RAPID RESEARCH LETTER
Hybrid Perovskites
On the True Band Gap of the (CH3NH3)2Pb(SCN)2I2
Hybrid Perovskite: An Interesting Solar-Cell Material
Josue I. Clavijo Penagos,* Eduard R. Romero, Gerardo Gordillo, John M. Correa Hoyos,
and Miguel A. Reinoso Sánchez
The hybrid halide perovskite methyl ammonium lead iodide thiocyanate –
(CH3NH3)Pb(SCN)2I2 – is synthesized both as a powder and as a thin film.
The crystal structure and key optical properties (band gap) are determined by
diffuse reflectance spectra and X-ray diffraction (Rietveld refinement) meas-
urements and compared to density functional theory (DFT) state-of-the-art
calculations. It is found that the refined orthorhombic crystal structure
presents 2D-layer confinement, and that the optical band gap presented in
this work does confirm some previous reports and rebuts other results, too.
In the pursuit of discovering new, lost-cost, and nontoxic solar-
cell materials, the scientific community has been brought into
attention of the methyl ammonium lead iodide thiocyanate
chemical compound, having the molecular formula
(CH3NH3)2Pb(SCN)2I2 (from now on abbreviated MAPSI),
which was theoretically proposed as a thermodynamically
stable alternative to CH3NH3PbI3 (hereafter abbreviated MAPI)
– the iconic hybrid halide perovskite material.
MAPSI 2D-layered structure and its optical band gap were
reported in Ref. [1] for the first time after the seminal work about
powder synthesis and single crystal structure determination by
Daub and Hillebrecht.[2] Aside from the MAPSI chemical
stability against ambient/atmospheric conditions, to present day
there is no consensus about the true MAPSI band gap (latter
discussed) and, by consequence, its real suitability as a solar cell
absorber material, being the band gap value a key property to
assign the role of absorber either for single-junction cells
(materials with band gap around 1.5 eV) or for multiple-junction
cells (materials with band gap around 1.8–2.3 eV).
Prof. J. I. Clavijo Penagos, Prof. E. R. Romero
Departamento de Quimica, Universidad Nacional de Colombia
Cra. 30 45-03, Bogota DC, Colombia
E-mail: jiclavijop@unal.edu.co
Prof. G. Gordillo, J. M. Correa Hoyos, M. A. Reinoso Sánchez
Departamento de Fisica, Universidad Nacional de Colombia
Cra. 30 45-03, Bogota DC, Colombia
 Reinoso Sánchez
M. A.
Facultad de Ciencias de la Ingeniera
Universidad Estatal de Milagro
Ciudadela universitaria, Milagro 091706, Ecuador
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/pssr.201700376.
DOI: 10.1002/pssr.201700376
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Taking into account all of the above, this
work does present a contribution in the
debate about the true band gap of MAPSI
and the potentialities of this MAPSI novel
photovoltaic material, starting from X-ray
diffraction (XRD) and diffuse reflectance
spectra (DRS) measurements for later to
study the crystal structure and to calculate
the optical band gap of MAPSI by applying
Rietveld XRD refinement and the Tauc
plots using the Kubelka–Munk transform
function, respectively, to end by comple-
menting the band gap analysis with the
results of density functional theory (DFT) calculations.
Details about chemical reagents, MAPSI powder and thin film
synthesis and materials characterization can be read in the
Supporting Information file.
Structure of MAPSI Powder and Thin Films: A powder sample
and a thin film of MAPSI are shown in Figure S1, Supporting
Information. The material was formed as a dark-reddish solid in
powder phase, and as a red thin film by the spin coating
technique, film showing good uniformity with a fast reaction
process (in the time range of seconds); the film appears even
before spinning stops. An important question is whether the
compound is formed as a single phase or mixed with other
secondary compounds such as MAPI, Pb(SCN)2, or CH3NH3I,
and to check the presence of secondary/impurity phases,
Figure S2, Supporting Information shows the XRD patterns
for MAPSI powder and thin film samples compared with the
XRD patterns of the chemical precursors. It is evident that both
powder and thin films samples are composed of the expected
MAPSI phase, and no impurities are present neither in the
MAPSI powder nor in the MAPSI thin films at least up to the
limit XRD can discern.[3]
Using the XRD Refinement software GSAS-II from Argonne
National Laboratory,[4] and starting from single crystal data from
Daub et al. experimental XRD patterns for powder and thin film
samples were simulated with the Rietveld refinement method
(presented in Figure S3 and S4, Supporting Information) in
order to find out the unit cell parameters, as shown in Table 1,
and the atomic coordinates that define the crystal structure also.
