Computational Condensed Matter xxx (xxxx) e00928

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Computational Condensed Matter

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

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Novel KXBr3 (X = Ca, Sr, Ba) lead-free halide perovskites for optoelectronic
applications: A DFT investigation of mechanical and optoelectronic

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properties
Redi Kristian Pingak ⁎, Zakarias S. Ngara, Albert Z. Johannes, Minsyahril Bukit,
Jehunias L. Tanesib
Department of Physics, Faculty of Science and Engineering, The University of Nusa Cendana, Kupang, Indonesia

ARTICLE INFO

Keywords:
DFT
Quantum espresso
Perovskites
ABSTRACT

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The present study proposes novel KXBr3 (X = Ca,Sr,Ba) perovskites as promising materials for applications in
various optoelectronic devices. The structural, mechanical and optoelectronic properties of the materials are pre-
dicted using first-principle calculations based on the Density Functional Theory (DFT) implemented in the Quan-
tum Espresso code. The structural optimization results in stable lattice constants of 5.71 Ȧ, 5.98 Ȧ, and 6.31 Ȧ,
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Optoelectronic properties
for the respective materials. The results confirmed their chemical and mechanical stability, with KSrBr3 and
Mechanical properties
KBaBr3 also exhibiting dynamical stability. Equally important, the perovskites possess ductile behavior, as indi-
cated by their Poisson and Pugh ratio found to be larger than 0.26 and 1.75, respectively. The ductility is also
confirmed by their positive Cauchy pressure. From the electronic band structure, it was found that the materials
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have indirect band gap (R→Γ) of 3.89 eV, 3.72 eV, and 3.58 eV, for KCaBr3, KSrBr3, and KBaBr3, respectively.
SCAN approximation was also implemented to obtain more reliable band gap energy of 4.43 eV, 4.27 eV, and
4.14 eV, for the respective compounds. One of the most remarkable optical properties found was their consider-
ably low reflectivity, with maximum values being less than 19 %. This is further reinforced by their high absorp-
tion coefficients, reaching 105 cm−1.
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1. Introduction solar cells was 3.8 %. Over a decade of development, the efficiency of
halide perovskite solar cells (HPSCs) has reached its highest value of
ABX3 compounds, known as perovskites, are a class of materials 26.1 % recently [3,4]. The efficiency is very close to that of conven-
sharing the same structure as the naturally occurring calcium titanate tional silicon solar cells, which have been used for around a half cen-
(CaTiO3). Within this ABX3 structure, A and B are cations while X is an tury [5]. A number of studies have explored some problems related to
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anion. The B-site element is octahedrally coordinated with X anions in practical applications of lead-based perovskites and offered some new
a BX6 configuration. Although the ideal structure of a perovskite is cu- strategies to improve their performance in devices [6,7]. Despite the
bic, the structural parameters of the BX6 octahedron can change with promising future of these lead-based perovskites in HPSCs, they have
tilt or twist, which can modify the properties of the perovskites. Mean- not yet been commercialized, mainly due to the toxicity issue of lead
while, the A-site element is coordinated with 12 X anions, which stabi- [8]. Therefore, one of the main focuses of recent research in halide per-
lizes the structure of perovskites [1]. There are two common classes of ovskite community is to find lead-free perovskites for applications in
perovskites, depending on the types of the X anions. The first class is HPSCs.
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known as oxide perovskites with X being oxygen and has the chemical The application of lead-free halide perovskites goes beyond solar
formula ABO3 whereas the second type is termed halide perovskites, cells. This is mainly because of various strategies to replace the toxic
within which X is a halide anion (X = F, Cl, Br, or I). Pb, which results in an enormous number of new lead-free materials
Halide perovskites have gained considerable attention since Kojima whose properties are suitable for various applications [9]. One of the
and co-workers [2] reported for the first time their application in solar strategies is to replace Pb with elements sharing the same valence con-
cells, where it was reported that the efficiency of the perovskite MAPbI3 figuration such as Sn [10–12] and Ge [13–15]. The heterovalent re-

⁎ Corresponding author.
E-mail address: [email protected] (R.K. Pingak).

