Experimental and computational phase boundary mapping of Co4Sn6Te6

Crawford, Caitlin M.; Ortiz, Brenden R.; Gorai, Prashun; Stevanović, Vladan; Toberer, Eric S.

doi:10.1039/c8ta07539e

Cited by 30 publications

(22 citation statements)

References 49 publications

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“…It is guided by Gibbs' Phase Rule, which states that the composition of each compound in a multi-phase system is fixed at a given temperature when there are sufficient phases in equilibrium. Applying phase boundary mapping has improved thermoelectric performance in several materials, [28][29][30][31][32][33] including the recent breakthrough of n-type Mg 3 Sb 2 compounds. 21,34 Achieving well-defined phase equilibrium for this technique involves controlling sample composition to the point where secondary phases can be characterized, complicating its applicability in samples that require phase purity, such as single crystals.…”

Section: Methodsmentioning

confidence: 99%

The importance of phase equilibrium for doping efficiency: iodine doped PbTe

et al. 2019

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Section: Methodsmentioning

confidence: 99%

The importance of phase equilibrium for doping efficiency: iodine doped PbTe

et al. 2019

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“…Subsequently, computational predictions have often been challenging to realize experimentally (e.g., LiZnSb). , Recent computational studies even suggest that the majority of the well-studied Zintl phases may be fated to exhibit p-type transport regardless of doping or growth conditions . Even the advent of phase-boundary mapping − may be powerless to realize equilibrium n-type transport in many of the Zintl materials due to the facile formation of alkali and alkali earth metal vacancies. The development of n-type Mg 3 Sb 2 is the most successful counterpoint, wherein Mg-rich conditions enabled n-type transport in a historically p-type semiconductor .…”

Section: Introductionmentioning

confidence: 99%

Discovery of n-Type Zintl Phases RbAlSb₄, RbGaSb₄, CsAlSb₄, and CsGaSb₄

Ortiz

Gorai

Braden

et al. 2020

ACS Appl. Energy Mater.

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Zintl phases are excellent candidates for high-efficiency thermoelectrics (TEs) due to their extremely low lattice thermal conductivity. The manufacturing of an all-Zintl module is particularly attractive for practical applications, as it alleviates concerns regarding the electronic, thermal, and mechanical compatibility of the p-and n-type legs. To date, a large majority of Zintl phases have been realized as p-type TE materials. Our recent discovery of n-type transport in Ba-doped KAlSb 4 and KGaSb 4 has helped demonstrate the potential of n-type Zintl thermoelectrics. In this paper, we report the experimental discovery of 4 ABX 4 Zintl phases: RbAlSb 4 , RbGaSb 4 , CsAlSb 4 , and CsGaSb 4 . Transport measurements on Ba-doped RbGaSb 4 and CsGaSb 4 demonstrate near glassy lattice thermal conductivity (<0.5 W m −1 K −1 , 350 °C) and lightly doped n-type transport. However, the doping efficiency of Ba in RbGaSb 4 and CsGaSb 4 is significantly impeded when compared to our prior work on KGaSb 4 . To investigate the underlying mechanism, we performed first-principles defect calculations and found that the effect of compensating alkali metal vacancies increases in the Rb-and Cs-based analogues. Considering the TE potential of the known ABX 4 n-type materials, we have also performed a computational survey over 27 plausible compositions where A = (K, Rb, Cs), B = (Al, Ga, In), and X = (As, Sb, Bi) to investigate the effect of chemistry on potential TE performance.

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“…The same experimental studies 30,31 report that halogen doping induces an anomalous p-n-p transition in the conductivity type with increasing temperature, which the authors attribute to weak, thermally unstable Cu-X (X = Cl, Br, I) bonds compared to the Cu-Se bond strength in the parent material. 31 Based on our results, we suggest that the different thermodynamic states of the quinary Bi-Cu-Se-O-X (X = Cl, Br, I) phase space be explored in detail e.g., through phase boundary mapping 66,79,80 to understand the observed p-n-p transition in the conductivity type. In phase boundary mapping, the presence of specific dopant-related competing phases in a sample is the signature of the corresponding thermodynamic state defined by the elemental chemical potentials e.g., Cu-/Cl-rich.…”

Section: Zhang Et Al Reported N-typementioning

confidence: 72%

Defect Chemistry and Doping of BiCuSeO

Toriyama

Qu²,

Snyder

et al. 2021

Preprint

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While p-type BiCuSeO is a well-known mid-temperature oxide thermoelectric (TE) material, computations predict that superior TE performance can be realized through n-type doping. In this study, we use firstprinciples defect calculations to show that Cu vacancies are responsible for the native p-type self doping; yet, we find that BiCuSeO is n-type dopable under Cu-rich growth conditions, where the formation of Cu vacancies is suppressed. We computationally survey a broad suite of 23 dopants and find that only Cl and Br are effective n-type dopants. Therefore, we recommend that future experimental doping efforts utilize phase boundary mapping to optimize the electron concentration and resolve the anomalous pn-p transitions observed in halogen-doped BiCuSeO. The prospects of n-type doping, as revealed by our defect calculations, paves the path for rational design of BiCuSeO chemical analogues with similar doping behavior and even better TE performance.

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Experimental and computational phase boundary mapping of Co₄Sn₆Te₆

Abstract: Experimental and computational investigation of the phase stability and thermoelectric properties of the Co4Sn6Te6 skutterudite.

Cited by 30 publications

References 49 publications

The importance of phase equilibrium for doping efficiency: iodine doped PbTe

The importance of phase equilibrium for doping efficiency: iodine doped PbTe

Discovery of n-Type Zintl Phases RbAlSb₄, RbGaSb₄, CsAlSb₄, and CsGaSb₄

Defect Chemistry and Doping of BiCuSeO

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Experimental and computational phase boundary mapping of Co4Sn6Te6

Abstract: Experimental and computational investigation of the phase stability and thermoelectric properties of the Co4Sn6Te6 skutterudite.

Cited by 30 publications

References 49 publications

The importance of phase equilibrium for doping efficiency: iodine doped PbTe

The importance of phase equilibrium for doping efficiency: iodine doped PbTe

Discovery of n-Type Zintl Phases RbAlSb4, RbGaSb4, CsAlSb4, and CsGaSb4

Defect Chemistry and Doping of BiCuSeO

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Product

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Experimental and computational phase boundary mapping of Co₄Sn₆Te₆

Discovery of n-Type Zintl Phases RbAlSb₄, RbGaSb₄, CsAlSb₄, and CsGaSb₄