Received: 4 May 2020 

|
  Revised: 5 August 2020 
|  Accepted: 2 September 2020

DOI: 10.1111/jace.17491

ORIGINAL ARTICLE

Evaluating the role of composition and local structure on alkali

out-diffusion in glasses for thin-film solar cells

Neetu Bansal1   | Mukul Gupta2   | Bhaskar Chandra Mohanty1   | Kulvir Singh1

1
School of Physics and Materials Science,
Thapar Institute of Engineering and
Technology, Patiala, India
2
UGC-DAE Consortium for Scientific
Research, University Campus, Indore, India
Correspondence
Kulvir Singh, School of Physics and
Materials Science, Thapar Institute of
Engineering and Technology, Patiala
147004, India.
Email: kusingh@thapar.edu
Funding information
Department of Science and Technology,
Ministry of Science and Technology, Grant/
Award Number: SR/WOS-A/PM-88/2016
Abstract
The presence of alkali ions has reportedly improved the performance of CIGS/
CZTS–based thin-film solar cells. The out-diffusion of the alkali ion, in particular,
Na, from the glass substrate offers a facile scalable route of supplying the alkali ions
during the growth of the absorber layer. In this work, we demonstrate the diffusion of
different alkali ions (Li/Na/K) from composition tuned glasses with intentionally in-
corporated excess alkali ions into a thin Mo film, typically used as a bottom electrode
in solar cells. We also evaluate the physical, mechanical, and thermal properties of
the glasses for suitability as a substrate in thin-film deposition. The out-diffusion of
alkali ions to the overlayer is found to be critically influenced by the composition and
the local structure of the glasses. The Na ions exhibit the highest extent of diffusion
among the alkali ions present in glass substrates, while that for the K-ions is the low-
est. For the glasses with mixed alkali ions, the presence of Li facilitated the out-dif-
fusion of Na, whereas K ions appear to inhibit the same. Differently with the existing
reports, we show that the activation energy and the presence of Ca ions as additional
modifiers play a crucial role in the transport mechanism of the ions. In addition,
the synthesized glasses exhibit hardness of the order 5-7 GPa, density ~2.55 g cm-3.
The glass transition temperature lies between 535 and 580°C and the coefficient of
thermal expansion 8.5-10 ppm/K, which is highly suitable for use as substrates in
thin-film solar cells.

KEYWORDS
alkali, diffusion, glass, secondary ion mass spectroscopy, substrate, XPS

1  |   IN T RO D U C T ION cells and optoelectronic devices have been widely studied.6-8

Fostered by the increasing demands for clean energy, thin-
film photovoltaic has drawn considerable research attention
due to low material consumption and the rapid progress in
the technology of cost-effective fabrication of thin films.1-
3
Inorganic compound semiconductors CuInGaSe2 (CIGS)
and Cu2ZnSnS4 (CZTS) have been the most popular can-
didates as the absorber layer in thin-film solar cells due to
their highly relevant optoelectronic properties.1,4,5 Thin-film
coatings on commercially available glass substrates for solar
Recently, apart from the optimization of the absorber films,
many groups have undertaken studies highlighting the criti-
cal influence of the alkali ions diffusing from the substrates
on the performance of the devices.9-12 In the conventional
architecture of the CIGS- and CZTS-based thin-film solar
cells, besides providing mechanical support and high pro-
cessing temperature, the substrate (most commonly used
soda lime glass) doubles up as a source of Na that out-dif-
fuses to the absorber layer via the bottom electrode (~1 μm
thick Mo film).13-16 Solar cells relying on the diffusion of Na

© 2020 American Ceramic Society (ACERS)     1

J Am Ceram Soc. 2020;00:1–9. wileyonlinelibrary.com/journal/jace |
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2      BANSAL et al.