https://doi.org/10.1016/j.cocom.2024.e00928
Received 22 April 2024; Received in revised form 7 June 2024; Accepted 10 June 2024
2352-2143/© 20XX

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R.K. Pingak et al. Computational Condensed Matter xxx (xxxx) e00928

placement of Pb can also be done by ion splitting and ordered vacancy, dient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) [35] was
to maintain the charge neutrality [16]. Furthermore, the reduction in applied in the calculation. The structure was relaxed based on the Broy-
the dimension of perovskites is also possible for perovskites [17], lead- den-Fletcher-Goldfarb-Shanno (BFGS) algorithm to obtain the opti-
ing to more diverse materials with unique properties for a diverse array mized lattice parameters of the compounds, which were subsequently
of applications. Such applications include light-emitting diodes used to calculate their electronic, mechanical, and optical properties.
[18,19], scintillators [20], photodetectors [21], superconductors [22], The calculation of the elastic and optical properties of the materials was
field-effect transistors [23], gas sensors [24], lasers [25], and thermo- performed using the Thermo_pw code, in which the polycrystalline
electric materials [26], to name a few. elastic moduli of materials are estimated based on the Voigt-Reuss-Hill
In particular, Br-containing lead-free halide perovskites have re- (VRH) average. Moreover, the Strongly Constrained and Appropriately
cently been reported to have excellent properties for a broad array of Normed (SCAN) approximation [36] was implemented to obtain more

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applications. For instance, Valizadeh and co-workers [27] explored var- accurate electronic density of states (DOS) and the band gap of the ma-
ious configurations of perovskite solar cells with RbGeBr3 as the absorb- terials.
ing layer and reported a reasonably high efficiency of over 11 %. More- The cut-off energy used to define the wave function was set to be 45

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over, some Br-based halide perovskites (MHPs) have recently been Ry whereas that for the charge density was 405 Ry. For the SCF and
found to have the potential as highly sensitive and sensor materials. As NSCF calculations, the k-points used were of size 6 × 6 × 6 and
an example, MAPbBr3 nanowires array sensors were found to outper- 12x12x12, respectively. The total energy convergence was set to be
form MAPbCl3 perovskites as sensors for H2S gas molecules [28]. The 10−8 Ry.
authors [28] also reported that in addition to their highest sensitivity
for H2S gas molecules, MAPbBr3 nanowires sensors also exhibited long- 3. Results and discussions
term stability. A recent study also demonstrated that CsBr/Cs3Bi2Br3I6

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heterostructure perovskite possesses a high sensitivity and stability for 3.1. Optimized structure
H2S gas detection at room temperature [29]. Furthermore, these mate-
rials were also promising for applications in photochemical water split- KCaBr3, KSrBr3, and KBaBr3 perovskites belong to space group
ting [30] and other optoelectronic and thermoelectric devices [31–33]. #221 ( ). The unit cell structure of the three compounds is pre-
Novel Br-containing lead-free perovskites in the forms of KCaBr3, sented in the top section of Fig. 1. The K cations are located at the cor-
KSrBr3, and KBaBr3 are comprehensively investigated in the present ner (0,0,0) while the Br anions are at (0.5,0.5,0.5), (0.5,0,0.5) and
study, aiming at computationally exploring their structural, mechani- (0,0.5,0.5). The center of the cube is occupied by Ca, Sr, and Ba in the
cal, electronic and optical properties. The DFT is employed in the pre- structure of KCaBr3, KSrBr3, and KBaBr3 perovskites, respectively.
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sent study to calculate the key properties of the perovskites. As the ma- Fig. 1 (down) shows how the calculated total energy of the com-
terials under study have not been previously studied, the results of the pounds varies with their unit cell volume. The optimization was con-
current work will be of great significance and interest to the halide per- ducted to obtain the optimized lattice constants. The results were fitted
ovskite community. using the Birch-Murnaghan equation of state, as shown in Eq. (1),
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where V0 and E0 represent the volume and the minimum energy, re-
2. Computational method spectively; meanwhile, B and B’ are the bulk modulus and its first de-
rivative with respect to pressure. The fitting results are listed in Table
The DFT calculation of optoelectronic and mechanical properties of 1 along with some derived structural parameters including the opti-
the materials under study was carried out using Quantum Espresso mized lattice parameters and the density of the compounds.
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package [34] with its associated Thermo_pw code. The generalized gra-
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Fig. 1. The unit cell structure of (a) KCaBr3, (b) KSrBr3, and (c) KBaBr3 (top) and the total energy as a function of the volume of (a) KCaBr3, (b) KSrBr3, and (c) KBaBr3
(bottom).

