JPH0398026A - Organic nonlinear optical material - Google Patents
Organic nonlinear optical materialInfo
- Publication number
- JPH0398026A JPH0398026A JP23519389A JP23519389A JPH0398026A JP H0398026 A JPH0398026 A JP H0398026A JP 23519389 A JP23519389 A JP 23519389A JP 23519389 A JP23519389 A JP 23519389A JP H0398026 A JPH0398026 A JP H0398026A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- group
- optical material
- main chain
- diacetylene
- 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.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 10
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 230000005855 radiation Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000010453 quartz Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- -1 p -dibutoxyphenylene group Chemical group 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KYIFLAPDJFQZSY-UHFFFAOYSA-N 1,4-dibutoxy-2,5-diethynylbenzene Chemical compound CCCCOC1=CC(C#C)=C(OCCCC)C=C1C#C KYIFLAPDJFQZSY-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WNJSKZBEWNVKGU-UHFFFAOYSA-N 2,2-dimethoxyethylbenzene Chemical compound COC(OC)CC1=CC=CC=C1 WNJSKZBEWNVKGU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- ILVDYAGPHFWNQI-UHFFFAOYSA-N deca-1,9-diyne Chemical compound C#CCCCCCCC#C ILVDYAGPHFWNQI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YEIGUXGHHKAURB-UHFFFAOYSA-N viridine Natural products O=C1C2=C3CCC(=O)C3=CC=C2C2(C)C(O)C(OC)C(=O)C3=COC1=C23 YEIGUXGHHKAURB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野）
本発明は、光波数逓倍素子、光シャッター及びＥ○変換
器等に利用される非線形光学材料に関し、さらに詳しく
は、主鎮にジアセチレン基を持つ高分子からなる有機非
線形光学材料に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to nonlinear optical materials used in optical wave number multipliers, optical shutters, E○ converters, etc. This paper relates to organic nonlinear optical materials consisting of polymers with .
（従来技術）
従来から、非線形光学材料としてはリン酸二水素化カリ
ウム（ＫＤＰ）や二オブ酸リチウム（Ｌ＋ＮｂＯｉ）等
の無機強誘電体材料が光周波数逓倍素子として実用化さ
れている。一方、有機非線形光学材料はより大きめ）非
線形光学定数、より速い非線形光学応答や高い破壊しき
い値等の特徴を有し、従来のオブトエレクトロニクス分
野の基幹材料として注目されている。また、有機材料は
材料化手法の多様性及び分子修飾が可能といった利点も
有しているため、有機非線形光学材料に関する研究は精
力的に行われている。三次の非線形光学効果を示す材料
は、光強度による屈折率の変化を利用した素子への応用
が可能であり、光メモリーや光論理素子等への展開が期
待できる。(Prior Art) Conventionally, as nonlinear optical materials, inorganic ferroelectric materials such as potassium dihydrogen phosphate (KDP) and lithium diobate (L+NbOi) have been put into practical use as optical frequency multipliers. On the other hand, organic nonlinear optical materials have characteristics such as larger nonlinear optical constants, faster nonlinear optical responses, and higher breakdown thresholds, and are attracting attention as key materials in the conventional field of electronics. In addition, organic materials have the advantage of having a variety of material preparation methods and the possibility of molecular modification, so research on organic nonlinear optical materials is being actively conducted. Materials that exhibit third-order nonlinear optical effects can be applied to devices that utilize changes in refractive index depending on light intensity, and are expected to be used in optical memories, optical logic devices, etc.
（発明が解決しようとする問題点）
大きな三次の非線形光学効果を示す有機材料としては、
π電子共役系を有するポリアセチレン、ポリジアセチレ
ンや金属フタロシアニンがよく知られている。しかしこ
れらの材料は融解しないだけでなく一般の有機溶剤に溶
解しないために、膜厚制御が困難であり機械的強度に優
れた薄膜を得ることが困難である。そのため光学素子へ
の展開に限度があるのが実状である。(Problems to be solved by the invention) Organic materials that exhibit large third-order nonlinear optical effects include:
Polyacetylenes, polydiacetylenes, and metal phthalocyanines having a π-electron conjugated system are well known. However, since these materials not only do not melt but also do not dissolve in common organic solvents, it is difficult to control the film thickness and it is difficult to obtain a thin film with excellent mechanical strength. Therefore, the reality is that there are limits to its application to optical elements.
