Journal of Taibah University for Science

Structural, Optoelectronic and Thermoelectric Properties of Ba3F2ASe3 (A = Zn and

Cd) Barium Fluroselenides for Solar Cell Application
--Manuscript Draft--

Manuscript Number: TUSC-2023-1168

Article Type: Research Article

Section/Category: Chemistry

Keywords: Fluroselenides; first principal calculations, electronic properties; , optical properties,

thermoelectric properties, solar cell application

Abstract: Structural, electronic, optical and thermoelectric properties of Barium fluroselenides

Ba3F2ZnSe3 and Ba3F2CdSe3 in orthorhombic in Pnma space group are studied
using density functional theory. Structural parameters show accordance with the
experimental outcomes. Electronic properties of Ba3F2ASe3 (A = Zn and Cd) shows
that these compounds are visible light active semiconductors with bandgap values of
1.80 and 1.67 eV. Additionally, electrical conductivity also provides information
regarding the semiconducting properties of the understudy compounds. In these
compounds the substitution of Cd for Zn results in a reduction of bandgap due to
increasing in atomic size. The optically dynamic nature of these compounds in the
visible region make them paramount applicant for optoelectronic devices and are
active aspirants for solar cell applications. The thermoelectric properties disclose that
these compounds are efficient compounds for thermoelectric applications at low
temperature.

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Structural, Optoelectronic and Thermoelectric Properties of Ba3F2ASe3 (A = Zn and Cd)

Barium Fluroselenides for Solar Cell Application

Abstract
Structural, electronic, optical and thermoelectric properties of Barium fluroselenides Ba3F2ZnSe3

and Ba3F2CdSe3 in orthorhombic in Pnma space group are studied using density functional theory.

Structural parameters show accordance with the experimental outcomes. Electronic properties of

Ba3F2ASe3 (A = Zn and Cd) shows that these compounds are visible light active semiconductors

with bandgap values of 1.80 and 1.67 eV. Additionally, electrical conductivity also provides

information regarding the semiconducting properties of the understudy compounds. In these

compounds the substitution of Cd for Zn results in a reduction of bandgap due to increasing in

atomic size. The optically dynamic nature of these compounds in the visible region make them

paramount applicant for optoelectronic devices and are active aspirants for solar cell applications.

The thermoelectric properties disclose that these compounds are efficient compounds for

thermoelectric applications at low temperature.

Keywords: Fluroselenides; first principal calculations; electronic properties; optical properties;

thermoelectric properties; solar cell application;

1. Introduction

Chalcogenides (CH) have recently received more attention in materials science community

because of their peculiar layered geometries and intriguing physical characteristics, such as due to

their superconductor nature at high temperature [1, 2] and thermoelectric properties [3, 4].

Fluorides (F) based chalcogenide consist of layered type structures with different layers of F and

1
CH due to the difference in sizes and coordination symmetry of the F and the CH. This play great

role and have potential appliances, like photoluminescence in BaFMn0.5Te [5], sizeable

thermoelectric power in SrFBiS2 [6], superconductivity in Eu3F4Bi2S4 [7] and magnetism in

Ba2F2Fe2-xSe3 [8, 9] and Ba3F2MnSe3 [10]. Recently, corner-sharing [MSe3], [Ba3F2] anion and

cationic coordination of the fluorite having orthorhombic Pnma (No. 62) space group have been

found to form one-dimensional chain structures in the Ba-F-A-Se system for new low-dimensional

materials with possible future applications.