The compound was found to have an orthorhombic unit cell,
space group Pmn21, and the thin film presents preferred
orientation in the [200] plane with some fractions of crystals
facing the [400] and [600/120] planes, and the crystallinity is very
high because only the above atomic planes contribute to the
diffraction pattern, in contrast with the XRD pattern for the
compound as a powder, which shows many diffraction peaks
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Table 1. Lattice constants for (CH3NH3)2Pb(SCN)2I2 (MAPSI) both as
a powder and as a thin film, from Rietveld refinement of experimental
XRD patterns. Single crystal data from Ref. [2].
Lattice parameters (Å )
MAPSI a b
Powder 18.5795(16) 6.2715(05)
Thin film 18.5984(05) 6.2732(07)
Single crystal 18.580(2) 6.2668(6)
instead. This results of high crystallinity and preferred
orientation for the thin film are in concordance with the Xiao
et al. and Lui et al. reports.[5,6] It is interesting to consider that
comparison of MAPSI XRD patterns for both as powder and as a
thin film film with other reports for similar SCN
-substituted
hybrid halide compounds such as CH3NH3Pb(SCN)3
xIx or
CH3NH3Pb(SCN)2I[7] clearly shows that the MAPSI compound
reported here and those other materials are related but not the
same.
One interesting key result from the XRD data is that the
refined crystal structure presents a 2D-layered type material
[layers of successive Pb-I octahedra (Pb-atom center, I-atoms
equatorial) with SCN
ions both in top and in bottom positions
(axial positions), see Figure 1], also as reported by Xiao.[6] This
reveals that the expected semiconductor band gap energy value
must not be as low as in the original report of Ganose et al.
(1.57 eV), taking into account that a 2D-layered structure
material is expected to have a quantum confinement effect
widening the band gap compared to similar 3D structures.[6,8]
MAPI, for example, has a 3D-type structure and a band gap of
1.59 eV (confirmed by state-of-the-art DFT calculations[9]), so
MAPSI must be of higher value for band gap.
Figure 1. Crystal structure of (CH3NH3)2Pb(SCN)2I2.
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K–M Function from DRS Spectra for Band Gap Determination:
The DRS spectra for a MAPSI thin film are shown in Figure 2. It
is evident the presence of two absorption features in shape of
reflection “drops”: an excitonic absorption around the absorp-
tion edge (named A feature), and the peak-and-well feature over
c the same absorption edge (named B feature), as expected for
6.4800(05) bound exciton absorption and quantum confinement effects. It
is known that hybrid halide perovskites have strong excitonic
6.4759(09)
features, exhibiting small exciton binding energies and long
6.4658(6)
exciton diffusion lengths,[10] so this excitonic behavior in light
absorption found in this work for MAPSI is not a surprise for
this kind of perovskite materials. The overall mid-to-low
reflectance values and the aforementioned excitonic absorption
suggest the thin film has strong optical absorptance, as expected
for hybrid halide perovskites. Comparing the optical absorption
on the Lead Iodide Thiocyanate with MAPI, the optical
absorptance of MAPI is stronger than that of MAPSI in the
visible region, as reported by other authors also.[11] This can be
explained in terms of a significant reduction in the optical
absorption coefficient for MAPSI, as suggested by Ref. [11], who
confirmed this observations by PL measurements for a SCN
-
doped MAPI material. The decreased optical absorption is
explained as reported by Tang, Yang, and Stroppa,[8] who affirm
that the optical absorption is weakened in MAPSI due to a
decrease in the imaginary part of the complex dielectric function
for MAPSI, as calculated by the authors using the VASP package
software. Further analysis on this point can be read on the
Supporting Information file.
