JPH04188118A - Nonlinear optical material - Google Patents
Nonlinear optical materialInfo
- Publication number
- JPH04188118A JPH04188118A JP31872190A JP31872190A JPH04188118A JP H04188118 A JPH04188118 A JP H04188118A JP 31872190 A JP31872190 A JP 31872190A JP 31872190 A JP31872190 A JP 31872190A JP H04188118 A JPH04188118 A JP H04188118A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- electron
- optical material
- organic compound
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 31
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 31
- 125000001424 substituent group Chemical group 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 17
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 150000003839 salts Chemical class 0.000 abstract description 5
- FUWINROKJJVHNT-UHFFFAOYSA-N azane N-hydroxy-N-phenylnitramide Chemical compound N.[O-][N+](=O)N(O)C1=CC=CC=C1 FUWINROKJJVHNT-UHFFFAOYSA-N 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 HCOCHa Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920013746 hydrophilic polyethylene oxide Polymers 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GVSPXQVUXHMUMA-MDWZMJQESA-N (e)-3-(3,5-ditert-butyl-4-hydroxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one Chemical compound C1=CC(OC)=CC=C1C(=O)\C=C\C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GVSPXQVUXHMUMA-MDWZMJQESA-N 0.000 description 1
- SLLFVLKNXABYGI-UHFFFAOYSA-N 1,2,3-benzoxadiazole Chemical class C1=CC=C2ON=NC2=C1 SLLFVLKNXABYGI-UHFFFAOYSA-N 0.000 description 1
- QIFZZXZSSXRDOT-UHFFFAOYSA-N 1-(4-aminophenyl)-3-(4-methoxyphenyl)prop-2-en-1-one Chemical compound C1=CC(OC)=CC=C1C=CC(=O)C1=CC=C(N)C=C1 QIFZZXZSSXRDOT-UHFFFAOYSA-N 0.000 description 1
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical class [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- MIDBJHVIQXKTQO-UHFFFAOYSA-N 7-chloro-4-nitro-1,2,3-benzoxadiazole Chemical compound [O-][N+](=O)C1=CC=C(Cl)C2=C1N=NO2 MIDBJHVIQXKTQO-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- GXCSNALCLRPEAS-CFYXSCKTSA-N azane (Z)-hydroxyimino-oxido-phenylazanium Chemical compound N.O\N=[N+](/[O-])c1ccccc1 GXCSNALCLRPEAS-CFYXSCKTSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CGTJUSQJKFEMEI-UHFFFAOYSA-N n'-(4-nitrophenyl)ethane-1,2-diamine Chemical compound NCCNC1=CC=C([N+]([O-])=O)C=C1 CGTJUSQJKFEMEI-UHFFFAOYSA-N 0.000 description 1
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical class C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 1
- HTOLGGNSOCNPBR-UHFFFAOYSA-N n,n'-bis(4-nitrophenyl)ethane-1,2-diamine Chemical compound C1=CC([N+](=O)[O-])=CC=C1NCCNC1=CC=C([N+]([O-])=O)C=C1 HTOLGGNSOCNPBR-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical class C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は高速光スイッチや光メモリその他の各種光素子
への応用が可能な非線形光学材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a nonlinear optical material that can be applied to high-speed optical switches, optical memories, and various other optical devices.
［従来の技術］
近年、光デバイスに有用なフォトニクス材料として、大
きな非線形光学効果を示し、且つ高速応答する材料がも
とめられており、広く探索研究がおこなわれている。こ
のような材料としては、格子の振動が関与する無機化合
物結晶よりも、π電子糸を有する有機化合物の方がすぐ
れているとされ、その設計指針としては、π電子共役系
を有する分子に強い電子供与性（ドナー性）置換基と電
子求引性（アクセプター性）置換基を導入する方法が有
力かつ一般的であった。[Prior Art] In recent years, there has been a demand for materials that exhibit large nonlinear optical effects and have high-speed response as photonics materials useful for optical devices, and exploration research is being carried out extensively. Organic compounds with π-electron threads are said to be better as such materials than inorganic compound crystals that involve lattice vibrations, and the design guidelines for such materials include The method of introducing an electron-donating (donor) substituent and an electron-withdrawing (acceptor) substituent has been effective and common.
