JPH0789188B2 - Novel organic nonlinear optical material and second harmonic generation method using the same - Google Patents
Novel organic nonlinear optical material and second harmonic generation method using the sameInfo
- Publication number
- JPH0789188B2 JPH0789188B2 JP19756788A JP19756788A JPH0789188B2 JP H0789188 B2 JPH0789188 B2 JP H0789188B2 JP 19756788 A JP19756788 A JP 19756788A JP 19756788 A JP19756788 A JP 19756788A JP H0789188 B2 JPH0789188 B2 JP H0789188B2
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- optical material
- harmonic
- group
- organic nonlinear
- 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.)
- Expired - Lifetime
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は波長変換素子等の非線形光学効果を利用する各
種素子に用いるに適した非線形光学材料に関する。ま
た、非線形光学材料を用いた第二高調波の発生方法に関
する。TECHNICAL FIELD The present invention relates to a nonlinear optical material suitable for use in various elements such as wavelength conversion elements that utilize nonlinear optical effects. Further, the present invention relates to a method of generating a second harmonic using a nonlinear optical material.
（従来の技術） 近年、非線形光学効果−レーザー光のような強い光電界
を与えたときに現われる、分極と電界との間の非線形性
−を有した材料が注目を集めている。(Prior Art) In recent years, a material having a non-linear optical effect-a non-linearity between a polarization and an electric field, which appears when a strong optical electric field such as a laser beam is applied, has been attracting attention.
かかる材料は、一般に非線形光学材料として知られてお
り、例えば次のものなどに詳しく記載されている。“No
nliner Optcal Properties of Organic and Polymeric
Materials"ACS SYMPOSIUM SERIES 233、David J.Willia
ms編（American Chemical Society,1983年刊）、「有機
非線形光学材料」加藤政雄、中西八郎監修（シー・エム
・シー社、1985年刊）。Such materials are generally known as nonlinear optical materials and are described in detail in, for example, the following. "No
nliner Optcal Properties of Organic and Polymeric
Materials "ACS SYMPOSIUM SERIES 233, David J. Willia
Edited by ms (American Chemical Society, 1983), "Organic Nonlinear Optical Materials", supervised by Masao Kato, Hachiro Nakanishi (CMC, 1985).
非線形光学材料の用途の１つに、２次の非線形効果に基
づいた第２高調波発生（SHG）および和周波、差周波を
用いた波長変換デバイスがある。これまで実用上用いら
れているものは、ニオブ酸リチウムに代表される無機質
のペロブスカイト類である。しかし近年になり、電子供
与基および電子吸引基を有するπ電子共役系有機化合物
は前述の無機質を大きく上回る、非線形光学材料として
の諸性能を有していることが知られるようになつた。One of the applications of the nonlinear optical material is a second harmonic generation (SHG) based on the second-order nonlinear effect and a wavelength conversion device using a sum frequency and a difference frequency. So far, those which have been practically used are inorganic perovskites represented by lithium niobate. However, in recent years, it has become known that a π-electron conjugated organic compound having an electron-donating group and an electron-withdrawing group has various performances as a nonlinear optical material, which greatly exceeds the above-mentioned inorganic substances.
しかしながら、高いSHGを示すことで知られているｐ−
ニトロアニリンの場合に代表されるように、分子状態で
は大きな非線形分極率を有していても、結晶状態では全
く２次の非線形光学効果を示さないものが頻々見られ
る。これは、結晶での分子の配列に反転対称性が生じた
結果である。このため、分子内に不斉炭素を有する置換
基を導入したり、分子の対称性を崩すことが検討されて
いる。しかし、これらの場合にも、必ずしも常に満足の
いく結果を与えるものではなかつた。However, p- which is known to show high SHG
As typified by the case of nitroaniline, it is often found that even if it has a large non-linear polarizability in the molecular state, it exhibits no second-order non-linear optical effect in the crystalline state. This is a result of inversion symmetry in the molecular arrangement in the crystal. Therefore, introduction of a substituent having an asymmetric carbon atom into the molecule or breaking the symmetry of the molecule has been studied. However, even in these cases, the result is not always satisfactory.
（発明が解決しようとする課題） 従つて、本発明の第一の目的は結晶状態において非線形
光学効果を示す新規な有機化合物を提供することにあ
る。(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a novel organic compound which exhibits a nonlinear optical effect in a crystalline state.
第二の目的は非線形光学効果のうちの第二高調波発生の
方法を提供することにある。A second object is to provide a method of generating the second harmonic of the nonlinear optical effect.
