JP5424441B2 - Organic dyes and organic semiconductor electronics elements - Google Patents
Organic dyes and organic semiconductor electronics elements Download PDFInfo
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- JP5424441B2 JP5424441B2 JP2008025859A JP2008025859A JP5424441B2 JP 5424441 B2 JP5424441 B2 JP 5424441B2 JP 2008025859 A JP2008025859 A JP 2008025859A JP 2008025859 A JP2008025859 A JP 2008025859A JP 5424441 B2 JP5424441 B2 JP 5424441B2
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- 239000000975 dye Substances 0.000 title description 65
- 239000004065 semiconductor Substances 0.000 title description 4
- 238000000862 absorption spectrum Methods 0.000 claims description 32
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 16
- 230000031700 light absorption Effects 0.000 claims description 11
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 33
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 24
- 239000002244 precipitate Substances 0.000 description 23
- 230000008859 change Effects 0.000 description 19
- 239000002904 solvent Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000002211 ultraviolet spectrum Methods 0.000 description 11
- 230000001419 dependent effect Effects 0.000 description 10
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- 238000010586 diagram Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
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- 238000000695 excitation spectrum Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000005388 cross polarization Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000005274 electronic transitions Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000010265 fast atom bombardment Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 229920002677 supramolecular polymer Polymers 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- IPFDTWHBEBJTLE-UHFFFAOYSA-N 2h-acridin-1-one Chemical compound C1=CC=C2C=C3C(=O)CC=CC3=NC2=C1 IPFDTWHBEBJTLE-UHFFFAOYSA-N 0.000 description 1
- CWNPOQFCIIFQDM-UHFFFAOYSA-N 3-nitrobenzyl alcohol Chemical compound OCC1=CC=CC([N+]([O-])=O)=C1 CWNPOQFCIIFQDM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000999 acridine dye Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004646 arylidenes Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 238000012617 force field calculation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Liquid Crystal (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Description
本発明は、有機色素に関し、さらに、これを用いた光電変換装置、偏光板、カラーフィルタ、インクジェットインク、メモリ装置、量子コンピュータ、有機トランジスタ、有機太陽電池、画像形成装置などの有機半導体エレクトロニクス素子に関する。 The present invention relates to an organic dye, and further relates to an organic semiconductor electronic element such as a photoelectric conversion device, a polarizing plate, a color filter, an inkjet ink, a memory device, a quantum computer, an organic transistor, an organic solar cell, and an image forming device using the same. .
非特許文献１には、無置換のペリレンビスイミド（Ｎ，Ｎ’−ビス（２−フェニルエチル）誘導体）に対して熱処理等を施すと、Ｈ会合体がＪ会合体に不可逆変換されることが開示されている。 Non-Patent Document 1 discloses that when an unsubstituted perylene bisimide (N, N′-bis (2-phenylethyl) derivative) is subjected to heat treatment or the like, an H aggregate is irreversibly converted to a J aggregate. Is disclosed.
また、非特許文献２には、ベイポジション（１，６，７，１２位）に置換基が導入されＪ会合体色素が開示されている。 Non-Patent Document 2 discloses a J-aggregate dye in which a substituent is introduced at the bay positions (positions 1, 6, 7, and 12).
しかし、非特許文献１に開示されている手法によると、Ｈ会合体がＪ会合体に不可逆変換されるため、結局のところ、Ｈ会合体の色素とＪ会合体の色素とのいずれかを選択的にしか用いることができない。これでは、会合様式が固定的となるため、用途は限定的である。 However, according to the method disclosed in Non-Patent Document 1, since the H aggregate is irreversibly converted to the J aggregate, eventually, either the dye of the H aggregate or the dye of the J aggregate is selected. Can only be used. This limits the use because the meeting style is fixed.
また、非特許文献１に開示されている色素は、溶液に対して不溶である。この点も、色素の用途が限定的であることを意味する。 Moreover, the pigment | dye currently disclosed by the nonpatent literature 1 is insoluble with respect to a solution. This point also means that the use of the dye is limited.
さらに、非特許文献２に開示されている色素は、ベイポジション（１，６，７，１２位）に置換基が導入されたものである。これは、立体障害によってペリレンコア部の平面性を損なわせ、横方向へのずれを強制することによってＪ会合体を選択的に形成させる手法であり、当該導入はペリレンコア部の電子状態までも変化させてしまうため、ペリレンが有する電子的・光学的性質も変化してしまう。これでは、本来のペリレンビスイミドに固有の特徴が損なわれてしまうので、別のアプローチが要求されている。 Further, the dye disclosed in Non-Patent Document 2 has a substituent introduced at the bay positions (positions 1, 6, 7, 12). This is a technique in which the planarity of the perylene core part is impaired by steric hindrance, and a J aggregate is selectively formed by forcing a shift in the lateral direction. The introduction also changes the electronic state of the perylene core part. Therefore, the electronic and optical properties of perylene also change. This impairs the inherent characteristics of the original perylene bisimide, thus requiring another approach.
そこで、本発明は、会合様式に自由度をもたせた色素を提供することを課題とする。 Then, this invention makes it a subject to provide the pigment | dye which gave the freedom degree to the meeting mode.
また、本発明は、この種の色素を用いた有機半導体エレクトロニクス素子を提供することを課題とする。 Moreover, this invention makes it a subject to provide the organic-semiconductor electronics element using this kind of pigment | dye.
上記課題を解決するために、本発明の色素は、可視光吸収スペクトルが４００〜５００ｎｍ付近と６２０ｎｍ付近との双方にピークを有する。このような色素は、可視光の変換効率が高まるため、例えば、有機半導体エレクトロニクス素子、特に、色素増感型太陽電池に好適に用いることができるという優れた効果を奏する。 In order to solve the above problems, the dye of the present invention has a visible light absorption spectrum having peaks in both the vicinity of 400 to 500 nm and the vicinity of 620 nm. Such a dye has an excellent effect that it can be suitably used for, for example, an organic semiconductor electronics element, particularly a dye-sensitized solar cell, since the conversion efficiency of visible light is increased.
なお、この色素は、第１会合体（Ｈ会合体）と第２会合体（Ｊ会合体）との間で可逆的変換が可能であれば、更に、用途に応じて、会合体様式を変更できるので好ましい。その際、第１会合体（Ｈ会合体）と第２会合体（Ｊ会合体）との間の境界温度は、５５℃〜６０℃に収まるとよい。さらに、色素は、インクジェット用インク等に用いることでムラ無く塗布できるように、可溶性であることが好ましい。 In addition, if this dye can be reversibly converted between the first aggregate (H aggregate) and the second aggregate (J aggregate), the form of the aggregate is further changed depending on the application. It is preferable because it is possible. At that time, the boundary temperature between the first aggregate (H aggregate) and the second aggregate (J aggregate) is preferably 55 ° C. to 60 ° C. Furthermore, it is preferable that the coloring matter is soluble so that it can be applied without unevenness when used in an inkjet ink or the like.
