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1. Examining the electron transport in chalcogenide perovskite BaZrS ₃

   https://doi.org/10.1039/d1tc00374g  

   Osei-Agyemang, Eric; Koratkar, Nikhil; Balasubramanian, Ganesh (March 2021, Journal of Materials Chemistry C)

   null (Ed.)

   Orthorhombic BaZrS 3 is a potential optoelectronic material with prospective applications in photovoltaic and thermoelectric devices. While efforts exist on understanding the effects of elemental substitution and material stability, fundamental knowledge on the electronic transport properties are sparse. We employ first principles calculations to examine the electronic band structure and optical band gap and interrogate the effect of electron transport on electrical and thermal conductivities, and Seebeck coefficient, as a function of temperature and chemical potential. Our results reveal that BaZrS 3 has a band gap of 1.79 eV in proximity of the optimal 1.35 eV recommended for single junction photovoltaics. An absorption coefficient of 3 × 10 5 cm −1 at photon energies of 3 eV is coupled with an early onset to optical absorption at 0.5 eV, significantly below the optical band gap. The carrier effective mass being lower for electrons than holes, we find the Seebeck coefficient to be higher for holes than electrons. A notable (≈1.0 at 300 K) upper limit to the thermoelectric figure of merit, obtained due to high Seebeck coefficient (3000 μV K −1 ) and ultra-low electron thermal conductivity, builds promise for BaZrS 3 as a thermoelectric. 

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2. Enhanced thermoelectric performance of F4-TCNQ doped FASnI ₃ thin films

   https://doi.org/10.1039/D0TA09329G  

   Zheng, Luyao; Zhu, Tao; Li, Yifan; Wu, Haodong; Yi, Chao; Zhu, Jiahua; Gong, Xiong (December 2020, Journal of Materials Chemistry A)

   null (Ed.)

   In the past decade, great efforts have been devoted to the development of organic–inorganic hybrid perovskites for achieving efficient photovoltaics, but less attention has been paid to their thermoelectric applications. In this study, for the first time, we report the thermoelectric performance of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) doped NH 2 CHNH 2 SnI 3 (FASnI 3 ) thin films. It is found that the electrical conductivities of the F4-TCNQ doped FASnI 3 thin films increase and then decrease along with increased doping levels of F4-TCNQ. Systematic studies indicate that enhanced electrical conductivities are attributed to the increased charge carrier concentrations and mobilities and superior film morphologies of the F4-TCNQ doped FASnI 3 thin films, and decreased electrical conductivities originate from the cracks and poor film morphology of the F4-TCNQ doped FASnI 3 thin films induced by excess F4-TCNQ dopants. The quantitative thermal conductivity scanning thermal microscopy studies reveal that the F4-TCNQ doped FASnI 3 thin films exhibit ultralow thermal conductivities. Moreover, the thermoelectric performance of the F4-TCNQ doped FASnI 3 thin films is investigated. It is found that the F4-TCNQ doped FASnI 3 thin films exhibit a Seebeck coefficient of ∼310 μV K −1 , a power factor of ∼130 μW m −1 K −2 and a ZT value of ∼0.19 at room temperature. All these results demonstrate that our studies open a door for exploring cost-effective less-toxic organic–inorganic hybrid perovskites in heat-to-electricity conversion applications at room temperature. 

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3. Modulation of transport properties via S/Br substitution: solvothermal synthesis, crystal structure, and transport properties of Bi ₁₃ S ₁₇ Br ₃

   https://doi.org/10.1039/D2DT02295H  

   Amarasinghe, Dinesh K.; Yox, Philip; Viswanathan, Gayatri; Adeyemi, Adedoyin N.; Kovnir, Kirill (November 2022, Dalton Transactions)

   The solvothermal synthetic exploration of the Bi–S–halogen phase space resulted in the synthesis of two bismuth sulfohalides with common structural motifs. Bi 13 S 18 I 2 was confirmed to have the previously reported composition and crystal structure. In contrast, the bromide analogue was shown to have a formula of neither Bi 19 S 27 Br 3 nor Bi 13 S 18 Br 2 , in contrast to the previous reports. The composition, refined from single crystal X-ray diffraction and confirmed by elemental analysis, high-resolution powder X-ray diffraction, and total scattering, is close to Bi 13 S 17 Br 3 due to the partial S/Br substitution in the framework. Bi 13 S 18 I 2 and Bi 13 S 17 Br 3 are n -type semiconductors with similar optical bandgaps of ∼0.9 eV but different charge and heat transport properties. Due to the framework S/Br disorder, Bi 13 S 17 Br 3 exhibits lower thermal and electrical conductivities than the iodine-containing analogue. The high Seebeck coefficients and ultralow thermal conductivities indicate that the reported bismuth sulfohalides are promising platforms to develop novel thermoelectric materials. 

