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Density functional theory prediction of thermoelectric properties of two-dimensional

Janus HfXY (X≠Y, X/Y=Cl, Br, I) monolayers with high carrier mobilities

Shi-Jia Huang, Tian Zhang, Zhao-Yi Zeng, Hua-Yun Geng, Xiang-Rong Chen

PII: S0042-207X(24)00189-1
DOI: https://doi.org/10.1016/j.vacuum.2024.113143
Reference: VAC 113143

To appear in: Vacuum

Received Date: 14 February 2024

Revised Date: 14 March 2024
Accepted Date: 14 March 2024

Please cite this article as: Huang S-J, Zhang T, Zeng Z-Y, Geng H-Y, Chen X-R, Density
functional theory prediction of thermoelectric properties of two-dimensional Janus HfXY (X≠Y, X/
Y=Cl, Br, I) monolayers with high carrier mobilities, Vacuum (2024), doi: https://doi.org/10.1016/
j.vacuum.2024.113143.

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 Density functional theory prediction of thermoelectric
properties of two-dimensional Janus HfXY (X≠Y,
X/Y=Cl, Br, I) monolayers with high carrier mobilities
Shi-Jia Huang 1, Tian Zhang 2, Zhao-Yi Zeng3,*, Hua-Yun Geng 4, Xiang-Rong Chen 1,*

1
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China;

2
College of Physics and Electronic Engineering, Sichuan Normal University, Chengdu

610066, China;

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3
College of Physics and Electronic Engineering, Chongqing Normal University, Chongqing

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401331, China；

4
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National Key Laboratory for Shock Wave and Detonation Physics Research, Institute of Fluid
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Physics, CAEP, Mianyang 621900, China
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Abstract: Two-dimensional (2D) materials have garnered significant attention due to their
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exceptional thermoelectric properties. In this study, 2D Janus HfXY (X≠Y, X/Y=Cl, Br, I)
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monolayer materials are comprehensively examined using ab initio methods to ascertain

their potential as promising thermoelectric (TE) materials. Our predictions reveal that these

Janus materials exhibit favorable dynamic, thermal and mechanical stabilities. These

materials are predicted to exhibit semiconductor characteristics, showcasing indirect HSE06

band gaps ranging from 1.30 eV to 1.44 eV when accounting for the spin-coupling effect.

Furthermore, the calculated lattice thermal conductivities are 22.38 W/mK for Janus HfBrCl,

11.86 W/mK for Janus HfBrI, and 7.79 W/mK for Janus HfClI monolayers. These figures

* Corresponding authors. E-mail: zhaoyizeng@cqnu.edu.cn; xrchen@scu.edu.cn

1
notably reside below the thermal conductivities found in the extensively employed transition

metal dichalcogenides (TMDCs). These Janus materials are predicted to have higher

electron carrier mobilities ranging from 1220 cm2/sV to 4289 cm2/sV, surpassing the

majority of other 2D materials. The enhanced electron carrier mobility result in good n-type

power factor parameters, ranging from 58.20 mW/mK2 to 247.40 mW/mK2 between 300 K

and 600 K. Such merits of lower thermal conductivities and higher power factor parameters

endow these monolayers with the large figure of merit (zT) values for n-doping types along

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x (y) directions: 0.87 (0.88) for Janus HfBrCl, 1.62 (1.80) for Janus HfBrI, and 1.67 (2.15)

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for Janus HfClI at 300 K. Furthermore, these zT values can further increase along with
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external temperature increasing. These calculated thermoelectric figure of merit values
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surpass those of Hafnium-based TMDCs. Our study highlights the promising prospects of

2D Janus HfXY (X≠Y, X/Y=Cl, Br, I) monolayers as strong contenders for applications in
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thermoelectric conversion devices.

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Key words: Two-dimensional Janus HfXY (X≠Y, X/Y=Cl, Br, I); Electronic structures;
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Thermoelectric figure of merit; Carrier mobility; First-principles calculations

1. Introduction

Based on the Seebeck effect, thermoelectric (TE) materials have the

capability to convert waste heat into electrical energy, providing a promising

solution for addressing the energy crisis[1, 2]. The performance of TE materials

is measured by a dimensionless figure of merit known as zT. High zT values can

be achieved through two ways: reducing the lattice thermal conductivity via

2
lattice softening[3] and enhancing the power factor through band structure

engineering[4-7]. For example, the thermoelectric properties of Mg3(Sb,Bi)2 can

be improved by tuning carrier scattering through chalcogen or transition metal

doping[8], as by vacancy and grain boundary engineering[9]. Since the

groundbreaking discovery of graphene exfoliation in 2004, a large number of

two-dimensional (2D) materials have captured considerable attention due to their

potential application in diverse fields, including catalysts[10-14],

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optoelectronics[15-19], and energy storage[20-24]. Moreover, 2D materials have

