Publications by authors named "Raagya Arora"

5 Publications

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Metavalent Bonding in GeSe Leads to High Thermoelectric Performance.

Angew Chem Int Ed Engl 2021 Feb 22. Epub 2021 Feb 22.

New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P.O., Bangalore, 560064, India.

Orthorhombic GeSe is a promising thermoelectric material. However, large band gap and strong covalent bonding result in a low thermoelectric figure of merit, zT≈0.2. Here, we demonstrate a maximum zT≈1.35 at 627 K in p-type polycrystalline rhombohedral (GeSe) (AgBiTe )  , which is the highest value reported among GeSe based materials. The rhombohedral phase is stable in ambient conditions for x=0.8-0.29 in (GeSe) (AgBiTe )  . The structural transformation accompanies change from covalent bonding in orthorhombic GeSe to metavalent bonding in rhombohedral (GeSe) (AgBiTe )  . (GeSe) (AgBiTe ) has closely lying primary and secondary valence bands (within 0.25-0.30 eV), which results in high power factor 12.8 μW cm  K at 627 K. It also exhibits intrinsically low lattice thermal conductivity (0.38 Wm  K at 578 K). Theoretical phonon dispersion calculations reveal vicinity of a ferroelectric instability, with large anomalous Born effective charges and high optical dielectric constant, which, in concurrence with high effective coordination number, low band gap and moderate electrical conductivity, corroborate metavalent bonding in (GeSe) (AgBiTe ) . We confirmed the presence of low energy phonon modes and local ferroelectric domains using heat capacity measurement (3-30 K) and switching spectroscopy in piezoresponse force microscopy, respectively.
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http://dx.doi.org/10.1002/anie.202101283DOI Listing
February 2021

Enhanced atomic ordering leads to high thermoelectric performance in AgSbTe.

Science 2021 02;371(6530):722-727

New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P.O., Bangalore 560064, India.

High thermoelectric performance is generally achieved through either electronic structure modulations or phonon scattering enhancements, which often counteract each other. A leap in performance requires innovative strategies that simultaneously optimize electronic and phonon transports. We demonstrate high thermoelectric performance with a near room-temperature figure of merit, ~ 1.5, and a maximum ~ 2.6 at 573 kelvin, by optimizing atomic disorder in cadmium-doped polycrystalline silver antimony telluride (AgSbTe). Cadmium doping in AgSbTe enhances cationic ordering, which simultaneously improves electronic properties by tuning disorder-induced localization of electronic states and reduces lattice thermal conductivity through spontaneous formation of nanoscale (~2 to 4 nanometers) superstructures and coupling of soft vibrations localized within ~1 nanometer around cadmium sites with local strain modulation. The strategy is applicable to most other thermoelectric materials that exhibit inherent atomic disorder.
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http://dx.doi.org/10.1126/science.abb3517DOI Listing
February 2021

Ferroelectric Instability Induced Ultralow Thermal Conductivity and High Thermoelectric Performance in Rhombohedral -Type GeSe Crystal.

J Am Chem Soc 2020 Jul 30;142(28):12237-12244. Epub 2020 Jun 30.

Department of Physical Sciences, Indian Institute of Science Education and Research Mohali, Sector 81, S. A. S. Nagar, Manauli 140306, India.

The orthorhombic phase of GeSe, a structural analogue of layered SnSe (space group: ), has recently attracted attention after a theoretical prediction of high thermoelectric figure of merit, zT > 2. The experimental realization of such high performance in orthorhombic GeSe, however, is still elusive (zT ≈ 0.2). The rhombohedral phase of GeSe, a structural analogue of GeTe (space group: 3), previously stabilized at high pressure (2 GPa) and high temperature (1600 K), is promising due to its theoretically predicted ferroelectric instability and the higher earth abundance of Se compared to Te. Here, we demonstrate high thermoelectric performance in the rhombohedral crystals of GeSe, which is stabilized at ambient conditions by alloying with 10 mol % AgBiSe. We show ultralow lattice thermal conductivity (κ) of 0.74-0.47 W/mK in the 300-723 K range and high zT ≈ 1.25 at 723 K in the -type rhombohedral (GeSe)(AgBiSe) crystals grown using Bridgman method. First-principles density functional theoretical analysis reveals its vicinity to a ferroelectric instability which generates large anomalous Born effective charges and strong coupling of low energy polar optical phonons with acoustic phonons. The presence of soft optical phonons and incipient ferroelectric instability in (GeSe)(AgBiSe) are directly evident in the low temperature heat capacity () and switching spectroscopy piezoresponse force microscopy (SS-PFM) experiments, respectively. Effective scattering of heat carrying acoustic phonons by ferroelectric instability induced soft transverse optical phonons significantly reduces the κ and enhances the thermoelectric performance in rhombohedral (GeSe)(AgBiSe) crystals.
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http://dx.doi.org/10.1021/jacs.0c03696DOI Listing
July 2020

