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 Phys. Scr. 98 (2023) 115914 https://doi.org/10.1088/1402-4896/acfd65

PAPER

DFT calculations of optoelectronic and thermoelectric properties of

RECEIVED
8 July 2023
K2NaTlX6 (X = Cl, Br, I) halide double perovskites for energy
REVISED
20 September 2023
harvesting applications
ACCEPTED FOR PUBLICATION
26 September 2023
PUBLISHED
Rabia Zafar1, Shahzad Naseem1, Saira Riaz1, N A Noor2 , Asif Mahmood3 and Khuram Shahzad4
6 October 2023 1
Centre of Excellence in Solid State Physics, University of the Punjab, Lahore, Pakistan
2
Department of Physics, Riphah International University, Lahore, Pakistan
3
College of Engineering, Chemical Engineering Department, King Saud University Riyadh, Saudi Arabia
4
School of communication and information engineering, Shanghai University, People’s Republic of China
E-mail: naveedcssp@gmail.com

Keywords: halide double perovskites, optoelectronic applications, figure of merit (ZT), direct bandgap, elastic properties

Abstract
The DFT approach was employed to investigate the mechanical, optical and thermoelectric properties
of double perovskites (DPs) compounds K2NaTlX6 (X = Cl, Br, I). PBEsol-GGA approximation along
with birch-Murnaghan equation is used to calculate the lattice constant, other structural and ground
state parameters. The structural, thermodynamic and mechanical stability of these compounds was
demonstrated by computing tolerance factor, formation energy and Born criteria. Poisson and Pugh
ratio are analyzed to describe the brittle or ductile nature of these studied double perovskites
compounds. The anion Cl, Br and I-based double perovskites exhibited direct bandgap as determined
from band structure calculations. The study further examined the optical absorption and dielectric
constant of the compounds across the energy range 0–10 eV confirming their ability to absorb light in
the infrared to visible spectrum. Furthermore, the suitability of the studied double perovskites for
thermoelectric applications was assessed using BoltzTraP coding. The Seebeck coefficient, electric
conductivity and figure of merit were analyzed, suggesting that these compounds hold promise as
viable candidates for thermoelectric applications.

1. Introduction

The spectacular optoelectronic properties of organic–inorganic hybrid perovskites, such as their own tunable
bandgap, ability to optically absorb around a wide spectrum, outstanding photo-conductivity, eminent mobility
to minor in effect masses of carriers, protracted lifetimes, as well as enhanced diffusion path lengths, have
recently made them an emergent class of materials which get a lot of attention in research. Furthermore, the
thermoelectric characteristics of such materials have significantly increased their investigation into the realm of
upcoming smart devices [1]. Its figure of merit (ZT) value is key to understanding and assessing its
thermoelectric characteristics. Thermo-electric devices are known to exhibit outstanding performance when
their ZT value approaches unity [2]. The solar cell’s construction necessitates a material with a notable capability
for converting power to energy measured by its power-to-energy conversion efficiency (PEC%). This efficiency
is a crucial parameter for evaluating the solar cell’s potential. From the inception of the inaugural solar cell
device, extensive research has been channel into identifying material that can yield solar cell processing both
economic viability and impressive efficiency and stability [3]. The recent exploration of perovskite materials for
employment in solar cell has propelled this field to unprecedented heights. Several research endeavors have been
documented; each aiming to enhance the efficiency of perovskite solar cells (PSCs) [4]. One crucial aspect
pertains to the influence of moisture on the operational efficacy of the device. Furthermore, challenges such as
inadequate stability and concerns regarding the toxicity stemming from the presence of Pb-elements in
perovskite soler cells (PSCs) which act as barrier to their widespread adoption have been subjected to thorough