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exhibited great potential in the field of TE materials, owing to their high carrier
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mobilities, distinctive anisotropy properties, and controllable direct energy
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gaps[25]. A great amount of 2D TE materials have been both predicted and

synthesized, such as black phosphorus (BP)[26, 27], transition metal

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dichalcogenides (TMDs)[28-30], as well as Xenes[31]. Especially the TMDs

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have emerged as powerful candidates for TE devices, owing to their

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comparatively low thermal conductivities and high electrical conductivities[32,

33]. Recently, a novel monolayer structure named Janus, exemplified by

monolayer MoSSe, has been successfully synthesized[34, 35]. In contrast to

conventional TMDs, Janus monolayers break the mirror symmetric in TMD

monolayers, which exhibit novel physical properties and have shown promise in

energy conversion, optoelectronics and TE devices[36-39]. For example, the

single-layer WS2 has been predicted the zT values of 0.006 at 300 K, whereas

the zT value of the Janus WSTe monolayer is 0.742, demonstrating that Janus

3
can effectively improve the TE performance of mirror-symmetric TMDs[40]. In

2020, Tao et al[41]. conducted a study on thermoelectric properties of all the

possible monolayers, including Janus structures MXY(M=Pt, Pd; X,Y=S, Se,

Te). Their findings predicted that the Janus PtSeTe monolayer exhibited a higher

zT value of 2.54 and a maximum zT 1.12, surpassing the values of rest materials,

in there also the Janus monolayers showed greater performance compared to

other structures.

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In recent years, Hafnium-based Janus have been widely investigated owing

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to its fascinating properties. In 2020, Hoat et al [42]. predicted that Janus HfSSe
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monolayer is a promising candidate for applications in optoelectronic devices.
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This material exhibits strong light absorption in both the visible and ultraviolet

spectra, while also predicting excellent thermoelectric performance attributed to

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its higher power factor. In 2021, Bera et al [43]. predicted the HfX2 (X = S, Se)
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and its Janus monolayer as potentially excellent 2D thermoelectric material for

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the fabrication of a high-performance thermoelectric power generator. In 2022,

Dat et al [44]. predicted the HfSO monolayer is a very excellent material for

photoelectric and electrical applications. In 2023, Nguyen et al [45].

recommended the HfSeO Janus monolayers as prospective 2D materials,

suitable for high-performance nanoscale optoelectronic and spintronic devices.

Considering the appealing properties and diverse applications of Janus HfXY (X

≠Y, X/Y=O, S, Se) monolayers, here we are inspired to choose elements from

the chalcogen group to halogen group (Cl, Br, I), and make a hypothetical

4
calculation in the hope of predicting novel Janus materials[46]. In 2023, Mezher

et al [47]. predicted the potential of the HfClBr Janus monolayer for applications

in solar cells and energy storage devices due to its unique optical and electrical

characteristics. However, the other properties of the new Janus HfXY (X≠Y,

X/Y=Cl, Br, I) monolayers have not been investigated yet.

In this work, the thermoelectric performances of the Janus HfXY (X≠Y,

X/Y=Cl, Br, I) monolayers are systematically investigated by using the first

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principle calculation. These materials are semiconductors with indirect band

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gaps, and exhibit excellent structural stabilities. Then we calculate their phonon
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transport properties and find that these materials have relatively low lattice
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thermal conductivities as compared to other 2D transition-metal dichalcogenides.

From the deformation potential (DP) theory [48], we compute their carrier
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mobilities and relaxation time. These Janus materials demonstrate significantly

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higher electron carrier mobilities, and better n-type power factor parameters,
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compared to those in other 2D materials. Hence, Janus HfBrCl, HfBrI and HfClI

monolayers possess excellent n-type TE properties with the large zT values of

0.88, 1.80, and 2.15 at 300 K, respectively. These findings suggest the Janus

HfXY monolayers have high heat-electric energy conversion efficiency in a

moderate temperature range.

