating single-source mag-
This work was supported by a project of Technology Research nesium precursor for MOCVD of MgF2 films, Chem. Mater. 21 (2009) 2062–2069.
[28] J. Noack, K. Scheurell, E. Kemnitz, P. Garcia-Juan, H. Rau, M. Lacroix, J. Eicher,
Centre (AI/1/65/ARCI/2014) sponsored by Department of Science and
B. Lintner, T. Sontheimer, T. Hofmann, J. Hegmann, MgF2 antireflective coatings by
Technology (DST), Govt. of India. Apart from that, the authors are sol–gel processing: film preparation and thermal densification, J. Mater. Chem. 22
grateful to Dr. G. Padbhanabham, Director of ARCI and Dr. T.N Rao, (2012) 18535–18541.
[29] J. Noack, F. Emmerling, H. irmse, E. Kemnitz, Sols of nanosized magnesium
Associate Director of ARCI for supporting for this research.
fluoride: formation and stabilization of nanoparticles, J. Mater. Chem. 21 (2011)
15015–15021.
References [30] I. Sevonkaev, E. Matijevic, Formation of magnesium fluoride particles of different
morphologies, Langmuir 25 (2009) 10534–10539.
[31] A.B.D. Nandiyanto, T. Ogi, K. Okuyama, Control of the shell structural properties
[1] B.E. Yoldas, D.P. Partlow, Formation of broad band antireflective coatings on fused and cavity diameter of hollow magnesium fluoride particles, ACS Appl. Mater.
silica for high power laser applications, Thin Solid films. 129 (1985) 1–14. Interfaces 1 (6) (2014) 4418–4427.
[2] J.Q. Xi, M.F. Schubert, J.K. Kim, E.F. Schubert, M. Chen, S.Y. Lin, W. Liu, [32] M. Cao, Y. Wang, Y. Qi, C. Guo, C. Hu, Synthesis and characterization of MgF2 and
J.A. Smart, Optical thin-film materials with low refractive index for broadband KMgF3 nanorods, J. Solid State Chem. 177 (2004) 2205–2209.
elimination of Fresnel reflection, Nat. Photonics 1 (2007) 176–179. [33] A.B.D. Nandiyanto, F. Iskandar, T. Ogi, K. Okuyama, Nanometer to submicrometer
[3] L.Q. Liu, X.L. Wang, M. Jing, S.G. Zhang, G.Y. Zhang, S.X. Dou, G. Wang, Broadband magnesium fluoride particles with controllable morphology, Langmuir 26 (2010)
and omnidirectional, nearly zero reflective photovoltaic glass, Adv. Mater. 24 12260–12266.
(2012) 6318–6322. [34] S. Wuttke, S.M. Coman, G. Scholz, H. Kirmse, A. Vimont, M. Daturi, S.L. Schroeder,
[4] H. Shimomura, Z. Gemici, R.E. Cohen, M.F. Rubner, Layer-by-layer-assembled high- E. Kemnitz, Novel sol–gel synthesis of acidic MgF2− x (OH)x materials, Chem.-Eur.
performance broadband antireflection coatings, ACS Appl. Mater. Interfaces 2 J. 14 (2008) 11488–11499.
(2010) 813–820. [35] A.J. Wang, Y.P. Lu, R.X. Sun, Recent progress on the fabrication of hollow micro-
[5] X. Li, J. He, W. Liu, Broadband anti-reflective and water-repellent coatings on glass spheres, Mater. Sci. Eng. 460 (2007) 1–6.
substrates for self-cleaning photovoltaic cells, Mater. Res Bull. 48 (2013) [36] J.S. Xu, Y.J. Zhu, Microwave-assisted ionic liquid solvothermal rapid synthesis of
2522–2528. hollow microspheres of alkaline earth metal fluorides (MF 2, M= Mg, Ca, Sr), Cryst.
[6] S.Y. Lien, D.S. Wuu, W.C. Yeh, J.C. Liu, Tri-layer antireflection coatings (SiO2/ Eng. Comm. 14 (2012) 2630–2634.
SiO2–TiO2/TiO2) for silicon solar cells using a sol–gel technique, Sol. Energy Mater. [37] A. Saberi, Z. Negahdari, S. Bouazza, M. Willert-Porada, Synthesis and character-
Sol. Cell. 90 (2006) 2710–2719. ization of crystalline nanosized MgF2 powder via microemulsion route, J. Fluor.
[7] R. Prado, G. Beobide, A. Marcaide, J. Goikoetxea, A. Aranzabe, Development of Chem. 131 (2010) 1353–1355.

264
K. Chandra Sekhar Reddy et al.
[38] X. Cui, R. Ding, M. Wang, C. Zhang, C. Zhang, J. Zhang, Y. Xu, In situ surface
assembly derived ultralow refractive index MgF2–SiO2 hybrid film for tri‐layer
broadband antireflective coating, Adv. Opt. Mater. 4 (2016) 722–730.
[39] D. Grosso, C. Boissière, C. Sanchez, Ultralow-dielectric-constant optical thin films
built from magnesium oxyfluoride vesicle-like hollow nanoparticles, Nat. Mater. 6
(2007) 572–575.
[40] H. Ishizawa, S. Niisaka, T. Murata, A. Tanaka, Preparation of MgF2-SiO2 thin films
with a low refractive index by a sol gel process, Appl. Opt. 47 (2008) C 200–C205.
[41] R. Ding, X. Cui, C. Zhang, C. Zhang, Y. Xu, Tri-wavelength broadband antireflective
coating built from refractive index controlled MgF2 films, J. Mater. Chem. C. 3
(2015) 3219–3224.
[42] D. Karthik, S. Pendse, S. Sakthivel, E. Ramasamy, S.V. Joshi, High performance
broad band antireflective coatings using a facile synthesis of ink-bottle mesoporous
MgF2 nanoparticles for solar applications, Sol. Energy Mater. Sol. Cell. 159 (2017)
204–211.
265
View publication stats
Solar Energy Materials and Solar Cells 176 (2018) 259–265
[43] T. Murata, H. Ishizawa, I. Motoyama, A. Tanaka, Investigations of MgF2 optical thin
films prepared from autoclaved sol, J. Sol.-gel Sci. Technol. 32 (2004) 161–165.
[44] M. Pietrowski, M. Wojciechowska, Microwave-assisted synthesis of spherical
monodispersed magnesium fluoride, J. Fluor. Chem. 128 (2007) 219–223.
[45] S.J. Gregg, K.S.W. Sing, Adsorption Surface Area and Porosity, 2nd ed., Academic
Press, New York, 1982.
[46] D.H. Everett, Adsorption Hysteresis, The solid-gas interface 2 Dekker, New York,
1967, pp. 1055–1113.
[47] M. Chen, J.M. Jin, S.D. Lin, Y. Li, W.C. Liu, L. Guo, L. Li, X.N. Li, SiO2-template
synthesis of mesoporous MgF2 highly effective for Cl/F exchange reaction, J. Fluor.
Chem. 150 (2013) 46–52.
[48] M. Wojciechowska, B. Czajka, M. Pietrowski, M. Zieliński, MgF2 as a non‐conven-
tional catalytic support, Surf. Struct. Charact., Catal. Lett. 66 (2000) 147–153.
[49] M.H. Lee, J.S. Cho, Better thermochromic glazing of windows with anti-reflection
coating, Thin Solid Films 365 (2000) 5–6.