（問題点を解決するための手段）
本発明者らは、前記問題点に鑑みて鋭意検討した結果、
主鎮にジアセチレン基を持つ高分子が非線形光学効果を
示しアルキル基またはアルキレン基を導入することによ
り有機溶剤に可溶となることを明かにした。さらにこれ
ら高分子の非線形光学効果が熱処理、光照射、又は放射
線照射により向上することを見いだした。すなわち本発
明の一殻概念は、、主鎮にジアセチレン基を有し、且つ
アルキル基又はアルキレン基を含む高分子非線型光学材
料であって、換言すると
一般式
−＋−ＣミＣ−Ｒ−ＣミＣ＋ｒ
〔式中、Ｒはアルキレン基あるいは、アルキルフェニレ
ン基またはアルコキシフェニレン基の如くアルキレン基
或いはアルキル基を含有する基である〕で現わされる主
鎮にジアセチレン基を持つ高分子からなる有機非線形光
学材料に関し、更には、これら高分子を熱処理、光照射
又は放射線照射して得られる有機非線形光学材料に関す
る。(Means for solving the problems) As a result of intensive study in view of the above problems, the present inventors found that
It was revealed that polymers with diacetylene groups as the main chain exhibit nonlinear optical effects and become soluble in organic solvents by introducing alkyl or alkylene groups. Furthermore, we have found that the nonlinear optical effects of these polymers can be improved by heat treatment, light irradiation, or radiation irradiation. That is, one shell concept of the present invention is a polymeric nonlinear optical material which has a diacetylene group as a main group and also contains an alkyl group or an alkylene group, in other words, it has the general formula -+-C-R -CmiC+r [In the formula, R is an alkylene group or a group containing an alkylene group or an alkyl group such as an alkylphenylene group or an alkoxyphenylene group] A polymer having a diacetylene group as the main group Furthermore, the present invention relates to an organic nonlinear optical material obtained by heat treating, light irradiation, or radiation irradiation of these polymers.
上式の定義において、Ｒの例としてはヘキシレン基、ｐ
−ジブトキシフエニレン基が挙げられる。In the definition of the above formula, examples of R include hexylene group, p
-dibutoxyphenylene group.
これら高分子の内、Ｒがアルキレン基であるものは塩化
メチレン、テトラヒド口フラン等の一般の有機溶剤に可
溶であり、またｐ−ジブトキシフ工二レン基であるもの
は１．３−ジメチルイミダゾリジノンに可溶であった。Among these polymers, those in which R is an alkylene group are soluble in general organic solvents such as methylene chloride and tetrahydrofuran, and those in which R is a p-dibutoxyfuran group are 1,3-dimethylimidazo It was soluble in lysinone.
これら高分子溶液から、スビンコートまたはキャスト法
によりボリマーフィルムが得られた。Polymer films were obtained from these polymer solutions by subin coating or casting methods.
上記一般式で表される材料は、一般的には二つの末端ア
セチレン基を持つモノマーを酸素による酸化カップリン
グ重合して得られる。The material represented by the above general formula is generally obtained by oxidative coupling polymerization using oxygen of a monomer having two terminal acetylene groups.
（発明の効果〉
従来から知られている三次の非線形光学効果を示す材料
では加工性に劣っており機械的強度に優れた薄膜が得ら
れていない。本発明の高分子は機械的強度に優れ三次の
非線形光学効果を示す薄膜を実現できる。また、薄膜形
或に際し簡便なキャスト法やスビンコート法が利用でき
るため膜厚の制御等が容易にでき、さらにこの高分子は
ジアセチレン基の固相反応を用いたフォトレジストであ
るためバターニングが可能であり、これを用いることに
より光集積回路等の実現が可能となる。(Effects of the Invention) Conventionally known materials exhibiting third-order nonlinear optical effects have poor processability and cannot provide thin films with excellent mechanical strength.The polymer of the present invention has excellent mechanical strength. It is possible to realize a thin film that exhibits a third-order nonlinear optical effect.In addition, since a simple casting method or spin coating method can be used to form a thin film, the film thickness can be easily controlled. Since it is a photoresist that uses a reaction, it can be patterned, and by using it, it becomes possible to realize optical integrated circuits and the like.
