JPH036538A - Organic nonlinear optical material and nonlinear optical element using this material - Google Patents
Organic nonlinear optical material and nonlinear optical element using this materialInfo
- Publication number
- JPH036538A JPH036538A JP14184889A JP14184889A JPH036538A JP H036538 A JPH036538 A JP H036538A JP 14184889 A JP14184889 A JP 14184889A JP 14184889 A JP14184889 A JP 14184889A JP H036538 A JPH036538 A JP H036538A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- optical
- nonlinear
- elements
- modulating elements
- 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 113
- 239000000463 material Substances 0.000 title claims abstract description 45
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000758 substrate Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000031700 light absorption Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 p-nitro-(2-hydroxymethyl-pyrrolinyl)phenylene Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004219 molecular orbital method Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 description 1
- XTTIQGSLJBWVIV-UHFFFAOYSA-N 2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1N XTTIQGSLJBWVIV-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000005374 Kerr effect Effects 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000005697 Pockels effect Effects 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- DFKBQHBEROHUNF-UHFFFAOYSA-N hydron;2-(methylamino)acetonitrile;chloride Chemical compound Cl.CNCC#N DFKBQHBEROHUNF-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005442 molecular electronic Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は、オプトエレクトロニクス分野で好適に使用
される有機非線形光学材料とそれを用いた非線形光学素
子に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an organic nonlinear optical material suitably used in the field of optoelectronics and a nonlinear optical element using the same.
〈従来の技術と考案が解決しようとする課題〉非線形光
学効果とは、結晶内部にかかる電場よって誘起される分
極Ｐが次式に示されるように、（１）
Ｐ−Ｘ Ｅ＋Ｘ（２）Ｅ−Ｅ−）−Ｘ”Ｅ−Ｅ−Ｅ＋
・・・Ｘ”）：ｎ次の非線形感受率
Ｅ：電場ベクトル
２次以上の項を有することによって生じる非線形性に伴
って発現する光学的効果である。そして、２次の非線形
光学現象としては第２高調波発生、光整流、光混合パラ
メトリック増幅及びポッケルス効果があり、３次のもの
としては第３高調波発生、光双安定性、カー効果等があ
る。<Problems to be solved by conventional technology and inventions> Nonlinear optical effects mean that the polarization P induced by the electric field applied inside the crystal is expressed as (1) P−X E+X (2) E as shown in the following equation. -E-)-X”EE-E-E+
... There are second harmonic generation, optical rectification, optical mixing parametric amplification, and Pockels effect, and third harmonic generation, optical bistability, Kerr effect, etc. are examples of tertiary harmonic generation.
特に、光の電場の２乗に比例して起る２次の非線形光学
効果は、光波長変換素子、光変五−１素子等の非線形光
学素子としてオプトエレクトロニクス分野の発展を約束
する素子への応用が可能であるため多くの注目を集めて
いる。In particular, the second-order nonlinear optical effect, which occurs in proportion to the square of the electric field of light, can be applied to nonlinear optical elements such as optical wavelength conversion elements and optical variable five-one elements, which promise the development of the optoelectronics field. It is attracting a lot of attention because it can be applied.
それらの素子を構成する材料は、現在のところＫＨ２Ｐ
Ｏ４などの一部の無機材料が実用されているにすぎない
。しかし、それら無機材料の非線形光学定数は小さく、
それゆえ素子の動作には極めて高い電圧、または極めて
強い光強度が必要であった。このため、非線形光学効果
の大きい材料への要求は極めて強く、様々な材料探索が
なされてきた。無機材料においては、ニオブ酸リチウム
（Ｌ ｉ ＮｂＯｘ ）が最も大きい非線形光学定数を
有しているが、ニオブ酸リチウムは強いレーザ光を照射
すると部分的に屈折率の変化を生じ、また容易に光で損
傷する欠点を有しており未だ実用化されていない。The materials that make up these devices are currently KH2P.
Only some inorganic materials such as O4 are in practical use. However, the nonlinear optical constants of these inorganic materials are small;
Therefore, the operation of the device requires extremely high voltage or extremely strong light intensity. For this reason, there is an extremely strong demand for materials with a large nonlinear optical effect, and various materials have been searched for. Among inorganic materials, lithium niobate (L i NbOx ) has the largest nonlinear optical constant, but when irradiated with intense laser light, lithium niobate partially changes its refractive index, and it is easily exposed to light. However, it has the disadvantage of being damaged by damage, so it has not been put into practical use yet.
最近、（ｉｔ大きな非線形分極率、（ｉｔ高い光損傷性
、（ｉｉｌ高速対電場応答性等の点で、本質的に無機材
料より優れているを機非線形光学材料が注目され、特に
、２次の非線形光学現象の一つである第２高調波発生（
ＳＨＧ）を利用して入射光（基本波）の波長を１／２に
変換する第２高調波発生素子の材料として注目されてい
る。Recently, nonlinear optical materials have attracted attention because they are essentially superior to inorganic materials in terms of large nonlinear polarizability, high optical damage resistance, and high response to electric fields, and in particular, Second harmonic generation (
It is attracting attention as a material for second harmonic generation elements that convert the wavelength of incident light (fundamental wave) to 1/2 using SHG.
上記第２高調波発生素子では、得られた第２高調波を効
率よく取り出すために、２次の非線形感受率Ｘ（２）が
大きいことが必要である。そして、第２高調波の波長が
入射光の波長の半分であることから、上記素子に用いら
れる有機非線形光学材料は、広い透明領域を有すること
が必要であり、またその光吸収波長領域が短波長である
ことが好ましく、特に光吸収端波長（λ ｃｕｔ ｏｆ
ｆ）が３９０ｒｖ以下であることが好ましい。In the second harmonic generation element, in order to efficiently extract the obtained second harmonic, it is necessary that the second-order nonlinear susceptibility X(2) is large. Since the wavelength of the second harmonic is half of the wavelength of the incident light, the organic nonlinear optical material used in the above element must have a wide transparent region, and its light absorption wavelength region must be short. It is preferably the wavelength, especially the optical absorption edge wavelength (λ cut of
f) is preferably 390 rv or less.