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R.K. Pingak et al. Computational Condensed Matter xxx (xxxx) e00928

Table 1
The optimized structure and fitting parameters of KXBr3 (X = Ca,Sr,Ba) per- (2)
ovskites.
3 3 Using this equation, negative formation energy is an indication of
Perovskite V0 (Ȧ ) a0 (Ȧ) B (GPa) B’ E0 (Ry) ρ (g/cm )
the chemical stability of the compounds. The results indicated that the
KCaBr3 186.46 5.71 19.6 4.13 −216.97 2.87 three perovskites possess negative formation energy and therefore they
KSrBr3 214.07 5.98 16.3 7.77 −212.20 2.89 are chemically stable. The formation energy values of KCaBr3, KSrBr3,
KBaBr3 250.80 6.31 15.5 3.25 −204.79 2.90 and KBaBr3 were found to be −1.24 Ry, −1.22 Ry, and −1.23 Ry, re-
spectively. Hence, it can be inferred that they can be experimentally re-
alized under ambient conditions.

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The dynamical stability of the studied compounds was investigated
(1) in the present work by calculating their phonon dispersion profile, pre-
sented in Fig. 2. The absence of negative frequency in the phonon dis-

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persions of a material implies its dynamical stability. It is obvious that
KSrBr3 and KBaBr3 are predicted to be dynamically stable as there is no
As seen from Fig. 1 (bottom), the replacement of Ca by Sr and Ba has negative frequency present in their phonon dispersion curves. On the
two marked effects on the structure of the perovskites. First, it changes other hand, the presence of negative frequency in the phonon disper-
the total energy of the compounds. This is expected as although the sion profile of KCaBr3 strongly suggests that it possesses dynamical in-
cations are isoelectronic, their valence electrons are of different energy. stability. It should be noted that even though KCaBr3 is predicted to be
The second effect is the expansion in the unit cell volume of the per- dynamically unstable, this material still deserves further investigation
ovskites, which is also anticipated due to the fact that the cations have as it was found that dynamically unstable perovskite materials can be