（課題を解決するための手段） 本発明者らは、鋭意研究を重ねた結果、下記一般式
（Ｉ）で表わされる化合物を非線形光学応答性化合物と
して用いることにより、本発明の目的が達成可能なこと
を見出した。(Means for Solving the Problems) As a result of intensive studies, the inventors of the present invention can achieve the object of the present invention by using a compound represented by the following general formula (I) as a nonlinear optical responsive compound. I found that.
すなわち、本発明は下記の（１）および（２）である。That is, the present invention is the following (1) and (2).
（１） 下記の一般式（Ｉ）で表わされる化合物からな
る有機非線形光学材料。(1) An organic nonlinear optical material comprising a compound represented by the following general formula (I).
一般式（Ｉ） 式中、Arはアリール基を表わし、Ｚは５員の含有窒素複
素環を形成するに必要な原子群を表わす。但し、該複素
環において、酸素原子に二重結合で結合した炭素原子に
は窒素原子が隣接する。General formula (I) In the formula, Ar represents an aryl group, and Z represents an atomic group necessary for forming a 5-membered nitrogen heterocycle. However, in the heterocycle, a nitrogen atom is adjacent to a carbon atom bonded to an oxygen atom by a double bond.
（２） レーザー光と非線形光学材料とを用いて第二高
調波を発生させる際に、非線形光学材料として前記
（１）の有機非線形光学材料を用いる第二高調波の発生
方法。(2) A method of generating a second harmonic using the organic nonlinear optical material according to (1) above as a nonlinear optical material when generating a second harmonic using a laser beam and a nonlinear optical material.
Arで表わされるアリール基としては、例えばフエニル基
および電子供与性基で置換されたフエニル基、ナフチル
基および電子供与性基で置換されたナフチル基が挙げら
れる。中でも電子供与性基で置換されたフエニル基が好
ましい。特に、アルキルチオ基（例えば、メチルチオ
基、エチルチオ基）、およびアルコキシ基（例えば、メ
トキシ基、エトキシ基）、およびアミノ基（例えば、ア
ミノ基、ジメチルアミノ基）で且つ炭素数９以下のもの
が好ましい。なお、上記の電子供与基とは置換基定数σ
＋が負の置換基を指す。Examples of the aryl group represented by Ar include a phenyl group substituted with a phenyl group and an electron donating group, a naphthyl group and a naphthyl group substituted with an electron donating group. Of these, a phenyl group substituted with an electron donating group is preferable. Particularly, an alkylthio group (for example, a methylthio group, an ethylthio group), an alkoxy group (for example, a methoxy group, an ethoxy group), an amino group (for example, an amino group, a dimethylamino group) and a carbon number of 9 or less are preferable. . The electron donating group is a substituent constant σ
+ Indicates a negative substituent.
上記置換基定数は、構造活性相関懇話会編「化学の領
域」像122号の「薬物の構造活性相関−ドラツクデザイ
ンと作用機作研究への指針」95〜111頁 南江堂社刊や
コルビン・ハンシユ（Corwin・Hansch）、アルバート・
レオ（Albert.Leo）著、「サブステイチユーアント・コ
ンスタンツ・フオー・コーリレーシヨン・アナリシス・
イン・ケミストリー・アンド・バイオロジー」（Substi
tuent Constants for Correlation Analysis in Chemis
try and Biology）69〜161頁 ジヨン・ワイリー・アン
ド・サンズ（John Wiley and Sons）社刊に示された値
を表わす。The above substituent constants can be found in "Structure-Activity Relationships of Drugs-Guideline for Drug Design and Mechanism of Action Studies", Image No. 122 edited by the Society for Structure-Activity Relationship Discussion, pages 95-111, Nankodo Publishing Co. Hanwin (Corwin · Hansch), Albert ·
By Albert.Leo, "Substation Youth Constants For Correspondence Analysis."
In Chemistry and Biology "(Substi
tuent Constants for Correlation Analysis in Chemis
try and Biology) 69 to 161 page Represents the value shown in John Wiley and Sons.
Ｈは水素原子を表わす。アリール基は前述のArと同義で
あり、炭素数は９以下のものが好ましい。なお、Ｒとし
ては水素原子が最も好ましい。H represents a hydrogen atom. The aryl group has the same meaning as Ar described above and preferably has 9 or less carbon atoms. Note that R is most preferably a hydrogen atom.
