{"created":"2023-06-19T10:29:42.179899+00:00","id":9678,"links":{},"metadata":{"_buckets":{"deposit":"e0cd7339-9ce3-46ec-92e6-1af5b2c7ead5"},"_deposit":{"created_by":18,"id":"9678","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"9678"},"status":"published"},"_oai":{"id":"oai:muroran-it.repo.nii.ac.jp:00009678","sets":["41:227"]},"author_link":["55174"],"item_81_date_granted_17":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"2018-03-23"}]},"item_81_degree_grantor_10":{"attribute_name":"学位授与機関","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_language":"ja","subitem_degreegrantor_name":"室蘭工業大学"},{"subitem_degreegrantor_language":"en","subitem_degreegrantor_name":"Muroran Institute of Technology"}],"subitem_degreegrantor_identifier":[{"subitem_degreegrantor_identifier_name":"10103","subitem_degreegrantor_identifier_scheme":"kakenhi"}]}]},"item_81_degree_name_11":{"attribute_name":"学位名","attribute_value_mlt":[{"subitem_degreename":"博士（工学）","subitem_degreename_language":"ja"}]},"item_81_description_25":{"attribute_name":"フォーマット","attribute_value_mlt":[{"subitem_description":"application/pdf","subitem_description_type":"Other"}]},"item_81_description_7":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"重希土類三二硫化物 Ln2S3 (Ln=重希土類元素)は，合成条件によって，7種類の結晶構造をとることが知られている。その中で，立方晶系Th3P4 構造（I-43d）は，γ 相と呼ばれ, 熱電変換材料，光学材料など機能性材料への応用が期待されている。しかし，重希土類三二硫化物の γ 相は, 常圧下では合成できず，高温高圧下でのみ合成報告がある。重希土類元素のLuを含む希土類三二硫化物の γ 相（γ-Lu2S3）は，低圧相を出発物質として，圧力7.7GPa，温度2000℃の条件下で，全試料の50％がγ 相に転移することが報告されているが，単一相試料の合成には至っていない。本研究では，出発物質に着目し，これまで先行研究では用いられていない ζ 相および各元素粉末を出発物質として用い，γ-Lu2S3 の単一相試料を得ることを試みた。出発物質として用いた ζ-Ln2S3 (Ln=Yb，Lu) は，常圧下でCS2硫化法を用いて合成した。希土類三二硫化物は温度・圧力条件によって複数の相が得られることから，単一相の生成は容易ではないことが予想される。そこで，γ 相の単一相試料が得られる最適な条件を探索するため，Lu2S3および高温高圧下で合成されLu2S3と類似の温度—圧力相図を持つものと予想され，比較的容易な条件で合成可能なYb2S3について，放射光Ｘ線を用いたその場観察実験を行い，Lu2S3およびYb2S3の詳細な温度—圧力相図を作成した。実験は，高エネルギー加速器研究機構フォトンファクトリーのビームラインAR-NE5Cおよび，SPring-8のビームラインBL-04B1で行った。その結果，Lu2S3の温度—圧力相図はYb2S3の相図と相似のものが得られたが，γ 相が得られる条件は，Lu2S3の方が，より高い温度・圧力条件を要することがわかった。γ-Yb2S3は2.5〜3GPa，1400℃以上で生成されるのに対し，γ-Lu2S3は5〜7GPa，1600℃を超えた範囲で合成されることがわかった。その場観察実験により決定した温度—圧力相図の結果を基に，大型の高圧合成装置を用いて，Lu2S3およびYb2S3のγ 相の単一相試料の高温高圧合成を試みた。その結果，出発物質に元素粉末を用いて，γ-Yb2S3および γ-Lu2S3の単一相試料の合成に成功した。","subitem_description_language":"ja","subitem_description_type":"Abstract"},{"subitem_description":"Heavy-lanthanide sesquisulfides Ln2S3 (Ln = Lanthanide) have seven forms of crystal structure. Among them, the γ-phase (cubic, I-43d), which has Th3P4-type structure, is expected for high-performance thermoelectric materials or optical materials. However, the γ-phase of heavy-lanthanide sesquisulfides Ln2S3 are difficult to synthesize at ambient pressure. While it has been reported that Lu2S3 was about 50% converted from the ε-phase (rhombohedral, R-3c) to the γ-phase under high pressure and high temperature, a high-quality single γ-phase sample of Lu2S3 (γ-Lu2S3) has not been obtained so far. In this study, we have tried to synthesize γ-Lu2S3 under high pressure using a low-pressure phase (named ζ-phase, orthorhombic, Sc2S3-type structure, Fddd), which was synthesized by CS2 sulfidation methods at ambient pressure, and the elements as starting materials. In order to obtain the optimum condition for preparing high-quality samples of γ-Lu2S3 under high pressure, detailed pressure-temperature (P-T) phase diagrams of Lu2S3 and an analogue compound Yb2S3 for comparison have been investigated by in-situ x-ray diffraction experiments using synchrotron radiation. The fundamental physical properties of the compounds were studied by electrical resistivity, specific heat, and magnetic susceptibility measurements between 2 K and 300 K. In-situ x-ray diffraction patterns were taken by an energy dispersive method using synchrotron radiation and a solid-state detector at Photon Factory (PF) in High Energy Accelerator Research Organization (KEK) and SPring-8. Large bulk samples of γ-Yb2S3 and γ-Lu2S3 were prepared at high