According to literature base knowledge, the compounds Ba2F2Fe2-xSe3 [8, 9], Ba3F2MnSe3

[10], BaFCuSe [11,12], BaFAgSe [13], Ba2F2SnSe3 [14], Ba2F2Sb2Se4 [15], and Ba7F8In2Se6 [16]

have attracted the attention from the researchers due to their exceptional structures and intriguing

magnetic properties. Examples of layered heterostructures include Ba2F2Fe2-xSe3, which consists

of PbO-type BaF2 layers interleaved with Fe2Se3. The vacancies have a profound effect on its

magnetic characteristics [8]. In contrast to Ba2F2Fe2-xSe3, the structure of Ba3F2MnSe3 consists of

a single-dimensional chain of [MnSe3] anion atoms that share corners indefinitely and a series of

[Ba3F2] cationic atoms that lie between them. Short-range anti-ferromagnetic order is observed in

Ba3F2MnSe3 at low temperatures [10]. The search for new compounds and the actualization of

their probable application in the Ba-F-M-Se type compounds need additional experimental or

theoretical efforts. Samples of polycrystalline Ba3F2ASe3 (A = Zn, Cd) have been produced by

Huang et al. [17]. Some measurements have been taken, such as heat capacity, optical spectrum

and magnetic susceptibility which show the optical gaps of 1.80 eV and 1.69 eV respectively. All

the data agrees with band structure simulations showing that Ba3F2ASe3 (A = Zn and Cd) are

semiconductors with band gap of 2.0 and 1.5 eV respectively. As the reported experimental optical

gap of the Ba3F2ASe3 (A = Zn and Cd) compounds are in the range of ideal band gap for

photovoltaic compounds [18] which signify their importance to study and elaborate their
2
 optoelectronic and thermoelectric properties for photovoltaic and thermoelectric application such

that compounds having 1.80 eV band gap are act as efficient solar cell materials [19 ]. Therefore,
*

the present study is focused on the First principle calculation of structural, optoelectronic and

thermoelectric characteristics of Barium fluroselenides Ba3F2ASe3 (A = Zn and Cd).

2. Computational Details

The full-potential linear augmented plane wave (FP-LAPW) approaches are used to execute the

structure and optoelectronic nature of barium fluroselenides Ba3F2ASe3 (A = Zn and Cd) inside a

density functional theory (DFT) [20] that is implemented in the WIEN2k package [21].

Generalized Gradient Approximation (GGA) [22, 23] is employed to treat the exchange-

correlation as a function of the PBE flavor, and GGA with Hubbard U (GGA+U) [24] modified

Becke-Johnson potential (mBJ) and (mBJ+U) [25] were also used for better treatment. To prevent

the outflow of charges, the FP-LAPW approach divides the area into an interstitial zone and a

muffin-tin sphere region. In a muffin-tin sphere, a harmonic expansion setup is located close to

around lMax=10 and is also set RMT=10.0/KMAX. Although a particular number of thousands of K-

points were used within a Brillouin Zone, the energy between subsequent iterations is assumed to

be 0.1 mRy, and the force is lowered to 1 mRy Bohr-1. Kramar-Kroning relation is used to estimate

the optical properties and the BoltzTraP package estimates the transport properties [26].

3. Discussion and Consequences

3.1 Structural Properties

The structural properties of these Barium fluroselenides Ba3F2ASe3 (A = Zn and Cd) compounds

are investigated employing experimentally reported structure data [17] depicted in Fig. 1. The

Birch-Murnaghan equation of state [27] is set up to optimize the cell structure for each compound

through the PBEsol flavor of GGA shown in Fig. 2 to determine the structure properties and the

detail of which are provided in Table 1. The lattice parameters from the Table 1 are a = 15.288, b
3
= 4.241 and c = 13.714 Å, a = 15.491, b = 4.317 and c = 13.937 Å for Ba3F2ASe3 (A = Zn and

Cd). The results reported for these compounds are relatively close to experimental results [17] and

are increasing Ba3F2ZnSe3 to Ba3F2CdSe3 due to increasing in their atomic radii (0.60Å /Zn and

0.87Å /Cd) and larger that the isotropic compound Ba3F2MnSe3 [10]. The estimated bulk moduli

(B0) for Ba3F2ZnSe3 to Ba3F2CdSe3 compounds are 74.837 and 96.850 GPa respectively. The

larger value of B0 for the Ba3F2CdSe3 than Ba3F2ZnSe3 indicates that Ba3F2CdSe3 is harder than

the Ba3F2ZnSe3 compound.

