1
Synergistic effects of Ag-Bi co-doping on thermoelectric properties of Mg2Si0.3Sn0.7 solid solutions
Assahsahi, I; Galatanu, A; El Bouayadi, R; Zejli, D; Popescu, B
SEP 10 2025, JOURNAL OF ALLOYS AND COMPOUNDS, 1039, 183310
DOI: 10.1016/j.jallcom.2025.183310
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Mg2Si1-xSnx solid solutions are promising thermoelectric materials due to the inexpensive and abundant nature of their components, their environmental friendliness and their flexibility in terms of optimising their thermoelectric properties. In this study, we report on the thermoelectric properties enhancement of n-type Mg2Si0.3Sn0.7 solid solutions doped with aliovalent elements, donor (Bi) and acceptor (Ag), respectively. Samples were synthesized via conventional melting followed by spark plasma sintering. Co-doping led to carrier concentration and mobility tuning, resulting in a significantly increased Seebeck coefficient while maintaining high electrical conductivity. Consequently, the power factor reached 44.67 x 10(-3) Wm(-)(1) K-2 at 650 K for Mg1.98Ag0.02Si0.29Sn0.69Bi0.02. Furthermore, lattice thermal conductivity was reduced via enhanced phonon scattering caused by point defects and suppressed bipolar conductivity attributed to a widened band gap and increased carrier density. The combined effects yielded improved ZT values, peaking at 1.12 at 674 K and 1.13 at 721 K for Mg1.99Ag0.01Si0.29Sn0.69Bi0.02 and Mg1.98Ag0.02Si0.29Sn0.69Bi0.02, respectively. These results highlight the potential of Ag-Bi co-doping as a robust strategy to enhance the thermoelectric efficiency of Mg2Si1-xSnx based materials.
2
Improved sulfurization process for enhancing the microstructure and transport properties of spray pyrolysis-deposited Cu2ZnSnS4 films
El Khouja, O; Popescu, B; Assahsahi, I; Negrila, CC; Leonat, LN; Nouneh, K; Touhami, ME; Galatanu, A; Galca, AC
NOV 2025, CERAMICS INTERNATIONAL, 51
DOI: 10.1016/j.ceramint.2025.08.041
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Cu2ZnSnS4 (CZTS) is an emerging material with significant potential as an absorber layer for solar cells. Precise control over the film preparation process is crucial for attaining optimal transport, electrical, and optical properties. This study investigates the effect of sulfurization duration on the properties of CZTS films deposited onto soda lime glass substrates via spray pyrolysis, followed by annealing at 550 degrees C in a sulfur-rich environment under argon flow. X-ray diffraction and Raman spectroscopy confirmed the formation of monophasic CZTS, with the highest phase purity observed for films sulfurized for 5 min. Scanning electron microscopy demonstrated notable morphological and microstructural enhancements due to the sulfurization process, while energydispersive spectroscopy confirmed near-ideal stoichiometric composition (Cu:Zn:Sn:S approximate to 2:1:1:4). Optical spectroscopy determined the band gap of the films to be between 1.40 and 1.50 eV. The electrical transport properties were investigated up to 130 degrees C, revealing p-type conductivity, with Seebeck coefficients ranging from 30 to 70 mu V K-2 and low electrical resistivity, displaying semiconductor-like behavior. The maximum power factor achieved was 0.36 mu W mK-2 at 130 degrees C for the sample sulfurized for 5 min. These findings suggest that a 5-min sulfurization time is optimal for producing single-phase CZTS films characterized by uniform morphology, accurate stoichiometric composition, and an ideal direct band gap. Given its favorable thermoelectric properties, CZTS shows significant promise as a material for thermoelectric applications, particularly in waste heat recovery systems. The results indicate that CZTS films could be further optimized for use in thermoelectric devices, and future studies could focus on enhancing their thermoelectric performance by adjusting sulfurization conditions and exploring material modifications.
3
Influence of synthesis method and processing on the thermoelectric properties of CoSb3 skutterudites
Kumar, MU; Swetha, R; Sahana, BV; Kuri, RS; Popescu, B; Assahsahi, I; Kumari, L
MAR 2024, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 35, 514
DOI: 10.1007/s10854-024-12277-1
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In the present work, single phase CoSb3 skutterudite nanomaterials were prepared via a ball milling method, and their thermoelectric characteristics were compared with the samples synthesized by the solvo-hydrothermal method. Thermoelectric transport properties were recorded in the temperature regime of 300-830 K. Both samples exhibit p-type conduction behavior with a positive sign of Seebeck coefficient. CoSb3 ball mill sample exhibit higher resistivity of 127 x 10(-5)Omega.m at 300 K as compared to CoSb3 solvo-hydrothermal sample with 4.85 x 10(-5)Omega.m. However, CoSb3 ball mill sample show enhanced Seebeck coefficient of 183 mu V/K at 473 K where CoSb3 solvo-hydrothermal sample depict 98 mu V/K at 650 K. Furthermore, the total thermal conductivity of sintered CoSb3 ball mill and CoSb3 solvo-hydrothermal samples was found to be 3.02 Wm(-1)K(-1) and 3.23 W m(-1)K(-1) at room temperature and reaches a significantly lower value of 2.47 W m(-1)K(-1) and 2.46 W m(-1)K(-1) at 580 and 670 K, respectively. The dimensionless figure of merit ZT values of CoSb3 ball mill and CoSb3 solvo-hydrothermal obtained are 0.053 and 0.060 at 650 and 700 K, respectively. A systematic tuning of processing parameters by ball milling method can lead to better thermoelectric efficiency.