また、本発明は、可視光吸収スペクトルが相互に異なる波長域でピークを有する色素の製造方法であって、１，６，７，１２位が無置換ペリレンビスイミドと単一の置換基を有するシアヌル酸とを混合する。 Further, the present invention is a method for producing a dye having visible light absorption spectra having peaks in mutually different wavelength ranges, wherein the 1, 6, 7, and 12 positions have unsubstituted perylene bisimide and a single substituent. Mix with cyanuric acid.
以下、本発明の実施形態について、図面を用いて説明する。
図１は、本実施形態の色素の製造工程を化学式ベースで表した図である。まず、ベイポジション（１，６，７，１２位）無置換ペリレンビスイミド（Perylene Bisimide：以下、「ＰＢＩ」と称する。）を用意する。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a diagram showing the production process of the dye of this embodiment on the basis of a chemical formula. First, bay positions (1, 6, 7, and 12 positions) unsubstituted perylene bisimide (Perylene Bisimide: hereinafter referred to as “PBI”) are prepared.
つぎに、ＰＢＩに対して単一の置換基（ドデシル基）を有するシアヌル酸（cyanuric acid：以下、「ＣＡ」と称する。）を、異なる化学量論的比率で混合する。この際、ＰＢＩに対するＣＡの混合割合を増加させるとＪ会合体が多く形成され、反対に、ＰＢＩに対するＣＡの混合割合を減少させるとＨ会合体が多く形成される。 Next, cyanuric acid (hereinafter referred to as “CA”) having a single substituent (dodecyl group) with respect to PBI is mixed at different stoichiometric ratios. At this time, when the mixing ratio of CA to PBI is increased, many J aggregates are formed, and conversely, when the mixing ratio of CA to PBI is decreased, many H aggregates are formed.
なお、ＰＢＩは、ＣＡと混合しなくても、低極性溶媒のメチルシクロヘキサン（以下、「ＭＣＨ」と称する。）中でπ−スタッキングを主な駆動力として自己集合し、コア部分が無置換であるＰＢＩの典型的なＨ会合体の吸収スペクトルを示す。 PBI does not mix with CA, but self-assembles with π-stacking as a main driving force in methylcyclohexane (hereinafter referred to as “MCH”), which is a low polarity solvent, and the core portion is unsubstituted. The absorption spectrum of a typical H aggregate of a PBI is shown.
ＰＢＩは、３点水素結合によってＣＡ誘導体と相補的に相互作用するメラミン部位を有している。ＣＡとそのアルキル置換誘導体は、隣接する同一分子との１点又は２点の水素結合によって、超分子格子構造を構築することが知られている。そして、後述する種々の実験から明らかとなるように、ＰＢＩ−ＣＡ−ＰＢＩという組成からなるＨ会合体にＣＡを加えると、拡張された超分子ネットワークが形成され、Ｊ会合体が生じる。Ｊ会合体においては、ＣＡの水素結合受容体−供与体−受容体からなる３点水素結合部位の１つは、メラミン部位に占有され、残りの水素結合部位は、超分子構造を拡張するために利用される。 PBI has a melamine moiety that interacts complementarily with the CA derivative through a three-point hydrogen bond. CA and its alkyl-substituted derivatives are known to build a supramolecular lattice structure by one-point or two-point hydrogen bonding with the same adjacent molecule. As will be apparent from various experiments described later, when CA is added to an H aggregate having a composition of PBI-CA-PBI, an extended supramolecular network is formed and a J aggregate is formed. In the J-aggregate, one of the three-point hydrogen bonding sites consisting of hydrogen bond acceptor-donor-acceptor of CA is occupied by the melamine site, and the remaining hydrogen bond sites are used to expand the supramolecular structure. Used for
図２（ａ）は、図１のＰＢＩ−ＣＡ−ＰＢＩのＨ会合体の分子モデル構造を示す図である。なお、図２（ｂ）は、図２（ａ）の図面左側からの図である。図２（ｃ）は、図２（ａ）の図面下側からの図である。なお、図２（ａ）〜図２（ｃ）は、シュレディンガー社のMacroModel ver 9.1に搭載されたAMBER force field計算法を用いて作図した。 Fig.2 (a) is a figure which shows the molecular model structure of the H aggregate | assembly of PBI-CA-PBI of FIG. 2B is a view from the left side of FIG. 2A. FIG.2 (c) is a figure from the drawing lower side of Fig.2 (a). 2 (a) to 2 (c) were drawn using the AMBER force field calculation method installed in the Schroedinger's MacroModel ver 9.1.
図２（ａ）〜図２（ｃ）に示すように、このＨ会合体は、２つのＰＢＩと１つのＣＡとが、三点水素結合により会合していて、分子がずれずに重なりあった安定状態にある。このため、このＨ会合体は、太陽電池に用いた場合には、この構造により、電化輸送層として、好適に用いることができる。 As shown in FIG. 2 (a) to FIG. 2 (c), in this H aggregate, two PBIs and one CA were associated by a three-point hydrogen bond, and the molecules were overlapped without shifting. It is in a stable state. For this reason, when this H aggregate is used for a solar cell, this structure can be suitably used as an electrotransport layer.
一方、後述するように、Ｊ会合体は、一般に、分子がずれて重なりあっている構造のためＨ会合体よりは通常熱的安定性が劣る。ただし、本実施形態の色素におけるＪ会合体は、この構造を維持しつつも安定状態にあり、高効率かつ高速のエネルギー伝達特性を実現できる。このため、このＪ会合体は、太陽電池の集光アンテナとして好適に用いることができる。 On the other hand, as will be described later, J-aggregates are generally inferior in thermal stability to H-aggregates because of the structure in which molecules are shifted and overlapped. However, the J aggregate in the dye of the present embodiment is in a stable state while maintaining this structure, and can realize high-efficiency and high-speed energy transfer characteristics. For this reason, this J aggregate can be used suitably as a condensing antenna of a solar cell.
ここで、太陽光には様々な波長の光が含まれているが、太陽光は、４００ｎｍから７００ｎｍの波長域の光を多く含む。詳しくは後述するが、上記Ｈ会合体における光吸収スペクトルが約５１５ｎｍであるのに対して、通常のＪ会合体における光吸収スペクトルは約６２０ｎｍである。したがって、太陽電池のように太陽光を用いるデバイスにおいては、５００ｎｍ〜６００ｎｍの波長域に対応する吸収スペクトルを有する色素は、公的に用いることができる。なお、上記Ｈ会合体の場合、６２０ｎｍ付近には光吸収スペクトルが存在しない。 Here, the sunlight includes light of various wavelengths, and the sunlight includes a lot of light in the wavelength range of 400 nm to 700 nm. As will be described in detail later, the light absorption spectrum of the H aggregate is about 515 nm, whereas the light absorption spectrum of a normal J aggregate is about 620 nm. Therefore, in a device using sunlight such as a solar cell, a dye having an absorption spectrum corresponding to a wavelength region of 500 nm to 600 nm can be used publicly. In the case of the H aggregate, there is no light absorption spectrum near 620 nm.
