{"_buckets": {"deposit": "5d14992e-9155-4c8e-b990-9a7d621a7978"}, "_deposit": {"created_by": 21, "id": "1465", "owners": [21], "pid": {"revision_id": 0, "type": "depid", "value": "1465"}, "status": "published"}, "_oai": {"id": "oai:ir.soken.ac.jp:00001465", "sets": ["9"]}, "author_link": ["0", "0", "0"], "item_1_biblio_info_21": {"attribute_name": "書誌情報（ソート用）", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "2009-03-24", "bibliographicIssueDateType": "Issued"}, "bibliographic_titles": [{}]}]}, "item_1_creator_2": {"attribute_name": "著者名", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "三宅, 雄介"}], "nameIdentifiers": [{"nameIdentifier": "0", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_creator_3": {"attribute_name": "フリガナ", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "ミヤケ, ユウスケ"}], "nameIdentifiers": [{"nameIdentifier": "0", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_date_granted_11": {"attribute_name": "学位授与年月日", "attribute_value_mlt": [{"subitem_dategranted": "2009-03-24"}]}, "item_1_degree_grantor_5": {"attribute_name": "学位授与機関", "attribute_value_mlt": [{"subitem_degreegrantor": [{"subitem_degreegrantor_name": "総合研究大学院大学"}]}]}, "item_1_degree_name_6": {"attribute_name": "学位名", "attribute_value_mlt": [{"subitem_degreename": "博士（理学）"}]}, "item_1_description_1": {"attribute_name": "ID", "attribute_value_mlt": [{"subitem_description": "2009013", "subitem_description_type": "Other"}]}, "item_1_description_12": {"attribute_name": "要旨", "attribute_value_mlt": [{"subitem_description": "1. Introduction\u003cbr /\u003e　　　Construction of well ordered surface structures with functional molecular\u003cbr /\u003ebuilding blocks have attracted much attentions because of their potential applications\u003cbr /\u003efor novel functional materials. In recent years, surface modification using\u003cbr /\u003eself-assembly of organic molecules has been significantly advanced by scanning\u003cbr /\u003etunneling microscopy (STM) in ultra-high-vacuum (UHV)\u003csup\u003e1,2\u003c/sup\u003e or under ambient\u003cbr /\u003econditions.\u003csup\u003e3,4,5,6,7,8\u003c/sup\u003eEspecially, in situ\u003c/i\u003e STM at the solid-liquid interfaces\u003csup\u003e3\u003c/sup\u003e is a powerful\u003cbr /\u003eand useful technique to characterize local surface structure, electronic state and\u003cbr /\u003esurface dynamics of materials composed by organic molecules with submolecular\u003cbr /\u003eresolution. Numbers of self-assembled structures on surfaces have been observed using \u003ci\u003ein situ\u003c/i\u003e STM at the solid-liquid interface. \u003csup\u003e3,4,5, 6,7,8\u003c/sup\u003e  However, few report focused on\u003cbr /\u003einfluence of intermolecular and/or moleculai-surface interactions of the component\u003cbr /\u003emolecules systematically for the stable structures formed at the solid-liquid interface. \u003cbr /\u003eI have investigated systematically the effects of the molecular structure on\u003cbr /\u003eself-organized structure of porphyrin and naphthalenediimide, and their surface\u003cbr /\u003edynamics to explore new surface modification method based on self-assembled\u003cbr /\u003estructures\u003cbr /\u003e\u003cbr /\u003e2. Investigation of Vanadyl and Cobalt(II) Octaethylporphyrin Self-Assembled\u003cbr /\u003eMonolayer Arrays on Highly Oriented Pyrolytic Graphite (HOPG) by STM\u003cbr /\u003e　　　Porphyrin and related compounds not only play an important role in\u003cbr /\u003ephotosynthesis, biochemistry and catalysis in nature, but are also important\u003cbr /\u003ecandidates for building blocks of future molecular devices.