Ground state energy (E0) is used in calculating the crucial stability parameters cohesive

energy and enthalpy of formation (Ecoh and H), which are displayed in Table 1, and detail is found

in Ref. [28]. The electrons, nuclei interaction and the number and size of the component particles

contribute to the Ecoh of material, with a higher Ecoh indicating a more tightly bound and integrated

system. The values of Ecoh and ΔH are -35.446, -37.749 and -3.938, -4.194 from Table 1 verify their

stability and make known that Ba3F2CdSe3 is more stable than Ba3F2ZnSe3 and also confirmed

from the bulk modulus.

The calculated bond lengths between the Ba-Fe, TM-Se and bond angle between Ba-F-Ba,

F-Ba-F and Se-TM-Se at different site in comparison with the experimental results are listed in

Table 1. From the Table 1 it is clear that the reported data are in agreement with the experiments

[17] and show that bond length between the Ba-F and TM-Se are varying in the range of 2.769 to

2.321 Å and 2.699 to 2.489 Å respectively for both the compounds and bond angle between the

Ba-F-Ba, F-Ba-F and Se-TM-Se are changing from 123.986 and 66.788 (o) respectively for both

compounds. As seen in the different plan view of Fig. 1(a), these compounds are made up of

[Ba3F2] cationic fluorite-type blocks and [ASe3] tetrahedra that are indefinitely extended along the

b-axis. Additionally, each [Ba3F2] cationic block is encircled by [ASe3] anion chains. 6 Ba and 4

F atoms make up the [Ba2F2] block (Fig. 1(b)), which has bond lengths that are almost identical to
4
those of the [Ba3F2] block in the Ba2F2Fe1.5Se3 [9]. The Zn and Cd atoms are located in the middle

of the Se atom-containing [ASe3] anion chain (Fig. 1(c)). The Zn and Cd atoms in these corning-

sharing polymeric chains are coordinated in a tetrahedral geometry that is comparable to that of

the [ZnSe2] tetragonal block in the La2O2ZnSe2 [29] and Ce2O2ZnSe2 [30]. It appears that

Ba3F2ASe3 (A = Zn and Cd) has similar physical properties to [ZnSe2] tetragonal block in the

La2O2ZnSe2 [29] and Ce2O2ZnSe2 [30] based on the bond angles and bond lengths in the [ASe3]

anion chain.

3.2 Electronic Properties

The number of states occupied by system energy is described by its density of states, and this

function determines the bulk characteristics of materials. The total density of states (TDOS) for

the compounds under investigation is calculated using GGA, GGA+U, mBJ and mBJ+U

approaches suggesting the Fermi level (EF) to be at 0 eV presented in Fig. 3. The TDOS for these

compounds reveals the presence of energy gap flanked by the valance band (VB) and conduction

bands (CB) is no overlapping of densities around the EF reveal the semiconductor nature of

Ba3F2ASe3 (A = Zn and Cd) compounds.

One can see the estimated bandgap values from Table 2. These values are 1.04, 1.05, 1.78

and 1.80 eV for Ba3F2ZnSe3 and 0.69, 0.70, 1.53 and 1.55 eV for Ba3F2CdSe3 by GGA to mBJ+U

approaches. The reported optical bandgap for Ba3F2ZnSe3 is 2.0 and for Ba3F2CdSe3 is 1.5 eV

respectively through VASP code and 1.80, 1.69 experimentally by Kubelka-Munk function [17]

which shows that the reported are comparable with the others, make the present study rational and

logical. In the current study different potentials were used to find out the correct and exact nature

of bandgap value for these compounds because of Huang et al. [17] used GGA-PBE approach

using VASP method which did not agree with the experimental measured value, same is the case

in the current study such that mBJ+U potential gives reliable results for these compounds.
5
Conversely, the mBJ potential is widely regarded as the most effective tool for estimating band

gaps [31]. Multiple comparisons show that it is superior to other potentials in terms of accuracy

and computational cost. Therefore, the band gaps reported for Ba3F2ZnSe3 and Ba3F2CdSe3 using

mBJ+U are suitable and trustworthy in the present study. Additionally, the band structures for

Ba3F2ZnSe3 and Ba3F2CdSe3 are calculated and displayed in Fig. 4 to further validate their

semiconducting nature. The figure shows that there is no overlapping at the EF and maxima of VB

align with the minima of CB at the central symmetry for both compounds indicate their direct band

gap character.