from the substrate to the overlayers have routinely yielded
high efficiencies, for example, 20.3% for CIGS and 12.6% for
CZTS (the highest efficiency, to date).17,18 On the other hand,
the devices having substrates without any alkali metal per-
formed poorly, thus, underscoring the importance of alkali
metals and the substrates facilitating their out-diffusion.19-21
Consequently, designing glasses with excess alkali metals
that can support their out-diffusion has become a key compo-
nent in photovoltaic technology.
Despite being the most mobile cations in solids, specifi-
cally glasses, the out-diffusion of alkali ions from the glass to
the overlayer is strongly dependent on the local structure and
composition of alkali oxide containing glass as well as the
microstructure of the thin film deposited onto the glass.22,23
While alkali ions inside the glass undergo diffusion influ-
enced by chemical gradient, along with contribution via
hopping from one interstitial site to another perpetuated by
the presence of vacant interstitial sites close to non-bridging
oxygens (NBOs) in the glass structure,24,25 the mechanism
of out-diffusion of alkali ions from the glass to the CIGS or
CZTS films via the Mo layer is not very clearly understood.
Recently, Neeway et al have suggested that solid-state diffu-
sion occurs via ion exchange between other available cations
at the interface between glass/thin film, and the alkali-ion ex-
change rate was determined by the local structure of the glass
involving the alkali ion and its role therein.22 For instance,
the diffusion of Mn from crystalline steel substrate to amor-
phous sodium metasilicate melt lubricated on its surface is
attributed to the chemical potential gradient existing between
the two structures.26 Mansas et al elucidated the complexity
of glass network and composition in diffusion/water trans-
port. While the presence of calcium strengthened the glass
network and reduced the density of bottlenecks to enhance
diffusion, the introduction of boron caused the chemical in-
teraction among H2O molecules, Ca and the network former
of the glass matrix.27 Hanh et al have simulated the sodium
and proton hopping mechanism in sodium silicate glass/water
interface to conclude that the sodium diffusion increases
with lowering the activation energy and proton diffusion is
enhanced due to its smaller size.28,29 Thus, the glass com-
position needs to be carefully selected in order to enhance
the diffusivity of ions. The importance of the choice of glass
composition is further heightened in that the out-diffusion of
the alkali ions should not critically distort the local structure
leading to the degradation of the glass properties in view of
the strong composition-property correlation in the glasses.
In the CIGS- or CZTS-based devices, distinct benefits of
alkali atoms such as Li, Na, and K have been reported.10,30-34
For instance, the out-diffusion of Na from the soda lime
glasses to the Mo layers has been modeled for different heat-
ing temperature and duration.15,35-39 Other than the single
alkali ion diffusion, Bunker et al elaborated the mechanism
behind alkali ion leaching in mixed alkali glasses and showed
that the presence of one alkali ion nonlinearly affected the
diffusivity of another alkali ion.40 However, studies on dif-
fusion of alkali atoms from a glass having more than one
type of alkali atom (eg, the simultaneous presence of Na and
K or Li) are very scarce, despite their crucial impact on the
performance of the thin-film devices. Thus, it is of very in-
terest to fabricate glasses having multiple alkali atoms with
an intention of their potential integration in thin-film photo-
voltaic technology and forms the basis of this work. Here, we
present the unreported results of fabrication of glasses with a
wide variation in the composition of Li, Na, and K, correlated
with the resulting mechanical and thermal properties deemed
suitable for a substrate in thin-film devices. We have clearly
elucidated the alkali-ion diffusivity dependence on the com-
position of glasses with single-alkali oxide and mixed-alkali
oxides.
2  |  EXPERIM ENTAL DETAIL S
Glasses with composition 65SiO2-5B2O3-15CaO-(15-x)
Na2O-xR2O (R  =  Li, K) (x  =  0, 5, 10, and 15) (Table  1)
were synthesized using the standard melt-quench technique.
A stoichiometric amount of SiO2 (Loba Chemie, 99.0%),
B2O3 (Loba Chemie, 99.0%), Na2CO3/ Li2CO3/ K2CO3, and

T A B L E 1   Composition of specially designed glasses along with their coefficient of thermal expansion (CTE) (150-500°C), dilatometric glass
transition temperature (Tgd), and dilatometric softening temperature (Td)