例えば、７８０ ｔｖ〜８４０ ｒｖの半導体レーザの
短波長化技術に用いられる光波長変換素子の非線形光学
材材料としては、第２高調波領域である３ ９０ ｒｖ
〜４．２０ ｒｖの波長領域で光吸収が小さい非線形光
学材料が好ましい。For example, as a nonlinear optical material for an optical wavelength conversion element used in short wavelength technology for semiconductor lasers of 780 tv to 840 rv, 390 rv, which is the second harmonic region, is used.
Nonlinear optical materials with low optical absorption in the wavelength range of ~4.20 rv are preferred.
しかし、従来知られている、下記のＮ−メチル−Ｎ−（
４−ニトロ）フェニルアミノアセトニトリル（以下、Ｎ
ＰＡＮと略称する）、２−メチル−４−ニトロアニリン
（以下、ＭＮＡと略称する）ｐ−ニトロ−（２−ヒドロ
キシメチル−ピロリニル）フェニレン（以下、ＮＰＰと
略称する）等の有機非線形光学材料は、そのほとんどが
３９０ｒｌｆｆｌ〜４２０ ｒｖの波長領域で大きな光
吸収を示すという問題があった。However, the following N-methyl-N-(
4-nitro)phenylaminoacetonitrile (hereinafter referred to as N
Organic nonlinear optical materials such as PAN), 2-methyl-4-nitroaniline (hereinafter referred to as MNA), p-nitro-(2-hydroxymethyl-pyrrolinyl)phenylene (hereinafter referred to as NPP) are However, there was a problem in that most of them exhibited large optical absorption in the wavelength range of 390rlffl to 420rv.
ＮＰＡＮ ＭＮＡＰＰ
また、有機非線形光学材料において、その２次の非線形
感受率Ｘ（２）を大きくするには、２次超分極率βが大
きなものを用いる必要があり、２次超分極率βは分子内
の電荷移動の大きさに、大きく依存している。NPAN MNAPP Furthermore, in order to increase the second-order nonlinear susceptibility X(2) of organic nonlinear optical materials, it is necessary to use a material with a large second-order hyperpolarizability β, and the second-order hyperpolarizability β is It is highly dependent on the magnitude of the charge movement within.
しかし、分子内の電荷移動が大きくなれば、２次超分極
率βは大きくなるが、同時に当該材料の光波長吸収領域
が長波長となるという問題がある。However, as the intramolecular charge movement increases, the secondary hyperpolarizability β increases, but at the same time, there is a problem that the light wavelength absorption region of the material becomes long wavelength.
さらに、非線形光学材料が２次の非線形光学効果を発現
するためには、その分子が一部いの分子の持つ永久非双
極子モーメントを打ち消さないこと、つまり、その分子
配列が反転対称心を有さないことが必要である。Furthermore, in order for a nonlinear optical material to exhibit a second-order nonlinear optical effect, some of its molecules must not cancel out the permanent non-dipole moment of other molecules, that is, the molecular arrangement must have an inversion symmetry center. It is necessary not to do so.
しかし、分子構造から分子配列を決定することは、現状
ではほとんど不可能であり、分子構造がよく似ていても
分子配列が同じであるとは限らず、２次超分極率βが大
きい有機非線形光学材料であっても、その結晶の分子配
列が、反転対称心を有するために２次の非線形光学効果
を示さないものがあるという問題があった。However, it is currently almost impossible to determine the molecular arrangement from the molecular structure, and even if the molecular structures are very similar, the molecular arrangement is not necessarily the same, and organic nonlinear Even optical materials have a problem in that some of them do not exhibit second-order nonlinear optical effects because the molecular arrangement of their crystals has an inversion symmetry center.
この発明は、上記問題に鑑みてなされたものであって、
大きな２次の非線形光学効果を示し、且つ光吸収波長領
域が短波長である有機非線形光学材料およびそれを用い
た素子を提供することを目的とする。This invention was made in view of the above problems, and
It is an object of the present invention to provide an organic nonlinear optical material that exhibits a large second-order nonlinear optical effect and has a light absorption wavelength region of a short wavelength, and an element using the same.
く問題点を解決するための手段、および作用〉上記問題
を解決するために、発明者等は、分子軌道法を用いて光
吸収極大波長（λｍａｘ ）および２次超分極率βの予
測を行い、それにより非線形光学素子に好適な分子構造
を決定するという手法を用いることによって、下記一般
式［１１で表される化合物が高い２次の非線形光学効果
を示し、特に第２高調波発生素子用の有機非線形光学材
料として好適に使用しつるという新たな事実を見出だし
、本発明を完成するに至った。Means and Effects for Solving the Problems In order to solve the above problems, the inventors used the molecular orbital method to predict the optical absorption maximum wavelength (λmax) and the second-order hyperpolarizability β. By using the method of determining a molecular structure suitable for nonlinear optical elements, it was found that the compound represented by the following general formula [11] exhibits a high second-order nonlinear optical effect, and is particularly suitable for second harmonic generation elements. The present inventors have discovered a new fact that it can be suitably used as an organic nonlinear optical material, and have completed the present invention.
［式中、Ｒは水素原子、メチル基、エチル基またはアセ
チル基を示し、ｎは１または２を示す］
すなわち、この発明に係るを機非線形光学材料は、上記
一般式（ＩＩで表される化合物からなることを特徴とす
る。[In the formula, R represents a hydrogen atom, a methyl group, an ethyl group, or an acetyl group, and n represents 1 or 2.] That is, the mechanical nonlinear optical material according to the present invention is represented by the above general formula (II). It is characterized by consisting of a compound.
また、この発明に係る非線形光学素子は、上記非線形光
学材料が先導枝部に用いられていることを特徴とする。Moreover, the nonlinear optical element according to the present invention is characterized in that the above-mentioned nonlinear optical material is used for the leading branch.