2. Theoretical method and computational details

The first-principles simulation for the 2D Janus HfXY (X≠Y, X/Y=Cl, Br,

5
I) monolayers were performed based on density functional theory (DFT) using

the VASP program package[49]. The projector augmented wave (PAW)

pseudopotentials with the generalized gradient approximation (GGA) of

Perdew–Burke–Ernzerhof (PBE) were employed[50, 51]. We utilized the PBE

functional and the Heyd–Scuseria–Ernzerhof (HSE06) hybrid functional to

calculate the band structure[52]. Due to the heavy element Hf atom, spin-orbital

coupling (SOC) was considered to compute the electronic properties. To omit

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the interlayer interactions, a vacuum region with a width of 18 Å along the z-

r
-p
direction was inserted. Additionally, the DFT-D3 method of Grimme was used
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to correct the potential van der Waals (vdW) interactions[53]. After a strict
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convergence test, the Monkhorst-Pack scheme[54] for k-point sampling of the

Brillouin zone was implemented with 11×11×1 k-meshes grid. A kinetic energy
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cutoff of 500 eV was selected for the plane-wave basis set. To ensure the
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convergence of calculations, we applied energy and force thresholds of 10-7 eV

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and 0.001 eV/Å, respectively.

The elastic properties of the HfXY monolayers were determined using the

stress–strain method, which was implemented through the VASPKIT code[55].

To assess the thermal stabilities of the Janus HfXY monolayers at temperatures

of 300 K and 600 K based on 5×5×1 sized supercell, the ab initio molecular

dynamics (AIMD) simulations were performed. The simulation time was 6 ps (1

fs per step) using an NVT ensemble with a Nose–Hoover thermostat.

6
 The phonon transport properties, including the lattice thermal conductivity,

were assessed using the ShengBTE code [56] with second-order, third-order and

four-order interatomic force constants (IFCs) as inputs. The phonon dispersions

and second-order IFCs were obtained with the PHONOPY packages[57], the

third-order IFCs were obtained by considering the third nearest neighbors with

the thirdorder.py code [58], and the four-order IFCs were obtained considering

the first nearest neighbors using the tourthorder.py code[59]. To ensure the

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convergence, the 4 × 4 × 1 sized supercells were employed in these IFC

r
-p
calculations, along with a Γ-centred k-point mesh of 4 × 4 × 1. After conducting
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a convergence test for the q-grid, a 21 × 21 × 1 q-grid was chosen to ensure the
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satisfactory convergence of lattice thermal conductivity.

The electrical transport properties, including the Seebeck coefficient (S),

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electrical conductivity over the relaxation time (σ/τ), and electrical thermal
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conductivity over the relaxation time (κe/τ), were obtained using the BoltzTraP2
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code based on the semiclassical Boltzmann theory with a 23 × 23 × 1 Γ-centred

k-point[60, 61]. The relaxation time was calculated based on the deformation

potential theory[48]. This approximation was deemed valid not only because the

relaxation time remains relatively stable within the energy scale of KBT[62], but

also it can be successfully employed to assess the thermoelectric properties of

many materials with acceptable accuracy[63].

3. Results and discussion

7
3.1 Structural stability

The initial structures of the 2D Janus HfXY monolayers were constructed

from the data presented in the Computational 2D Materials Database (C2DB)[64,

65]. After optimizing these structures, we obtained the top and side views of

relaxed structures with space group P3m1 (No. 156), as depicted in Fig. 1 (a)

and (b). In these structures, each hafnium (Hf) atomic is sandwiched between

atomic X and Y, forming X–M–Y configuration by strong intra-layer chemical

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bonding. The high-symmetry path in the first Brillouin zone is presented in Fig.

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-p
1 (c), where the path Γ–M–K–Γ is used within the first Brillouin zone of the
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primitive cell. Table 1 lists the optimized lattice parameters and bond lengths by
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PBE of the Janus HfXY monolayers. The lattice constants a of the HfBrCl, HfClI

and HfBrI monolayers are 3.43, 3.58 and 3.64 Å, respectively, in the order of
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aHfBrI > aHfClI > aHfBrCl, showing that the lattice would be larger in response to
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the growing of atomic number. Additionally, it's noteworthy that the bond length
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of Hf-Cl in HfBrCl, and HfClI is almost the same.

Table 1 The optimized parameters by PBE: lattice constants (a, b), bond length (d), elastic

coefficients (C11 = C22, C12) and elastic modulus Y of the Janus HfXY monolayers.

Material a=b(Å) dHf−X (Å) dHf−Y (Å) C11=C22 (N/m) C12 (N/m) Y(N/m)

HfBrCl 3.43,3.42a 2.67,2.61a 2.77,2.72a 88.60 70.41 32.65

HfClI 3.58 2.69 2.94 80.41 65.56 26.86

HfBrI 3.64 2.82 2.95 73.13 60.13 23.69

8
a
Obtained by Mezher et al [47].

Typically, there are several guidelines used to assess the stability of the materials,

and describe the realizability of predicted 2D materials[66, 67]: To verify the

dynamical stability of the HfXY monolayers, phonon dispersions spectra are

calculated with the PHONOPY packages[57], and the results are shown in Fig.