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different ionic radii. As a result, the optimized lattice parameter of stabilized at elevated temperature [61]. Ou and co-workers [61] found
KBaBr3 is predicted to be larger than that of KSrBr3, which is also higher that the dynamically unstable BaFeO3 perovskite, whose structure is
than that of KCaBr3 (Table 1). These two effects were also observed for identical to KCaBr3, becomes stabilized at 130 K.
a broad array of perovskites ABX3 in which A and B are replaced by Moreover, the Born-Huang stability criteria [62] were used to evalu-
other isoelectronic ions [37–53]. Such replacement of cations has been ate the mechanical stability of the materials under study. Using the cri-
found as an effective way tune the physical properties of perovskites. teria, the mechanical stability of a material is determined by the follow-
It can be seen from Table 1 that the optimized lattice constants of ing: C11 > 0, C44 > 0, (C11–C12)>0, (C11+2C12)>0, and C12
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KCaBr3, KSrBr3, and KBaBr3 perovskites are 5.71 Ȧ, 5.98 Ȧ, and 6.31 Ȧ, <B < C11, where Cij and B are the material's elastic constants and bulk
respectively. The systematic increase in the lattice parameters is also modulus, respectively. Table 2 summarizes the elastic constants and the
followed by a decline in the bulk modulus of the compounds from bulk modulus of KCaBr3, KSrBr3, and KBaBr3 perovskites, along with
19.6 GPa for KCaBr3, to 16.3 GPa for KSrBr3, and 15.5 GPa for KBaBr3. other elastic and mechanical properties of the materials. From Tables 2,
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A number of recent studies also observed this phenomenon [54–60], in- it can be shown that all studied materials satisfy the Born-Huang crite-
dicating that the expansion in the unit cell volume of the compounds ria, implying their mechanical stability.
has a direct consequence to their response to external compression. The
density of the compounds is also predicted to slightly increase, with 4.1. Elastic and mechanical properties
corresponding values being 2.87 g/cm3, 2.89 g/cm3, 2.90 g/cm3, for
KCaBr3, KSrBr3, and KBaBr3 perovskites, respectively. The calculated elastic properties of the perovskites under investiga-
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tion are listed in Table 2. Comparing the three elastic constants of the
4. Chemical, dynamical, and mechanical stability three compounds suggests that KCaBr3 exhibits the largest elastic con-
stants, followed by KSrBr3 and KBaBr3 perovskites. Similarly, KCaBr3 is
The chemical stability is an important property used to foresee also predicted to possess the highest values of mechanical moduli, with
whether a newly proposed material can be synthesized under ambient calculated values being 19.61 GPa, 24.99 GPa, and 9.73 GPa for the
conditions. In this study, the formation energy of the proposed bulk modulus, the Young modulus, and the shear modulus, respec-
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compounds was determined using Eq. (2), to analyze their chemical sta- tively. These figures are considerably higher than those of KSrBr3:
bility. Here, the total energy of KXBr3 is denoted by Etot (KXBr3) while 16.90 GPa, 19.30 GPa, and 7.44 GPa, respectively, which are also
the energy of individual K, X (X = Ca,Sr,Ba), and Br atoms is repre- larger than those of KBaBr3: 14.41 GPa, 14.19 GPa, and 5.41 GPa, for
sented by E(K), E(X), and E(Br), respectively. the respective mechanical moduli. Hence, it can be inferred that KCaBr3
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Fig. 2. The phonon dispersion of (a) KCaBr3, (b) KSrBr3, and (c) KBaBr3.

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R.K. Pingak et al. Computational Condensed Matter xxx (xxxx) e00928

Table 2 The Kleinman parameter ζ is a measure of the internal strain of a

The elastic and mechanical parameters of KCaBr3, KSrBr3, and KBaBr3 per- material [68]. Its values range from 0 to 1 for solids, with ζ = 0 corre-
ovskites. sponding to minimizing the bond bending and ζ = 1 corresponding to
Elastic parameters KCaBr3 KSrBr3 KBaBr3 the bond stretching [69]. As shown in Table 2, the calculated Kleinman
parameters of KCaBr3, KSrBr3, and KBaBr3 perovskites are 0.33, 0.28,
C11 (GPa) 43.28 40.37 35.78 and 0.25, respectively. Therefore, it is obvious that the bond bending is
C12 (GPa) 7.77 5.17 3.73
more dominant in these materials than the bond stretching. Finally, the
C44 (GPa) 6.35 3.80 2.07
B (GPa) 19.61 16.90 14.41 calculated anisotropic factor A represents the anisotropic nature of the
E (GPa) 24.99 19.30 14.19 materials. A = 0 represents isotropic nature of single crystals while A
G (GPa) 9.73 7.44 5.41 > 0 implies anisotropy nature of crystals [70–73]. The calculated

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Pugh ratio (B/G) 2.02 2.27 2.66 anisotropic factors are 0.36, 0.22, and 0.13 for KCaBr3, KSrBr3, and
Poisson ratio v 0.28 0.30 0.31 KBaBr3 perovskites, respectively. This implies that KCaBr3 possesses the
Cauchy Pressure (C12–C44) 1.42 1.37 1.66
highest extent of anisotropy, followed by KSrBr3 and KBaBr3 com-

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θ (K) 179.14 144.14 111.68
Kleinman Parameter ζ 0.33 0.28 0.25 pounds.
Anisotropy Factor A 0.36 0.22 0.13
4.2. Electronic properties
is projected to have better mechanical properties than the other two
materials, although they all show reasonably high mechanical moduli. The electronic band structure of the perovskites was calculated us-
As a result, the materials are expected to show excellent resistance to ing the GGA-PBE functional and it was chosen to follow Γ → X → M → Γ
any external force including tension, compression, and deformation, → R → X high-symmetry k-point path, as depicted in Fig. 4 alongside

