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OPEN Device simulation of highly

efficient eco‑friendly ­CH3NH3SnI3
perovskite solar cell
Piyush K. Patel

Photoexcited lead-free perovskite ­CH3NH3SnI3 based solar cell device was simulated using a solar
cell capacitance simulator. It was modeled to investigate its output characteristics under AM 1.5G
illumination. Simulation efforts are focused on the thickness, acceptor concentration and defect
density of absorber layer on photovoltaic properties of solar cell device. In addition, the impact
of various metal contact work function was also investigated. The simulation results indicate that
an absorber thickness of 500 nm is appropriate for a good photovoltaic cell. Oxidation of ­Sn2+ into
­Sn4+ was considered and it is found that the reduction of acceptor concentration of absorber layer
significantly improves the device performance. Further, optimizing the defect density ­(1014 cm−3)
of the perovskite absorber layer, encouraging results of the Jsc of 40.14 mA/cm2, Voc of 0.93 V, FF of
75.78% and PCE of 28.39% were achieved. Finally, an anode material with a high work function is
necessary to get the device’s better performance. The high-power conversion efficiency opens a new
avenue for attaining clean energy.

In the future, energy demand will be increased drastically. Nowadays, most of the energy consumption is obtained
from fossil fuels, and this energy reserve will be depleted in the coming days. Since it pollutes the environment,
therefore, the most challenging task is to establish a renewable energy source. The demand for renewable sources
of energy is increasing due to industrialization and growing populations. For this, solar energy is an up-and-
coming source because it is clean and no adverse effect on the ­environment1–7. Solar energy devices after a
sustainable solution in global energy are demanded.
Perovskite solar cell (PSC) has garnered tremendous attention to the scientific community due to increased
power conversion efficiency (PCE) day by day. Researchers started working on perovskite solar cells in 2­ 0098.
At that time, efficiency was relatively low (~ 3.8%). This organic–inorganic perovskite solar cell becomes a next-
generation device because it showed a step increase in PCE. The state-of-the-art certified PCE of PSC is exceeding
25%5–7,9,10. Apart from that, these materials exhibit peculiar features such as high absorption coefficient, good
charge carrier mobility, small exciton binding energy and large diffusion length of charge c­ arriers9,11–13. Therefore,
it is imperative to work on it. This energy can be converted into electricity using a photovoltaic e­ ffect14. How-
ever, it is cheap and clean energy; hence, it has dominated the Si-based solar cell in the photovoltaic m ­ arket15.
People studied pure and modified methylammonium lead halide as a perovskite material because of their good
photovoltaic ­performance16,17. Nowadays, some of the reports are coming on lead-based materials. However,
lead-based electronic devices have been sternly circumscribed by the European Union and other countries as
well. These materials showed a high value of power conversion efficiency. However, lead is not eco-friendly, which
is harmful to humans and the ­environment5,18–25.
To overcome this issue and owing to the superior optoelectronic properties lead-free perovskite ­CH3NH3SnI3
has been explored by many scientists and researchers as a photovoltaic material. This material exhibits a direct
band gap of 1.3 eV, a suitable range for the absorber. Recently, several group have successfully fabricated/simu-
lated organic–inorganic perovskites solar cells based C ­ H3NH3SnI3, which yields the good PCE. Freshly, the stud-
ied description stated that ­CH3NH3SnI3 is as favorable as its lead-based ­counterpart17,26–30. The electron transport
layer (ETL) is a crucial component of PSC. ­TiO2 is a promising candidate material because of its appropriate
energy level for electron injection, high electron mobility, chemical stability, low synthesis cost and environ-
mental ­friendliness31–34. ­TiO2 material has an appropriate band gap between diminishing the transportation of
­holes35. The hole transport layer (HTL) plays a crucial role for getting the high-power conversion efficiency in
PSC. HTL needs high hole carrier mobility and should form a less defect at the HTL/absorber layer to minimize
the charge carriers recombination at the interface. Recently, Yu et al. reported that C
­ u2O as an HTL showed high

Renewable Energy Laboratory, Department of Physics, Maulana Azad National Institute of Technology, Bhopal, M.
P., India. email: [email protected]