© 2023 IOP Publishing Ltd

Phys. Scr. 98 (2023) 115914 R Zafar et al

investigation. Another aspect to contemplate when assessing the viability of perovskite material for solar cell
application is its capacity to absorb light effectively within the visible spectrum [5].
Nonetheless, significant of obstacles persist. Notably, the-long term stability and large-scale
commercialization pose critical challenges. Both of these aspects necessitate the maintenance of structural
stability of peroskite materials against the impact of temperature and exposure to moisture/air. As a result, there
exist substantial imperative to identity stable and non-toxic perovskite materials aligning with the goal of
sustainable advancement within the realm of perovskite-based solar cells. In order to address the instability
concerns associated with perovskite solar cells, recent advancement have showcased effective strategies such as
carbon encapsulation substitution of cations and the integration of hydrophobic species within interlayers.
Nonetheless, definitive approach to eliminate toxicity involves substituting the ‘Pb’ element with non-toxic
alternatives. Among the alternatives, selecting elements from Group IV-A such as germanium (Ge) or tin (Sn)
emerges as the most viable option. Regrettably, literature reveals that Pb-free perovskite substituting Sn and for
Pb exhibit greater instability when contracted with Pb-inclusive perovskite. This heightened instability is
attributed to oxidation state of Sn2+ which accelerates the degradation of these perovskites in the presence of air
[6]. To overcome this problem, certain Pb-free perovskites, such as CsGeI3, CsSnI3, and others, have been
developed. However, these materials have limited solar cell performance (CsSnI3 = PCE 13%, for example) and
are unstable [7]. DPs using the cations metals Ag (Silver) and Tl (Thallium), X2AgTlCl6 (X = Rb, Cs), was
investigated. The unusual stability and significant absorption characteristics of vacancy-ordered DPs like
Rb2TeX6 (X = I, Cl, Br) also have led to their exploration.
Additionally, Pb can be substituted using a complicated mixture of monovalent as well as trivalent cations
through the structural formula A2B′ B′′X6, whereas A represents massive cations (such as Cs+), B′′ and B′ appear
as monovalent as well as trivalent cations. Consequently, then X designates oxygen or halogen [8]. Numerous
halide perovskites have been successfully synthesized and characterized in this context, including Cs2BiAgI6,
Cs2InAgCl6, Cs2BiAgCl6, and Cs2BiAgBr6. However, the majority of these materials have large bandgaps or
exhibit subpar optical properties, which leads to the result that they are ineffective or inappropriate for
photovoltaic applications [9]. Recently, a very significant double perovskites material called. Cs2BiCuI6 showed
electrical characteristics that were equivalent to those of MAPbI3. Another perovskite with such a direct
bandgap, Cs2AgInCl6, has additionally demonstrated the highest stability; nevertheless, it was discovered that
the stability of the perovskites decreased when other halides were added. Focusing on photoluminescence (PL)
studies, identified charge carrier relaxation shows that the trap states and structural abnormalities cause the
instability of perovskites nature [10]. Furthermore, according to another source, the perovskites Rb2AgInCl6
and Cs2AgInCl6 have significant direct band gaps, which are crucial to the pursuit of outstanding solar
characteristics [11].
Cs2CuSbCl6 double perovskite nanocrystals with an XRD pattern that assurances stability in the cubic phase,
including the space groups Fm-3m were synthesized by Zhou et al [12]. The band gap derived by the absorbing
plot was 1.6 eV, exceeding the bandgap value used in the current investigation. This could be explained by spin–
orbit pairing about heavy components (Cs, Cu, and Sb). The band gap was determined by Nabi et al [13] using
the mBJ potential, which is compatible with our computations (1.0 eV). These studies served as inspiration for
the work presented here, in which we thoroughly examined K2NaTlX6, where X = Cl, Br, and I, to examine the
influence of alkali halides substitute on its thermoelectric, optical, and electronic properties [14]. The finding
presented in this current report or not only novel and information-rich but also chart novel routes for the
research community to conceptualize upcoming solar cell devices.

2. Calculation method

To investigate DPs K2NaTlX6 (X = Cl, Br, I) via first-principle method, the DFT-based computational technique
integrated by Wien2k code has been used. In the Wien2k code, FP-LAPW method [15] has been used. The
crystal structures in cubic phase of studied DPs were initially optimized based on the PBEsol-GGA approach in
which the interatomic stresses were decreased, and a balanced crystal structure was attained [16]. Many
significant parameters were obtained by using the Murnaghan equation of state fitting, including the bulk
modulus, lattice constant, and ground state energy. The calculations were facilitated using the FP-LAPW + lo
method, wherein considerations of both pure and semi relativistic effects were integrated to determined the
characteristics of core and valance electrons [17]. In order to precisely determine the ground-state lattice
constants, Perdew-Bruke-Ernzerhof (PBE-sol) structural relaxation was used. The PBE-sol provides a lower
band gap ratio by precisely calculating structural properties. This problem was solved by using the modified
Becke Johnson potential (mBJ) [18]. For the purpose of achieving precise band gaps, mBJ + SOC is also
calculated, which consists of the spin–orbit coupling (SOC) caused by the presence of heavy elements.

