Study of Zn-substituted germanium clathrates as high performance thermoelectric materials assisted by first-principles electronic structure calculation

Takeshi Eto, Kengo Kishimoto, Kenji Koga, Koji Akai, Tsuyoshi Koyanagi, Hiroaki Anno, Terumitsu Tanaka, Hiroki Kurisu, Setsuo Yamamoto, Mitsuru Matsuura

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Abstract

The thermoelectric properties of the clathrate compounds Ba 8ZnxGe46-x were studied theoretically and experimentally. First, a first-principles electronic structure calculation was performed. The calculated result showed that Ba8Zn8Ge 38 is an intrinsic semiconductor with an indirect band gap, while Ba8Zn6Ge40 is an n-type degenerate semiconductor and Ba8Zn10Ge36 is a p-type degenerate semiconductor. A large x dependence for the band gap was found between x = 6 and 8, i.e., the widths of band gap Eg at x = 6, 8 and 10 were 0.83 eV, 0.40 eV, 0.35 eV, respectively. Thus, for a thermoelectric material with high performance at high temperatures, the band gap of the intrinsic semiconductor Ba8Zn8Ge38 is relatively small. On the other hand, it was found that the double substituted clathrate Ba8Zn6Ga4Ge36 is an intrinsic semiconductor with a relatively large band gap: Eg = 0.69 eV. Second, we synthesized Zn substituted clathrate compounds by using the mechanical alloying and spark plasma sintering method, and measured the thermoelectric properties of the synthesized samples to show the concrete advantage of the Ba-Zn-Ga-Ge system. The experimental results showed that all of the Ba8ZnxGe46-x (x = 6, 8, 10, 12) samples were n-type semiconductors, and that some of the Zn clathrates (x = 6∼10) had a reasonably good n-type thermoelectric ability. Moreover, it was confirmed that the band gap of Ba8Zn6Ga4Ge36 (Eg = 0.9 eV) is wider than that of Ba8Zn 8Ge38 (Eg = 0.4 eV), and that Ba 8Zn6Ga4Ge36 has better thermoelectric characteristics than Ba8Zn8Ge38 at high temperatures. Finally, the experimental thermoelectric properties were theoretically analyzed by using the results of the electronic structure calculation and good agreement was obtained.

Original languageEnglish
Pages (from-to)631-639
Number of pages9
JournalMaterials Transactions
Volume50
Issue number3
DOIs
Publication statusPublished - Mar 1 2009

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Germanium
thermoelectric materials
clathrates
Electronic structure
germanium
Energy gap
Semiconductor materials
electronic structure
n-type semiconductors
Spark plasma sintering
Mechanical alloying
sparks
alloying
sintering
Concretes
Temperature

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials
  • Mechanical Engineering

Cite this

Study of Zn-substituted germanium clathrates as high performance thermoelectric materials assisted by first-principles electronic structure calculation. / Eto, Takeshi; Kishimoto, Kengo; Koga, Kenji; Akai, Koji; Koyanagi, Tsuyoshi; Anno, Hiroaki; Tanaka, Terumitsu; Kurisu, Hiroki; Yamamoto, Setsuo; Matsuura, Mitsuru.

In: Materials Transactions, Vol. 50, No. 3, 01.03.2009, p. 631-639.