また、非線形光学特性を示す有機化合物を高分子化合物
中に導入させる手法としては、大きな双極子モーメント
、を待った分子をその非線形光学特性をより効率よく発
現させるために、電界を印加しなから配向制御し、結晶
化させる方法、結晶性ポリマー中で高分子と共に結晶化
させる方法（特開平１−２７４１２２．特開平１−１８
８８３５）、高分子の側鎖に非線形光学材料を導入させ
る方法、高分子鎖との間で化学反応を起こさせ、高分子
鎖間にクロスリンキングさせる方法がとられている。In addition, as a method for introducing organic compounds that exhibit nonlinear optical properties into polymer compounds, in order to more efficiently express the nonlinear optical properties of molecules that have a large dipole moment, we orient them without applying an electric field. A method of controlling and crystallizing, a method of crystallizing together with a polymer in a crystalline polymer (JP-A-1-274122, JP-A-1-18
8835), a method in which a nonlinear optical material is introduced into the side chain of a polymer, and a method in which a chemical reaction is caused between the polymer chains to cause cross-linking between the polymer chains.
［発明が解決しようとする課題］
しかし、非線形光学特性を大きく発現させるためにπ電
子共役系を有する有機化合物に強い電子供与性及び電子
求引性置換基を導入した有機化合物においては結晶化が
難しいことや、結晶かできても、大きな双極子モーメン
トを持つことでその双極子モーメントを打ち消し合うよ
うに結晶化か起こり非線形光学特性が発現しなくなると
いった課題があった。[Problems to be Solved by the Invention] However, in organic compounds having strong electron-donating and electron-withdrawing substituents introduced into organic compounds having a π-electron conjugated system in order to significantly develop nonlinear optical properties, crystallization is difficult. It was difficult, and even if a crystal could be formed, it had a large dipole moment, which caused crystallization to cancel out the dipole moments, resulting in the nonlinear optical properties not being expressed.
また、大きな非線形光学特性を持たせる為に分子内での
共役長を伸ばすことによる吸収端の長波長化といった課
題が存在した。吸収端が長波長化すると、例えば、出力
側の高調波を吸収してしまって出力が低下してしまうな
どの欠点が出てくる。Additionally, in order to provide large nonlinear optical properties, there was the issue of increasing the wavelength of the absorption edge by increasing the conjugation length within the molecule. When the wavelength of the absorption edge becomes longer, disadvantages arise such as, for example, harmonics on the output side are absorbed, resulting in a decrease in output.
本発明は非線形光学特性が高く、吸収端の短い非線形光
学材料を提供することを目的とする。An object of the present invention is to provide a nonlinear optical material with high nonlinear optical properties and a short absorption edge.
［課題を解決するための手段］
本発明は上記課題を解決するために次の構成を有するも
のである。[Means for Solving the Problems] In order to solve the above problems, the present invention has the following configuration.
（１）化学式 で示される化合物からなる非線形光学材料。(1) Chemical formula A nonlinear optical material consisting of the compound shown in
（２）化学式
で示される化合物と、電子供与性置換基及び電子求引性
置換基を備えたπ電子共役系有機化合物との組成物から
なる非線形光学材料。(2) A nonlinear optical material comprising a composition of a compound represented by the chemical formula and a π-electron conjugated organic compound having an electron-donating substituent and an electron-withdrawing substituent.
（３）π電子共役系有機化合物が芳香環もしくは複素芳
香環化合物である前記第２項に記載の非線形光学材料。(3) The nonlinear optical material according to item 2 above, wherein the π-electron conjugated organic compound is an aromatic ring or a heteroaromatic ring compound.
（４）電子求引性置換基がシアノ基である前記第２項に
記載の非線形光学材料。(4) The nonlinear optical material according to item 2 above, wherein the electron-withdrawing substituent is a cyano group.
（５）化学式
で示される化合物が高分子化合物中に分散されてなる非
線形光学材料。(5) A nonlinear optical material in which a compound represented by the chemical formula is dispersed in a polymer compound.
（６）高分子化合物がポリエチレンオキサイドである前
記第５項に記載の１線形光学材料。(6) The one-linear optical material according to item 5 above, wherein the polymer compound is polyethylene oxide.