\u003csup\u003e9\u003c/sup\u003e These compounds also have attracted significant attentions in the fields of life science, material science and\u003cbr /\u003ephysics because of their unique electronic structures, spectroscopic properties based\u003cbr /\u003eon the large conjugated π-electron system and existence of metal coordination sites. \u003cbr /\u003eFundamental characterization of porphyrin metallate self-assembled structures by\u003cbr /\u003eSTM will contribute significantly to future applications of molecular devices. \u003cbr /\u003eTwo-dimensional crystals of ［2,3,7,8,12,13,17,18-octaethyl 21\u003ci\u003eH\u003c/i\u003e,23\u003ci\u003eH\u003c/i\u003e-porphine］\u003cbr /\u003evanadium（IV)oxide and cobalt(II) (VOOEP and CoOEP, respectively) at the interface of\u003cbr /\u003e1-tetradecene and HOPG surface were studied by STM. The lattice parameters were\u003cbr /\u003edetermined for VOOEP (\u003ci\u003ea\u003c/i\u003e = 1.61\u0026plusmn;0.1 nm, \u003ci\u003eb\u003c/i\u003e= 1.46\u0026plusmn;0.05 nm, \u003ci\u003e\u0026Gamma;\u003c/i\u003e=61\u0026plusmn;3\u003csmall\u003e○\u003c/small\u003e) and CoOEP\u003cbr /\u003e(\u003ci\u003ea\u003c/i\u003e = 1.48\u0026plusmn;0.08 nm, \u003ci\u003eb\u003c/i\u003e= 1.42\u0026plusmn;0.07nm, \u003ci\u003e\u0026Gamma;\u003c/i\u003e=62.0\u0026plusmn;4\u003csmall\u003e○\u003c/small\u003e), which were calibrated using the\u003cbr /\u003eHOPG lattice as the reference. High-resolution STM showed different type of the\u003cbr /\u003eimages for these two porphyrin molecules. The STM image of VOOEP was a square\u003cbr /\u003eshape with four fold bright spots probably corresponding to the π-system of the\u003cbr /\u003eporphyrin ring, and that of CoOEP showed a bright spot at the center metal site. \u003cbr /\u003e3. Effect of Alkyl Chain Length to the Two-Dimensional Structure and STS Studies of\u003cbr /\u003eN, N\u0027-bis(alkyl)naphthalenediimide on HOPG\u003cbr /\u003e　　　Long alkyl chains are widely utilized as \"anchor\" groups for immobilizing\u003cbr /\u003eorganic molecules on graphite surface under ambient conditions in STM measurements. \u003cbr /\u003eHowever, few report focused on effects of the alkyl chain length to self-assembled\u003cbr /\u003estructures on HOPG systematically.　STM investigations of self assembled structures\u003cbr /\u003eof N,N\u0027-bis(alkyl)naphthalenediimide (NDI) with a series alkyl chains ranging from\u003cbr /\u003epropyl to octadecyl were carried out at l-tetradecene/HOPG interface. NDI derivatives\u003cbr /\u003ewere prepared by the usual condensation reactions. Each NDI derivatives is\u003cbr /\u003eabbreviated as CX-NDI (X is the corresponding carbon number of alkyl chains). The\u003cbr /\u003eself\u0027-assembled structure of them on HOPG showed strong dependence on the alkyl\u003cbr /\u003echain length. I classified them into six types; (1) linear arrays with row lattice\u003cbr /\u003estructure was observed in C3-NDI and C4-NDI, (2) chiral windmill structure in C4 and\u003cbr /\u003eC5-NDI, (3) honeycomb structure in C6〜C9-NDI, (4) chiral honeycomb structure in C10\u003cbr /\u003eand C12-NDI, (5) pseudo honeycomb structure containing super lattice in C11-NDI, (6) \u003cbr /\u003etypical alkyl lamellar structure in C13〜C18-NDI. In the self-assembled structure of C4, \u003cbr /\u003eC5, C10, C11 and C12-NDI, meta-stable state structures were also observed. Molecular\u003cbr /\u003edynamics (MD) simulation for C3, C4, C9 and C18 are well coincident with the STM\u003cbr /\u003eobservations. Results of STM, MD simulation and X-ray single crystallography of\u003cbr /\u003eC4-NDI clearly suggest that CH/O hydrogen bonding interaction is the critical driving\u003cbr /\u003eforce for the self-assembling. \u003cbr /\u003e\u003cbr /\u003e4. Surface Dynamics and Nano-Size-Manipulation on Self-Assembled N,N\u0027-bis(alkyl)\u003cbr /\u003enaphthalenediimide on Graphite\u003cbr /\u003e　　　During the STM observation of the self-assembled structure of NDI, thermally\u003cbr /\u003emeta-stable states were found. I investigated dependence of the self-assembled\u003cbr /\u003estructure of C11-NDI on temperature. A distort honeycomb structure was observed as a\u003cbr /\u003emeta-stable state of C11-NDI, which converted to the thermally stable structure\u003cbr /\u003econtaining super lattice upon heating.　