Sample ID SiO2 CaO B2O3 Li2O Na2O K2O CTE [ppm/K] Tgd [°C] Td [°C]
NCS 65 15 5 0 15 0 9.38 569 595
NL05 65 15 5 5 10 0 9.61 495 512
NL10 65 15 5 10 5 0 9.44 511 529
LCS 65 15 5 15 0 0 9.60 500 525
NK05 65 15 5 0 10 5 8.60 542 579
NK10 65 15 5 0 5 10 9.58 572 623
KCS 65 15 5 0 0 15 10.02 600 640
BANSAL et al.
CaCO3 were mixed and fine ground in agate mortar pestle in
acetone medium for 1 hour The glass batch was poured into
alumina crucibles and kept for drying overnight at 120°C in
an oven. Followed by drying, the reagents were thoroughly
mixed with a spatula and kept in a programmable high-resis-
tive furnace for melting. The furnace was so programmed to
heat at the rate of 5°C/min with a holding of 90 minutes at
300, 600, 900, and 1250°C to allow decomposition of car-
bonates into oxides. The glass batch finally melted at 1550°C
held for 30  minutes, followed by splat quenching between
copper plates. The glasses so obtained were annealed in a
preheated oven at 400°C for 6 hours for releasing the stress
induced while quenching.12
The annealed glass pieces were cut into sizes of
1 cm × 1 cm using a diamond cutter (Buehler Isomet) and
ground on emery sheets of 400/600/1000/1200/1500/2000
grades consecutively, to achieve a smooth surface. The mir-
ror-like surface finish was obtained by polishing them with
the diamond paste of 6 and 1 micrometer grade consecutively
for 20 minutes each. The polished glass samples were washed
with ethanol, followed by ultrasonic cleaning for 10 minutes
in DI water, and finally cleaned with isopropyl alcohol (IPA).
These cleaned glass pieces were used as substrates for sput-
ter deposition of the Mo thin films. The DC sputtering of
the bilayer Mo film on the synthesized and prepared glasses
(NCS:KCS) as substrates is carried out in a system as re-
ported in our previous work,13 at 75 W power with 20 min-
utes for high-pressure deposition (HPD) and 40 minutes for
low-pressure deposition (LPD). Since in the CIGS- or CZTS-
based solar cell technology, the absorber layers require a high
temperature (typically  >500°C) post-deposition annealing,
the deposited Mo films were vacuum annealed at 500°C for
1 hour to study the diffusion of the alkali ions in the Mo films
from various substrates.
X-ray diffraction pattern of the finely powdered glass
samples was obtained using a PANalytical X’Pert PRO sys-
tem with CuKα radiations (λ  =  1.5406  Å) @ scan rate of
2° min-1. Fourier transform infrared (FTIR) spectroscopy
of the samples was performed using Nicolet iS10 spectro-
photometer over the range 400-2000 cm-1 by making pallets
using KBr. X-ray Photoelectron Spectroscopy (XPS) was
performed on selected glass samples using a PHI VersaProbe
II with AES model. The XPS measurements were carried out
with nonmonochromatic AlKα radiation (hν = 1486.60 eV).
The C 1s XPS peak at 284.8 eV was used as a reference peak.
Thermogravimetric/Differential Thermal Analyser (TG/
DTA) from Perkin Elmer (model: Diamond Pyris) equipment
was used to estimate the glass transition temperature (Tg)
of the glasses. Thermal analysis was performed at a heating
rate of 10°C/min from 50 to 800°C under N2 atmosphere.
The coefficient of thermal expansion was determined using
Netzsch DIL 801-L dilatometer in the temperature range
100°C-600°C. Vicker's microhardness tester was used to test
|
     3
the hardness of the samples using a 300  g of load with an
indentation span of 15 seconds. The density of the samples
was measured based on Archimedes’ principle using xylene
as buoyant.41 The depth profile of all the elements (Na, Mo,
K, Li, Si, and B) from substrate source to Mo film is stud-
ied using  Hiden Analytical secondary ion  mass spectrome-
ter workstation (FG-300), equipped with oxygen sputter gun
with 400  nA target current, 5  kV acceleration voltage, and
detector operated in positive ion mode. The raw data of inten-
sity counts of ions with sputter time are converted into sput-
ter depth estimated from the Mo thickness of 1 μm obtained
from cross-sectional FESEM.
3  |  RESULTS AND DISCUSSIO N
3.1  |  Glasses with single-alkali ions
Typical SIMS diffusion profiles of individual alkali atoms
such as Na from NCS, Li from LCS, and K from KCS nor-
malized with respect to Mo94 are shown in Figure 1A. The
figure exhibits the highest diffusion concentration for Na
compared to Li and K. The normalized profiles assist in an
easy comparison since the Mo films were grown on each
glass substrates (GS) in identical conditions, thus, minimiz-
ing the error in estimating the intensities of the alkali ions.
As noted from the figure, although the glasses contain equal
mole percentage of the alkali ions in their respective glass
substrates (ie, 15  mol%), their extent of diffusion from
glass to the Mo film varies significantly. Considering that
the Mo films on different glass substrates were deposited
in the same conditions, the structure or morphology of the
Mo films resulting in the observed variation in the diffusion
profiles is ruled out.39,42,43 This indicates the critical influ-
ence of the composition and its effects. The Na exhibiting
higher potential to escape the glass surface as compared
to the other alkali ions is in agreement with our previous
study, which revealed the diffusion coefficient of Na ions in
NCS glass is higher followed by Li and K ions in LCS and
KCS glass.12 The trend in diffusivity obtained experimen-
tally from impedance spectroscopy and that from the SIMS
is in direct correlation. Similar and comparative diffusiv-
ity statement has been established by Natrup et al revealed
from tracer method, SIMS, and impedance analysis.44
While, the ionic radii are considered to govern the transport
phenomenon of alkali ions in glasses,45,46 the out-diffusion
profile of the alkali ions in the present case does not follow
the trend.
In order to clarify the above anomaly, the local chemical
environment of the samples was studied using the XPS spec-
tra. Figure  1B shows the typical indexed survey scan. The
high-resolution XPS spectrum of Si 2p (Figure  1C) shows
the shifting of the peak to the lower binding energy for the
 |
4      BANSAL et al.
F I G U R E 2   Cross-sectional FESEM (Left) of the Mo thin-film deposited onto (NCS) glass substrate, superimposed with the corresponding
SIMS depth profile of Mo, Na, and Si; (Right) schematic diagram exhibiting the diffusion of Na ions via hopping mechanism from composition
tuned glass to Mo overlayer (annealed at 500°C, the typical sulfurization temperature of CIGS/CZTS absorber layer for thin-film solar cells)
LCS glass containing the smaller modifier ion (Li), revealing
weaker bonds between Si-O.47-49 Alkali ions (R+) modify the
silicate units (Q4 → Q3), where Qn is the tetrahedral struc-
tural unit with n = number of bridging oxygens (BOs).
−Si − O − Si − Q4 + R2 O → −Si − O − R+ Q3
( ) ( )
(1)
+ − Si − OR− Q3
( )
Here, each alkali oxide breaks bonded Q4 units to form
two Q3 units. While Q4 units are covalently bonded to one
another, the Q3 unit is partially ionic (R-O) and partially
covalent (Si-O). One can estimate that Na2O and Li2O
are 42.74 and 43.62% ionic, respectively, whereas K2O is
38.71% ionic.50 The highest ionic character and high field
strength (0.26/Å2) of Li tend to weaken the Si-O bonds,
changing the local level symmetry in the silica tetrahedral.
The stronger the bond between R-NBO, the weaker is the
F I G U R E 1   A, Normalized SIMS depth
profile of [R]/[Mo], where R stands for
Na from NCS, Li from LCS, and K from
KCS glass substrate (GS) to high-pressure
deposited Mo (HPD-Mo) followed by
low-pressure deposited Mo (LPD-Mo) thin
films, respectively; (B) XPS survey scan of
respective glasses; high-resolution scan of
(C) Si2p and (D) O1s exhibiting a shift in
peak; and (E) variation in activation energy
for conduction phenomenon in glasses
with calcium-to-alkali ion radius ratio
obtained for LCS, NCS, and KCS glasses12
and previously reported R2O.2CaO.SiO2
glasses54
corresponding Si-O bond, as revealed by the shift of the
Si 2p peaks.49 A similar shift is also observed in the O 1s
spectrum displaying symmetric peak of Si-O-Si bond link-
ages (Figure 1D). The lower binding energy for Si-O bonds
in Li containing glass (ie, LCS) yielded the formation of
stronger Li-NBO bonds, resulting in lower mobility and dif-
fusivity of Li ions. On the other hand, the hindrance to the
diffusion of K ions is evident from the bigger ionic radii.
A typical schematic diagram in Figure 2 demonstrates the
diffusion via hopping mechanism of Na ions from the com-
position tuned glasses to the Mo overlayer via the grain
boundaries, investigated using the SIMS profile. Depth
profile corresponding to “Si” and “Mo” denotes the Mo/
Glass Substrate interface.
The role of Ca in the local structure of glasses is also be-
lieved to have an important influence as it modifies the Q4 units
as (Q4 → Q2).
BANSAL et al.      5
|