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rendering their potential application in various devices. with their total density of states (DOS). As seen in the figure, the re-
Among the elastic parameters, the Pugh ratio, the Poisson ratio and placement of Ca by Sr and Ba has a profound effect on both the valence
the Cauchy pressure are essential in predicting the ductility of brittle- and conduction bands: the conduction band is shifted to higher energy
ness of materials. It is well known that materials with Pugh ratio larger moving away from the Fermi level while the valence band moves closer
than 1.75 are ductile and vice versa [63]. The Pugh ratio values are cal- to the Fermi level. The conduction band minimum of the materials is lo-
culated to be 2.02, 2.27, and 2.66 for KCaBr3, KSrBr3, and KBaBr3 per- calized at the Γ point whereas their valence band maximum appears at
ovskites, respectively. Hence, based on these values, the three per- the R point, resulting in the indirect nature of the perovskites.
ovskites are all ductile with ductility behavior increasing as Ca is re- The cation replacement also leads to a slight reduction in the energy
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placed by Sr and Ba. The ductile behavior of the materials was also de- gap of the materials. The calculated values of the band gap of KCaBr3,
termined by the evaluation of their Poisson ratio, with a ratio larger KSrBr3, and KBaBr3 perovskites are 3.89 eV, 3.72 eV, and 3.58 eV, for
(smaller) than 0.26 implying ductile (brittle) nature [64]. As depicted the respective compounds. This phenomenon was also reported in a
number of studies, where it was found that the substitution of A, B, or X
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in Table 2, the calculated values of the Poisson ratio are 0.28, 0.30, and
0.31, for KCaBr3, KSrBr3, and KBaBr3 perovskites, respectively. This ions by others which are larger in size results in a narrower forbidden
confirms the ductile behavior of the materials, with KBaBr3 expected to gap [74–82]. As the electronic band of KBaBr3 is the narrowest (R→Γ:
be the most ductile perovskite. The visualization of the ductile behav- 3.58 eV), the energy needed to excite an electron from its valence band
ior, based on the Pugh and Poisson ratio, is presented in Fig. 3. The duc- to its conduction band is lower compared to KSrBr3 (R→Γ: 3.72 eV) and
tility of the materials is also confirmed by its positive Cauchy pressure. KCaBr3 (R→Γ: 3.89 eV). Although the materials are predicted to exhibit
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The predicted ductility of studied perovskites is of significant interest as quite large band gap energy, it is still a room to investigate these mate-
it enables them to be deposited as high-quality thin films for a wide rials in the future to tune their band gap to lower values such as by ap-
range of applications [65,66]. It is worth noting that the ductile nature plying hydrostatic pressure [83–87] and doping [88].
of KCaBr3 is an essential finding as its isoelectronic compound in the As GGA-PBE generally underestimates the electronic band gap of
form of KCaCl3 was found to be brittle [67]. This might provide an al- materials, the SCAN approximation is also applied in the present study
ternative way to change the brittle nature of materials, i.e. by replacing to generate more reliable electronic band gap energy of the perovskites
under study. While GGA only depends on the spin density and its gradi-
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the halide anions with their counterparts. On the other hand, the KSrBr3
exhibits the same ductile behavior as its isoelectronic counterpart ent, meta-GGAs, e.g. SCAN, also depend on the local spin kinetic energy
KSrCl3 as reported in Ref. [67]. density or its Laplacian. This makes the construction of the exchange-
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Fig. 3. The ductile behavior of KCaBr3, KSrBr3, and KBaBr3 perovskites based on the Pugh ratio (left) and Poisson ratio (right).