Research output: Contribution to journalArticle

Eto, Takeshi ; Kishimoto, Kengo ; Koga, Kenji ; Akai, Koji ; Koyanagi, Tsuyoshi ; Anno, Hiroaki ; Tanaka, Terumitsu ; Kurisu, Hiroki ; Yamamoto, Setsuo ; Matsuura, Mitsuru. / Study of Zn-substituted germanium clathrates as high performance thermoelectric materials assisted by first-principles electronic structure calculation. In: Materials Transactions. 2009 ; Vol. 50, No. 3. pp. 631-639.
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abstract = "The thermoelectric properties of the clathrate compounds Ba 8ZnxGe46-x were studied theoretically and experimentally. First, a first-principles electronic structure calculation was performed. The calculated result showed that Ba8Zn8Ge 38 is an intrinsic semiconductor with an indirect band gap, while Ba8Zn6Ge40 is an n-type degenerate semiconductor and Ba8Zn10Ge36 is a p-type degenerate semiconductor. A large x dependence for the band gap was found between x = 6 and 8, i.e., the widths of band gap Eg at x = 6, 8 and 10 were 0.83 eV, 0.40 eV, 0.35 eV, respectively. Thus, for a thermoelectric material with high performance at high temperatures, the band gap of the intrinsic semiconductor Ba8Zn8Ge38 is relatively small. On the other hand, it was found that the double substituted clathrate Ba8Zn6Ga4Ge36 is an intrinsic semiconductor with a relatively large band gap: Eg = 0.69 eV. Second, we synthesized Zn substituted clathrate compounds by using the mechanical alloying and spark plasma sintering method, and measured the thermoelectric properties of the synthesized samples to show the concrete advantage of the Ba-Zn-Ga-Ge system. The experimental results showed that all of the Ba8ZnxGe46-x (x = 6, 8, 10, 12) samples were n-type semiconductors, and that some of the Zn clathrates (x = 6∼10) had a reasonably good n-type thermoelectric ability. Moreover, it was confirmed that the band gap of Ba8Zn6Ga4Ge36 (Eg = 0.9 eV) is wider than that of Ba8Zn 8Ge38 (Eg = 0.4 eV), and that Ba 8Zn6Ga4Ge36 has better thermoelectric characteristics than Ba8Zn8Ge38 at high temperatures. Finally, the experimental thermoelectric properties were theoretically analyzed by using the results of the electronic structure calculation and good agreement was obtained.",
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T1 - Study of Zn-substituted germanium clathrates as high performance thermoelectric materials assisted by first-principles electronic structure calculation

AU - Eto, Takeshi

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AU - Koga, Kenji

AU - Akai, Koji

AU - Koyanagi, Tsuyoshi

AU - Anno, Hiroaki

AU - Tanaka, Terumitsu

AU - Kurisu, Hiroki

AU - Yamamoto, Setsuo

AU - Matsuura, Mitsuru

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AB - The thermoelectric properties of the clathrate compounds Ba 8ZnxGe46-x were studied theoretically and experimentally. First, a first-principles electronic structure calculation was performed. The calculated result showed that Ba8Zn8Ge 38 is an intrinsic semiconductor with an indirect band gap, while Ba8Zn6Ge40 is an n-type degenerate semiconductor and Ba8Zn10Ge36 is a p-type degenerate semiconductor. A large x dependence for the band gap was found between x = 6 and 8, i.e., the widths of band gap Eg at x = 6, 8 and 10 were 0.83 eV, 0.40 eV, 0.35 eV, respectively. Thus, for a thermoelectric material with high performance at high temperatures, the band gap of the intrinsic semiconductor Ba8Zn8Ge38 is relatively small. On the other hand, it was found that the double substituted clathrate Ba8Zn6Ga4Ge36 is an intrinsic semiconductor with a relatively large band gap: Eg = 0.69 eV. Second, we synthesized Zn substituted clathrate compounds by using the mechanical alloying and spark plasma sintering method, and measured the thermoelectric properties of the synthesized samples to show the concrete advantage of the Ba-Zn-Ga-Ge system. The experimental results showed that all of the Ba8ZnxGe46-x (x = 6, 8, 10, 12) samples were n-type semiconductors, and that some of the Zn clathrates (x = 6∼10) had a reasonably good n-type thermoelectric ability. Moreover, it was confirmed that the band gap of Ba8Zn6Ga4Ge36 (Eg = 0.9 eV) is wider than that of Ba8Zn 8Ge38 (Eg = 0.4 eV), and that Ba 8Zn6Ga4Ge36 has better thermoelectric characteristics than Ba8Zn8Ge38 at high temperatures. Finally, the experimental thermoelectric properties were theoretically analyzed by using the results of the electronic structure calculation and good agreement was obtained.

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