Thus, the simultaneous presence of R ions along with Ca

as modifying ions resulted in the cation-oxygen bonds, with
combinations of Q2, Q3, and Q4 structural units, with different
bond dissociation energies.51,52 The presence of these units
has been shown earlier in these glasses..12 It is believed that
the alkali ions those out-diffuse to the Mo overlayer originate
from the breakdown of the bonds with the existing nonbridg-
ing oxygens (NBOs) in the local glass structure.12 It may be
noted that the Ca ions in the glass, although are less mobile
compared to the alkali ions, significantly influence the trans-
port of alkali ions. The activation energy of conductivity and
diffusivity for glasses containing alkali or alkaline-earth ions
is influenced by the radius ratio of Ca to alkali ions (R), such
that Ea is found to show a minimum for rCa/rR ≈1 (Figure 1E).
Molecular dynamic simulation studies on sodium calcium
silicate glasses have revealed that the Ca in glass structure F I G U R E 3   Normalized [Na]/[Mo] depth profile as obtained from
has the susceptibility to coordinate with the NBOs, without SIMS for glasses containing (A) 10mol% Na2O with 5mol% Li2O and
any variation in coordination number.53 With a higher field K2O and (B) 5mol% Na2O with 10mol% Li2O and K2O, respectively
strength than the alkali ions, Ca occupies the sites close to
NBOs which fulfills all the structural requirements.53,54
The ionic radius of both the modifier ions Ca (1.00Å) and
Na (1.02Å) is very similar (rCa/rNa≈1). As Na ions tend to
move under the thermal activation phenomenon, the Ca ions
replace the negative NBO sites vacated by Na reducing the
backward jumps of Na ions, thus, supporting the higher dif-
fusion of Na ions as compared to other two alkali cations.