The element’s partial density of states (PDOS) is also considered to determine their relative

importance, as shown in Fig. 5. Fig. 5 demonstrates that densities are distributed in two sections

in the whole energy range. Ba-s, F-p, Zn/Cd-d and Se-p states take part in the section from -6 to 0

eV and from threshold value to 7 eV correspondingly in both compounds with variation in

contributions in the VB and CB such the contribution of F-p, Zn/Cd-d and Se-p are greater in the

VB as compare to CB. From the VB and CB, it is evident that their energy gap accurses between

the d state of Zn/Cd and Se-p atom in both compounds.

3.3 Optical Properties

It is significant to examine the interaction of light wave with these materials in response to the

optoelectronic application. Thus, optical properties for both the (Ba3F2ASe3 (A = Zn and Cd)

Barium fluroselenides are estimated in the energy range of 0 - 14 eV. In the presented work the

calculated optical factors are real and imaginary component of the dielectric function (ε1 (ω) and

ε2 (ω)), oscillator strength (σ (ω)), extinction coefficient (k (ω)), energy loss function (L (ω)),

reflectivity (R (ω)) refractive index (n (ω)), and optical conductivity (α (ω)) in the three (X, Y and
6
Z) axis and given in Fig. 6 (a-c). In Fig. 6(a), the compound's various physical properties are

represented by the real component of the ε1 (ω). The static dielectric function (ε1 (0)) is the value

occur at the 0 frequency limit. In Fig 6(a) and Table 3 the (ε1 (0) lie at 5.234, 3.947, 3.64 and 5.189,

3.866, 3.984 respectively in X, Y and Z direction for both compounds. Spectra are seen to increase

after the zero frequency, peak at their highest points lies in the range of at 9.797 and 6.330 at 2.761

to 5.04 eV respectively for Ba3F2ASe3 (A = Zn and Cd). The spectra are seen to decline and

eventually drop to zero after this highest peak. The substance has lost its dielectric properties and

has turned into metal.

The ε2 (ω)) is provided in Fig. 6(a) and indicate clearly that up to 2.19 eV there is no spectra

which correspond to the optical gap of these compounds in different crystallographic axis listed in

Table 2, The optical gap shrink from Zn to Cd as one moves from the starting point and their

optical gaps (1.23 and 1.02 eV at x-axis, 2.19 and 1.67 eV in y-axis and 1.80 and 1.42 eV in z-

axis) are found active in infrared region in x-axis, visible region in y-axis and visible and infrared

region in z-axis respectively which make these compounds anisotropic optical materials and are

potential applicant for solar cell application. The rise in the curve is apparent, and both compounds

almost reached their maximum limit in the range from 5.258 and 12.682 at 3.333 to 5.836 eV due

to major inter bond transition.

The relationship between the reported and experimental band gaps are presented in Fig.

6(b). The figure shows well resemblance with experimentally obtained band gap and decreasing

due to raise in the atomic radii and lattice parameters [32-37]. The optical gaps for Ba3F2ASe3 (A

= Zn and Cd) mentioned above are equivalent to those observed in BaZnPF (1.8 eV) [38] and are

lower than the band gaps of 2.9 eV for SrCuSeF [39] and 2.99 eV for BaCuSeF [40].

Fig. 6(a) shows the reflectivity (R (ω)) for the understudy compounds. According to the

graph, the zero-frequency reflectance (R (ω) at 0 Hz) for both compounds fall between 10.6 and
7
15.3 %. In contrast, the maximum reflectance (R (ω) at 59 and 58.1 %, respectively) correspond

to 13.56 eV for Ba3F2ASe3 (A = Zn and Cd). Curiously, reflectance increases as energy approach

the point where ε1 (ω) becomes zero. The UV domain is the only one where a high reflectivity

value occurs in these materials. For this reason, high-frequency radiation might be blocked by

using these materials.