一゛般式（１１で表される化合物の２次超分極率βが大
きいことは、Ｐ Ｐ Ｐ （Ｐａｒｌｓｅｒ−Ｐａｒｒ
−Ｐｏｌｅ） −ＭＯ法により確認できる。Ｐ Ｐ Ｐ
−ＭＯ法は一種の分子軌道法であり、簡便で広範囲に利
用されている計算方法である［：Ａ、 Ｍａｒｔｌｎ、
Ａｃｔａ Ｃｈｅｒ５１ｃａ＾ｃａｄｅｓｉａｅ ５
ｃｉｅｎｔ［ａｒｕＩＩＨｕｎｇａｒｉｃａｅ、 ８４
．７ｊ１１（１９７５）参照］。The fact that the second-order hyperpolarizability β of the compound represented by general formula (11) is large means that P P P (Parlser-Parr
-Pole) - It can be confirmed by the MO method. P P P
-MO method is a type of molecular orbital method, and is a simple and widely used calculation method [:A, Martln,
Acta Cher51ca＾cadesiae 5
cient [aruII Hungaricae, 84
．． 7j11 (1975)].
また、Ｐ Ｐ Ｐ−ＭＯ法により得られた各分子パラメ
ーターを用いて、次式より２次超分極率βを算出するこ
とができる ＣＪ、 Ｌ、 ０ｕｄａｒ、 Ｊ、 Ｃｈ
ｅｍ、＋Ｐｈｙｓ、、 ６７、４４６ （１９７７）参
照］。Furthermore, using each molecular parameter obtained by the P P P-MO method, the second-order hyperpolarizability β can be calculated from the following formula. CJ, L, Oudar, J, Ch
Phys, 67, 446 (1977)].
［ｅ：ｍ子の電荷、 ｉ：ｈ／２π（ｈはブランク定
数）、ｍ：電子の質量、 Ｖ：基底状態と励起状態のエ
ネギー差、重ω：入射光エネルギー ｒ：振動子強度
、 Δμｇ８ 基底状態と励起状態の双極子モーメン
トの差］
上記Ｐ Ｐ Ｐ−ＭＯ法により、上記一般式（ＩＩで表
される化合物について、極大光吸収波長（λＯ＋ａＸ
）を算出したところ、２７０ｒｖとなった。また、上記
式を用いて一般式（ＩＩで表される化合物の２次超分極
率βを算出したところ、２０ Ｘ １０−３０ｅｓｕと
なった。[e: charge of m child, i: h/2π (h is blank constant), m: mass of electron, V: energy difference between ground state and excited state, weight ω: incident light energy r: oscillator strength, Δμg8 Difference in dipole moment between ground state and excited state] By the above P P P-MO method, for the compound represented by the above general formula (II), the maximum optical absorption wavelength (λO+aX
) was calculated and found to be 270rv. Further, when the second-order hyperpolarizability β of the compound represented by the general formula (II) was calculated using the above formula, it was found to be 20 × 10 −30 esu.
なお、Ｐ Ｐ Ｐ−ＭＯ法および上記式を用いて算出し
た２次超分極率βの値は、前記の実測値′と良好な一致
が見られることが発明者等により報告されており（日本
化学会秋季年会予稿集、１９８７）、２次超分極率βの
計算にＰＰＰ−ＭＯ法および上記式を用いることは妥当
である。The inventors have reported that the value of the secondary hyperpolarizability β calculated using the P P P-MO method and the above formula is in good agreement with the above-mentioned measured value. Proceedings of the Autumn Annual Meeting of the Chemical Society of Japan, 1987), it is appropriate to use the PPP-MO method and the above formula to calculate the second-order hyperpolarizability β.
以上のように、この発明に係る上記一般式（Ｉｌで表さ
れる化合物は、上記ＭＮＡ （１７Ｘ １０−３０ｅｓ
ｕ ）等の、２次超分極率βは大きいが、光吸収波長領
域が４０ Ｏｒ＋ｍ台であるため非線形光学材料として
使用されていない化合物と同程度の２次超分極率βを有
し、かつその光吸収波長領域がより短波長であるため、
非線形光学材料として好適に使用できる。従って、前記
一般式（ＩＩで表される化合物からなるを機非線形光学
材料は、２次超分極率βが大きく、顕著な非線形光学効
果を有し、オプトエレクトロニクス分野で使用される非
線形光学素子用材料、例えば、光波長変換素子用材料、
位相変調素子、振幅変調素子、周波数変調素子、パルス
変調素子、偏波面変調素子等の光変調素子用材料として
好適である。As mentioned above, the compound represented by the general formula (Il) according to the present invention is the compound represented by the above MNA (17X 10-30es
Although the second-order hyperpolarizability β is large, such as U Because its light absorption wavelength region is shorter wavelength,
It can be suitably used as a nonlinear optical material. Therefore, the nonlinear optical material made of the compound represented by the general formula (II) has a large second-order hyperpolarizability β, has a remarkable nonlinear optical effect, and is suitable for use in nonlinear optical elements used in the optoelectronics field. Materials, for example, materials for optical wavelength conversion elements,
It is suitable as a material for optical modulation elements such as phase modulation elements, amplitude modulation elements, frequency modulation elements, pulse modulation elements, and polarization plane modulation elements.
また、上記一般式（１１で表される化合物であって、Ｒ
がメチル基であり、ｎが１であるものについてシクロヘ
キサン中で、その光吸収波長を調べたところ、λ Ｗａ
Ｘが２７０ｎｍであって、光吸収端波長（λ ｃｕｔ
ｏｆｆ）が３１５ｎｌ！であり、その結晶も無色で、可
視光領域における光吸収も小さいものであった。このこ
とより、この化合物は、光吸収波長帯が短波長であるの
で、少なくともこの化合物を含む本発明の有機非線形光
学材料は、特に好適に使用できることがわかる。Further, a compound represented by the above general formula (11), R
is a methyl group and n is 1. When the light absorption wavelength was investigated in cyclohexane, it was found that λ Wa
X is 270 nm, and the optical absorption edge wavelength (λ cut
off) is 315nl! The crystals were also colorless and had low light absorption in the visible light region. From this, it can be seen that the organic nonlinear optical material of the present invention containing at least this compound can be particularly suitably used since the light absorption wavelength band of this compound is short.