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Phys. Scr. 98 (2023) 115914 R Zafar et al

Figure 1. Cubic unit cell of DPs K2NaTlCl/Br/I6. The indigo color ball represents the K atom, the gray color ball represents the Tl
atom, and the green and orange color ball represents the Cl/Br/I and Na atom, respectively.

It’s interesting to note that electron densities are interpreted like spherical harmonics within muffin-tin
regions, whereas they are viewed as plane waves within interstitial regions. According to the FP-LAPW
approach, inside the interstitial area, the basic set is defined as 8 for RMT×Kmax, where Kmax and RMT stand for
maximal plane wave’s cut-off & shortest muffin-tin radius, appropriately [19]. The values for RMT, Kmax & Gmax,
which represent the potential Fourier expansion, were adjusted to eight and 18 Ry−1, respectively, to achieve
excellent convergence. Additionally, 12 × 12 × 12 k-mesh was used in the 1st Brillion zone for SCF to obtain the
convergence. Last but not least, the BoltzTraP codes were used for the calculation of thermoelectric
characteristics against temperature and chemical potential [20].

3. Results and discussion

3.1. Structural properties

The examined chemical K2NaTlX6 (X = Cl, Br, I) has a unit cell of cubic crystal structure and is a member of a
DPs family. This crystal structure is illustrated in figure 1.
PBEsol-GGA functional was utilized to obtain the optimize volume versus total energy graph of the studied
compounds [21]. Table 1 summarizes the optimized parameters determined by the Murnaghan equation of the
state [23] and shown in figure 2.
It is noteworthy that the lattice constant (ao) calculated for K2NaTlCl6 corresponds to 10.52 Å; but when the
anions are changed from Cl double perovskite to I double perovskite, the value of the lattice constant becomes
higher. This is due to the increase in the ionic radii of the halide ions. Similar trend of increasing lattice constant
were reported in double perovskites K2ScAgX6 (X = Cl, Br, I) [14]. On the other hand, a different pattern was
seen for the bulk modulus that reduces with the substitution of same halide ions. This is attributed to less dense
materials due to higher lattice constant values and lower bulk modulus values [24].
Their structural and thermal stability is crucial to investigate practical usage and some device-scale
production of different perovskites. The TF was analyzed to figure out structural stability, while for the stability
of thermodynamics, another quantity, formation energy (ΔHf), was calculated (table 1) using the following
relation [25]
DHf = E total (K l NamTlnX o)— l EK — mENa — nE Tl — oEX (1)

Here Etotal(KlNamTlnXo), EK, ENa, ETl, and EX represent the energies of K2NaTlX6, K, Na, Tl and X atoms.
Here, letters l, m, n and o represents the number of atoms. The negative values of formation energy suggest the
studied compounds are thermodynamically stable. Additionally, we have confirmed the stability using the
Goldsmith tolerance factor (TF). We have estimated the TF values to be 0.96, 0.94 and 0.92 for K2NaTlCl6,
K2NaTlBr6 and K2NaTlI6 respectively, which confirms that the material is stable in cubic phase. The TF is
expressed as the relation shown below [26, 27]:

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Phys. Scr. 98 (2023) 115914 R Zafar et al

Figure 2. Volume optimization of studied double perovskites K2NaTlX6 (X = Cl, Br, I)

Table 1. The calculated ao(Å): lattice constant, Bo(GPa): ground state bulk modulus, ΔHf (eV): Formation energy,
Elastic constant (C11(GPa), C12(GPa), C44(GPa)), G(GPa): Shear modulus, Y (GPa); Young Modulus, B/G: Pugh
ratio, and A: Anisotropy factor for cubic K2NaTlX6 (X = Cl, Br, I).