2. The absence of imaginary frequencies in the phonon modes indicate all of

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these monolayers are dynamically stable[67]. The thermal stability of the

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-p
monolayers is tested through AIMD simulations. As shown in Fig. 3, no broken
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bonds or obvious structural reconstructions are observed, indicating that HfXY
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monolayers can maintain their initial configurations within a narrow energy

range even at temperatures as high as 600 K.

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The calculated elastic stiffness values obtained through the stress–strain

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method listed in Table 1, satisfy the Born mechanical stability criteria[68] (𝐶11 >
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0 and 𝐶11 > |𝐶12 |) , indicating the mechanical stability of the HfXY

monolayers. The values of Young’s modulus Y follow the order of HfBrCl <

HfClI < HfBrI, indicating that the HfXY monolayers become increasingly brittle

with the rise in atomic number of X/Y. It's noteworthy that the value of Y is

smaller than that of graphene (344 N/m) [69] and h-MoS2 (200 N/m) [70],

indicating the HfXY monolayers possess greater mechanical flexibility.

To validate the thermodynamic stability of these Janus HfXY monolayers,

the cohesive energy can be calculated as the following formula [71]:

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 N Hf EHf + N X E X + NY EY − Etot
Ecoh = (1)
N Hf + N X + NY

where Etot is the total static energy of the specialized monolayer, and E Hf , E X , and

EY represent the single-atom energy of Hf, X, and Y atoms (X, Y = Cl, Br, I),

respectively. N Hf , N X , and N Y are the total numbers of Hf, X, and Y atoms in the

unit cell. The obtained cohesive energies are 3.93 eV, 3.53 eV, and 3.29 eV for HfBrCl,

HfBrI, and HfClI, respectively. These values are close to those of the experimentally

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existing phosphorene (3.22-3.43 eV)[72] and Janus SPtSe (3.56 eV) [73],

demonstrating the energetic stability of the Janus HfXY monolayers.

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3.2 Electronic structures
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The electronic structures are critical to the carrier mobility and electronic
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conductivity, which are calculated by using different density functionals, as

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shown in Fig. S1 (ESI†). Table 2 provides the band gaps of these HfXY
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monolayers. The results reveal that all monolayers are indirect band gaps
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semiconductors. Due to the heavy element Hf, spin orbit coupling (SOC) effect

has been considered and a spin splitting at VBM and CBM has been observed as

shown in the Fig. 4. For this reason, the influence of SOC effect is considered to

compute the electronic transport properties. For a more detailed view of the

electronic properties, Fig. 5 illustrates the projected band structures obtained at

the PBE+SOC level. It can be observed that the VBMs and CBMs of the three

materials are mainly composed of the d-orbitals of Hf atoms.

PBE PBE + SOC HSE06

Table 2 The band gaps from PBE (𝐸gap ), PBE + SOC (𝐸gap ), HSE06 (𝐸gap ), HSE06 +

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 HSE06 + SOC
SOC (𝐸gap ) methods for the Janus HfXY monolayers.

PBE PBE+ SOC HSE06 HSE06+SOC

Materials 𝐸gap (eV) 𝐸gap (eV) 𝐸gap (eV) 𝐸gap (eV)

HfBrCl 0.91 0.79 1.44 1.36

HfClI 0.91 0.76 1.36 1.28

HfBrI 0.80 0.66 1.30 1.18

To get the bonding information, the electron localization function (ELF)

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and Bader charge of the HfXY monolayers were analyzed. As shown in Fig. 6,

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the ELF values of Hf-X and Hf-Y bonds do not exceed 0.50, indicating the HfXY
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monolayers exhibit ionic compound characteristics[74]. To gain deeper insights
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into the ionic properties, Bader charge calculations are performed, and the results
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are listed in Table 3. These results reveal that the central Hf atom loses charge,

while the other atoms gain charge. More charge transfer means higher ionic
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nature in the bonding. The electron affinities of the atoms are in the order
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Cl>Br>I as the electronegativities, indicating the ionic character in the bonds

following the sequence Hf-I < Hf-Br < Hf-Cl.

Table 3 Bader charge on Hf, I, Br and Cl atoms in the HfXY monolayers.