上記有機非線形光学材料は、非線形光学素子の先導枝部
に使用することができる［Ｊ、 Ｚｙｓｓ、 Ｊ。The above organic nonlinear optical materials can be used in the leading leg of a nonlinear optical element [J, Zyss, J.
Ｍｏ１ｅｃｕｌａｒ Ｅｌｅｃｔｒｏｎｉｃｓ １．２
５ （１９８５）など参照］。Molecular Electronics 1.2
5 (1985) etc.].
この場合、導波部内に光を閉じ込めるので、光パワー密
度が大きくなり、また相互作用長を長くすることができ
るので高効率化を図ることができ、さらにモード分散を
利用した位相整合も可能である。In this case, since the light is confined within the waveguide, the optical power density increases, and the interaction length can be increased, making it possible to achieve high efficiency, and furthermore, it is possible to achieve phase matching using mode dispersion. be.
以下に、添付図面に基づいて、上記有機非線形光学材料
を用いた本発明の非線形光学素子について詳細に説明す
る。Below, the nonlinear optical element of the present invention using the above organic nonlinear optical material will be explained in detail based on the accompanying drawings.
第１図は本発明の光波長変換素子の一例であり、第２高
調波発生素子としての光フアイバー型光波長変換素子の
概略図を示し、一般式（１）で表される化合物を少なく
とも含有するを機非線形光学材料（以下、非線形媒質と
称する）からなるコア（１）が、ガラス等の２次の非線
形光学効果を示さない媒質（以下、等方性媒質と称する
）からなるクラッド（２）で被覆された構造を有し、同
図中、−点鎖線は入射された光の基本波を、二点鎖線は
第２高調波を示す。レーザ光等の光はレンズ等で集光さ
れ、上記光波長変換素子の一端面からコア（１）に入射
される。コア（１）を形成する非線形媒質は大きい２次
の非線形光学効果を示すので、コア（１）の他端面より
出射される光は基本波と第２高調波を含み、プリズム、
フィルタ等の分光手段により分離することができ、さら
にモード分散を利用した位相整合も可能である。FIG. 1 is an example of the optical wavelength conversion element of the present invention, and shows a schematic diagram of an optical fiber type optical wavelength conversion element as a second harmonic generation element, which contains at least a compound represented by the general formula (1). The core (1) is made of a nonlinear optical material (hereinafter referred to as a nonlinear medium), and the cladding (2) is made of a medium that does not exhibit a second-order nonlinear optical effect (hereinafter referred to as an isotropic medium) such as glass. ), and in the same figure, the dash-dot line indicates the fundamental wave of the incident light, and the dash-dot line indicates the second harmonic. Light such as a laser beam is focused by a lens or the like, and is incident on the core (1) from one end surface of the optical wavelength conversion element. Since the nonlinear medium forming the core (1) exhibits a large second-order nonlinear optical effect, the light emitted from the other end surface of the core (1) contains the fundamental wave and the second harmonic, and the prism,
Separation can be performed using a spectroscopic means such as a filter, and phase matching using mode dispersion is also possible.
以下に、添附図面に基づいて、上記有機非線形光学材料
を用いた本発明の非線形光学素子について詳細に説明す
る。Hereinafter, the nonlinear optical element of the present invention using the above organic nonlinear optical material will be described in detail based on the accompanying drawings.
第１図は本発明の光波長変換素子の一例であり、第２高
調波発生素子としての光フアイバー型光波長変換素子の
概略図を示し、一般式（１）で表される化合物を少なく
とも含有する有機非線形光学材料（以下、非線形媒質と
称する）からなるコア（１）が、ガラス等の２次の非線
形光学効果を示さない媒質（以下、等方性媒質と称する
）からなるクラッド（２）で被覆された構造を有し、同
図中、−点鎖線は入射された光の基本波を、二点鎖線は
第２高調波を示す。レーザ光等の光はレンズ等で集光さ
れ、上記光波長変換素子の一端面からコア（１）に入射
される。コア（１］を形成する非線形媒質は大きい２次
の非線形光学効果を示すので、コア（１）の他端面より
出射される光は基本波と第２高調波を含み、プリズム、
フィルタ等の分光手段により分離することにより第２高
調波が取り出される。FIG. 1 is an example of the optical wavelength conversion element of the present invention, and shows a schematic diagram of an optical fiber type optical wavelength conversion element as a second harmonic generation element, which contains at least a compound represented by the general formula (1). The core (1) is made of an organic nonlinear optical material (hereinafter referred to as a nonlinear medium) that exhibits a nonlinear optical effect, and the cladding (2) is made of a medium that does not exhibit a second-order nonlinear optical effect (hereinafter referred to as an isotropic medium) such as glass. In the figure, the dashed-dotted line indicates the fundamental wave of the incident light, and the dashed-two dotted line indicates the second harmonic. Light such as a laser beam is focused by a lens or the like, and is incident on the core (1) from one end surface of the optical wavelength conversion element. Since the nonlinear medium forming the core (1) exhibits a large second-order nonlinear optical effect, the light emitted from the other end surface of the core (1) contains the fundamental wave and the second harmonic, and the prism,
The second harmonic is extracted by separating it using a spectroscopic means such as a filter.
また第２図および第３図は、それぞれ光波長変換素子の
他の例を示す概略図であり、図面中、点鎖線および二点
鎖線はそれぞれ第１図と同様な意味を示す。Further, FIGS. 2 and 3 are schematic diagrams showing other examples of the optical wavelength conversion element, respectively, and in the drawings, a dashed dot line and a dashed double dotted line each have the same meaning as in FIG. 1.
第２図に示される光波長変換素子では、等方性媒質から
なる基板（２２）上に非線形媒質からなる光導波部（２
１）が形成されており、また第３図に示される光波長変
換素子においては、等方性媒質からなる基板（３２）と
、同じく等方性媒質からなるトップ層（３３）との間に
非線形媒質からなる光導波部（３１）が形成されている
。上記の光波長変換素子は、第１図に示される光波長変
換素子と同様にして使用される。In the optical wavelength conversion element shown in FIG. 2, an optical waveguide (22) made of a nonlinear medium is placed on a substrate (22) made of an isotropic medium.