Parameters K2NaTlCl6 K2NaTlBr6 K2NaTlI6

PBEsol Other Cal. PBEsol Other Cal. PBEsol Other Cal.

ao 10.52 10.68a 11.13 11.34a 12.03 12.28a
Bo 28.57 22.65 17.36
ΔHf −1.86 −1.64 −1.22
C11 65.06 55.80 26.57
C12 4.22 5.17 11.69
C44 9.53 8.76 14.12
B 24.50 22.04 16.65
G 15.51 13.62 10.91
Y 38.42 33.88 26.87
B/G 1.57 1.61 1.52
υ 0.24 0.24 0.23
A 0.31 0.34 0.40
ΘD 279.56 269.59 250.50

a
[22]

TF = (rK + r X) /  2̄ (rB + r X) (2)

Where B = Na + Tl/2 and represents the mean of Na and Tl. The letters ‘r’ stand for the atoms K, Na, Tl, and
X’s ionic radii. The mechanical properties offer essential insights into the structural stability of K2NaTlX6. To
further evaluate the compound’s mechanical stability, elastic constants were computed using Tensor Matrix
Analysis. For cubic structures, the analysis of the entire systems primarily relies on only three crucial elastic
constants C11, C12, and C44.
We employed Born criteria (C11 + 2C12 > 0, C44> 0, C12 < B0< C11, and C11—C12 > 0) to establish the
mechanical stability of the compounds under investigation. The positive values obtained from these criteria
confirmed the mechanical stability of the studied compounds. The relationship B0 = (C11 + 2C12)/3 is
consistent and the bulk moduli obtained from optimized graphs using Murnaghan’s equation-of-state
supported this. The results obtained strongly indicate the structural stability of the compounds and validate the
correlation among their elastic and structural characterises. Practical applications demand materials with ductile
characteristic. To assess the ductile or brittle nature of the compounds, Poisson’s ratio (υ) was employed with a
critical threshold of 0.26. When the calculated value falls below this limit, the compound is categorized as
ductile; conversely, if it surpasses this limit, it is considered brittle. Our computed Poisson’s ratio value of
K2NaTlX6 as presented in table 1, affirm their ductile nature. Similarly, the properties of brittleness and ductility
of the compounds were evaluated using the B0/G (Pugh ratio) with critical threshold of 1.75. This analysis
further affirming the ductile nature of the studied compounds. Additionally, anisotropic behavior (A) was
computed using the elastic constant A = 2C44/(C11–C12). A material is considered isotropic when A is

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Phys. Scr. 98 (2023) 115914 R Zafar et al

Figure 3. Calculated electronic band structures of K2NaTlCl6, K2NaTlBr6 and K2NaTlI6 using mBJ and mBJ+SOC potential.

approximately equal to unity; otherwise, it is classified as anisotropic. The investigated compounds as indicated
in table 1 exhibit anisotropic characteristics.

3.2. Electronic properties

The calculated band structure (BS) of examined DPs is shown in figure 3 using mBJ and mBJ+SOC potential to
explain the electronic behavior. For K2NaTlCl6, K2NaTlBr6, and K2NaTlI6, the direct bandgap values are 3.4/
3.35 eV, 2.1/2.0 eV, and 0.8/0.6 eV, respectively using mBJ/mBJ+SOC potentials, at the Γ-symmetry point.
This direct band gaps ensure the interband transition, an essential component solar cells and optoelectronics
[28]. Due to the increased ionic size of the tetrahedrons and octahedrons generated by anions, band gaps change
from 3.4 eV to 0.8 eV when Cl is substituted by Br and I atom, respectively. The VB (valance band) and CB
(conduction band) gap reduces as the anions’ sizes grow, forcing states closer to the Fermi level [29].
The DOS of K, Na, Tl, and Cl/Br/I are presented in figure 4 using mBJ to understand the contributions of
the different elements. Since the K states have low levels, they have little effect on how electrons move from VB
toward CB [30]. However, in the investigated DPs, the change in anion from Cl double perovskite to I double
perovskite causes these states to move to the Fermi level. At the Fermi level, the Tl (s, p, and d) states contribute
insignificantly. Na (s-states) as well as the halogen ions (Cl, Br, I), which are in the p state, are the main sources of
transition electrons. The main source of contribution to the CB minima is Tl (s p) states, with a minor
contribution from Na states and the p states of halide ions. The states exist in the lower VB (0 to −4.0 eV) and
upper CB (5.0 to 8.0 eV) belong to core regions, therefore, transformations from VB to CB need higher
energy [22].