ところで、本発明の色素の優れた点は、約４００〜５００ｎｍ付近と約６２０ｎｍ付近との双方に光吸収スペクトルが存在していることである。これは、本発明の色素が、通常のＨ会合体の光吸収スペクトルと通常のＪ会合体の光吸収スペクトルとの双方を併せ持った色素であって、光吸収スペクトルが劇的に変化していることを意味する。したがって、本発明の色素を太陽電池の集光アンテナに用いた場合、高効率かつ高速のエネルギー伝達特性を実現できることになる。 By the way, the excellent point of the pigment | dye of this invention is that a light absorption spectrum exists in both about 400-500 nm vicinity and about 620 nm vicinity. This is because the dye of the present invention has both a light absorption spectrum of a normal H-aggregate and a light absorption spectrum of a normal J-aggregate, and the light absorption spectrum changes dramatically. Means that. Therefore, when the pigment | dye of this invention is used for the condensing antenna of a solar cell, a highly efficient and high-speed energy transfer characteristic is realizable.
また、会合様式がＪ会合体である薄膜を１００℃付近まで加熱することで、Ｈ会合体に変化し、室温に戻れば再びＪ会合体に戻すことができるという極めて珍しい現象も見出している。なお、Ｊ会合体は緑色に見え、Ｈ会合体は赤色に見える。 In addition, a very rare phenomenon has also been found in which a thin film having an association mode of J-aggregate is heated to around 100 ° C. to change to an H-aggregate and can be returned to the J-aggregate again when the temperature returns to room temperature. The J aggregate appears green and the H aggregate appears red.
図３は、図１に示すＰＢＩの製造工程を化学式ベースで表した図である。 FIG. 3 is a diagram representing the manufacturing process of the PBI shown in FIG. 1 on a chemical formula basis.
まず、例えば、０．２７ｍｍｏｌのペリレン３，４：９，１０−テトラカルボン酸二無水物を１０７ｍｇ、０．２６ｍｍｏｌのメラミンを１６３ｍｇ、０．７７ｍｍｏｌのｎ−ブチルアミンを５６．５ｍｇ、溶媒として１７ｍｌの１−プロパノール及び４ｍｌの水を用意する。 First, for example, 107 mg of 0.27 mmol of perylene 3,4: 9,10-tetracarboxylic dianhydride, 163 mg of 0.26 mmol of melamine, 56.5 mg of 0.77 mmol of n-butylamine, 17 ml of solvent Prepare 1-propanol and 4 ml of water.
なお、上記各物質の濃度及び量は、一例であって、これらに限定されるものではない。既知のように、例えば、任意の物質については、高濃度にして少量用意するようにしてもよい。 In addition, the density | concentration and quantity of said each substance are examples, Comprising: It is not limited to these. As is known, for example, an arbitrary substance may be prepared in a high concentration and in a small amount.
つづいて、これらを混合してから、窒素又はアルゴン雰囲気下で約９時間還流させる。もっとも、ＰＢＩの収量を稼ぐ必要がない場合には、当該還流は、大気中で行ってもよい。そして、反応溶液の溶媒を留去して得た残留物をクロロホルム、ジクロロメタン、酢酸エチル又はエーテルに溶解し、水で洗浄し、シリカゲルカラムクロマトグラフィー（例えば、展開溶媒０．５％ＭｅＯＨ−ＣＨＣｌ３を溶離）によって精製する。分離した生成物をクロロホルムとメタノール混合溶媒から再沈殿することにより、約４４ｍｇのＰＢＩが得られる。 Subsequently, they are mixed and then refluxed for about 9 hours under a nitrogen or argon atmosphere. However, when it is not necessary to increase the yield of PBI, the reflux may be performed in the atmosphere. Then, the residue obtained by distilling off the solvent of the reaction solution was dissolved in chloroform, dichloromethane, ethyl acetate or ether, washed with water, and silica gel column chromatography (for example, developing solvent 0.5% MeOH-CHCl 3 Elution). By reprecipitating the separated product from a mixed solvent of chloroform and methanol, about 44 mg of PBI is obtained.
図４（ａ）は、ＰＢＩのみを含むＭＣＨ溶液の温度依存ＵＶスペクトルを示すグラフである。なお、ＰＢＩの濃度は、１．４×１０−５Ｍとし、スペクトル測定用の溶媒を用いた。図４（ａ）に示す矢印は、温度の上昇に伴う温度依存ＵＶスペクトルの変化を示している。温度依存ＵＶスペクトルのλが約４５０ｎｍ、４８０ｎｍ、５２０ｎｍ、５５０ｎｍの点で、モル吸光係数の大きな変化が見られる。なお、溶液の温度依存ＵＶスペクトルは、日本電子社製JASCO V660分光光度計を用いて測定した。 FIG. 4A is a graph showing a temperature-dependent UV spectrum of an MCH solution containing only PBI. The concentration of PBI was 1.4 × 10 −5 M, and a solvent for spectrum measurement was used. The arrows shown in FIG. 4A indicate changes in the temperature-dependent UV spectrum as the temperature increases. A large change in the molar extinction coefficient is observed when λ of the temperature-dependent UV spectrum is about 450 nm, 480 nm, 520 nm, and 550 nm. The temperature-dependent UV spectrum of the solution was measured using a JASCO V660 spectrophotometer manufactured by JEOL.
図４（ｂ）は、図４（ａ）における温度と会合度（α）との関係を示すグラフである。なお、ＰＢＩ単体は、２０℃では完全に会合しなかったので、後述する図５を参照して説明するように、ＰＢＩとＣＡとの混合割合を、２０℃で２：１とした溶液のモル吸光係数を１００％会合したものとして計算している。なお、図４（ｂ）に示すグラフから、脱会合度（α）＝０．５の温度である会合体分解温度は、約３１℃と推定できる。 FIG. 4B is a graph showing the relationship between the temperature and the degree of association (α) in FIG. Since PBI alone did not fully associate at 20 ° C., as described with reference to FIG. 5 described later, the molar ratio of the solution in which the mixing ratio of PBI and CA was 2: 1 at 20 ° C. The extinction coefficient is calculated as 100% associated. From the graph shown in FIG. 4B, the aggregate decomposition temperature at which the degree of deassociation (α) = 0.5 can be estimated to be about 31 ° C.