1) is formed, and in the optical wavelength conversion element shown in FIG. An optical waveguide (31) made of a nonlinear medium is formed. The above optical wavelength conversion element is used in the same manner as the optical wavelength conversion element shown in FIG.
また、光変調素子としても従来から用いられている形態
のデバイスとすることができる。第４図は、その−例と
して、位相変調素子として、横型動作の光導波路型光変
調素子の概略図を示し、等方性媒質よりなる基板（４２
）中に、非線形媒質からなる光導波部（４１）が設けら
れていると共に、該光導波部（４１）を介して２つの電
極（４３）が長さ方向に沿って対向する位置に設ζすら
れており、該電極（４３）間に電圧を印加することによ
り電界が形成される。上記素子において、光導波部（４
１）の長さ方向の一端から入射された光が光導波部（４
１）を通過し他端面から出射される際、光導波部（４１
）を構成する非線形媒質の屈折率が変化すると出射され
る光の位相も変化する。非線形媒質の屈折率は印加電圧
により変化するので、電極（４３）間の印加電圧を変化
させることにより、出射光の位相変調を行なうことがで
きる。Further, it is possible to use a conventionally used device as a light modulation element. As an example, FIG. 4 shows a schematic diagram of a horizontally operated optical waveguide type optical modulation element as a phase modulation element, and shows a substrate (42
) is provided with an optical waveguide section (41) made of a nonlinear medium, and two electrodes (43) are provided at opposite positions along the length direction via the optical waveguide section (41). An electric field is created by applying a voltage between the electrodes (43). In the above device, the optical waveguide (4
1) Light incident from one end in the length direction passes through the optical waveguide (4).
1) and exits from the other end surface, the optical waveguide (41
) When the refractive index of the nonlinear medium constituting the beam changes, the phase of the emitted light also changes. Since the refractive index of the nonlinear medium changes depending on the applied voltage, the phase of the emitted light can be modulated by changing the applied voltage between the electrodes (43).
上記第１図から第４図に示される光波長変換素子におい
て、コア（１）および光導波部（２１）（３１）（４１
）の形成は、例えば、非線形媒質原料を、それぞれ等方
性媒質からなるキャピラリー中、等方性媒質からなる導
波路基板上、または等方性媒質からなる導波路基板間で
、加熱溶融後、ゆっくりと冷却させて結晶を析出させる
方法、基板上に真空蒸着法、高周波スパッタリング法等
によって結晶を析出させる方法などにより行われ、また
、適当な有機溶媒に非線形媒質原料を溶解させた溶液か
ら、上記キャピラリー中、基板上または基板間に結晶を
析出させる方法によってもよい。さらに、場合によって
は、キャピラリー中、基板上または基板間で非線形媒質
との接触界面となるべき部分を配向処理剤で処理した後
、非線形媒質を析出、結晶成長させ光波長変換素子など
を形成してもよい。In the optical wavelength conversion element shown in FIGS. 1 to 4 above, the core (1) and the optical waveguide (21) (31) (41)
) is formed by, for example, heating and melting a nonlinear medium raw material in a capillary made of an isotropic medium, on a waveguide substrate made of an isotropic medium, or between waveguide substrates made of an isotropic medium, This can be done by slow cooling to precipitate crystals, or by depositing crystals on a substrate by vacuum evaporation, high frequency sputtering, etc. Alternatively, from a solution in which a nonlinear medium raw material is dissolved in an appropriate organic solvent, A method may also be used in which crystals are deposited in the capillary, on the substrate, or between the substrates. Furthermore, in some cases, after treating the part of the capillary, on the substrate, or between the substrates that should be the contact interface with the nonlinear medium with an alignment treatment agent, the nonlinear medium is precipitated and crystal-grown to form an optical wavelength conversion element. It's okay.
配向処理剤としては、無機塩および有機塩（例えば、臭
化へキサデンルトリメチルアンモニウムなど）、適当な
高分子（例えば、ポリアミドなど）からなる薄膜、金属
錯体、金属薄膜（例えば、斜め蒸着した金薄膜など）等
が例示される。Examples of alignment agents include inorganic and organic salts (e.g., hexadene trimethylammonium bromide), thin films made of suitable polymers (e.g., polyamide), metal complexes, metal thin films (e.g., obliquely deposited (gold thin film, etc.).
なお、本発明の非線形光学素子は上記例に限定されるも
のではなく、光変調素子としては、振幅変調することが
できる縦型動作の先導波路型光変調素子でもよく、また
結晶などの非線形媒質自体に直接電圧を印加する形態と
することもできる。Note that the nonlinear optical element of the present invention is not limited to the above example, and the optical modulation element may be a leading waveguide type optical modulation element with vertical operation capable of amplitude modulation, or a nonlinear medium such as a crystal. It is also possible to apply a voltage directly to itself.
なお、光変調素子においては、非線形媒質の対称性、結
晶軸の方向等により、位相変調を効率よく行なうための
電界印加方向が異なるので、それらに基づき電極の構成
を適宜変更するのがよい。Note that in a light modulation element, the electric field application direction for efficiently performing phase modulation differs depending on the symmetry of the nonlinear medium, the direction of the crystal axis, etc., so it is preferable to appropriately change the electrode configuration based on these factors.
〈実施例〉
以下に、実施例に基づいて本発明をより詳細に説明する
。<Examples> The present invention will be described in more detail below based on Examples.