3.2  |  Glasses with mixed-alkali ions

Glasses with multiple types of alkali ions (mixed-alkali

glasses) are known to exhibit a typical non-linearity in their
transport properties.55-57 Although not well defined, the
non-linearity is by the virtue of mobility of one alkali ion
in the presence of another alkali ion with a different ionic
radius.55,57 It seems that the presence of two or more alkali
ions in glasses has localized competitive effect, similar to
electron-electron interactions in conductors.58,59 Figure 3A
shows the normalized depth profile corresponding to Na-
ions for NL05 (10  mol% Na2O and 5  mol% Li2O) and
NK05 (10 mol% Na2O and 5 mol% K2O) glasses. Although
the concentration of Na in both the glasses is the same (ie,
10  mol%), the extent of diffusion is higher in NL05 glass
containing Li2O than NK05 glass containing K2O. Similar
results were also obtained for NL10 (5  mol% Na2O and
10 mol% Li2O) and NK10 (5 mol% Na2O and 10 mol% K2O)
glasses, as depicted in Figure 3B. It indicates that while the
presence of Li facilitated the out-diffusion of Na, K ions ap-
pear to inhibit the same. It can be evidently correlated with
the mobility of alkali ions, which influences their diffusivity
F I G U R E 4   A, Variation in normalized [Na]/[Mo] content with
mol% Na present in substrate composition for NL and NK series,
respectively, taken at different depth positions; and (B) composition
dependence of conduction activation energy for all the glasses
and, hence, the conductivity of the glasses owing to the
mixed-alkali effect.12
The presence of multiple modifier ions (Na, Li/K, and Ca)
in the glass composition leads to a complex structural role for
different ions, critically affecting the out-diffusion of the Na
ions, as evident from Figure 4. Figure 4A shows the variation
in Na concentration (normalized with respect to Mo) with
the composition of the glasses at different depths from the
 |
6      BANSAL et al.
surface. The figure clearly shows a higher amount of Na at all
depths for the NL series than that of the NK series glasses.
The trend is in direct correlation with the glass activation
energy Ea (Figure 4B). The details of the calculation of the
activation energy are shown in Figure  S1 in the electronic
supplementary information (ESI). For both NL and NK se-
ries, the values of Ea decreased nonlinearly with an increase
in the Na composition in the glasses. However, always a
higher value of Ea was obtained for the NK series, suggesting
a decreased mobility of ions or a potentially higher energy
barrier for out-diffusion of Na ions into the Mo overlayer.
The mixed-alkali effect is more clearly manifested in the
properties of the glasses. While the replacement of Li by Na
in NL series exhibited a decrease in density of the glasses, a
similar replacement of K in NK series showed a reverse trend
(Figure 5A). The Li ions with higher-field strength make a
stronger bond with NBOs resulting in shrinking of the Li-
NBO bond length, yielding a high glass density. This is in
agreement with the XPS analysis of the LCS glass discussed
in section 2.1. On the other hand, K ions being larger in size,
and having lower-field strength form weak bonds. Thus, the
15  mol%  K glass has a lower density. The variation in the
density of the glasses containing more than one type of alkali
ions is attributed to the change in the R-NBO bond strength
due to the replacement of one type of ions by another one. A
similar trend has been observed in binary silicate glasses.55
Since molar volume (Vm) is inversely proportional to density,
therefore, a reverse trend was observed, as shown in Figure 5B
Vm for the NL series increased with the increase in Na mol%,
whereas it decreased for the NK series. The estimated elastic
modulus also showed a similar trend (Figure 5C). In the case
of the NL series, stronger bonds influenced the network rigid-
ity leading to a linear increase in elastic modulus,60 whereas
roughly linear decrease due to weaker bonds was noted for the
NK series (Figure 5C). The Vicker's microhardness (H) for the
NL as well as the NK series increased nonlinearly (Figure 5D).
However, the hardness was found to be higher for the NL se-
ries compared to the NK series. Nevertheless, the values are
in close agreement with other alkali silicate glass composi-
tions51,61 and higher than alkali borates.62
The glass transition temperature (Tg) obtained from the
differential thermal analyzer was found to increase for the
NL series while it decreased for the NK series (Figure 5E).
This is supported by the XPS binding energy in the Si-O
bond. Stronger the silicate network, higher is the Tg and vice
versa.63 It is also evident from the higher mobility of ions
in NL series exhibited by SIMS depth profile and transport
inhibiting nature of K ions in NK series. The dilatometric re-
sults of the present glasses revealed a coefficient of thermal
expansion (CTE) in the range 8-10 ppm/K (Figure 5F) which
lies well in the expected range of alkali silicate glasses.51,63
More importantly, it is in close agreement with CTE of the
commercially available soda lime glass as desired for CIGS/
CZTS-based solar cell substrates,64 ruling out the possibility
of device failure due to thermal mismatch between substrate
and thin film. It may be noted that the absorber layers (ie,
F I G U R E 5   Composition dependence
of (A) density (ρ), (B) molar volume (Vm),
(C) elastic modulus (E), (D) Vicker's
microhardness (H), (E) glass transition
temperature (Tg), and (F) coefficient of
thermal expansion (CTE) for NL and NK
series glasses, respectively. The error in the
values is obtained as the standard deviation
