DOI: 10.1063/1.1519334. Nonstoichiometry and chemical purity effects in thermoelectric Ba8Ga16Ge30 clathrate

Nonstoichiometry and chemical purity effects in thermoelectric Ba8Ga16Ge30 clathrate

10.1063/1.1519334

Crossref journal-article

AIP Publishing

Journal of Applied Physics (317)

Abstract

Zone melting purification experiments have been carried out on the clathrate, Ba8Ga16Ge30. The impurities present have been identified and their approximate concentrations measured. Trace impurities were determined to be approximately 240 parts per million (ppm) in the most impure sample to 17 ppm in the most pure sample. The temperature-dependent Seebeck coefficient, thermal conductivity, and electrical conductivity are reported as a function of sample purity as well as the room-temperature Hall coefficient. Microprobe analysis suggests that the samples are nonstoichiometric with excess Ge relative to Ga, and there are indications of the presence of defects. Single-crystal x-ray investigations as well as synchrotron powder diffraction measurements support the presence of defects, but the x-ray data cannot accurately determine the relative amounts of Ga and Ge. Band-structure calculations in the generalized gradient approximation show that the measured Hall and Seebeck coefficients are consistent with a defect lattice of approximate stoichiometry Ba8Ga14Ge31. Although the figure of merit (ZT) is found to be the highest for the purest sample, the dominant contribution to transport is conjectured to arise from deviations from the ideal stoichiometry and not impurities.

Bibliography

Bryan, J. D., Blake, N. P., Metiu, H., Stucky, G. D., Iversen, B. B., Poulsen, R. D., & Bentien, A. (2002). Nonstoichiometry and chemical purity effects in thermoelectric Ba8Ga16Ge30 clathrate. Journal of Applied Physics, 92(12), 7281â7290.

Authors 7

J. Daniel Bryan (first)
Nick P. Blake (additional)
Horia Metiu (additional)
Galen D. Stucky (additional)
Bo B. Iversen (additional)
Rasmus D. Poulsen (additional)
Anders Bentien (additional)

References 23 Referenced 58

10.1103/PhysRevLett.82.779 / Phys. Rev. Lett. (1999)
10.1002/1521-3773(20001016)39:20<3613::AID-ANIE3613>3.0.CO;2-D / Angew. Chem. Int. Ed. Engl. (2000)
10.1103/PhysRevB.63.245113 / Phys. Rev. B (2001)
10.1103/PhysRevLett.86.2361 / Phys. Rev. Lett. (2001)
10.1063/1.373469 / J. Appl. Phys. (2000)
10.1063/1.121747 / Appl. Phys. Lett. (1998)
10.1063/1.1397324 / J. Chem. Phys. (2001)
10.1103/PhysRevB.60.3064 / Phys. Rev. B (1999)
10.1016/0022-5088(86)90609-0 / J. Less-Common Met. (1986)
{'key': '2024020713335248500_r10'}
{'key': '2024020713335248500_r11'}
{'key': '2024020713335248500_r12'}
{'key': '2024020713335248500_r13'}
{'key': '2024020713335248500_r14', 'first-page': '705', 'volume': '8', 'year': '1966', 'journal-title': 'Fiz. Tverd. Tela (Leningrad)'} / Fiz. Tverd. Tela (Leningrad) (1966)
{'key': '2024020713335248500_r15', 'first-page': '442', 'volume': '11', 'year': '1969', 'journal-title': 'Sov. Phys. Solid State'} / Sov. Phys. Solid State (1969)
{'key': '2024020713335248500_r15a', 'first-page': '545', 'volume': '11', 'year': '1969', 'journal-title': 'Sov. Phys. Solid State'} / Sov. Phys. Solid State (1969)
{'key': '2024020713335248500_r16', 'first-page': '1277', 'volume': '10', 'year': '1968', 'journal-title': 'Sov. Phys. Solid State'} / Sov. Phys. Solid State (1968)
10.1016/0022-0248(95)00607-9 / J. Cryst. Growth (1996)
{'key': '2024020713335248500_r18'}
10.1103/PhysRevB.44.13298 / Phys. Rev. B (1991)
{'key': '2024020713335248500_r20'}
10.1063/1.1370949 / J. Chem. Phys. (2001)
10.1063/1.1334366 / J. Appl. Phys. (2001)

Dates

Type	When
Created	22 years, 9 months ago (Dec. 2, 2002, 1:48 p.m.)
Deposited	1 year, 6 months ago (Feb. 7, 2024, 3:14 p.m.)
Indexed	1 year, 6 months ago (Feb. 7, 2024, 3:40 p.m.)
Issued	22 years, 8 months ago (Dec. 15, 2002)
Published	22 years, 8 months ago (Dec. 15, 2002)
Published Print	22 years, 8 months ago (Dec. 15, 2002)