実施例Ｉ
Ｎ−メチル−Ｎ−（４−シアノフェニル）アミノアセト
ニトリルの合成
塩酸メチルアミノアセトニトリル６２．３ｇ（０，５８
５モル）と無水炭酸カリウム９５，５ｇ（０゜６９２モ
ル）とをジメチルスルホキシド６５１ノに溶解させ、次
いでこれに、ｐ−フルオロベンゾニトリル６２．９ｇ
（０，５２モル）のジメチルスルホキシド６５１！の溶
液を５０℃の湯浴上で滴下した。滴下後、７０℃で１０
時間以上攪拌し、水４００ ｘＩに投入した。次いで、
酢酸エチルにより抽出後、水洗し、無水硫酸ナトリウム
を加えて乾燥させた後、濾過して無水硫酸ナトリウムを
除去した。該ａ液から酢酸エチルを留去し、褐色の粗生
成物を得た。Example I Synthesis of N-methyl-N-(4-cyanophenyl)aminoacetonitrile 62.3 g (0.58 g) of methylaminoacetonitrile hydrochloride
5 mol) and 95.5 g (0.692 mol) of anhydrous potassium carbonate were dissolved in 651 g of dimethyl sulfoxide, and then 62.9 g of p-fluorobenzonitrile was dissolved therein.
(0,52 mol) of dimethyl sulfoxide 651! The solution was added dropwise onto a 50°C water bath. After dropping, at 70℃ for 10
Stir for more than an hour and pour into 400 x I water. Then,
After extraction with ethyl acetate, the mixture was washed with water, dried with anhydrous sodium sulfate, and then filtered to remove the anhydrous sodium sulfate. Ethyl acetate was distilled off from the liquid a to obtain a brown crude product.
上記粗生成物を、クロロホルムを溶媒として、シリカゲ
ルクロマトグラフィーにより分離生成し、ベンゼンとｎ
−へキサンとを４：１の割合で混合したものより再結晶
させ、白色の結晶を得た。The above crude product was separated and produced by silica gel chromatography using chloroform as a solvent, and benzene and n
-Hexane in a ratio of 4:1 was recrystallized to obtain white crystals.
ＩＲ分析、融点、ＮＭＲスペクトル分析、元素分析、質
量スペクトル分析より、このものが白色のＮ−メチル−
Ｎ−（４−シアノフェニル）アミノアセトニトリルであ
ることを確認した。According to IR analysis, melting point, NMR spectrum analysis, elemental analysis, and mass spectrum analysis, this product is white N-methyl-
It was confirmed that it was N-(4-cyanophenyl)aminoacetonitrile.
ＩＲ（ＫＢｒ ｄｉｓｃ）ν： ２２２０ｃｍ−１（Ｃ
ミＮ） 、１６０５ｃｍ−’１５２０ｃｍ −ｔ、 ８
ＩＯｅｌｌ −１融点：８４−８５℃
４Ｈ−ＮＭＲ（ＣＤＣｆ３、ＴＭＳ標準）δ：３．１２
（３１（、’Ｓ、 ＣＨ３０）、４．２３（２Ｈ，Ｓ
。IR (KBr disc) ν: 2220 cm-1 (C
MiN), 1605cm-'1520cm-t, 8
IOell -1 Melting point: 84-85°C 4H-NMR (CDCf3, TMS standard) δ: 3.12
(31(,'S, CH30), 4.23(2H,S
.
ＣＨ２ＣＮ）、６．８（２Ｈ，ｄ）、７．６（２Ｈ，ｄ
）元素分析：計算値Ｃニア０．１６％、 Ｉｌ：５．３
０％、 Ｋ：２４．５４％分析値Ｃニア０．２５％、
Ｈ：５．２３％、 Ｎ：２４．５２％質量スペクトル（
Ｍ’ ） １７１（Ｍｙ−１７１，２０１２）実施例２
Ｎ−（４−シアノフェニル）アミノアセトニトリルの合
成
ｐ−アミノベンゾニトリル１１．８ｇ （０，１モル）
をジメチルスルホキシド５０１！に溶解させ、該溶液に
無水炭酸カリウム１０．０ｇ
（０，０７２モル）を加え、５０〜６０℃に加熱しつつ
攪拌した。次いで、ブロモアセトニトリル１２、Ｏｇ（
０，１モル）を滴下し、１００℃に加熱しつつ２！４時
間攪拌した。反応物を蒸溜水５００ ｘＩ中に投入し、
塩化メチレン１００ ｘＩで３回抽出し、水で洗浄し、
無水硫酸ナトリウムを加えて乾燥させた後、無水硫酸ナ
トリウムを濾別した、次いで、塩化メチレンを留去し、
シリカゲルカラムを用いて分離精製した（溶媒：クロロ
ホルム）。メタノールにより再結晶して、結晶３．０ｇ
を得た。ＩＲ分析、融点、ＮＭＲスペクトル分析、元素
分析、質量スペクトル分析より、このものが白色のＮ−
（４−シアノフェニル）アミノアセトニトリルであるこ
とを確認した。CH2CN), 6.8 (2H, d), 7.6 (2H, d
) Elemental analysis: Calculated value C near 0.16%, Il: 5.3
0%, K: 24.54% Analysis value C near 0.25%,
H: 5.23%, N: 24.52% mass spectrum (
M') 171 (My-171, 2012) Example 2 Synthesis of N-(4-cyanophenyl)aminoacetonitrile p-aminobenzonitrile 11.8g (0.1 mol)
Dimethyl sulfoxide 501! 10.0 g (0,072 mol) of anhydrous potassium carbonate was added to the solution, and the mixture was stirred while heating to 50 to 60°C. Then, bromoacetonitrile 12, Og (
0.1 mol) was added dropwise, and the mixture was stirred for 2 to 4 hours while heating to 100°C. The reactant was poured into 500 x I distilled water,
Extracted 3 times with 100 x I methylene chloride, washed with water,
After drying by adding anhydrous sodium sulfate, the anhydrous sodium sulfate was filtered off, and then methylene chloride was distilled off.
It was separated and purified using a silica gel column (solvent: chloroform). Recrystallize with methanol to obtain 3.0 g of crystals.
I got it. According to IR analysis, melting point, NMR spectrum analysis, elemental analysis, and mass spectrum analysis, this product is white N-
It was confirmed that it was (4-cyanophenyl)aminoacetonitrile.