（実施例〉 以下に本発明を実施例によりさらに具体的に説明する。(Example> The present invention will be explained in more detail below using Examples.
実施例ｌ
塩化第一銅１００■、Ｎ，Ｎ．Ｎ’ ，Ｎ’−テトラメ
チルエチレンジアミン１ｒｎｌをピリジン（２０一）、
クロロベンゼン（８０ｍｊｌ！）の混合溶媒に溶解し、
酸素を１５分間吹き込んで予備酸化した溶液に、モノマ
ーである１．９−デカジイン（５ｇ）を加え酸素を吹き
込みながら６０℃、５時間重合した。反応溶液を塩酸を
含んだメタノール５００一に投入し、析出した沈澱をロ
過しメタノール、純粋、アセトンで洗浄後、減圧乾燥し
て白色のポリ （ｌ，９−デカジイン〉を得た（４．２
ｇ，収率８４％）。Example 1 Cuprous chloride 100cm, N,N. N',N'-tetramethylethylenediamine 1rnl to pyridine (201),
Dissolved in a mixed solvent of chlorobenzene (80 mjl!),
A monomer, 1.9-decadiine (5 g), was added to the solution that had been preoxidized by blowing oxygen in for 15 minutes, and polymerization was carried out at 60° C. for 5 hours while blowing oxygen. The reaction solution was poured into methanol 500ml containing hydrochloric acid, and the precipitate precipitated was filtered, washed with methanol, pure water, and acetone, and dried under reduced pressure to obtain white poly(l,9-decadiine) (4. 2
g, yield 84%).
この高分子（３ｇ）を１．２−ジクロ口エタン（３００
ｄ＞に溶解し、石英カラス上にキャストして高分子薄膜
を得た。さらに、この薄膜を１５０℃で４８時間熱処理
した。第１図にこの高分子薄膜の熱処理前後での紫外可
視吸収スペクトルを示す。This polymer (3 g) was mixed with 1,2-dichloroethane (300
d> and cast on quartz glass to obtain a polymer thin film. Furthermore, this thin film was heat-treated at 150° C. for 48 hours. FIG. 1 shows the ultraviolet-visible absorption spectra of this polymer thin film before and after heat treatment.
三次の非線形光学効果は、光第三次高調波発生（ＴＨＧ
）の測定によった。Ｎｄ：ＹＡＧレーザーの基本波長（
１０６４ｎｍ）の光を高圧水素セル中に通して得られる
ラマンシフト光（１９０７ｎｍ）を用いてＴＨＧメーカ
ーフリンジ法を行った。測定は空気の影響を取り除くた
め減圧下で行った。The third-order nonlinear optical effect is called third-order harmonic generation (THG).
) according to measurements. Fundamental wavelength of Nd:YAG laser (
The THG Maker fringe method was performed using Raman-shifted light (1907 nm) obtained by passing light (1064 nm) into a high-pressure hydrogen cell. Measurements were performed under reduced pressure to remove the influence of air.
石英基板及び熱処理ボＩＪ （１．９−デカジイン）
／石英基板のＴＨＧメーカーフリンジの測定結果を第２
図、第３図に示す。参照試料である石英基板のフリンジ
パターンより入射光強度を算出し、その強度から三次の
非線形感受率（χＣ３》）を計算した。その結果、ポリ
（１，９−デカジイン）に対してｌ ２ Ｘ １ ０
−”（ｅｓｕ）の値を得た。Quartz substrate and heat-treated IJ (1.9-decadiyne)
/ Second measurement result of THG manufacturer fringe on quartz substrate
As shown in Fig. 3. The intensity of incident light was calculated from the fringe pattern of the quartz substrate, which was a reference sample, and the third-order nonlinear susceptibility (χC3) was calculated from the intensity. As a result, for poly(1,9-decadiyne), l 2
-” (esu) value was obtained.