For the determination of the fundamental band gap (optical
band gap energy) from DRS measurements, the Kubelka–Munk
(K–M) function
ð1
RÞ2
FðRÞ ¼ /α ð1Þ
2R
has been used successfully in band gap determination for hybrid
halide perovskites,[7] considering the F(R) function as an
analogue to optical absorption, where the incident photon
Figure 2. Diffuse reflectance spectra (DRS) for a MAPSI thin film,
featuring two excitonic absorption processes labeled A and B around the
fundamental absorption edge.
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energy (hv) and the optical band gap energy Eg are related in a
Tauc plot in the form of the transformed K–M function,


½FðRÞhν2 ¼ A hν
Eg
where A is the constant depending on transition probability and
n is the power index that is related to the optical absorption
process; n ¼ 2 and n ¼ 1/2 for direct and indirect absorption,
respectively.[12,13]
The DRS spectra and K–M functions for direct and indirect
optical absorption for a MAPSI thin film sample are shown in
Figure 3 and 4. The values of band gap Eg are both in fairly good
agreement with the report of Xiao[6] and in contrast with
Ganose,[1] presenting an indirect band gap of a fewer value than
the direct one, suggesting that true band gap of MAPSI are of
indirect nature. However, the very close proximity of values for
band gap, plus the already discussed strong MAPSI absorption
capabilities, points out that this material has a dual or even
dynamically shifting band gap nature.[14,15] The reported band
gap values are in excellent agreement with the reported band gap
energy for the similar 2D orthorhombic structure of
CH3CH2NH3PbI3 material (2.2 eV),[16,17] which reinforces the
conclusion that MAPSI has an 2D-layered structure and wide
band gap and the expected excitonic features of hybrid halide
perovskite materials.
DFT Calculations for Assessing the MAPSI Band Gap: The
fundamental absorption process was assessed also by DFT
computational calculations, in order to stablish whether the dual
direct/indirect band gap features could be as the DRS and XRD
measurements presents. (Details about the computational
calculations can be read in the Supporting Information file.
All calculations have been carried out using the PWSCF code as
implemented in the Quantum Espresso program suite.)
Being MAPSI a new material, a reasonable starting point to
evaluate its band gap value was to calculate the band structure for
a similar material having a well-known band gap value, namely,
MAPI. For methyl-ammonium lead iodide, the calculated
electronic structure reproduces the experimental band gap
Figure 3. Tauc plot using the K–M function for the DRS spectrum shown
in Figure 2, direct fundamental absorption. Features A and B explained in
Figure 2 and in the text.
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ð2Þ
Figure 4. Tauc plot using the K–M function for the DRS spectrum shown
in Figure 2, indirect fundamental absorption. Features A and B explained
in Figure 2 and in the text.
when using an α value of 0.17 in the HSEα Norm-conserving
pseudo-potential setting, where α ¼ 0.17 is the Hartree–Fock
portion as large enough as to reproduce the experimental values
of band gap; thus, using the unit cell information from the
Rietveld refinement for thin film XRD patterns, the DFT Kohn–
Sham band structure for the MAPSI unit cell was calculated and
it is presented in Figure 5. The main feature of the calculated
electronic structure for MAPSI thin films is that the electronic
band gap of MAPSI presents very close values for both direct and
indirect fundamental absorption processes, being the indirect
transition very slightly fewer than the direct one (ΔEg ¼ 0.036 eV,
Figure S5, Supporting Information).
In addition to the close values for direct and indirect band gap
energy, when the spin-orbit effect is included in the calculations,
the electronic structure shows a reduced band gap and clear
relativistic effects as also reported in Refs. [1,6,19] due to the
referred Rashba/Dresselhaus effect that creates a band splitting
in valence and conduction bands,[20] as shown in Figure S6,
Supporting Information.
Figure 5. Band structure for (CH3NH3)2Pb(SCN)2I2 crystal, mapping the
k-points path as suggested by Ref. [18].
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Table 2. DFT-calculated band gaps for MAPSI, at different levels of
theory. See details in Supporting Information file.