from measurement repeated 5 times in case
of density and Vicker's hardness. Error in
glass transition temperature is taken as ±5.
Errors in molar volume, elastic modulus,
and CTE are smaller than the size of
symbols. Calculation formulas of the above-
mentioned physical parameters are given in
detail in ESI
BANSAL et al.
F I G U R E 6   Normalized depth profile of (A) [Li]/[Mo] and (B)
[K]/[Mo] in the bilayer Mo films from respective glass substrates (GS)
CIGS or CZTS) routinely require postdeposition annealing
at temperatures ~500°C for crystallization and densification.
Hence, well-matched CTE along with Tg higher than sulfur-
ization temperature (500°C) is a crucial requirement for the
substrates on which these films are grown.
The dilatometric study of glasses gives the estimated pro-
cessing temperature range of all the synthesized glasses. The
dilatometric softening temperature (Td) of NCS glass lies
close to 595°C (Table 1), while that of NL series decreases
up to 510°C-530°C, and the same for NK series increases up
to 580°C-640°C. The dilatometric glass transition tempera-
ture (Tgd) (Table 1) for glasses is lower than the Tg obtained
from DTA owing to the lower heating rate. A variation of
20°C-30°C in the measurement of Tg is acceptable from two
different methods with different principles.65
3.3  |  Out-diffusion of Li/K ions
The anomalous behavior of Li and K ions is intrigued by
studying the diffusion profile of Li and K ions in the re-
spective glasses. Figure 6A,B presents the normalized Li/K
depth profile from glass to Mo film for NL and NK series
glasses, respectively. The extent of diffusion of Li and K ions
in respective glasses is lower by 2 orders of magnitude as
compared to Na. The extent of diffusion of Li (Figure 6A)
increased with the concentration of Li in the substrate com-
position, while K (Figure 6B) remained nearly the same and
negligible irrespective of the K composition. It indicates that
the diffusivity of Li ions is not much influenced by the pres-
ence of Na ions. On the other hand, the diffusivity of K ions
|
     7
from glasses containing 5 and 10 mol% Na is slightly higher
than KCS glass containing no Na. Thus, it shows that Na
ions support the diffusivity of both Li ions as well as K ions.
The higher activation energy (Figure 4B) and glass transition
temperature (Figure 5E) for NK glasses evidently show that
the K ions are strongly bound in the glass network leading to
negligible mobility of ions in this particular glass.
4  |  CONCLUSION
We have fabricated glasses with intentionally incorporated
excess alkali ions and investigated the limiting factors for out-
diffusion of these ions onto the overlayer, a critical require-
ment in the thin-film photovoltaic technology. The diffusion
of alkali ions into the sputter-deposited Mo overlayer is re-
vealed to have a complex dependence on the composition and
the local glass structure. The Na ions exhibit the highest extent
of diffusion among the alkali ions present in glass substrates,
while that for the K ions is the lowest. For the glasses with
mixed alkali ions, the presence of Li facilitated the out-diffu-
sion of Na, whereas K ions appear to inhibit the same. In con-
trast to the reported size-dependent transport mechanism of the
ions, we show that the activation energy and the presence of
Ca ions as additional modifiers play a crucial role. Typically, a
stronger alkali ion-nonbridging oxygen bond limits the overall
diffusion profile of the alkali ion into the Mo overlayer. The
synthesized glasses demonstrate mechanical and thermal prop-
erties deemed suitable for a substrate in thin-film solar cells.
ACKNOWLEDGMENTS
We thank Mr Purushottam Kumar Singh and Mr Kaushlendra
Pandey for their help during substrate preparation and thin-
film deposition. NB is also thankful to Ms Nidhi Pandey and
her laboratory mates for their help in carrying out SIMS at
UGC-DAE CSR Indore. This work is financially sponsored by
the Department of Science and Technology (DST-WOS-A),
Govt. of India vide letter no. SR/WOS-A/PM-88/2016(G).
CONFLICTS OF INTEREST
There are no conflicts of interest to declare.
DATA AVAILABILIT Y STATEMENT
The raw/processed data required to reproduce these findings
cannot be shared at this time as the data also form part of an
on-going study.
ORCID
Neetu Bansal  https://orcid.org/0000-0002-9331-5612
Mukul Gupta  https://orcid.org/0000-0002-9622-656X
Bhaskar Chandra Mohanty  https://orcid.
org/0000-0002-9823-8548
Kulvir Singh  https://orcid.org/0000-0002-6671-4829
 |
8      BANSAL et al.
R E F E R E NC E S
1. Katagiri H. Cu2ZnSnS4 thin film solar cells. Thin Solid Films.
2005;480–481:426–32.
2. Shin B, Gunawan O, Zhu Y, Bojarczuk NA, Chey SJ, Guha S. Thin
film solar cell with 8.4% power conversion efficiency using an
earth-abundant Cu2ZnSnS4 absorber. Prog Photovoltaics Res Appl.
2013;21:72–6.
3. Zhang C, Tao J, Chu J. An 8.7% efficiency co-electrode-
posited Cu2ZnSnS4 photovoltaic device fabricated via a
pressurized post-sulfurization process. J Mater Chem C.
2018;6(48):13275–82.
4. Scragg JJ, Dale PJ, Peter LM. Towards sustainable materials for
solar energy conversion: Preparation and photoelectrochem-
ical characterization of Cu2ZnSnS4. Electrochem commun.
2008;10(4):639–42.
5. Katagiri H, Kazuo J, Maw WS, Oishi K, Makota Y, Araki H, et
al. Development of CZTS-based thin film solar cells. Thin Solid
Films. 2009;517:2455–60.
6. Reinhardt HM, Maier P, Kim HC, Rhinow D, Hampp N.
Nanostructured transparent conductive electrodes for applications
in harsh environments fabricated via nanosecond laser-induced
periodic surface structures (LIPSS) in Indium-Tin Oxide films on
glass. Adv Mater Interfaces. 2019;6(16):1–6.