4 Open Access
Effects of Ti and Sn Substitutions on Magnetic and Transport Properties of the TiFe2Sn Full Heusler Compound
Popescu, B; Assahsahi, I; Galatanu, M; Galatanu, A
DEC 2024, INORGANICS, 12, 322
DOI: 10.3390/inorganics12120322
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The synthesis of polycrystalline TiFe2Sn samples by a route including arc melting and spark plasma sintering with Hf, Y, and In substitutions at the Ti and Sn sites is investigated. For a reduced amount of substitution, around 2 at%, the samples are single phase, while for increased amounts, secondary phases segregate. As is characteristic of these compounds, the Fe-Ti atomic disorder generates a weak ferromagnetic ordering, which is also influenced by the type of substitutional atoms and the secondary phases in the samples with a higher Hf content. The Seebeck coefficient values show an increase for Ti0.98Hf0.02Fe2Sn and for samples with an adjusted Sn content, resulting in slightly increased power factor values. These values reach a maximum for Ti0.98Hf0.02Fe2Sn at approximately 300 K and for TiFe2Sn1.05 at approximately 325 K, namely, 2.69 x 10(-)(4) Wm(-1)K(-2) and 2.52 x 10(-)(4) Wm(-1)K(-2), respectively. The thermal conductivity of all the samples with substitutions increases with respect to the pristine sample. The highest figure of merit value of 0.016 is also obtained for Ti0.98Hf0.02Fe2Sn at 325 K.
5 Open Access
Structural, Magnetic, and Transport Properties of Ti(Fe,Re)2Sn Heusler Alloys
Assahsahi, I; Popescu, B
DEC 2024, METALLURGICAL AND MATERIALS TRANSACTIONS A-PHYSICAL METALLURGY AND MATERIALS SCIENCE, 55
DOI: 10.1007/s11661-024-07619-x
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This study investigates polycrystalline samples of TiFe2-xRexSn (with x = {0, 0.02, 0.04, 0.06, 0.2}) synthesized using conventional arc-melting and spark plasma sintering. Structural and morphological analysis shows that low Re substitutions result in good phase purity with minor traces of secondary phases, while higher Re content leads to the segregation of additional phases. The magnetism and electrical resistivity of the samples are affected by inherent Fe-Ti atomic disorder, with the effects of secondary phases becoming more prominent in the samples with higher Re content. The Seebeck coefficient values increase only for TiFe1.98Re0.02Sn, while the power factor increases for x = {0, 0.02, 0.04}, reaching maximal values for x = 0.02 at similar to 300 K and x = 0.04 at similar to 325 K, i.e., (2.22 +/- 0.2) x 10(-4) Wm(-1) K-2. The thermal conductivity of the samples increases with x, resulting in modest values of the figure of merit, with the maximum achieved for x = 0.02 at 325 K, i.e., 0.015 +/- 0.002. (c) The Author(s) 2024
6
Possible reduction of lattice thermal conductivity in n-type CoSb2.875Te0.125 skutterudite originating from collaborative adjustment between Indium micro and α-WC nano inclusions
Kumar, MU; Swetha, R; Sahana, BV; Kuri, RS; Popescu, B; Assahsahi, I; Kumari, L
OCT 2024, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 35, 1960
DOI: 10.1007/s10854-024-13713-y
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In this work, single-phase Te-doped CoSb3 polycrystalline bulk (Indium powder) and nanocomposites (alpha-WC nanopowder) were synthesized via a ball milling, hand-grinding and consolidated by spark plasma sintering technique. The thermoelectric and mechanical characteristics of as-synthesized composites were studied. The electrical resistivity varies between 11.82 and 12.82 mu Omega-m for CoSb2.875Te0.125 + x (x = 0.33% In, 1% In, 2% In, 4% In and 1% In + 0.33% alpha-WC, respectively) composites. At temperature of 300 K, composite with x = 1% In exhibit the lowest resistivity of 11.82 mu Omega-m. Also, negative values of Seebeck coefficients confirm that electrons are the predominant charge carriers. The maximum power factor of 2566 and 2482 mu Wm-1 K-2 are observed from x = 1% In and x = 1% In + 0.33% alpha-WC composites at 673 K, respectively. Notably, the power factor of 1% In and 1% In + 0.33% alpha-WC composites is slightly higher (1.05 times) than the CoSb2.875Te0.125 sample. The composites with lowest weight percent of 1% In and 1% In + 0.33% alpha-WC have a considerably improved power factor. For the composite with x = 1% In + 0.33% alpha-WC, the minimum thermal conductivity of 2.32 W/m-K at 300 K was achieved through a combination of doping and dispersion in the CoSb2.875Te0.125 matrix. It is possible that the multi-scale size distributions of grains will reduce the lattice thermal conductivity by scattering phonons over a large wavelength range. As a result, an increased figure of merit of 0.82 was achieved for CoSb2.875Te0.125 + 1% In + 0.33% alpha-WC composites at 823 K. The results suggest that the doping with composite approach could boost thermoelectric efficiency in n-type CoSb3-based materials.