石英基板上に作製した熱処理ポリ （１．９−デカジイ
ン）（厚さ１．７μｍ）について第４図に示される装置
を用いて光の導波を行った。この装置は、プリズム底面
で全反射してくる光を入射角度を変えて測定するもので
ある。光源にはＨｅ−Ｎｅレーザー（６３３ｎｍ＞を用
いた。光入射は、プリズム（材質： ＦＤ−１ １）を
カップリング法によりＴＥモードで行い、フィルム中に
入射されずにプリズムの底面で全反射した光の強度につ
いて測定した。第５図に、入射角度との反射光強度の関
係を示した。反射光強度は三つの角度、図中のａ、ｂ，
ｃで極小値をとりこれらの入射角度で高分子フィルム中
に入射され導波していることがわかった。Light waveguiding was performed using the apparatus shown in FIG. 4 on heat-treated poly(1.9-decadiyne) (thickness 1.7 μm) fabricated on a quartz substrate. This device measures the light that is totally reflected at the bottom of the prism by changing the incident angle. A He-Ne laser (633 nm>) was used as the light source.The light was incident on a prism (material: FD-11) in TE mode using the coupling method, and was totally reflected at the bottom of the prism without entering the film. The intensity of the reflected light was measured. Figure 5 shows the relationship between the incident angle and the reflected light intensity. The reflected light intensity was measured at three angles, a, b, and
It was found that the light had a minimum value at c, and was incident on the polymer film at these incident angles and was guided.
実施例２
塩化第一銅５ ０ｍｇ，Ｎ．Ｎ，Ｎ’ ．Ｎ’−テトラ
メチルエチレンジアミン０． ５ ｍｌ！をビリジン（
１０ｒｎｌ）、クロロベンゼン（４（ｌｍｌ）の混合溶
媒に溶解し、酸素を１５分間吹き込んで予備酸化した溶
液に、モノマーである１，４−ジエチニル−２，５−ジ
ブトキシベンゼン（５００■）を加え酸素を吹き込みな
がら６０℃、５時間重合した。反応溶液を塩酸を含んだ
メタノール３００ｍｉ！に投入し、析出した沈澱をロ過
しメタノール、純粋、アセトンで洗浄後、減圧乾燥して
暗黄色のボ’Ｊ （１． ４ジｘチ＝ル−２．５−ジ
ブトキシベンゼン）ＰＤＢＤＢＢを得たく４２０■、収
率８４％〉。第６Ａ図、第６Ｂ図にこの高分子（第６Ａ
図はボリマー１６Ｂ図はモノマー）の”Ｃ−ＮＭＲスペ
クトルを示す。Example 2 Cuprous chloride 50 mg, N. N, N'. N'-tetramethylethylenediamine 0. 5ml! Viridine (
The monomer 1,4-diethynyl-2,5-dibutoxybenzene (500μ) was added to a solution dissolved in a mixed solvent of chlorobenzene (10rnl) and chlorobenzene (4 (lml)) and preoxidized by blowing oxygen for 15 minutes. Polymerization was carried out at 60°C for 5 hours while blowing oxygen.The reaction solution was poured into 300ml of methanol containing hydrochloric acid, and the precipitate was filtered, washed with methanol, pure water, and acetone, and dried under reduced pressure to form a dark yellow bottle. 'J (1.4 dix-thyl-2.5-dibutoxybenzene) PDBDBB was obtained with a yield of 420 cm and 84%. Figures 6A and 6B show the composition of this polymer (6A
The figure shows the C-NMR spectrum of Polymer 16B (monomer shown in the figure).
このＰＤＢＤＢＢを（１００■）を１．３−ジメチルイ
ミダゾリジノン（１００ｍｆ）に加え１２．０ｔに加熱
して溶解させた。この溶液を石英基板上にキャストする
ことにより厚さ１．５μｍの高分子フィルムを得た。第
７図にこのフィルムの紫外可視吸収スペクトルを示す。This PDBDBB (100 ml) was added to 1,3-dimethylimidazolidinone (100 mf) and heated to 12.0 t to dissolve it. A polymer film with a thickness of 1.5 μm was obtained by casting this solution onto a quartz substrate. FIG. 7 shows the ultraviolet-visible absorption spectrum of this film.
三次の非線形光学効果は、光第三次高調波発生（ＴＨＧ
＞の測定によった。Ｎｄ ：ＹＡＧレーザーの基本波
長（１０６４ｎｍ）の光を高圧水素セル中に通して得ら
れるラマンシフト光（１９０７ｎｍ）を用いてＴＨＧメ
ーカーフリンジ法を行った。測定は空気の影響を取り除
くため減圧下で行った。The third-order nonlinear optical effect is called third-order harmonic generation (THG).