ＩＲ（ＫＢｒ ｄｉｓｃ）： ３３６００１１−１（Ｎ
−Ｈ）、２２２Ｃ１ｃｍ−’（ＣミＮ）
融点：１１９℃
’Ｈ−ＮＭＲ（ＣＤＣ／、 、７ＭＳ標準）：δ７．６
２ （２Ｈ，ｄ）、６．７８（２Ｈ，ｄ） 、４．６
５（ＬＨ，ｓ ｂｒ、 ＮＨ）、４．２０ （２
Ｈ，ＣＨ）元素分析：計算値Ｃ：６８．７８％、 Ｈ：
４．４９％、 Ｎ：２Ｇ、７ｔ％分析値Ｃ：８ｇ、６６
％、 Ｈ：４．５４％、 Ｎ：２Ｂ、８０％質量スペク
トル（Ｍ” ＞ １５７
実施例３
実施例１で得られた結晶を融点（８５℃）以上に加熱溶
融させた後、ガラスキャピラリー（内径２〜８−１外径
０．２〜１ｍｍ５長さ５〜３０ ｍｍ ）の中に、毛細
管現象を利用して注入しなた。このガラスキャピラリー
を８５〜１２０℃の高温炉から温度１０〜３５℃の室温
中へ１〜１０Ｍ／時間の速度で引き出して、ガラスキャ
ピラリー内に結晶を成長させた。IR (KBr disc): 3360011-1 (N
-H), 222C1cm-' (CmiN) Melting point: 119°C 'H-NMR (CDC/, , 7MS standard): δ7.6
2 (2H, d), 6.78 (2H, d), 4.6
5 (LH, s br, NH), 4.20 (2
H, CH) Elemental analysis: Calculated value C: 68.78%, H:
4.49%, N: 2G, 7t% analysis value C: 8g, 66
%, H: 4.54%, N: 2B, 80% mass spectrum (M''> 157 Example 3 After heating and melting the crystal obtained in Example 1 to a temperature above the melting point (85°C), a glass capillary ( Capillary action was used to inject the glass capillary into a glass capillary with an inner diameter of 2 to 8-1, an outer diameter of 0.2 to 1 mm, and a length of 5 to 30 mm. Crystals were grown in glass capillaries by drawing them into room temperature at 35° C. at a rate of 1-10 M/hr.
次いで、偏光光学顕微鏡で観察しながら単結晶成長して
いる部分を長さ２〜１８Ｍに切り取った後、顕微鏡で観
察しながら、上記単結晶からなるコア端面をさらにカッ
ターナイフで所定長さに切り出し、ファイバー型素子を
作製した。Next, while observing with a polarizing optical microscope, the portion where the single crystal grows is cut to a length of 2 to 18M, and then, while observing with a microscope, the end face of the core made of the single crystal is further cut to a predetermined length with a cutter knife. , a fiber-type device was fabricated.
実施例４
実施例２て得られた結晶を高温炉で融点（１１９℃）以
上に加熱したほかは、実施例３と同様にしてファイバー
型素子を作成した。Example 4 A fiber-type element was produced in the same manner as in Example 3, except that the crystal obtained in Example 2 was heated to the melting point (119° C.) or higher in a high-temperature furnace.
試験１
実施例１で得られた結晶に波長１．０６４μｍのＮｄ
： ＹＡＧレーザを照射したところ、第２高調波である
波長０．５３２μｍの緑色光が観測された。Test 1 Nd with a wavelength of 1.064 μm was added to the crystal obtained in Example 1.
: When irradiated with YAG laser, green light with a wavelength of 0.532 μm, which is the second harmonic, was observed.
なお、上記結晶を粉末とし、これを２枚のプレパラート
ガラス間に挾み、波長１．０６４μｍのＮｄ：ＹＡＧレ
ーザを照射した際に観測される２次高調波の強度は、上
記結晶の粉末の代わりに尿素粉末を用いた際に測定され
る２次高調波の強度の１９倍の強さであった。The intensity of the second harmonic observed when the above crystal is made into a powder and is sandwiched between two pieces of prepared glass and irradiated with a Nd:YAG laser with a wavelength of 1.064 μm is the same as that of the above crystal powder. The intensity of the second harmonic was 19 times higher than that measured when urea powder was used instead.
試験２
また、実施例２で得られた結晶についても同様の試験を
行ったところ、前記の場合と同様に第２高調波である０
、５３２μｍの強い緑色光が観測された。Test 2 A similar test was also conducted on the crystal obtained in Example 2, and as in the case described above, the second harmonic, 0
, 532 μm strong green light was observed.
試験３
実施例３得られたファイバー型素子の一端から波長１．
０６４μｌのＮｄ：ＹＡＧレーザを照射したところ、他
端面から第２高調波である波長０．５３２μ麿の緑色光
が観測された。Test 3 Wavelength 1.1 from one end of the fiber type element obtained in Example 3.
When irradiated with 0.064 μl of Nd:YAG laser, green light with a wavelength of 0.532 μm, which is the second harmonic, was observed from the other end surface.
試験４
実施例４でえられたファイバー型素子についても試験３
と同様の試験を行ったところ、試験３の場合と同様に、
第２高調波である波長０．５３２μｍの緑色光が観測さ
れた。Test 4 Test 3 was also conducted for the fiber type element obtained in Example 4.
When a similar test was conducted, as in Test 3,
Green light with a wavelength of 0.532 μm, which is the second harmonic, was observed.
試験１〜４の結果より、実施例１．２で得られた化合物
および実施例３．４で得られたファイバー型素子は、２
次の非線形光学効果を示すことがわかる。From the results of Tests 1 to 4, the compound obtained in Example 1.2 and the fiber type element obtained in Example 3.4 were
It can be seen that the following nonlinear optical effect is exhibited.
〈発明の効果〉
以上のように本発明の非線形光学材料によれば、前記一
般式（１）で表される化合物は、２次超分極率βが大き
く、光吸収波長領域が短波長であり、その結晶が反転対
称心を有さないので、少なくともこの化合物からなる本
発明の非線形光学材料は、顕著な非線形光学効果を示し
、またその結晶が反転対称心を有さないので、特に２次
の非線形光学材料として好適なものである。<Effects of the Invention> As described above, according to the nonlinear optical material of the present invention, the compound represented by the general formula (1) has a large secondary hyperpolarizability β and a short wavelength light absorption wavelength region. , since its crystal does not have an inversion symmetry center, the nonlinear optical material of the present invention consisting of at least this compound exhibits a significant nonlinear optical effect, and since its crystal does not have an inversion symmetry center, it exhibits a particularly secondary It is suitable as a nonlinear optical material.