Materials Hf I Br Cl

HfBrCl +1.33 e — -0.62 e -0.71 e

HfClI +1.28 e -0.58 e — -0.70 e

HfBrI +1.23 e -0.60e -0.63 e —

11
3.3 Phonon transport properties

For 2D materials, the zcell/zeff correction is applied to the lattice thermal

conductivity results, where zcell is the unit cell length along the z-direction, and

zeff is the effective thickness of the 2D materials[75]. The effective thickness,

which includes both the monolayer thickness and the van der Waals radius of

surface atoms, is estimated to be 2.50 Å, 2.38 Å, and 2.41 Å for the Janus

HfBrCl, HfBrI, and HfClI monolayers, respectively. The rescaled lattice thermal

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conductivity κlat of the Janus HfXY monolayers obtained by the ShengBTE

r
-p
code[56] is plotted in Fig. 7 across a temperature range of 300 K to 900 K. As
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temperature increases, κlat decreases due to enhanced phonon-phonon
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scattering[76]. On account of the inherent enhancement of phonon–phonon

scattering versus temperature, the κlat of the Janus HfXY monolayers are
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proportional to 1/T. At 300 K, the value of the rescaled lattice thermal

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conductivity for the HfBrCl, HfBrI, and HfClI monolayers are 22.38 W/mK,
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11.86 W/mK, 7.79 W/mK, respectively. These values are considerably lower

compared to those of monolayers compared to ZrBrCl, MoSe2, and PtS2 (with

κlat of 76.94 W/mK, 61.80 W/mK, and 54.25 W/mK, respectively) [77, 78], and

close to the thermal conductivity value of the PtSe2 monolayer, which is 18.07

W/mK [79]. These findings indicating that the Janus HfXY monolayers satisfy

the initial requirements as thermoelectric materials.

Fig. 8 shows the relative contribution of each mode to the total κlat of the

monolayers. It can be found that the total contributions of the all acoustic

12
branches (ZA, TA, and LA) far surpass those of the optical branches. When

comparing HfBrCl and HfBrI monolayers, it becomes apparent that the

contributions from the TA and ZA modes are fairly similar. However, for the

HfClI monolayers, the TA branch plays a dominant role, contributing as much as

58.30% to the total κlat. Among these three materials, the lattice thermal

conductivity of HfClI contributed by the ZA branch is minimized, which is the

main reason why the lattice thermal conductivity of HfClI is the smallest.

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To gain a deeper understanding in the principles, the group velocity and the

r
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scattering rates at 300 K are further analyzed. As presented in Fig. 9(a), all of the
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modes exhibit relatively similar group velocities, accompanying the overlaps of
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the low-frequency regions. The Janus HfBrCl, HfBrI, and HfClI monolayers

exhibit maximum group velocities of 2.45 km/s, 2.04 km/s, and 2.06 km/s,
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respectively. As HfBrI has heavier atoms in comparison to HfBrCl and HfClI,

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which makes the material have a lower group velocity. Fig. 9(b) illustrates the
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scattering rates at 300 K, revealing a predominance of acoustic phonons in the

low-frequency range. Since the scattering rate is inversely proportional to the

lattice thermal conductivity, the comparison indicates the lattice thermal

conductivity of the Janus HCII is the lowest among these materials.

3.4 Electronic transport and thermoelectric properties

The electrical transport coefficients were obtained using the BoltzTraP2

code based on the semiclassical Boltzmann theory [61, 62], which relies on

13
constant relaxation time. The relaxation time (τ) is estimated through the

 md*
expression:  = . According to the Bardeen−Shockley deformation
e

potential theory [80], the carrier mobility μ is approximated for 2D materials by

e 3C2 D
the formula [81-83]: 2 D = , where ħ is the reduced Planck constant,
md* m*k BTE12

𝑘B is the Boltzmann constant, T is the temperature. The effective mass of the

carrier 𝑚∗ can been obtained from fitting parabolic functions to the band edge

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states actualized by the VASPKIT code [55], and md* = m*x m*y is the average

r
-p 1 2 E
effective mass. C2D is the elastic modulus and defined as C2 D = , where
So  2
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S o is the area of unit cell and E is the total energy after applying the uniaxial
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strain 𝜀 from –2% to +2%. E1 is the deformation potential constant which can
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Eedge
be obtained by taking partial derivatives with band edges via E1 = , where

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Eedge is the energy of the VBM/CBM and depends on a slight strain. Combined
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the μ2D and md*, the τ can be obtained. The main results are listed in Table 4,

and the fitted functions of C2D and E1 are shown in Fig. S2 and S3 (ESI†).

The calculations reveal that the n-type HfXY monolayers exhibit ultrahigh

carrier mobilities, ranging from 1220 cm2/sV to 4289 cm2/sV, primarily due to

low deformation potential. Such ultrahigh carrier mobilities also imply good

thermoelectric performance for the n-type HfXY monolayers.

Table 4 For electron and hole carriers, the deformation potential constant (E1), elastic

14
modulus (C2D), calculated effective mass (m*), carrier mobility (μ), and relaxation time (𝜏)

of the Janus HfXY monolayers at 300 K along the x and y directions.