3.3. Optical properties

The optical characteristics of the various perovskites are thoroughly examined to ensure their ability for
optoelectronic as well as photovoltaic [31]. According to the literature, optical response is solely dependent on
the amount of light and bonded electrons in the valence band. These bonded electrons become energized and
shift towards VB to CB after absorption of the incoming light by a particular photon energy. Such electrons
remain in the conduction band before de-exciting, leaving photon energy as well as rearranging in the valence
band [32]. The real (ε1(ω)) as well as imaginary (ε2(ω)) dielectric constants, absorption coefficient, reflectivity,
refractive index (n(ω)), and loss factor of K2NaTlX6 have been explored in the range of 0–10 eV [33].
Figure 5(a) shows the response of ε1(ω) in relation to energy. It’s interesting to note that when Cl double
perovskite is altered individually by Br double perovskite and I double perovskite, the static ε1(ω), or ε1(0),
increases [34]. Perovskites K2NaTlCl6 has a ε1(0) = 2.51 value, while K2NaTlBr6 and K2NaTlI6 have a 2.97 and
3.96 value, respectively. Furthermore, it is clear from the diagram that initially, ε1(ω) increases and reaches its
maximum value before beginning to decline. 5.6 eV for ε1(ω) peaks of polarized lights specifically K2NaTlCl6,
4.7 eV for K2NaTlBr6, and 3.5 eV for K2NaTlI6. K2NaTlCl6, K2NaTlBr6, and K2NaTlI6 have static dielectric
values that are 2.51, 2.97, and 3.96, respectively, which show an inverse relationship with the band gaps of 3.4 eV,
2.1 eV, and 0.8 eV, respectively. Therefore, this relation satisfies the Penn formula for ε1 (0) ≈ 1 + (ћωp/Eg)2. Eg,
and ωp stand for optical bandgap and plasma frequency, respectively, and ћ for planks constant.
Additionally, refractive index n(ω) is plotted against energy and illustrated in figure 5(c) to describe the
material’s transparency [35]. The relationship between the static values of n(ω) and ε1(ω), expressed as n20 =
ε1(0). The optical parameters ε1(ω) and n(ω) showed a similar trend in the graph, satisfying the abovementioned

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Phys. Scr. 98 (2023) 115914 R Zafar et al

Figure 4. Calculated total density of states (TDOS) of K2NaTlX6, and partial density of states of K atom, Na atom, Tl atom and X atom.

relation. The static values of n(ω) for K2NaTlCl6, K2NaTlBr6, and K2NaTlI6 are 1.58, 1.72, and 1.99 respectively,
before falling to the lowest values, as shown in figure 5(c). The examined compounds’ potential for
optoelectronic applications was demonstrated by the measured values for n(ω) that lie between 1–2 [36].
Furthermore, the Kramers–Kronig relation was used to estimate the ε2(ω) [37]. Figure 4(b) shows the
investigation of ε2(ω) versus energy from 0 to 10 eV. For different energies, ε2(ω) reaches its maximum value.
The bulging peaks for the compound K2NaTlX6 under investigation occur at various energies, including
5.97 eV, 4.96 eV, and 3.86 eV for K2NaTlCl6, K2NaTlBr6, and K2NaTlI6, respectively. This is consistent with the
pattern shown in the TDOS instance, where a smaller band gap was found when X shifted from Cl double
perovskite to Br double perovskite and I double perovskite. It is possible to determine the DOSs participating in
electronic transitions by estimating the intensity of the ε2(ω) peaks.
A material displays both light transmissions by the surface and reflection from its surface when positioned in
front of an external beam of light [38]. The absorption coefficient is determined by the proportion of the
intensity of light that decays over a unit distance when transmitted across a medium. Figure (e) shows the
absorption coefficient versus external energy. The specific form of α(ω) is nearly identical to that of ε2(ω),
demonstrating a direct correlation between the two parameters. No absorption occurred when the energy level
reached a critical level [39]. This information reveals the researched materials transparent energy, corresponding
to the band gap. The value of α(ω) is different on the substitution of Cl double perovskite to Br double perovskite
and I double perovskite and starts shifting towards lower energy. The analyzed DPs semiconducting nature is
demonstrated by the linearly rising tendency in absorption until crossing its limited energy [40].
Reflectivity, denoted as R(ω), is used to calculate a portion of energy that returns from the material medium’s
surface. Figure 5(f) shows the plots of R(ω) against energy for the studied materials. The static reflectivity R(0) of
K2NaTlCl6, K2NaTlBr6, and K2NaTlI6 are calculated as 0.05, 0.07, and 0.10, respectively. Since the highest
reflectivity takes place for those energy values where ε1(ω) shows a negative value. Therefore, these materials can be
suitable for optoelectronic devices. Furthermore, the curves of extinction k(ω) co-efficient is related to ε2(ω) [41].

