{"created":"2021-03-01T06:47:47.075145+00:00","id":41360,"links":{},"metadata":{"_buckets":{"deposit":"f95fcaa9-b4e5-4144-a1cd-6efe191cb554"},"_deposit":{"id":"41360","owners":[],"pid":{"revision_id":0,"type":"depid","value":"41360"},"status":"published"},"_oai":{"id":"oai:teapot.lib.ocha.ac.jp:00041360","sets":["391:396"]},"item_10_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1997-12-22","bibliographicIssueDateType":"Issued"}}]},"item_10_date_granted_74":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"1997-12-22"}]},"item_10_degree_grantor_72":{"attribute_name":"学位授与機関","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_name":"お茶の水女子大学"}],"subitem_degreegrantor_identifier":[{"subitem_degreegrantor_identifier_name":"12611","subitem_degreegrantor_identifier_scheme":"kakenhi"}]}]},"item_10_degree_name_71":{"attribute_name":"学位名","attribute_value_mlt":[{"subitem_degreename":"博士(理学)"}]},"item_10_description_17":{"attribute_name":"フォーマット","attribute_value_mlt":[{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"text/plain","subitem_description_type":"Other"},{"subitem_description":"text/plain","subitem_description_type":"Other"},{"subitem_description":"text/plain","subitem_description_type":"Other"},{"subitem_description":"text/plain","subitem_description_type":"Other"},{"subitem_description":"text/plain","subitem_description_type":"Other"},{"subitem_description":"text/plain","subitem_description_type":"Other"},{"subitem_description":"text/plain","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"},{"subitem_description":"application/pdf","subitem_description_type":"Other"}]},"item_10_description_46":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"subitem_description":"学位論文","subitem_description_type":"Other"}]},"item_10_description_6":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"現在、複数の分子を混合することにより混合物の結晶構造を変える研究がなされているが、このような材料は、X線構造解析で分子配向を調べることができるほど良質の単結晶を得ることは難しい。その代わりに結晶構造に敏感であるSHG効率を結晶構造変化のモニターに利用することができる。しかし、粉末状態で測定されるSHG効率は、従来の方法では定量性に欠けるため、反転対称の有無までしか言えず、細かい議論に進むことはできなかった。本論文では、この系にSHEW法を適用して粉末状態のdを決定し、理論計算との比較から、微結晶内で分子が平行に並んでいることを見いだした。\\\\r\\\\\\<br/>　この手法は、非線形光学材料として開発された材料でなくても、単体の結晶に反転対称性がなければ、原理的にはどんなものにも適用することができる。粉末状態しか得られないような試料に対しても、結晶構造の知見を与えることができるため結晶工学への貢献が期待できる。\\\\r\\\\\\<br/>　この論文は５つの章からなる。まず非線形光学の一般的な背景から入る。その中で特に取り上げている有機非線形光学材料についても述べる。第２章では、測定法として用いたSHEW法の原理を説明する。それを基礎として、粉末のSHEW法の結果を厳密に議論するために、まず単結晶に適用して理論と実験結果の一致を確認した。続いて、粉末試料に適用するために、非線形光学テンソルの空間平均の取り方を示す。第３章では、２章で述べた空間平均を用いた解析を行うことで、新規有機非線形光学材料のdテンソルの成分を求めた。これは、適当な自然成長面が育たなかったためメーカーフリンジだけでは求められなかったものをSHEW法の力を借りて求めたものである。第４章では、同様に空間平均を用いた解析により、２種類の有機物を混合して作製した混晶に適用し、混晶の中では分子がともに平行に並んでいることを示唆した。最後の章ですべてのまとめを行う。","subitem_description_type":"Abstract"},{"subitem_description":"我々の開発してきた全反射を用いた非線形光学定数測定法が、粉末試料でも定量的な結果が得られることを活用し、粉末状態では従来得られなかった情報が引き出せることを示した。すなわち、新規非線形光学材料の結晶の非線形光学定数dのテンソル成分の導出であり、またdの評価にとどまらず、結晶中の分子の配向状態に関する知見が得られることを示したことである。\\\\r\\\\\\<br/>　ここで用いている非線形光学定数測定法（second-harmonic generation with the evanescent wave法：SHEW法）は、エバネセント波を励起光とすることを特徴とする２次非線形光学定数dの測定法である。高屈折率プリズムと試料を密着させその界面で光を全反射させ、試料表面にわずかにしみこむエバネセント波による２次高調波発生（SHG）を観測する。他の測定法のように基本波・２次高調波のどちらも試料中を透過していくことがないので、基本波・２次高調波の位相速度が一致しないために起こる位相不整合の問題を、この方法では回避することができる。このため、粉末試料を用いても、従来の粉末法に比べより定量的な測定が可能となる。\\\\r\\\\\\<br/>　これまでにSHEW法は、いくつかの既知の粉末有機材料について適用され、実効的なdの値が求まることが示されている。本論文ではまず、SHEW法でdのテンソル成分が求まることを示すために、dテンソル成分と結晶軸方向が明らかな単結晶試料を用いて厳密な解析を行った。その結果、理論値と実験値が一致することを示し、後に述べる粉末結晶へ適用したときの解析の基礎とした。\\\\r\\\\\\<br/>　粉末試料に適用した場合は、微結晶がランダムに試料中に分布しているので、SHEW信号に現れる非線形光学定数テンソルもそれに伴い、単結晶の場合に用いた式を空間的に平均化したものにしなければならない。ここではこのことを考慮して解析した。これにより、より厳密な議論が可能となり、以下の二つの知見を新たに得ることができた。\\\\r\\\\\\<br/>　一つは、単結晶を用いる従来の測定法、メーカーフリンジ法では不十分な情報しか得られなかった試料について、粉末試料に対するSHEW法を併用してdのテンソル成分まで求めることができたことである。我々は、この新規有機試料をSHEW法によるスクリーニングによって見いだし、単結晶を作製した。しかし、出ている自然成長面が不適当であったために、メーカーフリンジ法によるdテンソルの各成分を求めることはできなかった。このようなことは、切削・研磨が難しい有機物結晶にしばしば付随する問題である。こうした場合にも、粉末試料で行ったSHEW法の結果でメーカーフリンジ法の結果を補い、分子の非線形性が一次元的と見なしてよいことを明確にし、dテンソルの各成分を求めることができた。