Materials Carrier E1 (eV) C2D (N/m) m* (mo) μ (cm2 /sV) 𝜏(fs)

HfBrCl n(x) -1.64 91.40 0.78 1334 592

p(x) -2.28 91.40 0.40 2401 546

n(y) -1.34 91.34 0.62 2513 886

f
p(y) -2.28 91.34 0.38 2526 546

oo
HfClI n(x) -1.50 83.05 0.84 1220 583

r
p(x) -2.44 -p
83.05 0.43 1646 402
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n(y) -1.03 83.05 0.70 3106 1236
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p(y) -2.46 83.05 0.41 1698 396

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HfBrI n(x) -1.36 77.05 0.74 1862 784

p(x) -2.55 77.05 0.36 2004 410

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n(y) -1.03 77.02 0.56 4289 1366

p(y) -2.55 77.02 0.34 2121 410

Considering the high thermodynamic stabilities of Janus HfXY (X≠Y,

X/Y=Cl, Br, I) monolayers at 600 K, the electronic transport coefficients as a

function of the carrier (electron and hole) concentrations are calculated for the

temperature range of 300–600 K. As depicted in Fig. 10 (a)-(f), the absolute S

(|S|) display nearly linear decline with the carrier concentrations increasing. For

each Janus material, the higher Seebeck coefficient for n-type doping suggests a

15
more efficient thermoelectric performance, compared to that for p-type doping.

The calculated highest |S| values for n-type of the Janus HfBrCl, HfBrI, and

HfClI monolayers are 672.69 uV/K, 675.06 uV/K and 668.00 uV/K, at a carrier

concentration of 7.41 × 1012 cm−2, 6.13 × 1012 cm−2, and 7.62 × 1012 cm−2,

respectively. Overall, the |S| value is one of the important parameters to affect

the thermoelectric properties, and a larger |S| usually means a better

thermoelectric performance.

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Furthermore, we have estimated the electrical conductivity (σ), as shown

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-p
in Fig. S4 (ESI†). The σ become larger with increasing carrier concentrations for
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all these Janus monolayers, and this trend is exactly opposite to that of |S|.
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Furthermore, we have obtained the electronic thermal conductivity using the

BoltzTraP2 code [61]. As shown in Fig. S5 (ESI†), the variation in κe with the
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carrier concentration follows the same trend as σ.

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Since S and σ show a competitive relationship, the dynamic values of power

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factor PF (S2σ) are adopted as a descriptor to determine the TE performance. The

PF changes of both electrons and holes at a given temperature are exhibited in

Fig. 10 (g)-(l). The findings reveal that the power factor (PF) for p-type doping

increases, reaching a maximum value of 43.14 mW/mK at a carrier concentration

of 7.82 × 1014 cm−2. This escalation can be primarily attributed to the

augmentation of electrical conductivity σ. However, as carrier concentrations

surge beyond 3.05 × 1015 cm−2, the PF values subsequently decrease. This

decline is mainly due to the dominant suppression of the Seebeck coefficient (S)

16
under these higher carrier concentration conditions. In comparison to hole

carriers, the electron carriers exhibit slightly higher PF values. The values of PF

for electron carriers between 58.20 mW/mK2 and 247.40 mW/mK2 as the

temperature changed from 300 to 600 K. At 300 K, the highest PF values for n-

type of the Janus HfBrCl (126.30 mW/mK2), HfBrI (247.40 mW/mK2), and

HfClI (184.0 mW/mK2) monolayers are larger than those of the HfS2 (50.80

mW/mK2), HfSe2 (36.20 mW/mK2), and HfSSe (39.60 mW/mK2) [43],

f
oo
indicating the superior thermoelectric performance of the Janus HfXY (X≠Y,

r
X/Y=Cl, Br, I) monolayers. -p
re
Combining all the gained electronic and phonon transport coefficients, the
lP

zT values for the Janus HfXY monolayers can be predicted. As plotted in Fig. 11,

similar to the PF, the zT values initially increase with carrier concentrations
na

firstly and then decrease due to the opposite trends of S and σ. The optimal
ur

thermoelectric parameters at different temperatures are listed in Table 5. Notably,