図５（ａ）は、ＰＢＩとＣＡとを２：１の割合で混合したＭＣＨ溶液の温度依存ＵＶスペクトルを示すグラフである。なお、ＰＢＩの濃度は、１．４×１０−５Ｍとし、スペクトル測定用の溶媒を用いた。図５（ａ）に示す矢印は、温度の上昇に伴う温度依存ＵＶスペクトルの変化を示している。波長λが、約４５０ｎｍ、４８０ｎｍ、５２０ｎｍ、５５０ｎｍにおいて、モル吸光係数の大きな変化が見られる。なお、溶液の温度依存ＵＶスペクトルは、日本電子社製JASCO V660分光光度計を用いて測定した。 FIG. 5A is a graph showing a temperature-dependent UV spectrum of an MCH solution in which PBI and CA are mixed at a ratio of 2: 1. The concentration of PBI was 1.4 × 10 −5 M, and a solvent for spectrum measurement was used. The arrows shown in FIG. 5 (a) indicate changes in the temperature-dependent UV spectrum with increasing temperature. When the wavelength λ is about 450 nm, 480 nm, 520 nm, and 550 nm, a large change in the molar extinction coefficient is observed. The temperature-dependent UV spectrum of the solution was measured using a JASCO V660 spectrophotometer manufactured by JEOL.
図５（ｂ）は、図５（ａ）における温度と脱会合度（α）との関係を示すグラフである。なお、図５（ｂ）に示すグラフから、脱会合度（α）＝０．５の温度である会合体分解温度は、約６８℃と推定できる。 FIG. 5B is a graph showing the relationship between the temperature and the degree of disassociation (α) in FIG. From the graph shown in FIG. 5B, the aggregate decomposition temperature at which the degree of deassociation (α) = 0.5 can be estimated to be about 68 ° C.
図４（ｂ）と図５（ｂ）とを対比すると、脱会合度（α）＝０．５の温度である会合体分解温度に顕著な変化が見られる。また、ＰＢＩとＣＡとの混合物のＨ会合体溶液を数週間放置すると、緑色の沈殿物（つまり、Ｊ会合体）が形成されることが目視により観測できた。なお、ＰＢＩとＣＡとの混合物に対して、ＰＢＩの濃度を５×１０−３Ｍまで高めて、他の条件は変更しなかった場合には、数時間で緑色の沈殿物が形成されることが目視により観測できた。 When FIG. 4 (b) is compared with FIG. 5 (b), a significant change is observed in the aggregate decomposition temperature, which is the temperature of the degree of deassociation (α) = 0.5. Further, when the H aggregate solution of the mixture of PBI and CA was allowed to stand for several weeks, it was visually observed that a green precipitate (that is, J aggregate) was formed. In addition, when the PBI concentration is increased to 5 × 10 −3 M and the other conditions are not changed with respect to the mixture of PBI and CA, a green precipitate should be formed within a few hours. Could be observed visually.
また、ＰＢＩとＣＡとの混合割合が２：１程度まで場合には、徐々に色素のモノマー発光が減衰し、それに伴い、極大吸収波長６３６ｎｍの典型的なＨ会合体由来のエキシマー発光が観測されたことになる。 In addition, when the mixing ratio of PBI and CA is up to about 2: 1, the monomer emission of the dye gradually attenuates, and accordingly, excimer emission derived from a typical H aggregate having a maximum absorption wavelength of 636 nm is observed. That's right.
そして、ＰＢＩとＣＡとの混合割合を１：１程度までとした場合には、発光波長は、５３ｎｍくらいのストークスシフトが見られ、６７３ｎｍとなった。 When the mixing ratio of PBI and CA was up to about 1: 1, the emission wavelength showed a Stokes shift of about 53 nm, which was 673 nm.
図６（ａ）は、ＰＢＩとＣＡとを１：１の割合で混合したＭＣＨ溶液の温度依存ＵＶスペクトルを示すグラフである。なお、ＰＢＩの濃度は、１．４×１０−５Ｍとし、スペクトル測定用の溶媒を用いた。図６（ａ）の実線は、２０℃、５５℃および９０℃のスペクトルを示している。また、矢印Ａは、温度の増加によるスペクトル変化を示している。矢印Ｂおよび矢印Ｃは、それぞれ、第一推移点（２０〜５５℃，５５４ｎｍ）、および、第二推移点（６０〜９０℃，５２３ｎｍ）の等吸収点を指す。 FIG. 6A is a graph showing a temperature-dependent UV spectrum of an MCH solution in which PBI and CA are mixed at a ratio of 1: 1. The concentration of PBI was 1.4 × 10 −5 M, and a solvent for spectrum measurement was used. The solid lines in FIG. 6A show the spectra at 20 ° C., 55 ° C., and 90 ° C. An arrow A indicates a spectrum change due to an increase in temperature. Arrows B and C indicate isoabsorption points of the first transition point (20 to 55 ° C., 554 nm) and the second transition point (60 to 90 ° C., 523 nm), respectively.
図６（ｂ）は、図６（ａ）の４００ｎｍ、５４４ｎｍ、および、６２０ｎｍにおけるモル吸光係数の温度変化を示している。 FIG. 6B shows the temperature change of the molar extinction coefficient at 400 nm, 544 nm, and 620 nm in FIG.
図６（ａ），図６（ｂ）に示すように、温度によるスペクトルの変動は、ほぼ２つの独立した温度領域に分けられる。つまり、等吸収点を５５４ｎｍに示す２０〜５５℃の変化がＪ会合体からＨ会合体への変遷であり、等吸収点５２３ｎｍに示す６０〜９０℃の変化がＨ会合体から単量体への変遷である。ゆえにＨ会合体とＪ会合体との境界温度は、約５５℃〜６０℃に収まると考えられる。 As shown in FIGS. 6 (a) and 6 (b), the fluctuation of the spectrum due to temperature is divided into almost two independent temperature regions. That is, a change at 20 to 55 ° C. showing the isosbestic point at 554 nm is a transition from the J-aggregate to the H-aggregate, and a change at 60 to 90 ° C. shown at the isosbestic point 523 nm is from the H-aggregate to the monomer. It is the transition of. Therefore, the boundary temperature between the H-aggregate and the J-aggregate is considered to be within about 55 ° C to 60 ° C.
境界温度以下の温度では、４００ｎｍ及び６２０ｎｍのεの値が減少することからわかるように、主として、Ｊ会合体からＨ会合体への変換が起こる。また、境界温度以上では、Ｊ会合体とＨ会合体がともに吸収を示す５４４ｎｍのεの値が一旦増加したあとに減少していることから、Ｈ会合体からモノマーへの変換が起こることがわかる。 At temperatures below the boundary temperature, conversion from J-aggregate to H-aggregate mainly occurs, as can be seen from the decrease in the values of ε at 400 nm and 620 nm. Also, above the boundary temperature, the value of ε at 544 nm, which shows the absorption of both J-aggregate and H-aggregate, decreases once and then decreases, indicating that conversion from H-aggregate to monomer occurs. .