Funders 0

None

BibTeX

@article{Bryan_2002, title={Nonstoichiometry and chemical purity effects in thermoelectric Ba8Ga16Ge30 clathrate}, volume={92}, ISSN={1089-7550}, url={http://dx.doi.org/10.1063/1.1519334}, DOI={10.1063/1.1519334}, number={12}, journal={Journal of Applied Physics}, publisher={AIP Publishing}, author={Bryan, J. Daniel and Blake, Nick P. and Metiu, Horia and Stucky, Galen D. and Iversen, Bo B. and Poulsen, Rasmus D. and Bentien, Anders}, year={2002}, month=dec, pages={7281–7290} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2024,
        2,
        7
      ]
    ],
    "date-time": "2024-02-07T20:40:06Z",
    "timestamp": 1707338406566
  },
  "reference-count": 23,
  "publisher": "AIP Publishing",
  "issue": "12",
  "content-domain": {
    "domain": [
      "pubs.aip.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        2002,
        12,
        15
      ]
    ]
  },
  "abstract": "<jats:p>Zone melting purification experiments have been carried out on the clathrate, Ba8Ga16Ge30. The impurities present have been identified and their approximate concentrations measured. Trace impurities were determined to be approximately 240 parts per million (ppm) in the most impure sample to 17 ppm in the most pure sample. The temperature-dependent Seebeck coefficient, thermal conductivity, and electrical conductivity are reported as a function of sample purity as well as the room-temperature Hall coefficient. Microprobe analysis suggests that the samples are nonstoichiometric with excess Ge relative to Ga, and there are indications of the presence of defects. Single-crystal x-ray investigations as well as synchrotron powder diffraction measurements support the presence of defects, but the x-ray data cannot accurately determine the relative amounts of Ga and Ge. Band-structure calculations in the generalized gradient approximation show that the measured Hall and Seebeck coefficients are consistent with a defect lattice of approximate stoichiometry Ba8Ga14Ge31. Although the figure of merit (ZT) is found to be the highest for the purest sample, the dominant contribution to transport is conjectured to arise from deviations from the ideal stoichiometry and not impurities.</jats:p>",
  "DOI": "10.1063/1.1519334",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2002,
        12,
        2
      ]
    ],
    "date-time": "2002-12-02T18:48:21Z",
    "timestamp": 1038854901000
  },
  "page": "7281-7290",
  "update-policy": "http://dx.doi.org/10.1063/aip-crossmark-policy-page",
  "source": "Crossref",
  "is-referenced-by-count": 58,
  "title": "Nonstoichiometry and chemical purity effects in thermoelectric Ba8Ga16Ge30 clathrate",
  "prefix": "10.1063",
  "volume": "92",
  "author": [
    {
      "given": "J. Daniel",
      "family": "Bryan",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106"
        }
      ]
    },
    {
      "given": "Nick P.",
      "family": "Blake",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106"
        }
      ]
    },
    {
      "given": "Horia",
      "family": "Metiu",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106"
        }
      ]
    },
    {
      "given": "Galen D.",
      "family": "Stucky",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106"
        }
      ]
    },
    {
      "given": "Bo B.",
      "family": "Iversen",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, University of Aarhus, DK-8000 Aarhus C, Denmark"
        }
      ]
    },
    {
      "given": "Rasmus D.",
      "family": "Poulsen",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, University of Aarhus, DK-8000 Aarhus C, Denmark"
        }
      ]
    },
    {
      "given": "Anders",
      "family": "Bentien",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Max Planck Institute for Chemical Physics of Solids, N\u00f6thnitzer Strasse 40, D-01187 Dresden, Germany"
        }
      ]
    }
  ],
  "member": "317",
  "reference": [
    {
      "key": "2024020713335248500_r1",
      "doi-asserted-by": "crossref",
      "first-page": "779",
      "DOI": "10.1103/PhysRevLett.82.779",
      "volume": "82",
      "year": "1999",
      "journal-title": "Phys. Rev. Lett."
    },
    {
      "key": "2024020713335248500_r2",
      "doi-asserted-by": "crossref",
      "first-page": "3613",
      "DOI": "10.1002/1521-3773(20001016)39:20<3613::AID-ANIE3613>3.0.CO;2-D",
      "volume": "39",
      "year": "2000",
      "journal-title": "Angew. Chem. Int. Ed. Engl."
    },
    {
      "key": "2024020713335248500_r3",
      "doi-asserted-by": "crossref",
      "first-page": "245113",
      "DOI": "10.1103/PhysRevB.63.245113",
      "volume": "63",
      "year": "2001",
      "journal-title": "Phys. Rev. B"
    },
    {
      "key": "2024020713335248500_r4",
      "doi-asserted-by": "crossref",
      "first-page": "2361",
      "DOI": "10.1103/PhysRevLett.86.2361",
      "volume": "86",
      "year": "2001",
      "journal-title": "Phys. Rev. Lett."
    },
    {
      "key": "2024020713335248500_r5",