Jo

the high optimal PF value combined with low thermal conductivity leads to a

high zT value. For n-type doping at 300 K, the maximum zT values are 0.86

(0.88), 1.62 (1.80) and 1.67 (2.15) at the carrier concentrations of 6.42 × 1014

cm−2 (4.28 × 1014 cm−2), 3.88 × 1014 cm−2 (3.88 × 1014 cm−2) and 2.69 × 1014

cm−2 (2.69 × 1014 cm−2), along the x(y)-direction for the Janus HfBrCl, HfBrI

and HfClI monolayers, respectively. These values can increase to 2.65 (2.65),

4.20 (4.80) and 3.83 (4.60) at 600 K at the carrier concentrations of 6.09 × 1014

cm−2 (6.09 × 1014 cm−2), 3.44 × 1014 cm−2 (3.44 × 1014 cm−2) and 5.51 × 1014

17
cm−2 (3.45 × 1014 cm−2). The optimal zT values of the Janus HfXY (X≠Y,

X/Y=Cl, Br, I) monolayers are larger than those of the HfS2 (0.68), HfSe2 (0.70),

and HfSSe (0.63) at 300 K [43], indicating their superior thermoelectric

performance.

In general, the value of zT is influenced by many factors, including the

power factor, lattice thermal conductivity, and carrier mobility. For the Janus

HfXY monolayers, the influence of the higher electron carrier mobility result in

f
oo
good power factor. The maximum zT values for the Janus HfBrCl, HfBrI and

r
-p
HfClI monolayers are 2.65, 4.80, and 4.60 at 600 K, respectively. According to
re
the criteria for good thermoelectric materials (zT = ~1.00) [84], these Janus
lP

HfXY (X≠Y, X/Y=Cl, Br, I) monolayers are excellent thermoelectric materials

at medium temperature.
na
ur

Table 5 The optimal zT value of the Janus HfXY (X≠Y, X/Y=Cl, Br, I) monolayers at 300
Jo

K, 500 K and 600 K.

Materials Directions Carrier types zT (300 K) zT (500 K) zT (600 K)

HfBrCl x n 0.87 2.05 2.65

p 0.35 0.82 1.14

y n 0.88 1.91 2.65

p 0.32 0.80 1.06

HfClI x n 1.67 2.95 3.83

p 0.54 1.10 1.51

18
 y n 2.15 1.97 4.60

p 0.53 1.02 1.50

HfBrI x n 1.62 3.30 4.20

p 0.38 0.93 1.03

y n 1.80 3.87 4.80

p 0.41 0.88 1.23

f
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4. Conclusions -p
re
In summary, we have conducted a comprehensive investigation into the
lP

electronic, thermal and thermoelectric performances of Janus HfXY (X≠Y,

na

X/Y=Cl, Br, I) monolayers. Our findings indicate that these monolayers exhibit

thermally, dynamically, and mechanically stability. The electronic structure

ur

calculations reveal that these materials exhibit semiconductor characteristics,

Jo

with indirect HSE06 band gaps ranging from 1.18 eV to 1.36 eV when

accounting for the spin-coupling effect. Meanwhile, at 300 K, their small phonon

group velocities and low converged scattering rates result in low lattice thermal

conductivities of 22.38 W/mK for the Janus HfBrCl, 11.86 W/mK for the Janus

HfBrI, and 7.79 W/mK for the Janus HfClI. These values compare favorably to

extensively used transition metal dichalcogenides (TMDCs). Notably, their

higher electron carrier mobilities (1382-5344 cm2/sV) result in their better power

factor parameters ranging from 58.20 mW/mK2 to 247.40 mW/mK2, over the

19
temperature range of 300 to 600 K. The combined effect of low thermal

conductivities and the higher power factors results in superior TE performances

for the Janus HfXY monolayers. The Janus HfBrCl, HfBrI and HfClI monolayers

demonstrate zT values for n-type doping, reaching 0.87 (0.86), 1.23 (1.60), and

1.60 (1.81) along the x (y) direction at 300 K, respectively. These calculated

thermoelectric figure of merit values surpass those of Hafnium-based TMDCs.

The ultra-high zT values indicate that the Janus HfXY (X≠Y, X/Y=Cl, Br, I)

f
oo
monolayers hold significant promise for high-performance thermoelectric

r
applications. -p
re
lP

CRediT authorship contribution statement

Shi-Jia Huang: Investigation, Methodology, Writing –original draft, Writing –

na

review & editing. Tian Zhang: Writing–review & editing. Zhao-Yi Zeng: Methodology,
ur

Writing – review & editing, Supervision. Hua-Yun Geng: Project administration,

Jo

Software. Xiang-Rong Chen: Visualization, Supervision, Project administration.

Acknowledgments

This work was supported by the National Natural Science Foundation of China

(Grant Nos. 12074274, 12004269).

Conflicts of interest

There are no conflicts of interest to declare.