なお、濃度１．４×１０−５ＭのＪ会合体の分解温度は、約４０℃と算出されたことから、このＪ会合体は、比較的弱い相互作用によって形成されていることがわかる。完全なＨ会合体とＪ会合体との間の可逆的変換は、超分子温度計として利用できる可能性を有している。 Since the decomposition temperature of the J aggregate having a concentration of 1.4 × 10 −5 M was calculated to be about 40 ° C., it can be seen that the J aggregate is formed by a relatively weak interaction. The reversible conversion between the complete H and J aggregates has the potential to be used as a supramolecular thermometer.
図７は、ＰＢＩのみの１Ｈ ＮＭＲスペクトルの測定結果を示す表である。なお、図７には、化学シフトδ（ｐｐｍ）＝８．４〜８．７付近を拡大したグラフを付記している。また、この測定は、共鳴周波数が５００ＭＨｚ，溶媒が重クロロホルム，温度が６０℃という条件下で行った。 FIG. 7 is a table showing measurement results of 1 H NMR spectrum of only PBI. In addition, in FIG. 7, the graph which expanded chemical shift (delta) (ppm) = 8.4-8.7 vicinity is attached. This measurement was performed under the conditions that the resonance frequency was 500 MHz, the solvent was deuterated chloroform, and the temperature was 60 ° C.
ＰＢＩは、図７に示すように、化学シフトδ（ｐｐｍ）＝８．６２（ｄ，Ｊ＝８Ｈｚ，２Ｈ)，８．６１（ｄ，J＝８Ｈｚ，２Ｈ）, ８．５３（ｄ，Ｊ＝８Ｈｚ，２Ｈ），８．５１（ｄ，Ｊ＝８Ｈｚ，２Ｈ），５．０５（ｂｒ−ｓ，１Ｈ），４．５５（ｂｒ−ｓ，１Ｈ），４．４７（ｔ，Ｊ＝７Ｈｚ，２Ｈ），４．２２（ｔ，Ｊ＝７Ｈｚ，２Ｈ），３．８１（ｍ，２Ｈ），３．２０（ｍ，２Ｈ），１．７７（ｍ，２Ｈ），１．２１（ｍ，４６Ｈ），１．００（ｍ，３Ｈ），０．８５（ｍ，９Ｈ）でピークとなるスペクトルが得られた。なお、測定装置は日本電子社製JEOL LA400分光計を用い、化学シフトはテトラメチルシランのシグナルを元に算出した。 As shown in FIG. 7, PBI has chemical shifts δ (ppm) = 8.62 (d, J = 8 Hz, 2H), 8.61 (d, J = 8 Hz, 2H), 8.53 (d, J = 8 Hz, 2H), 8.51 (d, J = 8 Hz, 2H), 5.05 (br-s, 1H), 4.55 (br-s, 1H), 4.47 (t, J = 7 Hz) , 2H), 4.22 (t, J = 7 Hz, 2H), 3.81 (m, 2H), 3.20 (m, 2H), 1.77 (m, 2H), 1.21 (m, 46H), 1.00 (m, 3H), and 0.85 (m, 9H) peaks were obtained. The measuring device was a JEOL LA400 spectrometer manufactured by JEOL Ltd., and the chemical shift was calculated based on the signal of tetramethylsilane.
また、ＰＢＩは、溶媒としてｍ−ニトロベンジルアルコールを用いて、ＦＡＢ（Fast Atom Bombardment）によって、分子量測定（ＨＲＭＳ）を行った結果、ｍ／ｚ計算値は９９１．６５３７［ＭＨ＋］、測定値は９９１．６４６９［Ｍ＋］であり、元素分析Ｃ６１Ｈ８２Ｎ８Ｏ４・Ｈ２Ｏの計算値はＣ７２．５９Ｈ８．３９，Ｎ１１．１０、測定値はＣ７２．６４、Ｈ８．２９，Ｎ１１．１６であった。なお、測定装置は、日本電子社製JEOL JMS-AX500質量分析計を用い、元素分析は、千葉大学の分析センターで行った。 PBI was measured by molecular weight measurement (HRMS) by FAB (Fast Atom Bombardment) using m-nitrobenzyl alcohol as a solvent. As a result, the m / z calculated value was 991.6537 [MH + ], the measured value. Is 991.6469 [M + ], the calculated values of elemental analysis C 61 H 82 N 8 O 4 .H 2 O are C 72.59 H 8.39 , N 11.10 . And the measured values are C 72.64. , H 8.29 , N 11.16 . The measuring device used was a JEOL JMS-AX500 mass spectrometer manufactured by JEOL Ltd. Elemental analysis was performed at the analysis center of Chiba University.
図８は、溶液内から遠心分離により単離された緑色の沈殿物の１Ｈ ＮＭＲスペクトルを示す図である。図８に示すスペクトルは、ＰＢＩとＣＡとの混合割合を２：１としたＭＣＨ溶液で形成した緑色の沈殿物を、重クロロホルムを溶媒とし、６０℃の測定温度下で測定した。 FIG. 8 is a diagram showing a 1 H NMR spectrum of a green precipitate isolated from the solution by centrifugation. The spectrum shown in FIG. 8 was measured at a measurement temperature of 60 ° C. using a deuterated chloroform solvent as a green precipitate formed with an MCH solution in which the mixing ratio of PBI and CA was 2: 1.
ここで、図８と図７とを対比すると、図８，図７に示す各スペクトルは、近似している。実際に、図８のＰＢＩとＣＡとのメチレンプロトンシグナルを積分解析することにより、緑色の沈殿物の組成を検証してみたところ、ＰＢＩとＣＡとが１：１の割合で存在していて、沈澱の組成比がＰＢＩ：ＣＡ＝１：１であることが判明した。 Here, when FIGS. 8 and 7 are compared, the spectra shown in FIGS. 8 and 7 are approximated. Actually, when the composition of the green precipitate was verified by integrating and analyzing the methylene proton signals of PBI and CA in FIG. 8, PBI and CA were present at a ratio of 1: 1. The composition ratio of the precipitate was found to be PBI: CA = 1: 1.
溶液内から単離された緑色の沈殿物の光学的性質を調べてみたところ、溶液中でのＪ会合体の場合とほぼ一致していることも確認できた。 When the optical property of the green precipitate isolated from the solution was examined, it was confirmed that it almost coincided with the case of the J aggregate in the solution.