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R.K. Pingak et al. Computational Condensed Matter xxx (xxxx) e00928

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Fig. 4. The band structure and total DOS of (a) KCaBr3, (b) KSrBr3, and (c) KBaBr3 using the GGA-PBE functional.

correlation (XC) energy functional more flexible in meta-GGAs, leading The partial density of states of the perovskites is visualized in Fig. 6,
to correction of some physical phenomena which cannot be appropri- where the contribution from the orbitals of each atom is visualized. The
ately treated by the GGA functional [36]. The SCAN functional is avail- figure clearly depicts that the Br states make an enormous contribution
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able from the Libxc library [89] and was successfully implemented in to the valence band maximum of the three studied perovskites, signifi-
some recent studies [90,91], resulting in more accurate energy gap of a cantly higher than the contribution of the states of the other atoms. On
number of materials. In terms of computational efficiency and accu- the other hand, close to the conduction band minimum, K-states con-
racy, the SCAN approximation can be comparable to HSE functional sisting of the 4s and 3p orbitals are the most dominant ones, followed
[92–94]. Fig. 5 displays the electronic band structure and the total den- by Ca/Sr/Ba states. Moreover, a notable shift of the states of the valence
sity of states obtained by implementing the SCAN functional. As seen bands of all atoms towards the Fermi level is observed, narrowing the
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from Fig. 5, the conduction band of the materials under study is shifted forbidden gap as previously discussed.
to higher energy regions, leading to the widening of the forbidden gap The electron distribution is also an important property which can be
between the valence band and the conduction band. Using the SCAN used to evaluate the chemical bonds present in the materials. The elec-
functional, more reliable energy gap values of KCaBr3, KSrBr3, and tron density of the materials under investigation along the (110) plane
KBaBr3 are 4.43 eV, 4.27 eV, and 4.14 eV, respectively. is presented in Fig. 7. A comparison of the electron density of the three
Moreover, it is interesting to consider the relationship between the perovskites indicates a marked similarity, which is consistent with the
electronic band gaps and the bulk modulus of the studied materials as band structure and the density of states. It is obvious that Ca–Br bond is
Reddy et al. [95] reported that the band gap is linearly proportional to covalent in nature while K–Br is mostly ionic. This aligns well with a
the bulk modulus of some materials. This is also the case in the present previous study on an isoelectronic perovskite KCaCl3 [98], where it was
study, where it is observed that the reduction in the electronic band gap reported that Ca–Cl and K–Cl bonds are mainly covalent and ionic at
as Ca is replaced by Sr and Ba is accompanied by a decrease in the bulk ambient pressure, respectively. It can also be inferred that Ba–Br bond
modulus of the compounds (Table 2). It is worth noting that this might is stronger than Sr–Br and Ca–Br bonds, indicated by more electrons lo-
not apply for other materials such as alloys as the combination of sev- calized between Ba and Br.
eral factors including dimensions and chemical effects also plays an im-
portant role [96,97].

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R.K. Pingak et al. Computational Condensed Matter xxx (xxxx) e00928

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Fig. 5. The band structure and total DOS of (a) KCaBr3, (b) KSrBr3, and (c) KBaBr3 using the SCAN functional.
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Fig. 6. The partial density of states of (a) KCaBr3, (b) KSrBr3, and (c) KBaBr3 perovskites.

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R.K. Pingak et al. Computational Condensed Matter xxx (xxxx) e00928

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Fig. 7. The (110) electron density of KCaBr3, KSrBr3, and KBaBr3 perovskites.

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4.3. Optical properties electronic performance [101,102]. In general, better optoelectronic
materials possess larger ε1(0) values. Based on this criterion, with the
The Thermo_pw package, linked with the Quantum Espresso, was largest ε1(0) magnitude of 2.71, KCaBr3 is predicted to possess better
implemented in the present study to calculate the optical characteristics optoelectronic performance compared to KSrBr3 (ε1(0) = 2.52) and
of the KCaBr3, KSrBr3, and KBaBr3 perovskites. One of the most impor- KBaBr3 (ε1(0) = 2.46). Interestingly, the trend does not satisfy the
tant response functions of a material which describes the interaction be- Penn model for semiconductors [103], stating that the static dielectric
tween a material and an applied electric field is the complex dielectric function of semiconducting materials is inversely proportional to their