［作用］
本発明の上記化学式で示される有機化合物は短いπ共役
長を有するので、吸収端が短くなり、従って出力される
高調波を吸収するおそれが少な（なり、大きな非線形光
学特性を発現させることかできる。また上記化学式で示
される有機化合物は分子内塩の構造をとっているために
、結晶状態が安定で結晶が作製しやすくなる。[Function] Since the organic compound represented by the above chemical formula of the present invention has a short π conjugation length, the absorption edge is shortened, and there is therefore less risk of absorbing output harmonics (which results in the development of large nonlinear optical properties). Furthermore, since the organic compound represented by the above chemical formula has an inner salt structure, the crystal state is stable and crystals can be easily produced.
さらに、本発明の第２ならびに第３の発明においては、
分子レベルでは大きな非線形光学特性が期待されるにも
かかわらず、結晶が中心対称構造を持つために非線形光
学特性を示さない電子供与性置換基及び電子求引性置換
基を備えたπ電子共役系有機化合物であっても、上記化
学式で示される化合物と複合化させ組成物とする事によ
り、中心対称構造を持たない結晶構造に変化させ、高い
非線形光学特性を有する組成物からなる非線形光学材料
を得ることができる。Furthermore, in the second and third aspects of the present invention,
A π-electron conjugated system with electron-donating and electron-withdrawing substituents that does not exhibit nonlinear optical properties because the crystal has a centrosymmetric structure, although it is expected to have significant nonlinear optical properties at the molecular level. Even if it is an organic compound, by compounding it with the compound represented by the above chemical formula to form a composition, it can be changed to a crystal structure that does not have a centrosymmetric structure, and a nonlinear optical material made of a composition that has high nonlinear optical properties can be created. Obtainable.
第４の発明においては、電子求引性置換基がシアノ基で
あるπ電子共役系有機化合物を用いるので、より吸収端
の短波長化が容易になる。In the fourth invention, since a π-electron conjugated organic compound in which the electron-withdrawing substituent is a cyano group is used, it becomes easier to shorten the wavelength of the absorption edge.
また、第５ならびに第６番目の発明においては高分子化
合物中に均一分散させることにより、この非線形光学材
料を用いる際の成形性を向上させることが可能である。Furthermore, in the fifth and sixth inventions, it is possible to improve the moldability when using this nonlinear optical material by uniformly dispersing it in a polymer compound.
特に、コーティングやスピンコードなども適用できるの
で均一な薄膜状成形物も容易に作製できる。この際にも
、上記化学式の有機化合物の吸収端が短いこと、分子内
塩構造を持つことにより組成物の結晶安定性を高くし、
吸収端の短波長化が可能になる。In particular, since coatings, spin cords, etc. can also be applied, uniform thin film-like molded products can be easily produced. In this case, the organic compound of the above chemical formula has a short absorption edge and an inner salt structure, which increases the crystal stability of the composition.
It becomes possible to shorten the wavelength of the absorption edge.
また、さらに、第６番目の発明においては高分子化合物
として親水性のポリエチレンオキサイドを使用している
ので、前述の有機化合物の分散が一層容易になる。Furthermore, in the sixth invention, hydrophilic polyethylene oxide is used as the polymer compound, so that the above-mentioned organic compound can be further easily dispersed.
［実施例］
本発明の前記化学式で示される有機化合物であるクペロ
ン（Ｎ−ニトロソフェニルヒドロキシルアミンアンモニ
ウム塩）は良好な非線形光学特性を示すので、クペロン
単独で非線形光学材料とすることもできる。[Example] Since cuperone (N-nitrosophenylhydroxylamine ammonium salt), which is an organic compound represented by the above chemical formula of the present invention, exhibits good nonlinear optical properties, cuperone alone can be used as a nonlinear optical material.
また、電子供与性置換基及び電子求引性置換基を備えた
π電子共役系有機化合物と複合化させて組成物として用
い、両者の非線形光学特性を良好に発現させることもで
きる。In addition, it can be used as a composition in a composite with a π-electron conjugated organic compound having an electron-donating substituent and an electron-withdrawing substituent, and the nonlinear optical properties of both can be expressed well.