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Phys. Scr. 98 (2023) 115914 R Zafar et al

Figure 5. The calculated (a) real part ε1(ω), (b) imaginary part ε2(ω) of the complex dielectric function, (c) refraction n(ω) and (d)
extinction k(ω) co-efficient, (e) absorption α(ω), (and (c) reflectivity R(ω) for K2NaTlX6 (X = Cl, Br, I).

3.4. Thermoelectric properties

The investigation of thermoelectric characteristics is necessary for the performance of thermoelectric devices.
Usually in DFT the Boltzmann equation is used to explore these properties [42]. The BoltzTraP code is based on
the classical transport theory. Most significant factors including electrical conductivity (σ), thermal conductivity
(κ) and Seebeck coefficient (S) are determined against the chemical potential (μ(eV)) and temperature (T(K)).
Additionally, the figure of merit (ZT) is calculated using formula ZT = σS2/κT [43]. It evaluates the compounds
thermoelectric performance. Its valuable to note that a material may exhibit increased thermoelectric efficiency
if it has a high value for σ while having a low value for κ. The two components of the factor κ are the electronic
component κe and the lattice component κph, and they are connected by the formula κ = κe + κph [44]. We have
only included κe here due to limitations in the BoltzTraP. It has been noted that thermoelectric properties are
significantly influenced by band gaps and electrical behavior [45]. The materials with narrow band gaps are
strong candidates for thermoelectric uses. The electrons move easily from valence to conduction bands in
narrow band gap semiconductors, increasing electric conductivity and decreasing thermal conductivity (See
figures 6 and 7). The computed results show the existence of n-type as well as p-type charge carriers under
negative and positive values of μ(eV), respectively, as seen in figures 6(a), (b) [46].
The movement of carriers across materials affects their electrical conductivity that thermoelectric
applications. Figure 6(a) depicts the contributions of electrons and holes to conduction, which are connected to
-ve as well as +ve values of μ [47].
The results demonstrate that the peak value of electrical conductivity at −1.02/ −1.31 eV for Cl/Br with an
intensity of 3.96/4.28 × 1019 (1/Ωms), while for I-based DPs it touches 4.47 × 1019 (1/Ωms) at −1.46 eV. The
peaks have a substantial intensity in the regions of extremely striking potential at around −0.81 eV, as seen in
figure 6(a).

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Phys. Scr. 98 (2023) 115914 R Zafar et al

Figure 6. The calculated (a), (b) electrical conductivity (σ/τ), (c), (d) thermal conductivity (ke/τ) and (e), (f) Seebeck coefficient (S)
against chemical potential and temperature for K2NaTlX6 (X = Cl, Br, I).