Realization of Both n- and p-Type GeTe Thermoelectrics: Electronic Structure Modulation by AgBiSe Alloying.

J Am Chem Soc 2019 Dec 2;141(49):19505-19512. Epub 2019 Dec 2.

Successful applications of a thermoelectric material require simultaneous development of compatible n- and p-type counterparts. While the thermoelectric performance of p-type GeTe has been improved tremendously in recent years, it has been a challenge to find a compatible n-type GeTe counterpart due to the prevalence of intrinsic Ge vacancies. Herein, we have shown that alloying of AgBiSe with GeTe results in an intriguing evolution in its crystal and electronic structures, resulting in n-type thermoelectric properties. We have demonstrated that the ambient rhombohedral structure of pristine GeTe transforms into cubic phase in (GeTe)(AgBiSe) for ≥ 25, with concurrent change from its p-type electronic character to n-type character in electronic transport properties. Such change in structural and electronic properties is confirmed from the nonmonotonic variation of band gap, unit cell volume, electrical conductivity, and Seebeck coefficient, all of which show an inflection point around ∼ 20, as well as from the temperature variations of synchrotron powder X-ray diffractions and differential scanning calorimetry. First-principles density functional theoretical (DFT) calculations explain that the shift toward n-type electronic character with increasing AgBiSe concentration arises due to increasing contribution of Bi p orbitals in the conduction band edge of (GeTe)(AgBiSe). This cubic n-type phase has promising thermoelectric properties with a band gap of ∼0.25 eV and ultralow lattice thermal conductivity that ranges between 0.3 and 0.6 W/mK. Further, we have shown that (GeTe)(AgBiSe) has promising thermoelectric performance in the mid-temperature range (400-500 K) with maximum thermoelectric figure of merit, , reaching ∼1.3 in p-type (GeTe)(AgBiSe) at 467 K and ∼0.6 in n-type (GeTe)(AgBiSe) at 500 K.
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http://dx.doi.org/10.1021/jacs.9b11405DOI Listing
December 2019

Stabilizing n-Type Cubic GeSe by Entropy-Driven Alloying of AgBiSe : Ultralow Thermal Conductivity and Promising Thermoelectric Performance.

Angew Chem Int Ed Engl 2018 Nov 15;57(46):15167-15171. Epub 2018 Oct 15.

New Chemistry Unit and School of Advanced Materials, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P.O., Bangalore, India.

The realization of n-type Ge chalcogenides is elusive owing to intrinsic Ge vacancies that make them p-type semiconductors. GeSe crystallizes into a layered orthorhombic structure similar to SnSe at ambient conditions. The high-symmetry cubic phase of GeSe is predicted to be stabilized by applying 7 GPa external pressure or by enhancing the entropy by increasing to temperature to 920 K. Stabilization of the n-type cubic phase of GeSe at ambient conditions was achieved by alloying with AgBiSe (30-50 mol %), enhancing the entropy through solid solution mixing. The interplay of positive and negative chemical pressure anomalously changes the band gap of GeSe with increasing the AgBiSe concentration. The band gap of n-type cubic (GeSe) (AgBiSe ) (0.30≤x≤0.50) has a value in the 0.3-0.4 eV range, which is significantly lower than orthorhombic GeSe (1.1 eV). Cubic (GeSe) (AgBiSe ) exhibits an ultralow lattice thermal conductivity (κ ≈0.43 W m  K ) in the 300-723 K range. The low κ is attributed to significant phonon scattering by entropy-driven enhanced solid-solution point defects.
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http://dx.doi.org/10.1002/anie.201809841DOI Listing
November 2018