\\\\r\\\\\\<br/>　もう一つは、二種の分子を混ぜてつくる混合物に対して、SHEW法を用いてその微結晶中の分子の配向に関する知見を与えたことである。","subitem_description_type":"Abstract"},{"subitem_description":"This technique provides information about the crystal structure of compounds which are difficult to crystallize in single phase, that is, the SHEW technique is expected to contribute to the crystal engineering.","subitem_description_type":"Abstract"},{"subitem_description":"The paper describes that a new technique for evaluating the nonlinear optical susceptibility using the total reflection can provide information other than the effective value of nonlinear optical susceptibility for powder samples. The technique provides the elements of the nonlinear optical susceptibility tensor d in spite of using powder samples. Additionally it gives information about the orientation of the molecules in the crystal. \\\\r\\\\\\<br/>  This technique for evaluating the nonlinear optical susceptibility is characterized by using the evanescent wave as an incident wave, thus we call it the second-harmonic generation with the evanescent wave technique (SHEW technique). The evanescent wave is produced by the total reflection at the interface between a sample and a total reflection prism, and the second-harmonic wave generates from the interface. The result of the conventional technique for evaluating the nonlinear optical material in powder form depends not only on the efficiency of the material, but also on the powder size and the birefringent phase-matchability. On the other hand, the SHEW technique provides reasonable results even though using powder samples. This is because the total reflection geometry avoids the fundamental and second-harmonic waves passing through the samples thus the result does not depend on the phase-matchability of the sample.\\\\r\\\\\\<br/>  We have applied the SHEW technique to known organic nonlinear optical materials and have demonstrated that it provides the effective d values. In this paper, firstly we applied the SHEW technique to a single crystal where all the elements of its d tensor are measured for showing that the SHEW technique can provide the d tensor elements. Consequently the calculated value and the measured value agreed thus this result is the base of the analysis in the application to the powder samples.\\\\r\\\\\\<br/>  Secondary we have applied the SHEW technique to powder samples. In this case, the fine crystals oriented randomly in all directions, thus we have to consider that the d value provided by the SHEW technique is the spatially averaged value of each d element. This analysis allows us more detailed discussion and provides the following results.\\\\r\\\\\\<br/>  1) The Maker fringe technique is known as a useful technique which provides the d elements. However, the requirement for a sample is so severe that even though using a single crystal sample, unless the crystal surface is appropriate, it doesn’t always provide the d elements. A new compound we have developed is just the case, as often-shown in organic molecular crystals which are difficult to cut and polish. Thus we combined the SHEW and the Maker Fringe techniques and found that the molecule can be regarded as a quasi one-dimensional molecule and obtained the d tensor elements.\\\\r\\\\\\<br/>  2) We applied the SHEW technique to a mixture sample and obtained the molecular orientation. There are many studies to control the crystal structure by mixing different molecules. The molecular orientation of these compounds is difficult to characterize using X-ray diffraction because of the difficulty of obtaining single crystal samples Thus we used the second-harmonic efficiency to monitor the structure change. However, the conventional powder technique cannot measure the second-harmonic efficiency quantitatively. It can only tell whether the sample has a center of symmetry or not, thus it cannot lead to a detailed discussion. In this paper, instead of the conventional technique, we applied the SHEW technique which can provide the d value for powder samples. By comparing the calculated result we found that the molecules are aligned parallel in the fine crystals.\\\\r\\\\\\<br/>  In principle this technique can be applied to any materials lacking a center of symmetry even if it is not developed as a nonlinear optical 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