20
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 f
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Fig. 1 (Color online) (a) Top view and (b) side view of the Janus HfXY (X≠Y, X/Y=Cl, Br, I)
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monolayers. The yellow, brown and green balls mean Hf, X and Y atoms in materials, respectively.
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The red background shows a hexagonal primitive cell in the 5 × 5 × 1 sized supercell and the blue

background shows a square cell that denotes the armchair and zigzag directions. (c) The first

Brillouin zone of the conventional cell with the high symmetry path Γ-M-K-Γ.

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Fig. 2 (Color online) Phonon dispersion curves of the (a) HfBrCl (red line), (b) HfBrI (green line)

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and (c) HfClI (blue line) monolayers along the high symmetry path Γ-M-K-Γ.

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Fig. 3 (Color online) Evolution of potential energy with respect to simulation time at (a) 300 K and

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(b) 600 K for the HfBrCl (red line), HfBrI (green line) and HfClI (blue line) monolayers with
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6 ps (1 fs per step) simulation time.
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Fig. 4 (Color online) Electronic band structures of monolayer (a) HfBrCl (b) HfBrI and (c) HfClI

along Γ-M-K-Γ path without SOC (black lines) and with SOC (red lines).

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Fig. 5 (Color online) Projected band structures of (a) HfBrCl (b) HfBrI and (c) HfClI monolayers

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along Γ-M-K-Γ path from the PBE +SOC level.

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Fig. 6 (Color online) The electron localization function of (a) HfBrCl (b) HfBrI and (c) HfClI
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monolayers on the (110) plane. The gamut bars with values from 0.0 to 1.0 in a step size of 0.5
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indicate the degree of delocalization of the electrons. Blue indicates no localization, and red
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indicates perfect localization.

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Fig. 7 (Color online) Rescaled lattice thermal conductivities of HfBrCl (red line), HfBrI
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(green line) and HfClI (blue line) monolayers across a temperature range of 300 K to 900

K.
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Fig. 8 (Color online) Calculated contributions of acoustic (ZA, TA, and LA) and optical

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branches of the Janus HfXY monolayers to their total thermal conductivity at 300 K.
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Fig. 9 (Color online) Calculate (a) group velocity and (b)converged scatting rate at 300 K of

the Janus HfBrCl, HfBrI and HfClI monolayers.

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Fig. 10 (Color online) Calculated (a)-(f) Seebeck coefficient and (g)-(l) power factor

depending on the carrier concentrations of the Janus HfXY monolayers along the x and y

directions at 300 K (red lines), 500 K (green lines), and 600 K (blue lines) for p-doping type

(hole) and n-doping type (electron) cases.

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Fig. 11 (Color online) Calculated figure of merit depending on the carrier concentrations of
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the Janus HfXY monolayers along the x and y directions at 300 K (red lines), 500 K (green
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lines), and 600 K (blue lines) for p-doping type (hole) and n-doping type (electron) cases.
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 Highlights for

Density functional theory prediction of thermoelectric

properties of two-dimensional Janus HfXY (X≠Y,
X/Y=Cl, Br, I) monolayers with high carrier mobilities
Shi-Jia Huang 1, Tian Zhang 2, Zhao-Yi Zeng3,*, Hua-Yun Geng 4, Xiang-Rong Chen 1,*

1
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China;

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2
College of Physics and Electronic Engineering, Sichuan Normal University, Chengdu

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610066, China;

College of Physics and Electronic Engineering, Chongqing Normal University, Chongqing

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401331, China；
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4
National Key Laboratory for Shock Wave and Detonation Physics Research, Institute of Fluid
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Physics, CAEP, Mianyang 621900, China

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Our predictions reveal 2D Janus HfXY (X≠Y, X/Y=Cl, Br, I) monolayer materials exhibit

dynamic, thermal and mechanical stabilities. These materials are predicted to have higher

electron carrier mobilities ranging from 1220 cm 2/sV to 4289 cm2/sV, surpassing the

majority of other 2D materials. The enhanced electron carrier mobility result in good n-type

power factor parameters, ranging from 58.20 mW/mK2 to 247.40 mW/mK2. Such merits of

lower thermal conductivities and higher power factor parameters endow these monolayers

with the large figure of merit (zT) values for n-doping types along x (y) directions: 0.87 (0.88)

* Corresponding authors. E-mail: zhaoyizeng@cqnu.edu.cn; xrchen@scu.edu.cn

for Janus HfBrCl, 1.62 (1.80) for Janus HfBrI, and 1.67 (2.15) for Janus HfClI at 300 K.

These calculated thermoelectric figure of merit values surpass those of Hafnium-based

TMDCs. Our study highlights the prospects of 2D Janus HfXY (X≠Y, X/Y=Cl, Br, I)

monolayers as contenders for applications in thermoelectric conversion devices.

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Conflicts of interest

There are no conflicts of interest to declare.

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