      "doi-asserted-by": "crossref",
      "first-page": "7871",
      "DOI": "10.1063/1.373469",
      "volume": "87",
      "year": "2000",
      "journal-title": "J. Appl. Phys."
    },
    {
      "key": "2024020713335248500_r6",
      "doi-asserted-by": "crossref",
      "first-page": "178",
      "DOI": "10.1063/1.121747",
      "volume": "73",
      "year": "1998",
      "journal-title": "Appl. Phys. Lett."
    },
    {
      "key": "2024020713335248500_r7",
      "doi-asserted-by": "crossref",
      "first-page": "8060",
      "DOI": "10.1063/1.1397324",
      "volume": "115",
      "year": "2001",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020713335248500_r8",
      "doi-asserted-by": "crossref",
      "first-page": "3064",
      "DOI": "10.1103/PhysRevB.60.3064",
      "volume": "60",
      "year": "1999",
      "journal-title": "Phys. Rev. B"
    },
    {
      "key": "2024020713335248500_r9",
      "doi-asserted-by": "crossref",
      "first-page": "43",
      "DOI": "10.1016/0022-5088(86)90609-0",
      "volume": "118",
      "year": "1986",
      "journal-title": "J. Less-Common Met."
    },
    {
      "key": "2024020713335248500_r10"
    },
    {
      "key": "2024020713335248500_r11"
    },
    {
      "key": "2024020713335248500_r12"
    },
    {
      "key": "2024020713335248500_r13"
    },
    {
      "key": "2024020713335248500_r14",
      "first-page": "705",
      "volume": "8",
      "year": "1966",
      "journal-title": "Fiz. Tverd. Tela (Leningrad)"
    },
    {
      "key": "2024020713335248500_r15",
      "first-page": "442",
      "volume": "11",
      "year": "1969",
      "journal-title": "Sov. Phys. Solid State"
    },
    {
      "key": "2024020713335248500_r15a",
      "first-page": "545",
      "volume": "11",
      "year": "1969",
      "journal-title": "Sov. Phys. Solid State"
    },
    {
      "key": "2024020713335248500_r16",
      "first-page": "1277",
      "volume": "10",
      "year": "1968",
      "journal-title": "Sov. Phys. Solid State"
    },
    {
      "key": "2024020713335248500_r17",
      "doi-asserted-by": "crossref",
      "first-page": "28",
      "DOI": "10.1016/0022-0248(95)00607-9",
      "volume": "161",
      "year": "1996",
      "journal-title": "J. Cryst. Growth"
    },
    {
      "key": "2024020713335248500_r18"
    },
    {
      "key": "2024020713335248500_r19",
      "doi-asserted-by": "crossref",
      "first-page": "13298",
      "DOI": "10.1103/PhysRevB.44.13298",
      "volume": "44",
      "year": "1991",
      "journal-title": "Phys. Rev. B"
    },
    {
      "key": "2024020713335248500_r20"
    },
    {
      "key": "2024020713335248500_r21",
      "doi-asserted-by": "crossref",
      "first-page": "10063",
      "DOI": "10.1063/1.1370949",
      "volume": "114",
      "year": "2001",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020713335248500_r22",
      "doi-asserted-by": "crossref",
      "first-page": "1730",
      "DOI": "10.1063/1.1334366",
      "volume": "89",
      "year": "2001",
      "journal-title": "J. Appl. Phys."
    }
  ],
  "updated-by": [
    {
      "updated": {
        "date-parts": [
          [
            2003,
            3,
            21
          ]
        ],
        "date-time": "2003-03-21T00:00:00Z",
        "timestamp": 1048204800000
      },
      "DOI": "10.1063/1.1556591",
      "type": "correction",
      "source": "publisher",
      "label": "Correction"
    },
    {
      "updated": {
        "date-parts": [
          [
            2003,
            4,
            1
          ]
        ],
        "date-time": "2003-04-01T00:00:00Z",
        "timestamp": 1049155200000
      },
      "DOI": "10.1063/1.1556591",
      "type": "correction",
      "source": "publisher",
      "label": "Correction"
    }
  ],
  "container-title": "Journal of Applied Physics",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://pubs.aip.org/aip/jap/article-pdf/92/12/7281/19319552/7281_1_online.pdf",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pubs.aip.org/aip/jap/article-pdf/92/12/7281/19319552/7281_1_online.pdf",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        2,
        7
      ]
    ],
    "date-time": "2024-02-07T20:14:25Z",
    "timestamp": 1707336865000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jap/article/92/12/7281/761101/Nonstoichiometry-and-chemical-purity-effects-in"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        2002,
        12,
        15
      ]
    ]
  },
  "references-count": 23,
  "journal-issue": {
    "issue": "12",
    "published-print": {
      "date-parts": [
        [
          2002,
          12,
          15
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.1519334",
  "relation": {},
  "ISSN": [
    "0021-8979",
    "1089-7550"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        2002,
        12,
        15
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        2002,
        12,
        15
      ]
    ]
  }
}