7
Thermoelectric properties of p-type Mg2Si0.3Sn0.7 doped with silver and gallium
Assahsahi, I; Popescu, B; El Bouayadi, R; Zejli, D; Enculescu, M; Galatanu, A
MAY 25 2023, JOURNAL OF ALLOYS AND COMPOUNDS, 944, 169270
DOI: 10.1016/j.jallcom.2023.169270
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Structure, composition, and transport properties of Mg2-xAgx(Si0.3Sn0.7)1-yGay (x = {0, 0.021, y = {0, 0.02, 0.04, 0.061) solid solutions produced by melting followed by spark plasma sintering are investigated. The preparation method is adjusted to control sample stoichiometry and phase composition. Doping with two types of dopants at different sites, while employing synthesis methods which generate a small amount of secondary phase, is an uncommon approach in this materials, expected to enhance their thermoelectric performance. An enhanced carrier concentration but diminished mobility is observed in the samples with higher amounts of dopant, which leads to the highest values of the power factor, for Mg1.98Ag0.02Si0.27Sn0.67Ga0.06 in a narrow temperature range (575-675 K) around the peak value, of 9.10-4 Wm-1 K-2 at 625 K. The two types of dopants have opposing effects on the thermal conductivity, with Ag promoting strong phonon scattering and decreasing its values while Ga increases them because of its en-hanced carrier concentration. The rather high thermal conductivity values of the double doped compounds produce low values of the ZT without exceeding 0.29 at 627 K for Mg1.98Ag0.02Si0.3Sn0.7 sample.(c) 2023 Elsevier B.V. All rights reserved.
8
Structural and transport properties of Cu2CoSnS4 films prepared by spray pyrolysis
El Khouja, O; Assahsahi, I; Nouneh, K; Touhami, ME; Secu, M; Talbi, A; Khaaissa, Y; Matei, E; Stancu, V; Galatanu, A; Galca, AC
NOV 1 2022, CERAMICS INTERNATIONAL, 48
DOI: 10.1016/j.ceramint.2022.07.185
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In the present work, stannite Cu2CoSnS4 (CCTS) films were elaborated using spray pyrolysis method on soda-lime glass, at different deposition temperatures (T-d = 250, 300, and 350 degrees C), followed by different chosen sulfurization temperatures (T-s = 450, 500, and 550 degrees C). X-ray diffraction (XRD) revealed the nearly single-phase formation of CCTS films at 300 degrees C deposition temperature. After sulfurization in argon flow, the XRD lines become narrower, the average crystallite size expanding above 70 nm. The Raman spectroscopy analysis confirmed the stannite structure formation, as well as the presence CoS2 secondary phases, which reduces at higher sulfurization temperature (550 degrees C). The energy dispersive spectroscopy results indicated atomic ratios of Cu/Co/Sn/S close to the ideal stoichiometric ratio 2:1:1:4. The room temperature photoluminescence emission is recorded with maximum in the 1.35-1.40 eV range. Thermoelectric properties are measured up to 130 degrees C, the films show poor power factor as a result of small positive Seebeck coefficients 10-45 Of K -1 and low electrical conductivity despite of having relatively high carrier concentration (similar to 10(20) cm(-3)).
9
Influence of the synthesis parameters on the transport properties of Mg2Si0.4Sn0.6 solid solutions produced by melting and spark plasma sintering
Assahsahi, I; Popescu, B; Enculescu, M; Galatanu, M; Galca, AC; El Bouayadi, R; Zejli, D; Galatanu, A
APR 2022, JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS, 163, 110561
DOI: 10.1016/j.jpcs.2021.110561
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In this work, the influence of the preparation route on the structural, morphological, and thermoelectric properties of the Mg2Si0.4Sn0.6 solid solutions is investigated. The synthesis based on melting the constituent elements in a closed graphite crucible followed by spark plasma sintering allows mixing elements with a large difference of their melting temperatures and a good control of sample stoichiometry. The optimized synthesis route is validated by the doped V and Sb samples, which yield good thermoelectric performance. The n-type doping leads to two orders of magnitude increase of the carrier concentration, and thus a subsequent increase of the electrical conductivity, which, in turn, augments greatly the power factor of the Mg1.98V0.02Si0.385Sn0.6Sb0.015 to 42.61 x10(-4) Wm(-1)K 2 at 650K. Although doping slightly enlarges the thermal conductivity, a peak value of the figure of merit ZT similar to 1.15 is obtained at 723K, which is 20 times higher than the ZT of un-doped material.