Fig. 6(a) correspond to refractive index (n(ω)). For both (Ba3F2ASe3 (A = Zn and Cd)

compounds, the value correspond to zero frequency of the refractive index (n(0)) is generally

determined between 1.966 and 2.287, respectively. After a n(0) the n(ω) enhances and achieve its

maximum value where energy ranges from 2.734 eV to 5.102 eV in the same way for Ba3F2ZnSe3

and Ba3F2CdSe3. The prominent values of n(ω) observed for the compounds under investigation

(3.393 and 3.027) respectively are a result of the decrease in the maximum number of photons

upon entry to the materials [41].

The extinction coefficient measure the attenuation of an electromagnetic wave in a material

represented by k(ω) [42–46]. Accordingly, if a material's k(ω) is very small, it will have a small

absorbance and a large transmittance. The extinction coefficient for little-studied chemicals is

close to ε2 (ω).

In Fig. 6(c), it is apparent that mostly up to band gap the k(ω) have zero value and show

little absorbance and high transmittance. Beyond the zero, the k(ω) goes to highest value from

3.387 to 7.959 eV shown in Table 4 respectively for both Ba3F2ZnSe3 and Ba3F2CdSe3 compounds

convey that in the area these compounds have poor wave transmission and strong wave absorption.

Electrons will conduct through the material when an electromagnetic field is produced, and

optical conductivity is a crucial optical property for this to happen. The (α(ω)) spectra of

Ba3F2ZnSe3 and Ba3F2CdSe3 are displayed in Fig.6(c) According to Fig. 6(c), optical conduction

begins around the threshold value and continues to increase beyond it, reaching maximal
8
conductivity between the 4141.5 to 5931.98 Ω-1 cm-1 at 3.333 and 3.387 eV correspondingly for

these compounds. Ba3F2AnSe3 has a maximum conductivity of 5931.98 Ω-1 cm-1, while

Ba3F2CdSe3 gets a maximum conductivity of 4719.19 Ω-1 cm-1.

L (ω) is the energy loss function for moving electrons inside a material is seen in Figure

6(c). The peak in the curve of the understudy compounds is caused by plasma frequency resonance.

L (ω), which depends on loss of energy and momentum transfer, measures the material response

to an electromagnetic perturbation. According to Fig. 6(c), the lower energy related with photons

than the bandgap value results in no scattering. Fig. 6(c) and Table 4 shows that the presence of

discrete energy bands causes the Ba3F2ASe3 (A = Zn and Cd) compounds to exhibit the greatest

energy loss between 12.503 and 12.911 eV.

To quantify the quantity of electrons concerned in an optical transition, the oscillator

strength (σ (ω)) or sum rule is needed. The calculation of oscillator strength was done for current

compounds which are under studies; Fig. 6(c) demonstrates when energy increase then σ (ω) also

enhances. As the energy increases past the bandgap, the number of electrons in the system rapidly

increases from zero when the energy is low. It is obvious from Fig. 6(c) that the σ (ω) demonstrates

that 86-97 number of electron involve in the optical transition appropriately in different

orientations of Ba3F2ASe3 (A = Zn and Cd).

The optical properties show different responses in different crystallographic direction as

clear from Fig. 6 (a and c) and from Table 3 and 4 which demonstrate that these compounds are

anisotropic optical materials and from the band gap value and optical conductivity these

compounds are potential candidates for solar cell and photovoltaic applications.

3.4 Thermoelectric Properties

The thermoelectric generator converts thermal energy to electrical power. As a result, the study

explaining the thermoelectric (TE) properties is rapidly expanding. When thermoelectric materials
9
are employed on a large scale (computer cooling and TE refrigeration), their TE characteristics

should be researched to evaluate their actual performance at relatively high temperature. Active

thermoelectric materials have been discovered in semiconductors with a narrow bandgap.