また、本発明の非線形光学素子によれば、先導液部に上
記非線形光学材料を用いているため、２次の非線形光学
効果を示し、光強度の弱いレーザ光でも高強度の第２高
調波を分離でき、また少ない電圧変化でも電気光学効果
を効率よく発現することができるという特有の効果を奏
する。Further, according to the nonlinear optical element of the present invention, since the above-mentioned nonlinear optical material is used in the guide liquid part, it exhibits a second-order nonlinear optical effect, and even a laser beam with a low light intensity can generate a high-intensity second harmonic. It has the unique effect of being able to separate and efficiently exhibit the electro-optic effect even with a small voltage change.
第１図は、本発明の非線形光学素子の一実施例としての
光波長変換素子の概略図、
第２図および第３図は、それぞれ光波長変換素子として
の非線形光学素子の他の例を示す概略図、第４図は、位
相変調素子としての非線形光学素子の一例を示す概略図
である。
（１）・・・・・・コア、（２）・・・・・クラッド、
（２１）（３１）（４１）・・−光導波部、（２２）
（３２） （４２）・・・琶板、（３３）・・トップ、
層、（４３）・・・電極。FIG. 1 is a schematic diagram of an optical wavelength conversion element as an embodiment of the nonlinear optical element of the present invention, and FIGS. 2 and 3 each show other examples of the nonlinear optical element as an optical wavelength conversion element. The schematic diagram, FIG. 4, is a schematic diagram showing an example of a nonlinear optical element as a phase modulation element. (1)・・・Core, (2)・・・Clad,
(21) (31) (41)...-optical waveguide, (22)
(32) (42)...Top board, (33)...Top,
Layer, (43)...electrode.
Claims (1)
を特徴とする有機非線形光学材料。 ▲数式、化学式、表等があります▼（ I ） ［式中、Ｒは水素原子、メチル基、エチル基またはアセ
チル基を示し、ｎは１または２を示す］ ２、前記一般式（ I ）で表される化合物において、Ｒ
が水素原子またはメチル基であって、ｎが１である請求
項１記載の有機非線形光学材料。 ３、請求項１または請求項２のいずれかに記載された有
機非線形光学材料が光導波部に用いられていることを特
徴とする非線形光学素子。[Claims] 1. An organic nonlinear optical material comprising a compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R represents a hydrogen atom, methyl group, ethyl group, or acetyl group, and n represents 1 or 2] 2. In the above general formula (I) In the compound represented, R
The organic nonlinear optical material according to claim 1, wherein is a hydrogen atom or a methyl group, and n is 1. 3. A nonlinear optical element, characterized in that the organic nonlinear optical material according to claim 1 or 2 is used in an optical waveguide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14184889A JPH036538A (en) | 1989-06-02 | 1989-06-02 | Organic nonlinear optical material and nonlinear optical element using this material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14184889A JPH036538A (en) | 1989-06-02 | 1989-06-02 | Organic nonlinear optical material and nonlinear optical element using this material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH036538A true JPH036538A (en) | 1991-01-14 |
Family
ID=15301570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14184889A Pending JPH036538A (en) | 1989-06-02 | 1989-06-02 | Organic nonlinear optical material and nonlinear optical element using this material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH036538A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07182073A (en) * | 1993-09-10 | 1995-07-21 | Compaq Computer Corp | Emulation method of user input device existence in computer system, loss prevention method of device constitution on standby, controller circuit for emulation of device existence and controller circuit for capture of device constitution |
-
1989
- 1989-06-02 JP JP14184889A patent/JPH036538A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07182073A (en) * | 1993-09-10 | 1995-07-21 | Compaq Computer Corp | Emulation method of user input device existence in computer system, loss prevention method of device constitution on standby, controller circuit for emulation of device existence and controller circuit for capture of device constitution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS61296332A (en) | High performance non-linear type optical substrate | |
| JP2676379B2 (en) | Third-order nonlinear optical material and device | |
| JPS62256808A (en) | Novel diacetylene and polydiacetylene type polymer | |
| JPH1192433A (en) | Compound | |
| JPH036538A (en) | Organic nonlinear optical material and nonlinear optical element using this material | |
| US5406406A (en) | Molecular crystal and wavelength conversion devices using the same | |
| JPH04277724A (en) | Organic nonlinear optical material | |
| US5467421A (en) | Nonlinear optical material and devices utilizing said material | |
| JP2539834B2 (en) | Non-linear optical element | |
| JPH03284735A (en) | Organic nonlinear optical material and element using this material | |
| JPH036536A (en) | Organic nonlinear optical material | |
| JPH04277725A (en) | Organic nonlinear optical material | |
| JPH08179389A (en) | Nonlinear optical material and nonlinear optical waveguide element | |
| JP2539849B2 (en) | Nonlinear optical material and nonlinear optical element using the same | |
| JPH01229234A (en) | Organic nonlinear optical material and nonlinear optical element using same | |
| EP0615152A1 (en) | Method of preparing materials having good non-linear optical properties | |
| JP2871202B2 (en) | Nonlinear optical element | |
| EP0431200A1 (en) | Quadratic nonlinear optical element | |
| CA2122428A1 (en) | Process for the production of materials having good nonlinear-optical properties | |
| JPH036537A (en) | Organic nonlinear optical material and nonlinear optical element using this material | |
| JPH01229235A (en) | Organic nonlinear optical material and nonlinear optical element using same | |
| JPH03154035A (en) | Organic nonlinear optical material and element using the same | |
| JPH08184866A (en) | Stilbene derivative for organic nonlinear optical material and its use | |
| JPH0770104A (en) | Nitrochromene compound and nonlinear optical material using the same | |
| JPH01159617A (en) | Nonlinear optical material |