Ｚによつて形成される５員含窒素複素環としてはデービ
ツド エム スターマー（David M.Sturmer）著「ケミ
ストリー オブ ヘテロサイクリツク コンパウンズ」
（Chemistry of Heterocyclic Compounds）；アーノル
ド ワイスバーガー（Arnold Weisberger），エドワー
ド シー テイラー（Edward C.Taylor）共編、第30
巻、第８章「シンセーゼス アンド プロパテイーズ
オブ シアニン アンド リレーテイツドダイズ」（Sy
ntheses and Properties of Cyanine and Related Dye
s）ジヨン ワイリー アンド サンズ（John Wiley＆S
ons）社 19年刊 459頁に示されているものが挙げられ
る。The 5-membered nitrogen-containing heterocycle formed by Z is described in "Chemistry of Heterocyclic Compounds" by David M. Sturmer.
(Chemistry of Heterocyclic Compounds); co-edited by Arnold Weisberger and Edward C. Taylor, No. 30
Volume 8, Chapter 8 "Syntheses and Properties"
Of cyanine and relayed soybean ”(Sy
ntheses and Properties of Cyanine and Related Dye
s) John Wiley & S
ons) company 19 years page 459 is shown.
これらのうち、２−チオヒダントイン類、ロダニン類、
５−ピラゾロン類、チアゾリジン−2,4−ジオン類、オ
キサゾリジン−2,4−ジオン、ヒダントイン、２−チオ
キソオキサゾリジン−４−オンの５員複素環が好まし
く、特にこれらの窒素原子上の置換基の炭素数が４以下
のものが好ましい。Of these, 2-thiohydantoins, rhodanins,
5-membered heterocycles of 5-pyrazolones, thiazolidine-2,4-diones, oxazolidin-2,4-diones, hydantoin, 2-thioxooxazolidin-4-one are preferable, and substituents on these nitrogen atoms are particularly preferable. Having 4 or less carbon atoms are preferable.
以下に、本発明に用いられる化合物の具体例を示すが、
本発明の範囲はこれらのみに限定されるものではない。The specific examples of the compounds used in the present invention are shown below,
The scope of the present invention is not limited to these.
これらの化合物の合成は、活性メチレンを有する複素環
化合物と、芳香族ケトン又はアルデヒドとを脱水縮合さ
せることにより容易に行なえる。その際の反応条件につ
いては「オーガニツク・グループ・プリパレーシヨン
ズ」（Organic Functional Group Preparations）第２
章,C頃,;S.R.サンドラー（Sandler）;W.カロー（Karo）
著アカデミツク出版（New York London）1968年刊など
を参考にすることができる。 The synthesis of these compounds can be easily carried out by dehydration condensation of a heterocyclic compound having active methylene and an aromatic ketone or aldehyde. Regarding the reaction conditions at that time, please refer to "Organic Group Preparations" No. 2
Chapter, Around C ,; SR Sandler; W. Karo
Author Academic Academic Publishing (New York London) 1968, etc. can be referred to.
後述の実施例より明らかなように、本発明の非線形光学
材料は波長変換用の材料として特に有用なものである。
しかしながら本発明の非線形光学材料の用途は波長変換
素子にかぎられるものではなく、非線形光学効果を利用
するものであればいかなる素子にも使用可能である。As will be apparent from the examples described below, the nonlinear optical material of the present invention is particularly useful as a material for wavelength conversion.
However, the application of the nonlinear optical material of the present invention is not limited to the wavelength conversion element, and it can be used for any element as long as it utilizes the nonlinear optical effect.
本発明の化合物は、例えば粉末の形、宿主格子（ポリマ
ー、包接化合物、固溶体、液晶）中の分子の包有物の
形、支持体上に沈積した薄層の形（ラングミーア・ブロ
ジエツト膜など）、単結晶の形、溶液の形等、種々の形
で非線形光学材料として用いることができる。The compounds according to the invention are, for example, in the form of powders, inclusions of molecules in the host lattice (polymers, clathrates, solid solutions, liquid crystals), in the form of thin layers deposited on supports (Langmere Brodgett's membranes, etc.). ), A single crystal form, a solution form, and the like, and can be used as a nonlinear optical material in various forms.
また本発明の化合物をペンダントの形でポリマー、ポリ
ジアセチレンなどに結合させて用いることもできる。Also, the compound of the present invention can be used in the form of a pendant linked to a polymer, polydiacetylene or the like.
これらの方法について詳しくは前述のD.J.Williams編の
著作などに記載されている。Details of these methods are described in the above-mentioned book edited by DJ Williams.
（実施例） 次に、本発明を実施例に基づいて詳しく説明する。(Example) Next, the present invention will be described in detail based on an example.