7. Nefzi C, Souli M, Cuminal Y, Kamoun-Turki N. Effect of substrate
temperature on physical properties of Cu2FeSnS4 thin films for
photocatalysis applications. Mater Sci Eng B Solid-State Mater
Adv Technol. 2020;254:114509.
8. Kuo DH, Hsu JT, Saragih AD. Effects of the metallic target composi-
tions on the absorber properties and the performance of Cu2ZnSnSe4
solar cell devices fabricated on TiN-coated Mo/glass substrates. Mater
Sci Eng B Solid-State Mater Adv Technol. 2014;186(1):94–100.
9. Kronik L, Cahen D, Schock HW. Effects of sodium on polycrys-
talline Cu(In, Ga)Se2 and its solar cell performance. Adv Mater.
1998;10:31–6.
10. Jackson P, Hariskos D, Wuerz R, Kiowski O, Bauer A, Friedlmeier
TM, et al. Properties of Cu(In, Ga)Se2 solar cells with new record
efficiencies up to 21.7%. Phys Status Solidi - Rapid Res Lett.
2015;9(1):28–31.
11. Ishizuka S, Yamada A, Islam MM, Shibata H, Fons P, Sakurai
T, et al. Na-induced variations in the structural, optical, and
electrical properties of Cu(In, Ga)Se2 thin films. J Appl Phys.
2009;106(3):034908.
12. Bansal N, Mohanty BC, Singh K. Designing composition tuned
glasses with enhanced properties for use as substrate in Cu2ZnSnS4
based thin film solar cells. J Alloys Compd. 2020;819:152984.
13. Bansal N, Pandey K, Singh K, Mohanty BC. Growth control of
molybdenum thin films with simultaneously improved adhesion
and conductivity via sputtering for thin film solar cell application.
Vacuum. 2019;161:347–52.
14. Fleutot B, Lincot D, Jubault M, Li Kao ZJ, Naghavi N, Guillemoles
JF, et al. GaSe formation at the Cu(In, Ga)Se2/Mo interface-A
novel approach for flexible solar cells by easy mechanical lift-off.
Adv Mater Interfaces. 2014;1(4):1400044.
15. Ashrafee T, Aryal K, Rajan G, Karki S, Ranjan V, Rockett A,
et al. IEEE 42nd photovoltaic specialist conference. PVSC.
2015;2015(2015):1–5.
16. Blösch P, Nishiwaki S, Kranz L, Fella CM, Pianezzi F, Jäger T,
et al. Sodium-doped molybdenum back contact designs for Cu(In,
Ga)Se2 solar cells. Sol Energy Mater Sol Cells. 2014;124:10–6.
17. Jackson P, Hariskos D, Lotter E, Paetel S, Wuerz R, Menner R, et
al. New world record efficiency for Cu(In, Ga)Se2 thin-film solar
cells beyond 20%. Prog Mater Sci. 2011;19:894–7.
18. Wang W, Winkler MT, Gunawan O, Gokmen T, Todorov TK, Zhu
Y, et al. Device characteristics of CZTSSe thin-film solar cells with
12.6% efficiency. Adv Energy Mater. 2014;4(7):1301465.
19. Wei SH, Zhang SB, Zunger A. Effects of Na on the electrical and
structural properties of CuInSe2. J Appl Phys. 1999;85(10):7214–8.
20. Li JV, Kuciauskas D, Young MR, Repins IL. Effects of sodium
incorporation in Co-evaporated Cu2ZnSnSe4 thin-film solar cells.
Appl Phys Lett. 2013;102(16):163905.
21. Choi PP, Cojocaru-Mirédin O, Wuerz R, Raabe D. Comparative atom
probe study of Cu(In, Ga)Se2 thin-film solar cells deposited on soda-lime
glass and mild steel substrates. J Appl Phys. 2011;110(12):124513.
22. Neeway JJ, Kerisit SN, Liu J, Zhang J, Zhu Z, Riley BJ, et al. Ion-exchange
interdiffusion model with potential application to long-term nuclear
waste glass performance. J Phys Chem C. 2016;120(17):9374–84.
23. Yoon JH, Cho S, Kim WM, Park JK, Baik YJ, Lee TS, et al. Optical
analysis of the microstructure of a Mo back contact for Cu(In, Ga)
Se2 solar cells and its effects on Mo film properties and Na diffu-
sivity. Sol Energy Mater Sol Cells. 2011;95(11):2959–64.
24. Martin SW, Christensen R, Olson G, Kieffer J, Wang W. New in-
terpretation of Na+ -ion conduction in and the structures and prop-
erties of sodium borosilicate mixed glass former glasses. J Phys
Chem C. 2019;123:5853–70.
25. Soules TF, Busbey RF. Sodium diffusion in alkali silicate glass by
molecular dynamics. J Chem Phys. 1981;75(2):969–75.
26. Wang L, Tieu AK, Zhu H, Cui S, Deng G, Hai G, et al.
Contribution of sodium metasilicate to the diffusion of Mn in steel
under tribological contact at high temperatures. J Phys Chem C.
2019;123(23):14468–79.
27. Mansas C, Delaye JM, Charpentier T, Bruguier F, Bouty O,
Penelon B, et al. Drivers of water transport in glass: chem-
ical or topological effect of the glass network? J Phys Chem C.
2017;121(30):16201–15.
28. Hahn SH, Rimsza J, Criscenti L, Sun W, Deng L, Du J, et al.
Development of a ReaxFF reactive force field for NaSiOx/water
systems and its application to sodium and proton self-diffusion. J
Phys Chem C. 2018;122(34):19613–24.
29. Hahn SH, Van Duin ACT. Surface reactivity and leaching of a so-
dium silicate glass under an aqueous environment: a ReaxFF mo-
lecular dynamics study. J Phys Chem C. 2019;123:15606–17.
30. Chirilǎ A, Reinhard P, Pianezzi F, Bloesch P, Uhl AR, Fella C, et al.
Potassium-induced surface modification of Cu(In, Ga)Se2 thin films
for high-efficiency solar cells. Nat Mater. 2013;12(12):1107–11.
31. Hsieh YT, Han Q, Jiang C, Bin ST, Chen H, Meng L, et al.
Efficiency enhancement of Cu2ZnSn(S, Se)4 solar cells via alkali
metals doping. Adv Energy Mater. 2016;6(7):1502386.
32. Mönig H, Lockhorn D, Aghdassi N, Timmer A, Kaufmann CA,
Caballero R, et al. Heat induced passivation of CuInSe2 surfaces:
a strategy to optimize the efficiency of chalcopyrite thin film solar
cells? Adv Mater Interfaces. 2014;1(2):1300040.
33. Bodeg Ård M, Granath K, Stolt L. Growth of Cu(In, Ga)Se2 thin
films by coevaporation using alkaline precursors. Thin Solid Films.
2000;361:9–16.
34. Jackson P, Wuerz R, Hariskos D, Lotter E, Witte W, Powalla M.
Effects of heavy alkali elements in Cu(In, Ga)Se2 solar cells with
efficiencies up to 22.6%. Phys Status Solidi - Rapid Res Lett.
2016;10(8):583–6.
BANSAL et al.
35. Belfore B, Ayala O, Ashrafee T, Rajan G, Karki S, Marsillac S.