図９（ａ）は、１当量以上のＣＡを含むＰＢＩ（すなわち、ＰＢＩよりもＣＡが多い）のＭＣＨ溶液の光学顕微鏡写真である。このＭＣＨ溶液から得られる緑色の沈殿物には、過剰なＣＡ（図面内で黒くピラミッド状に見える部分。）が微結晶として明確に観測された。このことは、沈澱の組成比がＰＢＩ：ＣＡ＝１：１であることを確固たるものとしている。 FIG. 9 (a) is an optical micrograph of an MCH solution of PBI containing 1 equivalent or more CA (ie, more CA than PBI). In the green precipitate obtained from the MCH solution, excessive CA (a portion that looks black and pyramid in the drawing) was clearly observed as microcrystals. This confirms that the composition ratio of the precipitate is PBI: CA = 1: 1.
図９（ｂ）は、交差偏光条件下におけるＭＣＨ溶液の光学顕微鏡写真である。図９（ｂ）に示すように、過剰なＣＡが黒い斑点として観測できる。なお、ＰＢＩとＣＡとの混合割合が１；１である場合に得られる沈殿物は、このような斑点は観測されなかった。このことからも、ＰＢＩとＣＡとの１：１の共会合が確認できる。 FIG. 9B is an optical micrograph of the MCH solution under cross polarization conditions. As shown in FIG. 9B, excessive CA can be observed as black spots. In addition, such a spot was not observed in the precipitate obtained when the mixing ratio of PBI and CA was 1: 1. This also confirms the 1: 1 co-association of PBI and CA.
図１０は、ＰＢＩとＣＡとを１：１の割合で混合したＭＣＨ溶液の２５℃における濃度依存吸収スペクトルを示す図である。図１０に示す矢印は、濃度の減少に伴うスペクトルの変化を示している。各スペクトルλの溶液濃度は、３５０ｎｍ付近におけるグラフ内の上から、順次、１．５×１０−４，７．５×１０−５，３．８×１０−５，１．９×１０−５，１．３×１０−５，１．０×１０−５，９×１０−６，７×１０−６，６×１０−６，５×１０−６Ｍとした。なお、急速な沈殿物形成によって散乱光が生じるため、溶液濃度の増加に伴って、短波長側の吸収増加が起こる。 FIG. 10 is a diagram showing a concentration-dependent absorption spectrum at 25 ° C. of an MCH solution in which PBI and CA are mixed at a ratio of 1: 1. The arrows shown in FIG. 10 indicate changes in the spectrum as the concentration decreases. The solution concentration of each spectrum λ is 1.5 × 10 −4 , 7.5 × 10 −5 , 3.8 × 10 −5 , 1.9 × 10 −5 in order from the top in the graph near 350 nm. 1.3 × 10 −5 , 1.0 × 10 −5 , 9 × 10 −6 , 7 × 10 −6 , 6 × 10 −6 , and 5 × 10 −6 M. In addition, since scattered light is generated by rapid precipitate formation, absorption on the short wavelength side increases with an increase in solution concentration.
図１０に示す濃度依存吸収スペクトルから、長波長域と短波長域との可逆的なスペクトル強度の増減が濃度の変化に伴って同期して起こっており、このことから、これらの２種の吸収帯は、同一の会合体種に由来することがわかる。 From the concentration-dependent absorption spectrum shown in FIG. 10, a reversible increase / decrease in spectral intensity between the long wavelength region and the short wavelength region occurs synchronously with the change in concentration. It can be seen that the bands are derived from the same aggregate species.
図１１は、ＰＢＩとＣＡとが１：１．２の割合である混合物のＭＣＨ溶液の励起波長λが７００ｎｍのときの蛍光励起スペクトルと吸収スペクトルとを示すグラフである。図１１において、蛍光励起スペクトルは実線で示し、吸収スペクトルは点線で示してある。 FIG. 11 is a graph showing a fluorescence excitation spectrum and an absorption spectrum when the excitation wavelength λ of the MCH solution of the mixture in which PBI and CA are in a ratio of 1: 1.2 is 700 nm. In FIG. 11, the fluorescence excitation spectrum is indicated by a solid line, and the absorption spectrum is indicated by a dotted line.
図１１に示すように、吸収スペクトルは４６０ｎｍ付近及び６３０ｎｍ付近に各々ピークを有するが、蛍光励起スペクトルは６２０ｎｍ付近に唯一のピークを有し、短波長側の吸収帯が消失していることがわかる。このことは、これら２種のエネルギー準位間の電子遷移がほぼ禁制であることを意味している。なお、蛍光励起スペクトルは、JASCO FP6600蛍光分光計を使って測定し、スペクトル測定用の溶媒を用いた。 As shown in FIG. 11, the absorption spectrum has peaks near 460 nm and 630 nm, respectively, but the fluorescence excitation spectrum has a unique peak near 620 nm, and the short wavelength side absorption band disappears. . This means that electronic transition between these two energy levels is almost forbidden. The fluorescence excitation spectrum was measured using a JASCO FP6600 fluorescence spectrometer, and a solvent for spectrum measurement was used.
図１２（ａ）は、ＰＢＩとＣＡとの混合溶液の写真及びそこに含まれる緑色の沈殿物の光学顕微鏡写真である。図１２（ａ）に示すように、この混合溶液では、緑色の沈殿物がほぼ定量的に形成される。この混合溶液は、ＰＢＩとＣＡとの混合割合を１：１とし、ＰＢＩの濃度を１．４×１０−５Ｍとして得ている。そして、ＰＢＩとＣＡとを混合してから、室温で約１時間放置すると、図１２（ａ）に示す状態となる。この沈殿物は、攪拌によって容易に壊れ、吸収スペクトルも沈殿の前後でほぼ変化がないことがわかった。 FIG. 12A is a photograph of a mixed solution of PBI and CA and an optical micrograph of a green precipitate contained therein. As shown in FIG. 12A, in this mixed solution, a green precipitate is formed almost quantitatively. In this mixed solution, the mixing ratio of PBI and CA was 1: 1, and the concentration of PBI was 1.4 × 10 −5 M. Then, after mixing PBI and CA, if left at room temperature for about 1 hour, the state shown in FIG. This precipitate was easily broken by stirring, and the absorption spectrum was found to be almost unchanged before and after precipitation.