電子供与性置換基としては、例えば−０Ｈ１−〇ＣＨ１
−ＯＣＯＣＨ３、−ＮＨ２、−Ｎ（ＣＨ３） ２ 、Ｎ
ＨＣＯＣＨａ 、ＣＨ３などのアルキル基、 Ｃ：
６Ｈｓなどのアリール基などが挙げられる。As the electron-donating substituent, for example, -0H1-〇CH1
-OCOCH3, -NH2, -N(CH3)2,N
Alkyl group such as HCOCHa, CH3, C:
Examples include aryl groups such as 6Hs.
また、電子求引性置換基としては、例えば、−ＮＨ３、
−ＣＦ３、−ＣＣ１１−ＮＯ２、−ＣＮ、−ＣＨｏｌ−
ＣＯＣＨ３、−ＣＯ２Ｃ２Ｈ５、−ＣＯＯＨ，−８ｏ２
ＣＨ３、−８ｏ３Ｈ，−Ｆ。In addition, examples of electron-withdrawing substituents include -NH3,
-CF3, -CC11-NO2, -CN, -CHol-
COCH3, -CO2C2H5, -COOH, -8o2
CH3, -8o3H, -F.
−ＣＩ、 Ｂｒ、 Ｉ、 ＣＨ２ＣＩ、 ＣＨ＝
ＣＨＮＯ２などが挙げられる。-CI, Br, I, CH2CI, CH=
Examples include CHNO2.
電子供与性置換基及び電子求引性置換基を備えたπ電子
共役系有機化合物としては、例えば、ｐ−ニトロアニリ
ン、Ｎ−（ｐ−ニトロフェニル）エチレンジアミン、ジ
（ｐ−二トロフェニル）エチレンジアミン等のニトロア
ニリン系化合物誘導体の他に、ｐ−シアノアニリン等の
シアノアニリン系化合物誘導体などの電子供与性置換基
及び電子求引性置換基を有する芳香環化合物や、電子供
与性置換基及び電子求引性置換基を備えたスチルベン系
化合物誘導体やベンザルアセトフェノン誘導体等の共役
オレフィン化合物、電子供与性置換基及び電子求引性置
換基を備えたベンゾオキサジアゾール誘導体やニトロピ
リジン誘導体等の複素環化合物、ベンジリデンアニリン
誘導体等の芳香環を有するシッフベース化合物等が挙げ
られる。Examples of the π-electron conjugated organic compound having an electron-donating substituent and an electron-withdrawing substituent include p-nitroaniline, N-(p-nitrophenyl)ethylenediamine, and di(p-nitrophenyl)ethylenediamine. In addition to nitroaniline compound derivatives such as p-cyanoaniline, aromatic ring compounds having electron-donating substituents and electron-withdrawing substituents, Conjugated olefin compounds such as stilbene compound derivatives and benzalacetophenone derivatives with an electron-withdrawing substituent; complex compounds such as benzoxadiazole derivatives and nitropyridine derivatives with an electron-donating substituent and an electron-withdrawing substituent; Examples include ring compounds and Schiff base compounds having an aromatic ring such as benzylidene aniline derivatives.
具体的には、電子供与性置換基及び電子求引性置換基を
備えた１、４置換ナフタレン誘導体、４−シメチルアミ
ノー４−スチルベン、３−（４−メトキシフェニル）−
１−（４−アミノフェニル）−２−プロペン−１−オン
、電子供与性置換基及び電子求引性置換基を備えたカル
コン誘導体、４−ニトロ−７−クロロベンゾオキサジア
ゾール、４° −二トロペンジリデン−３−アセチルア
ミノ−４−メトキシアニリン、Ｎ−（４−ピリジニルメ
チレン）−４−ジメチルアミノベンゼナミン・ジメチル
スルフェート、Ｎ−［２−（５−ニトロベンジリデン）
］ −］４−メトキシベンゼナミン及びこれらの類似化
合物が適用可能である。Specifically, 1,4-substituted naphthalene derivatives with an electron-donating substituent and an electron-withdrawing substituent, 4-dimethylamino-4-stilbene, 3-(4-methoxyphenyl)-
1-(4-aminophenyl)-2-propen-1-one, chalcone derivative with electron-donating and electron-withdrawing substituents, 4-nitro-7-chlorobenzoxadiazole, 4° - Nitropenzylidene-3-acetylamino-4-methoxyaniline, N-(4-pyridinylmethylene)-4-dimethylaminobenzenamine dimethylsulfate, N-[2-(5-nitrobenzylidene)
]-]4-methoxybenzenamine and similar compounds thereof are applicable.