Transport parameters of these compounds are investigated in a temperature from 25 to 800

K using the BoltzTraP program [26]. Electrical conductivity (σ) examines the flow of free charges.

The estimated σ for Ba3F2ASe3 (A = Zn and Cd) compounds is presented in Fig. 7. At lower

temperatures, the σ for Ba3F2ASe3 (A = Zn and Cd) are very low, while increasing with rises in

temperature. Furthermore, σ also increases with changing Zn by Cd. The conductivity of the

Ba3F2CdSe3 is greater than the Ba3F2ZnSe3 because it possess low band gap as compare to

Ba3F2ZnSe3.

The variation in energy gap causes the alteration in electrical conductivity. At 300 K, the

electrical conductivity of these compounds Ba3F2ASe3 (A = Zn and Cd) 5.66×1018 and 7.76×1018

S/ms respectively.

Lattice vibrations and electron conduction usually cause heat conduction in materials. Due

to the BoltzTraP package's limitations, the electrical component of thermal conductivity (κ) for the

understudied compounds is estimated, as given in Fig. 8. The κ increases substantially as the

temperature rises, as shown in the graph. At low temperatures, the κ of the investigated compound

are nearly constant, but they fluctuate as the temperature grows. The κ of these compounds are

2.58×1013 and 4.10×1013 W/mks at 300 K for Ba3F2ASe3 (A = Zn and Cd) respectively. The κ for

these compounds rises from Ba3F2ZnSe3 to Ba3F2CdSe3.

The level of the thermoelectric voltage rises when two different materials are held at

different temperatures. Limited voltage patterns result from temperature changes between two

materials. When the temperature gradient is established, high thermoelectric voltage values verify

10
increased degrees of efficiency. The efficiency of thermocouples is determined by the Seebeck

coefficient (S), which determine the voltage ratio to the temperature differential.

Fig. 9 shows the S for Ba3F2ASe3 (A = Zn and Cd) compounds. Positive value of S suggests

a p-type semiconductor, while negative value indicates an n-type semiconductor. The S is negative

for both compounds propose that both Ba3F2ZnSe3 and Ba3F2CdSe3 are n-type semiconductors and

show that electrons are principal carrier. The S enhance with growing temperature for all these

compounds.

The enhancement in the thermoelectric application of the compounds arises by changing

constituent elements. The absolute value of -76.6and -70.4 μV/K at 300 K respectively for

Ba3F2ASe3 (A = Zn and Cd) and comparable with the - 85 μV/K for Ba3Cd2P4 Zintl [47]. The

seebeck value indicates that both compounds are probable candidates for thermoelectric

appliances.

A thermoelectric component called the power factor (PF) governs the power generation

ability of materials. The calculated PF for these compounds is shown in Fig. 10; the PF of all

compounds increases as the concentration of carriers grows with increasing temperature up to 300

and 350 K for Ba3F2ASe3 (A = Zn and Cd). The greatest value of PF for Ba3F2ASe3 (A = Zn and

Cd) compounds at 300 K temperature are 3.70×1010 and 3.32×1010 W/mk2s respectively.

The figure of merit is the most crucial indicator of thermoelectric material performance.

Fig.12 displays the calculated ZT for each of these compounds; for Ba3F2ASe3 (A = Zn and Cd)

the values are 1.87 and 1.84 at 75 K and 0.74, 0.85 at 100 K respectively; this extremely high value

of ZT makes them suitable for use in a variety of thermoelectric applications, consist of but not

restricted to: nano-thermocouples, thermoelectric Peltier micro coolers, and thermoelectric power

generators for wearable systems at low temperature [48].

11
 The specific heat for Ba3F2ASe3 (A = Zn and Cd) compounds are considered and shown in

Fig. 12. The figure revel that the specific heat (C) is increasing with increasing temperature

gradually with no anomaly evidence about phase transition and shows resemblance with the

experimental results [17]. At 300 K the value of heat capacity for these compounds are 219 and

263 J/mol K respectively indicates that Ba3F2CdSe3 can store more heat as compare to Ba3F2ZnSe3

and can be used for central heating system.