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function ε* = ε1+iε2. It is an intrinsic property that is dependent on energy gap. This can be attributed to the fact that the materials under
the frequency and provides information about the degree to which a study were found to be large gap semiconductors, which can also be
material can contain the incident electric flux [99]. The real part ε1 pro- classified as insulators.
vides valuable information about the retardation of the velocity of light Fig. 8b illustrates the imaginary part of the dielectric function ε2
while the imaginary part ε2 describes the absorption loss of light due to (ω) of the studied perovskites, which is a measure of the absorption
polarization while propagating through the material [100]. Fig. 8a and behavior of the compounds. The figure clearly indicates that the ab-
b illustrate the calculated dielectric function ε1(ω) and ε2(ω) of KCaBr3, sorption threshold of KBaBr3 is slightly lower than that of KSrBr3 and
KSrBr3, and KBaBr3 perovskites, which was subsequently used to calcu- KCaBr3. This aligns well with their calculated energy gap values with
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late the remaining optical properties. KBaBr3 projected to possess the smallest band gap, slightly narrower
From Fig. 8a, there is a close similarity in the general feature of the than KSrBr3 and KCaBr3. Even though a remarkable resemblance is
real dielectric function of the studied perovskites, with that of the observed in the main attributes of the three perovskites, a shift of the
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KSrBr3 and KBaBr3 having the most striking resemblance. As a result, main peak of KCaBr3 to a lower energy region makes it a slightly bet-
the general feature of the remaining optical attributes of the two per- ter absorber of photons of relatively lower energy. In the middle en-
ovskites is expected to show a noticeable resemblance. The common ε1 ergy region, approximately between 10 eV and 15 eV, KCaBr3 is also
(ω) features of KCaBr3 is also similar with the highest peak shifted to predicted to be better in absorbing light.
lower energy. The maximum point of ε1(ω) for KCaBr3 appears at One of the most important findings in this research is that all studied
5.15 eV (with magnitude of 4.73), compared to 5.77 eV for KSrBr3 perovskites possess very low reflectivity values, as shown in Fig. 9a.
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(3.97 in magnitude) and KBaBr3 (4.11 in magnitude). Beyond these The static values of the reflectivity of KCaBr3, KSrBr3, and KBaBr3 per-
main peaks, the calculated ε1(ω) values of the three compounds fluctu- ovskites were calculated to be 5.96 %, 5.16 %, and 4.90 %, respec-
ate with negligible magnitudes compared to the maximum points. In tively. The reflectivity of the materials rises as a function of the photon
addition, the static dielectric function ε1(0) is an essential characteristic energy until it reaches its first peak, beyond which it sees an overall
of a compound, which is strongly related to the charge recombination downward trend. The maximum values of the reflectivity of KCaBr3,
in the compound and therefore can be used to predict its overall opto- KSrBr3, and KBaBr3 perovskites were 18.80 % at 7.83 eV, 18.24 % at
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Fig. 8. The real dielectric function ε1(ω) (a) and the imaginary dielectric function ε2(ω) (b) of KCaBr3, KSrBr3, and KBaBr3 perovskites.

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Fig. 9. The reflectivity (a) and the absorption coefficient (b) of KCaBr3, KSrBr3, and KBaBr3 perovskites.

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6.60 eV, and 16.74 % at 6.19 eV, respectively. The reflectivity of the reach its maximum values of 2.23 (at 5.36 eV), 2.06 (at 6.19 eV), and
compounds is predicted to decline after their maximum points, reach- 2.08 (at 5.77 eV), for the respective perovskites. Beyond these highest
ing very low values (below 5 %) at a high energy range (above 15 eV). points, a significant downward trend is observed for the refractive in-
The low reflectivity implies a high absorption and or transmittance. dex of the compounds, following the common feature of the real di-
The absorption coefficient of the perovskites is presented in Fig. 9b, electric function (Fig. 8a). Meanwhile, the extinction coefficient of the
where they are projected to possess remarkable optical absorption, compounds is displayed in Fig. 10b. Since it is a measure of how
reaching 105 cm−1. The region between 5 eV and 10 eV is where the re-
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strongly the materials absorb the incoming light at a particular wave-
flectivity of the studied materials is higher than other energy intervals. length, its common attributes should resemble those of the imaginary
Similarly, the highest peaks of the absorption coefficient of the com- dielectric functions of the materials (Fig. 8b). A comparison between
pounds also appear in this energy interval, implying very high absorp- the two figures clearly confirms this. Fig. 10b clearly indicates that the
TE