前記化学式で示されるクペロンと電子供与性置換基及び
電子求引性置換基を備えたπ電子共役系有機化合物との
組成物における両者の配合割合は、前者２０〜８０モル
％に対し後者８０〜２０モル％の範囲が好ましい。In a composition of cuperone represented by the above chemical formula and a π-electron conjugated organic compound having an electron-donating substituent and an electron-withdrawing substituent, the proportion of both is 20 to 80 mol% for the former and 80 to 80 mol% for the latter. A range of 20 mol% is preferred.
この組成物は通常クペロンと電子供与性置換基及び電子
求引性置換基を備えたπ電子共役系有機化合物とを混合
し、溶融させて結晶とする事により調整される。This composition is usually prepared by mixing cuperone and a π-electron conjugated organic compound having an electron-donating substituent and an electron-withdrawing substituent, and melting the mixture to form a crystal.
前記化学式で示される化合物クペロン、あるいはクペロ
ンと電子供与性置換基及び電子求引性置換基を備えたπ
電子共役系有機化合物とからなる組成物を高分子化合物
に分散させる場合には、クペロン、あるいはクペロンと
電子供与性置換基及び電子求引性置換基を備えたπ電子
共役系有機化合物とからなる組成物の配合割合は、通常
５〜２０重量％程度である。The compound cuperone represented by the above chemical formula, or π containing cuperone and an electron-donating substituent and an electron-withdrawing substituent
When dispersing a composition consisting of an electron-conjugated organic compound in a polymer compound, cuperone, or a composition consisting of cuperone and a π-electron-conjugated organic compound having an electron-donating substituent and an electron-withdrawing substituent. The blending ratio of the composition is usually about 5 to 20% by weight.
これらを分散させる高分子化合物としては、ポリエチレ
ンオキサイド、ポリビニルアルコール、ポリメタクリル
酸メチル、ポリビニルアセタール、エポキシ樹脂などが
好ましく、その他、水ないし溶媒に可溶性の合成樹脂な
どの高分子化合物が適用できる。As the polymer compound for dispersing these, polyethylene oxide, polyvinyl alcohol, polymethyl methacrylate, polyvinyl acetal, epoxy resin, etc. are preferable, and other polymer compounds such as synthetic resins soluble in water or solvents can be used.
クペロン、あるいはクペロンと電子供与性置換基及び電
子求引性置換基を備えたπ電子共役系有機化合物とから
なる組成物を高分子化合物に分散させるには、通常は、
これらの共通の溶媒を用いて溶液状にして配合すること
が均一な分散ができるので好ましい。In order to disperse cuperone or a composition consisting of cuperone and a π-electron conjugated organic compound having an electron-donating substituent and an electron-withdrawing substituent in a polymer compound, usually,
It is preferable to formulate a solution using these common solvents and blend them, since uniform dispersion can be achieved.
以下に具体的な実施例を用いて本発明をさらに詳細に説
明する。The present invention will be explained in more detail below using specific examples.
実施例１
白色粉末結晶状のクペロン（Ｃ６Ｈ９Ｎ３０２）（和光
紬薬、特級）にＮｄ：ＹＡＧレーザ−（１０６４ｎｍ）
を入射すると尿素と同程度のＳＨＧ （第２次高調波発
生）が観測された。第１図に示す様に紫外・可視分光分
析の測定結果から、この吸収端は３７０ｎｍであった。Example 1 Nd:YAG laser (1064 nm) was applied to white powder crystalline Cuperon (C6H9N302) (Wako Tsumugi Pharmaceutical, special grade).
When urea was injected, SHG (second harmonic generation) comparable to that of urea was observed. As shown in FIG. 1, the absorption edge was 370 nm from the measurement results of ultraviolet/visible spectroscopy.
従って、出力される５３２ｎｍの波長の第２次高調波が
吸収されるおそれがなく、良好な非線形光学特性を有す
ることがわかった。Therefore, it was found that there is no fear that the second harmonic of the wavelength of 532 nm that is output is absorbed, and that it has good nonlinear optical characteristics.