図１２（ｂ）は、ＰＢＩとＣＡとの混合溶液の偏光光学顕微鏡写真である。図１２（ｃ）は、ＰＢＩとＣＡとの混合溶液の蛍光顕微鏡写真である。図１２（ｂ）に示すように、偏光光学顕微鏡を用いると、偏光条件下における復屈折現象によって、秩序だった分子配列をとっていることが観察できる。また、単離された沈殿物は、後述するように、均一溶液の場合と同様の吸収スペクトルを示し、かつ、図１２（ｃ）に示すようなペリレン色素のモノマーの吸収波長は完全に失われて６８８ｎｍで最大となる赤色発光が見られる。これは、水素結合の相互作用とπ−スタッキングとによって定量的にＪ会合体が形成されていることを示す。なお、偏光光学顕微鏡及び蛍光顕微鏡として、オリンパス社のOlympus BX51 optical microscopyを用いた。 FIG. 12B is a polarization optical micrograph of a mixed solution of PBI and CA. FIG. 12C is a fluorescence micrograph of a mixed solution of PBI and CA. As shown in FIG. 12B, when a polarizing optical microscope is used, it can be observed that an ordered molecular arrangement is taken due to the birefringence phenomenon under the polarization condition. In addition, as will be described later, the isolated precipitate shows an absorption spectrum similar to that in the case of a homogeneous solution, and the absorption wavelength of the monomer of the perylene dye as shown in FIG. The maximum red emission is observed at 688 nm. This indicates that a J-aggregate is quantitatively formed by the hydrogen bond interaction and π-stacking. Olympus BX51 optical microscopy manufactured by Olympus was used as a polarizing optical microscope and a fluorescence microscope.
図１３（ａ），図１３（ｂ）は、図１２に示す緑色の沈殿物の原子間力顕微鏡（Atomic force microscopy：ＡＦＭ）像である。緑色の沈殿物は、高配向性熱分解グラファイト上で１分間あたり３０００回転でスピンコートさせることによって得ている。図１３（ａ）には凹凸像を示し、図１３（ｂ）には位相像を示している。なお、原子間力顕微鏡測定は、セイコーインスツル社のSII NanoNavi stationを用いて測定し、プローブとして同社のSPA-400 Probe unitをdynamic force modeで用いた。 FIGS. 13A and 13B are atomic force microscopy (AFM) images of the green precipitate shown in FIG. A green precipitate has been obtained by spin coating at 3000 revolutions per minute on highly oriented pyrolytic graphite. FIG. 13A shows an uneven image, and FIG. 13B shows a phase image. Atomic force microscope measurement was performed using a SII NanoNavi station manufactured by Seiko Instruments Inc., and the company's SPA-400 Probe unit was used in dynamic force mode as a probe.
緑色の沈殿物は、原子間力顕微鏡で観察をした結果、幅が約３０〜１００ｎｍの範囲で、かつ、長さが数マイクロメートルのからまった繊維状のナノ構造であることが観察できる。 As a result of observing with an atomic force microscope, the green precipitate can be observed to be a fibrous nanostructure having a width in the range of about 30 to 100 nm and a length of several micrometers.
図１４は、ＰＢＩとＣＡとの混合割合を１：１としたＭＣＨ溶液から取得された緑色の沈殿物を用いて形成された薄膜の吸収スペクトルと発光スペクトルとを示す図である。図１４には、吸収スペクトルを実線で示し、発光スペクトルを点線で示している。薄膜の吸収スペクトルは、システムインスツルメンツ社のSIS-50 optical waveguide UV/Vis分光計を用いて測定した。 FIG. 14 is a diagram showing an absorption spectrum and an emission spectrum of a thin film formed using a green precipitate obtained from an MCH solution in which the mixing ratio of PBI and CA is 1: 1. In FIG. 14, the absorption spectrum is indicated by a solid line and the emission spectrum is indicated by a dotted line. The absorption spectrum of the thin film was measured using a SIS-50 optical waveguide UV / Vis spectrometer manufactured by System Instruments.
ここで、図１４に示す吸収スペクトルは、図１１に点線で示すスペクトルと同様である。一方、発光スペクトルは、モノマーの光学的性質とは異なり、６８８ｎｍに発光波長を有することがわかる。 Here, the absorption spectrum shown in FIG. 14 is the same as the spectrum shown by the dotted line in FIG. On the other hand, it can be seen that the emission spectrum has an emission wavelength at 688 nm, unlike the optical properties of the monomer.
図１５（ａ）〜図１５（ｃ）は、ＰＢＩとＣＡとの１：１の会合体として予測される超分子構造を示す図である。ここで、図示しているＲ１はＣ１２Ｈ２５を指し、Ｒ２はＣ８Ｈ１７を指す。また、図１５（ａ）〜図１５（ｃ）には、化学式近傍に、ペリレン色素を模式的に四角で示している。 FIG. 15 (a) to FIG. 15 (c) are diagrams showing supramolecular structures predicted as 1: 1 associations of PBI and CA. Here, the illustrated R 1 refers to C 12 H 25 and R 2 refers to C 8 H 17 . Further, in FIGS. 15A to 15C, perylene dyes are schematically shown by squares in the vicinity of the chemical formula.
図１５（ａ），図１５（ｂ）に示すように、ペリレン色素間の相互作用は、水素結合超分子構造内及び超分子構造間で生じうる。ＣＡ−ＣＡの水素結合からなる超分子ポリマー構造に、メラミンとＣＡとの水素結合によりＰＢＩが端にぶら下がった構造をとっていることが予測される。そして、ペリレン色素のＪ会合体の配列は、ペリレン骨格の長軸に沿って大きくずれて積層しているだけではなく、ペリレン色素同士が回転して積層していると考えられる。これにより、基底状態からの電子遷移がDavidov***によって生じる高エネルギーおよび低エネルギーの励起準位に起こるようになる。 As shown in FIGS. 15 (a) and 15 (b), the interaction between perylene dyes can occur within a hydrogen-bonded supramolecular structure and between supramolecular structures. It is predicted that the supramolecular polymer structure composed of CA-CA hydrogen bonds has a structure in which PBI is suspended at the ends by hydrogen bonds between melamine and CA. The arrangement of the J aggregates of the perylene dyes is considered not only to be largely shifted and laminated along the long axis of the perylene skeleton but also to be laminated by rotating the perylene dyes. This causes electronic transitions from the ground state to occur in the high and low energy excited levels produced by Davidov splitting.
一方、図１５（ｃ）に示すように、ペリレン色素とＪ会合体との間で相互作用は、超分子構造間でのみで生じる構造も考えられる。 On the other hand, as shown in FIG. 15C, a structure in which the interaction between the perylene dye and the J aggregate is generated only between the supramolecular structures is also conceivable.
図１６は、ＰＢＩと物質３と混合させたＭＣＨ溶媒を用いた実験手順を示す化学式ベースの図である。 FIG. 16 is a chemical formula-based diagram showing an experimental procedure using an MCH solvent mixed with PBI and substance 3.