Modeling Diffusion of impurities in molybdenum thin films
as a function of substrate temperature. IEEE J Photovoltaics.
2019;9(1):339–43.
36. Lakshminarayana G, Wondraczek L. Photoluminescence and en-
ergy transfer in Tb3+/Mn2+ co-doped ZnAl2O4 glass ceramics. J
Solid State Chem. 2011;184(8):1931–8.
37. Mattinen M, Hatanpää T, Sarnet T, Mizohata K, Meinander K,
King PJ, et al. Atomic layer deposition of crystalline MoS2 thin
films: New molybdenum precursor for low-temperature film
growth. Adv Mater Interfaces. 2017;4(18):1700123.
38. Ayala O, Ashrafee T, Rajan G, Karki S, Aryal K, Ranjan V, et al.
Modeling of the effect of substrate temperature on Na diffusion
through molybdenum films. In: 2016 IEEE 43rd Photovoltaic
Specialists Conference, PVSC 2016. Portland, OR: IEEE; 2016.
p. 2132–4. https://doi.org/10.1109/PVSC.2016.7750010
39. Forest RV, Han K, Eser E, Chen JG, Birkmire RW. Understanding
the effect of Na in improving the performance of Cu(InGa)Se2-
based photovoltaics. In: 2013 IEEE 39th Photovoltaic Specialists
Conference PVSC 2013. Tampa, FL: IEEE; 2013. p. 371–5. https://
doi.org/10.1109/PVSC.2013.6744170
40. Bunker BC, Arnold GW, Beauchamp EK. Mechanisms for al-
kali leaching in mixed-Na-K silicate glasses. J Non Cryst Solids.
1983;58:295–322.
41. Bansal N, Kaur G, Singh K. Braunite phase embedded Y2O3/
MnO2-Al2O3-CaO-SiO2 glass ceramics and their properties. Mater
Res Bull. 2018;98:34–40.
42. Mehrer H. Diffusion in solids: fundamentals, methods, materi-
als, diffusion-controlled processes. New York: Springer, Berlin
Heidelberg; 2007.
43. Park M, Zhang X, Chung M, Less GB, Sastry AM. A review of
conduction phenomena in Li-ion batteries. J Power Sources.
2010;195(24):7904–29.
44. Natrup FV, Bracht H, Murugavel S, Roling B. Cation diffusion and
ionic conductivity in soda-lime silicate glasses. Phys Chem Chem
Phys. 2005;7(11):2279–86.
45. Neyret M, Lenoir M, Grandjean A, Massoni N, Penelon B, Malki
M. Ionic transport of alkali in borosilicate glass. Role of alkali na-
ture on glass structure and on ionic conductivity at the glassy state.
J Non Cryst Solids. 2015;410:74–81.
46. Wang Z, Hu Y, Lu H, Yu F. Dielectric properties and crystal-
line characteristics of borosilicate glasses. J Non Cryst Solids.
2008;354(12–13):1128–32.
47. Sawyer R, Nesbitt HW, Secco RA. High resolution X-ray
Photoelectron Spectroscopy (XPS) study of K2O-SiO2 glasses:
Evidence for three types of O and at least two types of Si. J Non
Cryst Solids. 2012;358(2):290–302.
48. Hensley DA, Garofalini SH. XPS investigation of lithium borate
glass and the Li/LiBO2 interface. Appl Surf Sci. 1994;81(3):331–9.
49. Nesbitt HW, Bancroft GM, Henderson GS, Ho R, Dalby KN,
Huang Y, et al. Bridging, non-bridging and free (O2-) oxygen in
Na2O-SiO2 glasses: An X-ray Photoelectron Spectroscopic (XPS)
and Nuclear Magnetic Resonance (NMR) study. J Non Cryst
Solids. 2011;357(1):170–80.
50. Lide DR. CRC Handbook of Chemistry and Physics, 84th edn.
CRC Press LLC. CRC Press; 2003.
     9
|
51. Shih YT, Jean JH. Mixed modifier effect in lithium-calcium boro-
silicate glasses. J Am Ceram Soc. 2017;100(12):5482–9.
52. Miyoshi H, Chen D, Masui H, Yazawa T, Akai T. Effect of calcium
additive on structural changes under heat treatment in sodium bo-
rosilicate glasses. J Non Cryst Solids. 2004;345–346:99–103.
53. Cormack AN, Du J. Molecular dynamics simulations of so-
da-lime-silicate glasses. J Non-Crystalline Solids. 2001;283:
293–5.
54. Natrup F, Bracht H, Martiny C, Murugavel S, Roling B. Diffusion
of calcium and barium in alkali alkaline-earth silicate glasses. Phys
Chem Chem Phys. 2002;4(14):3225–31.
55. Day DE. Mixed alkali glasses - Their properties and uses. J Non
Cryst Solids. 1976;21(3):343–72.
56. Miller MJ, Wang J. Influence of Na diffusion on thermochromism of
vanadium oxide films and suppression through mixed-alkali effect.
Mater Sci Eng B Solid-State Mater Adv Technol. 2015;200:50–8.
57. Terai R. The mixed alkali effect in the Na2O-Cs2O-SiO2 glasses. J
Non Cryst Solids. 1971;6(2):180.
58. Pollak M. Effect of electron-electron interactions on hopping
and on delocalization. Philos Mag Part B Phys Condens Matter.
1980;42(6):781–98.
59. Altshuler BL, Aronov AG. Electron–electron interaction in dis-
ordered conductors. In: Modern Problems in Condensed Matter
Sciences. USSR; 1985. p. 1–153.
60. Battu AK, Manandhar S, Ramana CV. Molybdenum incorpora-
tion induced enhancement in the mechanical properties of Gallium
Oxide films. Adv Mater Interfaces. 2017;4(19):1700378.
61. Sharma G, Singh K. Dielectric and optical properties of glasses
and glass-ceramics synthesized from agro-food wastes. J Mater
Chem Phys. 2020;246:122754.
62. Arya SK, Danewalia SS, Singh K. Frequency independent low-: K
lithium borate nanocrystalline glass ceramic and glasses for micro-
electronic applications. J Mater Chem C. 2016;4(15):3328–36.
63. Arya SK, Kaur B, Kaur G, Singh K. Optical and thermal properties
of (70–x)SiO2-xNa2O-15CaO-10Al2O3-5TiO2 (10≤x≤25) glasses.
J Therm Anal Calorim. 2015;120(2):1163–71.
64. Salomé PMP, Rodriguez-Alvarez H, Sadewasser S. Incorporation
of alkali metals in chalcogenide solar cells. Sol Energy Mater Sol
Cells. 2015;143:9–20.
65. Jha PK, Pandey OP, Singh K. Non-isothermal crystallization kinet-
ics of K2O modified sodium-phosphate glasses. J Non Cryst Solids.
2016;440:76–84.
SUPPORTING INFORMATION
Additional supporting information may be found online in
the Supporting Information section.
How to cite this article: Bansal N, Gupta M,
Mohanty BC, Singh K. Evaluating the role of
composition and local structure on alkali out-diffusion
in glasses for thin-film solar cells. J. Am. Ceram. Soc.
2020;00:1–9. https://doi.org/10.1111/jace.17491