Peaks for Br double perovskite and I double perovskite are located in the n-type side (+ve μ) at 1.78 and
2.81 eV, respectively, with intensities of 3.1 × 1019 (1/Ωms). The study confirms that electrons are the bulk of
carriers. Figure 6(b) also shows the trends, which increased from 0.5/1.71 to 1.69/2.27 × 1019 (1/Ωms) at 100 K
to 400 K, but K2NaTlCl6 value slightly decreased from 2.28 to 2.25 × 1019 (1/Ωms). As a result, bond breakage
and the high kinetic energy of electrons may be the reasons of this decreasing in Cl double perovskite [48].
According to figure 6(c), the patterns of κe for electrons in n-type regions and holes in the p-type regions are
similar [49]. The κe rises from 0.5 W mK−1 at 100 K to 4.21 W mK−1 at 800 K for Br, from 1.1 W mK−1 at 100k to
4.68 W mK−1 at 800 K for I, and 1.1 W mK−1 at 100 K to 5 W mK−1 at 800 K for Cl double perovskite (see
figure 6(d)). These factors are crucial for improving thermoelectric devices’ overall performance. For
K2NaTlCl/Br/I6, the room temperature values calculated for σ are 2.28/0.6/1.71 and κe are 1.0/0.5/1.0 respectively
The thermoelectric efficiency of a material can be determined using the Seebeck coefficient (S). The Seebeck
coefficient is derived from the potential gradient generated as a result of the temperature disparity [50]. S is
positive when the carriers are holes, whereas S is negative when the carriers are electrons. Additionally, chemical
potential with positive values of S that exhibit n-type behavior and negative numbers that exhibit p-type [51]. At
0.4 to 2.8 eV, the peaks occur in the n-region, the peaks transfer at 0.9 eV in positive trend for I/Br/Cl (see
figure 6(e)). Additionally, the influence of T on S was depicted in figure 6(f), which indicates a reducing tendency
for Br from 190 μV K−1 to 168 μV K−1. In contrast, for I, there is a slight increase from 110 μV K−1 to
122 μV K−1 at first then linear behavior is observed, and for Cl, it rises from 48 μV K−1 to 118 μV K−1 [52].
Figure 7(a) compares μ with thermoelectric strength as shown by the power factor (PF = σS2) as well as
against the T in figure 7(b). The PF peaks appear in the p-type region between 0 and −2 eV, while there is only
one peak at 1.8 eV for I in the n-type region. For Cl, Br, and I based DPs, the PF rises from
0.5/1.8/2.1 W mK−2s−1 to 3.2/3.7/3.35 W mK−2s−1, respectively. The σS2/κ expression is used to evaluate
figure of merit (ZT) which is essential for information of thermoelectric devices [53]. The ZT is closer to unity in
the energy ranges −1 to −2 eV for the studied DPs (see figure 7(c)). In figure 7(d), the graphs of ZT versus T have
been displayed in temperature range of 200 to 800 K. It is observed that ZT rises from 0.1 to 0.5 for Cl-based and

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Phys. Scr. 98 (2023) 115914 R Zafar et al

Figure 7. The calculated (a), (b) power factor (PF = σS2/τ) and (c), (d) figure of merit (ZT) for K2NaTlX6 (X = Cl, Br, I).

from 0.42 to 0.58 for I-based but constant behavior for Br-based DP. Therefore, DPs are appropriate for
thermoelectric device that operates at low temperatures based on calculated result. However, their performance
declines as temperature increases [54].

4. Conclusion

Utilizing Density functional theory (DFT), an exploration into the structural, electrical, optical and
thermoelectric characteristics of double perovskites compounds K2NaTlX6 (X = Cl, Br, I) has been conducted.
The structural stability is affirmed by the computed TF values near about 1, while the presence of negative
formation energy indicates their thermodynamic stabilities. These Cl, Br and I-based double perovskite
compounds exhibit direct band gaps 3.4 eV, 2.1 eV, and 0.8 eV respectively as determined through band
structure (BS) calculation. The reduction in band gap from Cl double perovskite to I double perovskite is
attributed to the hybridization of Na, Tl, and halogen ions in their (s, p, d) electron states. Notably, these double
perovskites exhibit absorption spectra across ultraviolet (UV), visible, and Infrared (IR) regions. Furthermore,
the computationally determined elevated values of thermoelectric parameters (S, σ) combined with
concurrently low thermal conductivity (κ) plat a pivotal role in substantial enhancement of the figure of merit
(ZT), thus rendering these materials exceptionally intriguing for applications in thermoelectric devices.

Acknowledgments

The authors would like to acknowledge the Researchers Supporting Project Number (RSP2023R43), King Saud
University, Riyadh, Saudi Arabia.

Data availability statement

All data that support the findings of this study are included within the article (and any supplementary files).

ORCID iDs

N A Noor https://orcid.org/0000-0001-8039-1424
Asif Mahmood https://orcid.org/0000-0003-1803-8384

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Phys. Scr. 98 (2023) 115914 R Zafar et al

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