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hole mobility, good energy level alignment with C ­ H3NH3PbI3 and a longer lifetime of photo-generated charge
­carriers33. ­Cu2O is used as an HTL because of abundant availability on Earth, environmental-friendly, perfectly
band alignment with C ­ H3NH3SnI3 and easily synthesized materials. It decreases the barrier height of metal
contact and reduces the recombination loss of minority at a­ node11,36,37. Device simulation provides a strong way
to improve PSC’s efficiency after the optimization of various physical parameters. Solar cell capacitance simula-
tor (SCAPS) was utilized by many theoreticians to predict the open circuit voltage (Voc), short circuit current
density (Jsc), fill factor (FF) and PCE of the perovskite based solar ­cell27,38,39. Hence, the simulation of lead-free
­CH3NH3SnI3 as a photoactive material was studied using SCAPS. The impact of rectifying and ohmic contact
behaviour on lead-free C ­ H3NH3SnI3 based PSC was also investigated.

Device structure and simulation

In this work, a numerical simulation of a planar heterojunction tin-based perovskite solar cell was performed
using SCAPS. To obtain the performance parameters of the device like current density–voltage (J-V) curve,
quantum efficiency and energy bands, Poisson Eq. (1) is solved with continuity equation of electron (2) and hole
(3). These curves are used to calculate Jsc, Voc, FF and PCE of the solar cell device.
 
d dψ
−ε(x) = q[p(x) − n(x) + ND+ (x) − NA− (x) + pt (x) − nt (x)] (1)
dx dx

dpn pn − pn0 dξ dpn d 2 pn

= Gp − + pn µp + µp ξ + Dp 2 (2)
dt τp dx dx dx

dnp np − np0 dξ dnp d 2 np

= Gn − + np µn + µn ξ + Dn 2 (3)
dt τn dx dx dx
where, G, τn, τp, D, q, Ψ, µn, µp, n (x), p (x), nt (x), pt (x), NA− (x) , ND+ (x) and ξ denote the generation rate, electron
life time, hole life time, diffusion coefficient, electron charge, electrostatic potential, electron mobility, hole mobil-
ity, concentration of free electrons, concentration of free holes, concentration of trapped electrons, concentration
of trapped holes, ionized acceptor concentrations, ionized donor concentrations and electric field, respectively.
x denotes the direction along the t­ hickness29.
The device’s structure in the simulation is transparent conduction oxide (TCO)/buffer (ETL)/interface defect
layer 1/absorber/interface defect layer 2/HTL. The simulation was done under the illumination of 1000 W/m2,
at 300 K and an air mass of AM 1.5G. The active area of the studied device is 1 ­cm2. The device’s configuration
is illustrated in Fig. 1a where, p-type ­Cu2O is used as an HTL, ­CH3NH3SnI3 is used as an absorber layer and
n-type ­TiO2 is used as an ETL. In addition, fluorine doped tin oxide (FTO) is selected as the contact material and
various materials like Ag, Cu, Au and Pt is selected as an anode. The energy level diagram of the corresponding
materials utilized in the device architecture is depicted in Fig. 1b.
The values of the device and material parameters that are adopted from theories, experiments and literature
are summarized in Tables 1 and 227–29,39. Initially, the thickness of FTO (500 nm), T ­ iO2 (120 nm) and C ­ u 2O
(420 nm) were optimized for high PCE, as mentioned in Table 1.
Herein, χ is the electron affinity, Eg is the band gap, εr is the relative permittivity, Nc is the density of state of
the conduction band, Nv is the density of state of the valence band, µn is the mobility of electron, µp is the mobil-
ity of hole, NA is the acceptor density, ND is the donor density and Nt is the defect density. The thermal velocity
of electron and hole are set be ­107 cm/s. The absorption coefficient of FTO, ­Cu2O, ­CH3NH3SnI3 and ­TiO2 were
extracted from experimental r­ esults15,40–42. The diffusion lengths of electron and hole were set to 260 nm and
560 nm, respectively, similar to the experimentally observed value of Ma et al.28.