> based on measurements. The THG Maker fringe method was performed using Raman shifted light (1907 nm) obtained by passing light at the fundamental wavelength (1064 nm) of an Nd:YAG laser into a high-pressure hydrogen cell. Measurements were performed under reduced pressure to remove the influence of air.
ＰＤＥＤＢＢ／石英基板のＴＨＧメーカーフリンジの測
定結果を第８図に示す。参照試料である石英基板のフリ
ンジパターンより入射光強度を算出し、その強度から三
次の非線形感受率（χ（３Ｉ）を計算した。その結果、
ＰＤＩ！ＤＢＢに対して９ Ｘ １０−” （ｅｓｕ）
の値を得た。The measurement results of the THG manufacturer fringe of the PDEDBB/quartz substrate are shown in FIG. The incident light intensity was calculated from the fringe pattern of the quartz substrate, which was a reference sample, and the third-order nonlinear susceptibility (χ(3I)) was calculated from that intensity.As a result,
PDI! 9 x 10-” (esu) to DBB
obtained the value of
第１図は、石英基板上に作製したボＩＪ（１，９−デカ
ジイン〉フィルムの紫外可視吸収スペクトルを表す図面
である（Ａ；熱処理前、Ｂ：熱処理後）。
第２図、第３図はそれぞれ石英基板、ポリ （１．９一
デカジイン）／石英基板のＴＨＧメーカーフリンジの測
定結果を表す図面である。
第４Ａ図、第４Ｂ図は、ポＩＪ（１．９〜デヵジイン）
の導波特性の測定に用いた装置の図面である。
第５図は、ボ！Ｊ （１．９−デヵジイン）の導波特
性を表す図面である。
第６Ａ図、第６Ｂ図は、ＰＤＥＤＢＢのボリマー（第６
／ｌ？ｌ） 、％／７− （第６Ｂ図）（７）”Ｃ−Ｎ
ＭＲスペクトルを表す図面である。
第７図は、Ｐ［ｌＢＯ８１３の紫外可視吸収スペクトル
を表す図面である。
第８図は、ＰＤＥ’ＤＢＢ／石英基板のＴＨＧメーカー
フリンジの測定結果を表す図面である。
和ヌ寸第３；欠高調波強度
ネ目ヌ４第３冫欠高言周５皮強度
反劃光弦度
ネ目ヌ寸第３２欠高調波強度FIG. 1 is a drawing showing the ultraviolet-visible absorption spectrum of a BoIJ (1,9-decadiyne) film produced on a quartz substrate (A: before heat treatment, B: after heat treatment). are drawings showing the measurement results of THG manufacturer fringe of quartz substrate and poly(1.9-decadiyne)/quartz substrate, respectively.
1 is a drawing of an apparatus used to measure the waveguide characteristics of Figure 5 shows Bo! It is a drawing showing the waveguide characteristics of J (1.9-decadiyne). Figures 6A and 6B show the PDEDBB polymer (6th
/l? l) ,%/7- (Figure 6B) (7)"C-N
It is a drawing showing an MR spectrum. FIG. 7 is a drawing showing the ultraviolet-visible absorption spectrum of P[lBO813. FIG. 8 is a drawing showing the measurement results of THG manufacturer fringe of PDE'DBB/quartz substrate. 3rd missing harmonic intensity 4th 3rd missing harmonic intensity 5th skin intensity
Claims (3)
はアルキレン基を含む高分子非線型光学材料。(1) A polymeric nonlinear optical material that has a diacetylene group in its main chain and also contains an alkyl group or an alkylene group.