Method
PBE PBE þ SOC HSE HSE þ SOC
Band gap energy (eV) 2.00 1.04 2.14 1.16
It is noteworthy that the band gap energy difference calculated
by DFT is much fewer than the difference found out by DRS
measurements (ΔEg,DRS ¼ 0.090 eV); this is due to two main
reasons: the calculation was performed for just the MAPSI unit
cell, and changes in electronic structure arising for interactions
of billions of atoms in thin film are not taken into account, and
the structural relaxation algorithm used in the calculation does
vary the crystal lattice parameters with respect to the XRD
refined ones, so the inter-band closer proximity for the calculated
band energy values compared to the band gaps coming from
DRS is not a surprising outcome. Nevertheless, the qualitative
conclusion is that DFT band structure supports the DRS finding
of very close values for the direct and indirect MAPSI band gap
energy, being the indirect fundamental absorption of fewer
value. Calculated values for band gap Eg using the PBE,
PBE þ SOC, HSE, HSE þ SOC approaches are shown in Table 2.
It is necessary to clarify that the argument of closer calculated
band gap values is made along the T–Z direction in the Brillouin
zone (Figure S5, Supporting Information), and not along the R-T
direction, because the latter path is lesser in importance as the
carrier conduction is impossible, according to the values of
effective masses for electron and hole as calculated by Ref. [6];
the carriers generated by optical absorption could not be
extracted from the material along the R-T path (i.e., across the
MAPSI 2D layers).
Effect of the SCN
Anion on the Electronic Properties of MAPSI:
In order to study the effect of the presence of the SCN
anion in
the MAPSI compound on the electronic structure of MAPSI, the
projected density of states (PDOS) were also calculated, and it is
shown in Figure 6. It is clearly seen that the SCN
anion
Figure 6. Total and projected density of states (PDOS) for (CH3NH3)2Pb-
(SCN)2I2 crystal, showing the contribution of SCN
anions to valence
band and deep energy zone. CH3 NHþ 3 cation states not included, as they
do not contribute to states near the band gap.
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dominates the low energy zone (
5 to
2 eV), and that I 5p, Pb
6s, and S 3p states populate the valence band zone also; Pb 6px
and 6py states populate the conduction band. This results are in
concordance with similar reports,[6,8] and also demonstrates that
substitution of I atoms in axial positions by SCN
anions does
not affect the electronic transport properties of MAPSI by
eventually depopulating the conduction band zone (there is not a
significant SCN
anion–Pb interaction that could cause a
decrease in the density of Pb states in conduction band); the
valence band, in contrast with the MAPI compound, shows a
major SCN
contribution suggesting that the SCN
anion
participates in Van Der Waals interactions between the 2D-layers
in the MAPSI thin film. The PDOS for MAPSI taking into
account SOC are shown in Figure S7, Supporting Information
with the main change in DOS comparing to the non-relativistic
approach is a noticeable decrease in density of states in higher
conduction bands, which does not affect significantly the
electronic conduction in MAPSI; apart from the expected band
gap reduction when spin–orbit coupling is included in DFT-
based calculations.
Conclusion: In this work we report the synthesis, XRD and
DRS characterization, and DFT calculations on MAPSI
(CH3CH2NH3PbI3), a promising solar cells material. It has
been found that the optical fundamental absorption is of indirect
nature, with a very close value of band gap for the direct process;
thus confirming Eg values reported by some authors,[6] but at the
same time in serious contradiction with the original report of
Daub and Hillebrecht.[2] DFT calculations support the very close
values for band gap determined by Tauc plots based on DRS
measurements, via the K–M transformed function. The band
gap value for MAPSI thin films suggests that this material can be
used as the second absorbing layer in tandem solar cells or
multiple-junction cells.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgments
The funding for this work was granted by DIB (code 35852), the Research
Division of the Universidad Nacional de Colombia. The authors wish to
thank to the Chemistry and the Physics Departments of the Universidad
Nacional de Colombia for bringing access and technical support to X-Ray
and DRS equipments, and to Professional Operative Technicians Julieth
Cifuentes and Johon Pavas who acquired the DRX patterns and DRS
spectra.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
density functional theory, Kubelka–Munk function, perovskites, quantum
espresso, semiconductors, solar cells, X-ray diffraction
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Received: October 30, 2017
Revised: December 25, 2017
Published online: February 6, 2018
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