Results and discussion
With these initial parameters in Tables 1 and 2, energy band diagram, J-V characteristic and quantum efficiency
of the cell was plotted, as shown in Fig. 2a–c, respectively. After illumination, electron–hole pairs are generated
inside the absorber layer. Due to the junction field electrons and holes move towards ETL and HTL, respectively.
These electrons and holes are collected at the cathode and anode, respectively and generates a voltage. The Jsc of
39.72 mA/cm2, Voc of 0.66 V, FF of 69.82%, and PCE of 18.31% are obtained. The Jsc of the device depends upon
the absorption coefficient, thickness and mobility of the active material. The higher the absorption coefficient,
the higher the photo current will b ­ e9,12,29,39,43. The second important parameter is the thickness of the absorber.
It must be thick enough to absorb the highest cut off wavelength of the incident solar r­ adiation27,29. Apart from
that, mobility plays a very crucial role for getting the high Jsc. Ideally, the Jsc is equivalent to solar cell current after
illumination. Ma et al. and Stoumpos et al. reported the very high value of mobility of electron (2000 c­ m2/Vs)
and hole (300 ­cm2/Vs) for C ­ H3NH3SnI3 sample synthesized by open tube ­method28,44. Similar values of carriers
mobilities have been utilized by Lazemi et al. and stated a high value of Jsc (~ 37 mA/cm2)27. In this simulation,
the mobility of electron and hole was adopted from recently studied ­researcher27,28,43,44. Since, current density is
linearly proportional to the mobility of charge carriers, and hence the high value of Jsc was achieved. However,
Devi et al.45 and Khattak et al.46 have considered the significantly smaller and identical values of electron and hole
mobilities, which are 1.6 c­ m2/Vs and 0.16 c­ m2/Vs, respectively and reported good Jsc (~ 30 mA/cm2). Another
aspect is that diffusion length is proportional to the square root of m ­ obilit45. Hence, diffusion length becomes
more for high mobility of charge carrier, and hence recombination of charge carriers decreases. This may be
other reasons for getting the comparatively higher value of Jsc as compare to recently reported ­results45,46. The

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Figure 1.  (a) Lead-free ­CH3NH3SnI3 solar cell structure. (b) Energy level diagram.

Parameters FTO (TCO) TiO2 (ETL) CH3NH3SnI3 (absorber) Cu2O (HTL)

Thickness (nm) 500 120 450 (variable) 420
Eg (eV) 3.4 3.2 1.3 2.17
χ (eV) 4.5 4.1 4.17 3.2
εr 9.1 9.0 8.2 7.1
Nc ­(cm−3) 1.1 × 1019 2.2 × 1018 1 × 1018 2 × 1017
Nv ­(cm−3) 1.1 × 1019 1.8 × 1019 1 × 1018 1.1 × 1019
µn ­(cm2/Vs) 20 0.05 2000 200
µp ­(cm2/Vs) 10 0.05 300 80
ND ­(cm−3) 1.1 × 1019 1 × 1018 0 0
NA ­(cm−3) 0 0 1 × 1014 (variable) 1 × 1018

Table 1.  Parameters for the optoelectronic simulation.

CH3NH3SnI3/Cu2O
Parameters TiO2 CH3NH3SnI3 Cu2O TiO2/CH3NH3SnI3 interface interface
Defect type Neutral Neutral Neutral Neutral Neutral
σn ­(cm−2) 1 × 10–15 2.5 × 10–13 1 × 10–15 1 × 10–15 1 × 10–15
σp ­(cm−2) 1 × 10–15 8.5 × 10–15 1 × 10–15 1 × 10–15 1 × 10–15
Energy distribution Single Gaussian Single Single Single
Energy level with respect to
0.600 0.650 0.100 0.600 0.600
Ev (above Ev) (eV)
Characteristic energy (eV) – 0.100 – – –
Nt ­(cm−3) 1 × 1014 3.029 × 1016 (variable) 1 × 1014 1 × 1010 1 × 1010

Table 2.  Parameters for the defects in materials and at interfaces.