4. Conclusions

In summary the FP-LAPW technique with, GGA, GGA+U, mBJ and mBJ+U approaches are used

in the domain of DFT to examine the structural, optoelectronic and thermoelectric properties of

the barium fluroselenides Ba3F2ASe3 (A = Zn and Cd) in orthorhombic phase. The computed

structural parameters are in agreement with the available experiments. The results attained through

band structures and density of states indicates that both compounds are direct bandgap

semiconductors and their electrical conductivity also discloses the semiconductor nature of the

corresponding compounds. The calculated band gap values are 1.80 and 1.67 eV respectively for

Ba3F2ASe3 (A = Zn and Cd) and become diminishing with the substitution of Cd by Zn. The

findings demonstrate that both materials are optically dynamic in the visible region of

electromagnetic spectrum signifying that they could be employed suitable candidates for solar cell

devices. The reported thermoelectric properties also suggest that these compounds are suitable

materials at low temperature for thermoelectric applications.

12
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Figure Captions

Fig. 1 Crystal structure of Ba3F2ASe3 (A = Zn and Cd) compounds.

Fig. 2 Volume optimization plots of Ba3F2ASe3 (A = Zn and Cd) compounds.

Fig. 3 Total density of states of Ba3GaSe4Br and Ba3InSe4Br compounds.

Fig. 4 Band structure of the Ba3F2ASe3 (A = Zn and Cd) compounds.

Fig. 5 Partial density of states of Ba3F2ASe3 (A = Zn and Cd) compounds.

Fig. 6 (a-c) Optical parameters of Ba3F2ASe3 (A = Zn and Cd) compounds.

Fig. 7 Electrical conductivity versus temperature plots of Ba3F2ASe3

Fig. 8 Thermal conductivity versus temperature plots of Ba3F2ASe3

Fig. 9 Seebeck coefficient versus temperature plot of Ba3F2ASe3 (A = Zn and Cd) compounds.

Fig. 10 Power factor versus temperature plot of Ba3F2ASe3 (A = Zn and Cd) compounds.

Fig. 11 Figure of merit versus temperature plot of Ba3F2ASe3 (A = Zn and Cd) compounds.

Fig. 12 Heat capacity versus temperature plot of Ba3F2ASe3 (A = Zn and Cd) compounds.

20
Fig. 1

21
Fig. 2

22
Fig. 3

23
Fig. 4

24
Fig. 5

25
Fig. 6(A)

26
Fig. 6(B)

27
Fig. 6(C)

28
Fig. 7

29
Fig. 8

30
Fig. 9

31
Fig. 10

32
Fig. 11

33
Fig. 12

34
Table 1 Calculated lattice constants, bulk modulus, ground state energy, cohesive energy,
enthalpy of formation Bond length and Bond angles of the Ba3F2ASe3 (A = Zn and Cd) Barium
Parameters Ba3F2ZnSe3 Experimental[17] Ba3F2CdSe3 Experimental[17]
a (Å) 15.288 15.309 15.489 15.491