実施例 第２高調波発生の測定をエス・ケー・クルツ（S.K.Kurt
z）、テイー・テイー・ペリー（T.T.Perry）著、ジヤー
ナル オブ アプライド フイジツクス（J.Appl.Phy
s.）39巻3798頁（1968年刊）中に記載されている方法に
準じて、本発明の化合物の粉末に対して行つた。Example The measurement of the second harmonic generation is performed by SK Kurt.
z) by TTPerry, Journal of Applied Physics (J.Appl.Phy)
s.) 39, page 3798 (published in 1968), according to the method described in the powder of the compound of the present invention.
第１図に示した装置により測定を行つた。The measurement was performed by the apparatus shown in FIG.
すなわち、測定は、パルスYAGレーザー光（λ＝1.064μ
ｍ、ビーム径≒1mmφ、ピークパワー≒10Mw/cm2）を基
本波に用い、第１図に示す評価装置にて、その第２高調
波の強度を測定した。測定は、尿素の第２高調波の強度
との相対比較で行った。また強度が弱い場合には目視に
よる観測を行った。特に、基本波の２光子吸収による発
光（おもに黄、赤の発光）と第２高調波とを区別するた
めに、分光器を入れ、第２高調波のみを測定する様にし
た。さらに粉末法の測定は、その物質の非線形性の有無
を判断することが主目的であり、その強度比は非線形性
の大きさの、参考値であることから、フオトマルによる
検出だけでなく、目視による観測も同時に行った。In other words, the measurement is based on pulsed YAG laser light
m, beam diameter ≈ 1 mmφ, peak power ≈ 10 Mw / cm 2 ) was used as the fundamental wave, and the intensity of the second harmonic was measured by the evaluation device shown in FIG. The measurement was performed by relative comparison with the intensity of the second harmonic of urea. When the strength was weak, visual observation was performed. In particular, in order to distinguish the light emission (mainly yellow and red light emission) due to the two-photon absorption of the fundamental wave and the second harmonic wave, a spectroscope is inserted and only the second harmonic wave is measured. Furthermore, the main purpose of powder method measurement is to determine the presence or absence of non-linearity of the substance.Since the intensity ratio is a reference value for the magnitude of non-linearity, it is not only detected by Futomaru but also visually. The observation was also done at the same time.
結果を表１に示した。The results are shown in Table 1.
第１図に粉末法の測定装置を示すが、図中の番号は下記
を示す。 1:粉末試料、2:基本波カツトフイルター 3:分光器、4:フオトマル、5:アンプ （11）：波長1.064μｍ、（12）:0.532μｍFIG. 1 shows the measuring apparatus of the powder method, and the numbers in the figure indicate the following. 1: powder sample, 2: fundamental wave cut filter 3: spectroscope, 4: photometer, 5: amplifier (11): wavelength 1.064 μm, (12): 0.532 μm
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｄ 263/46 277/34 277/36 413/06 ３１７ 417/06 ３１７ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C07D 263/46 277/34 277/36 413/06 317 417/06 317
Claims (2)
ら成る有機非線形光学材料。 一般式（Ｉ） 式中、Arはアリール基を表わし、Ｚは５員の含有窒素複
素環を形成するに必要な原子群を表わす。但し、該複素
環において、酸素原子に二重結合で結合した炭素原子に
は窒素原子が隣接する。1. An organic nonlinear optical material comprising a compound represented by the following general formula (I). General formula (I) In the formula, Ar represents an aryl group, and Z represents an atomic group necessary for forming a 5-membered nitrogen heterocycle. However, in the heterocycle, a nitrogen atom is adjacent to a carbon atom bonded to an oxygen atom by a double bond.
二高調波を発生させる際に、非線形光学材料として請求
項１記載の該有機非線形光学材料を用いる第二高調波の
発生方法。2. A method of generating a second harmonic using the organic nonlinear optical material according to claim 1 as a nonlinear optical material when generating a second harmonic using a laser beam and a nonlinear optical material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19756788A JPH0789188B2 (en) | 1988-08-08 | 1988-08-08 | Novel organic nonlinear optical material and second harmonic generation method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19756788A JPH0789188B2 (en) | 1988-08-08 | 1988-08-08 | Novel organic nonlinear optical material and second harmonic generation method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0246433A JPH0246433A (en) | 1990-02-15 |
| JPH0789188B2 true JPH0789188B2 (en) | 1995-09-27 |
Family
ID=16376650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19756788A Expired - Lifetime JPH0789188B2 (en) | 1988-08-08 | 1988-08-08 | Novel organic nonlinear optical material and second harmonic generation method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0789188B2 (en) |
-
1988
- 1988-08-08 JP JP19756788A patent/JPH0789188B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0246433A (en) | 1990-02-15 |
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