The dynamic transition of\u0027 the former\u003cbr /\u003estructure to the latter was also observed. \u003cbr /\u003e\u003cbr /\u003e5. Conclusion\u003cbr /\u003e　I have investigated self-assembled structures of porphyrin and NDI derivatives in\u003cbr /\u003eorder to explore new self-assembled method and phenomena of surface dynamics. \u003cbr /\u003e　Self-assembled structures of two metallo octaethylporphyrins, VOOEP and CoOEP, \u003cbr /\u003ewere structurally characterized using STM. High-resolution STM images reflecting\u003cbr /\u003edifference of the central metal were obtained. \u003cbr /\u003e　Self assembled structures of NDI with a series of alkyl chain length ranging from\u003cbr /\u003epropyl to octadecyl (excluding heptadecyl) were characterized using STM at\u003cbr /\u003e1-tetradecene / HOPG interface. Structural transition induced by the difference of\u003cbr /\u003ealkyl chain length was observed on self-assembled 2D structures of NDI derivatives. \u003cbr /\u003eCompetition of inter-molecular CH/O type hydrogen bonding interaction and intermolecular alkyl-alkyl interaction lead to complex self-assembled structures on\u003cbr /\u003eHOPG. Thermal effects to the self-assembled structures were also investigated. \u003cbr /\u003eDirect observation of a local structural transition was succeeded on C11-NDI\u003cbr /\u003eself-assembled structure. \u003cbr /\u003e　These surface studies described above will open a new method for self-assembled and solution-processed nano-fabrication.", "subitem_description_type": "Other"}]}, "item_1_description_7": {"attribute_name": "学位記番号", "attribute_value_mlt": [{"subitem_description": "総研大甲第1221号", "subitem_description_type": "Other"}]}, "item_1_select_14": {"attribute_name": "所蔵", "attribute_value_mlt": [{"subitem_select_item": "有"}]}, "item_1_select_16": {"attribute_name": "複写", "attribute_value_mlt": [{"subitem_select_item": "複写不可"}]}, "item_1_select_17": {"attribute_name": "公開状況", "attribute_value_mlt": [{"subitem_select_item": "要旨のみ公開"}]}, "item_1_select_8": {"attribute_name": "研究科", "attribute_value_mlt": [{"subitem_select_item": "物理科学研究科"}]}, "item_1_select_9": {"attribute_name": "専攻", "attribute_value_mlt": [{"subitem_select_item": "07 構造分子科学専攻"}]}, "item_1_text_10": {"attribute_name": "学位授与年度", "attribute_value_mlt": [{"subitem_text_value": "2008"}]}, "item_creator": {"attribute_name": "著者", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "MIYAKE, Yusuke", "creatorNameLang": "en"}], "nameIdentifiers": [{"nameIdentifier": "0", "nameIdentifierScheme": "WEKO"}]}]}, "item_files": {"attribute_name": "ファイル情報", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2016-02-17"}], "displaytype": "simple", "download_preview_message": "", "file_order": 0, "filename": "甲1221_要旨.pdf", "filesize": [{"value": "308.7 kB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_11", "mimetype": "application/pdf", "size": 308700.0, "url": {"label": "要旨・審査要旨", "url": "https://ir.soken.ac.jp/record/1465/files/甲1221_要旨.pdf"}, "version_id": "34befe5c-45bd-4ad4-a1de-f56dc4f8b282"}]}, "item_language": {"attribute_name": "言語", "attribute_value_mlt": [{"subitem_language": "eng"}]}, "item_resource_type": {"attribute_name": "資源タイプ", "attribute_value_mlt": [{"resourcetype": "thesis", "resourceuri": "http://purl.org/coar/resource_type/c_46ec"}]}, "item_title": "Analysis of Versatile Self-assembled Two Dimensional Structures of N, N\u0027-bis (alkyl) Naphthalene-diimide on Graphite Using Scanning Tunneling Microscopy and Computer Simulation", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "Analysis of Versatile Self-assembled Two Dimensional Structures of N, N\u0027-bis (alkyl) Naphthalene-diimide on Graphite Using Scanning Tunneling Microscopy and Computer Simulation"}, {"subitem_title": "Analysis of Versatile Self-assembled Two Dimensional Structures of N, N\u0027-bis (alkyl) Naphthalene-diimide on Graphite Using Scanning Tunneling Microscopy and Computer Simulation", "subitem_title_language": "en"}]}, "item_type_id": "1", "owner": "21", "path": ["9"], "permalink_uri": "https://ir.soken.ac.jp/records/1465", "pubdate": {"attribute_name": "公開日", "attribute_value": "2010-03-25"}, "publish_date": "2010-03-25", "publish_status": "0", "recid": "1465", "relation": {}, "relation_version_is_last": true, "title": ["Analysis of Versatile Self-assembled Two Dimensional Structures of N, N\u0027-bis (alkyl) Naphthalene-diimide on Graphite Using Scanning Tunneling Microscopy and Computer Simulation"], "weko_shared_id": -1}