図１７（ａ）は、図１６に示す分子種の吸収スペクトルによる滴定の実験結果を示すグラフである。図１７（ｂ）は、図１７（ａ）における波長５４２ｎｍの吸収スペクトル強度をＰＢＩの濃度に対してプロットした様子を示すグラフである。なお、この実験は、ＰＢＩの濃度が１．４×１０−５Ｍ、測定温度が２５℃であり、スペクトル測定用の溶媒を用いた。 FIG. 17A is a graph showing the results of a titration experiment using the absorption spectrum of the molecular species shown in FIG. FIG. 17B is a graph showing a state in which the absorption spectrum intensity at a wavelength of 542 nm in FIG. 17A is plotted against the PBI concentration. In this experiment, the PBI concentration was 1.4 × 10 −5 M, the measurement temperature was 25 ° C., and a solvent for spectrum measurement was used.
図１７（ａ）に示すように、物質３の濃度が増加すると、色素のスタッキング力が弱まり、このことより、ＰＢＩのドデシル鎖が明らかにＰＢＩのπ−πスタッキングを阻害することがわかる。この変化より見かけの結合定数は２３０００Ｍ−１であることが非線形最低２乗解析によって計算された。 As shown in FIG. 17 (a), when the concentration of the substance 3 is increased, the stacking power of the dye is weakened. This indicates that the dodecyl chain of PBI clearly inhibits π-π stacking of PBI. From this change, the apparent coupling constant was calculated to be 23000 M −1 by non-linear least squares analysis.
なお、緑色の沈殿物を含む溶液から固体薄膜を作成し、その固体薄膜に対して温度変化を与えてみた。その結果、固体薄膜においても、緑色と赤色との間の色彩変化が見られた。これは、色素の空間配列の変換が生じたことを意味する。しかも、この固体薄膜の表面を引掻いてみたところ、この場合にも、色彩変化が見られた。色彩変化が生じた箇所の吸収スペクトルを調べてみたところ、Ｈ会合体の吸収スペクトルを示した。 In addition, the solid thin film was created from the solution containing a green precipitate, and the temperature change was given with respect to the solid thin film. As a result, a color change between green and red was also observed in the solid thin film. This means that a conversion of the spatial arrangement of the dye has occurred. Moreover, when the surface of the solid thin film was scratched, a color change was also observed in this case. An examination of the absorption spectrum of the portion where the color change occurred showed the absorption spectrum of the H aggregate.
さらに、色彩変化が生じた箇所を、粉末Ｘ線回折（ＸＲＤ）測定したところ、ｄ＝３４．５，２０．８と１０．３Åの鋭いピークが消えていた。これは、Ｊ会合体の超分子構造に変化が起こったことを示唆する。また、色彩変化が生じた箇所を数秒間１３０℃で加熱したところ、緑色に再び変色した。これは、色素が、加熱によって、Ｊ会合体へ再配列したことを示している。このように、本発明の色素には、ピエゾクロミズムが見られる。この色素は、溶液中と同様、固体状態でも加熱をするという簡単な処理によって、Ｊ会合体からＨ会合体へ変換できるという利点を有している。そして、そのために、外部刺激として他の物質を付加する、或いは、溶媒の極性変化を行なうということも不要である。 Furthermore, when the location where the color change occurred was measured by powder X-ray diffraction (XRD), sharp peaks at d = 34.5, 20.8 and 10.3 Å disappeared. This suggests that a change has occurred in the supramolecular structure of the J-aggregate. Further, when the portion where the color change occurred was heated at 130 ° C. for several seconds, the color changed to green again. This indicates that the dye was rearranged to the J aggregate by heating. Thus, piezochromism is observed in the dye of the present invention. Similar to the solution, this dye has the advantage that it can be converted from a J-aggregate to an H-aggregate by a simple treatment of heating even in a solid state. For this purpose, it is not necessary to add another substance as an external stimulus or change the polarity of the solvent.
ところで、本発明の色素に対する加熱や引掻きに対する応答性の構造的メカニズムは、溶液中での加熱による場合とは明らかに異なる。なぜなら、固体状態では、大きな構造変換は不可能なはずだからである。むしろ、固体状態の場合には、加熱や引掻きに対する超分子ポリマー構造の無秩序化と秩序化が局所的な色素の配列に影響を与えているように見受けられる。 By the way, the structural mechanism of the responsiveness to the heating and scratching of the pigment of the present invention is clearly different from the case of heating in a solution. This is because a large structural transformation should not be possible in the solid state. Rather, in the solid state, the disorder and ordering of the supramolecular polymer structure with respect to heating and scratching appear to affect the local dye arrangement.
本明細書では、ペリレン色素を用いる場合を例に説明したが、この他にも、シアニン色素、スチリル色素、ヘミシアニン色素、メロシアニン色素、３核メロシアニン色素、４核メロシアニン色素、ロダシアニン色素、コンプレックスシアニン色素、コンプレックスメロシアニン色素、アロポーラー色素、オキソノール色素、ヘミオキソノール色素、スクアリウム色素、クロコニウム色素、アザメチン色素、クマリン色素、アリーリデン色素、アントラキノン色素、トリフェニルメタン色素、アゾ色素、アゾメチン色素、スピロ化合物、メタロセン色素、フルオレノン色素、フルギド色素、フェナジン色素、フェノチアジン色素、キノン色素、インジゴ色素、ジフェニルメタン色素、ポリエン色素、アクリジン色素、アクリジノン色素、ジフェニルアミン色素、キナクリドン色素、キノフタロン色素、フェノキサジン色素、ポルフィリン色素、クロロフィル色素、フタロシアニン色素、金属錯体色素などを用いることもできる。ただし、ペリレン系の色素のように、簡易に合成が可能な色素を用いるとよい。 In the present specification, the case where a perylene dye is used has been described as an example. , Complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye , Fluorenone dye, fulgide dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphe Triethanolamine dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, and metal complex dyes can also be used. However, a dye that can be easily synthesized, such as a perylene dye, may be used.
また、本実施形態で説明した色素は、既述のように、色素増感型太陽電池、温度計に好適に用いられるが、その他の用途として、偏光板、カラーフィルタ、インクジェットインク、有機トランジスタ、画像形成装置などのように色素を利用するもの、さらには、上記温度計の変形例として外力の有無を記憶し、加熱によってリフレッシュするメモリ装置、量子コンピュータなどに広範に適用可能である。特に、この色素は、溶解性であるので、均一にムラ無く塗布対象に塗布が行えるという利点もある。 In addition, as described above, the dye described in the present embodiment is suitably used for a dye-sensitized solar cell and a thermometer, but as other uses, a polarizing plate, a color filter, an inkjet ink, an organic transistor, The present invention can be widely applied to an apparatus that uses a dye such as an image forming apparatus, and a memory device that stores the presence or absence of external force as a modification of the thermometer and refreshes by heating, a quantum computer, and the like. In particular, since this dye is soluble, there is also an advantage that it can be applied to a coating object uniformly and without unevenness.
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