tion in this energy range. The high absorption of perovskites was also KBaBr3 is predicted to start absorbing light at slightly lower energy
reported for a diverse array of perovskite materials [104–117]. Mean- than KSrBr3, which is also expected to begin absorbing photons at
while, the lowest reflectivity of the compounds is observed in the en- slightly lower energy compared to KCaBr3. This is also consistent with
ergy region between 15 eV and 20 eV, where the absorption coefficient their electronic band gap energy previously discussed, where KBaBr3
is also lower than that in the energy interval [5,10] eV. This strongly exhibits the lowest electronic band gap energy, followed by KSrBr3
suggests that transmittance is high in the energy region of [15,20] eV. and finally by KCaBr3. This is because the lower the electronic band
EC

This phenomenon was also observed in CsBX3 (B Sn, Ge; X = I, Br, gap energy, the lower energy required to excite electrons from the va-
Cl) perovskites [8]. lence band to the conduction band of the materials.
Fig. 10a demonstrates how the refractive index of the studied per- Although the materials exhibit quite wide band gap, their outstand-
ovskites varies with frequency. The static refractive index values n(0) ing optical properties supported by their predicted ductility as well as
were predicted to be 1.65, 1.59, and 1.57, for KCaBr3, KSrBr3, and the mechanical and chemical stability make them promising for appli-
KBaBr3 perovskites, respectively. The refractive index increases to cations in optoelectronic devices. In particular, the ultra-wide band gap
RR
CO

Fig. 10. The refractive index (a) and the extinction coefficient (b) of KCaBr3, KSrBr3, and KBaBr3 perovskites.

8
R.K. Pingak et al. Computational Condensed Matter xxx (xxxx) e00928

materials with energy gap larger than 3.1 eV can be applied as ultravio- bert Z. Johannes: Writing – review & editing, Visualization, Methodol-
let photodetectors [118,119]. Furthermore, the band gap of the materi- ogy, Investigation. Minsyahril Bukit: Writing – review & editing, In-
als under investigation can also be tuned to lower values by doping, vestigation. Jehunias L. Tanesib: Writing – review & editing, Investi-
which has been recently demonstrated to be very effective in tuning the gation.
electronic and optical properties of a broad range of perovskites
[120–125]. For instance, Shahzad and co-workers [126] observed that Declaration of competing interest
the incorporation of hydrogen significantly reduces the band gap of
RbMgF3 from 6.263 eV to 2.124 eV. Replacing one of the cations with The authors declare that they have no known competing financial
its counterpart can also be used to tune the optoelectronic properties of interests or personal relationships that could have appeared to influ-
perovskites, as demonstrated by Rehman et al. [127] who reported that ence the work reported in this paper.

F
the band gap of Cs2GaAgCl6 decreases as Cs is replaced by Rb. The tun-
ability of the perovskites renders their applications in a wide range of Data availability
applications.

OO
As the band gap energy values of KXBr3 perovskites (X = Ca,Sr,Ba) Data will be made available on request.
in the present study are quite wide (from 4.14 eV to 4.43 eV), it is im-
portant to highlight their potential applications by comparing them Acknowledgement
with existing materials with similar properties that have been applied
in devices. As an example, the calcium stannate (CaSnO3) perovskite This work is supported by Penelitian Dasar Unggulan Perguruan
has energy gap ranging from 4.2 eV to 4.4 eV [128], which is very simi- Tinggi (PDUPT) research grant of the Faculty of Science and Engineer-
lar to our materials. Tran et al. [128] recently demonstrated that ing, University of Nusa Cendana, 2024 (Contract Number: 6/

PR
CaSnO3 exhibits remarkable optoelectronic properties as well as pos- UN15.18.PPK/SPP/FST/IV/2024).
sesses chemical and mechanical stability, consistent with our findings
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