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4. The impact of site selectivity and disorder on the thermoelectric properties of Yb ₂₁ Mn ₄ Sb ₁₈ solid solutions: Yb ₂₁ Mn _4−x Cd _x Sb ₁₈ and Yb _21−y Ca _y Mn ₄ Sb ₁₈

   https://doi.org/10.1039/d1ma00497b  

   He, Allan; Cerretti, Giacomo; Kauzlarich, Susan M. (August 2021, Materials Advances)

   Thermoelectric materials can convert heat into electricity. They are used to generate electricity when other power sources are not available or to increase energy efficiency by recycling waste heat. The Yb 21 Mn 4 Sb 18 phase was previously shown to have good thermoelectric performance due to its large Seebeck coefficient (∼290 μV K −1 ) and low thermal conductivity (0.4 W m −1 K −1 ). These characteristics stem respectively from the unique [Mn 4 Sb 10 ] 22− subunit and the large unit cell/site disorder inherent in this phase. The solid solutions, Yb 21 Mn 4− x Cd x Sb 18 ( x = 0, 0.5, 1.0, 1.5) and Yb 21− y Ca y Mn 4 Sb 18 ( y = 3, 6, 9, 10.5) have been prepared, their structures characterized and thermoelectric properties from room temperature to 800 K measured. A detailed look into the structural disorder for the Cd and Ca solid solutions was performed using synchrotron powder X-ray diffraction and pair distribution function methods and shows that these are highly disordered structures. The substitution of Cd gives rise to more metallic behavior whereas Ca substitution results in high resistivity. As both Cd and Ca are isoelectronic substitutions, the changes in properties are attributed to changes in the electronic structure. Both solid solutions show that the thermal conductivities remain extremely low (∼0.4 W m −1 K −1 ) and that the Seebeck coefficients remain high (>200 μV K −1 ). The temperature dependence of the carrier mobility with increased Ca substitution, changing from approximately T −1 to T −0.5 , suggests that another scattering mechanism is being introduced. As the bonding changes from polar covalent with Yb to ionic for Ca, polar optical phonon scattering becomes the dominant mechanism. Experimental studies of the Cd solid solutions result in a max zT of ∼1 at 800 K and, more importantly for application purposes, a ZT avg ∼ 0.6 from 300 K to 800 K. 

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5. Characterization and Performance of Cement-based Thermoelectric Materials

   Jani, R.; Holmes, N.; West, R.; Gaughan, K.; Liu, X.; Orisakwe, E.; Johnston, C.; Qu, M.; Kohanoff, J.; Stella, L.; et al (August 2020, Civil Engineering Research in Ireland (CERI) 2020)

   Thermoelectric materials enable the direct conversion of thermal energy to electricity. Ambient heat energy harvesting could be an effective route to convert buildings from being energy consumers to energy harvesters, thus making them more sustainable. There exists a relatively stable temperature gradient (storing energy) between the internal and external walls of buildings which can be utilized to generate meaningful energy (that is, electricity) using the thermoelectric principle. This could ultimately help reduce the surface temperatures and energy consumption of buildings, especially in urban areas. In this paper, ongoing work on developing and characterizing a cement-based thermoelectric material is presented. Samples are fabricated using cement as a base material and different metal oxides (Bi₂O₃ and Fe₂O₃) are added to enhance their thermoelectric properties. A series of characterization tests are undertaken on the prepared samples to determine their Seebeck coefficient, electrical and thermal conductivity. The study shows that cement paste with additives possesses physical properties in the range of semiconductors whereby, initially, the resistivity values are low but with time, they increase gradually, thus resulting in lower electrical conductivity. The thermal conductivity of the cement paste with additives is lower than the control sample. Seebeck coefficient values were found to be relatively unstable during the initial set of measurements because the internal and external environment needed to be kept in a thermally stable condition to achieve steady results. The detailed analysis helped determine and eliminate the source of errors in the characterization process and obtain repeatable results. Parameters such as moisture content, temperature, and age were found to have a significant impact on the properties of cement-based thermoelectric materials. 

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