All-Scale Hierarchically Structured p-Type PbSe Alloys with High Thermoelectric Performance Enabled by Improved Band Degeneracy

Gangjian Tan, Shiqiang Hao, Songting Cai, Trevor P. Bailey, Zhongzhen Luo, Ido Hadar, Ctirad Uher, Vinayak P. Dravid, Christopher Wolverton, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

We show an example of hierarchically designing electronic bands of PbSe toward excellent thermoelectric performance. We find that alloying 15 mol % PbTe into PbSe causes a negligible change in the light and heavy valence band energy offsets (ΔE V ) of PbSe around room temperature; however, with rising temperature it makes ΔE V decrease at a significantly higher rate than in PbSe. In other words, the temperature-induced valence band convergence of PbSe is accelerated by alloying with PbTe. On this basis, applying 3 mol % Cd substitution on the Pb sites of PbSe 0.85 Te 0.15 decreases ΔE V and enhances the Seebeck coefficient at all temperatures. Excess Cd precipitates out as CdSe 1-y Te y , whose valence band aligns with that of the p-type Na-doped PbSe 0.85 Te 0.15 matrix. This enables facile charge transport across the matrix/precipitate interfaces and retains the high carrier mobilities. Meanwhile, compared to PbSe the lattice thermal conductivity of PbSe 0.85 Te 0.15 is significantly decreased to its amorphous limit of 0.5 W m -1 K -1 . Consequently, a highest peak ZT of 1.7 at 900 K and a record high average ZT of ∼1 (400-900 K) for a PbSe-based system are achieved in the composition Pb 0.95 Na 0.02 Cd 0.03 Se 0.85 Te 0.15 , which are ∼70% and ∼50% higher than those of Pb 0.98 Na 0.02 Se control sample, respectively.

Original languageEnglish
Pages (from-to)4480-4486
Number of pages7
JournalJournal of the American Chemical Society
Volume141
Issue number10
DOIs
Publication statusPublished - Mar 13 2019

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Valence bands
Alloying
Precipitates
Temperature
Seebeck coefficient
Carrier mobility
Charge transfer
Thermal conductivity
Substitution reactions
lead selenide
Thermal Conductivity
Chemical analysis
Light

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

All-Scale Hierarchically Structured p-Type PbSe Alloys with High Thermoelectric Performance Enabled by Improved Band Degeneracy. / Tan, Gangjian; Hao, Shiqiang; Cai, Songting; Bailey, Trevor P.; Luo, Zhongzhen; Hadar, Ido; Uher, Ctirad; Dravid, Vinayak P.; Wolverton, Christopher; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 141, No. 10, 13.03.2019, p. 4480-4486.

Research output: Contribution to journalArticle

Tan, Gangjian ; Hao, Shiqiang ; Cai, Songting ; Bailey, Trevor P. ; Luo, Zhongzhen ; Hadar, Ido ; Uher, Ctirad ; Dravid, Vinayak P. ; Wolverton, Christopher ; Kanatzidis, Mercouri G. / All-Scale Hierarchically Structured p-Type PbSe Alloys with High Thermoelectric Performance Enabled by Improved Band Degeneracy. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 10. pp. 4480-4486.
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AU - Luo, Zhongzhen

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AB - We show an example of hierarchically designing electronic bands of PbSe toward excellent thermoelectric performance. We find that alloying 15 mol % PbTe into PbSe causes a negligible change in the light and heavy valence band energy offsets (ΔE V ) of PbSe around room temperature; however, with rising temperature it makes ΔE V decrease at a significantly higher rate than in PbSe. In other words, the temperature-induced valence band convergence of PbSe is accelerated by alloying with PbTe. On this basis, applying 3 mol % Cd substitution on the Pb sites of PbSe 0.85 Te 0.15 decreases ΔE V and enhances the Seebeck coefficient at all temperatures. Excess Cd precipitates out as CdSe 1-y Te y , whose valence band aligns with that of the p-type Na-doped PbSe 0.85 Te 0.15 matrix. This enables facile charge transport across the matrix/precipitate interfaces and retains the high carrier mobilities. Meanwhile, compared to PbSe the lattice thermal conductivity of PbSe 0.85 Te 0.15 is significantly decreased to its amorphous limit of 0.5 W m -1 K -1 . Consequently, a highest peak ZT of 1.7 at 900 K and a record high average ZT of ∼1 (400-900 K) for a PbSe-based system are achieved in the composition Pb 0.95 Na 0.02 Cd 0.03 Se 0.85 Te 0.15 , which are ∼70% and ∼50% higher than those of Pb 0.98 Na 0.02 Se control sample, respectively.

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