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Figure 2.  (a) Energy band diagram, (b) ­Jsc and (c) quantum efficiency of PSC.

simulated device performance is auspicious and consistent with the tin-based P ­ SC27,29,39. The quantum efficiency
curve covers the entire visible spectrum, which is in good accordance with the recently published r­ esults47,48.
Further enhancement in photovoltaic performance is possible. Figure 2a displays the energy band diagram of
PSC. The positive conduction band offset (CBO) of about 0.36 eV is observed at absorber/ETL interface. Due to
this positive CBO, a spike is formed at the absorber/ETL interface. This spike acts as a barrier for photo-generated
electron flow towards the e­ lectrode49–52.

Absorber thickness.  The absorber layer plays a significant role in the performance of device. The previ-
ously published report shows that the photovoltaic parameters such as Jsc, Voc, FF and PCE are influenced by
the absorber layer ­thickness27,39. To get the absorber layer’s role in the device simulation, the absorber layer’s
thickness was varied from 100 to 1000 nm, and other parameters tabulated in a Tables 1 and 2 remain the same.
The simulation results, i.e., the variation of photovoltaic parameters concerning the absorber layer’s thickness, is
shown in Fig. 3. It is observed that Jsc increases steeply up to 700 nm and then varies slowly with thickness. The
large value of Jsc was obtained (~ 42.70 mA/cm2) with a thickness 900 nm is mainly due to the large absorption
coefficient of the ­perovskite29. Voc falls off smoothly, which may be attributed to the enhanced recombination
of free charge carriers in the thicker ­absorber27. The decreasing value of FF with respect to absorber thickness
may be due to the increased series ­resistance29,53. In addition, PCE initially increases and reaches a maximum
(~ 18.36%) at 500 nm and decreases with a further increase in absorber thickness. Firstly, the absorber thick-
ness is smaller than the diffusion length of charge carriers; therefore, most of the charge carriers reach at the
electrodes, and therefore PCE increases. However, recombination occurs for thick absorber layer, and hence PCE
decreases with a further increase in ­thickness27,29,39.

Acceptor carrier concentration ­(NA) of the absorber.  Apart from the absorber layer thickness, the pho-
tovoltaic cell’s device performance is significantly affected by the acceptor density of holes in the absorber layer.
­CH3NH3SnI3 oxides in which ­Sn2+ is converted into ­Sn4+ (self-doping process) when the device is exposed to air.
Unfortunately, this process deteriorates the performance of the device and making it a p-type ­semiconductor28.
Addition of S­ nO2 suppresses the formation of ­Sn2+ to ­Sn4+15,43,54. Feng et al. calculated the dark carrier density of
­1014 cm−3 to 1­ 017 cm−3 by Hall- effect ­measurement55. Takashi et el. found out that the hole concentration in the
­CH3NH3SnI3 absorber layer can be varied up to ­1019 cm−356. Therefore, to get to know how acceptor doping con-
centration affects the photovoltaic parameters, the acceptor density of the C ­ H3NH3SnI3 layer was varied from
­1014 to ­1018 cm−3. Figure 4 provides the variation of J-V characteristics and PCE with respect to acceptor densi-

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Figure 3.  Photovoltaic response as a function of absorber layer thickness.

Figure 4.  (a) J-V curve for different acceptor density and (b) PCE versus acceptor density.

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Figure 5.  Photovoltaic response as a function of defect density.

ties of the perovskite layer. The slight change in photovoltaic parameters up to 1­ 015 cm−3 acceptor concentration
implies that the generation rate of photo-generated carriers does not change with acceptor densities under the
incident of the same photon n ­ umber39. With increasing the acceptor doping concentration, the Fermi energy
level of the hole decreases and hence Voc increases, as shown in Fig. 4a. Another aspect is that built-in potential
increases with increasing the acceptor doping concentration. Due to this, charge separation promotes and hence
Voc increased. However, initially, Jsc decreases slightly up to ­1015 cm−3 and then decreases drastically. It may be
due to the increase in the recombination rate of charge carriers inside the perovskite absorber ­layer39. However,
PCE drops rapidly when NA exceeds ­1015 cm−3. The absorber layer’s defect state leads to a considerable drop in
power conversion efficiency, as exposed in Fig. 4b.