temperatures and high pressures using a Kawai-type multi-anvil high-pressure apparatus. Using the ζ-phase as the starting materials, the phase diagrams of Yb2S3 and Lu2S3 were investigated for the first time. Furthermore, we expanded the temperature and pressure region of the phase diagrams using elements as the starting materials. The P-T phase diagram of Lu2S3 is basically similar to that of Yb2S3. However, the sequence of each crystal structure shifts to much higher temperature and pressure region for Lu2S3. In order to obtain single phases of γ-Yb2S3 and γ-Lu2S3, appropriate temperature and pressure conditions are needed (for γ-Yb2S3, pressure above 2.5 GPa and temperature above 1400oC, for γ-Lu2S3, pressure range between 5 and 7 GPa, above 1600oC). Based on the P-T phase diagrams, we succeeded in synthesizing single γ-phase samples of the compounds under high pressure. This results contribute development of next-generation thermoelectric and optical materials.","subitem_description_language":"en","subitem_description_type":"Abstract"}]},"item_81_dissertation_number_13":{"attribute_name":"学位授与番号","attribute_value_mlt":[{"subitem_dissertationnumber":"甲第409号"}]},"item_81_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.15118/00009630","subitem_identifier_reg_type":"JaLC"}]},"item_81_subject_9":{"attribute_name":"日本十進分類法","attribute_value_mlt":[{"subitem_subject":"436","subitem_subject_scheme":"NDC"}]},"item_81_text_12":{"attribute_name":"学位の種別","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"課程博士"}]},"item_81_text_14":{"attribute_name":"報告番号","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"甲第409号"}]},"item_81_text_15":{"attribute_name":"学位記番号","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"博甲第409号"}]},"item_81_text_16":{"attribute_name":"研究科・専攻","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"工学専攻・先端情報電子工学コース"}]},"item_81_version_type_24":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_970fb48d4fbd8a85","subitem_version_type":"VoR"}]},"item_access_right":{"attribute_name":"アクセス権","attribute_value_mlt":[{"subitem_access_right":"open access","subitem_access_right_uri":"http://purl.org/coar/access_right/c_abf2"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorAffiliations":[{"affiliationNameIdentifiers":[],"affiliationNames":[{"affiliationName":""}]}],"creatorNames":[{"creatorName":"金澤, 昌俊","creatorNameLang":"ja"},{"creatorName":"KANAZAWA, Masatoshi","creatorNameLang":"en"},{"creatorName":"カナザワ, マサトシ","creatorNameLang":"ja-Kana"}],"familyNames":[{},{},{}],"givenNames":[{},{},{}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-06-06"}],"displaytype":"detail","filename":"A409.pdf","filesize":[{"value":"4.7 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"A409","objectType":"fulltext","url":"https://muroran-it.repo.nii.ac.jp/record/9678/files/A409.pdf"},"version_id":"85018cba-70c8-4b26-97a8-6f98cb572fcb"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-06-06"}],"displaytype":"detail","filename":"A409_summary.pdf","filesize":[{"value":"174.1 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"A409_summary","objectType":"abstract","url":"https://muroran-it.repo.nii.ac.jp/record/9678/files/A409_summary.pdf"},"version_id":"ecc11e37-e00d-47d6-a63d-f9f5236c43cb"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"jpn"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"doctoral thesis","resourceuri":"http://purl.org/coar/resource_type/c_db06"}]},"item_title":"重希土類三二硫化物Ln2S3 (Ln=Yb, Lu)の高温高圧合成","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"重希土類三二硫化物Ln2S3 (Ln=Yb, Lu)の高温高圧合成","subitem_title_language":"ja"}]},"item_type_id":"81","owner":"18","path":["227"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2018-06-06"},"publish_date":"2018-06-06","publish_status":"0","recid":"9678","relation_version_is_last":true,"title":["重希土類三二硫化物Ln2S3 (Ln=Yb, Lu)の高温高圧合成"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2024-01-22T02:36:29.608483+00:00"}