実施例２
白色粉末結晶状のクペロンをｐ−シアノアニリンとモル
比１：１で１５０°Ｃ〜１６０℃に加熱し混合溶融させ
た後、冷却固化さた。得られた組成物にＮｄ：ＹＡＧレ
ーザーを入射すると、尿素の数倍程度のＳＨＧが観測さ
れた。単独での結晶が白色であるのに対し、複合化させ
た物質が淡黄色に着色したことから分子間で新たな相互
作用が起きたものと考える。第２図に得られた結晶の紫
外・可視分光分析結果を示した。Example 2 Cuperone in the form of white powder crystal was mixed and melted with p-cyanoaniline at a molar ratio of 1:1 at 150°C to 160°C, and then cooled and solidified. When the resulting composition was irradiated with a Nd:YAG laser, several times as much SHG as urea was observed. While the crystals alone are white, the composite material is pale yellow, suggesting that a new interaction has occurred between the molecules. FIG. 2 shows the results of ultraviolet/visible spectroscopic analysis of the obtained crystals.
実施例３
ポリエチレンオキサイド（以下ＰＥＯと略称する）５ｇ
を１００ｍ ｌのメタノール中に撹拌しながら溶解させ
、均一なＰＥＯ溶液とした。このＰＥＯ溶液中に白色粉
末結晶状のクペロン１ｇを溶解させ、均一な溶液状態と
した後、ガラス基板上にスピンコードし、６０℃で加熱
してメタノールを蒸発させた。得られたＰＥＯ，／クペ
ロンの薄膜に、Ｎｄ二ＹＡＧレーザーを入射したところ
、ＳＨＧが観測された。溶媒であるメタノールを蒸発さ
せる際に、電界を印加しながらおこなうと、さらにクペ
ロン分子の配向性が向上し、より大きなＳＨＧが観測さ
れ得る。Example 3 5 g of polyethylene oxide (hereinafter abbreviated as PEO)
was dissolved in 100 ml of methanol with stirring to obtain a homogeneous PEO solution. 1 g of cuperone in the form of a white powder crystal was dissolved in this PEO solution to form a uniform solution, which was then spin-coded onto a glass substrate and heated at 60° C. to evaporate methanol. When a Nd2YAG laser was applied to the obtained PEO/cuperon thin film, SHG was observed. If methanol, which is a solvent, is evaporated while applying an electric field, the orientation of cuperone molecules is further improved, and a larger SHG can be observed.
実施例４
白色粉末結晶状のクペロンを蒸着装置の坩堝に入れ、１
Ｏ−７Ｔｏｒｒの真空下で１００℃で加熱気化させると
ともにガラス基板上に蒸着した。Example 4 White powdered crystalline cuperone was put into a crucible of a vapor deposition device, and 1
It was vaporized by heating at 100° C. under a vacuum of O-7 Torr and was deposited on a glass substrate.
（膜厚１μｍ）。(Film thickness 1 μm).
得られた非線形光学材料薄膜にＮｄ：ＹＡＧレーザーを
入射したところ、ＳＨＧが観測された。When a Nd:YAG laser was applied to the obtained nonlinear optical material thin film, SHG was observed.
［発明の効果コ
本発明は前記化学式で示される有機化合物からなる非線
形光学材料を用いたので、吸収端が短くなり、大きな非
線形光学特性を発現させることができる非線形光学材料
を提供できる。また上記化学式で示される有機化合物は
分子内塩の構造をとっているために、結晶状態が安定で
結晶が作製しやすくなる。[Effects of the Invention] Since the present invention uses a nonlinear optical material made of an organic compound represented by the above chemical formula, it is possible to provide a nonlinear optical material that has a short absorption edge and can exhibit large nonlinear optical characteristics. Furthermore, since the organic compound represented by the above chemical formula has an inner salt structure, the crystal state is stable and crystals can be easily produced.