はアルコキシフェニレン基である］で現わされる主鎖に
ジアセチレン基を持つ高分子からなる有機非線形光学材
料。(2) A polymer with a diacetylene group in the main chain represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is an alkylene group, an alkylphenylene group, or an alkoxyphenylene group] An organic nonlinear optical material consisting of
材料を熱処理、光照射、又は放射線照射して得られる有
機非線形光学材料。(3) An organic nonlinear optical material obtained by heat treating, light irradiation, or radiation irradiation the polymer nonlinear optical material according to claims (1) to (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1235193A JPH0670697B2 (en) | 1989-09-11 | 1989-09-11 | Organic nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1235193A JPH0670697B2 (en) | 1989-09-11 | 1989-09-11 | Organic nonlinear optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0398026A true JPH0398026A (en) | 1991-04-23 |
| JPH0670697B2 JPH0670697B2 (en) | 1994-09-07 |
Family
ID=16982460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1235193A Expired - Lifetime JPH0670697B2 (en) | 1989-09-11 | 1989-09-11 | Organic nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0670697B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5475133A (en) * | 1994-11-28 | 1995-12-12 | The Regents Of The University Of California | Bis-propargyl thermosets |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5643220A (en) * | 1979-06-25 | 1981-04-21 | University Patents Inc | Method of using novel nonlinear optical substance and diacetylenes |
| JPS6160638A (en) * | 1984-08-31 | 1986-03-28 | Nippon Telegr & Teleph Corp <Ntt> | Organic nonlinear optical material |
| JPS61148432A (en) * | 1984-12-21 | 1986-07-07 | Agency Of Ind Science & Technol | Optical treatment |
| JPS61210332A (en) * | 1985-03-15 | 1986-09-18 | Nippon Telegr & Teleph Corp <Ntt> | Material for nonlinear optical element and formation of pattern |
| JPS6252505A (en) * | 1985-09-02 | 1987-03-07 | Nippon Telegr & Teleph Corp <Ntt> | Formation of light guide using organic crystalline compound |
| JPS62255475A (en) * | 1986-04-25 | 1987-11-07 | Agency Of Ind Science & Technol | Novel diacetylene compound polymerizable in solid phase |
| JPS6341515A (en) * | 1986-08-07 | 1988-02-22 | Agency Of Ind Science & Technol | Molecule orientating thin film |
| JPS63175835A (en) * | 1987-01-16 | 1988-07-20 | Nippon Telegr & Teleph Corp <Ntt> | Organic nonlinear optical material, optical device using the same and production thereof |
| JPS63279230A (en) * | 1987-05-11 | 1988-11-16 | Keisuke Sasaki | Optical modulating element |
| JPH01188836A (en) * | 1988-01-25 | 1989-07-28 | Fujitsu Ltd | Production of organic nonlinear optical film |
-
1989
- 1989-09-11 JP JP1235193A patent/JPH0670697B2/en not_active Expired - Lifetime
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5643220A (en) * | 1979-06-25 | 1981-04-21 | University Patents Inc | Method of using novel nonlinear optical substance and diacetylenes |
| JPS6160638A (en) * | 1984-08-31 | 1986-03-28 | Nippon Telegr & Teleph Corp <Ntt> | Organic nonlinear optical material |
| JPS61148432A (en) * | 1984-12-21 | 1986-07-07 | Agency Of Ind Science & Technol | Optical treatment |
| JPS61210332A (en) * | 1985-03-15 | 1986-09-18 | Nippon Telegr & Teleph Corp <Ntt> | Material for nonlinear optical element and formation of pattern |
| JPS6252505A (en) * | 1985-09-02 | 1987-03-07 | Nippon Telegr & Teleph Corp <Ntt> | Formation of light guide using organic crystalline compound |
| JPS62255475A (en) * | 1986-04-25 | 1987-11-07 | Agency Of Ind Science & Technol | Novel diacetylene compound polymerizable in solid phase |
| JPS6341515A (en) * | 1986-08-07 | 1988-02-22 | Agency Of Ind Science & Technol | Molecule orientating thin film |
| JPS63175835A (en) * | 1987-01-16 | 1988-07-20 | Nippon Telegr & Teleph Corp <Ntt> | Organic nonlinear optical material, optical device using the same and production thereof |
| JPS63279230A (en) * | 1987-05-11 | 1988-11-16 | Keisuke Sasaki | Optical modulating element |
| JPH01188836A (en) * | 1988-01-25 | 1989-07-28 | Fujitsu Ltd | Production of organic nonlinear optical film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5475133A (en) * | 1994-11-28 | 1995-12-12 | The Regents Of The University Of California | Bis-propargyl thermosets |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0670697B2 (en) | 1994-09-07 |
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