Defect density ­(Nt).  The effect of defect density of absorber was also investigated. Defects are inevitable in
absorber layer. They exist in the bulk and at surfaces. In perovskite absorber layer, defects present in the form
of point defects such as lattice vacancy, interstitial, Schottky and Frenkel defects. Apart from that, the higher
order defects like dislocations and grain boundaries may also be p ­ resent57. The self-doping process, which makes
the semiconductor p-type, produces impurity defect in absorber ­layer15,28,43,55. These defects introduce deep or
shallow levels in the energy band ­gap57. As a result of these defects, charge carriers can trap and facilitate non-
radiative electron–hole ­recombination27,39. It is noted that the diffusion length of charge carriers is increased up
to ~ 3 µm in Sn-based perovskite absorber layer using tin-reduced precursor ­solution58. Since, diffusion length of
charge carriers is related to the defect ­density45. Therefore, in order to see the effect of diffusion length on photo-
voltaic responses, diffusion length of electron was varied from 0.046 to 4.6 µm by changing defect density from
­1018 to ­1014 cm−359. Similar change in defect density has also been adopted by Lazemi et al., Du et al. and Hao
et al.27,30,39. Based on these studies, the defect density was varied from ­1014 to 1­ 018 cm−3 and depicted its variation
on photovoltaic properties in PSC, as shown in Fig. 5. It is observed that the performance of the device improved
with the reduction of defect density. The absorber layer’s initial defect density was set to be 3.029 × 1016 cm−3 (as
per Table 2). Because for this value of defect density, the diffusion length of electron and hole is nearly similar
to experimentally observed v­ alues28. When the defect density is 1­ 015 per ­cm−3, the cell performance is signifi-
cantly improved, attaining the Jsc of 40.13 mA/cm2, Voc of 0.81 V, FF of 75.17% and PCE of 24.54%. Now, further
decrease of Nt, from ­1015 to ­1014 cm−3, slight variation is observed in Jsc (40.14 mA/cm2) and FF (75.78%) but
considerable changes occurred in Voc (0.93 V) and PCE (28.39%). However, experimentally, it is not easy to syn-
thesize a material with such a low value of defect ­density39.
The Shockley–Read–hall (SRH) recombination model can be utilized to get information about the influence of
the absorber layer’s defect density on device ­performance27,29,52. To get the influence of Nt on the performance of
the device acutely, the effect of defect density on the recombination rate based on the SRH recombination model
was studied. Figure 6 shows the variation of recombination rate with depth from the surface for different value of
Nt. It is detected that with increasing the defect density recombination rate increases, which is the reason for the

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Figure 6.  Variation of recombination rate with depth from surface for various defect density along with inset
shows the close-up image.

reduction of cell performance with the increased value of defect density. Since, recombination rate increases with
increasing the defect density; therefore, Voc decreases with increasing the defect concentration, as shown in Fig. 5.
According to SRH model, the recombination rate (R) can be expressed like
−1 (np − n2 )
τn,p
R= i  (4)
n + p + 2ni coh EtkT−Ei

where, τn,p, n, p, ni, Ei and Et are the lifetime of charge carriers, the density of electron, the density of hole, intrinsic
density, intrinsic energy level and energy level of the trap defects, respectively.
Lifetime of charge carriers is given by
1
τn,p =
σn,p vth Nt (5)

where, σn,p, vth and Nt are the capture cross section of charge carriers, velocity of charge carriers, and the absorber
layer’s defect density, respectively. Therefore, with increasing the defect density, the relaxation time of charge car-
riers decreases (as per Eq. 5) and hence recombination rate increases (according to Eq. 4) as confirmed by Fig. 6.
The interface recombination depends upon the conduction band offset between the buffer and absorber layer.
The interface recombination at the absorber/buffer interface reduces due to the creation of positive ­CBO49–51.
Minemoto et al. theoretically studied the effect of CBO at the absorber/buffer i­ nterface49. He reported that about
0.3 eV CBO offset minimizes the recombination at the interface due to this photovoltaic parameter increases.
Hence, the recombination rate is significantly low at the absorber/ETL interface as compared to previously
reported ­results39,52.
The diffusion length of charge carriers can be written like
√
LD = Dτ (6)
where, D is the diffusion coefficient. Since, the diffusion coefficient is proportional to the mobility of charge
carriers and the mobility of electron (~ 2000 ­cm2/Vs) and hole (300 ­cm2/Vs) is large as experimentally observed
by various ­researchers30,44. Due to the large value of mobility, diffusion length is large, which is why obtaining
the very high value of PCE (28.39%). Because of the low recombination rate and large diffusion length, a very
high value of PCE was achieved. Hence, the obtained outcomes are found to be better than previously published
­results27,29,39,60.