さらに、本発明の第２ならびに第３の発明においては、
分子レベルでは大きな非線形光学特性が期待されるにも
かかわらず、結晶が中心対称構造を持つために非線形光
学特性を示さない電子供与性置換基及び電子求引性置換
基を備えたπ電子共役系有機化合物であっても、前記化
学式で示される化合物と複合化させ組成物とする事によ
り、高い非線形光学特性を有する非線形光学材料を提供
することができる。Furthermore, in the second and third aspects of the present invention,
A π-electron conjugated system with electron-donating and electron-withdrawing substituents that does not exhibit nonlinear optical properties because the crystal has a centrosymmetric structure, although it is expected to have significant nonlinear optical properties at the molecular level. Even if it is an organic compound, a nonlinear optical material having high nonlinear optical properties can be provided by compounding it with a compound represented by the above chemical formula to form a composition.
第４の発明においては、電子求引性置換基がシアノ基で
あるπ電子共役系有機化合物を用いるので、より吸収端
の短波長化が容易になる。In the fourth invention, since a π-electron conjugated organic compound in which the electron-withdrawing substituent is a cyano group is used, it becomes easier to shorten the wavelength of the absorption edge.
また、第５ならびに第６番目の発明においては高分子化
合物中に均一分散させることによりこの非線形光学材料
を用いる際の成形性を向上させることが可能になる。こ
の際にも、上記化学式の有機化合物の吸収端が短いこと
、分子内塩構造を持つことにより組成物の結晶安定性を
高くし、吸収端の短波長化が可能になる。Furthermore, in the fifth and sixth inventions, it is possible to improve the moldability when using this nonlinear optical material by uniformly dispersing it in a polymer compound. In this case, the organic compound having the above chemical formula has a short absorption edge and has an inner salt structure, thereby increasing the crystal stability of the composition and making it possible to shorten the wavelength of the absorption edge.
また、さらに、第６番目の発明においては高分子化合物
として親水性のポリエチレンオキサイドを使用している
ので、前述の有機化合物の分散が一層容易になる。Furthermore, in the sixth invention, hydrophilic polyethylene oxide is used as the polymer compound, so that the above-mentioned organic compound can be further easily dispersed.
本発明の非線形光学材料は、非線形光学特性が優れてい
るので、光スィッチ、光メモリなどの各種光素子に適用
できる。Since the nonlinear optical material of the present invention has excellent nonlinear optical properties, it can be applied to various optical devices such as optical switches and optical memories.
第１図はクペロンの紫外・可視分光分析結果を示す図で
ある。
第２図はクペロンとｐ−シアノアニリン組成物の紫外・
可視分光分析結果を示す図である。
特許出願人 松下電器産業株式会社
代理人の氏名 弁理士 池内寛幸 ほか１名第１図FIG. 1 is a diagram showing the results of ultraviolet/visible spectroscopic analysis of Cuperon. Figure 2 shows the ultraviolet radiation of cuperone and p-cyanoaniline composition.
FIG. 3 is a diagram showing visible spectroscopic analysis results. Patent applicant: Matsushita Electric Industrial Co., Ltd. Name of agent: Patent attorney Hiroyuki Ikeuchi and one other person Figure 1
Claims (6)
置換基を備えたπ電子共役系有機化合物との組成物から
なる非線形光学材料。(2) Nonlinear optical material consisting of a composition of a compound represented by the chemical formula ▲ Numerical formula, chemical formula, table, etc. ▼ and a π-electron conjugated organic compound having an electron-donating substituent and an electron-withdrawing substituent .
香環化合物である請求項２に記載の非線形光学材料。(3) The nonlinear optical material according to claim 2, wherein the π-electron conjugated organic compound is an aromatic ring or a heteroaromatic ring compound.
載の非線形光学材料。(4) The nonlinear optical material according to claim 2, wherein the electron-withdrawing substituent is a cyano group.
線形光学材料。(5) A nonlinear optical material in which a compound represented by the chemical formula ▲Mathematical formula, chemical formula, table, etc.▼ is dispersed in a polymer compound.
求項５に記載の非線形光学材料。(6) The nonlinear optical material according to claim 5, wherein the polymer compound is polyethylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31872190A JPH04188118A (en) | 1990-11-22 | 1990-11-22 | Nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31872190A JPH04188118A (en) | 1990-11-22 | 1990-11-22 | Nonlinear optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04188118A true JPH04188118A (en) | 1992-07-06 |
Family
ID=18102224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31872190A Pending JPH04188118A (en) | 1990-11-22 | 1990-11-22 | Nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04188118A (en) |
-
1990
- 1990-11-22 JP JP31872190A patent/JPH04188118A/en active Pending
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