b (Å) 4.241 4.255 4.317 4.327

c (Å) 13.714 13.804 13.937 13.949

V(Å)3 889.271 899.393 932.031 935.143

B0(GPa) 74.837 ------- 96.350 -------

E0 (Ry) -269509.028 ------- -299898.271 -------

Ec (Ry) -35.446 ------- -37.749 -------

ΔH (Ry) -3.938 ------- -4.194 -------

Ba1-F1(Å) 2.436 2.449 2.531 2.546

Ba1-F2(Å) 2.565 2.587 2.981 2.986

Ba2-F2(Å) 2.557 2.564 3.321 3.330

Ba3-F1(Å) 2.377 2.380 2.594 2.606

Ba3-F2(Å) 2.769 2.775 2.332 2.337

TM-Se1(Å) 2.511 2.515 2.699 2.705

TM-Se2(Å) 2.531 2.535 2.537 2.548

TM-Se3(Å) 2.489 2.493 2.669 2.671

Ba1-F1-Ba3(deg) 105.987 106.742 109.256 110.284

Ba2-F2-Ba1(deg) 117.265 117.801 137.116 137.224

Ba2-F2-Ba3(deg) 114.11 114.92 106.476 106.611

F1-Ba1-F1(deg) 70.122 71.087 72.902 74.005

F2-Ba1-F1(deg) 123.986 124.331 66.788 67.414

Se1-TM-Se3(deg) 107.361 107.543 110.423 110.684

Se2- TM-Se1(deg) 111.789 112.000 107.120 107.951

Se2- TM-Se3(deg) 106.098 106.336 109.214 109.665

fluro-selenides.

35
Table 2 Comparison of present and others band gap energy (eV) of the Ba3F2ASe3
(TM= Zn and Cd) Barium fluro-selenides.
Band Gap Ba3F2ZnSe3 Others[17] Ba3F2CdSe3 Others[17]
GGA 1.04 2.0 0.691 1.5

GGA+U 1.05 ---- 0.706 ----

mBJ 1.785 ---- 1.533 ----

mBJ+U 1.807 ---- 1.551 ----

Optical x-axis 1.23 ---- 1.02 ----

Optical y-axis 2.19 ---- 1.67 1.69

Optical z-axis 1.80 1.80 1.42 ----

36
Table 3 Calculated value of the optical parameters against their respective energy (eV) of
the Ba3F2ASe3 (A= Zn and Cd) Barium fluro-Selenides.
Optical Parameters Ba3F2ZnSe3 Energy (eV) Ba3F2CdSe3 Energy (eV)
ε1(0)x 5.234 0 5.189 0

ε1(0)y 3.947 0 3.866 0

ε1(0)z 3.964 0 3.984 0

ε1(ω)xmax 9.797 3.197 8.914 2.761

ε1(ω)ymax 7.232 4.06 6.633 3.904

ε1(ω)zmax 6.494 5.04 6.330 3.986

ε2(ω)xmax 12.682 3.387 9.236 3.333

ε2(ω)ymax 6.012 5.836 5.258 4.122

ε2(ω)zmax 8.331 5.292 6.548 5.210

R(0)x 0.153 0 0.152 0
R(0)y 0.109 0 0.106 0
R(0)z 0.109 0 0.110 0
R( ω)xmax 0.590 13.56 0.581 13.56
R( ω)ymax 0.557 13.56 0.533 13.56
R( ω)zmax 0.572 13.56 0.575 13.56
n(0)xmax 2.287 0 2.278 0
n(0)ymax 1.986 0 1.966 0
n(0)zmax 1.991 0 1.996 0
n(ω )xmax 3.393 3.251 3.027 2.734
n(ω)ymax 2.723 4.367 2.654 3.932
n(ω)zmax 2.760 5.102 2.587 4.585

37
Table 4 Calculated value of the optical parameters against their respective energy (eV) of
the Ba3F2ASe3 (A = Zn and Cd) Barium fluroSelenides.

Optical Parameters Ba3F2ZnSe3 Energy (eV) Ba3F2CdSe3 Energy (eV)

κ(ω)xmax 2.239 3.442 1.742 3.387

κ(ω)ymax 1.209 4.693 1.465 7.959

κ(ω)zmax 1.736 5.374 1.573 6.435

α(ω)xmax 5779.36 3.387 4141.5 3.333

α(ω)ymax 4764.79 5.891 4390.56 7.523

α(ω)zmax 5931.98 5.292 4719.19 6.353

L(ω)xmax 0.576 12.911 0.655 12.585

L(ω)ymax 0.838 12.503 0.835 12.558

L(ω)zmax 0.624 12.530 0.679 12.939

σ(ω)xmax 97 13.56 96 13.56

σ(ω)ymax 89 13.56 86 13.56

σ(ω)zmax 91 13.56 90 13.56

38