Metal electrode work function.  To study the ohmic or rectifying behaviour at metal contact/HTL inter-
face, a work function study was carried out by varying various anode materials. Simulation was done using
Ag, Cu, Au and Pt as an anode for PSC. The work function of Ag, Cu, Au and Pt are 4.74 eV, 5.0 eV, 5.1 eV and
5.7 eV, ­respectively61,62. The energy band diagram with various anode materials is shown in Fig. 7a,b. As clearly
shown that the barrier layer for hole increases with decreasing the wave function of contact materials (Fig. 7a).
Figure 8a,b presents the anode material’s effect on J-V characteristics and photovoltaic properties of PSC. We can
see that PCE decreases with decreasing the work function of the anode. In the case of Ag, Cu and Au, the anode’s
work function is less than the work function of ­Cu2O61,62. Hence, a rectifying Schottky barrier contact was
formed for Ag, Cu and Au anode materials at an anode/Cu2O interface, as indicated by the dashed oval frame in
Fig. 7a. This Schottky barrier hinders the hole transport to the anode, decreasing the FF and PCE as confirmed

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Figure 7.  Band diagram of PSC with various anode materials (a) Ag, Cu, Au and (b) Pt.

Figure 8.  (a) J-V characteristics with varied work function (b) FF and PCE as a function of work function of
anode materials.

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by Fig. 8b29. However, in the case of Pt anode, the work function of Pt is higher than the work function of C
­ u2O63.
The ohmic contact was formed at an anode/Cu2O interface, as indicated by the dashed oval frame in Fig. 7b. The
ohmic contact allows the hole transport at the i­ nterface62. Therefore, further improvement in Jsc (42.63 mA/cm2)
and PCE (19.67%) are observed as shown in Fig. 8.
The surface potential energy barrier ( φB ) at the anode/Cu2O interfaces is given by
Eg
φB = + χ − φM (7)
q
Here, Eg is the band gap of C
­ u2O, χ is the electron affinity of C
­ u2O and φM is the anode’s work function. Due to
the decrease in the value of work function the surface potential energy barrier increases (as per Eq. 7), hence
the FF and PCE decreases.

Conclusion
Lead-free ­CH3NH3SnI3 perovskite as light harvester is investigated. A planner heterojunction perovskite solar
cell with the structure FTO/TiO2/CH3NH3SnI3/Cu2O/anode was numerically analysed. Photovoltaic parameters
were optimized with respect to several factors such as absorber layer thickness, acceptor density, defect density
and work function of anode materials. The optimized perovskite thickness of 500 nm significantly enhances the
PCE (18.36%). Reducing the defect density and improving the S­ n2+ stability of absorber layers are the critical
issues for future research, which might be resolved by refining the device’s fabrication techniques. The results
indicated that the appropriate defect density improves the cell performance; however excessive concentration
leads to a higher recombination rate of charge carriers and poor cell performance. The Schottky junction was
formed at an anode/Cu2O interface for lower work function contact materials; therefore, high work function
material is necessary for ohmic contact like Pt. The reported C
­ H3NH3SnI3-based PSC provide a viable path to
realizing environmentally benign, low-cost, and high-efficiency PSC.

Data availability
The data that support the findings of this study are available from the corresponding author upon reasonable
request.

Received: 11 October 2020; Accepted: 18 January 2021

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Acknowledgements
The authors would like to acknowledge Dr. Marc Burgelman (University of Gent) for providing the simulation
software SCAPS.

Author contributions
P.K.P.: conceptualization, investigation, formal analysis, data curation, methodology, visualization, software.

Competing interests 
The author declares no competing interests.

Additional information
Correspondence and requests for materials should be addressed to P.K.P.
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